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Handbook of Magnetic Materials, Volume 9 Elsevier, 1995 Edited by: K.H.J. Buschow ISBN: 978-0-444-82232-1
by kmno4
PREFACE TO VOLUME 9
The Handbook series Magnetic Materials is a continuation of the Handbook series Ferromagnetic Materials. The original aim of Peter Wohlfarth when he started the latter series was to combine new developments in magnetism with the achievements of earlier compilations of monographs, producing a worthy successor to Bozorth's classical and monumental book Ferromagnetism. This is the main reason that Ferromagnetic Materials was initially chosen as title for the Handbook series, although the latter aimed at giving a more complete cross-section of magnetism than Bozorth's book. Magnetism has seen an enormous expansion into a variety of different areas of research in the last few years, comprising the magnetism of several classes of novel materials that share with truly ferromagnetic materials only the presence of magnetic moments. For this reason the Editor and Publisher of this Handbook series have carefully reconsidered the title of the Handbook series and changed it into Magnetic Materials. It is with much pleasure that I can introduce to you now Volume 9 of this Handbook series. The magnetism of the majority of metallic systems can adequately be described by the well known concepts of localised or itinerant moment magnetism. These traditional concepts are, however, not able to describe the magnetism of a fairly large class of materials generally indicated as heavy-fermion systems. The magnetism of these strongly correlated charge-carrier systems has developed from two different sources, the Kondo-impurity concept and the intermediate-valence concept. The last decade has seen a strong proliferation in experimental and theoretical studies of such systems. Progress made in this field by means of inelastic neutron scattering was described already in Chapter 6 of Volume 7 of the Handbook. A more general account of the magnetism of heavy-fermion systems is presented in Chapter 1 of the present Volume. Towers of strengths to the understanding of the physics of magnetism are theory and experiment. In Volume 7 of the Handbook two different chapters were devoted to the former, emphasising results of electronic band structure calculations and their beneficial influence on the understanding of magnetism in many materials. As a counterweight, two novel experimental techniques will be described in the present Volume. The first one, Chapter 2, deals with muon spin rotation, the second one, Chapter 5, gives an account of the possibilities offered by photon beam spectroscopy. In both chapters it is shown how these sophisticated experimental methods can be
vi
PREFACE TO VOLUME 9
used to obtain experimental information not easily obtainable by conventional experimental methods. Interstitially modified intermetallic compounds of rare earth and 3d elements are described in Chapter 3. These materials can be obtained from the pure intermetallics by filling some of the available interstitial hole sites in their crystal structure with carbon, nitrogen or hydrogen atoms. Though the drastic changes of magnetocrystalline anisotropy and magnetic couplings are of substantial fundamental interest, a large part of the Chapter is devoted to practical consequences as found in modern permanent magnet technology. In one of the preceding volumes, Vol. 7, a major updating of the experimental results was presented for intermetallics in which rare earths are combined with 3d transition metals, while progress in ferrite research was presented in Vol. 8. Both groups of materials are fairly extensive, as are the many experimental results that have accumulated over the years. Of particular interest in these two groups of materials is the occurrence of field-induced phase transitions. These phase transitions are commonly treated in a rather phenomenological way, and at best, are described in terms of anisotropy and moment couplings. The last chapter of the present volume deals with the thermodynamic approach and shows how the understanding and description of these magnetic phase transitions can be considerably enriched. Volume 9 of the Handbook on the Properties of Magnetic Materials, as the preceding volumes, has a dual purpose. As a textbook it is intended to be of assistance to those who wish to be introduced to a given topic in the field of magnetism without the need to read the vast amount of literature published. As a work of reference it is intended for scientists active in magnetism research. To this dual purpose, Volume 9 of the Handbook is composed of topical review articles written by leading authorities. In each of these articles an extensive description is given in graphical as well as in tabular form, much emphasis being placed on the discussion of the experimental material in the framework of physics, chemistry and material science. The task to provide the readership with novel trends and achievements in magnetism would have been extremely difficult without the professionalism of the NorthHolland Physics Division of Elsevier Science B.V., and I wish to thank Joep Verheggen and Wim Spaans for their great help and expertise. K.H.J. Buschow Van der Waals-Zeeman Institute University of Amsterdam
CONTENTS Preface to V o l u m e 9 . . . . . . . . . . . . . . . . . . . . Contents .
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Contents o f Volumes 1-8
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1. H e a v y F e r m i o n s and R e l a t e d C o m p o u n d s G.J. N I E U W E N H U Y S . . . . . . . . . . . . . . . . .
1
2. M a g n e t i c M a t e r i a l s Studied b y M u o n Spin Rotation S p e c t r o s c o p y A. S C H E N C K and E N . G Y G A X . . . . . . . . . . . . . .
57
3. Interstitially M o d i f i e d Intermetallics o f Rare Earth and 3d Elements H. F U J I I and H. S U N . . . . . . . . . . . . . . . . . .
303
4. F i e l d I n d u c e d P h a s e Transitions in F e r r i m a g n e t s A.K. ZVEZDIN . . . . . . . . . . . . . . . . . . . .
405
5. Photon B e a m Studies o f M a g n e t i c Materials S.W. L O V E S E Y . . . . . . . . . . . . . . . . . . .
545
Author Index
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631
Subject Index
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679
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689
List o f Contributors
Materials Index
vii
CONTENTS OF VOLUMES 1-8 Volume 1 1. 2. 3. 4. 5. 6. 7.
Iron, Cobalt and Nickel, by E.P. Woh!farth . . . . . . Dilute Transition Metal Alloys: Spin Glasses, by J.A. Mydosh Rare Earth Metals and Alloys, by S. Legvold . . . . . . Rare Earth Compounds, by K. H.J. Buschow . . . . . . Actinide Elements and Compounds, by W. Trzebiatowski . . Amorphous Ferromagnets, by E E . Luborsky . . . . . . Magnetostrictive Rare Earth-Fe2 Compounds, by A. E. Clark
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1
and G.J. Nieuwenhuys .
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71 183 297 415 451 531
Volume 2 1. 2. 3. 4. 5. 6. 7. 8.
Ferromagnetic Insulators: Garnets, by M.A. Gilleo . . . . . . . . . . . . . Soft Magnetic Metallic Materials, by G. Y Chin and J. 14. Wernick . . . . . . . . Ferrites for Non-Microwave Applications, by P L Slick . . . . . . . . . . . Microwave Ferrites, by J. Nicolas . . . . . . . . . . . . . . . . . . . Crystalline Films for Bubbles, by A.H. Eschenfelder . . . . . . . . . . . . Amorphous Films for Bubbles, by A.H. Eschenfelder . . . . . . . . . . . . Recording Materials, by G. Bate . . . . . . . . . . . . . . . . . . . Ferromagnetic Liquids, by S. W. Charles and J. Popplewell . . . . . . . . . .
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1 .
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55 189
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243
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297 345 381 509
. . .
Volume 3 1. Magnetism and Magnetic Materials: Historical Developments and Present Role in Industry and Technology, by U. Enz . . . . . . . . . . . . . . . . . . . . . . 2. Permanent Magnets; Theory, by 11. Zifistra . . . . . . . . . . . . . . . . 3. The Structure and Properties of Alnico Permanent Magnet Alloys, by R.A. McCurrie . . 4. Oxide Spinels, by S. Krupi&a and P Novdk . . . . . . . . . . . . . . . . 5. Fundamental Properties of Hexagonal Ferrites with Magnetoplumbite Structure, by 14. Kojima
6. 7. 8. 9.
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Properties of Ferroxplana-Type Hexagonal Ferrites, by M. Sugimoto Hard Ferrites and Plastoferrites, by H. St~blein . . . . . . . . Sulphospinels, by R. P van S t @ d e . . . . . . . . . . . . Transport Properties of Ferromagnets, by I.A. Campbell and A. Fert
ix
1
37 107 189
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305 393
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441
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603 747
x
CONTENTS OF VOLUMES 1-8
Volume 4 1. 2. 3. 4. 5.
Permanent Magnet Materials Based on 3d-rich Ternary Compounds, by K. H. J. Buschow Rare Earth-Cobalt Permanent Magnets, by K.J. Strnat . . . . . . . . . . . . . Ferromagnetic Transition Metal Intermetallic Compounds, by J. G. Booth . . . . . . Intermetallic Compounds of Actinides, by V. Sechovsky and L. Havela . . . . . . . Magneto-optical Properties of Alloys and Intermetallic Compounds, by K. H.J. Buschow
1
131 211 309 493
Volume 5 1. Quadrupolar Interactions and Magneto-elastic Effects in Rare-earth Intermetallic Compounds, by P. Morin and D. Schrnitt . . . . . . . . . . . . . . . . . 2. Magneto-optical Spectroscopy of f-electron Systems, by W. Reim and J. Schoenes . . 3. INVAR: Moment-volume Instabilities in Transition Metals and Alloys, by E. E Wasserman 4. Strongly Enhanced Itinerant Intermetallics and Alloys, by P E. Brommer and J. J.M. Franse 5. First-order Magnetic Processes, by G. Asti . . . . . . . . . . . . . . . . . 6. Magnetic Superconductors, by ~. Fischer . . . . . . . . . . . . . . . . .
1
133 237 323 397 465
Volume 6 1. Magnetic Properties of Ternary Rare-earth Transition-metal Compounds, by H.-S. Li and J . M . D . Coey
2. 3. 4. 5. 6.
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Magnetic Properties of Ternary Intermetallic Rare-earth Compounds, Compounds of Transition Elements with Nonmetals, by O. Beckman Magnetic Amorphous Alloys, by P. Hansen . . . . . . . . . Magnetism and Quasicrystals, by R.C. O'Handley, R.A. Dunlap and Magnetism of Hydrides, by G. Wiesinger and G. Hilscher . . .
by A. Szytula and L. Lundgren . . . . . . . M.E. McHenry . . . . . . . .
1
85 181 289 453 511
Volume 7 1. Magnetism in Ultrathin Transition Metal Films, by U. Gradmann . . . . . . . . . 2. Energy Band Theory of Metallic Magnetism in the Elements, by V.L. Moruzzi and P.M. Marcus
. . . . . . . . . . . . . . . . . . . . . . . . . . .
3. Density Functional Theory of the Ground State Magnetic Properties of Rare Earths and Actinides, by 34. S. S. Brooks and B. Johansson . . . . . . . . . . . . . . . 4. Diluted Magnetic Semiconductors, by J. Kossut and W. Dobrowolski . . . . . . . . 5. Magnetic Properties of Binary Rare-earth 3d-transition-metal Intermetallic Compounds, by J.J.M. Franse and R.J. Radwarlski
. . . . . . . . . . . . . . . . . .
1
97 139 231 307
6. Neutron Scattering on Heavy Fermion and Valence Fluctuation 4f-systems, by M. Loewenhaupt and K.H. Fischer
. . . . . . . . . . . . . . . . . .
503
Volume 8 1. Magnetism in Artificial Metallic Superlattices of Rare Earth Metals, by J.J. Rhyne and R. W. Erwin
. . . . . . . . . . . . . . . . . . . . . . . . . . .
1
2. Thermal Expansion Anomalies and Spontaneous Magnetostriction in Rare-Earth Intermetallics with Cobalt and Iron, by A. V. Andreev . . . . . . . . . . . . . . . . . . 59 3. Progress in Spinel Ferrite Research, by V.A.M. Brabers . . . . . . . . . . . . 189 4. Anisotropy in Iron-Based Soft Magnetic Materials, by M. Soinski and A.J. Moses 325 5. Magnetic Properties of Rare Earth-Cu 2 Compounds, by Nguyen Hoang Luong and J. J.M. Franse . . . . . . . . . . . . . . . . . . . . . . . . . . 415
chapter 1 HEAVY FERMIONS AND RELATED COMPOUNDS
G.J. NIEUWENHUYS Kamerlingh Onnes Laborato~ Leiden University RO. Box 9506, 2300 RA Leiden The Netherlands
Handbook of Magnetic Materials, Vol. 9 Edited by K. H.J. Buschow ©1995 Elsevier Science B.V. All rights reserved
CONTENTS 1. I n t r o d u c t i o n
.................................................................
1.1.
S c o p e o f this c h a p t e r
.....................................................
1.2.
The picture
1.3.
Archetypal heavy fermions
1.4.
The terms
1.5.
Other reviews
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..............................................................
3 3 3 5 6
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10
2. E x p e r i m e n t a l results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
10
2.1.
122-compounds
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10
2.2.
111-compounds
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21
2.3.
U2T2X-compounds
2.4.
U-compounds with CaCu5 structure and related borides .........................
27
2.5.
334-compounds
34
2.6.
Gaps
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.........................................................
..................................................................
26
36
2.7.
Magnetism and superconductivity ...........................................
39
2.8.
Miscellaneous compounds
40
2.9.
Yb-compounds
2.10. T h i n films 3. C o n c l u s i o n
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4. A c k n o w l e d g e m e n t s References
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42 44 45 45 45
1. Introduction
1.1. Scope of this chapter As always, this review has to be restricted for many reasons, few of them being the interest and knowledge of the author. In this chapter some magnetic properties of heavy fermions and related compounds will be emphasized and presented mainly in tabular form. For other aspects of these very interesting new materials the reader will be referred to other reviews at the end of this introduction.
1.2. The picture Heavy fermions have been intensively studied during the last decade. The name 'heavy fermion' stems from the fact that these materials exhibit an anomalous specific heat. At temperatures much lower than the Debye temperature (and much lower then the Fermi temperature) the specific heat of a conductor can be described by Cp = 3`T +/3T 3,
(1)
where 3`T is the so-called linear term due to the excitations of the itinerant electrons and ¢3T3 is the low temperature approximation of the specific heat of the lattice. For normal conductors, 3' is of order 1 ... 10 mJ/(moleK2). However, a new class of materials - the heavy fermions - showed 3"-values up to 1000 mI/(moleK2). The expression for 3' in terms of the effective mass of the itinerant electrons reads
3" = (m*kF/Trzhz)(k2/3),
(2)
where kF is the Fermi wavevector and hB is Boltzmann's constant. The large value for 3' is then ascribed to a large value for ra*, hence the name heavy fermion. On the other hand, if the specific heat, Cv(T), is described in terms of the number of possible excitations at temperature T, Cp(T) c< nhB(T/To), then the characteristic temperature, To, is estimated at 10 to 100 K, much lower than the Fermi temperature of ordinary metals. Heavy fermions are typically found amoung the Ce and U containing compounds. The magnetic susceptibility of these compounds follows a Curie-Weiss law at high temperatures, with an effective moment approximately given by Hund's rule, but at low temperatures the magnetic susceptibility flattens off (sometimes after attaining a maximum) and becomes constant with decreasing temperature. This constant, T --+ 0, value is much larger than the Pauli susceptibility
4
G.J. NIEUWENHUYS
of normal metals. In fact, for those heavy fermions where no magnetic ordering is found, the enhancement of the magnetic susceptibility for T --+ 0 is as large as that of the specific heat. The crystal structure of most of the heavy fermions is tetragonal or hexagonal. A large anisotropy in the magnetic susceptibility is generally observed, e.g., in tetragonal URuzSi2 the magnetic susceptibility measured with the magnetic field directed along the c-axis shows the features mentioned above, with the field along the a-axis no temperature dependence at all is found for T ~< 100 K. The same is roughly true for hexagonal UPdzA13, however with a change in the role of the a- and c-axis. In both cases the susceptibility can be very well described by a simple crystalline electric field, CEF, model. A direct consequence of the large contribution of the itinerant electrons to the (linear term) of the specific heat is that at a temperature of only a few Kelvin the entropy gain of the itinerant electrons is already R ln(2), R being the gas constant, a value only expected for localized magnetic moments. Therefore, in spite of the linear term in the specific heat the question arises whether the f-electrons of the Ce or the U should be described in an itinerant model. Moreover, some heavy fermions are superconducting and the jump in the specific heat at Tc equals about 3'To indicating that the heavy electrons are involved in the superconductivity. Still the large entropy gain at low temperatures has to be explained as well, within the same model for heavy fermions. A priori it is not clear whether charge or spin degrees of freedom cause the entropy (Kagan et al. 1992). The same ambiguity between itinerancy and localization governs the role of the crystalline electric fields, CEF. Whereas inelastic neutron scattering can observe CEF levels in a number of Ce based compounds, the non-observation in U-based compounds is almost a rule rather than an exception. On the other hand, as mentioned above the strong magnetic anisotropy can easily be explained by CEF as is the case also for a number of other macroscopic properties such as specific heat and magnetic susceptibility as functions of temperature and external magnetic field. The electrical resistance of heavy fermions is anomalous too. At low temperatures it can be described by
p(T) = p(O) + A T 2,
(3)
where A was experimentally found by Kadowaki and Woods (1986) to be 10-53 '2 #~cm/(moleKZ/mJ)2, and where 3' is the coefficient of the linear term in the specific heat. In other words, A is (ra*/m) 2 larger than in normal metals. On increasing the temperature a maximum is attained followed by a logarithmic decrease towards higher temperatures. A number of different ground states has been found in heavy fermions. Some stay paramagnetic down to the lowest temperatures (20 mK), others order antiferromagnetically (ferromagnetism is seldom found), and a number of superconductors are observed. Finally, even a semiconducting ground state is possible. The transition temperature for the superconductivity is rather low, ~< 2 K, and the superconductivity coexists with antiferromagnetism in almost all cases (UBe13 seems to be the exception amoung the superconducting heavy fermions as it is with respect to its crystal structure, being cubic). The type of superconducting order parameter is not known with great certainty, but is not expected to be a simple
HEAVY FERMIONS AND RELATED COMPOUNDS
5
one. UNiaA13 and UPd2A13 have rather normal spontaneous moments as measured by neutron scattering ( ~ I#B) and the ordering is of long range. URu2Si2 has an ordered moment of only 0.02#B and the range of order parameter is restricted to only about 100 A. UPt3 and CeCu2Si2 show only short range correlations of small moments. These magnetic correlations have been observed, e.g., with magnetic Xray scattering (Isaacs et al. 1989, Mason et al. 1990 and Isaacs et al. 1994). In the case of CeCu2Si2, there is even growing evidence that the superconductivity and the antiferromagnetic order live in different parts of the sample, Feyerherm et al. (1995) and Luke et al. (1994). Another general feature of heavy fermions is the large sample dependence of the magnetic and superconducting properties. Low concentration replacements by other atoms or slight departures from the exact stoichiometry induce large effects. For example, small changes in the Cu content in CeCu2Si2 can alter the volume fractions mentioned above from zero to one hundred percent. Heat treatments can change the properties also in strange ways, without any evidence for a change the crystallographic structure. Neutron diffraction experiments (F5k et al. 1995) have shown that annealing URu2Si2 changes the temperature dependence of the ordered moment drastically without changing the Ndel temperature or the zerotemperature value of the ordered moment. This strong dependence on the samples indicates that heavy fermions live close to an instability. It makes experimental research in this field rather difficult and supports clearly the statement that the quality of the experimental results ~ the quality of the sample. The need for good sample analysis is evident. Maybe we are slowly reaching the point where we cannot improve our single crystalline samples, since starting materials have limited purity and thermodynamics tells us that the minimum of the free energy at final temperature (normal annealing temperature) is obtained for a finite number of imperfections.
1.3. Archetypal heavy fermions TABLE 1 Main features of archetypal heavy fermions. Compound
Tc (K)
TN (K)
"7 X(0) A (mJ/moleK2) (10-9m3/mole) (Iz~ cm/K2)
Crystal- Ref. structure
CeCuzSi2 UBel3 UPt3 URuzSi2 UPdzA13 U2Znl7 UCdl 1 CeA13 CeCu6 YbCu4Ag UA12
0.65 0.9 0.5 1.5 2.0 -
5 17 14 9.7 5 -
1000 1100 450 180 150 500 840 1620 1300 245 142
tetrag. cubic hexag. tetrag. hexag. rhomb. cubic hexag. orthor. cubic cubic
98 172 95 67 110 545 468 263 224 342 53
35 10.7 0.06
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11]
6
G.J.N~UWENHUYS
References: [1] [2] [3] [4] [5] [6]
Bredlet al. (1983) Ott et al. (1983) Stewart et al. (1984) Palstra et al. (1985) Geibel et al. (1991a) Ott et al. (1984)
[7] [8] [9] [10] [11]
Fisket al. (1984) Andreset al. (1975) Fujitaet al. (1985) Rosselet al. (1987) Stewart (1984)
1.4. The terms This section bears on the very well readable reviews by Lee et al. (1986), and by Bauer (1991).
1.4.1. Single impurity Since f-electron ions play the major role in heavy fermions and Anderson (1961) has invented a simple, nontrivial, successful and well understood model for an single impurity in a metal, this should be the starting point for a theoretical description. In its simplest form the three ingredients are the conduction electrons, an f-ion with a single orbital and a hybridization matrix element Vfk that couples this orbital with the conduction band. The Hamiltonian then reads
H:
+ ~-~ 6(k)nks q- 6f ~ nfs ~- Unfsnf$ + ~ (Wfkf+Ck~+ VfkekJ~), ks s ks
(4)
where U is the Coulomb correlation energy associated with double occupancy of the f orbital. The width, F, of the f level is given by ~rN(ez)lVfkFI2, where N(eF) is the single-spin density of states at the Fermi level. Ce has Nf degenerate orbitals with maximum total occupancy, nf of 1, since U is estimated to be 5 eV. The f orbitals have an energy of a few eV below the Fermi level. For Uranium the relevant configurations are f2 (angular momentum, J = 4) and f3 ( j = 9/2), The correlation energy is estimated to be 2 eV. The hybridization has often been taken as an adjustable, constant, parameter, but ab initio band structure calculations have been carried out, e.g., by Sheng et al. (1990). In order to obtain absolute information on this parameter Endstra et al. (1993a) have used a simple model to estimate Vek to explain trends in the magnetic ordering temperatures. The energy of the f level, cf, with respect to the chemical potential and the bandwidth, F, govern the equilibrium occupancy of the f levels, thus non-integer occupancies may occur, leading to socalled valence fluctuations. Additionally, because of these fluctuations, f electrons may exchange spin components with the conduction band, without an actual charge transfer. In that case one speaks of spin fluctuations. Crystalline electric fields, CEF, effects tend to lower the degeneracy, on the other hand, the hybridization can renormalize the strength of the CEF downwards. During the last decade many exact results have been obtained for the degenerate Anderson model taking into account the effects due to crystalline electric fields, spin-orbit coupling and external magnetic fields (Schlottmann 1989).
HEAVY FERMIONS AND RELATED COMPOUNDS
7
1.4.2. Kondo Under strict conditions (nondegeneracy and integer occupation) the Hamiltonian in eq. (4) can be transformed (Schrieffer and Wolff 1966) into H K = -23S.s(0),
(5)
which is exactly the Hamiltonian that Kondo (1964) used to describe the on site interaction of an S -- 1/2 single impurity interacting with the electron density s(0). Since 3 is negative, this interaction favours antiparallel alignment of the conduction electron spins with respect to the impurity spin at low temperatures, finally leading to a singlet state at T = 0. This moment compensation leads to a result for the magnetic susceptibility which agrees with the observations in heavy fermions. The compensation or screening also leads to a term in the electrical resistivity ~ ln(TK/T) in the vicinity of the Kondo temperature, TK. In the limit for U --+ oo the interaction 3 = - v Z / @ f - EF), where Vfk is replaced by a constant V. As a consequence of the singlet ground state of the impurity, the low-temperature properties of the system can be described within a Fermi liquid picture. In the degenerate case, the transformation from eq. (1) to eq. (2) can also be made for integer occupation (no charge fluctuations) and then leads to the Coqblin-Schrieffer model (Coqblin and Schrieffer 1969). Heavy fermions, consisting of a regular lattice of Ce or U atoms, are called Kondo lattices, but one should bear in mind that the Kondo Hamiltonian can only be obtained exactly in the single impurity case with integer occupation.
1.4.3. The compounds In a heavy fermion compound, we are dealing with a regular array of magnetic 'impurities'. In that case the interactions between the Ce or U ions cannot be neglected in general; the problem has acquired a translation symmetry and charge transfer between the f states and the conduction band can no longer be considered as a minor perturbation. The hybridization causes on the one hand the screening as in the single impurity model, but at the other hand induces an interaction between the magnetic moments mediated by the conduction electrons. The screening picture itself has to be reconsidered, since there are not enough conduction available for all magnetic moments. Charge transfer now renormalizes the chemical potential when a finite number of f electrons is promoted into the conduction band. As this process is temperature dependent, the chemical potential becomes temperature dependent, because of the conservation of the total number of electrons. On the one hand, this notion of the 'lattice' aspect of the Kondo problem has led to an item like correlation, which denotes the subtle antiferromagnetic correlations between the - partly - screened magnetic moments thought to cause the rapid decrease in the electrical resistance with decreasing temperature observed in heavy fermion compounds even without long range magnetic order. On the other hand, Strong and Millis (1994) showed that most properties (e.g., specific heat, magnetic susceptibility) of the archetypel heavy fermions CeA13 and CeCu6 c a n be beautifully explaned using crystal field and Kondo effects of single atoms only. The exception is the electrical resistance, where the agreement between calculation and experiment is less satisfactory. Ab initio calculations of the size of the magnetic moments and of the transition temperatures of
8
G.J. NIEUWENHUYS
magnetically ordering compounds have been carried out by Cooper et al. (Cooper 1992; Hu and Cooper 1993). In their calculation scheme, they have treated both hybridization and Coulomb exchange effects simultaneously in the presence of interconfigurational correlation effects. In this way, they are able to successfully compute the magnetic moments and transition temperatures of a number of U- and Ce-based compounds adopting the NaC1 structure. Band-structure calculations (Norman and Koelling 1992) are not able to correctly predict these magnetic properties because they include only those aspects of the valence fluctuations that can be captured by time averaging. Therefore, the true character of the 4f or 5f states is missed and has to be included by adding an additional on-site scattering term (Fulde et al. 1988) or interconfigurational correlation effects. Due to computational limits such calculations have not been carried out for the compounds we will discuss in this chapter. We will therefore limit ourselves to rough estimates of the interactions involved and use that as a guidline through the experimental results. To lowest order the strength of the conduction electron mediated interaction between the magnetic atoms, the RKKY interaction, is proportional to 32, and thus proportional to V 4. As long as this interaction does not dominate, the screening process is still effective and the physical properties of the concentrated systems can roughly be considered as a summation of the single impurity effects. The most apparent exception is seen in the electrical resistance of stoichiometric compounds, where coherent excitations of the f electrons become important. In the single impurity limit the electrical resistance increases as ln(TK/T) with decreasing temperature and saturates as T --+ 0. Coherency causes the resistance to decrease again for T << TK, which leads to the AT 2 term mentioned earlier. When the RKKY interaction dominates, the system will order magnetically, although sometimes with very small ordered moments. The competition between the 'screening', with a characteristic strength TK oc (1/N(cv) ) exp ( - 1/N(eF)3),
(6)
and the RKKY interaction with a characteristic strength TRKKY ~
32N(eF),
(7)
has lead to a phase diagram for the present type of compounds (Doniach 1977, Brandt and Moshchalkov 1984) depicted schematically in fig. 1. This phase diagram draws the boundaries between the magnetically ordering compounds, the 'Kondo-lattices' and the paramagnetic systems. Although it does not provide quantitative information for three dimensional systems, it has been shown by Endstra et al. (1993a) that it serves very well as a guidline for experimentalists to order the compounds within a given series based on a rude estimate of the hybridization parameter. Recognizing that :J ~x V 2 / ( e f
-
eF)
(8)
and assuming that: (i) the hybridization is mainly due to the d-itinerant electrons, so that 3 can be replaced by 3dr and (ii) that ef - eF is nearly constant over a given
HEAVY FERMIONS AND RELATED COMPOUNDS
9
2.0
1.5
i1.0 f /r.
PARAMAGNET e
0.5
0,5 d/W~
KONDO METAL
1.0
Fig. 1. The one-dimensional Kondo-necklace phase diagram as derived by Doniach (1977).
series of analogous compounds, 3 can by assumed to be proportional to V~. Using an approach put forward by Harrison and Straub (Harrison 1969, 1980, 1983, 1987, and Straub and Harrison 1985) the hybridization matrix elements can be written as ggl, m =(771l,mj~2/~'~e)[(T21--1~'2/'-l)1/2/dl+l'+1]
(9)
The input parameters are the atomic radii of the respective atoms (rl and rv), the interatomic distance d, the angular momenta l, l' (l = 0, 1, 2, 3 for s, p, d, f orbitals), and the symmetry of the bond m. Note that me in eq. (9) is the electron mass. r/u,,~ is given by (Harrison and Straub 1987) (-1) z'+l (l + 1')!(2l)!(2l')! ?]ll'm -- - -
6rr
× (-1)~ [
2z+Z' l!l, !
X
( 2 / + 1)(2/' + 1)
I 1/2
(1 + m ) ! ( l -- m ) ! ( l ' + m ) ! ( l ' -- m ) !
with m = 0, 1, 2, 3 for ~r, re, 5 and ~o bounds. This simple approach has enabled Endstra et al. (1993a) to order compounds of several series and to predict the behaviour of a number of pseudo binary compounds. This picture makes it clear why some compounds do order magnetically, while others don't. The typical heavy fermion compounds have to be placed near the right-hand side of the phase diagram, which partly explains their sensitivity for the exact composition.
10
G.J. NIEUWENHUYS
1.5. Other reviews Numerous reviews on several aspects of the heavy fermion phenomena have appeared in the literature. Reviews with emphasis on the development of the theory can be found in Lee et al. (1986), Gor'kov (1987), Fulde et al. (1988), Schlottmann (1989), Grewe et al. (1990) and Hewson (1993). An experimental review of the superconductivity is given in Fisk et al. (1986), while Fisk et al. (1988) deal mainly with the Fermi-liquid character. Other experimental reviews are: Stewart (1984), Ott (1987), Ott and Fisk (1987), Sechovsky and Havela (1988) (actinide compounds), Sigrist and Ueda (1991) (unconventional superconductivity), Bauer (1991) (CeCu and YbCu compounds), Sarma et al. (1992) (sound experiments), Aeppli and Fisk (1992) (Kondo insulators), Endstra et al. (1993b) (122-compounds), Schenck (1993) and Schenck and Gygax (this volume) (#+SR), Hess et al. (1993), Loewenhaupt and Fisher (1994) (neutron scattering), Knetsch et al. (1994) (URuzSi2), Sauls (1994) (phase diagram of UPt3), and Ott (1994) (superconductivity).
2. Experimental results The number of papers on experimental results on heavy fermion materials and related compounds amounts to a few thousands. Only in the last few years our data base grew with 2000 titles. Ineventable, a selection had to be made for this review paper. The consistency and readability of this chapter were the only criteria used. In view of the large number of papers, the idea about a world-wide data base for storing experimental data and there interpretation should be given some serious though, bearing in mind that the technical infrastructure is available. 2.1. 122-compounds There has been an extensive research on the MT2X 2 compounds, with M a magnetic (rare-earth or actinide) ion, T a transition metal and X being Si, Ge, Sn or Sb. Hundreds of compounds exist which makes these series very suitable for comparison along the periodic table. Almost all compounds crystallize in a tetragonal structure with a e/a ratio of order of 2.3. However, two different allotropic derivatives exist: The body-centered ThCrzSi2 structure (I4/mmm) and the primitive CaBe2Ge2 one (P4/nmm). These structures are depicted in fig. 2. Note the structures differ in the sequence of the atomic planes, being M-X-T-X-M-X-T-X-M for the bodycentered cell and M-T-X-T-M-X-T-X-M for the primitive cell. Since the extra X-ray diffraction lines from the primitive structure can be rather weak, it is not always clear from the literature which structure is the correct one for a given compound. Some compounds (e.g., UCo2Ge2) can be stabilized in either of the two structures. The magnetic properties appear to be strongly different in those cases. A general rule about the electrical resistivity, p, has been found by Steeman et al. (1990b). Compounds which crystallize in the ThCrzSi2 structure have Pt[c < P±c, while it is the other around for the compounds with the CaBezGe2 structure. Up to now the only exception is UNizSi2 (Ning et al. 1990). The family of 122-compounds has
HEAVY FERMIONS AND RELATEDCOMPOUNDS (a)
11
(b)
T I_ _T I
(~M ©T oX Fig. 2. A schematic drawing of (a) the ThCrzSi2 and CaBezGe2 crystal structure. The origin of the CaBe~Ge2 unit cell is shifted by (3/4, 3/4, --ZM)to facilitate a comparison with the ThCrzSi2 unit cell. M denote the rare-earth atoms, T are the transition-metal atoms and X the metalloids Si, Ge, Sn, etc. (after Endstra 1992). two famous members: CeCu2Si2, being the first heavy fermion materials found to become superconducting (Steglich et al. 1979), and URu2Si2 found to be an antiferromagnetically ordering (TN = 17.5 K) superconductor with moderately heavy electrons (Palstra et al. 1985). Extensive investigations have been devoted to these two compounds since the discovery of their peculiar properties. In both cases the physics is not straightforward and a large sample dependence has been found. In the case of CeCuaSi2 superconductivity can only be found if the material is melted with an excess amount of Cu (up to 10%). However, e.g., microprobe analysis shows the compound to be of the correct stoichiometric composition. The superconductivity is remarkable in the sense that the temperature derivative of the upper critical field is enhanced as much as the effective mass of the electrons and that the 'jump' in the specific heat at Tc divided by the now enhanced 3' is still of order 2. This means that the heavy electrons (being quasi particles) attain the superconducting ground state. Bearing in mind that the large effective mass of the quasi particles also means that the Fermi temperature, TF, is exceptionally low (~ 100 K), superconductivity is found now in a compound where TF is much smaller then the Debye temperature and that Tc is of order 1% of TF. Note that a similar situation exists in the high temperature superconductors. Recently (Feyerherm et al. 1995 and Luke et al. 1994) magnetic order of a spin glass type has been found in CeCu2Si2. However,
12
G.J. NIEUWENHUYS
depending on the starting composition, the volume fraction of the magnetically ordering part of the sample and the volume fraction of the superconducting part are both a function of temperature, in such a way that the total is 100%. Therefore, superconductivity and magnetic order do not coexist in CeCu2Si2 on a microscopic scale. We mention 'starting composition' on purpose, since microprobe analyse is not able to distinguish between the samples obtained. The other famous member of the family, URu2Si2, shows antiferromagnetic order at TN = 17.5 K, as evidenced by, e.g., specific heat (Palstra et al. 1985) and neutron diffraction (Broholm et al. 1987 and 1991). The latter experiments also showed that the magnetic order persists into the superconducting state below Tc = 1.3 K, and that the magnetic order must be of a peculiar type, since the magnetic moment in the ordered state is only 0.03#B per U atom. The smallness of the ordered moment seems not to be of any consequence, neither for the size of the anomaly in the specific heat at TN (being large), nor on the dependence of the magnetic properties in large external fields. For example, a transition to ferromagnetic alignment has been observed (de Boer et al. 1986) at B = 36 T, which would point, together with TN = 17.5 K, to a normal value of the ordered moment. A number of attempts has been made the explain the magnetic behaviour of URu2Si2 on the basis of CEF effects. The first one (Nieuwenhuys 1987) could describe the magnetic anisotropy and the general features of the specific heat and the magnetic susceptibility, but certainly not the small ordered moment, the last one (Santini and Amoretti 1994) ascribes the main features as being due to quadrupolar ordering and considers the staggered magnetic moment as a weak secondary effect. This, however, should assume that the quadrupolar ordering is not observable via neutron diffraction, since the detailed experiments by Walker et al. (1993) did not reveal any other order parameter than the magnetization along the crystallographic c-axis. A further remarkable effect is that the electrical resistivity first increases while cooling below TN, indicating the formation of a charge gap. We will come back to this point later. Pressure has an anisotropic effect on the properties of URu2Si2. Bakker et al. (1992) found for the magnetism dTN/dPa = 126 mK/kbar and dTN/dPc = -41 mK/kbar. The pressure dependence of the superconductivity can be described by dTc/dPa = - 3 5 mK/kbar and dTc/dPc = 25 mK/kbar. A hydrostatic high pressure experiment revealed a value of 36 K for TN at 80 kbar (Kagayama et al. 1994). The magnetic ordering is, in spite of the very small ordered moment, rather stable as a function of sample preparation. This in contrast to the superconductivity, where a large sample dependence can be observed (Ramirez et al. 1991). The large sample dependence has lead to conclusions pointing towards a double transition to superconductivity as observed in UPt3, but, e.g., the detailed specific heat investigation by Knetsch et al. (1992) has refuted this idea. Superconductivity in URu2Si2 is also not of a simple type. The power-law behaviour of the specific heat below Tc already indicates that the energy gap due to superconductivity does not exists over the whole Fermi-surface. Measurements of the penetration depth (Knetsch et al. 1992) support this conclusion. Very remarkable are the results of #+SR experiments (Luke et al. 1990): for fields along the c-axis a reasonable penetration depth (about 8000 A) is observed, however for fields directed perpendicular to the c-axis no sign of superconductivity, neither in the Knight shift
HEAVY FERMIONS AND RELATED COMPOUNDS
13
nor in the relaxation rate can be discerned. That all in spite of the observation by Knetsch et al. (1992) that Bcl is isotropic. For details on of the ~+SR results, the reader is referred to the review by Schenck and Gygax in this volume, more detailed information on URu2Si2 has been collected by Knetsch et al. (1994). The tetragonal character of the structure of the 122-series almost immediately leads to anisotropic magnetic behaviour. The investigation of single crystals is therefore sometimes a condition for the research. The materials can be grown into single crystal form via the tri-arc method (Menovsky et al. 1983). Quite a number of these systems show magnetic ordering (mainly antiferromagnetic) 1. The exact valency of the magnetic atom is of importance, particularly for Ce, since Ce 3+ has one 4f-electron and thus a magnetic moment and C e 4+ is nonmagnetic. In the CeTzX2 series the valency attains a maximum of 3.18 for T = Co and X = Si (Neifeld et al. 1985). The valency approaches 3 going to 4d and 5d transition metals and/or to X = Ge or Sn. Since magnetic C e 3+ is a Kramers ion with J = 5/2, the J-multiplet is split up by the crystalline electric field into 3 doublets. The energy difference between the two lowest doublets can be remarkably small (10-100 K) which is of the same order as the magnetic ordering temperature or the characteristic energy of the Kondo effect (TK). CEF effects in U based compounds are less clear, but they certainly play a role, e.g., in determining the magnetic anisotropy. For U, the ground state can be a non-magnetic singlet, assuming that U is in 4+ valence state.
2.1.1. CeTzX2 In table 2 the main structural and magnetic properties of the Ce based 122-compounds are lis(ed. In this table (and in the following tables) the structure is denoted by I for the inversion symmetric ThCr2Si2 tetragonal type and P for the primitive CaBezGe2 one. The lattice parameters are in ,~. The value of the linear specific heat coefficient, 7, is given in mJ/mole K: only if it is not disturbed by magnetic ordering and/or CEF effects. The magnetic ordering is denoted by A for antiferromagnetism, F for ferroor ferrimagnetism, C for complex ordering and G for spin-glass type ordering. The temperatures, TM and T~: (TM being the magnetic ordering temperature), and the energy of the first excited state in the CEF level scheme A 1 divided by Boltzmann's constant are in Kelvin. The crystal structure of CePt2Si2 is a unique type for REPt2Si2 compounds and has the P4/mm space group, and CePt2Ge2 crystallizes in a monoclinic deformation of the CaBe2Ge2 with space group P21, b -- 4.402 and fi = 90.83 °. CelrzSi2 can crystallize in two different structures, depending on the heat treatment (see discussion below on UCo2Ge2). CeNizSn2 adopts a structure which is slightly monoclinically distorted with respect to the CaBezGe2 structure (Liang et al. 1990). Most Kondo temperatures and crystalline electric field splittings have been obtained from the detailed neutron research by Severing et al. (1989a and b) and Loidl et al. (1992), others from have been estimated on the basis of bulk measurements such as specific heat and magnetic susceptibility. CeCuzGe: exhibits 1 We will not consider compounds with Mn, since Mn is the only transition metal carrying a magnetic moment in these type of compounds.
14
G.J. NIEUWENHUYS
TABLE 2 Structural and magnetic properties of CeT2X 2. The structure is denoted by I for the inversion symmetric ThCr2Si2 tetragonal type and P for the primitive CaBe2Ge 2 one. The lattice parameters are in ,~. The specific heat coefficient, % is given in mJ/(mole) K 2 only if it is not disturbed by magnetic ordering and/or CEF erects. The magnetic ordering is denoted by A for antiferromagnetism, F for ferro- or ferrimagnetism, C for complex ordering and G for spin-glass type ordering. The temperatures, T M and TK (TM being the magnetic ordering temperature), and the energy of the first excited state in the CEF level scheme A 1 divided by Boltzmann's constant are in Kelvin. Compound
Struc. a
c
7
Magn.
TM
TK
A1
Ref.
CeAg2Ge 2 CeAgzSi 2 CeAlzGa2 CeAuzGe2
I I I I I I P I I P I I P P I P I P I P I I I P * * P I I P I I
10.93 10.66 10.95 10.41 10.20 10.24 9.78 10.26 10.16 9.93 10.35 10.48 9.88 10.10 9.85 10.16 10.04 9.85 9.97 9.57 10.11 9.85 10.06 9.89 10.48 9.80 9.80 10.39 10.45 10.18 10.56 10.00 9.80
80 100 1000 350 400 600 89 -
A A F A A A P C A G A P P P P P A P P P A P A A A A P A A A A F P
6.3 9.5 9 15 10.1 29.5 7.7 4.15 0.8 2.1 4.1 1.8 5.1 10 0.5 2.2 0.88 14 36 0.47 7.91 -
3 2 6 10 2 28 30 7 10 2 2 60 1 33 2 15
0 100 127 200 171 20 190 145 150 3 17 110 230 194 29 500 220
[1-4] [5-8] [3] [2, 4] [5-10] [11] [5, 6] [12] [4, 13-16] [7, 9, 17-20] [21-23] [24] [25] [26] [27] [27] [22, 23] [28] [12, 21] [6] [21-23, 29] [27, 30] [31, 32] [7-9, 27, 31, 33] [22, 23] [34, 35] [10, 27, 36-39] [22, 23, 40, 41] [42--44] [8, 9, 27, 45] [22, 23] [2, 4, 31, 46, 47] [9, 27, 37, 48]
CeAu2Si 2
CeCozGe2 CeCozSi 2 CeCul.3 Sb2 CeCuzGe2 CeCu2Si2 CeCuzSn2 CeFe2Ge2 CeFe2Si2 CeIrzGe2 CeIrzSi 2 CelrzSi z CeIr2Sn 2 CeNizGe2 CeNi2Sb2 CeNi2Si2 CeNizSn 2 CeOs2Si2 CePdzGe2 CePd2Si 2 CePdzSn2 CePtzGe 2 CePtzSi 2 CePt2Sn2 CeRh2Ge2 CeRh2Si2 CeRh2Sn2 CeRu2Ge2 CeRu2Si2
4.280 4.250 4.203 4.367 4.310 4.099 3.953 4.341 4.140 4.105 4.433 4.070 3.995 4.246 4.143 4.085 4.499 4.150 4.416 4.036 4.409 4.162 4.369 4.237 4.554 4.400 4.252 4.581 4.161 4.089 4.472 4.256 4.197
References: [1] [2] [3] [4] [5] [6] [7] [8] [9]
Gignoux et al. (1988) B6hm et al. (1988) Rauchschwalbe et al. (1985) Loidl et al. (1992) Palstra (1986) Palstra et al. (1986a) Severing et al (1989a) Grier et al. (1984) Severing et al. (1989b)
[10] [li] [12] [13] [14] [15] [16] [17] [18]
Heeb et al. (1991) Fujii et al. (1988) Mentink et al. (1994) de Boer et al. (1987) Knopp et al. (1989) Jaccard et al. (1992a) Jaccard et al. (1992b) Bredl et al. (1983) Luke et al. (1994)
HEAVY FERMIONS AND RELATED COMPOUNDS [19] Jarlborg et al. (1983) [20] Feyerherm et al. (1995) [21] Kaczmarska et al. (1993) [22] Beyermann et al. (1991) [23] Selsane et al. (1990) [24] Felner et al. (1975) [25] Rogl (1984) [26] Francois et al. (1985) [27] Hiebl et al. (1986) [28] Knopp et al. (1988) [29] Takabatake et al. (1990) [30] Horvath et al. (1983) [31] Besnus et al. (1992) [32] Rossi et al. (1979) [33] Steeman et al. (1988)
15
[34] Sampathkumaranet al. (1991) [35] Das et al. (1991) [36] Ayache et al. (1987) [37] Gignoux et al. (1991) [38] Bhattacharjee et al. (1989) [39] Hiebl et al. (1985) [40] Mignot et al. (1993) [41] Shigeoka et al. (1992) [42] Thompson et al. (1994) [43] Venturini et al. 1988a [44] Venturini et al. (1998b) [45] Quezel et al. (1984) [46] Besnus et al. (1991) [47] Godart et al. (1987) [48] Regnault et al. (1988)
an accidental quartet as the excited state, while CeAg2Ge2 attains such a quartet as ground state. The calculated ordered moment obtained from CEF splittings is in excellent agreement with the measured values for Si and Ge compounds, except for CeCu2Ge2. This indicates that the ground state is not much influenced by the Kondo effect, i.e. A1 is much larger than TK, as shown in the table. However, for the Sn compounds these energies are of comparable magnitude. The ratio of the Kondo temperature and the CEF-splitting can therefore be used to classify these magnetic compounds. Small CEF splittings can easily lead to incorrect determinations of the linear specific heat contribution, e.g., CeNi2Sn2 with 7 K and CeNi2Sb2 with 3.2 K, have maxima in the low temperature specific heat at about 3 or 1.5 K, respectively, which could appear as an enormous "~ when C/T is plotted versus T over a restricted temperature range. CeCul.3Sb2 is a remarkable compound in the sense that it has the correct crystal structure, but that part of the Cu sites are not occupied. The magnetism in this compound is rather complex including field cooling effects, suggestive for spin-glass or some random ordering (Mentink 1994a). Polycrystalline CePt2Sn2 does show the magnetic ordering at TN = 0.47 K, however, a single crystalline sample exhibited at m a x i m u m only short range order (Mignot et al. 1993). We will come back to this point in connection with a detailed studied example: CePd2A13. Using eqs (8-10) and the structure parameters given in table 2 and in the references mentioned therein, an estimate can be given for the strength of the hybridization and thus of the magnetic ordering temperature, see section 1.4.3. Doing so, the CeT2Si2 and CeT2Ge2 can be placed in a phase diagram, as has been done by Endstra et al. (1993a) and displayed in figs 3 and 4. As can be seen from these figures, the Ce-based alloys can be classified within this magnetic phase-diagram. The Sn and Sb compounds have a smaller hybridization then their Si and Ge counterparts. This then would suggest that these compounds should be found at the left-hand side of the phase diagram, and thus order magnetically as well localized systems. However, it appears that the ordering temperatures are much lower or even zero, but at the same time these compounds have a considerable electronic contribution to the specific heat, which would point to the right-hand side of the diagram. On the other hand, for all transition metals there is a clear trend when going from Si --+ Ge --+ Sn and Sb, which suggest that a renormalization of the T/W axis would fit the Sn and
16
G.J. NIEUWENHUYS
CeT2Si 2
I--
Rh
Ru P t
Ir Lr
Ir~
Os
J._,/W Fig. 3. Schematic phase diagram for the Kondo lattice with magnetic ordering temperature of the
CeT2Si2 compounds (after Endstra et al. 1993a).
CeT2G %
I.-
Rh
ge
rid_/W
Fig. 4. Schematic phase diagram for the Kondo lattice with magnetic ordering temperature of the CeT2Ge2 compounds (after Endstra et al. 1993a).
Sb compounds without much difficulty. The fact that almost all above mentioned materials crystallize in a similar crystal structure implies that probably also pseudo binary mixtures can be made, which then opens the possibility to tune parameters like the Kondo temperature and/or the hybridization via small changes in the lattice parameters and the density of the d-electrons. For example, very rich phase diagrams have been found for Ce(Cul_~Ni=)2Ge2 by Steglich et al. (1990a, b), while Heeb et al. (1991) have shown that CePtAuSi2 forms a heavy fermion system between the local moment antiferromagnet CeAu2Si2 and the typical Kondo-type compound CePt2Si2. Another beautiful experiment was carried out by Jaccard et al. (1992a and b) on CeCu2Ge2, which is on the right-hand side of the phase diagram in fig. 4. By applying pressure the volume was decreased, thus the hybridization increased, pushing the compound towards the right. Indeed the magnetic ordering temperature decreased, a heavy fermion region was entered leading finally to superconductivity. Other pressure experiments were performed by Thompson et al. (1986) on CeM2Si2,
HEAVY FERMIONS AND RELATED COMPOUNDS
17
M = Ag, Au, Pd and Rh, where TN was determined as a function of the volume of the unit cell. Again these early experimental result are in good agreement with the phase diagram shown above.
2.1.2. CeCuX3 As an intermezzo, we will discuss here the properties of two new 113-compounds, which almost the same structure as the 122. CeCuA13 and CeCuGa3 have been prepared and investigated by Mentink et al. (1993a). CeCuA13 crystallizes in a disordered variant of the ThCr2Si2 structure, with a = 4.256 ,~ and e = 10.633 A, while CeCuGa~ adopts the atommically ordered primitive tetragonal BaNiSn3 structure (space group I4/mm), depicted in fig. 5, with lattice parameters a = 4.266 ,~ and c = 10.434 A. CeCuA13 orders antiferromagnetically at 3 K, while CeCuGa3 stays paramagnetic down to 0.4 K in spite of the fact the former one has a site disordered structure and the latter a atommically ordered lattice. From magnetic susceptibility and specific heat measurements an estimate can be given for the crystalline electric field splitting, being 13.1 K for the A1 compound and 3.7 K for the other one. The linear terms in the specific heat are 25 and 72 mJ/(moleK2), respectively. Based on the difference in the magnitude of the magnetisation a [ + 1/2) ground state is inferred for CeCuGa3 and a I + 3/2) ground state for CeCuA13. 2.1.3. UT2X2 Magnetism in UT2X2 have been studied quite extensively, partly because interesting phenomena are present, but of course also because of the presence the heavy fermion antiferromagnetic superconductor URu2Si2 in this series. Except for the so-called low-temperature phase of UIr2Ge2, again all compounds crystallize in a tetragonal
@M,
0 T,
•
Q X
Fig. 5. The BaNiSn3-type crystal structure (after Mentink et al. 1993).
18
G.J. NIEUWENHUYS
structure. The structural and main magnetic properties are given in table 3 based on the review paper by Endstra et al. (1993b). In those cases where neutron diffraction has been carried out, it was generally found that the ordered magnetic moment is directed along the crystallographic c-axis. The antiferromagnetic ordered state in general consists of ferromagnetic magnetic planes (being the crystallographic basal planes) stacked antiferromagnetically along the c-axis. This stacking is not always of the simple + - + - type, some compounds even change their stacking as a function of temperature, e.g., UNi2Si2 (Lin et al. 1991). This ge.neral anisotropy can be understood if we assume that the U ions are in the 4+ state. If we may apply Hund's rule, then the magnetic quantum number J equals 4, which leads to the possibility of non-magnetic singlet states. Konno (1993) has given algebraic expressions for the eigenvalues and eigenstates for the J = 4 case in a tetragonal surrounding. Assuming the CEF picture to be completely valid, the magnetism of the tetragonal U-based compounds is of the induced type and since the transition-matrix elements between the low-lying eigenstates are only non-zero for the Jz operator, the moments are confined to the c-axis (Nieuwenhuys 1987). Although this simple picture does explain major features, it should be noted that the calculated magnitude of the ordered moment is generally too large. Also, inelastic neutron scattering experiments have great difficulty to reveal the CEF levels, which of course might be due to a large broadening by hybridization. Nevertheless, the crystalline electric field plays a important role in determining the anisotropy of these compounds. In a number of cases, table 3 denotes the magnetic ordering as C, meaning complex, implying that more then one magnetic structure has been found depending on temperature. For example, UCu2Ge2 orders ferrromagnetically at 100 K and changes its structure to a + - - + type of antiferromagnetic order below 50 K. UCo2Ge2 and UIr2Ge2 have been mentioned twice in table 3 because of the different crystal structures. UCo2Ge2 forms at the melting point in the CaBe2Ge2 structure (P) and transforms at annealing at 1300 K into the ThCr2Si2 structure (I), thereby increasing its c-axis considerably. Details of this transformation have been studied by Drost (1995) via in situ neutron diffraction experiments. Note that this structural transformation is accompanied by a large change in the magnetism, the I structure orders antiferromagnetically at 175 K, while the P structure is a paramagnet down to 35 inK. UIr2Ge2 also adopts the P structure at its melting point, but transforms upon annealin~ into orthorhombic structure (space group Pmmm) with a = 4.054 A, b = 4.195 A and c = 10.25 A. Here the Nrel temperature increases. There are not many UT2Ge2 compounds with the 4d transition metal series. Only Rh and Pd exist, for Ru a compound U4RuTGe6 has been found. This is a ferromagnet with Tc = 6.8 K (Mentink et al. 1991, Endstra et al. 1992b). The magnetic properties of the superconducting compound URu2Si2 have already been mentioned above. As in the case of the Ce-based compounds, the trends of the magnetic ordering temperatures (including the absence of ordering) can be described in a simple model based on a calculation of the hybridization strength (Endstra et al. 1993a). In fig. 6 we display their results for the Si compounds, while fig. 7 shows the Ge compounds. As can be seen from these figures, the model indeed explains the trends, also, e.g., the absence of magnetic ordering in the P-phase of UCo2Ge2. Ab initio self-consistent density-functional band structure calculations in
HEAVY FERMIONS AND RELATED COMPOUNDS
19
TABLE 3 Structural and magnetic properties of UT2X 2. The structure is denoted by I for the inversion symmetric ThCr2Si2 tetragonal type and P for the primitive CaBe2Ge 2 one. The lattice parameters are in ,~. The specific heat coefficient, "3', is given in mJ/(mole K 2) only if it is not disturbed by magnetic ordering and/or CEF effects. The magnetic ordering is denoted by A for antiferromagnetism, F for fen'o- or ferrimagnetism, C for complex ordering and G for spin-glass type ordering. The temperatures, TM and TK (TM being the magnetic ordering temperature), and the energy of the first excited state in the CEF level scheme A1 divided by Boltzmann's constant are in Kelvin. Compound
Struc. a
e
3'
Magn. TM
TK
A1
Ref.
UAu2Si 2 UCo2Ge 2 UCozGe2 UCo2P2
I I P P I I I I I I P * P I I I I I P P I ? I I
10.29 9.88 9.30 8.97 9.61 10.50 10.23 9.95 9.96 9.53 9.77 10.25 9.83 9.48 9.51 9.68 10.23 10.19 9.75 9.69 9.76 10.06 9.59
62 24 18 105 22 32 305 180
C A P C A A C F P P A A A A C P A A A A P P A A
-
50
[1-4] [5, 6] [7] [8, 9] [3, 10] [3, 11] [7, 12, 13] [4, 10, 11] [7, 12, 14] [14, 15] [16] [16] [3, 17] [7, 10, 12] [4, 18, 19] [2] [20] [2, 20] [21] [22] [2] [23] [2, 20] [24]
UCozSi 2 UCr2Si2 UCu2Ge2 UCu2Si2 UFe2Ge2 UFezSi2 UIr2Ge2 UIrzGe~ UlrzSi 2 UNizGe2 UNizSi2 UOszSi 2 UPdzGe 2 UPd2Si 2 UPt2Ge2 UPtzSi 2 URezSi 2 URhzGe 2 URhzSi 2 URu2Si2
4.280 4.010 4.043 3.955 3.917 3.911 4.063 3.984 4.024 3.951 4.156 4.087 4.095 3.958 4.121 4.200 4.121 4.330 4.197 4.154 4.012 4.128
48 174 230 85 30 100 104 19 33 4.9 77 124 140 97 72 35 130 17.5
References: [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12]
Rebelsky et al. (1991) Palstra et al. (1986a) Buschow and de Mooij (1986) Torikachvili et al. (1992) Kuznietz et al. (1989) Endstra et al. (1991) Dirkmaat et al. (1990b) Reehuis et al. (1991) Trod et al. (1993) Chelmieki et al. (1985) Hiebl et al. (1990) Endstra et al. (1990)
the local approximation
[13] Kuznietz et al. (1990) [14] Szytula et al. (1988a) [15] Szytula et al. (1988b) [16] Lloret et al. (1987) [17] Dirkmaat et al. (1990a) [18] Lin et al. (1991) [19] Ning et al. (1991) [20] Ptasiewicz-Bak et al. (1981) [21] Endstra et al. (1992) [22] Steeman et al. (1990) [23] Dirkmaat et al. (1990c) [241 Palstra et al. (1985)
( t r e a t i n g t h e U 5 f s t a t e s as b a n d s t a t e s ) b y S a n d r a t s k i i a n d
Ktibler (1994) on the UT2Si2 compounds
correctly predict the occurrence
of mag-
n e t i s m i n t h e s e m a t e r i a l s . U R u 2 S i 2 f o r m s i n d e e d a n e x c e p t i o n i n t h e s e n s e t h a t it is p r ed i c t e d as n o n - magnetic,
whereas the experiment shows a very small magnetic mo-
20
G,J. NIEUWENHUYS tI
1"
T K iI
£--
tI
iI I
T~,Ky
i /
UT2Si 2
J
/ / I/ I/ H g
O
Ir
OS
jd_f/W
Fig. 6. Schematic phase diagram for the Kondo lattice together with magnetic ordering temperatures of the UT2Si 2 compounds. The dashed curves indicate the Kondo and the RKKY temperature. The thick curve indicates the effective magnetic ordering temperature (after Endstra et al. 1993a).
UT2Ge 2
P
C o ~r
j
Fe coRh
Jo_/W
Fig. 7. Schematic phase diagram for the Kondo lattice together with magnetic ordering temperatures of the UT2Gez compounds (after Endstra et al. 1993a).
ment. In the compound UCo2P2, the Co atoms also have a small magnetic moment so that this compound does not fit into the total picture. Another P containing compound is UCuzP2, which crystallizes in the hexagonal CaA12Si2 structure (Zolnierek et al. 1987) was reported to be a ferromagnetic with the record breaking Tc of 216 K (Kaczorowski and Tro6 1990). Magneto-optical spectroscopy has been carried out on this compound by Schoenes et al. (1989) and Fumagalli et al. (1988). They found a max~imum Kerr rotation of 3 ° and could characterize UCu2P2 as a semi-metal. Polarized neutron diffraction experiments (Delapalme et al. 1994) suggest that U is in the 3+ state in this compound and that the U 6d-electrons play an important role. In the course of the search for new boron-carbide superconductors, two new U compound have been found by Takabatake et al. (1994b): UNi2B2C and URh2B2C. Both crystallize in the ThCrzSi2 structure with a = 3.513 ,~, c -- 10.54 ,~ and a -- 3.782 ,~, c = 10.214 ,~, respectively. UNizBzC is a antiferromagnetic with the remarkable
HEAVY FERMIONS AND RELATED COMPOUNDS 200
U(C°'-xNix;2Ge2
150
\
- 1
21
0.28
t 0.26
¢
0.24
>
100 50 0
. . . . . . . . . . 0.0 0.5
1
0.22
1.0
x Fig. 8. Magnetic ordering temperature (n) and calculated Vdf (o) versus x for U(Col_~Ni~)2Ge2 compounds (after Endstra et al. 1993c).
high TN of 218 K and URh2B2C orders ferromagnetically at also a relatively high temperature of 185 K. The similarity between the crystal structures and the lattice parameters enables, as mentioned before, the study of pseudobinary compounds. This tuning of the various parameters makes comparison with Endstra's model more challenging. The U(Col_xNix)2Ge2 system has been studied by Endstra (1992) and Kuznietz et al. (1990b). The U(Col_xCux)2Ge2 system has been a subject of another paper by Kuznietz et al. (1990a), while the compounds U(Nil_zCux)2Ge2 were reported by Kuznietz et al. (1992a, b). Finally, the U(Co1_~Fe~)2Gez compounds has been investigated by van Rossum (1993). The U(Col_zNix)zGe2 is particularly interesting, since looking at fig. 7, one would expect the transition temperature to vary monotonously between the parent compounds. However, a minimum was found, which could be explained easily by the occurrence of a maximum in the hybridization strength (both parent compounds are on the right-hand side of the phase diagram). Figure 8 shows this result.
2.2. l l l-compounds 2.2.1. CeTX compounds The CeTX compounds crystallize in a large variety of structures, resulting in a broad spectrum of magnetic properties. It is therefore rather difficult to describe a general line. However, one thing is clear, there is always a relation between the volume of the unit cell and the valency of Ce. As pointed out above, the latter is of essential importance for the magnetic behaviour. Crystalline electric field effects do play a important role, they can be observed via inelastic neutron scattering. No extremely small splittings between the ground state and the first excited state have been found in this series. Remarkably, the influence of the CEF is mentioned always in the literature, but it is seldom taken into account, e.g., when analyzing the temperature dependence of the electrical resistance. Table 4 gives the main structural, magnetic en electrical properties of the CeTX compounds. The entries have their usual meaning; under the head 'conduc.' there is an M for metallic behaviour and an S for semiconducting behaviour. The latter may occur only at low temperatures.
22
G.J. NIEUWENHUYS
TABLE 4 Structural and magnetic properties of Ce 111-compounds. 'Crys.' denotes the symmetry of the lattice, 'Struc.' the structure type. The lattice parameters are given in ,~. Under the heading 'Magn.' an A means antiferromagnetism and F ferromagnetism. TM is the magnetic transition temperature in Kelvin. An M under 'Conduc.' means metallic and S semiconducting. Compound
Crys. Struc.
a
b
c
CeA1Ga CeAuIn CeCuGe CeCuSi CeCuSn CeIrGe CeNiAI CeNiGe CeNiIn CeNiSb CeNiSi CeNiSn CePdAI CePdGa CePdGe CePdln CePdSb CePdSn CePtGa CePtGe CePtIn CePtSb CePtSi CePtSn CeRhGe CeRhIn CeRhSb
hex hex hex hex hex o.rh hex o.rh hex hex tetra o.rh hex o.rh o.rh hex hex o.rh o.rh o.rh hex hex tetra o.rh o.rh hex o.rh
4.378 7.698 4.311 4.238 4.583 7.073 6.978 4.317 7.552 4.384 4.061 7.522 7.221 4.488 7.709 4.935 7.535 4.45l 7.657 4.533 4.202 7.463 7.430 7.547 4.609
4.374 7.388 4.555 7.300 4.700 7.344 4.628 4.466 7.416
4.329 A 4.256 A 7.933 A 7.988 A 7.865 A 7.575 4.020 7.201 3.986 4.110 F 14.0457.6024.233 A A 7.676 A 4.078 A 7.890 F 7.955 A A 7.616 A 4.069 8.058 F 14.4848.016 A 7.120 A 4.050 7.846 -
A1B 2 Fe2P Ni2 NizIn NizIn TiNiSn ZrNiA1 TiNiSn ZrNiA1 A1B2 LaPtSi E-TiNiSi ZrNiA1 TiNiSi CeCu2 ZrNiA1 GaGeLi c-TiNiSi TiNiSi CeCu2 FezP GaGeLi LaPtSi ~-TiNiSi TiNiSi Fe2P CeCu2
Magn. TM 6 5.7 10.2 14.9 8 7 2.7 2.2 3.4 1.7 17 7.5 3.5 3.4 4.5 7.5 9 -
References: [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18]
Fremy et al. (1989) Pleger et al. (1987) Nakotte (1994) Fuming et al. (1991) Sakurai et al. (1993) Rogl. et al. (1989) Kuang et al. (1992) Buschow (1979) Singhal et al. (1993) Lee et al. (1987b) Satoh et al. (1990) Fujii et al. (1987) Fujii et al. (1989) Takabatake et al. (1990b) Pecharski et al. (1983) Skolozdra et al. (1994) Aliev et al. (1990) Takabatake et al. (1990)
[19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36]
Nakamura et al. (1991) Koghi et al. (1992) Yamaguchi et al. (1990) Kyogatu et al. (1990) Kalvius et al. (1993) Nohara et al (1993) Hulliger (1993) Schank et al. (1994) Kitazawa et al. (1994) Hovestreydt et al. (1972) Adroja et al. (1994) Rainford et al. (1994) Sakurai et al. (1989) Bruck et al. (1993) Adroja et al. (1991) BrUck et al. (1988) Maeno et al. (1987) Suzuki et al. (1990)
Conduc. Ref. M M M M M M M M M M M S M M M M M M M M M M M M M S
[11 [2] [3, 4] [3, 4]
[3-5] [6]
[3, 7-10] [3, 7] [3, 7, 11-14] [15, 16] [3, 7] [3, 7, 17-24] [25-27] [28-31] [6, 31] [11, 12, 32-37]
[38-40] [19, 20, 30, 31, 41, 42] [31, 43] [6, 31]
[11, 44] [45] [10, 46--49] [21, 31, 50, 51]
[6] [32, 52] [53-55]
HEAVY FERMIONS AND RELATEDCOMPOUNDS [37] Fujii et al. (1990) [38] Malik and Adroja (1991b) [39] Trovarelli et al. (1994) [40] Riedi et al. (1994) [41] Adroja et al. (1992) [42] Fujita et al. (1992) [43] Uwatoko et aL (1995) [44] Fujita et al. (1988) [45] Rainford and Adroja (1994) [46] Lee et al. (1987a)
23
[47] Krimmel et al. (1992) [48] Ott et al. (1992) [49] Mielke et al. (1993) [50] Adroja et al. (1988) [51] Takabatake et al. (1993) [52] Adroja et al. (1989) [53] Malik and Adroja (1991a) [54] Takabatake et al. (1994) [55] Nishigori et al. (1994)
Two compounds show the S for the conductance, CeNiSn and CeRhSb. The first one shows semiconducting behaviour for temperatures below 6 K, signalled by a rapid increase in the electrical resistance and a sharp drop in the specific heat. The size of the corresponding energy gap is only 2.4, 5.5 and 5 K for the current along the a-, b- and e-axis, respectively (Takabatake et al. 1990b). Also, nuclear magnetic resonance (Kyogatu et al. 1990) reveals the gap via a more rapid decrease of the relaxation rate, l/T1, as function of temperature. The Knight shift follows the magnetic susceptibility, exhibiting a maximum at 12 K. The experimental results could be described assuming that the structure of the gap is that of a pseudo gap, i.e. the density of states varies linearly as function of energy in stead of making a jump. Preliminary vacuum tunneling experiments (Aarts and Volodin 1995) confirm this picture. Within the CeNiX compounds, CeNiSn is situated at the end of a monotonic gradual trend, starting with A1, towards integer valency. CeNiA1 is a typical mixed valence compound, while CeNiSn for temperatures above 6 K should be characterized as a medium heavy fermion with 7 = 173 mJ/(moleK2). CeNiSn does not show magnetic ordering. If Ni is replaced partly by Pd, as done by Kasaya et al. (1991), then magnetic ordering starts at CeNi0.8Pd0.zSn; CePdSn is a ferromagnet with the same crystal structure as CeNiSn. CeRhSb shows the semiconducting behaviour at temperatures below 20 K, again a pseudo gap is found with a width of about 4 K. It should be noted, that in both cases, CeNiSn and CeRhSb, the corresponding nonmagnetic compound (with La in stead of Ce) has a normal metallic behaviour. We will come back to this point later. Also, 20% Ce replaced by La in CeRhSb recovers the metallic conductance. CePdSb is a ferromagnet with Tc = 17 K as found from magnetic measurements, which is a remarkable high temperature for Ce compounds in this series. The corresponding Nd, Gd and Sm compounds have ordering temperatures of similar values. Ce is here in the trivalent state, the CEF excitations are found at 240 and 560 K, respectively. The absolute value for the electrical resistance is quite high, 4 m~2cm. The specific heat, however, shows no sharp feature at Tc, only a swallow maximum around 10 K has been found. No clear explanation has been given yet. CePtIn shows no magnetic order. In contrast the electronic contribution to the specific heat has a coefficient of 1100 mJ/(mole K 2) at T = 0 K due to an upturn with decreasing temperature starting at 0.5 K. This would characterize this compound as extremely heavy. However, an external magnetic field of 5 T suppresses this -,/ value down to 500 mJ/(mole K2). The overall temperature dependence can be described by a Kondo contribution with TK = 11 K and a CEF splitting of the lowest two levels of A = 80 K. CePdIn,
24
G.J. N1EUWENHUYS
with 7 = 700 mJ/(moleK2), orders ferromagnetically at Tc = 1.7 K and CeRhln has an unstable moment. Mixtures of these two latter compounds show a gradual change of the Ce valency, accompanied by a related change of the volume of the unit cell (Brtick et al. 1993). Going from Rh towards Pd the hybridization and the mass enhancement (7) increase with a maximum for 3' at 800 mJ/(mole K 2) just before the ordering sets in at 80% Pd. Replacing Pd by Pt (Fujita et al. 1992) causes the magnetic order to disappear. CePtIn shows no magnetic order down to 60 mK. CePtSb and CeA1Ga both order antiferromagnetically at 4.5 and 6 K, respectively. In order to fit the data for the crystalline electric field, the addition of a 043 term is necessary. For CePtSb this could be related via detailed neutron diffraction to the GaGeLi structure, with is an atomically ordered version of the Cain2 structure. Probably, this implies that CeA1Ga is also not exactly in the A1B2 structure. CePtSi can be characterized as a heavy fermion system: specific heat measurements have shown a upturn in C/T starting at 10 K and resulting in a zero temperature extrapolation of about 700 mJ/(mole K2). In this case, an external magnetic field of 13 Tesla does not change essentially the results, ruling out short range magnetic order as a cause of the specific heat increase. Via replacing Pt by Ni, Lee et al. (1987b) have shown the gradual change from a heavy fermion system to a typical mixed valence behaviour. The magnetic order in case of antiferromagnetism is generally not of a simple type. For example, CePtSn (Sakurai et al. 1989) and CeCuSn (Nakotte 1994) show two peaks in the specific heat. Both anomalies are influenced by external magnetic fields in different ways. To explain these type of phenomena, detailed microscopic investigations should be carried out.
2.2.2. UTX-compounds The equiatomic UTX compounds have been studied quit extensively, starting with the work of Dwight (1974), Buschow et al. (1985) and Palstra et al. (1986b, 1987a, b). A review has been given by Sechovsky and Havela (1988) in vol. 4 of this book series and by Sechovsky et al. (1990). Therefore, I will restrict here to some new developments. As is the case with the Ce compounds, different crystal structures are found in the UTX system. The structure seems to be governed by the number of d-electrons of the transition metal atom (Nakotte 1994), starting with the hexagonal MgZn2 structure for Mn-, Tc- or Re-compounds, though the hexagonal Fe2P or orthorhombic CeCu2 structures towards the cubic MgAgAs and hexagonal Cain2 structures for the compounds containing Cu, Ag or Au. Compounds with the cubic MgAgAs structure are semiconductors, the other ones show metallic behaviour. Note that the corresponding non-magnetic Th compounds with the MgAgAs structure are also semiconductors, so that in these cases the magnetism is not a condition for the semiconducting behaviour. UNiSn is a rather famous compound crystallizing in the cubic MgAgAs structure. It undergoes an exotic phase transition from semiconducting paramagnetism for T > TN (= 43 K) to a metallic antiferromagnetic phase below TN (Palstra et al. 1986b, Fujii et al. 1989b). Neutron diffraction experiments have shown UNiSn to order in a type I antiferromagnetic structure (Kawanaka et al. 1989), while indications for a lattice distortion were found from far-infrared measurements (Kilibarda-Dalafave et al. 1993). The crystalline electric field scheme has
HEAVYFERMIONSAND RELATEDCOMPOUNDS
25
been deduced by Aoki et al. (1993) to consist for the U 4+ ion of a non-magnetic doublet ground state and a first excited triplet state at 180 K. From these scheme it can be shown that the phase transition in UNiSn should be of first order and includes the spins as well as the lattice, which was nicely confirmed by Suzuki et al. (1994) by powder X-ray and ultra-sonic measurements. The series URhIn, UPtIn and UPdIn (Nakotte et al. 1992, Havela et al. 1994a, Sugiura et al. 1990) can be classified as magnetic heavy fermions; the strength of the magnetism increases when going from Rh towards Pd, i.e. the moment increases from 1.2 to 1.6#B and TN increases from 7 to 20.4 K. This trend can be explained be the decrease in the hybridization. From the specific heat there are indications that the bandstructure changes at TN, optical and tunneling experiments should clarify this point. UPdSn and UAuSn both order antiferromagnetically at 37 and 40 K, respectively (De Boer 1992, Robinson et al. 1993a, 1994a, Nakotte et al. 1993a, b). From neutron diffraction it appears that both compounds have a very rich magnetic phase diagram. In both cases the magnetic unit cell of orthorhombic symmetry, while the crystallographic cell is hexagonal. This implies that different domains are possible. UPdSn has two transitions in zero external field. At both transition temperatures, 40 and 25 K, different Cartesian components of the magnetic moments order. Similar effects have been seen in the pure rare-earth metals. The electrical resistances of the two compounds is rather different, the one of UPdSn decreases by a factor of 4 below the magnetic ordering temperature, the resistivity of UAuSn increases gradually with decreasing temperature over the whole range from room temperature to the lowest temperatures. UPdGe, UPtGe and UNiGe also show quit complicated magnetic structures (Kawamata et al. 1992, Proke~ et al. 1994, Robinson et al. 1994a, b, Havela et al. 1994a and Sechovsky et al. 1994a, b). The electronic properties of UNiA1 have been described by Brtick et al. (1994). Theoretical or phenomenological predictions of this variety of magnetic structures are not (yet) possible, due to the delicate balance between the different interactions. The latter also implies that excellent sample quality is essential for this research. In all cases there is a huge magnetocrystalline anisotropy due to several reasons: crystalline electric fields, anisotropic interaction and/or anisotropic hybridization. As a general trend, as far as single crystals have been investigated, compounds crystallizing in the ZrNiA1 structure have their ordered moments directed along the c-axis, while the moments in the TiNiSi derived compounds prefer the b-c plane. Other structures reveal more complicated anisotropies. Evidence for anisotropic hybridization stems from detailed neutron diffraction studies on URhA1, URuA1 and UPdSn, where also a large orbital moment for the essentially itinerant 5f-electrons is found (Paixao et al. 1993, Nakotte 1994). Measurements of this kind (U-formfactor) as a function the external magnetic field - and thus for metamagnetic transitions as a function of the magnetic structure - should be able to shed light on the intriguing questions concerning the magnetic order in heavy fermion compounds (Wulff et al. 1990). The electrical resistance of the 111-compounds (and of heavy fermions in general) is rather high, several hundreds of # ~ cm. Also, it sometimes drastically changes as a result of magnetic order, although, as mentioned above, there are exceptions where the temperature dependence of the electrical resistance does not change at all at the ordering temperature. This implies that a simple conduction electron vs.
26
G.J. NIEUWENHUYS 1.6
/
|.0
v
/ 0.5
/
UNIGa T : 4.2
•
t
/ . t l v v
v
. . . .
15o, m ~ x ~ 100 E
V
50
UNiGa
~
A ~
T = 4.2K i //
~ //
c
0, 0 0.0
0.5 B
1.0 03
1.5
Fig. 9. Field dependence of the magnetization for BIle and of the electrical resistivity of UNiGa at 4.2 K for i[[BlJc and i±Blle. The open symbols represent the result obtained with increasing field, while the full symbols represent the one obtained with decreasing field (after Nakotte 1994).
local moment scattering picture is much too simple. There is in general a very strong interaction between the conduction electrons and the magnetic degrees of freedom of the 5f-electrons. The latter are also believed to take part in the electrical conductance. Then, the magnetic structure is going to play an important role, since the conduction electrons now also have to obey the symmetry of the magnetic unit cell. Conductivity calculations should now be carried out on the basis of band-structure calculations which include the various magnetic structures. We will come back to this point. For the case of the UTX compounds it is interesting to note that very large magnetoresistance effects have been observed, larger than in the multilayer materials, see, e.g., Havela et al. (1994a), de Boer et al. (1994) and Nakotte et al. (1994a, b). A typical example is UNiGa, which orders antiferromagnetically at 40 K (Havela et al. 1991), the ground state is characterized by the sequence + + - - + - . At low temperatures, an external magnetic field of 1 Tesla is sufficient to align the moments along the c-axis, which leads to a reduction of the electrical resistivity to only 15% of its zero-field value. In fig. 9 the magnetization and the resistivity are displayed.
2.3. UzT2X-compounds A new family of heavy fermion compounds have been synthesized with the composition UzTzX (Peron et al. 1994, Nakotte et al. 1994b, Mirambet et al. 1993, 1994, Nakotte 1994, Havela et al. 1994b). The compounds with T -= Co, Rh, Ni, Pd, Ir, Pt
HEAVYFERMIONSAND RELATEDCOMPOUNDS
c
27
C) U OT @X
Fig. 10. Schematicrepresentation of the unit cell of U2T2X crystallizingin the U3Si2 structure. The two shortest inter-uraniumdistances are indicated(after Nakotte 1994). and X = In, Sn all crystallize in the tetragonal U3Si2 structure, depicted in fig. 10. The shortest distances between the uranium atoms in this series of compounds ranges from 3.40 ,~ to 4.00 A, that is just around and above the famous Hill limit of 3.5 ,~ (Hill 1970). Therefore, these compounds are expected to cover the range between non-magnetic behaviour via heavy-fermion behaviour towards magnetic ordering. In table 5 the structure parameters, together with the magnetic ordering temperature and the linear coefficient for the specific heat are given. All magnetic ordering is antiferromagnetic. Note, that the value for 7 is still in mJ/(mole/.~. K2), but that the formula unit now contains two uranium atoms. High-field magnetization experiments (Nakotte et al. 1994b) have confirmed the antiferromagnetism by revealing metamagnetic transitions and confirmed the paramagnetism of the other compounds by showing that the magnetization is a linear function of the external field at higher fields. Calculations of the strength of the hybridization shows that indeed the magnetically ordering compounds have a lower value than the paramagnetic ones, placing this series of compounds to the right-hand side of the Doniach phase diagram.
2.4. U-compounds with CaCu5 structure and related borides A number of rare-earth intermetallic borides are excellent magnet materials with strong uniaxial magnetocrystalline anisotropy, see, e.g., Strnat (1988). Uranium borides, unfortunately, have not so many useful properties. The main structural and magnetic properties of a number of these compounds are given in table 6. The heading 'Magn.' now shows AF for antiferromagnetism, PP for Pauli paramagnetism and SF for spin fluctuator, meaning that the magnetic susceptibility is still rather temperature independent, but that the electrical resistivity shows a heavy-fermion like decrease for temperatures decreasing below ~ 150 K. Because of the similarity of the structure, also some 123-compounds are listed in table 6, including the new
G.J. NIEUWENHUYS
28
TABLE 5 Structural and magnetic properties of U2T2X. The lattice parameters are in ,~. The specific heat coefficient, "7, is given in mJ/(mole K 2) only if it is not disturbed by magnetic ordering and/or CEF effects. TN is the N6el temperature in Kelvin. Compound
a
c
U2Co2In U2Ni2In UzRhzIn UzPdzIn UzPtzIn UzCo2Sn U2Ni2Sn U2Rh2Sn U2Pd2Sn U21r2Sn U2Pt2Sn
7.361 7.375 7.553 7.637 7.654 7.654 7.263 7.524 7.603 7.566 7.670
3.431 3.572 3.605 3.752 3.725 3.725 3.691 3.630 3.785 3.601 3.698
TN 14.3 36.6 26.0 24.4 40.6 -
78 237 850 261 98 305
TABLE 6 U-compounds with CaCu5-type structure and related borides. 'Crys.' denotes the symmetry of the lattice, 'Struc.' the structure type. The lattice parameters are given in A. The specific heat coefficient, 7, is given in mJ/(mole K 2) only if it is not disturbed by magnetic ordering and/or CEF effects. Under the heading 'Magn.' A F means antiferromagnetism, S F spinfluctuator and P P Pauli paramagnet. TM is the magnetic transition temperature in Kelvin. Compound
Crys.
Struc.
a
U(Coo.25 Nio.75)4B U(Coo.5 Nio.5)4B U(Coo.75 Ni0.25)4B U(Ruo.7Rho.3)4B 4 UCosB 2 UCo4B UCo4B 4 UFesB 2 UlrsB 2 UNi2A13 UNi4B UOssB2 UOs4B 4 UPd2A13 UPd2Ga 3 URusB 2 URu4B 4
hex hex hex tetra hex hex tetra hex hex hex hex hex tetra hex hex hex tetra
CeCo4B CeCo4B CeConB LuRu4B 4 CeCosB 2 CeCo4B CeCo4B 4 CeCosB 2 CeCosB 2 PrNi2A13 CeCo4B CeCosB 2 LuRu4B 4 PrNi2A13 CeCo4B CeCosB 2 LuRu4B 4
4.931 4.924 4.910 4.947 4.895 5.027 5.047 5.373 5.204 4.950 5.511 5.365 5.295 5.473 7.460
c
3'
Magn.
TM
Ref.
6.964 6.954 6.928 3.065 6.933 7.030 2.997 3.181 4.018 6.962 2.971 4.191 8.505 2.965 15.000
73 114 48 52 32 64 37 55 21 88
AF SF SF PP SF SF PP PP SF AF AF PP PP AF AF PP SF
5 -
[1] [1] [11 [2] [3, 4] [5] [2] [3, 41 [3, 4] [6-81 [1, 9] [3, 4] [2] [6,7, 10, 11] [12] [3, 41 [2]
References: [1] [2] [3] [4] [5] [6]
Mentink et al. (1994e) Mentink et al. (1992) Yang et al. (1984) Mentink (1994) Nakotte et al. (1993c) Geibel et al. (1991b)
[7] Geibel et al. (1992) [8] Scr6der et al. (1994) [9] Mentink et al. (1994b) [10] de Visser et al. (1992) [11] de Visser et al. (1993) [12] Siillow (1994)
-
5.2 21 14 13 -
HEAVYFERMIONSAND RELATEDCOMPOUNDS
29
magnetic heavy fermion superconductors UPd2A13 and UNi2A13. Inspired by the anomalous ferromagnetism in CeRh3B2 (Dhar et al. 1981) with Tc = 115 K, CeT3B2 and UT3B2 materials have been investigated by Yang et al. (1984, 1985), Ku et al. (1980), Kasaya et al. (1990) and Mentink et al. (1994e). The compounds crystallize in CeCo3B2 structure, see fig. 11. All the uranium compounds of this series are either Pauli paramagnets or spin fluctuating materials with rather small temperature independent 7 values. This can be understood from the small inter-uranium distances (< 3.5 ]k) causing an overlap of the 5f-wavefunctions. UCo3B2 and UIr3B2 have somewhat larger distances and therefore exhibit the spin fluctuation phenomena as also found in typical heavy fermions. The 141-compounds order in the CeCo4B structure, depicted in fig. 12. The formation of a magnetic moment on the U-site
c I
3g la 2c
a @U,
© T,
eB
Fig. 11. The CeCo3Bz-typestructureas adoptedby the UT3B2compounds(afterMentink1994).
c ] ~
l
b
~-
-
~
z~-~--~__-_. - - = ~© :
6i
la ~:
a
u
2c
O U, © T, • B Fig. 12. The CeCo4B-typestructureas adoptedby the UT4B compounds. Notethe presenceof two differentU- and T-atomsites. The uraniumatomshave a triangulararrangementin the basalplane(after Mentink 1994).
30
G.J. NIEUWENHUYS
d
',,o/",o , ' \ o ,' ',,o/",o , ' \
,i_o
ok
/o,, O/o',,o ,,'o',, o ,,'0',, O/o',,o / ~
',, o .-' ,-,
.....
,~,
.... ~
,'t
oo ,'o, -.,,o , , ,' o'.,._ o . ' ,o , ° , , ' o \
'~' ~ ~ - - ~ d
/\7,,'
,,
', o / " , , o / \ o
,d
....~,
,,, ',, o f
o__k, o , /
Fig. 13. Magnetic structure of hexagonal UNi4B, projected on to the crystallographic basal plane. Given the FM coupling along the e-axis, every layer at z = 0 and z = 1/2 exhibits the same moment orientations. The thin solid line represents the magnetic unit cell. Note the presence of the 'free' uranium moments with two different magnetic environments (after Mentink 1994). in U(Co~Nil_~)4B can be understood since the d-band shifts downwards in energy with decreasing z (more Ni-rich), thereby decreasing its density at EF, while also the distance between the U-atom and the transition metal increases. Both effects will decrease the hybridization and enable the formation of moments on the Usite. At the end of this series, nature has placed a remarkable partially ordered antiferromagnet: UNi4B. In the ordered state, the magnetic moments are confined to the basal-plane of the crystal structure. According the neutron diffraction experiments (Mentink et al. 1994b) two-thirds of the magnetic moments order in a vortex-like structure in the basal plane, while being ferromagnetically aligned along the c-axis, see fig. 13. The other one-third of the magnetic moments are free to rotate in the basal plane. They are only coupled ferromagnetically along the c-axis, but a one-dimensional ferromagnetic chain does not order at finite temperature. Note that the nearest-neighbour coupling in the basal plane cancels for all magnetic moments, while the next-nearest-neighbour ones cancel for the 'free' moments. The unique magnetic structure is also reflected by the magnetic susceptibility, see fig. 14. The low-temperature upturn in small external magnetic fields represents the response of the ferromagnetic linear chains, which can easily be saturated by larger fields. A similar extra contribution is found in the specific heat. Also the large anisotropy is evident from these susceptibility results. This anisotropy of about a factor of ten remains present in the paramagnetic region, it is therefore not caused by a spatial anisotropy of the magnetic interaction between the moments. Probably, crystalline
HEAVY FERMIONS AND RELATED COMPOUNDS | o
300
m
i
Ooooo
*~. °o o
"6" O
31
~'~.o
200
"
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100 U~m
annjllmmIe ° °
,
0 0
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•
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o ooe
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,
30
T (K) Fig. 14. Magnetic susceptibility of a UNi4B single crystal, measured in fields of 0.3 mT (o), 0.5 T (+) and 5 T (rn), perpendicular to the c-axis. The lower points (-) represent the result for a field of 0.5 T directed parallel to the c-axis (after Mentink 1994).
electric field effect and anisotropic hybridization dictate the magnetic moments to lie preferentially in the crystallographic basal plane. Small steps have been observed in the magnetization versus field curves at low temperatures for fields parallel to the a-axis and pm'allel to the b-axis. These could be explained by assuming a small 6-fold anisotropy in the basal plane (Mentink et al. 1994c). Remains the question why one-third of the spins behave differently from the others. The same neutron diffraction experiments also showed that UNi4B does not crystalize exactly in the CeCo4B structure, but that it adopts a superstructure with a unit cell of size av/3 with the axis rotated by 30 ° with respect to the CeCo4B cell. This superstructure persists to temperatures above TN. Presently the atomic positions are being investigated by single crystal X-ray diffraction. The new heavy fermion superconductors, UPd2A13 and UPd2A13 crystallize in the PrNi2A13 structure, which is depicted in fig. 15. This structure is an ordered variant of the CaCu5 type, where 3 of the Cu atom are replaced by A1. The existence of magnetic moments in these compounds is caused by the for the CaCu5 structure - relatively large volume of the unit cell, leading to interuranium distances larger than Hill's limit. The Ni system has an ordered magnetic moment of (0.24 + 0.1)#B (Schr6der et al. 1994), the transition temperature is 5.2 K and the compound becomes superconducting below a temperature of about 1 K. Its Pd counterpart has a larger ordered moment of 0.85#B (Krimmel et al. 1992b), an higher TN of 14 K and a superconducting transition temperature of ~2 K. The exact temperature of the transition to superconductivity depends on the sample preparation (Sakon et al. 1993). We will come back to that point. The magnetic structure of UPd2A13 consists of ferromagnetic layers in the crystallographic basal planes with
32
G.J. N1EUWENHUYS
c I
3g
la >
Et
U,
© Pd,
•
2c
A1
Fig. 15. The PrNi2A13-type structure adopted by UPd2AI3 and UPd2A13. The uranium-transition metal layers are separated by an aluminium layer at z = 1/2 (after Mentink 1994).
250
i
| 2.00
200 © 0
E o
150 100
x
50 i
0
I
i
100
I
200
i
I
300
T (K) Fig. 16. Magnetic susceptibility of UPd2A13 along the a-axis (o) and c-axis (+). The solid lines denote a fit to a CEF model with a singlet ground state described in the text. The inset shows the highfield magnetization at T = 4.2 K parallel to the a-axis. Again, the solid line represents the calculated magnetization (after de Visser et al. 1993 and Mentink 1994). the m o m e n t s in the plane. The layers are stacked antiferromagnetically along the c-axis. For UNi2A13 the magnetic structure is slightly different, the ordering wave vector is n o w (½ + 3 , 0 , ½), with 5 = 0 . 1 1 0 + 0 . 0 0 3 . In both compounds the magnetic order persists into the superconducting phase as evidenced by neutron diffraction
HEAVY FERMIONS AND RELATEDCOMPOUNDS and #+SR experiments (see Krimmel et al. 1993 and Schenck and Gygax volume). The magnetic susceptibility of UPd2A13 is strongly anisotropic picted in fig. 16. The experimental results were explained on the basis of 1( model for the U 4+ ion with a singlet ground state, /"4 = ~ I + 3) - I -
33 in this as dea CEF 3)), a
first excited state, F1 = 10) at 33 K, a third state, /"6 = I + 1) at 102 K, a fourth state, F}2~ = a I q: 2) - bl + 4) at 152 K and other states at much higher energy (Grauel et al. 1993, Mentink 1994). The magnetic moment of UPd2A13 then is assumed to be due to an admixture of the first and second excited state as a consequence of an external and/or internal magnetic field. Note that this admixture will give rise to large moments in the basal plane. Any magnetic moment induced along the c-axis must come from an admixture between the/"4 and/"3 states, having an energy difference of about 560 K and is therefore relatively small. The maximum in the susceptibility versus temperature curve is due to the depopulation of the first excited state with decreasing temperature. The step in the magnetization as function of external field (inset to fig. 16) can be understood as a jump to ferromagnetic alignment of the moments due to the external field. Similar explanations for the magnetic susceptibility and the magnetization as a function of external fields were given in the case of URu2Si2 (see above). In that case (due to the tetragonal crystal symmetry) the level scheme is such that a field along the c-axis causes the largest admixture, and thus the moments are directed only along the c-axis, i.e. the basal-plane component simply does not exist. Note, however, that direct observations of the crystalline electric field levels by inelastic neutron scattering have not been successful up to now. The value of the ordered magnetic moment as well as the magnetic anisotropy have also been successfully explained on the basis of self-consistent density-functional calculations by Sandratskii et al. (1994), where the U 5f states are treated as band states. The magnetism in UPd2A13 is rather robust versus doping with other elements, this in contrast to the superconductivity (Geibel et al. 1994). In order to investigate the sample dependences further, Mentink et al. (1994d) have studied the sister compound CePd2A13. This compound does not become a superconductor so that the investigations can be focussed on the magnetism. In poly-crystalline form, after sufficient heat treatment, CePdaA13 orders antiferromagnetically at 2.7 K. However, as-cast samples as well as the best single crystals show at most only short range magnetic order. Such a discrepancy has also been observed in CePt2Sn2. Detailed nuclear quadrupole resonance experiments have shown that, e.g., in as-cast polycrystalline samples 11% of the A1 experience a different surrounding from the other 89%. In view of the number of nearest neighbours of the A1, this would imply that 2% of the A1 atom are wrongly placed. In the annealed polycrystal this number is about 1%. This experiment shows in a quantitative way the extreme sensitivity of the magnetism in heavy fermions compounds for the exact structure of the samples, and thus for the sample preparation. In other words this experiment emphasizes the notion that the ground state in heavy fermions is a result of a delicate balance between interactions.
34
G.J. NIEUWENHUYS
2.5. 334-compounds A remarkable set of compounds is formed by the U- and Ce-containing M 3 T 3 X 4 compounds, with T a transition metal and X is Sb, Sn or Bi. The existence of the Sb compounds had already been reported by Dwight in 1979, but it took a few years before the remarkable electronic and magnetic properties were studied in more detail (Buschow et al. 1985, Takabatake et al. 1990c and Endstra et al. 1990b). All compounds crystallize in the cubic Y3Au3Sb4 structure (space group 1 2~3d). The unit cell, depicted in fig. 17, contains 4 formula units. The inter-uranium distances are relatively large (~ 4.4 A), much larger than the distances between the magnetic atoms and the transition metal atoms (~ 3.3 A). Therefore, reasonable magnetic moments are expected, since no direct f - f overlap will occur. Most of the Sb compounds are semiconductors. In the case of U3T3Sb4 the gap in the density of states is rather large (,.~ 0.2 eV) in contrast to the tree Ce containing compounds mentioned, where gaps are found of the order of meV. The U compounds are therefore considered as 'normal' semiconductors, while the Ce compounds are most probably hybridization induced semiconductors. The normal semiconducting properties were confirmed by bandstructure calculation (Takegahara et al. 1990). Table 7 summarizes the structural, electronic and magnetic properties. It should be noted that in the case of U 3 C u 3 S b 4 electron-microprobe analysis shows that the Cu content was less than 3, so this is a Cu deficient material. From table 7 it is clear that the semiconducting compounds have a small coefficient of the linear term in the specific heat, i.e. no density of states at the Fermi level. Also, these compounds do not order magnetically, indicating that the conduction electrons are essential for the magnetic interaction. Again the trend in the magnetic properties in these system can be understood in terms of the strength of the hybridization. For example, replacing Ni by Cu in the Sn series
Fig. 17. The Y3Au3Sb4 crystal structure type. Small open circles indicate the Y atoms, small patterned circles are the Au atoms and the large open circles the Sb atom (after Takegahara et al. 1990).
HEAVY FERMIONS AND RELATED COMPOUNDS
35
TABLE 7 334-compounds. The lattice parameter is given in ,~. The specific heat coefficient, % is given in mJ/(mole K2) only if it is not disturbed by magnetic ordering and/or CEF effects. An M under 'Conduc.' means metallic and S semiconducting. Under the heading 'Magn.' an A means antiferromagnetism and F ferromagnetism. TM is the magnetic transition temperature in Kelvin. The effective moment/Zeff is given in/~B. Compound
a
Ce3Au3Sb4 Ce3Pt3Bi4 Ce3Pt3Sb4 U3Au3Sn4 U3Co3Sb4
10.058 9.998 9.820 9.824 9.284 9.415 9.522 9.393 9.380 9.684 9.683 9.675 9.531
U3Cu3 Sb4
U3Cu3Sn4 U3Ni3Sb4 U3Ni3Sn4 U3Pd3Sb4 U3Pt3Sb4 UPt3Sn4 URh3Sb4
3' 3 0 280 69 380 2 92 94 -
Conduc. S S S M M M M S M S S M -
Magn. F F A F
TM
#eff
Ref.
10 91 12 105
2.45 2.5 3.58 2.1 3.39 3.34 3.65 1.8 3.58 3.68 1.84 2.4
[ 1] [2] [1] [3] [4] [3, 4] [3] [3, 4] [3, 4] [3] [3] [3] [4]
References: [1] Kasaya et al. (1991b) [2] Hundley et al. (1990)
[3] Takabatake et al. (1990c) [4] Endstra et al. (1990)
will d e c r e a s e the f - d h y b r i d i z a t i o n b e c a u s e the d - b a n d shifts a w a y from the F e r m i level and the lattice p a r a m e t e r increases. In U3Ni3Sn4 the h y b r i d i z a t i o n is too large to f o r m o r d e r e d m a g n e t i s m and the c o m p o u n d is close to the h e a v y f e r m i o n regime, while U3Cu3Sn4 is an antiferromagnet. In the s e m i c o n d u c t i n g U3T3Sb4 c o m p o u n d s a r e p l a c e m e n t o f Ni b y Pd or Pt ( s a m e c o l u m n in the p e r i o d i c system) does not c h a n g e m u c h in the g r o u n d state, e x c e p t for the size o f the gap. H o w e v e r , substituting Cu for Ni (different c o l u m n ) drastically changes the features o f the c o m p o u n d s as was shown in detail b y Fujii et al. (1992) b y investigating the transition f r o m s e m i c o n d u c t i v i t y to f e r r o m a g n e t i s m in U3(Nil_xCux)3Sb4. The increasing n u m b e r o f d-electrons with increasing first causes the b a n d gap to close and subsequently i m p r o v e s the m a g n e t i c ordering via a R K K Y - t y p e interaction b e t w e e n the m a g n e t i c atoms. Substituting Sn b y Sb in the series U3Ni3(Sbl_xSn~)4 has two effects: the b a n d gap is r e m o v e d and the h y b r i d i z a t i o n is g r a d u a l l y increased, reflected b y a m o n o t o n e o u s reduction o f the effective m o m e n t o b s e r v e d at high temperature (Endstra et al. 1992b). A m a x i m u m for 7 is f o u n d for z = 0.5. The z e r o - t e m p e r a t u r e resistivity changes b y a factor o f 105. A s m e n t i o n e d above, Ce3Pt3Bi4 has been c o n s i d e r e d as so-called K o n d o insulator (see A e p p l i and F i s k 1992). Note that in this case, as for C e N i S n , the charge gap is e x t r e m e l y small, 0.01 e V for Ce3Pt3Bi4 and 0.001 e V for CeNiSn. Interestingly, the charge gaps in Ce3Pt3Bi4 and in C e N i S n are a c c o m p a n i e d b y a spin gap o f c o m p a r a b l e m a g n i t u d e as o b s e r v e d b y neutron scattering ( S e v e r i n g et al. 1991, M a s o n et al. 1992). As m e n t i o n e d in the section on i l l - c o m p o u n d s , substituting L a for Ce b r e a k s the f-lattice s y m m e t r y and leads rapidly to a metallic like resistivity ( T h o m p s o n et al. 1993a, b). Severing et al. (1994) have shown that
36
G.J. NIEUWENHUYS
the spin gap is less sensitive to doping with non-magnetic elements. Probably the formation of a spin gap is a more local phenomenon. The charge gap in Ce3Pt3Bi4 has also been observed via reflectivity and optical conductance measurements by Bucher et al. (1994). These experiments showed that for temperatures below 100 K a charge gap develops. The spectral weight depends on temperature, its decrease scales with the decrease of the Ce 4f-moments, but the size of the gap is temperature independent. Electronic band structure calculations in Ce3Pt3Sb4 and Ce3Pt3Bi4 by Takegahara et al. (1993) show a gap of 300 K, while the experiment reveals 900 K for the Sb compound. In the Bi compound the calculated gap is 3.5 larger than the experimental one of 100 K. From these results the conclusion can be drawn that Ce3Pt3Sb4 the term 'Kondo insulator' is not appropriate. If the small value of the gap in Ce3Pt3Bi4 can be associated with impurity states, then the term Kondo insulator is also in doubt for this compound. Other band structure calculations by the same group (Takegahara et al. 1992, 1993) have shown that the non-magnetic compounds Th3Ni3Sb4 and La3Au3Sb4 have a narrow gap at the Fermi level. Therefore, the related compound U3Ni3Sb4 and Ce3Au3Sb4 are 'normal' semiconductors. The same is true for the 111-compounds crystalizing in the MgAgAs structure, where the nonmagnetic equivalents are also found to be semiconducting (Palstra et al. 1987a and b).
2.6. Gaps Several types of energy gaps in a dispersion relation can occur in metallic (magnetic) systems: • The gap in the conduction band due to superconductivity. • The gap in the conduction band, which leads the semiconducting behaviour. This gap is found in a number of magnetic and non-magnetic compounds, see above. • The gap in the spin wave spectrum of magnetically ordered systems. The resulting low-temperature electrical resistance has been described by Hessel Anderson et al. (1979, 1980), who showed that for temperatures smaller than the gap size the contribution to the resistivity should follow a behaviour given by: T T(l +-~)e -zVT
(11)
If the gap in the spin wave spectrum is zero than the normal contributions proportional to the second and fifth power of the temperature remain. It is rather difficult to distinguish the normal behaviour from the one described by eq. (11). • Gaps in the dispersion relation of the conduction electrons due to the lowering of the symmetry of the crystal lattice as a consequence of the magnetic ordering. Necessary conditions are that the symmetry is lowered (ferromagnets will not exhibit this phenomena) and that the itinerant electrons "see" the lowering of the
HEAVYFERMIONSAND RELATEDCOMPOUNDS
37
symmetry, thus a band electron - magnetic moment interaction must be present. Changes in the band structure can cause changes in the electrical conduction through a change in the number of electrons available at the Fermi surface, even sometimes in an anisotropic way. A textbook example is the c-axis resistivity of pure Er due to a cone-like structure between 20 and 80 K, see Miya (1963), Freeman (1972) and Coqblin (1977) • Gaps in Kondo insulators as described above, probably there are charge gaps as well as spin gaps in these materials. Note that only the last type of gap is typical for heavy fermions, the other ones are found in normal metals, semiconductors and magnets, and thus also in some heavy fermions. Of course it is very interesting how these 'normal' gaps behave when they are formed in a band of heavy quasi particles. Magnetic gaps in spin or in spin wave excitation spectra can be observed via inelastic neutron scattering, see Broholm et al. (1991), Severing et al. (1991), Mason et al. (1992). Charge gaps can be seen in optical experiments and in vacuum tunneling measurements (Wolff 1985). The latter type of experiments is rather new in the research on heavy fermions (Aarts and Volodin 1995), although the tunneling spectra of the most famous ones have been investigated. URu2Si2 does show a gap in the spin wave excitation spectrum, it shows the exponential term in the resistivity (Palstra et al. 1986a) and in the specific heat (Maple et al. 1986). URu2Si2 also shows an increase in the electrical resistivity when the temperature is lowered through TN, indicative of a change in the band structure. Indeed, optical data (Bonn et al. 1988) and vacuum tunneling experiments (Aarts et al. 1994) confirmed this conclusion. The latter experiment clearly showed that in the antiferromagnetic phase a gap exits for electrons tunneling in the basal plane, which gap decreased on increasing temperature and disappeared at TN. No such gap could be detected for electrons tunneling along the crystallographic c-axis. UPd2A13 has no gap in the spin wave spectrum (Mason 1994). Vacuum tunneling experiments (Aarts et al. 1994) show the same type of gap as observed in URu2Si2. This could be expected, bearing in mind that in both compounds the magnetic ordering consists of ferromagnetic layers in the basal plane stacked antiferromagnetically along the c-axis. Thus in both cases the symmetry of the crystal along the c-axis is broken be the antiferromagnetic ordering. On the other hand, the electrical resistivity of UPd2A13 shows no increase at TN, which can be explained by assuming that the effects on the number of conduction electrons near the Fermi level is accidentally too small to overcompensate the decrease in the electrical resistivity due to the decrease in magnetic disorder scattering. However, also optical experiments do not show a charge gap developing at TN (Degiorgi et al. 1994a) and that has still to be explained. Gaps have also been observed via optical experiments in UNi2Si2 (Cat et al. 1993) and UCus, but no gap was detected in U2Zn17 (Degiorgi et al. 1994b). Note that the resistivity of UCu5 also increases for temperatures below TN (Ott et al. 1985a). Finally, I show two other examples where strong indications emerge form electrical resistance that the antiferromagnetic order changes the band structure. The first one is a series of pseudo binary compounds U(Col_xFe~)2Ge2 (van Rossum 1993). The resistivity is shown in fig. 18.
G.J. NIEUWENHUYS
38 1.50
re
q.
1 .OO j,,¢.a~
oooo
o.
°° °
oo U(Co
0.50
I
O
1-X F e x i
)2Ge2
I
100
I
200 T
( K
300
)
Fig. 18. Normalized resistivity versus temperature for U(CoI_~Fe=)2Ge2 after van Rossum (1993).
500
J
~t--8.XlS
250
--
0
i//b-axis
--
i//c-axis
1.10
g. 5 o o 0
.-
,~
1.05 1.00
095
25O
0.90 i
0 4OO
i
i
0.85
35
40
45
50
T [K]
200 I
0
20
I
40 T (~<)
60
Fig. 19. Temperature dependence of the electrical resistivity of UNiGe for current along the three principal directions. The fits with an additional exponential term involving electron-magnon scattering are shown by solid lines. The right hand side figure shows an enlargement of the area around 41.5 K (after Proke~ et al. 1994).
HEAVYFERMIONSAND RELATEDCOMPOUNDS
39
Also U(Col_xNi~)2Ge2 (Endstra et al. 1993c) shows strong increases in the resistance. The other example is UNiGe, which exhibits a transition from a commensurate antiferromagnet to an incommensurate structure at T* = 41.5 K (Prokeg et al. 1994). The electrical resistivity as a function of temperature is depicted in fig. 19, where nothing can be seen when the current is directed along the a-axis, an increase at T* when the current flows parallel with the b-axis and finally a sharp decrease for currents along the c-axis. Clearly the change in the band structure has an anisotropic influence on the conduction and also it is clear that this change can induce an increase as well as a decrease in the number of available carriers. The same experiment gives indications for a gap in the spin wave spectrum, shown by fits to the expression given in eq. (11) (Proke~ et al. 1994). Another remarkable signature of the change of the band structure was found from M/3ssbauer experiments by Mulder (1994). He has determined the electric field gradient at the site of the magnetic ion - in the case Gd - by measuring the quadrupolar splitting of the 155Gd nucleus. The electric field gradient is governed by the symmetry of the crystal lattice and in particular its size by the band structure. It appeared that in some antiferromagnetic compounds, the gradient changes at the magnetic transition temperature, whereas in ferromagnetic compounds no change could be observed. Evidently, careful experiments is the area of spin and charge gaps will reveal more about the mechanisms in effect in magnetic and semiconducting heavy fermion materials.
2.7. Magnetism and superconductivity The interplay between magnetism and superconductivity plays an important role in heavy fermion physics. Almost all superconducting heavy fermions also show magnetic ordering, the only exception seems to be the cubic UBe13. In good samples of UPt3 two superconductivity transitions can be seen in the specific heat as a function of temperature. This double transition is though to be caused by the symmetry breaking effect of the antiferromagnetic order in the basal plane present below TN = 5 K (Aeppli et al. 1988). Extensive measurements as function of external magnetic field and external pressure have revealed a rich phase diagram where the different crossings of the phase separating lines merge in a tetracritical point at 2.6 kbar (Boukhny et al. 1994a, b; see also van Dijk 1994 and references therein). Keller et al. (1994) observed a clear dependence of the upper critical field, Bc2, on the angle between the magnetic field and the crystalline axis. As mentioned above URuzSi2 and UPdzAI3 show anisotropic gaps at the Fermi surface due to the antiferromagnetic order. The superconductivity therefore develops in this already partly gapped state and is evidently influenced by its symmetry. It is difficult to obtain really hard facts on this aspect, but, e.g., as mentioned earlier, the observation of superconductivity in URuzSi2 by #+SR is also highly anisotropic in this compound in spite of the apparent isotropic behaviour of the lower critical field. In the case of UPd2A13 it has been argued that the superconductivity and the magnetism are carried by two different f-electron systems (Caspary et al. 1993 and Feyerherm et al. 1994), being itinerant for the superconductivity and more localized for the magnetism. When U in UBe13
40
G.J. NIEUWENHUYS
is partly (few atomic percent only) replaced by Th, a rather exotic phase diagram is found, see, e.g., Ott (1994). Between 2 and 4 at.%, a second transition is observed from a second maximum in the specific heat (Ott 1989). Heffner et al. (1989a, b; 1990) have shown that below the second transition temperature the superconductivity coexists with a magnetic state, characterized at least by static randomly distributed internal magnetic fields as seen via #+SR. In all cases it is rather clear that the superconductivity cannot be described by an ordinary order parameter.
2.8. Miscellaneous compounds 2.8.1. CeCu6 and derivatives CeCu6 has been studied for a long time. Onuki et al. (1985b) found the first indication for its Kondo lattice or heavy fermion behaviour based on resistivity measurements on a single crystal. Rapidly other measurements followed (a.o. Ott et al. 1985b, Amato et al. 1987) showing that no long range magnetic order nor superconductivity was present down to temperatures of 15 mK. See also Bauer (1991) for a review. The compound CeCu6 crystalizes in an orthorhombic structure, space group Pnma, having 4 formula units per unit cell and lattice parameters a = 8.109 A, b = 5.098 A, and c = 10.172 A. Below a temperature of 220 K, the compound transforms into a monoclinic structure, space group P21/c, with gradually increasing angle /3 up to 91.36 ° and lattice parameters a = 5.080 A, b = 10.221 A and e = 8.067 A (Asano et al. 1986 and Gratz et al. 1987). With its 3' value of 1600 mJ/(molK2) it is now considered as an archetypal heavy fermion system. Neutron diffraction experiments showed the development of antiferromagnetic correlations below 1 K (Aeppli et al. 1986, Rossat-Mignod et al. 1988), while #+SR (Amato et al. 1993) reveals that the moment associated with these correlations should be smaller then 0.01#B. This then places CeCu6 really at the borderline between magnetic ordering and heavy fermion behaviour. Small amounts of Ag or Au (Gangopadhyay et al. 1992, Germann and von L6hneysen 1989) drive the compound into the long range ordered region, most probably by increasing the volume of the unit cell and thereby decreasing the Kondo temperature. Another beautiful experiment was carried out by Stroka et al. (1993) on CeCu6_~Au~ compounds showing that the Schottky anomaly due to the crystalline electric field splitting develops from a broadened maximum into the well-known free ion behaviour with increasing x from 0 to 0.9. At x = 0.9 the long range magnetic order is observed at 2 K. Non-Fermi-liquid behaviour has also been observed in Au doped CeCu6, at the composition CeCus.9Au0A by von LShneysen et al. (1994). CeCu6 is a famous heavy fermion without magnetic ordering, by increasing x in CeCu6_~Aux antiferromagnetism is rapidly obtained for small values of x, the transition is zero for the critical concentration x = 0.1. 2.8.2. UxYl-xPd3 UxYl-xPd3 forms a series of strongly correlated electron systems with a complex and rich magnetic phase diagram (Seaman et al. 1991, 1992, Andraka and Tvselik 1991). For x ~< 0.2 the specific heat, magnetization and electrical properties indicate non-Fermi liquid behaviour, while for 0.3 ~< x ~< 0.5 a spin-glass type ordering
HEAVYFERMIONSAND RELATEDCOMPOUNDS
41
is found. The lower concentration samples obey remarkably well the theoretical predictions for the two-channel Kondo effect (Cox 1987). The T -+ 0 behaviour is not completely clear, Andraka and Tvselik suggest a T = 0 second-order magnetic phase transition, while Cox assumes a collective Jahn-Teller instability. Stillow et al. (1994) have shown via detailed metallurgical analysis that compounds with z ~ 0.2 are intrinsically inhomogeneous. For example, for z = 0.2, the measured concentrations vary from 0.14 to 0.23. A long term heat treatment could only halve the range of concentrations. Nevertheless, the magnetic and electrical properties did not depend strongly on the homogeneity. Remains the question what the behaviour of a homogeneous alloy will be.
2.8.3. CeCu5 and UCu5 and derivatives CeCu5 crystallizes in the hexagonal CaCu5 structure, it orders antiferromagnetically at 3.9 K, and has a '7-value of 100 mJ/(mole K 2) and a logarithmic contribution to the electrical resistivity (Bauer 1991 and references therein). Inelastic neutron scattering experiments (Alekseev et al. 1992) and magnetic measurements have shown that the I + 1) is the ground state of the CEF levels and that the I + 23-}is at 17 meV (200 K) the first excited state. At the ordering temperature only the ground state plays a significant role. Remarkably, in spite of the [ 4- ½) ground state, from which a large magnetic moment in the basal can be expected, neutron diffraction (Bauer et al. 1994a) showed that the ordered moment is directed along the c-axis and has 1 a value of 0.36#B. The propagation vector of the magnetic structure is (0, 0, ~). The measured moment is smaller than the one calculated from the CEF scheme and also the entropy involved in the magnetic transition is smaller than R ln(2), indicating that the Kondo effect is present. The unexpected direction of the ordered moment points to a strongly anisotropic (in spin space) interaction between the Cemoments, i.e. the compound is Ising like (Bauer et al. 1994a). #+SR experiments (Wiesinger et al. 1994) showed some evidence for inhomogeneous magnetic order. These experiments also showed the strong anisotropic susceptibility from the Knight shift, confirming the Ising like behaviour. The study of CeCu5 is of particular interest because substituting A1 or Ga for Cu destroys the long range magnetic order (Bauer 1991, Bauer et al. 1990) and drastically increases "7 up to a value of 2.8 mJ/(mole K 2) for CeCu4A1. Presumably this large "7 should be interpreted as being due to short range magnetic correlations, since it appeared to be strongly dependent on external magnetic fields (Andraka et al. 1991). The electrical resistivity of CeCu4Ga is not pressure dependent (Eichler et al. 1994). UCu5 orders antiferromagnetically below 16 K. The crystal structure is of the cubic fcc AuBe5 type, and the magnetic structure has been determined via neutron diffraction (Murasik et al. 1974 and Schenck et al. 1990). The U sublattice orders ferromagnetically in the (111) planes, which are stacked antiferromagnetically. The ordered moments are aligned along the (111) direction and have a magnitude of ,.~ 1.55#B. The specific heat reveals a second transition at 1 K (Ott et al. 1985a, b), which is hysteretic in temperature, suggesting first order although no latent contribution could be observed. Schenck et al. (1990) showed that this transition could not be observed in the neutron diffraction, and that
42
G.J. NIEUWENHUYS
for the #+SR only the relaxation, not the frequency of the spontaneous precession changes at about 1 K. A possible explanation that remains is that besides the already preset antiferromagnetic order a second ordering takes place of small moments like in, e.g., UPt3 and URuzSi2 (Schenck 1993). If that interpretation is correct, then this would be a strong indication for the existence of to different f-electron systems. Nakamura et al. (1994) interpreted the 1 K transition as a spin reorientation on the bases of the an analysis of the nuclear magnetic resonance data. When part of the Cu atoms in UCu5 are replaced by Pd, the antiferromagnetism rapidly disappears. UCus_~Pd~ is an antiferromagnet only for z < 0.75 and becomes a spin glass for z > 2. For z = 1.5 the specific heat divided by temperature diverges logarithmically for T --+ 0 (Andraka and Stewart 1993). No Fermi liquid behaviour could be detected for this alloy down to 0.3 K, thereby characterizing this material as a non-Fermi liquid one, like Uo.zY0.8Pd3. The pseudo binary compounds mentioned in this section give the experimentalist in principle the opportunity to scan the zero-temperature transition between heavy fermion behaviour and long rang magnetic order. Such ideas are known for some time (Lawrence 1982) and elaborate theories are available (Millis 1993, 1994). Whether it will be possible to really investigate the critical region depends on our ability to engineer our samples or the use other external variables such as pressure or magnetic field sufficiently cleverly. See for a recent review: Andraka (1994) and Abrahams (1994).
2.9. Yb-compounds Not many Yb compounds can be considered as heavy fermions. Most of them are typical valence fluctuators. Yb 3+ is in the 4f 13 state and thus magnetic since it is off by 1 electron from the full 4f-shell. Yb 2+ is non magnetic. This should be contrasted with the Ce-compounds, where adding one f-electron leads to the magnetic state. Therefore, e.g., pressure dependences of the properties of Yb-compounds are just opposite from those in Ce-compounds. The counterpart of UBe13, YbBel3 is a simple antiferromagnet with an ordering temperature of 1.115 K and the crystal field splittings in this cubic material are rather small. The ground state is /"6, the first excited state a/"8 at 37 K and the last state is a/"6 at 51 K. These observation could be made by neutron scattering (Walter et al. 1985) and via specific heat measurements (Ramirez et al. 1986), indicating that hybridization and/or Kondo effects hardly play any role. YbCu5 acts as a parent compound for various substitution at the Cu site, see Bauer (1991) and references therein. A few of the resulting doped materials are heavy fermions. Two crystal structures seem to be possible for YCus, the simple hexagonal CaCu5 (Iandelli and Palenzona 1971) or the MgSnCu4 structure, related to the cubic AuBe5 (Hornstra and Buschow 1971). Substitution by A1 or Ga stabilize the CaCu5 and substitutions by Au, Ag, Pd or In stabilize the MgSnCu4 structure. Yb in YbCu5 is close to the divalent state and thus non magnetic. All the substitutions mentioned above drive the Yb ion into the trivalent state, thereby initiating magnetism. YbCu4Au orders antiferromagnetically below 1 K, the Kondo temperature is of order of 0.3 K (Bonville et al. 1992). The crystal field levels are /"7, /"8 and/"6 at 0, 46 and 81 K, respectively. YbCu4Pd behaves in the same way. The only compound in this series with a large -,/-coefficient for the specific
HEAVYFERMIONSAND RELATEDCOMPOUNDS
43
heat is YbCu4Ag. Rossel et al. (1987) found 200 mJ/(mole K2). A value of 245 was determined for the Pd sample, but this may be in error because of the magnetic order and the crystal field states. The magnetic and thermodynamic properties of the systems mentioned can be remarkably well described by the Coqblin-Schrieffer model (Besnus et al. 1990, Schlottmann 1993). The same can be said about YbCu2Si 2 (Rasul and Schlottmann 1989) and YbPdzSi2 (Schlottmann 1992). The interpretation of the neutron data obtained by Severing et al. (1990a) for YbCu4Ag is not unambigeous. The original authors could not find a consistent fit over the whole temperature range. A reanalyzis by Polatsek and Bonville (1992) revealed a characteristic temperature (approx. Kondo temperature) of 60 K and a crystal field level scheme such as that for YbCu4Au. On the other hand, Schlottmann (1993) concludes that the observed inelastic scattering is a result of transitions from the Kondo resonance to the Fermi level. YbCu4In is a remarkable compound. It exhibits a first-order phase transition at T~ = 41 K from the divalent (non-magnetic) state at low temperatures to a magnetic trivalent one at higher temperatures. The transition is marked by a sudden change in the magnetic, thermodynamic and transport properties (Felner and Novik 1986, Felner et al. 1987). Of course also the signature of the crystal field splittings in the inelastic neutron scattering (Severing et al. 1990b) disappears upon cooling below T~. The CEF scheme in the magnetic phase is Fs, F6 and F7 at 0, 38 and 45 K, respectively, almost the same as that for the stable trivalent YbNi4In. The pressure and magnetic field dependence of the electrical and thermal properties of YbCu4Ag have been studied by Graf et al. (1994), Bauer et al. (1994b, 1995), Thompson et al. (1994a) and Lacerda et al. (1995). In general the observations can be described by a decrease of the Kondo temperature with increasing pressure. A magnetic field of 8 T appears to be equivalent to 30 kbar. Thompson et al. (1994a) show that the relation between the quadratic term in the electrical resistivity and the linear term in the specific heat, A c< 72
(12)
holds when the pressure is the implicit variable. The same is not true for the external magnetic field (Lacerda et al. 1995). This is probably due to the small CEF splittings, so that external fields can effectively change the ground state of the system. The N6el temperature of YbCu4Au, being 0.6 K at ambient pressure, increases to more than 2 K at 50 kbar. The pressure dependence of the resistivity was described by a low Kondo temperature, consistent with the earlier observations (Bonville et al. 1992). A1 and Ga substitution also drive the YbCu5 system towards the magnetic state of Yb (Bauer et al. 1992, 1995) and the full trivalent state is reached around 40 at.% A1 or Ga. YbPtBi has received lots of attention due to its very large value of the extrapolation of Cp/T to zero temperature, being 8000 mJ/(mole K 2) (Canfield et al. 1991, Fisk et al. 1991). The specific heat exhibits a small maximum at 0.4 K, #+SR experiments showed spatially inhomogeneous disordered static magnetism below ~0.5 K, with a small moment of ~ 0.1#B in about 50% of the total sample volume. (Amato et al. 1992). In fact, the #+SR data suggest a spin-glass like behaviour for YbPtBi, although also a incommensurate spin density wave is possible (Heffner et
44
G.J. NIEUWENHUYS
al. 1994). The latter is in accord with the resistivity measurements by Movshovich et al. (1994a, b), who found an increase in p when cooling down below 0.4 K, indicating an ordering such that the band structure changes and at least the number of carriers at the Fermi level decreases. They also showed that a pressure of only 1 kbar is sufficient to suppress the low temperature state. The crystal structure has been solved by Robinson et al. (1994b). YbPtBi crystallizes in the cubic MgAgAs structure, Pt occupies the 4a sites, Bi the 4c, the 4b site is vacant and the 4d site is occupied by Yb. The same neutron diffraction experiment showed that any ordered moment should by smaller than 0.25#B. An inelastic neutron scattering experiment, also made by Robinson et al. (1993b) gives information about the CEF splitting. Most probably the order of the levels is FT, Fs and F6, the corresponding splittings however are of order of 1 K and about 65 K. The near degeneracy of the two lowest states is important. As Thompson et al. (1993b) pointed out, it is the fact that the CEF energies, the ordering temperature and possibly the Kondo interaction are of comparable strength which gives YbPtBi its peculiar properties. Remarkably, most of the properties are not influenced by doping with non-magnetic elements like Lu and Y (Lacerda et al. 1993): down to 50 at.% Yb the thermal and magnetic properties are proportional to the Yb content, even the temperature of the maximum in the specific heat does not depend on dilution of the Yb sub-lattice. Thompson et al. (1993b) also showed that the isostructural YbPtSb orders normally at T = 0.35 K and shows accordingly contributions from the nuclear specific heat at lower temperatures.
2.10. Thin films Thin films of heavy fermion materials have already been made occasionally for a number of years (e.g., Tedrow and Quateman 1986, Roessler and Tedrow 1990). The general conclusion is that the typical properties of the heavy electron persist in the thin film. Note, however, that these were thicker than any characteristic length of the heavy fermion state. A systematic effort was undertaken by the Darmstadt group: Huth et aI. (1993, 1994a, b, c, 1995), Hessert et al. (1995) (UPd2A13 films) and Lunkenheimer et al. (1994) (UCua+xA18_x films). The UPd2A13 films are highly c-axis oriented, the films show the antiferromagnetic transition at 14 K as well as the superconducting one at 1.8 K. The availability of these oriented films enables detailed investigation of the Hall effect and of the critical current in the superconducting state. The Hall coefficient exhibits a maximum around 55 K and a minimum at 6 K and saturates quadratically towards zero temperature. The temperature dependence can be understood as a superposition of skew scattering (dominating at high temperatures) and coherent effects at low temperatures. Critical current measurements in the superconducting state showed this magnetic heavy fermion superconductor to be able to carry 6.5 x 107 A]m2 at 0.32 K and 1 T external field. The activation energy for flux greep appeared to be 25 K in zero external field and to decrease with field along the c-axis to 5 K at 3 T. UCu4A18 crystallizes in the ThMn~2 structure and orders antiferromagnetically below 30 K. When z is increased in the series UCu4+xA18_x, then the antiferromagnetism decreases for z > 1.5 and a heavy fermion state emerges resulting in 7 = 800 mJ/(mole K2) at z = 1.9 (Geibel et al. 1990, K/3hler et al. 1990). Thermal and transport properties can be described
HEAVY FERMIONS AND RELATED COMPOUNDS
45
in a single ion Kondo effect model. Lunkenheimer et al. (1994) have prepared this system in amorphous thin film form. In this state the onset of magnetic order is suppressed with respect to the crystalline results at low z values and the coherent heavy-fermion behaviour is suppressed at large z values. From dc- and ac-resistivity measurements they conclude that all sample reveal a single ion Kondo behaviour, but that significant deviations from dipolar Kondo effect are found for the lowest temperatures. 3. Conclusion Heavy fermions and other related magnetic compounds have attracted lots of attention over the last decade. They still from the subject of many publications: the subject is alive. In spite of this efforts a number of questions have remained unanswered up to now, see, e.g., Coleman (1995) in the final talk of the Amsterdam conference on Strongly Correlated Electron Systems. Future attention will probably be focussed on the zero-temperature transition from the 'paramagnetic' state to magnetic order and the accompanying non-Fermi liquid behaviour. Also the band structure will become more important, via further ab initio calculations, and via spectroscopic experiments. 4. A c k n o w l e d g e m e n t s During the past ten years I have had the pleasure to work with a number of PhD students: T.T.M. Palstra, A.J. Dirkmaat, T. Endstra, R.A. Steeman E.A. Knetsch, S.A.M. Mentink, A. Drost and S. Stillow. Without their efforts this chapter would not have been written. I thank J. Aarts and J.A. Mydosh for many stimulating discussions. Without the cooperation and friendship of many colleagues around the world the research on heavy fermion would be dule, if not impossible.
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chapter 2 MAGNETIC MATERIALS STUDIED BY MUON SPIN ROTATION SPECTROSCOPY
A. SCHENCK and F.N. GYGAX Institute for Particle Physics of ETH ZBrich CH-5232 Villigen PSI Switzerland
Handbook of Magnetic Materials, Vol. 9 Edited by K.H.J. Buschow 01995 Elsevier Science B.V. All rights reserved 57
CONTENTS 1. Introduction
.................................................................
2. Muon spin rotation (/~SR) spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.
Parameters + phenomenology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
60 62 62
2.2.
Muon site and local fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
72
2.3.
More on spin-lattice relaxation in the paramagnetic and ordered state . . . . . . . . . . . . . .
76
3. Review of results in elemental metals and alloys
...................................
80
3.1.
Spontaneous dipole and hyperfine fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Critical phenomena
3.3.
Ferromagnetic 3d-element based alloys
3.4.
Chromium and its alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
102
3.5.
/~-SR in Fe and Ni . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
103
...................................................... ......................................
4. Review of results in intermetallic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
96 101
104
4.1.
Compounds involving transition elements
4.2.
Intermetallic compounds containing rare earth elements . . . . . . . . . . . . . . . . . . . . . . . . .
114
4.3.
Intermetallic compounds containing actinide elements
175
5. Review of results in magnetic insulators 5.1.
....................................
84
..........................
..........................................
Oxides with corundum-type structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.
Orthoferrites and RNiO3 perovskites
5.3.
Miscellaneous mostly Cu-based and layered oxides
........................................ ............................
..................................................................
104
199 199 209 212
5.4.
MnO
5.5.
Magnetic fluorides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
215
5.6.
COC12.2H20 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
219
5.7.
Solid oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6. Review of results in layered cuprate (high Tc) compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1.
215
220 221
La2CuO 4 and related compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
221
6.2.
YBa2Cu30= and related compounds
244
6,3.
Bi-based (2212)-compounds
........................................
...............................................
58
269
MUON SPIN ROTATION SPECTROSCOPY 7. Study of magnetic order in organic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.1.
(TMTSF)2X
............................................................
7.2.
Ni2(C2HsN2)2NO2(C104) (NENP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.3. p-NPNN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . List of some of the used abbreviations and symbols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
59 274 274 279 280 281 281 284
1. Introduction
This chapter contains a review of results on magnetic materials obtained by a single technique, namely Muon Spin Rotation (#SR) Spectroscopy. In this respect the present chapter is quite different from most other contributions in this series of volumes which focus on (all) the magnetic properties of certain materials as collected by different methods and techniques. The reader will find that the application of #SR-spectroscopy has in many instances just confirmed what was known already from other studies, but often has added a new flavour or twist to our knowledge and understanding of established magnetic phenomena. Beyond that, however, when using positive muons (#+) #SR spectroscopy has shown the potential to uncover new and unexpected magnetic features owing to its high sensitivity to very small magnetic fields and spatially inhomogeneous properties. Thus #SR-spectroscopy is most powerful in the field of small moment magnetism and in all instances when magnetic order is of a random or very short range nature and where neutron scattering will fail. Compared to NMR-spectroscopy #SR-spectroscopy will work also in the case of very broad lines (up to 100 MHz) and very short relaxation rates (down to 10 -8 s). On the other hand relaxation phenomena involving Ta > 100 #s are out of the time window accessible by #SR. In this respect #SR and NMR are rather complementary techniques. But note that generally the implanted positive muons (#+) are found at interstitial sites and, therefore, probe the magnetism from a different perspective. The local probe aspect of #SR and its sensitivity to inhomogeneous features has in particular brought the real nature of solids into light which are never perfect in lattice structure, stoichiometry and morphology, and hence also magnetic properties do not show up in an ideal manner. For example, in many intermetallic compounds magnetic order is found to be established in a spatially inhomogeneous way, leaving sometimes a fraction of the sample in the paramagnetic state even far below the phase transition temperature. There are even examples where magnetic order evolves so gradually in space and with temperature that the concept of a cooperative phase transition looses its meaning and consequently no anomalies in the specific heat are observed. It is in fact an open question whether such observations have to be correlated only with the sample quality (sample quality certainly matters) or whether they could also reflect more intrinsic properties. Such distinction, on the other hand, may be quite artificial: real solid compounds are what they are and their imperfections are an integral part of them. To perform #SR measurements positive muons have to be implanted into the material of interest. How innocent are the implanted #+? Do they, by their presence, 60
MUON SPIN ROTATIONSPECTROSCOPY
61
modify local properties, including magnetic ones? Note that practically only one muon will be present at a time in the sample (average # lifetime is 2.2 #s) and that the total number of #+ implanted during an experiment exceeds rarely 101° which number is to be compared with the usual density of host lattice atoms. In effect radiation damage will be of no concern whatsoever. In metals the muons's positive charge will be screened jointly by the conduction electrons piling up at and around the #+. The screening is usually, at normal conduction electron densities, accomplished within a distance of the order of the Bohr radius which is small compared with interatomic distances in a solid. Friedel oscillations will cause a ripple in the conduction electron density distribution outside of the screening cloud which will produce additional electric field gradients at the nearest host neighbor sites (also in cubic systems). Most importantly the presence of the #+ causes a local lattice dilatation: the nearest neighbor host atoms may be pushed away by a few % of their rigid lattice distance from the interstitial positions, changing also locally the interatomic distances. These are all well known effects when hydrogen is introduced into a metal in small concentrations (with #+ one probes the infinite dilution limit!). It is conceivable that the changed distances could have an effect on the magnetic coupling of the atoms in the vicinity of the #+, but so far there is no compelling evidence for such a possibility. In any case #SR-data have always reflected magnetic phase transitions at temperatures in agreement with bulk determinations of Tc or TN. The only clearly established effect of a #+ induced local modification was found in PrNi5 (see section 4.2.4) where the crystalline electric field (CEF) splitting of the ground state of the #+ nearest Pr 3+neighbor was significantly altered. The consequences of this observations for the interpretation of magnetic features observed by #SR in other rare earth or actinide based compounds are not clear yet but will require attention in all future investigations. In insulators the #+ is observed to be present in the form of the strongly paramagnetic muonium (#+e-) atom or is found to be bound chemically to one of the constituents (in particular to oxygen, if present). So far muonium has only been observed in the magnetic compound MnF2, while in all other investigated magnetic insulators the #+ appears to be in a diamagnetic state (see section 5). No indications for #+ induced modification in local magnetic features were ever manifest. So the answer to the above questions is that, as far as experience teaches, the positive muon is a fairly innocent magnetic probe, but that this has to be studied in each case, where it could matter, with care. Another problem in #SR studies is connected to the question of the #+ site in the lattice after implantation. To extract quantitive information from #SR-data knowledge of the site is a prerequisite, but often the site is not known. Therefore the reader will notice that the discussion of #SR results is almost always intimately interwoven with considerations of the muon's possible or actual site or sites. This review attempts to include all material on #SR studies of magnetic compounds up to the sixth international conference on #SR spectroscopy, held in June 1993 on the island of Maui, Hawai. However, we were forced by space and time limitations to skip one very important field of #SR-applications in magnetism, namely the very
62
A. SCHENCKand F.N. GYGAX
successful study of spin glasses. It is hoped that this very special subject will find coverage in some future review article.
2. Muon spin rotation (pSR) spectroscopy #SR spectroscopy is a variant of other well known hyperfine probe techniques such as NMR, 7"/PAC and PAD, and M6ssbauer spectroscopy. Therefore in #SR spectroscopy one measures basically the same parameters as in the other methods. In the following section 2.1 these parameters will be briefly recapitulated and some specialities, when using the #SR technique, will be pointed out. The technique itself will only be sketched briefly. The interested reader is referred to the many articles that describe the technique in detail (see, e.g., Chappert 1984, Schenck 1985, Chappert and Yaouanc 1986a, Cox 1987, Seeger and Schimmele 1992, Smilga and Belousov, 1994). Section 2.2 discusses the connection between the #+ site and local magnetic fields and section 2.3 provides some material on #+ spin relaxation due to the temporal fluctuations of the host magnetic moments. By far most of the investigations were done by using positive muons (#+). In a very few cases also negative muons (#-) have been applied. Positive muons are usually implanted at an interstitial site (the same site that is usually occupied by hydrogen in metals) and probe the magnetism from this point of reference. In contrast negative muons are captured into a ground state Bohr orbital of the host crystal atoms at substitutional positions. In this respect # - S R has more in common with NMR. However, the negative charge of the # - , close to the host nucleus, reduces the total nuclear charge seen by the electrons to effectively ( Z - l), thereby transforming the #--atom to an impurity atom, different in valency from the original one. In addition the captured # - has a much reduced polarization in the lowest Bohr orbital (< 1/6 of initial polarization) and a reduced effective free decay rate which renders # - S R much more difficult and limited in applications.
2.1. Parameters + phenomenology 2.1.1. Brief description of the #+SR technique #SR spectroscopy rests on the weak decay of the #+ : #+ --+ e + + ue + ~u which, because of parity violation in the weak interaction, leads to an asymmetric distribution of the decay positron with respect to the spin of the decaying #+: Are+(0) oc 1 + A cos 0,
(2.1)
where 0 is the angle between the e+-trajectory and the #+ spin. (Other relevant properties of the #+ are listed in table 2.1.) Hence by measuring the positron distribution it is possible to determine the original #+ spin direction. This, of course, requires the observation of many decays and implies that the participating #+ all possess initially the same spin orientation, i.e. that they are polarized. Polarized #+-beams with polarizations up to ~ 100% are available at the so called meson
MUON SPIN ROTATION SPECTROSCOPY
63
TABLE 2.1 Some properties of the muon where me is the electron mass, mp the proton mass and /~p the proton magnetic moment. Property
Values
Mass (m u)
206.76835(1 l)me = 0.1126096mp = 105.6595 MeV c -2 +e, - e ! h 2 3.1833455(5) 13.553879 (± 0.2 ppm) kHzG -1 2.002331848(17) ±l-y~lI (+ : #+, - : # - ) 2.19703(4)/~s
Charge Spin (I) Magnetic moment (/~) (in units of/~p) Gyromagnetic ratio (7~/2r) 9 factor (g~) Direction o f / ~ Lifetime (%)
TABLE 2.2 List of proton accelerators with #SR facilities (1993). Name
Country
Beam mode /z+-beamlines and/~SR-instrumentation
PSI
Switzerland
DC
ISIS(RAL)
UK
pulsed
JINR (Dubna)
Russia
pulsed or DC
PNPI (Gatchina) Russia LAMPF USA TRIUMF Canada
pulsed pulsed DC
BOOM (KEK) Japan
pulsed
2 surface (4 MeV)/~+ beamlines (1 dedicated to/~SR), 2 decay beamlines (20-50 MeV), 6 spectrometers available, including a low temperature set-up (dilution refrigerator) and a high pressure set-up. Good for ZF, LF, TF-measurements. Ultra slow muon beam line under development. dedicatedsurface/~+ beamline with 3 experimental ports, one equipped with a dilution refrigerator. Best for ZF and LF-measurements. 1 decay beamline with several ports (RIKEN-RAL), under construction. 1 decay beamline, several ports 1 general purpose spectrometer(MUSPIN). LF, ZF, TF-measurements possible. Surface muons also available in the future. 1 decay beamline, ZF, TF-measurements possible. 1 surface/z + beamline, best for ZF, LF-measurements. 3 surface/z + beamlines, 2 decay beamlines. Dilution refrigerator available, 5 T-SC-magnet, two general purpose spectrometers with various cryostats. 1 dedicated #+ surface beamline, dilution refrigerator available, if-resonance spectrometer, superconducting magnet for LF-measurements. Ultra-slow-muon beamline under development.
factories and a few other m e d i u m energy accelerator centers (see table a s y m m e t r y parameter A in eq. (2.2) is basically given by A = Pa,
2.2). T h e
(2.2)
where P is the b e a m polarization and a an intrinsic asymmetry parameter which is determined b y the weak interaction decay m e c h a n i s m . If all decay positrons,
64
A. SCHENCK and EN. GYGAX
irrespective of their energy 1, are detected 2 with the same efficiency, an average of = 0.3 will result. The total asymmetry is thus quite sizable and generally much larger than in nuclear 13-decays. If the spin polarized #+ are stopped or implanted in a target in which they are ~bjected to magnetic interactions, their polarization/5 may become time dependent: P(t). The evolution of/5(t) can be monitored by measuring the positron distribution as a function of elapsed #+ life time. In fact it suffices to monitor only the positron rate into a particular direction, say along the direction of the initial polarization /5(0). This geometry will be assumed throughout this section. It is straightforward to extend the discussion to other directions of observation. The positron rate dN~+ (t)/dt as a function of elapsed #+ life time is then given by the expression (see, e.g., Schenck 1985). dN~+(t) 1 d-----~ - No ~ exp(-t/%)(1 + A/5(t)./5(O)/P(O)),
(2.3)
where % = 2.2 #s is the average/z + life time and the exponential factor accounts for the decay of the #+. /5(t) •/5(0)/P(0) 2 can be identified with the normalized #+ spin auto correlation function
G'(t) -
(s(o) 2)
(2.4)
This function contains all the physics involved in the magnetic interaction of the #+ inside the target or sample. Henceforth we will define P(t) as the projection of fi(t) onto the initial polarization/5(0), choosen to be the direction of the positron observation, i.e. P(t) =/5(t)./5(O)/P(O) = G(t)P(O). P(t) is called the #SR signal, sometimes it is also referred to as the asymmetry since it determines the effective decay asymmetry in the distribution eq. (2.1). Figure 2.1 represents in a schematic way a typical experimental arrangement for measuring the distribution given by eq. (2.3) and to extract P(t). Since it involves the measurement of individual #+ life times (on an event after event basis in a continuous (dc) #+ beam; in a somewhat different fashion in a pulsed beam with pulse width << %) it is referred to as a time differential technique. For details see Schenck (1985). Also time integral detection schemes have been developed which we will not discuss here. Actual #SR experiments benefit from the availability of two types of #+-beams. The first, conventional type, is formed from pions decaying in flight (Tr+ -+ #+ + u~) and involves relatively high #+ energies (~ 40-50 MeV) and spin polarizations in the range (60-80)%. Muons in such a beam need first to be 1 Since the decay of the # + involves three particles (e +, Ue, r~,) the e + energy will vary continuously between zero and a maximum energy E ~ _~ 1/2muc 2 ,-- 52 MeV. On the average the e + energy amounts to ~ 30 MeV. 2 To detect both incoming # + and outgoing positrons plastic scintillators connected via light pipes to photomultipliers are commonly used.
MUON SPIN ROTATION SPECTROSCOPY
~÷
65
e÷
defector
® B
detector ,
)j*
,
,
~ 0,1~
PU
be'am-
= ~J*Larmorfrequency
i
,
i
,
"
,
,
,
,
,
,
POLARIZATION
~0.0
.
".'"
~'.=
01
target
asymmetric decay e+ distribut.
0 12,/3
/,
S
6
TIME[psec]
lysis Sfarf _I
Clock
I Hisfogramming memory
3
]_Stop
/
'1 ' ' ~' ' ' ' ~ / i , i J
IDispta y 0
~
0 1 2 3 4
S 6 7 TIHE[ysec]
Fig. 2.1. Schematic illustration of the/~SR-method pertaining to the transverse field technique, i.e. the initial /z+-polarization /3(0) is perpendicular to the applied field and the /z+ will perform a Larmor precession.
degraded by a suitable moderator (the stopping range at 50 MeV is about 15 g cm -2) before they are brought to rest in the sample of interest, which usually has a mass per unit area (facing the beam) smaller than the stopping range. The sample has to have a certain minimum thickness if all #+ are to be stopped. This minimum is related to the momentum resolution of the #+ beam and to range straggling effects and amounts to typically several g/cm 2, which prevents the use of thin samples. The advantage of this type of beam is that/z + will stop rather homogeneously throughout the sample and that one can be sure, therefore, to really probe bulk properties. The other type of beam is called a surface beam and originates from pions decaying at rest close to the surface of the primary pion production target 3. Those #+ have an energy of < 4.1 MeV, almost 100% spin polarization and a range in matter of 170 mg/cm 2. The main advantage of this type of beam is the possibility to use rather thin samples (some fraction of a mm), while required lateral dimensions are similar to those in a decay beam (,-~ (0.5-4) cm2). Occasionally it is observed that the top layer in which the 4.1 MeV #+ are stopped is different from the bulk so that rather misleading results are obtained. P(t) can be monitored under three different conditions: (i) no external field is present, P(t) evolves solely by the interaction of the #+-spin with internal fields. This is referred to as zero field (ZF)-#SR; (ii) an external field ~r is present perpendicular to /3(0). This is referred to as transverse field (TF)-#SR; (iii) an external field is present parallel to/3(0). This is referred to as longitudinal field (LF)-#SR. Accessible parameters are discussed below. 3 Pions are produced by high energy (> 180 MeV) protons impinging on a suitable target, e.g., graphite.
66
A. SCHENCK and EN. GYGAX
2.1.2. Larmor or precession frequency: wu The Larmor frequency or the splitting frequency of the #+ (ra = +l/2)-Zeeman states is usually measured by~ arranging a magnetic f i e l d / t to be perpendicular to the initial spin polarization P(0) of the implanted #+ (transverse field (TF)-pSR). The signal then observed is equivalent to the free induction decay signal in NMR. Alternatively the splitting can be measured by magnetic resonance techniques in which case /4 is directed parallel to /5(0). wu and H are related to each other through the gyromagnetic ratio %, i.e.
wu=%H.
(2.5)
wu is independent of the relative directions o f / ~ and/5(0). For arbitrary angles 0 between/~ and fi(0) the evolution of the #+ polarization component along/5(0) is given by (precession on the surface of a cone with aperture 0)
P(t)/IP(0)l
= cos 2 0 q- sin 2 0 cos wut.
(2.6)
The field H may be extemally applied or may be intrinsically present at the #+stopping site. Of course there could be different fields at different sites in which case several differently precessing components may be observed, i.e.
P(t)/IP(O)I = ~ Ai (cos 20i + sin 2 0i cos wit)
(2.7)
i
with
Ai = ~ Pi(O)/P(O) = 1. i
(2.8)
i
To make the splitting readily visible P(t) is often subjected to a Fourier analysis (Brewer 1982). The measurement of wi determines the local fields Hi.
2.1.3. Signal amplitudes: Ai Ai determines 4 the fraction of #+ or, since the #+ are implanted more or less homogeneously across the sample volume, the fraction of sites or of the sample volume which is associated with a particular Hi. Because the initial /5(0) is usually well known and because of the normalization condition, eq. (2.8), the Ai can be absolutely determined, including the identification of a so called missing fraction which may arise from extremely quickly depolarizing or from extremely rapidly precessing #+, introducing a time dependence too fast to be resolved by the spectrometer. The cos 2 0 term(s) in eqs (2.6) and (2.7) may also be invisible due to their time independence. The amplitude of the time dependent term, Ai sin 2 0i, allows to determine Oi and therefore the direction of Hi with respect to the initial polarization/~(0). This is, 4 The Ai may also be called (partial) asymmetries as follows from eqs (2.7) and (2.8) and the fact that P(t) determines the effective decay asymmetry.
MUON SPIN ROTATION SPECTROSCOPY
67
of course, restricted to one domain monocrystalline samples. In polycrystalline or monocrystalline samples with randomly oriented domain magnetizations all possible directions of Hi with respect to /5(0) may occur and one has to integrate over all possible directions in which case X
2
P(t)/lfi(O)l=~)--~A~ ~1 + -c ocos it3
1
/) = 3 +
2
~
Ai cos
wit.
(2.9)
The amplitude of the precessing component is reduced to 2/3. The l/3-term just reflects the fact that for a completely random orientation of/~i on the average 1/3 of all #+ will experience a n / t i parallel to their spin and hence will not precess. More complicated situations may be visualized in systems with complex or incommensurate magnetic structures. In any case a careful study of signal amplitudes as a function of sample orientation could be of great help in unravelling the structure of internal fields.
2.1.4. Knight shifl: Ku The Knight shift is defined as usual:
Hint-Next K• --
(47r - N ) X ,
(2.10)
Hext
where the second term corrects for the demagnetization and Lorentz field. N is the demagnetization factor of the sample and X the bulk magnetic susceptibility (in emu/cm3). For more details see section 2.2.
2.1.5. Spin lattice relaxation rate:
/~i =
1/T1
It describes the rate of repopulation between the #+-Zeeman states (m = ±1/2), if there is a deviation from thermal equilibrium, and involves spin flip transitions. The spin flip transitions are induced by fluctuating magnetic fields with components perpendicular to /5(0). Each spin flip transition requires an energy transfer of wh from or to the lattice heat reservoir. The initially polarized/z + (being in one of the two Zeeman states) will become depolarized according to
P(t) =
I~(O)l exp(-Alt).
(2.11)
In #SR, P(t) is measured either in zero external field (ZF-#SR): PZF(t) or in an external field (defining the z-axis) parallel to P(0) (longitudinal field (LF)-#SR): PLF(t). In ZF-field PzF(t) may be also affected by static field distributions (see below) and it may not be possible to distinguish dynamic and static features. In longitudinal fields one can decouple the #+ spin from static fields (see below) and PLF(t) will only reflect spin lattice relaxation. However spin lattice relaxation may be affected by the applied field (see, e.g., Abragam 1970, Slichter 1978). For more details on spin-lattice relaxation mechanisms see section 2.3.
68
A. SCHENCK and EN. GYGAX
2.1.6. Spin-spin or transverse relaxation rate: /~2 = ] / 7 2 (homogeneous line broadening) It describes the loss of polarization of the ~recessing spins, usually observed by applying a magnetic field perpendicularly to P(0) (cos 0 = 0): PTF(t). Equation (2.6) has then to be modified to PTF(t) = I/:3(0)le -'k2t COS totzt.
(2.12)
Relaxation is a result of dephasing of the precessing #+. It does not involve any energy transfer between the #+-spin system and the lattice. For very fast dynamics T2 -~ Ta (see, e.g., Slichter 1978). For arbitrary direction of H with respect to/5(0) eq. (2.6) can be written as
P(t)//5(9)1
= c°s2 0
e -*IT' + sin 20 e -t/T2 cos tout.
(2.13)
2.1.7. Inhomogeneous line broadening, Gaussian relaxation rate Inhomogeneous line broadening is a result of an inhomogeneous field distribution. #+ at different sites will feel more or less different fields. Such an inhomogeneity can be caused by nuclear or electronic dipole fields, which are static on the scale of the #+ life time. Inhomogeneous line broadening can be observed in a TF-#SR experiment. Choosing the applied field Hext to be much stronger than any fields arising from internal sources only the distribution of the internal field components H int along/~ext are of concern. If the spectral distribution of H int is given by F ( H int) with f + ~ --zHintb-'(/-/int'~dH' ; -i-nt--,--z - z = 0, eq. (2.6) (cos 0 = 0) can be written as
1F
PTF(t)/Ifi(O) I = ~
dto~ F(toz) cos (too + to~)t 0(3
=
= G ~ ( t ) cos coot,
too = %Hext.
(2.14)
The precessing spins suffer a loss of polarization (again by dephasing) which is described by the relaxation function GTF(t). The latter is given by the Fourier transform of the spectral distribution /;'(Hint). In favorable cases F ( H int) may be made visible directly by Fourier transforming the measured PTF(t). If F ( H int) is given by a Gaussian distribution: ( 1 / ~ ) e x p ( - H e z / 2 M 2 ) , GTF(t) will be given by a Gaussian as well GTF(T) = exp
( 1 2 2 ) -- -~ 7~Met
= exp
(
1 ) - - a2t2 2
(2.15)
where M2 is the second moment of the field distribution and ~r in this case is usually referred to as the relaxation rate. If F(H~) is given by a Lorentzian distribution GTF(t) assumes a simple exponential behaviour as in the case of homogenous line broadening.
MUON SPIN ROTATION SPECTROSCOPY
69
2.1.8. Inhomogeneous line broadening, zero field (ZF) case First realized with #+ and so far also restricted to #SR-applications this is a very powerful speciality in #SR-spectroscopy. No external field is applied but the implanted #+ are exposed to randomly oriented internal fields which are also statistically distributed in absolute values. If each cartesian component of the internal fields is Gaussian distributed with identical second moment A 2, P(t) (measured along/5(0)) assumes the form
P(t)/I/5(O) I --
1
2 (1 - ' y u2A 2t 2) exp ( - 1 2A2.2"~ ~ ")'/zZ3 t ) .
GGKT(t)=- ~ q- ~
(2.16)
This is the famous Kubo-Toyabe function first derived by Kubo and Toyabe (1967) and later redetected for #SR by Yamazaki (1979) and first observed by Hayano et al. (1979). If the components are Lorentzian distributed one derives instead 1 2 GLT(t) = ~ 3 + ~ (1 - %at) exp(-%at),
(2.17)
where a is the half width at half maximum of the Lorentzian distributions.
2.1.9. Decoupling from static internal fields in longitudinally applied fields (LF) The Kubo-Toyabe expressions can be generalized to include a longitudinally (i.e. parallel to fi(0)) applied field H. For Gaussian distributions Hayano et al. (1979) derive
G~w(t, H) = 1 - 2 H--~
H03 ao
1 - exp
i1
)
)
- ~ "/2AZt2 cos(%Ht) +
exp(-y2/2) sin(Hy/A)dy.
(2.18)
Figure 2.2 displays G~KT(t,H) for various H including the zero field Kubo-Toyabe function. The effect of H is to remove the time dependence and eventually for very large H (i.e. Hext/A >> 1) to restore P(t) to the initial IP(0) I even at long times, reflecting the decoupling of the #+ spin from the internal fields (the cone on which a #+-spin precesses shrinks to zero aperture). In case of very large A the rapid initial decay of GKT(t) may occur within the dead time of the spectrometer and only the asymptotic GKT(Oe) may be observed. Even in this case A can be determined by measuring the field dependence of GKT(ee, H).
2. i. i0. The effect of slow fluctuations (motional averaging) on the Kubo-Toyabe signal In the two previous sections static inhomogeneous field distributions were assumed from the outset. If there is also some time dependence involved, i.e. the internal fields
70
A. SCHENCK and EN. GYGAX 1.0
_5
0.8 0.6
L~
0.4
0.2
0.0 0.0
0.4
0.8
1.2
1.6
2.0
2.4
2.8
3.2
3.6
4.0
Time ((},uA) "1 )
Fig. 2.2. Display of the LF and ZF Gaussian Kubo-Toyabe function GGKT(t,H). The time is measured in units of (%,A) -1 and the applied field H in units of zl. For H/A >> 1 G~T stays close to 1 reflecting the decoupling from the internal fields.
become stochastic functions of time, the ZF Kubo-Toyabe function modifies to what is called a dynamic Kubo-Toyabe function. In general this function cannot be written in analytical form. Assuming a Gaussian-Markovian process Kubo and Toyabe in their seminal 1967 paper were the first to include also stochastic fluctuations. In #SR the dynamic Kubo-Toyabe function is usually calculated on the basis of a strong collision model, which implies a pure Markovian process (Hayano et al. 1979). The parameter introduced in the latter treatment is a fluctuation rate u of the local fields, whereby each fluctuation event destroys the correlation between the internal field distributions before and after the event completely. In order to produce an effect the spectral distribution in the static limit has to be Gaussian or such that it has a finite second moment. This excludes a Lorentzian distribution from the present considerations. Figure 2.3 displays the effect of u on a Gaussian Kubo-Toyabe signal. For very small u (i.e. u/TA << 1) only the 1/3-term is affected and decays like GzF(t) =
G~T(t, u)lt>3/za =
1 ( 2 )ut
~ exp
reflecting directly the fluctuations rate u. For very fast fluctuations (i.e. one gets
GzF(t) =
GP~T(t,u) =
(2.19)
-- ~
( 22)
u/%A
>> 1)
27u A
exp
--
/J
t
(2.20)
which is of the form of eq. (2.11) and we are back in the spin lattice relaxation regime.
MUON SPIN ROTATION SPECTROSCOPY
71
1.0 0.8
0.6
0
0.4
~\\ \
\
_
~
v/A = 0
0.2
0.0
0
2
4
6
8
10
Time ((~t/~) -1 )
Fig. 2.3. Display of the ZF dynamic Kubo-Toyabe function OGT(t, u), where u is the fluctuation rate of the local fields, u is expressed in units of 7 u A and the time in units of (%~A)-I.
Similarly the longitudinal field Kubo-Toyabe signal can be calculated. For very rapid fluctuations eq. (2.11) is again recovered. For extremely rapid fluctuations we enter again the spin lattice relaxation regime where depolarization in a longitudinal field is only arising from spin flip transitions. See also section 2.3.
2.1.1 I. Special features in dilute magnetic systems By dilute systems we mean on the one hand spin glasses, where the magnetic ions are indeed only present in small concentrations but on the other hand also perfectly ordered magnetic systems which contain a small number of randomly missing moments (magnetic holes) or which contain a few lattice defects or impurity atoms, perturbing the magnetic structure only slightly. Implanted/z + in such systems possess a wide distribution of distances to the magnetic ions or the defect centers and hence also a wide distribution of magnetic coupling strength with these centers. As is well known the spectral distribution of fields probed by the #+ (or any other hyperfine probe) assumes under such circumstances a Lorentzian distribution (Walstedt and Walker 1974) and the W-evolution of the #+ polarization follows eq. (2.12) or in ZF eq. (2.17), respectively. (For refined expressions in the case of real spin glasses see Uemura et al. 1985) If the internal fields are allowed to fluctuate in time with a unique rate u eq. (2.11) changes to PLF(t) = I/3(0)1 exp ( - x/~¢)
(2.21)
(McHenry et al. 1972). For very fast fluctuations GTF(t) and GGT(t) assume likewise this square root stretched exponential form. Note that for an ideal Lorentzian distribution the fluctuations should have no effect on the time evolutions of the #+ polarization. However, in reality even for very dilute magnetic systems the spectral
72
A. SCHENCK and EN. GYGAX
distributions always possess a finite second moment, facilitating motional averaging effects (see, e.g., Uemura et al. 1980). An obvious generalization of eq. (2.21) is the stretched exponential expression
IF(o)l exp ( - ( A l t ) ~)
PLF(t) =
(2.22)
which sometimes describes #SR-data quite well. Its implication may not always be clear. One cause could be a distribution of fluctuation rates u rather than an unique u. 2.2. Muon site and local fields Like any other hyperfine field probe the #+ interacts with magnetic atoms through the dipole-dipole interaction and more indirectly in metals through the RKKY mechanism by means of which a non zero spin density is induced at the #+ site leading to a contact hyperfine interaction. In insulators a non-zero spin density at the #+ may be caused by transferred hyperfine fields involving covalency effects. In general the effective magnetic field at the #+-site in the absence of an external field is given by /31oc =/3¢ + B~ip,
(2.23)
where/3c is the contact hyperfine field and Bdip the net dipolar field. /~dip can be expressed as
.
(ff(ei) = ~
3(ei
-
~'.)(/7(,~i)
• (,~i -
e.)) "~
)
~dip (~/z -- ~ ) ' ~(ri),
(2.24)
(2.25)
i
where the sum runs over all magnetic atom positions ~ (lattice sum) and fi(~) is understood to be the static component (thermal average) of the total moment at a given site. The #+-position ~'u and the atomic sites are measured from some convenient origin. It is clear that Bdip depends crucially on the assumed #+-position +-~
and on the assumed orientations of the fi(Y0- The symbol Adip denotes the dipolar tensor with tr(Adip) = 0. In the ferromagnetic case all fi(~) will point in the same direction and are usually of the same magnitude. The evaluation of the lattice sum is split into two parts by separating the volume of the sample into a sphere around the ~+ (the Lorentz sphere) and the rest. Summing over the rest yields the Lorentz field BL = (47r/3))~rs and the +-+
demagnetization
field
/~dem
=
-- N
-
J~b, where -Ms is the magnetization of a single ++
domain (containing the #+) and .~rb is bulk magnetization of the whole sample. N is the demagnetization tensor. It is hereby assumed that the Lorentz sphere is smaller than a typical domain size. In non-magnetized ferromagnetic samples (all domain
MUON SPIN ROTATIONSPECTROSCOPY
73
magnetizations will add up to a zero total magnetization) Bde m = 0. Evaluation of the lattice sum inside the Lorentz sphere can be done by using the Ewald method (Meier et al. 1987) which assures a rapid convergence of the lattice sum. From symmetry considerations it will become immediately evident that in cubic systems with the #+ at a site of cubic point symmetry (e.g., tetrahedral and octahedral interstices in an fcc-crystal) the net dipolar field from the sources inside the Lorentz sphere will be zero. The tetrahedral and octahedral interstices in a bcc-crystal, on the other hand, which possess no cubic point symmetry, are associated with a non-zero net dipolar field. In this case the two types of sites each split into up to three magnetically inequivalent sub-sites with populations depending on the direction of the ordered moments (or the domain magnetization). The overall cubic symmetry then requires that the sum of net dipolar fields, weighted by the relative population of the sub-sites, yields zero again. Hence, if the #+ should happen to be implanted at tetrahedral sites in a ferromagnetic bcc lattice one may expect to find up to three different precession frequencies, the sum of which weighted by the signal amplitudes yielding indeed zero (see, e.g., the #SR-results on ferromagnetic iron, section 3.1). In antiferromagnetically ordered systems J~dem a n d /3L are necessarily zero. For simple antiferromagnets the lattice sum may be split into sums over ferromagnetic sublattices. Again symmetry considerations can help to identify those interstices at which the dipolar fields will cancel. Powerful programs have been developed which allow to calculate the net dipolar fields or the lattice sums for any kind of antiferromagnetic structure, whether single ~ or multiple q*, helical or with modulated moments. Commensurate structures will always lead to distinct net dipolar fields at a given type of site, but there may be many magnetically inequivalent sub-sites leading to a corresponding number of distinct precession frequencies. Incommensurate structures are more difficult to handle and usually are approximated by invoking very large magnetic unit cells. In any case implanting #+ in such systems a more complicated extended frequency spectrum can be expected, reflecting a more or less inhomogeneous field distribution over the #+-sites, which will lead to relaxation by dephasing (see section 2.1). If the local fields over the #+ sites vary sinusoidally in one dimension P(t) will be given by the Bessel function Jo(t). In metals the contact hyperfine field, or local spin density, respectively is induced by the magnetic moments via the RKKY mechanism which is linear in the moments. In ferromagnetic metals Bc is therefore proportional to the domain magnetization, i.e. /~c = Ac_~r~,
(2.26)
where Ac is a contact hyperfine coupling constant. Although Bdip may be zero at certain sites Bc will in general be different from zero. On the basis of the RKKY mechanism Ac may be expressed as (Kittel 1966, Schenck 1993) Ac -
87r g] - 1 __ Jsf(~,)r/(,Ftz), 3 gj
(2.27)
74
A. SCHENCKand EN. GYGAX
where gj is the Land6 factor of the electronic moment, Jsf(ft,) is an effective exchange coupling constant which depends on the #+ site via the distance to the neighboring electronic moments, and r/(Yu) is the so called spin density enhancement factor which incorporates changes in the local electronic density distribution due to the presence of the #+. r/(~'u) may be determined from Knight shift measurements in the paramagnetic state at high temperature (only the Pauli spin paramagnetism is left). In an antiferromagnetic structure Be may be written as ..,
Be(r,,)
8~
gj
: T rl(%) ~
-- 1
~
Jsf ([g~, - ~l)fi(~),
(2.28)
i
where we assumed that the spin density induced at the #+ by each electron moment fii at position ~ can be simply superimposed. 0Vsf(l~'u- ~l) is an effective exchange coupling constant for each moment fi(r~). This expression shows that in an antiferromagnetic structure Be can become zero at certain sites of high symmetry with r_eespect to the magnetic structure. From symmetry considerations follows that also Bdip will vanish at such sites quite in contrast to the ferromagnetic case. So far we assumed the #+ to be fixed at the geometrical center of an interstitial site. In reality the #+ performs zero point vibrations around this position. As Meier (1980) has shown this has no effect on Bdip as long as the #+-wave function is well confined to the interstitial site volume and does not overlap with the neighboring host magnetic moments. In contrast the contact hyperfine field/3c may be modified considerably by both the >+ zero point vibration as well as lattice vibrations (Manninen and Nieminen 1981, Estreicher and Meier 1982, 1984). Inclusion of such effects can account for small deviations between the temperature dependence of/3c and _~rs or the sublattice magnetization in antiferromagnetic systems, respectively. In the paramagnetic phase static magnetic moments can be induced by an external field Hext. At each magnetic atom site one has (2.29)
#+ : X++ a t " /~ext, ++
where Xat is an atomic susceptibility tensor. The moment arrangement corresponds to a ferromagnetic order. Bdip (eq. 2.25) can then be rewritten as follows /~dip(~'/~) = ~
~dip,i (7~/~ -- ~i)" ~ a t " / t e x t
(2.30)
i = Adip (r/z) " ++ Xat" /~ext,
(2.31)
..o.
where Adip (UIz) is again a traceless and symmetric tensor which depends on the assumed #+-site in a given crystal structure. Its calculation is straightforward. The total field (neglecting now BL and Bdem) at the #+ is
B. : I( xt + ETdip)l H xt + (&ip. B xt)/H xt + . . . .
(2.32) (2.33)
MUON SPIN ROTATIONSPECTROSCOPY
75
from which follows the dipolar Knight shift constant +4
+at
Kdip= (JtIext • Adip (r/z)' Xat" [text)/H2xt • Similarly the contact hyperfine field is given by
(2.34)
/3c(r~) = Ac Xat" /r~ext,
(2.35)
from which we obtain the contact hyperfine Knight shift constant 2 Hext)/Hext"
Kc = Ac (I-Iext ' ++ Xat" "
(2.36)
+-1.
This constant is isotropic as long as Xat is isotropic. Often one has to deal with axially symmetric systems in which case the total Knight shift is given by 1
/
\
K = ~ Ac ~(XII + 2X±) + 2(Xll - x±)Pz(cos 0))
+51 Adip ((Xll -- X±) + (X± + 2XII)P2(cos O)),
(2.37)
where 11, _1_refer to directions of/text parallel or perpendicular to the axis of axial symmetry. Specifically one finds Kit = (Ac + Adip)X[],
K± = (Ac- ~1 Adip)X±.
(2.38)
If X is taken to be the molar susceptibility in emu, Ac and Adip will be given in units of (mol/emu). If X is understood to be the atomic susceptibility measured in units of (#B/emu) Ac and Adip will be given in units of (emu/# B) per atom. Very often Ac and Adip are quoted in these latter units. Ac contains quite important information in that it depends on the exchange interaction between the conduction electrons and a local magnetic moment. The same exchange Hamiltonian is also responsible for the Kondo mechanism. However Ac depends also on the electronic structure established at and around the implanted #+. This feature has so far prevented, with some rare exceptions, a detailed analysis of measured' Ac-values. Kdip (or /~dip in the ordered state) is less affected by the presence of the #+ and reflects more directly intrinsic properties. Some lattice relaxation around the/z + will lead usually to a small reduction of Adip. Basically Adip is proportional to the atomic susceptibility (or the local moment) of just the nearest neighbours which are placed far enough away from the #+ to remain usually unaffected by its presence. Recently, however, some evidence has been obtained that the #+ could cause a change in the crystalline electric field splitting of rare earth atoms thereby changing their magnetic response (see section 4.24, Feyerherm et al. 1994b). Whether this could also have an effect on the size and orientation of ordered moments next to the #+ is not known. In any case one has never found any indications that the phase transition temperature measured locally by #SR is any different from its bulk value.
76
A. S C H E N C K a n d E N .
GYGAX
2.3. More on spin-lattice relaxation in the paramagnetic and ordered state #+ spin lattice relaxation or spin flip transitions are induced by fluctuations of the local field components perpendicular to the initial spin polarization. As in the static case the local fields may be of dipolar origin or of the contact hyperfine field typg. The fluctuations reflect the dynamics of the electronic moments or spins at the magnetic atom positions. Among other hyperfine probes #SR is special in that dipolar fields can be as strong as the contact hyperfine fields and contribute strongly to the #+ spin lattice relaxation rate. In contrast, in NMR and M6ssbauer spectroscopy dipolar field induced relaxation is usually negligible and not taken into account (see, e.g., Hohenemser et al. 1989)• Quasi-elastic neutron scattering is another method to investigate the spin dynamics. The differential cross section dcr2/dOd03 for magnetic scattering is proportional to the frequency and wave vector (momentum transfer) dependent Van Hove response function S(q, co) (Lovesey 1987), which can be approximated by
v(¢)
s(¢, w)= _1kBTx(0") 71"
(2.39) 032 q - / ' ( 0 " ) 2
X(0~) is the wave vector dependent susceptibility a n d / ' ( ( ) is inversely proportional to the lifetime of excitations with wave vector ¢. The #+ spin lattice relaxation on the other hand, can be expressed in the simplest case as A1 --- A 2 7r ~ ,S'(~, co), N ¢
(2.40)
which in zero field or for co/l'(() << 1 is simply
kBTA 2 -
x(q) q
(2.41)
r(¢)
A is proportional to the magnetic coupling strength. More complete expressions can be found in Yushankhai (1989), Lovesey et al. (1992a, b), Yaouanc et al. (1993a) and Keren et al. (1994b). Three important temperature regions have to be distinguished: (i) ordered regime (ii) critical regime just above the ordering temperature and (iii) high temperature paramagnetic regime• (i) In the ordered regime the dynamics arises mainly from spin wave excitations• However, since magnon energies are usually much larger than the #+ Zeeman splitting energy, conservation of energy forbids a direct (single step) process in which a single magnon is created or absorbed by a muon spin flip. Relaxation can only be affected in lowest order by a two step or Raman process. On this basis and describing the interactions of the host magnetic moments by a Heisenberg Hamiltonian and including a magnetic anisotropy term Yaouanc et al. (1991) have calculated in an
MUON SPIN ROTATIONSPECTROSCOPY
77
approximate way the #+-spin lattice relaxation rate in a ferromagnetic system. In the limit of Ean (= anisotropy energy) << k B T they arrive at
9 (.y,g,,B)2a k T2 In (k,r)
-
167r3
h:D 3
(2.42)
\ ~an ]"
G is a factor which depends on the #+ site and the lattice geometry (it may be zero) and D is the spin wave stiffness constant. Note that only the dipolar coupling of the #+ to the electronic moments leads to eq. (2.38) while the isotropic contact hyperfine interaction does not contribute. It is also found that )~1 is dominated by contributions from near the center of the Brillouin zone, i.e. by long wave length magnon excitations. Another remarkable feature is the fact that only longitudinal spin fluctuations (i.e. parallel to the easy axis) are effective in inducing/,+-relaxation also in zero external field - and can thus be studied by #SR under zero field conditions while polarized neutron scattering requires a non zero applied field. Two magnon induced relaxation in a ferromagnetic has also been considered by Lovesey et al. (1992a) with special reference to #+ stopped in EuO. Keren(1994) has considered a different, possibly quite efficient depolarization mechanism for the #+ with special reference to antiferromagnetic MnFe2 by noting that typical magnon energies could match well with the splitting of vibrational states of the #+. In this case absorption of a single magnon could promote the #+ to an excited vibrational level accompanied by a spin flip conserving both energy and the total angular momentum. It is expected that the temperature dependence of the thus induced relaxation rate will follow an Arrhenius law. (ii) In the critical regime just above Tc the spin dynamics is crucially affected by also the dipole-dipole interaction between the magnetic ions (Frey and Schwabl 1988, 1989b). This gives rise to the appearance of two separate terms which describe the spin dynamics along q (longitudinal mode, L) and perpendicular to ( (transverse mode, T). The two modes are differently effective in inducing #+ spin relaxation depending on the relative strength of the contact hyperfine and the dipolar coupling of the /~+ to the magnetic ions with angular momentum J and Land6 factor 9L. For an isotropic dipolar cubic (fcc) ferromagnet Yaouanc et al. (1993a, b) derive the following expression for zero applied field in the small q" limit (appropriate for temperatures close to Tc) =
-
v ao
dqq 2
2p 2 - + (1 _p)2 Ur(g) ~
'
(2.43)
where the weight factor p is given by
1 P=3+
n.H - -
47r
(2.44)
H is the contact hyperfine coupling constant (in units of 9 L # B / V where v is the volume of the primitive cell of the Bravais lattice) between the #+ and one of
78
A. SCHENCK and EN. GYGAX
the nu nearest neighbour magnetic ions and 1/3 arises from the dipolar coupling. If nuH/47r >> 1 (dominating contact hyperfine interaction) the transverse mode is dominantly contributing while in the other extreme of dominant dipolar interaction the longitudinal mode is most effective. xL'T(() and/~L,T(q) obey scaling laws in the critical temperature regime (dynamic scaling theory, renormalization-group calculations). Actual expressions may be obtained from the mode-coupling theory (Frey et al. 1988, 1989a, b). The susceptibility can be written in the Ornstein-Zernike form like xT(q ) _
T
q2 + ~-2
(2.45)
r q2 + q~ + ~ - 2 '
(2.46)
and xL(q ) =
where £ is the correlation length and qD is a dipolar wave vector (Yaouanc et al. 1993a). The correlation length has a power law temperature dependence T-Tc) =
~o
gc
-~ '
(2.47)
where u = 0.705 for a three dimensional Heisenberg magnet. I'L'T(() is more difficult to evaluate and the reader is referred to Yaouanc et al. (1993a) and Lovesey et al. (1992b). Using the scaling relation
F(¢) c
(2.48)
with 1
x = --
~q
(2.49)
(z is a critical exponent) and neglecting the dipolar interaction between the ionic moments (spin conserving dynamics, z = 5/2) and between the #+ and the ionic moments one finds (for z > 0) ~1 (3( ~3/2 --~ ¢ 2 + z - d - r t ,
(2.50)
where d = 3 is the dimensionality, r/~_ 0.03 for a 3D-Heisenberg system. Admitting now also non spin-conserving dipole-dipole interactions between the ionic moments one finds that z = 2 for the transverse mode and z = 0 for the longitudinal mode if the dipolar interaction is dominating over the Heisenberg exchange (i.e. q << qo)Consequently AT o( ~
(2.51)
MUON SPIN ROTATION SPECTROSCOPY
79
and k } is temperature independent. In the general case AI,ZF may be written as /kl,ZF = W [2p2/T(qo) + (1 - p)2IL(T)],
(2.52)
where ~ = arctan (qD~) and the functions IT'L(~o) are universal functions which have been evaluated by Frey and Schwabl (1988). A similar expression can be derived for a body centered cubic (bcc) lattice (Yaouanc et al. 1993a). Critical behaviour in an antiferromagnet has been considered by Lovesey (1992) (see also Keren et al. 1993), in the latter paper a comparison between #SR and neutron data has been worked out). For an isotropic antiferromagnet the #+ spin lattice relaxation rate diverges on approaching TN like (2.53)
)~1 (X {1/2
for both contact hyperfine and dipolar coupling. In an uniaxial antiferromagnet critical fluctuations are ineffective in inducing #+ relaxation if the coupling to the ionic moments is mediated by the contact mechanism. On the other hand, if the coupling is of dipolar origin one finds
(T-TN ) -~'
(2.54)
where ~z is the correlation length along the anisotropy axis. The temperature dependence in eqs (2.53) and (2.54) are precisely the same predicted for the NMR line width (l/T2). Equation (2.54) has been used to explain #SR results in MnF2 (see chapter 5). (iii) Spin lattice relaxation induced by paramagnetic fluctuations of local moments at high temperatures, i.e. far above any critical regime, have not been treated to any great extent. Assuming that the local moments fluctuate uncorrelated at high temperatures (F(q) = 1"(0) = r c 1, x(O) e< l / T ) one finds ),1 ~x rc,
(2.55)
where rc is a local correlations or relaxation time associated with the ionic moments. Two processes may be responsible: the RKKY interaction and the Korringa mechanism. The former induces a temperature independent, the latter a linear Tdependence of the ionic moment fluctuation rate %-z, i.e. (Hartmann et al. 1986)
7-c =
i ( c'Tc
J / ( J + 1)
+ -£ (IsfN(eF))
,
(2.56)
where e' is a constant, Tc is the ordering temperature (or the paramagnetic CurieWeiss temperature), Isf is the conduction electron - local spin exchange integral and N(eF) the Fermi energy density of states. Tc is proportional to the effective RKKY
80
A. SCHENCKand F.N. GYGAX
exchange coupling constant between a local moment and all other local moments which in turn is proportional to j2f. The RKKY part of eq. (2.52) follows also from a treatment by Lovesey et al. (1992b). Our discussion of the #+ spin lattice relaxation rate has been limited here to local moment magnets, ignoring also possible effects of the crystalline electric field (CEF) splitting of the ground state multiplet in f-electron ions. CEF-effects will be mentioned in some of the sections in chapter 4. Spin lattice relaxation in itinerant magnets is considered in section 4.1.
3. Review of results in elemental metals and alloys Since in general the magnetic properties of elemental metals are very well known, the results of #SR investigations on such systems have served primarily to develop a better understanding of technique and role of the implanted #+ as a magnetic probe. As a consequence the present section is organized somewhat differently than the following sections. While in the latter ones the results are listed compound by compound, in the present section the results on various elemental metals are collected in different paragraphs with respect to particular properties. The most salient features of crystal structures and magnetic properties for the magnetic elemental metals are sketched in table 3.1. Lists of essential data obtained in # + S R experiments, together TABLE 3.1 Schematics of the crystal structures and the magnetic orders for the magnetic 3d-transition metals and the lanthanides. The/z+ site is also indicated; it is in parenthesis if there is only a strong indication for that option. Element or alloy
Crystal structure
Fe Co Ni Cr
bcc hcp fcc fcc bcc
Pd (alloys) Pr Nd Sm Eu Gd Tb
fcc hex hex complex bcc hcp hcp
Dy Ho
orth hcp hcp
Er
hcp
T r a n s i t i o n Magnetic temperature o r d e r -+ 690 K
--+85 K
FM FM FM FM LIAF TIAF CAF AF AF AF AF FM FM AF FM AF FM AF FM AF
Critical /z+ temperature site -+ 1044 K ~ 1398 K --+ 627 K --+ 124 K -+ 312 K varying --+ 27 K -+ 19 K --+ 106 K --+ 89 K -+ 292 K -+ 223 K -+ 229 K -+85K -+ 178 K -+20 K --+ 132 K -+19K -+ 85 K
(O) O (O) (T±)
0 (0)
M U O N SPIN ROTATION SPECTROSCOPY
81
o N
r~
-~
#.
o
o
=o
~oN o
oo
~ ~ o •
o
~ ' ~ =.~
o~
u~ ¢0
O
09
o
odo
o
O9
~+
N
~,.~
V/
F'~NN
[-~
n~
+
O
9 "O
oo
o -I-
+
+
-l-
±
O
O
O
O
o
82
A. SCHENCK and EN. GYGAX
~ N - ~
~
. ~
~oz~z.~=&~ ed
~,~,~
~...~
~
~
~'-"
;~oe~'°
:~z
~.~
~ ~v,,
~<~
u
d
d
+
+
Z
~
~u
++
~mm
MUON SPIN ROTATION SPECTROSCOPY
o
..
o~
r~
o9
+
r~
t'¢3
0
"~
g N
~2
N
o
o
83
84
A. SCHENCKand EN. GYGAX
with the basically used experimental procedures are presented in tables 3.2 (3delements and their alloys) and 3.3 (lanthanides). These two tables are meant to give in the shortest form an overview with reference lists of the experimental #+ studies subject of the present chapter(sections 3.1 to 3.4). In section 3.5 we report briefly the results of investigations with negative muons (#-SR) in Fe and Ni.
3.1. Spontaneous dipole and hyperfine fields This section deals with the results obtained for the 3d-transition metals Fe, Co, Ni, Cr and for the lanthanides in the magnetically ordered states. Ferromagnetic Gd is presented as an introductory example in section 3.1.1. This choice is motivated by the fact that several problems related to the method can be treated in this case and because the #SR method has shown for Gd its best contribution to the understanding of magnetism in elemental metals.
3.1.1. Ferromagnetic Gd: an example The local field at the #+ in ferromagnetic Gd was first measured for two temperatures by Gurevich et al. (1975a), but the influence of the local dipole field was not considered in the interpretation. A thorough study was carried out in polycrystalline Gd by Graf et al. (1977). The results, together with the studies in Co, Dy, Fe and Ni are comprehensively reported in Denison et al. (1979). According to section 2.2 the local field at a #+ in an unmagnetized ferromagnet in zero field is given by /3.(~.) =/3L + B~ip(f.) +/3c(rn).
(3.1)
B~ip(/V~) is the lattice sum inside the Lorentz sphere. Gd has a hcp crystal structure. Between the Curie temperature Tc = 292 K and 230 K the Gd spins are aligned along the c-axis. Below 230 K the easy axis of magnetization deviates from the c-axis. The (non-pSR) literature lists various inconsistent temperature dependences of the angle 0 between magnetization and c-axis. Figure 3.1 shows ]B.[ versus temperature in zero field. Clearly this behaviour is very different from Ms(T), the domain magnetization in Gd. The interpretation (Denison et al. 1979) is summarized in the following points. (i) One starts with 4 7r~rs(T) '
(3.2)
where 2~rs is the domain or saturation magnetization. (ii) #+ sites: The hcp lattice offers tetrahedral (T) and octahedral (O) interstitial sites for the muon. A calculation of the dipole field tensor (assuming an undistorted lattice) indicates that the fields at T sites, O sites as well as at substitutional (S) sites are all parallel - but not parallel to the Gd moments - with of course different magnitudes.
MUON SPIN ROTATION SPECTROSCOPY
85
(iii) The complicated behaviour of B , versus T is essentially due to Bdip, more precisely to the variation of B~ip with 0. This is illustrated considering the behaviour of the field vector 3~, defined as the sum of/3L and/3c, left term of the equation (3.3) It is expected that/3c(T) and hence also J((T) will be approximately proportional to ~rs(T) - note that BL, Bc and )( are all parallel to Ms. The dependence O(T) can now be determined in the following way: For a given #+ stop site one draws a series of X(T) curves with 0 as parameter, using the measured values of B~(T) and the calculated B~ip(0 , r'tz)Such sets of curves are shown in fig. 3.2 a-c for substitutional, tetrahedral and octahedral p,+ sites. Since only the magnitude o f / 3 , ( T ) was determined experimentally, combinations using both B,(T) > 0 and B,(T) < 0 are retained. The boundary condition that X(T) has to follow the 0 = 0 ° curve between 230 K and Tc has to be considered - the points are indicated by solid circles in fig. 3.2 a-c. From the figure it is obvious that only the assumption of the octahedral site with Bu > 0 allows X(T) to be approximately proportional to Ms (monotonous dotted line in fig. 3.2 c). The O(T) dependence is so determined with an accuracy exceeding that of the neutron diffraction data, the resulting temperature dependence and the values obtained by other means are presented in fig. 3.2 d. The hyperfine field Be, obtained from I
I
I
I
I
I
1.5
20
1.0
v
z
g,
v
10
-t m
G_.~a 0.5 5
0
I
0
r 1 O0
tr LL
I
Temperature
I 200
i hl
m =
0
300
(K)
Fig. 3.1. Absolute value of the measured local field B~ vs. temperature in zero external field for polycrystaUine Gd. The right-hand scale corresponds tothe directly measured/zSR frequency. The solid line through the data points is meant to guide the eye (Denison et al. 1979).
86
A. SCHENCK and F.N. GYGAX
1.5 1.0
0 5 l Substitutional Site~
1~
~o.o
~ 0.0
X "0.5
Bl' < 0
-1.5
g . o , 5
-
i
-o.5 .,o..-.,. - 70"
0
-1.5
-2.0 0
-2.0
1O0
200
300
0
90
2.0
(b)
7O
1.0 '90"
60
0.5
50
~v 0.0
40
-1.o
B,, < 0
,"~f
1O0 '
(d)
8O
1.5
X -0.5 .
-I
B,,
20
-1.5
't
'
300 '
'|
1 I
°i#
30
F"
'
200
?""
?.',
r, ' t'ITo
10
-2.0
0
1O0 200 Temperature (K)
30(
0
0
1O0 200 Temperature (K)
300
Fig. 3.2. In a, b and c: field 2 =/3~, - / ~ d i p = /~c + BL plotted as function of temperature for three possible/~+ residence sites and for Bu > 0 and B~, < 0. The solid lines correspond to the indicated fixed values of the angle 0. For T > 230 K it is known that 0 = 0, the values of X deduced from the IB~,I measurements are displayed as solid circles for that temperature domain. Only the assumption of the octahedral/~+ site with B~, > 0 allows X(T) to be smooth and monotonous (dotted line in (c)) over the full temperature range. From that curve the function O(T)is determined and displayed in (d) as a solid line; in (d) the 0 values from neutron diffraction (full circles) and torque (full triangles) measurements are also indicated (from Denison et al. 1979). Be = X - B L (BL = (47r/3)Ms), is finally s h o w n in fig. 3.3. Bc is o p p o s i t e ( n e g a t i v e ) to Ms. T h e i n t e r p r e t a t i o n o f B c ( T ) for G d will b e briefly d i s c u s s e d t o g e t h e r with that for the o t h e r f e r r o m a g n e t i c e l e m e n t s i n section 3.1.3. N e w d a t a o b t a i n e d in a s i n g l e crystal G d s a m p l e b y H a r t m a n n et al. ( 1 9 9 4 ) call for slight a d j u s t m e n t s in the c o n c l u s i o n s w h i c h h a v e j u s t b e e n p r e s e n t e d - see s e c t i o n 3.1.2.
MUON SPIN ROTATION SPECTROSCOPY I
6 ~
,
I
~
i
I
n
°
I
r
m
4 o
I
87 I
)
\',
~
2
0
I
0
I
1oo
I
I
200
I
II
300
Temperature (K)
Fig. 3.3. Extracted hyperfine field Bc plotted as function of temperature. The dashed curve is the magnetization normalized to Bc(T = 0 K); Bc is opposite (negative) to the local magnetization. The particular interpretation of the Bu(T) measurements in Gd illustrates how new information about magnetism can be obtained from #SR. One has to stress, however, that since certain features of the #+ in the sample material are not always perfectly known, great importance has to be attached to the use of adequate assumptions, estimates of the importance of effects escaping control, and particularly to the consistency of the over-all picture obtained after analysis. Let's just mention two type of problems one can encounter in this context: - As far as the dipole field calculation is concerned, it matters of course to know the exact (interstitial) position of the #+. This achieved, the #+ zero-point motion, #+ tunnelling, departure from the ideal site position, e.g., because of bonding (in compound substances) or trapping at impurities may also play a role. Moreover, the muon can deform locally (mainly expand) the lattice possibly modifying the local structure anisotropy. - In case of sufficiently fast #+ motion (i.e. diffusion) a sampling of (magnetically) non-equivalent sites will average the v a l u e s / ~ ( ~ i) corresponding to the different sites i:
B.~eff= ~ a~/~u(~'.i),
(3.4)
i
where a~ stands for the #+ population fraction at site i. So it is possible, as, e.g., in Fe, to encounter an averaging, possibly to zero, of the different dipolar field contributions and thus to observe a single B~ff value instead of the characteristic multiplet corresponding to the number of non-equivalent #+ sites.
88
A. SCHENCKand F.N. GYGAX
3.1.2. Local fields Bu(~'u) and dipole fields in magnetic elemental metals Figure 3.4 a-d shows IBu[ as function of temperature for Fe, Co, Ni and Dy. As in the case of Gd (fig. 3.1), the complexity of these dependences is essentially due to Blip(T ). Where the dipole fields/3~i p vanish, in Ni because of its fcc structure, or in bcc Fe because of rapid #+ diffusion among interstitial sites (see section 2.1), Bu(T) (= BL + Be) is smooth and monotonous, whereas, e.g., in Co the drastic effect of B~ip is obvious (Graf et al. 1976b). In hcp Co (as in hcp Gd), the ordered magnetic moments produce a unique dipole field at each type of interstitial site. This is, therefore, not modified by diffusion, provided that diffusion takes place only among interstitial sites of the same type. Thus =
-
&
-
(3.5)
B~ip(~/~) can be calculated, e.g., as described by Denison et al. (1979). From the same ref. one see that/3 lip(T) deviates markedly from ~rs(T) if the direction of the axis of easy magnetization varies with respect to the crystal structure as a function of T. As for Gd, this is the case for Co, where in addition a modification from a hcp to a fcc structure at 690 K changes the picture even more. B~ip vanishes for the fcc structure. Measurements on Gd single crystal samples (Hartmann et al. 1990b and 1994, Kratzer et al. 1994a) confirm in essence the analysis presented in section 3.1.3 but show that the spin re-orientation between 245 and 220 K is steeper than anticipated and accompanied by a peak in the #+ depolarization rate. At a closer look a complex precession signal, which can be separated into two frequencies, is detected in this temperature range. Hartmann et al. (1994) conclude that the spin turning does not occur simultaneously in two different domains of the sample. The single crystal data imply that B~ and B~i obtained by Denison et al. (1979) cannot both be strictly correct. Either Bc un~fergoes a change around 230 K which is directly coupled to the spin turning, or the value of the dipolar field used in the earlier evaluation is slightly too low. It is noteworthy that so far all the #SR data obtained from the magnetic elements have been explained using the dipolar field calculation under the assumption of localized dipole moments. The pressure dependence of B , in Gd was measured by Hartmann et al. (1990a). The changes by pressure are much larger than those observed in the 3d-metais Fe, Co and Ni (Lindgren et al. 1987 and Butz et al. 1987). The essential contribution to dB,/dp comes from the turning of the axis of easy magnetization with pressure at low temperature and from the reduction of Tc with pressure at higher temperature. See section 3.1.4 for the effect of pressure on Bc. Dy shows rather interesting magnetic properties - see the schematic arrangement of the Dy spins in fig. 3.4 d. Between TN = 178 K and Tc = 85 K it is a helical antiferromagnet. The spins lie in the basal plane of the hcp lattice, the helix axis is parallel to the c-axis and the helix angle c~ between the ferromagnetically ordered planes is temperature dependent. Below 85 K a discontinuous orthorhombic distortion occurs, with a corresponding phase change to a ferromagnetic state. The spins
MUON SPIN ROTATION SPECTROSCOPY
89
are then along the a-axis. The striking features of the #SR measurements (Denison et al. 1979) are: (i) B u is observed in the two magnetic phases (i.e. the first time for an antiferromagnetic state in a metal), which can only be explained if the #+ is not diffusing through the lattice; (ii) a continuous variation of Bu occurs across the magnetic and structural phase transition. Interestingly the calculations of B~ip(T ) show also a smooth behaviour across the phase change for #+ at the octahedral sites and only a weak discontinuity of about 4% at this transition for #+ at the tetrahedral sites. From the measurements neither the muon site nor the sign of Bu could be determined. See section 3.1.3 and fig. 3.4 h for the deduced Be(T). Several studies were made about the influence of an elastic strain on Bu in Fe (Namkung et al. 1984, Kossler et al. 1985, Herlach et al. 1989, Fritzsche et al. 1990). The conclusion is that the observed effect stems essentially from a change in B~ip, due to a shift in #+ population between magnetic non-equivalent interstitial sites reduced by modified elastic energies. In this context see also the effect of impurity induced strain in section 3.3.1. 3.1.3. Temperature dependence of the hyperfine field For Fe, Co, Ni and Dy the dependence Bc(T) is deduced from B u at the #+, BL and the calculated/3~i p, using eq. (3.5), and is shown in fig. 3.4 e-h (bottom section). The hyperfine fields measured with t~- in Fe and Ni are treated separately in section 3.5. For Fe and Ni no knowledge of the #+ site is required, as discussed previously. For Co the octahedral interstitial site is assumed in order to obtain a smooth variation of Be with temperature (except for the discontinuity at the 690 K structural transition), following approximately the Co magnetization curve Ms(T). In that metal the sign of B~ (with respect to Ms) was determined to be negative for T < 500 K, below the spin reorientation between 500 and 600 K, and positive after completion of the easy axis reorientation for T > 600 K. This was obtained by measuring the precession sense of the muon (via the #SR signal phase information) in presence of an additional external magnetic field. (Another way to obtain the sign of Bu is to follow the measured ]B~[ as function of increasing external field values driving the sample beyond magnetic saturation - see the case of Ni, Denison et al. (1979), illustrated in fig. 3.5.) In a-Fe at low temperature Schimmele et al. (1990 and 1994) have observed an oscillating signal in a longitudinal #SR experiment on a magnetically saturated crystal between 30 mK and 600 mK. In the experiment the high-purity single crystal sphere was magnetically saturated in a (111) direction, say [111]. The dipolar magnetic fields at the interstitial sites of tetragonal symmetry (like O- or T-sites) are perpendicular to [111] (Seeger and Monachesi 1982). The fields at different sites transform into each other through rotations by 120 ° or 240 ° around [111], their /~(111) absolute value is labeled ~dip . The only remaining contributions to the local field are/~ext and/~o, both parallel or antiparallel to [111]. Therefore the local field value is given by Bu =
{ ~,(111)\2] 1/2 (Bext -t- Bc) 2 -~- I/Zldip )
j
(3.6)
90
A. SCHENCK and EN. GYGAX
(a)
(b)
I
I
t
[
I
Fe
~6 %
a
5O
qb
I
I
J
I l
600
800
1000
12
I
I I I I
~2 400
8 6
,¢
~ le"q
200
\
I
0 0
f
==
(e)
O3 2
I
200
~
I
I
I
600 1000 Temperature (K)
Temperature (K)
0 1400
(f) i
i
t
I
1.0
i
0.8
10
i
i
~
i
;
I
:
i
'
i
i
6
5 4
o.o
0.4
8
I
0.2
6
m
4
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_o.o
I
200
I
[
I
400 600 800 Temperature (K)
I
1000
i
2
1
if-i-.i~we~J iI
-0.4
2 0
!
4
10 T~ ! 400
I
Co
600
3o ~ 2o
1
I
10
40
%
OlD 0
i 2oo
J
"I-
~2
o
I
800
Bdip h~p . ~ c ic~ci -
Bc 0.8 ~ 1.0 i 0 200
i
T,
0
tcc
I I
: ',
I I
i
'
I
i I I 600
-3 _, -5 -6 I
r 1000
I 140
Temperature(K)
Fig. 3.4. In (a), (b), (c) and (d): temperature dependence of the measured absolute value of B u for Fe, Co, Ni and Dy respectively, for polycrystalline (o) and single crystal ([3) samples in zero field. The spin structures in the ferro- and helical antiferromagnetic phase of Dy (d) are indicated. In (e), (f), (g) and (h): temperature dependence of the hyperfine field Bc for Fe, Co, Ni and Dy respectively, extracted from the IBul measurements (a~l). For Dy the two possibilities due to the unknown sign of Bu are indicated. For Fe and Ni the magnetization Ms(T) is indicated, whereas for Co the field contributions B~ip and BL as well as the deduced temperature dependence of Bu are displayed, together with a sketch of the spin turning and the structural phase transition (Denison et al. 1979).
MUON SPIN ROTATION SPECTROSCOPY
(c)
(d) 14
I
i
Ni 1.5 mllhl=l~
91
20
"Ib-,,,-
i
1
12
C i
•
I
Dy 150
c
t5! 28
qk
T
~oo
v
ell
u?. ,+ I
0.5
m 4 I I I
0
0
I
I
200
400
tl 600
5
0
2 -Ferromagnelic--b*-Ant=ferromagnetic1 I t I 100 150 5O Temperature (K)
0 0
Temperature (K)
(g) 0.8
5O
orthorhombic
1
0 200
(h) I
I
l
- - T
i
r
24 20
0.6
-Bc = 16
vO.4 Ferromagnelic-
8
0.2
4
I
I
I
200
400
600
Bc=
0 2 0
Temperature (K)
Fig. 3.4. (Continued).
100 150 5O Temperature (K)
200
co
92
A. SCHENCK and EN. GYGAX I
I
I
I
I 3
I 4
N
g= 21
t
I !
0
I 1
0
~s 2 Bext (ka)
Fig. 3.5. Local field [B~I as function of external field Bext for a single crystal Ni sphere. At the saturation field Bs = (4rr/3)Ms the /*SR frequency starts to increase with Bext, indicating that B u is positive, i.e. in the direction of the bulk magnetization (Denison et al. 1979).
95 AT= O T= O T= Jr T =
90 85 N 32 v
>=
80
30mK 70 mK 200 mK 300 mK
z~ rh T
x T = 400 mK O T = 600 mK
m
L~
R.~
75 70
m A
65 60 55
I
0.6
I
I
0.8
I
I
1.0
I
I
1.2
I
I
1.4
I
I
1.6
Bext (T) Fig. 3.6. /zSR frequency observed in longitudinal measurements on c~-Fe as function of the externally applied field at different temperatures - Schimmele et al. (1994).
Figure 3.6 shows the #SR frequency ut, = Bu%/(2rr) (% = gyromagnetic ratio of #+) obtained in the experiment for various values of Bext and temperature. The /zSR signal is moderately relaxed, which indicates that at such low temperatures the #+ hopping rate in Fe is slow compared to the observed #SR frequency, which is about 60 MHz at its minimum. The measurement of uu as function of the applied external magnetic field gives directly the dipolar magnetic field and Be, the latter value amounts to (-1.13 + 0.02) T, in close agreement with the earlier measurements by Denison et al. (1979) - see also table 3.4. For Dy, where, coupled to the structural change at 85 K (from orthorhombic to hcp), the magnetic order also changes (from ferromagnetic to a helical antiferromag-
MUON SPIN ROTATION SPECTROSCOPY
~
93
~o
o~
+.~
I
e~
I
~
~
i
I
I
I
I
H
.~ ~ . ~ ~ = g"Ng
. ~ ,'
o oo
o
o
,-~ o ~
rm
I
~=~ 8
I
-t-
-t-
~
-H
I
94
A. SCHENCK and EN. GYGAX
netic order), Bc can be determined along the same lines as described (Denison et al. 1979), calculating B~i p in the appropriate way for the antiferromagnetic phase, where of course Ms is zero. Over the full temperature range B~ip(T ) does not differ significantly if one assumes T- or O-sites for the #+. The fact that B u is observed in the antiferromagnetic phase of Dy can only be explained if the #+ is not diffusing through the lattice. In the experiment it was not possible to determine the sign of Bu, thus the two possibilities for Bc are indicated in fig. 3.4 h. For the ferromagnetic elements a compilation of Ms, Bj, and Bc is presented in table 3.4 for all data extrapolated to T - 0 K, basically following Denison et al. (1979). In addition the table shows hyperfine fields B ° derived from neutron diffraction results and values B the°r resulting from various theoretical calculations. The fact that Bc is not just caused by the undisturbed interstitial spin density, as measured by neutron scattering, is obvious - except for Ni. One common feature of the Be values is the negative sign, meaning that the magnetic densities at the #+ are opposite to the average magnetic density in the unit cell. This feature is explained by the Daniel-Friedel model (Daniel and Friedel 1963). The temperature dependence of both Bc(~'t,) for Fe, Co, Ni and Dy and the normalized domain magnetization Ms for Fe and Ni are shown in fig. 3.4 e-h and for Gd in fig. 3.3. Be is not strictly proportional to Ms. Nishida et al. (1978) defined the 'deviation' function A(T):
Be(T) Be(0)
Ms(T) -
A(T)
(3.7)
- - ,
Ms(O)
which is shown for Fe, Co and Ni in fig. 3.7. For Fe, Co and Gd Bc is below the normalized Ms for T # 0 K, whereas Bc is above Ms normalized in Ni. Schenck 0.10
I
I
I
Ni 0.05
'7, t-
0.00
-0.05
-0.10 0.00
i 0.25
i 0.50
p 0.75
1.00
T/mc Fig. 3.7. Temperature dependence of the reduced hyperfine field A ( T ) for Fe, Co and Ni: A(T) = {Bc(T)/Bc(O)}/{Ms(T)/Ms(O)} - Nishida et al. (1978).
MUON SPIN ROTATIONSPECTROSCOPY
95
(1985) lists possible reasons for such a behaviour and reviews various theoretical models dealing with that matter. For rare earth elements, Campbell (1984) has pointed to a complication one may encounter in the deduction of Bc from B , measurements. In such samples the electric field gradient (EFG) created by the #+ charge will affect the orientation of the neighboring lanthanide moments and so will lead to altered dipolar fields at the #+ site. Estimates are presented for Tb, Dy, Ho, Er and Tm in the cited paper. For Gd, which has no orbital moment contribution to the total moment, the effect is negligible.
3.1.4. Pressure dependence of the hyperfine field The possibility that the deviation between the temperature dependence of Bc and Ms originates from the different manner in which thermal volume changes affect the two quantities has been studied by measurements of the pressure dependence of Be (Butz et al. 1980, Lindgren et al. 1987, Butz et al. 1987, Hartmann et al. 1990a, and Kratzer et al. 1994a). Figure 3.8 show such measurements in Ni and Fe (Butz et al. 1980). Schenck (1985) discusses some implications. The emerging picture is not clear. Whereas for Ni half of the deviation between the temperature dependence of Be and Ms is explained by the volume change, the effect has the opposite sign for Fe. Other causes must be considered.
1.004
1.002
1.000
0 Ni • Fe
:=L t,n Q. v
0.998
m=
0.996
0.994
0.992
0
1
2
3
4
5
6
7
p (kbar)
Fig. 3.8. Pressure dependence of the local field B~ at 298 K for ferromagnetic Ni and Fe. B~ is normalized to unity at zero pressure (Butz et al. 1980).
96
A. SCHENCK and EN. GYGAX
3.2. Critical phenomena In their pioneering study in Ni and Fe, Foy et al. (1973) noticed that #SR could be used to examine critical behaviour near the magnetic critical temperature. Antiferromagnetic phase transitions were observed by Gurevich et al. (1976) in Dy and Ho and then by the same group (Grebinnik et al. 1979a) for the rest of the magnetic lanthanides. The experimental studies dealing specifically with critical phenomena are listed in tables 3.2 and 3.3 with the indication that the #SR measurements were performed near the critical temperatures Tc or TN or that the essential data (like the #+ depolarization rate, F, the spin fluctuation, SF, the Knight shift, K , , etc.) were obtained also near Tc or TN. The first #SR studies aimed at extracting quantitative information from experiments probing critical phenomena were performed by Barsov et al. (1983 and 1984) around the N6el temperature in Er, and in parallel by Nishiyama et al. (1983 and 1984) around the Curie temperature in Ni. In their study of Fe in the Tc region Herlach et al. (1986) stress some of the difficulties one encounters trying to extract static and dynamical exponents using the various #SR methods. This paper also reports K~(T) and transverse depolarizationrate versus temperature data obtained in FeCo and FeZr alloys. The results permit to follow the critical exponents deduced from the two temperature dependences as function of the increasing concentration of the elements alloyed to Fe.
3.2.1. Critical behaviour of the muon Knight shift In a first approximation we expect the measured muon Knight shift to follow the magnetization (or susceptibility) of a paramagnetic sample. This would give a #SR frequency shift (after correction for demagnetization field and Lorentz field) like ]¢Bext
Av~---(T - Tc) well above Tc, with possible deviation in the critical region. This is effectively so in Ni, where Gygax et al. (1980) have measured Ku over a wide temperature range above Tc. The strong T-dependence follows exactly that of the bulk magnetic susceptibility X, also in the critical regime. Figure 3.9 a shows the low temperature results, from which a critical exponent 3' ,-~ 1.28 is extracted, in good agreement with the value of 3' -- 1.35±0.02 obtained for the susceptibility in the same temperature domain. Figure 3.9 b - a Clogston-Jaccarino plot - shows that the high temperature #+ Knight shift is also strictly proportional to X. Since the temperature dependence of the total susceptibility is associated with the d-electrons' susceptibility term, the slope dK~/dx can be identified with the induced contact hyperfine field at the #+ per unpaired d-electron per atom, Ac,d (from K~,,d = Ac,d • x~t/#B , X~t is the atomic susceptibility). In this instance it is interesting to compare Ac,d with the induced hyperfine field per d-electron per atom in the ferromagnetic state of Ni, which is AcV,d = Bc(f'~,)/Ms (see Schenck 1985). The two values are -1.224(23), resp. -1.14(2) kG/(# B • atom), i.e.
MUON SPIN ROTATION SPECTROSCOPY
97
AT (K) 6 8 101215 2 0 2 5 3 0 4 0 5 0 6 0 80100
II
I II
I I II
/
I II
I I
"N'l•
,AKp (2~ mol = -0.223 AZ ' "emu
-1000
-500
X
X,
y = 1 . 2 8 /
V\ /
-
'\.
Q.
~ = 1.35
2
(fromz)
1 O0
\
-1000
-1500
\ \,
(a) -10 0.5
I 1.0
I 1.5
log (T-Tc)
-2000
I 2
-2500
(b)
\
'~",
I
I
I
40
80
120
I
160 xlO 6
Z (emu/g)
Fig. 3.9. Muon Knight shift for paramagnetic Ni, plotted against log(T -/Pc) in the low temperature region (a), and plotted against the bulk magnetic susceptibility with temperature as implicit parameter in the high temperature region (b). The critical exponent deduced for K u (solid line in a) is compared to the con'esponding value obtained from bulk susceptibility measurements (dashed line in a). The high temperature region extends to 270 K above TC (Gygax et al. 1980).
different by about 8%. A step has also been observed by Nishiyama et al. (1983). No explanation does exist so far - see Schenck (1985). However, the basic equality of the induced hyperfine field in the paramagnetic phase and in the ferromagnetic phase seems to be the rule - see, e.g., for Gd W~ickelg~rd et al. (1986). In this same paper it is further reported that closer to T¢, say in the critical region below 1.05T¢, the muon frequency shift deviates from the simple Curie-Weiss behaviour. Moreover, the frequency deviation observed indicates an exponent below 1.0 for (T - T¢), whereas the susceptibility for polycrystalline Gd has an exponent around 1.24 in the same temperature range. This deviation is however trivial, it is expected from the magnetization curves measured for Gd at the same applied field as in the /ZSR experiment (Karlsson 1990). 3.2.2. Muon-spin relaxation or depolarization rate in 3d-elements For Ni, Nishiyama et al. (1984) observed that above Tc the practically field independent longitudinal/z-spin relaxation rate (A1 = l/T1) measured at low field displayed loss of the critical behaviour when T approaches T¢ (fig. 3.10). It was ascribed to the establishment of short range ordering around the /z+, tending to diminish the dipolar field sum at the/z+ because of the cubic symmetry. The temperature dependences of the #+ depolarization rate (as well as of the muon Knight shift) have been studied in the giant moment alloys PdFe and PdNi,
98
A. SCHENCK and EN. GYGAX Illlll
t
I
I
III1111
,
,
,,,,,,I
I
I
IIIIII
,
,
,,,H,I
I
I
1 IIII
,
,
0.1 :=k
0.01
0.001 ,,,,,,I
0.1
1
,,t,
10
T-TC (K)
Fig. 3.10. Temperaturedependence of the/zSR damping rate for metallic Ni. The points are the data of Nishiyamaet al. 1984. The solid line is the result of the model from Yaouancet al. (1993a), taking the/z + dipolar interaction into account, whereas the dashed line gives the prediction when this latter interaction is neglected. which display ferromagnetic ordering, by Gygax et al. (1981). The measurements were performed in the paramagnetic state for both alloys and also below Tc for Pd0.97Fe0.03. The results are tentatively ascribed to the presence of slowly fluctuating ferromagnetically coupled clusters. One had to wait for Yaouanc et al. (1993a) who established a thorough scheme to compute the paramagnetic critical zero-field muon-spin relaxation rate, at first only for cubic ferromagnets (see section 2.3). This calculation includes the full (long range) dipolar interaction between the muon and the lattice dipole moments in a mode-coupling theory. It appears that the damping rate is determined by the relative weight of the hyperfine interaction and the dipolar interaction between muon moment and the lattice ions magnetic moments. The data from Nishiyama et al. (1983) are well explained by this model (fig. 3.10), as well as the #+-spin relaxation rates measured in paramagnetic Fe by Herlach et al. (1986).
3.2.3. Muon-spin relaxation in the lanthanides Compared with 3d magnetism, the magnetism of the lanthanide 3+ ions, with a well localized 4f shell, is characterized by much more pronounced effects of the orbital contribution and strongly localized magnetic moments. This last fact has important consequences for the positive muon occupying an interstitial site: (i) the hyperfine field (contact field) is small due to the rather low spin density of the conduction electrons, because of the indirect mediation of polarization from d-electrons, (ii) the local dipolar field is high and often the dominating field since the neighboring lanthanide moments are large and (iii) the symmetry of the dipolar coupling is low compared to that of the hyperfine coupling, which is isotropic with respect to the crystalline axes. The latter property means that the muon probes paramagnetic fluctuations along different axes with different weight. A judicious selection of the relative orientation of
MUON SPIN ROTATION SPECTROSCOPY
99
initial #+ polarization axis, crystal axes and applied magnetic field allows a selective weighting of the z-, y- and z-components of the spin correlation functions in the investigated material (Karlsson 1990). Due to its large gyromagnetic ratio (in comparison to nuclear hyperfine probes) the #+ can measure lanthanide relaxation times as short a s 10 -13 s. #SR measurements on lanthanide paramagnetism provide important information on the collective behaviour of coupled localized spins, particularly at high temperature. They are a valuable complement to other methods, mainly because of their sensitivity to short-lived correlations, their general applicability - independent of the choice of element - and their flexibility allowing to select among the different relaxation parameters. Gd. The #+ spin relaxation in Gd has been experimentally studied by W~ickelghrd et al. (1986 and 1989) in the temperature region from Tc to 2Tc; additional information and discussions are provided by Hartmann et al. (1990b), Karlsson (1990), and Dalmas de Rrotier and Yaouanc (1994a). The major results are that magnetic correlations extend to far above Tc, with a temperature evolution containing two different terms, for e > 0.03 (e = ( T - T c ) / T c ) and for e < 0.03. For single crystal measurements an anisotropy of the relaxation rate with respect to the crystalline c-axis is observed, at least up to a few K above Tc (Karlsson 1990). This behaviour, similar but weaker than in Er, is surprising for Gd which is a S-state ion. Let's mention that anisotropy has also been observed in the susceptibility of Gd (Geldart et al. 1989). Dalmas de Rrotier and Yaouanc (1994a) have adapted their #SR depolarizationrate model (Yaouanc et al. (1993a) - see section 3.2.2) to the special case of hcp Gd. Although their theoretical results are only valid for truly zero magnetic field, they assumed that the 10 mT transverse-field data obtained by W~ckelghrd et al. (1986) i
i
~L~II
I
i
i
i~11111
i
Ising
~
i l l ~ J
I
i
Heisenberg 4 dipolar q
isotropic
~ 1.o
0
average over single crystal measurements
\&
0.1 i
t
lliHI
t
1
i
irll~ll
i
10
i
l l r t H t
i
100
T-Tc (K) Fig. 3.11. Temperature dependence of the/~SR damping rate for Gd. The polycrystalline data are from Wackelgftrd et al. (1986) and the single crystal data from Hartmann et al. (1990b). The full line is the prediction of the dipolar Heisenberg model from Dalmas de Rrotier and Yaouanc (1994a); the different temperature regimes are indicated (see text).
100
A. SCHENCK and EN. GYGAX
on a polycrystalline sample could be fitted by the theory. The result (fig. 3.11) follows well the polycrystalline data, whereas the zero-field single-crystal data by Hartmann et al. (1990b) are less-convincingly described. In this theory the magnetic dipole-dipole interactions cause a crossover as the temperature is reduced in the paramagnetic region from an isotropic Heisenberg regime to a dipolar Heisenberg regime at about Tc + 15 K. As the temperature is reduced further, their is possibly a second crossover temperature to Ising behaviour at roughly Tc +4 K. For a discussion of the different features derived from #SR and susceptibility measurements as well as the discrepancies between #SR data the reader is referred to the original work. Er. The data obtained in partially oriented crystals by Barsov et al. (1983 and 1986)
indicated first the occurrence of an anisotropic paramagnetic relaxation rate. Later single crystal zero-field data were presented and commented by Hartmann et al. (1990c), Karlsson (1990) and W~ippling et al. (1993) for the temperature region extending from TN to 2TN. In contrast to the weakly anisotropic Gd, Er shows an extreme anisotropy of the relaxation rate which survives up to at least 2TN (fig. 3.12). The rate ),± (#+ polarization perpendicular to the c-axis) shows the usual strong divergence when approaching TN from above. This arises from the slowing down of the 4f-electron spin dynamics due to the evolution of paramagnetic spin correlations (Karlsson 1990). In contrast, All remains independent of temperature at the value corresponding to the spin fluctuation in a free paramagnet, i.e. the high temperature limit (fig. 3.12). Hence, solely the component of Er spin which undergoes magnetic ordering at TN develops also paramagnetic correlations and fluctuates with the c-axis as quantization axis. (Below the N6el temperature of TN ~ 85 K first the c-axis components of the Er magnetic moment orders in a sinusoidally modulated incommensurate arrangement!) For the perpendicular orientation the initial signal asymmetry drops sharply when decreasing T through TN and the signal is effectively lost at lower temperature, whereas the parallel signal remains altogether unaffected down to 58 K (Hartmann et al. 1990c). This confirms that magnetic order is totally restricted to the Er spin component parallel to the e-axis and that not even short range order develops for the perpendicular component.
6!
rN'
'
5-
2 I 0
Ln
0
0
I-1
ooooo¢ 0 gi ~ l og g 100
200
Temperature (K) Fig. 3.12. Muon spin depolarization rate in Er single crystal for two orientations: circles for the muon polarization parallel to the c-axis and squares for the muon polarization perpendicular to the c-axis (Hartmann et al. 1990c).
MUON SPIN ROTATIONSPECTROSCOPY
101
In their conclusion W~ippling et al. (1993) state that the long range nature of the dipolar interaction between the #+ spin and the lattice spins has to be taken into account to explain the measured relaxation rates. A correct evaluation of the data would have to proceed along the lines proposed by Yaouanc et al. (1993a) (section 3.2.2), but such calculations have so far not been applied to Er.
3.3. Ferromagnetic 3d-element based alloys 3.3.1. Fe, Co, Ni Several authors have measured the variation of Bu with impurity concentration in the elemental 3d-ferromagnets (see in table 3.2 the entries for Fe-, Co- and Ni-alloys). The goal was to find how the deduced Bc changes with concentration in relation to the corresponding changes in the bulk magnetization. However, it became clear that in such experiments the #+ did not randomly sample the lattice sites because of the attractive or repulsive interaction with the impurities. This showed up in the interplay of trapping and diffusion of the #+ in the 'dirty' host lattice, as reported by Nishida et al. (1979) and Kossler et al. (1979) in Fe- and Ni-alloys. Together with the studies of Stronach et al. (1979, 1981, 1983), and of Herlach et al. (1986) in Fe- and Coalloys, a total of over 15 different types of dilute alloys were examined. Because of the mentioned impurity dependent modification of the #+ behaviour these B~ dependences give only limited information on the intrinsic host magnetism. They can however provide an interesting contribution in conjunction with the results of other methods applied to study the magnetism in a specific alloy. Stronach et al. (1981, 1983) discuss the effect of the impurity induced strains upon Bu and Be. Herlach et al. (1986) have studied several Fe-Co alloys as well as an amorphous FeZr alloy. In particular the disturbing effects of sample inhomogeneities are discussed. Solt et al. (1992) have performed first #SR measurements in neutron-irradiated pure Fe and Fe-based copper containing alloys. This study was part of a general investigation undertaken with various methods on the radiation generated fast precipitation from supersaturated metastable FeCu solutions. #SR has shown its great sensitivity to both vacancy-like defects and to the Cu-depletion of the solvent matrix. The average and distribution-width of Bu changes with n-irradiation fluence as a consequence of the broad size distribution of created voids and other defects in the pure metal and of the induced Cu-precipitates in the alloys. Annealing after irradiation produces agglomeration of vacancies or defects, which again changes the field distribution sampled by the muons. A modeling of the experimental results is presented and the preliminary #SR study shows that due to the high sensitivity of the technique samples with higher purity and less irradiation damage are required for a better resolution of defect spectra. 3.3.2. Pd-based alloys Pure Pd is paramagnetic, but close to a magnetic instability. Alloying it, e.g., with Fe or Ni at atomic % concentration can strongly polarize the d holes on neighboring Pd sites, producing 'giant moments'. These moments can show ferromagnetic order or couple antiferromagnetically and exhibit spin-glass ordering, depending on the alloy concentration and the temperature.
102
A. SCHENCKand EN. GYGAX
Different #SR studies were performed on Pd-based alloys (see the references in table 3.2). The general meaning of the results is not at all clear. Again the peculiar effects of the impurity atoms on the #+ are difficult to assess. Even in 'pure' Pd the role of the muon is dubious. For example, Nagamine et al. (1977) interpret their data assuming a localized #+ at low temperature (in analogy to the behaviour of H in Pd), whereas Hartmann (1990) seems to believe that for very pure Pd the #+ diffuses fast for temperatures at least as low as 18 K. For weakly doped Pd, Dodds et al. (1983) assume a negligible #+ diffusion rate below 100 K (based on the muon diffusion measured in Pd lightly doped with Gd) and interpret their data in PdMn (2 at.%) assuming randomly distributed #+ locations, whereas the same group consider the muon as static in PdFe0.0o35Mn0.05 at low temperature, but physically excluded from the interstitial sites closest to the Mn sites (Gist et al. 1986).
3.4. Chromium and its alloys The three first #SR studies in Cr (Kossler et al. 1977, Grebinnik et al. 1979b, Weidinger et al. 1981) did not succeed in detecting spontaneous muon precession in this antiferromagnetic metal. The measurements yielded #+ depolarization rates as function of temperature or field and showed only a modest consistency. As Weidinger et al. (1981) noticed, it seems that the influence of impurities on the #+ behaviour partly biases the experimental outcomes. The question of the #+ localization was addressed but not conclusively answered. The Stuttgart group (Major et al. 1986, Templ et al. 1990) was able to see a #+ precession signal in a zero-field measurement in Cr below 12.5 K. The frequency of about 84 MHz shows up with a small amplitude, implying that only a small fraction of the muons see a distinct local field. Below 124 K Cr is in an incommensurate longitudinal spin-density wave (SDW) state. The Stuttgart group explain their data assuming that for T < 12.5 K the #+ stays at a tetrahedral interstitial site with tetragonal symmetry axis perpendicular to the crystalline [100] direction (labeled T ±site). The other tetrahedral site and the octahedral sites are excluded and #+ hopping has a low probability during the muon lifetime. In addition it is assumed that the #+ resides preferentially near a field maximum of the SDW. This situation can result either if the SDW maximum is pulled towards the #+ or if the muons thermalize and stop at the SDW antinodes (in Cr the SDW or better the accompanying charge density waves produce also strain waves - the effect of strain on muon trapping has already been mentioned in sections 3.1.2 and 3.3.1). In a further study (Grund et al. 1994) proton-irradiated Cr was used to vary the possible pinning/trapping conditions for muons and SDW. For the low temperature regime the data are now interpreted assuming a localization of the #+ at random position in the host; the surviving coherent signal at long times corresponding to the (small) fraction of the #+ stopping near the SDW maximum, as indicated by the calculation. Therefore, the muons neither cause SDW motion nor have to undergo long range diffusion. In a study by Noakes et al. (1992) it is shown that the zero-field coherent #SR frequency of 84 MHz previously observed in Cr has a dramatic impurity dependence.
MUON SPIN ROTATION SPECTROSCOPY
103
It is known that alloying Cr with small amounts of other metallic elements has strong effects on the magnetism (Fawcett 1988). In their experiment Noakes et al. (1992) were able to suppress, shift dramatically or split the 84 MHz #+-frequency observed in pure Cr by alloying with, e.g., V, A1 or Mn at atomic % concentrations and varying the temperature. So far only speculative explanations are suggested. Another contribution dealing with the condensation of incommensurate SDW and the onset of the AF state stems from a ZF #SR study in the Cr-like alloy Cr85Mo15 by Telling et al. (1994). As in other instances (see, e.g., section 3.3.2) the effect of impurities on the #+ behaviour in the Cr host is possibly pathological, i.e. very interesting for a defect therapist, but rather an annoying complication for the simple magnetically-minded pedestrian.
3.5. #-SR in Fe and Ni A # - stopped in a solid forms a muonic atom # - z X in which the bound # - behaves like a heavy electron (mu = 207me). The muonic radius % = aome/(muZ) is much less than the Bohr radius a 0, hence the pseudonucleus # - z X appears to the atomic electrons very similar to an isolated impurity nucleus of charge Z - 1 (Yamazaki et al. 1979 and Yamazaki 1981). However, for light elements (Z < 30) the muonic atom 1s-wave function extends noticeably outside the nucleus. For example, in the case of /z-Fe, % is about twice the nuclear radius Ro. In contrast to the previously discussed #+SR measurements, which yield information on the hyperfine field (i.e. the electron spin density) at the interstitial #+ position,/~-SR leads to inforrnations on the radial distribution of the electron spin density p(r) near the (pseudo-impurity) nucleus. This is much like NMR, M6ssbauer spectroscopy and time-differential perturbed angular correlation, all techniques studying the hyperfine fields acting upon the nuclei of adequately selected impurity atoms in the host. Calling B~f the average hyperfine field acting upon the # - bound to z X and B hf the average hyperfine field acting upon the impurity nucleus of charge Z - 1, one usually defines the hyperfine anomaly as AX = ( ~ h f _
BhNf)/Bhf.
(3.8)
Assuming that the muonic atom and the impurity atom occupy the same type of site in the lattice and have the same electronic structure, a non-zero A value will be due to the fact that the # - samples p(r) over a more extended region of space than the Z - 1 nucleus. Yamazaki (1981) has discussed some aspects of the hyperfine anomaly and their importance in the study of magnetic materials. Imazato et al. (1984) reported the first results in a ferromagnetic material, i.e. Ni, and Keller et al. (1987) extended the measurements to ferromagnetic iron. In Ni a comparison of the hyperfine field for #-Ni with that for 59Co yields nNi = -2.4(3)% to -2.8(5)% over the temperature range 23-303 K (Imazato et al. 1984). The results indicate that the electron spin density near the Ni nucleus decreases with increasing r more steeply than the s-state electron charge density, a behavior which is a consequence of core polarization (see Freeman and Watson 1965, Freeman et al. 1984). The values are in good agreement with the unrestricted Dirac-Fock calculation by Freeman et al. (1984).
104
A. SCHENCK and EN. GYGAX 25
I
I
I
I
1.0 2O
0.8 "o -~
15
o "a
10
0.6 0.4
E
& E "~ :~ "0
5
o/,
• 0 0
5SMn
NMR
0.2
rr
p Fe I 0.2
r 0.4
1 0.6
i 0.8
0.0 1.0
T/T c
Fig. 3.13. Magnitude of local field in Fe as a function of reduced temperature T/TC (TC = 1043 K). Solid triangle: data for 52MnFe (dilute limit) obtained with NMR on oriented nuclei from Hagn et al. (1982). Open circles and open triangles: 55Mn data for (1.5 at.%) 55MnFe from Koi et al. (1964) and Yamagata et al. (1983), respectively. The solid circles are the/~-Fe data for iron and the solid line represents a fit using a simple mean-field model (Keller et al. 1987). For comparison the reduced magnetization curve of pure iron is also shown (right scale). In Fe # - S R in zero applied field was used to study the hyperfine field in the temperature range 320-690 K (Keller et al. 1987). Bhuf departs from the magnetization curve of pure iron in the same way as the hyperfine field acting upon a 55Mn impurity in diluted (1.5 at.%) MnFe measured by N M R by several groups with different N M R techniques (Koi et al. 1964, Rubinstein et al. 1966, Yamagata et al. 1983), see fig. 3.13. This indicates that the electronic structure of # - F e is very similar to that of a Mn impurity in Fe. AFe is found to be - 0 . 9 ( 3 ) % and temperature independent over the temperature range investigated. The anomalous behavior of the impurity B~f has been discussed by Jaccarino et al. (1964), Low (1966) and Shirley et al. (1968), and can be understood on the basis of a mean-field approach. The A value measured by Keller et al. (1987) is significantly smaller than expected if core polarization plays a similar role in # - F e relative to Mn as in # - N i relative to Co. The reason for the small AFe is not known. In this case, in contrast to Ni, no unrestricted Dirac-Fock calculation are available.
4. Review of results in intermetallic compounds 4.1. Compounds involving transition elements Only a few intermetallic compounds with no lanthanides or actinide constituents have been studied up to now, by #SR. In this section we discuss the weak itinerant magnets MnSi, Y9Co7 and Nbl_=Zr=Fe2 (see table 4.1). Other Y containing compounds are included in section 4.2.
M U O N SPIN ROTATION SPECTROSCOPY
oo
~
oo o~
N~v e~
©
0
--1 r~
I.~ gT., .C~
M
©
c.i
~8 cq
o~< o~
g~
0 0
r..)
8
105
106
A. SCHENCK and EN. GYGAX
4.1.1. MnSi The interest in this system was motivated by the possibility to extend spin lattice relaxation rates (Ta l) measured by 55Mn NMR (Yasuoka et al. 1978a) to much lower temperatures and higher rates by using the #+. This extension appeared very important since detailed predictions on the temperature dependence of T1-1 on the basis the self consistent renormalization (SCR) theory for itinerant ferromagnetic electrons (Moriya et al. 1973, 1974, Moriya 1977) and applied to MnSi (Makoshi et al. 1978), could only sensibly be checked in this way. In fact MnSi is known to be a weak helimagnet with a period of ,-~ 180 A below Tc = 29.5 K (Ishikawa et al. 1976, Motoya et al. 1978) but since the helical structure has such a long period it was expected that T~-1 behaves almost like the spin lattice relaxation rate in an itinerant-electron ferromagnet (Hayano et al. 1978a). We start with a review of the measurements in the paramagnetic phase (T > Tc). In a first study the #+-Knight shift was measured in a transverse field experiment with Hext = 0.29 T (Yasuoka et al. 1978b). It was found to scale well with the magnetic susceptibility from which the coupling parameter Ac~+ could be determined (see table 4.2 which includes also the corresponding A Mn determined by NMR). According the SCR theory above Tc the spin lattice relaxation rate T1-1 (see also eq. (2.41)) is predicted to be given by Im X L(g wo) coo
2 ,u,,Mn 2 1/T1 (., Mn) = 271,(Mn ) (Ac ) T Z 1
(4.1)
T
= TI(~) T - Tc
(4.2)
,'~^,2 ( d,u,Mnh2 T C(~I/~(Mn) L~c ) T - Tc '
(4.3)
and hence 2 Mn 2 2 T(U)/T(Mn) =- "yfvln(A c ) /'yu(Ac/ ,)2 .
(4.4)
First results on (Ta~)-~ obtained in a longitudinal field of 700 G agreed with the SCR-predictions appropriate for an itinerant ferromagnetic system quite well. TABLE 4.2 Compilation of hyperfine fields and coupling parameters in MnSi (Tc = 29.5 K).
T > Tc T < TC
Acu (kG/#B)
B~f (T = 0) (W)
A Mn (kG//~B)
-4.8 ± 0.2 -6.94 -3.94
-0.273 -0.155
-138(1)
MUON SPIN ROTATION SPECTROSCOPY
107
Comparison with a few NMR results above 100 K proved also the validity of the scaling relation eq. (4.4) (Hayano et al. 1978a, 1980). Later it was realized that ZF-#SR measurements could not only be used to determine TI-t(# +) but also Tll(Mn) at the same time. This is a consequence of the fact that in ZF the #+ will also feel the 55Mn-nuclear dipole fields. If they are static the effect on the #+-polarization is described by the static Kubo-Toyabe relaxation function (see section 1.8). However, since the nuclear spins relax as well under the action of the spin fluctuations of the itinerant electrons a dynamic picture applies and the induced/z+-depolarization has to be described by a dynamic Kubo-Toyabe function GKT(t, u(Mn)), where u(Mn) = Ta-a(Mn) is the nuclear spin lattice relaxation rate. In this case the overall #+-depolarization function is then given by (two channel relaxation) CzF(t) = exp (--
t/T} ")) GKT(t, u(Mn)).
(4.5)
Analyzing zero field data with eq. (4.5) both 1/T~u) and 1/T~ Mn) could be determined over a much wider temperature range (Matsuzaki et al. 1987, Kadono et al. 1990). The results are compiled in fig. 4.1. The solid line through the 1/T1 (Mn)-data is a fit of the function 1 -
-
-
a
T1 (Mn)
-
T -
T + b
T - Tc
.
(4.6)
(T - Tc) 2
The second term is included to account for a somewhat modified temperature dependence in the vicinity of Tc following from numerical solutions of the SCR-theory I
I~
IIItl
I
101
I
I
I
I IIII
I
I
I
i
i iiii
I
i
_oc_ :,zedm_o_ ent.
10 0 "1 v
~.,._
10-1 'T'--
I1~:
=2 ",it--
10 -2 ~/j,, o
II
"+2,<, II
10-3
10-1
,,,,,,,
10 0
101
, ,,',',J,I
,
10 2
T-T c (K) Fig. 4.1. Log-log plot of both the #+ (open symbols) and the Mn-nuclear spin (filled symbols) lattice relaxation rates l/T1 versus temperature. The filled circles and diamonds are extracted from ZF-/zSR measurements, the filled squares are from NMR measurements. The solid lines follow eq. (4.6), the dashed lines represent various other theoretical models (Hayano et al. 1978a, Kadono et al. 1993).
108
A. SCHENCKand EN. GYGAX
(Moriya et al. 1973). The solid line through the 1/Ta(#)-data is obtained by just scaling the upper solid curve with the factor (UMnAcMn/l/IzAc#)2 = 5.0. Another nice verification of the SCR-theory follows from #SR measurements of the temperature dependence of the electrical field gradient (EFG) at the #+ nearest neighbour Mn-nuclei (Kadono et al. 1993). Applying the muon-quadrupolar level crossing technique (Kreitzman et al. 1986) the EFG showed a diverging behaviour as Tc is approached from above. This is shown in fig. 4.2 where the temperature dependence of the quadrupolar splitting frequency UQ of the 55Mn-nucleus (I = 5/2) is displayed. Also shown are results from NMR-measurements performed at higher temperatures (Yasuoka et al. 1978a). The two data sets do not agree too well (and do not scale either) in the temperature range where they overlap. The reason for this is not known at present. In the SCR-model the temperature dependence is explained by the coupling of charge density to spin density fluctuations (Takahashi and Moriya 1978). In this model the net EFG at the Mn-nucleus is given by q/ = q=qo+qel qo+ ( 1 / x ) + d ,
(4.7)
where q0 is the contribution from the positive ion cores including the #+ and qel arises from the deviation of the conduction electron charge density from a cubic distribution. The parameter q~ and d are related to the EFG in the absence of electron-electron interactions and of the effect of exchange enhancement. Inserting the Curie-Weiss law for the susceptibility the temperature dependence of UQ can be
1.5
i
j
i
t
MnSi
1.25 1 N
-1-
.75
o
.5
°Ooo
O O 0000
.25 0
0
I
I
I
I
I
100
200
.300
400
500
Temperoture
600
(K)
Fig. 4.2. Temperaturedependence of the quadrupole coupling parameter //Q in MnSi. Triangles are from the #+ level crossing measurements, octagons stem from NMR measurements (from Kadono et al. 1993).
MUON SPIN ROTATION SPECTROSCOPY
109
expressed as 1
3e2Q
[
q~
]
UQ(T) -~ 27r 2 M ( 2 I - 1) qo + (T - T c ) / c + d
.
(4.8)
This equation can indeed be used to fit the #SR data well (Kadono et al. 1993). Using c = 0.6 (emu/mol)K and Q = 0.55 barn one obtains q0 = 6.75(3) x 102z cm -3, q' = 1.30(1) x 1025 c m - 3 e m u - l m o l and d = 1.68(1) x 102 mol/emu. In summary the SCR-model can describe very well the temperature dependence of both the 55Mn and/z+-spin lattice relaxation rate and the EFG at the Mn-nuclei in the paramagnetic phase. We now review results obtained below Tc (Takigawa et al. 1980, Kadono et al. 1990). ZF-measurements reveal two distinct precession frequencies (with relative populations Pl/P2 = 0.77(9)) the temperature dependence of which is shown in fig. 4.3 (Kadono et al. 1990, Takigawa et al. 1980). The data are compared with
0.25
[
I
I
I
I
I
0.20 -
0.15
0.10 -
--.
\iO
"
IP
0.05 qb A . f = "6.94kg/~ B I Ahf = -3.94kg/l~B 0.00
0
I
5
I
10
I I 15 20 25 Temperature (K)
\~
1I 30
35
Fig. 4.3. Temperature dependence of local fields Btz in MnSi below T C. The solid lines represent theoretical calculations of MQ(T)/MQ(O)and the dashed lines show MQ(T)/MQ(O)obtained from neutron scattering (from Kadono et al. 1990).
110
A. SCHENCK and EN. GYGAX
the temperature dependence of the saturation magnetization MQ(T) (determined by neutron scattering, Ishikawa et al. 1976) and a perfect scaling is observed implying (after correcting for the Lorentz field) Bhf(T) = A2 + MQ(T).
(4.9)
The resulting coupling constants A2 are to be found in table 4.1. The weighted average Ac~ = pl Acu(1) + p2Acu(2) = -5.63 kOe//z B
(4.10)
is 17% larger than the coupling constant in the paramagnetic state (see table 4.2). It is suggested that this discrepancy may be due to the ordered helical structure causing two magnetically inequivalent sites and also dipolar field contributions. Note that in the paramagnetic state only one signal showed up in the TF-data. Possible #+-sites in MnSi were not discussed. 400
/
¢) Ahf = -6.9kg/g B / 0 Anf =-3.9kg/g g
/
~)
300
o o~
200 e4
=t.
100
0
5
10
15 20 25 Temperature (K)
30
35
Fig. 4.4. Temperature dependence of/z + spin lattice relaxation rates, multiplied with the respective u 2 from the oscillating components below T C in MnSi. The SCR theory predicts a linear dependence (from Kadono et al. 1990).
MUON SPIN ROTATIONSPECTROSCOPY
111
The solid lines in fig. 4.3 represent the predictions of the SCR-theory for Me(T) below To As can be seen the data do not follow very well the predicted Me(T ). This is discussed further in Takigawa et al. (1980). Information on the spin lattice relaxation rate below Tc is obtained from the exponential decay of a third nonprecessing component in the #SR-signal. This component, actually consisting of two contributions, arises from those #+ whose spins happen to be parallel to the static internal fields in the randomly oriented multi-domain sample but which spins are affected by fluctuating field components perpendicular to their direction (see eq. 2.13). In the analysis of these non-precessing components it is assumed that 1/T( 0 o( w2%, where wi are the frequencies of the corresponding precessing components and % is a common correlation time arising from the Mn-spin fluctuations. Figure 4.4 shows the temperature dependence of (wi/21r)2/T( O. According to the SCR-theory one expects 1/T1 c( T / [ M o ( T ) ] 2
(4.11)
and hence w~i)/T1 oc T. This linear dependence is indeed seen for temperatures T < T c / 2 but it breaks down for larger T. Takigawa et al. (1980) suggests that the deviation of 1/T(O(T) from eq. (4.15) may be a consequence of the helical structure: "Since it has a finite Q, although very small, the spin fluctuations in a small region around Q may play an important role in the relaxation process, at least near Tc ". In this case an antiferromagnetic SCR-model would be more appropriate which predicts 1/TI o( T / M e ( T ). At least qualitatively this can describe the trend of the data closer to Tc. 4.1.2. Y9Co7 This compound shows a magnetic phase transition at Tc ~ 6 K and becomes superconducting below Tc ~- 2.7 K in coexistence with the magnetic order (Sarkissian 1982). The ordered magnetic phase below 6 K is believed to be an itinerant ferromagnetic state (Sarkissian 1982, Huang et al. 1983a, b). In the latter reference it is reported that application of pressure suppresses the magnetic order and increases the superconducting transition temperature and Hc2. It is further concluded that the long range ferromagnetic- and superconducting order parameter coexist but vary spatially. NMR measurements (Takigawa et al. 1983b) suggest that only at the Co-sites in the 2b positions (for notation see Grover et al. 1982), forming a linear chain along the c-axis, a sizable spin density is to be found associated with a ferromagnetic moment of 0.2#B per atom. ZF-pSR measurements were performed with the aim to collect further information on the peculiar magnetic behaviour of this compound (Ansaldo et al. 1985). Figure 4.5 displays ZF-spectra for temperatures around and below To At temperatures above Tc a well developed static Kubo-Toyabe signal was visible which arises from the 59Co-nuclear dipole fields and proves the absence of #+ diffusion up to at least 220 K. The results shown in fig. 4.5 could only be adequately fitted by invoking two components, one of which is the afore mentioned Kubo-Toyabe signal
112
A. SCHENCK and F.N. GYGAX
.30 ~ 6 . 1 K
Co 7
,
.20 O3 < .10
0
-
0
10 20
-
30 40 50 60 70 Time (#s)
80
Fig. 4.5. ZF-/~SR signal in Y9Co7 at various temperatures. The solid lines represent fits with two components. See text (from Ansaldo et al. 1985).
.30
Y9 0 ° 7 •
O0 ~ Slow Signal
~>, .2o E <
a)
.10
©
O
Fast Signal
4.0
go • 1 I I I L 2.0 3.0 4.0 5.0 6.0 Temperature (K) ~)
3.0
I
0 0
~
°~c__~
'~
o
I 1.0
b)
O
~-'- 2.0 .o_
Fast Signal
_~ ¢ 1.0
0
q 0
1.0
slow Signal
•
•
O
OC~DO-
2.0
3.0
i
4.0
5.0
Temperature (K) Fig. 4.6. Temperature dependence of (a) signal amplitudes (asymmetries) and (b) relaxation rates from a two component fit to the ZF-#SR signal in Y9Co7 (from Ansaldo et al. 1985).
MUON SPIN ROTATIONSPECTROSCOPY
113
(below Tc to be replaced by a dynamic Kubo-Toyabe function) which shrinks with decreasing temperature while a second more rapidly relaxing signal grows by the same proportion. The data could be equally well described by choosing for the second 'fast' signal a heavily damped oscillating function or alternatively a dynamical Kubo-Toyabe expression with a much more rapid overall relaxation as compared to the first signal. Using the first approach one finds at 2 K an average field of ,,o 100 G at the #+. The fit results from the second approach are shown in fig. 4.6. Figure 4.6a displays impressively the shrinking of the 'paramagnetic' component and the rise of the new 'fast' component below Tc. Qualitatively the same result is found in the first approach. Figure 4.6b displays the fluctuation rates following from the dynamic Kubo-Toyabe fit of the 'fast' signal. The static line width for this signal amounts to A ~ 4.5 #s -1 corresponding to a field width of ~,, 53 G which must arise from the ordered Co-moments. These results are quite different from the ones in MnSi and do also not show any resemblance with what is observed in spin glasses. Similar behaviour, however, is found in some of the compounds classified as heavy fermion materials (see sections 4.2.6 and 4.3.4). The most remarkable feature of the present data is the temperature dependence of the two component structure. It could imply that the paramagnetic phase persists well into the ordered state in part of the sample volume. It would be interesting to find out whether superconductivity is associated with only this fraction of the total volume. TF-#SR measurements on monocrystalline samples should allow to check on this conjecture (see also the discussion on CeCu2Si2, section 4.2.6). The other noteworthy result is the lack of any indication for a truly long range magnetic order. The present data indicate a rather random or extremely short range magnetic order. In contrast to ordinary spin glasses no slowing down of spin-fluctuations is seen when approaching Tc from above.
4.1.3. Nbl_~ZrxFe2 NbFe2 is considered to be a weak itinerant antiferromagnet (TN = 13 K) with a rather small ordered moment (~ 0.1#B) (Yamada et al. 1990). The antiferromagnetic state is very sensitive to the exact stoichiometry and weak ferromagnetism is observed in compounds with either enhanced Fe or Nb content. The mixing of dynamic ferromagnetic and antiferromagnetic correlations in NbFe2 may be the result of topological frustration associated with the Kagome lattice like structure of the Fe sites in NbFe2. The development of itinerant ferromagnetism is also observed in compounds in which Nb is partially replaced by Zr up to a concentration of 20%. At larger Zr-concentrations the system converts back to weak antiferromagnetism (Yamada et al. 1984) #SR-measurements were started with the aim to study the phase diagram of Nbl_xZr~Fe2 in more detail. So far only preliminary results on a powdered sample of Nb0.9Zro.lFe2 (Tc -~ 43 K) were presented (Crook et al. 1994). These results from ZF- and LF-measurements seem to imply that already below 90 K (the temperature at which the susceptibility X, on cooling, tends towards the Curie-Weiss form) some static behaviour of the atomic moments develops in coexistence with dynamical fluctuations. It is also found that the static field distribution shows a trend from a Gaussian shape to a more Lorentzian one as the temperature is lowered down from
114
A. SCHENCKand EN. GYGAX
90 K. This could suggest the development of dilute inhomogeneities in an otherwise regular spin arrangement, perhaps as a consequence of the topologically frustrated lattice of Nbl_xZrzFe2. Below Tc the amplitude of the ZF-#SR signal drops rapidly to 1/3 of its initial value, marking clearly the onset of the ferromagnetic state. From the relaxation of the residual signal it can be concluded that also in the ordered state some spin fluctuations must persist. No oscillating signal below Tc was seen which could be due to the limited time resolution at the pulsed #+-source at ISIS. These preliminary results together with magnetization data suggest that Nb0.9Zr0.1Fe2 cannot be viewed as a simple weak itinerant ferromagnet. 4.2. Intermetallic compounds containing rare earth elements 4.2.1. Rare earth aluminides: RAI2 (except R = Ce) The rare earth aluminides with the exception of CeA12 all show a ferromagnetic state with Curie temperatures ranging from 6 K for TmAI2 to 160 K for GdA12 (see table 4.3). Their crystalline structure is of the cubic Laves phase type MgCu2 (C15). The magnetism is believed to be associated with well localized 4f-moments. Whereas it is known that in certain itinerant magnetic systems short range correlations among the spins persist to temperatures well above the transition temperatures the situation with respect to local moment systems is less clear. #SR-measurements were performed with the specific aim to search for such correlations by studying the spin dynamics of the 4f-moments via #+-relaxation measurements in the paramagnetic phase (Chappert et al. 1981, 1986b, Kalvius et al. 1984, Gradwohl et al. 1986, Hartmann et al. 1984, 1986, Dalmas de R6otier et al. 1990b). The results on CeA12 will be treated in section 4.2.7 (heavy fermion compounds). From TF-measurements in the nonmagnetic compound LaAI2 it was concluded that the #+ most likely resides at the so called (2-2) site, having two R and two Al-atoms as nearest neighbours (see fig. 4.7). ZF- and LF-measurements in DyAI2 below Tc showed a drop in the signal amplitude to 1/3 of its value above Tc which is typical for a ferromagnet with randomly oriented domain magnetizations (Gradwohl et al. 1986, Asch et al. 1986). The remaining signal displays an exponential relaxation indicating that fluctuating field components are still present below Tc. Detailed measurements in the other RA12 compounds below Tc are lacking. Above Tc mostly TF-measurements were done, supplemented later by ZF- and LF-studies (Kalvius et al. 1984, Gradwohl et al. 1986, Chappert et al. 1986b, Dalmas de Rfotier et al. 1990b). From an analysis of the Knight shift from TFmeasurements it was established that the contact hyperfine field is vanishingly small with the exception of GdA12, and that dipolar fields from the 4f-moments5 must be responsible for the dynamically induced ~+-depolarization (Hartmann et al. 1986). With respect to the extraction of the #+ spin lattice relaxation rate from the TFspectra a correction for powder broadening had first to be applied. Some room temperature relaxation rates A2, AzF of the #+-polarization are collected in table 4.4. It is seen that grosso modo the corrected )~2 and the )~zF agree reasonably well with each other. Az,zF can be compared with predictions based on the RKKY interaction 5 Dipolarcouplingparameters for all RA12are quoted in Hartmannet al. (1986).
MUON SPIN ROTATION SPECTROSCOPY
r~
mm
~
u
H
~o ~
115
116
A. SCHENCK and EN. GYGAX
001 projection
,,~
®
f
®
®
® Rare Earth o A~iuminum 2-2 muon position ,, 3-I muon position Fig. 4.7. Crystal structure of the cubic laves phase compounds RA12. The most probable # + location is the so called (2-2) site. TABLE 4.4 Compilation of contact hyperfine field constants Ac, room temperature relaxation rates A2 (from TF measurements, extrapolated to Hexp = 0) and AZF (from ZF-measurements), calculated values Aff based on the RKKY mechanism and assuming the/z + at the (2-2) site, calculated values Aj at 300 K including the Korringa mechanism, and calculated total fluctuation times ~-j (ct = 1.477 × 1011 s - 1 K - 1 , eq. (2.52)) (Hartmann et al. 1986).
PrA12 NdA12 GdAI2 DyA12 HoA12 ErAlz TmA12
[Ac I
>'2 (300 K)
AZF(300 K)
),ff
~j (300)
(kG//~B)
(#s -1 )
(/zs -1 )
(/zs -1 )
(/zs -1 )
(10-12s)
-~ 0 ~- 0 ~_ 0.46 -~ 0 "~ 0 "~ 0 "~ 0
0.05 0.02 0.38 1.05 1.16 0.84 0.43
0.133 0.059 0.11 0.96 2.14 3.76 4.42
0.09 0.04 0.11 0.71 1.17 1.36 1.02
0.39 0.19 0.089 0.34 0.57 0.81 0.98
(3) (3) (6) (7) (8) (5) (4)
0.22 (6), 0.23 (1) 1.4, 0.67 (8) ~ 1.05 ~ 1.4
~'j (300 K)
among the 4f-moments and on the Korringa mechanism (see eq. (2.52)), assuming the #+ to reside at the (2-2) site. The exchange interaction constant Isf, entering into the RKKY interaction, is calculated from the Curie temperature T¢. The Korringa mechanism involves the quantity [IsfN(EF) I which, according to L6wenhaupt et al. 1983, is of the order of 0.08(4) and includes de Gennes' factor. For PrA12 and NdA12, A2 are rather small and nearly temperature independent. The data are consistent with a temperature independent 4f-moment fluctuation rate of the order of several 1012 s -1 (see table 4.4) which is caused by the RKKY interaction alone. In the heavier HoA12 AzF is much larger but shows also a relatively weak temperature
MUON SPIN ROTATION SPECTROSCOPY II I
I
I
i
I
I
I [1111111111
I
o
0.20 -,$ 0.15 E E 0.10 c,O
<
0.05
117
0 0 0 0 (30
0.00
HoAI 2 2.0 b,
0' /%oooo Ooo o
1.5 ¢,.
1.0
o
oo
o
0.5 rr
I
0.0 III
20
I
Tc t
I
I
I Illlflllt~l
100
200
Temperature (K)
Fig. 4.8. Plot of signal amplitude (asymmetry)and relaxation rate of the ZF-/zSR signal in HoAI2 versus the logarithm of temperature. Note the collapse of the amplitude below Tc (from Dalmas de R6otier et al. 1990b). dependence (see fig. 4.8). The RKKY prediction amounts to an even larger rate. Inclusion of the Korringa mechanism brings the value of the calculated )`ZF,calc. down to nearly the measured one at room temperature and reproduces roughly the temperature dependence. The same seems to be true for TmA12. The remaining compounds GdAI2, DyA12 and ErAI2 in contrast show a very pronounced variation of ),2 and/or )`ZF with temperature (see fig. 4.9) displaying an almost divergent behaviour as Tc is approached from above. Hartmann et al. 1986 take this as evidence for the evolution of short range dynamic correlations as Tc is approached. Dalmas de Rdotier et al. 1990b argue that some of the temperature dependencies are strongly influenced by crystal field (CEF) effects. (Not, of course, in GdAI2.) Data on a single crystal DyAI2 show an even more peculiar behaviour. There a maximum in )`1 shows up at T ~ 100 K, clearly above Tc, f o l l o w e d by a shoulder at ~ 125 K. Attempts were made to explain this behaviour i n terms of #+ trapping and diffusion (Gradwohl et al. 1986). Asch et al. 1986 h a v e also found differences when investigating differently prepared polycrystalline DyA12-samples, but all samples showed a clear temperature dependence of )`1. Finally Kaplan et al. (unpublished data) investigated another polycrystalline sample
118
A. SCHENCK and EN. GYGAX l
I0 -, v
I
I
I
+
i
o~
f
8
I
I
I I I llllllll~
I
ErAI 2
6 tO
4
x
~
2
rr
0
O
o o Oooom I
20
I
I
i
I
I
I
I [ I I I I I [ I I I I
1O0
200
Temperature (K) Fig. 4.9. Plot of the relaxation rate of the ZF-/zSR signal in ERA12 versus the logarithm of temperature. Note the diverging character of ~ZF when the temperature approaches TC. The signal is lost already about 10 K above TC (from Dalmas de R6otier et al. 1990b).
which displayed a near temperature independent )~1 ,-,o 1 #s -1. From all those results it must be concluded that sample dependent features are involved and the question whether dynamical short range correlations persist above Tc in some of the RAlz-compounds or whether CEF-effects are responsible cannot be answered with certainty. Systematic investigations in the LF-mode may remedy our present ignorance. 4.2.2. Other cubic Laves phase (C15) compounds RM2 with M a 3d transition metal 4.2.2.1. RM2 (M = Ni, Fe, Co). All compounds with M = Ni, Fe, Co, considered here (see table 4.5), show ferromagnetic order within the local moment rare earth sublattice and the more itinerant 3d-element sublattice. The coupling of the two sublattices is ferromagnetic for light R elements (Ce-Sm, no such compounds have yet been investigated by #SR) and antiferromagnetic for the heavier ones. Included here is also the compound YFe2 in which, as well as in LuFe2, only the Fe-moments, of course, can order. Below Tc, in zero external field, well developed #+-precession signals were observed in GdFe2, GdCo2, YFe2, LuFe2, TmFe2 and ErFe2, using polycrystalline samples (Barth et al. 1986a, Graf et al. 1981). In each case only one distinct precession frequency was observed. The temperature dependence of these frequencies is in part rather peculiar (see, e.g., fig. 4.10-4.13) and does not scale with the macroscopic magnetization. The analysis is made difficult by the presence of #+ diffusion and probably trapping at defect sites and the presence of two sublattices. #+-diffusion, already quite rapid at the lowest temperatures (4.2 K), has to be invoked in order to explain the occurance of just one frequency.
M U O N SPIN ROTATION S P E C T R O S C O P Y
119
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0
0
,,,el
,-'
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120
A. SCHENCK and F.N. GYGAX
B. (T) 0.9
120 M(T)/M(O) ~
,
0.8
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0.6
80 o e,,,,
0.5
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-~GdFe2-B~xt= 0 T
+
40
0.3 0.2
20 0.1 0
0
e
I
=
I
=
I
200 400 600 Temperature(K)
i
800
Fig. 4.10. Temperature dependence of the spontaneous field/3~ from ZF-/~SR measurements in GdFe 2. The solid lines show the temperature dependence of the saturation magnetizations (from Barth et al. 1986a).
Adopting again the (2-2) site as the site of #+ residence (this site is also found to be occupied by hydrogen or deuterium at low concentrations (Didisheim et al. 1980)) one finds that there are 96 interstices of this type in the crystalline unit cell of the C15-structure (see fig. 4.7) which are not all magnetically equivalent. This leads to the appearance of different dipole fields at these sites which should have lead to a well resolvable splitting of the #SR-signal into several distinct frequency components. Averaging over all (2-2)-sites results, of course, in a cancelation of the dipolar fields in accord with the overall cubic symmetry. The absence of any splitting suggests that rapid #+-diffusion provides such an effective averaging mechanism. The remaining static field at the #+ is then simply given by (see eq. (3.5)) 471
B u = B c + -~- Ms,
(4.12)
MUON SPIN ROTATION SPECTROSCOPY ,
i
i
121
l
• q,
B~ (T)
0.8
-
100
•
Gd 002 T
80
- 0.7 - 0.6
-r
0.5 60
>" = m EL
0.4 40
0.3 0.2
20
\T o= 404K
0
I 100
0
I 200
i 300
0. 1
t 400
Temperature (K) Fig. 4.11. Temperature dependence of the spontaneous field B~ from ZF-/~SR measurements in GdCo2. The solid lines show the temperature dependence of the saturation magnetizations (from Barth et al. 1986a).
0.4
5 0 l l e ~-~ l ~
N
'
40
,
, YFezl
i _ B. (T) 0.3
Bext = 0 T
•
-
-130 --
v
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ro tCT
20
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u..
10 0
I
0
100
I
I
I
200 300 400 Temperature (K)
t d
500
= si]5t
600
Fig. 4.12. Temperature dependence of the spontaneous field B~ from ZF-/~SR measurements in YFe2. The solid lines show the temperature dependence of the saturation magnetizations (from Barth et al. 1986a).
122
A. SCHENCK and EN. GYGAX '
140
•
'
'
'
'
t
•
1.0 O~
TmFe2
120
0.9 B~,~= 0 T
~" -r
100
>,
80
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O
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0.8 0.7
•
t-
0.6
•
0
•
o" ,~
B~ (T)
0.5
60
•
0.4
40 -
0.3 0.2
200.1
I 0
100
200
300
400
500
600
Temperature (K) Fig. 4.13. Temperaturedependenceof the spontaneous field B~ from ZF-/zSRmeasurements in TmFe2. The solid lines show the temperature dependence of the saturation magnetizations (from Barth et al. 1986a). where the contact hyperfine field is the only microscopic field contribution. The temperature dependencies of the extracted Bc are shown in fig. 4.14. The contact hyperfine field seems to derive mainly from the M-sublattice. In YFe2 and LaFe2 this is a trivial conclusion. It is found from the study of the dependence of B~, on an external field that/3c is antiparallel to the Fe-moment direction or the Fe-sublattice magnetization. In GdFe2 and GdCo2, /3c is determined to be parallel to the total magnetization. Since the total magnetization is determined by the Gd-sublattice magnetization and in view of the antiferromagnetic coupling of the two sublattices one arrives again at the conclusion that Be and the Fe or Co-sublattice magnetizations are antiparallel. Finally in TmFe2 the total magnetization drops to zero at ~ 225 K (see fig. 4.13), where the two sublattice magnetizations happen to cancel, but this is not reflected at all in the #SR-data suggesting again that Bc is induced by the M-sublattice alone. Extrapolating Bc(T) in fig. 4.14 to zero temperature and plotting the Bc(0) versus the value of the ordered moment on the M-atoms one finds indeed a reasonable linear scaling as can be seen in fig. 4.15. No scaling is observed if Bc(0) is plotted versus the value of the ordered moment on the R-atoms. To the extend that #+-diffusion and trapping can be ignored fig. 4.14 displays then basically the temperature dependence of the M-sublattice magnetization in qualitative agreement with results from neutron scattering experiments (Bargouth et al. 1971). ZF-studies were also performed on DyNi2 and GdNi2 in the paramagnetic phase (Chappert et al. 1986b, Dalmas de R6otier et al. 1990b) with the aim to study
MUON SPIN ROTATION SPECTROSCOPY I ]
!
I
t
..,,.To
Bhf 0.4 ~ (T) 0.0
I
l
123
I
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I
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~
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Oom~ i
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i
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-
/
0.4 [-0.0~
• T. I
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~°
t
I -
GdFe2
• • leIO
0.4n0
,
-
" " " ''.~L,. 200
t 4
400 600 Temperature (K)
800
Fig. 4.14. Temperature dependence of the contact hyperfine field Be(0 K) in various RMa-compounds (from Barth et al. 1986a).
I
1.0-
I
I
T = OK
"--
TmFe2 e ~ _~.41~GdFe2 ~ ' ~ e 2 eC°' ErFe2 GdC°2
-z m___ 0 . 5 - ~ 0.0 ~" 0
I
t 0.5
i I 1.0 1.5 I~ of M atom (~ta)
I 2.0
2.5
Fig. 4.15. Correlation of/3c(0) with the M-atom magnetic moment in various RM2-compounds (from Barth et al. 1986a).
124
A. SCHENCKand EN. GYGAX
the spin dynamics in this range. The observed ZF #+-relaxation rate in GdNi2 is very similar to the corresponding one in GdA12. At room temperature one finds ,kzF(GdA12)/)~zF(GdNi2) = 0.23/0.42 ~_ 0.55(10) which agrees reasonably well with a calculated ratio of 0.32 invoking only the RKKY mechanism. The temperature dependence of ~zF(DyNi2) is also quite similar to the one in DyA12 but the room temperature ratio ,kzF(DyA12)/),zF(DyNi2)= 0.67/0.37 = 1.8(4) is in severe disagreement with a calculated value of 0.21. Various possible explanations for this disagreement are discussed in Chappert et al. (1986b).
4.2.2.2. RMn2 (R = Y, Tb, Dy). In contrast to the compounds covered in the two preceedings sections the cubic Laves phase compounds with M = Mn are antiferromagnets (see table 4.5). Of particular interest is YMn2 which displays a first order strongly hysteretic phase transition to an antiferromagnetic, long wave length helical state at ~ 100 K built from local moments (/~m ~ 2.7#B), while its behaviour above TN is that characteristic for a weak itinerant electron Pauli paramagnet and is described by the self consistent renormalization (SCR) theory of Moriya (1985). The collaps of the local moment at TN by ,,o 30% is accompanied by a decrease of the unit cell volume of 5%. The local moment can be destabilized by external pressure or by replacing Mn by an element with a smaller ionic radius. On the other hand substitution by an element with a larger ionic radius (providing 'negative' chemical pressure) is expected to stabilize the local moment on the Mn site. Similar effects can be induced by substitution of Y. Neutron scattering work revealed that strong antiferromagnetic correlations persist to at least 6TN. #SR work on this system was started with the aim to learn more about the spin dynamics and the change from local to itinerant moment behaviour (Asch et al. 1990, Cywinski et al. 1990a, 1991, Cywinski and Rainford 1994, Weber et al. 1994). Pure YMn2 has been investigated by both ZF and TF-techniques. TF-results (Hext = 22 mT) of Cywinski et al. (1991) are displayed in fig. 4.16 for both ascending and descending temperature scans. The hysteretic nature of the phase transition is clearly visible from the shifted drop in the signal amplitude, which signals the onset or the destruction of the ordered phase. The loss of asymmetry below TN reflects the appearance of a very wide internal field distribution over the #+ sites which induces an extremly rapid #+ depolarization within the dead time of the spectrometer. The appearance of a wide field distribution is in line with the long wave length helical magnetic structure in the ordered state. The approach of the transition temperature from above in both scans is accompanied by a quasi divergent behaviour of the TF-relaxation rate )~2 = l/T2. )k2 could be affected by various contributions and effects which were not considered in detail: powder broadening, nuclear dipole fields, fluctuating fields from the electronic moments, #+-diffusion etc. Weber et al. (1994) by a combination of TF, LF and ZF results find a somewhat modified temperature dependence of the signal amplitude A as shown in fig. 4.17. Most interesting is a drop of A starting below ~ 150 K. This drop results from the appearance of a rapidly damped component which is not taken into account in the analysis leading to fig. 4.18 and which signals the evolution of another magnetic phase in part of the sample volume above TN. Interestingly this fast component is
MUON SPIN ROTATIONSPECTROSCOPY 0.10
I
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125
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(a)
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-
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300
0.25
II
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llll~
..iil.I.II ~ ~warming
.I6 ....
0.20
~" 0.15 E E >.,
o~
<
cooling
22
0.10
0.05
0.00
(b)
II I IIIII IIIII II II IIIII IIII1 0
1O0 200 Temperature (K)
300
Fig. 4.16. Temperaturedependence of signal amplitude (asymmetry) and relaxation rate ),2 from TF measurements (Hext = 2.2 mT) in YMn2. The solid lines are guides to the eye. Not shown explicitely are the ),z-data points on cooling. Note the hysteretic behaviour (from Cywinski et al. 1991). best fitted by a stretched-square root-exponential decay function (see eq. (2.21)) as appropriate for a dilute spin glass above the freezing temperature. LF-measurement show that this component is purely dynamical in origin and independent of the applied field strength (Hext < 0.2 T). The evolution of the fast component could be interpreted as following from the development of spin glass like clusters, starting well above the transition into the long range ordered state. The same and even more pronounced behaviour was also found in Tb doped samples of composition Yo.9Tbo.lMn2 (Asch et al. 1990) and Y0.95Tb0.osMn2 (Weber et al. 1994). Here the damping rate in the spin glass like phase could be extracted (~1 ~- 1 #s -1) and
126
A. SCHENCK and EN. GYGAX I
I
I
I
100
50 13.
E <
0 0
1 O0
200
Temperature (K) Fig. 4.17. Temperature dependence of the signal amplitude derived from a combination of TF, LF and ZF measurements in YMn2. For the slight drop at 150 K see text (from Weber et al. 1994).
~ 3.014 >
3.012 I
4-"
,5~
o
~ 3.013 I
I
~' I
I
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/
Q ,..z-~3£X300.O o °_~ ' ' - - P-- - - 0 - - 0 - 0 - 0 - 0 - . . 0 - - 0 -
0.20
b)
2• 015
1
0.20
015
,~ o.lo
o.lo .~
0.05
0.05
0.0
t
0
t
t
100 Temperature
t
200
t
300
(K)
Fig. 4.18. Temperature dependence of signal amplitude (asymmetry), relaxation rate ),2 and precession frequency from TF-measurements (Hext = 22 roT) in Y(Mn097Fe0.03)2 (from Cywinski et al. 1990a). was found to have no significant temperature dependence. Some preliminary studies were also undertaken on Sc-doped (substituting for Y) samples (Weber et al. 1994). Due to the limited amount of data the results will not be discussed here. Further TF-#SR studies were performed on Fe substituted Y(Mnl_=Fex)2 (Cywinski et al. 1990a). Neutron diffraction and susceptibility measurements (Cywinski et al. 1990b) imply that as little as 2.5% substitution of Fe for Mn suffices to suppress magnetic order altogether and to induce Pauli paramagnetism. This was basically confirmed by #SR results on a sample with z = 0.03. However, neutron polarization analysis measurements (Cywinski et al. 1990a) show the persistence
MUON SPIN ROTATION SPECTROSCOPY
127
TABLE 4.6 #+-hyperfine fields extrapolated to T = 0 K and contact hyperfine coupling parameters Ac. Also listed is the ordered moment on the M-ions (Barth et al. 1986a).
GdFe2 GdCo2 YFe2 TmFe2 ErFe2
/~hf(0)
Ac
(T)
(T/LtB)
0.7 0.41 -0.6 0.8 0.6
-0.43 -0.40 -0.41 -0.47 -0.35
/ZM/#B 1.62 1.02 1.45 1.7 1.7
of antiferromagnetic correlations in the paramagnetic state over a wide temperature range. The neutron results could not distinguish between the possibilities that these correlations are static, reflecting perhaps topological magnetic frustration of localized Mn moments on a tetrahedral lattice, or are dynamic on the time scale of longitudinal fluctuations of the Mn spins. The TF-#SR relaxation function is very well described by an exponential function implying a dynamical origin and the temperature dependence of the relaxation rate A2 is displayed in fig. 4.18. It is well reproduced by the expression A2(T) = C T - x with z = 0.75, C = 1.12 # s - l ( K ) x. In contrast no temperature dependence in the precession frequency (Knight shift) could be detected in agreement with the picture of a Pauli paramagnet. The increase of A with decreasing temperature signals a slowing down of the Mn spin dynamics. It is argued that it does not arise from a slowing down of transverse spin fluctuations but instead from a slowing down of longitudinal spin fluctuations reflecting the localization of the moments on the Mn(Fe) sites. In any case the #SR-data are inconsistent with the evolution of static correlations and thus help in the interpretation of the neutron results. Substituting Mn by A1 instead of Fe leads to a 'negative' chemical pressure and the expectation that it stabilizes the local moment on the Mn site. Indeed a slowing down of spin fluctuations has been claimed in A1 substituted Y(Mnl_~AI~)2 (Motoya et al. 1991) and for z > 0.06 the volume collapse is suppressed and a spin glass like state is found at low temperatures. #SR-measurements on a sample with z = 0.1 clearly confirms spin glass order below Tg = 60 K (Cywinski et al. 1994b). Powder samples of DyMn2 and TbMn2 were studied by a few TF-#SR measurements only (Cywinski et al. 1992). Below TN the #SR-signal is lost completely. Above TN Fourier transforms of the #SR-spectra show the development of a pronounced asymmetric line shape as the temperature approaches TN from above. This feature which, in part, may be due to powder broadening has so far prevented a detailed interpretation of the results. Very preliminary ZF-measurements on TbMn2 (Weber et al. 1994) show a rather complex behaviour suggesting the coexistence of static and dynamic correlations already at relatively high temperatures (250 K).
128
A. SCHENCKand EN. GYGAX
4.2.3. Binary compounds with NaCl and CsCl-structure A list of compounds studied by #SR is found in table 4.7. The magnetic behaviour of all these compounds is rather complex and is characterized by a delicate interplay of various exchange and anisotropy mechanisms.
CsAs. W-measurements (0.02 T) in this compound display a strongly temperature dependent exponential relaxation rate ),2 below 9 K with a sharp singularity at 7.6 K, as shown in fig. 4.19 (Asch et al. 1988, Litterst et al. 1990). This temperature is identified with TN. At the same temperature the onset of a spontaneous spin precession is observed (at 4 K: u, -~ 24 MHz or B , "-~ 0.177 T). ZF-measurements reveal additional subtle features. Here a rapidly damped component appears already below 9 K and can be followed down to 7.6 K. At 7.3 K the spontaneous oscillating component undergoes a drastic change in spectral appearance (see fig. 4.20). The following scenario is suggested by these results: above 100 K the Ce-spins fluctuate freely (paramagnetic fluctuations); below this temperature spin correlations develop which, in part of the volume, lead to short range order below 9 K; at 7.6 K long range order sets in with a change in magnetic structure at 7.3 K. The change in structure at 7.3 K may reflect a transition between the single ( a n d triple q structure which both may have been seen in CeAs (H~tlg and Furrer 1986, Buffet et al. 1984) and which theory predicts to be nearly degenerate (Prelovsek and Rice 1987). Some interesting correlations are found in another neutron scattering study (H~ilg et al. 1987), where magnetic Bragg peaks appear already at 8.5 K and where short range ordered critical spin fluctuations peak at 7.3 K. A problem is connected with the observation of a rather broad spontaneous precession signal. If, as usual for these cubic compounds (see also section 4.3.2) the #+ is placed at the center of the cube formed by four Ce and four As atoms (see fig. 4.21) dipolar field calculations lead for both the single ~ and the triple q"structures to zero net dipolar fields at this site. As a way out it has been suggested that the presence 0.30
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v
0
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._o 0.15
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Temperature (K)
Fig. 4.19. Temperaturedependenceof transverse fieldrelaxationrate ,k2 ( n e x t Litterst et al. 1990).
=
20 mT) in CeAs (from
MUON SPIN ROTATION SPECTROSCOPY Ox O~
o~ ,,~
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129
130
A. SCHENCK and EN. GYGAX 2.0
1.0
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8K
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7.5K
2.o o
7.4K
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0
7.OK ~
lb
1~ 2b 2~
3'o
1.0 o
0
4K 10 20 30 Frequency(MHz)
40
Fig. 4.20. Fourier power spectra from ZF-measurements in CeAs. Note the change of the spectral distribution around 7.4 K (from Litterst et al. 1990).
of the #+ alters locally the spin structure which may not be unreasonable in view of the delicate balance of the various competing exchange interactions etc. CeSb. A total of 6 different AF phases are observed in this compound (Fischer et al. 1978). The magnetic structure results from a temperature dependent stacking of paramagnetic and ferromagnetic (001)-layers with the Ce 3+ spins pointing along +(001). The observed spin modulations can be described by a single wave vector q'0 = (27r/c)(0, 0, q) where q falls between 1/3 and 2/3 in fractions of integers and hence indicates a commensurate behaviour of the spin modulations (see table 4.8).
MUON SPIN ROTATION SPECTROSCOPY
)o
•
( ®
I
131
( @
o
~:
Fig. 4.21. Crystal structure of fcc RX-compounds (X = pnictides, chalcogenides). Indicated is the most likely/z+-site.
Placing the #+ again at the previously assumed site (see fig. 4.21) three different magnetic environments can be identified with populations depending on the exact value of q. At one type of site the net dipolar field vanishes ( u u = 0), at the two other sites non zero dipolar fields are calculated corresponding to precession frequencies of u~ = 16.5 MHz and u~ = 33 MHz. ZF-pSR measurements show the following behaviour (Klauss et al. 1994): Below TN two signals are found, one reflecting spin precession at 29.4(5) MHz and a second non oscillating signal displaying a stretched square root exponential behaviour. The relative amplitudes mirror nearly the expected populations for the sites associated with the u~, = 0 and u u = 33 MHz sites (see fig. 4.22). The sum of the amplitudes do not add up to the full asymmetry, seen above TN. The missing amplitude is assigned to the uu = 16.5 MHz site. Its absence is explained in terms of a very rapid damping of the corresponding #SRsignal arising from relatively slow fluctuations of the spins in the paramagnetic plane adjacent to this site. Consistent with the first order nature of the transition at TN the spontaneous frequency of 29.5 MHz is nearly constant in the whole antiferromagnetic temperature regime. In contrast above TN a rising relaxation rate (following from both TF and ZF measurements) with decreasing temperature proves the existence of TABLE 4.8 List of AF phases and related quantities in CeSb (Klauss et al. 1994). Phase
Temperature range (K)
q
I II III IV V VI
15.9-16.1 15.3-15.9 13.7-15.3 11.0-13.7 8.9-11.0 2.2-8.9
2/3 8/13 4/7 5/9 6/11 1/2
Population (in %) of sites with u=0
u=16.5MHz
u=33MHz
33.3 38.5 42.8 44.4 45.4 50
66.7 46.1 28.6 22.2 18.2 0.0
0 15.4 28.7 33.3 36.4 50.0
132
A. SCHENCK and EN. GYGAX 0.05
I
I
I
I 10
I 15
0.04
E E
0.03
I
I
0.02 0.01 0 0
5
20
Temperature (K) Fig. 4.22. Temperature dependence of the amplitude (asymmerty) of the 29.5 MHz signal (from ZF and 5 mT-TF measurements) in CeSb. The horizontal solid lines represent the predictions according to table 4.8 (from Klauss et al. 1994).
spin fluctuations which slow down upon the approach of TN. This has also been observed in diffuse critical neutron scattering (Halg et al. 1985).
DySb. This compound shows a MnO-like antiferromagnetic (AF II) structure (Felcher et al. 1973). Dipolar field calculations predict a single frequency of 210 MHz at the #+-site considered before. In contrast ZF-#SR measurements (Klauss et al. 1994) reveal two signals with nearly the same amplitudes, one displaying a spontaneous precession with uu _~ 240 MHz and zero frequency the other one. The latter signal displays again a square root exponential relaxation with A ,-~ 10 #s -1. The relaxation seems to be purely of dynamical origin since it could not be quenched in LF-runs up to 0.6 T. The appearance of two signals can be understood if instead of the MnOlike magnetic structure a CoO-type structure is considered. One then predicts two magnetically inequivalent sites with the same statistical weight and zero frequency at one site and ~300 MHz at the other site. Such a structure, however, seems to be severly at odds with earlier neutron results (Felcher et al. 1973). Again the observed spontaneous precession frequency is nearly temperature independent consistent with the first order nature of the transition. However, the ZF relaxation rates show a strong increase as TN is approach from both above and below. TF-measurements above TN reveal an anomalously strong increase of the (negative) Knight shift below 20 K on approaching TN (Klauss et al. 1994). If the CoO-type structure is adopted it can be explained by the onset of a quadrupolar anisotropy some degrees above TN which would be in line with earlier structure studies (Chen and Levy 1971).
CeAg, CeAgo.97Ino.03.CeAg as well as other RX (X = Cu, Ag etc.) compounds with cubic CsC1 structure have attracted much attention due to their magnetic and structural properties which are governed by one ion magnetoelastic couplings and two
MUON SPIN ROTATION SPECTROSCOPY 0.20
133
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CeAg l_xlnx(x=O.03)
O CeAg O
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Fig. 4.23. Temperaturedependence of ZF signal amplitude(asymmetry)and relaxation rate in CeAg and CeAgo.97Ino.o3(fromHyomiet al. 1988). ion quadrupolar interactions (Morin and Schmitt, 1990a). CeAg shows a martensitic transition into a tetragonal phase at TQ _~ 15 K which is followed at Tc = 5 K by a second order transition into a ferromagnetically ordered state. The structural phase transition is driven by quadrupolar ordering (Morin, 1988). Substituting In for Ag it is found that TQ increases strongly with In concentration (Ihrig and Lohmann, 1977). There is some debate as to the nature of the structural instability in substituted compounds CeAgl_xIn= with z > 0.01 which does not seem to arise from quadrupolar ordering. ZF- and TF-#SR measurements on polycrystalline samples of CeAg and CeAg0.97In0.03 were aimed at a study of the structural phase transition (Hyomi et al. 1988) while the magnetically ordered phase was not investigated. Previously the #+ Knight shift was studied in the nonmagnetic series LaAga_=In= for 0 ~< z < 0.3 (Wehr et al. 1983). Figure 4.23 shows ZF relaxation rates ),ZF and the signal amplitudes as a function of temperature. In CeAg0.97In0.03 Azv starts to rise below ~ 25 K, reflecting the slowing down of the spin dynamics as the second order magnetic phase transition is approached, but no sign of the structural phase transition is manifest in these data. In contrast the behaviour of AZF in CeAg is totally different. Again below about 25 K AZF starts to rise. But concomitantly the signal amplitude starts to drop pronouncedly. This is due to the development of a very rapidly decaying component which could not be resolved in these experiments performed at the pulsed #+ source at KEK (Tsukuba, Japan). These results suggest that static spin correlations develop already around and below 25 K, leading to a wide distribution of static fields at the #+-sites quite in contrast to the situation in the In doped compound. Whether this different behaviour is connected to the nature of the structural phase transitions remains to be studied. Measurements with much improved time resolution would be extremely interesting.
DyAg. This compound displays antiferromagnetic order below TN = 60 K but no structural instability. Neutron diffraction has established that the spin order just
134
A. SCHENCK and EN. GYGAX
below 60 K is an incommensurate sinusoidally modulated structure which below 51 K transforms to a type I non-collinear triple (structure (Kaneko et al. 1987). The presence of two transition temperatures is also indicated by bulk magnetic and transport studies (Morin et al. 1990b, Sousa 1990). These findings are nicely corroborated by ZF and LF-#SR measurements on poly and monocrystalline samples (Asch et al. 1984, Kalvius et al. 1986, 1987, 1990). Approaching TN from above one observes a strongly rising relaxation rate as expected for a second order phase transition. At 300 K one finds )~ = 0.9 #s -1 which is of the same order of magnitude as in DyAI2 (see table 4.4). At TN the relaxation function changes from exponential to a stretched exponential without any drastic change in the overall relaxation rate. A further change occurs at ,,~ 51 K, below which a dynamic Lorentz-Kubo-Toyabe function describes the ZF-signal best. With further decreasing temperature a more and more static Lorentz-Kubo-Toyabe signal develops. Figure 4.24 shows the temperature dependence of the width A and of the fluctuation rate u extracted from the dynamic Lorentz-Kubo-Toyabe fits. No oscillating signal is seen below TN. This finds its explanation in the fact that at interstitial sites of high symmetry the sum of all dipolar fields from the ordered moments is zero. The Lorentzian shape of the residual field distribution at the #+ implies that the magnetic structure is nearly perfect and that any distortions (e.g., magnetic holes) are dilute and not too close to the #+. A surprising and unusual result is the increase of the width ,4 with increasing temperature. It is interpreted as being due to an increasing de-locking of the triple (magnetic structure and concomitantly, a progressive increase of a slight 10
,
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rr
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P Rate
,
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00
I
10
I
I
20 30 40 Temperature (K)
L
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0
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MUON SPIN ROTATIONSPECTROSCOPY
135
incommensurability (invisible to neutrons) as one moves toward the incommensurate phase commencing at ~ 51 K (Kalvius et al. 1990). The stretched (power) exponential relaxation behaviour between ~ 51 K and 60 K, which should be associated with the incommensurate sinusoidally modulated structure, has not been rationalized yet. Some #SR-measurements have also been performed on amorphous DyAg which orders ferromagnetically at Tc = 18 K (Kalvius et al. 1986, 1987). A very rapid relaxation is seen to develop below 100 K leading to a loss of the signal below 90 K consistent with M6sslauer measurements (Chappert et al. 1982). This signals a massive slowing down of the spin dynamics and a wide distribution of local fields due to random distortions of the local symmetry in the amorphous state.
4.2.4. RNi5 compounds The RNi5 compounds crystallize in the hexagonal CaCu5 structure (see fig. 4.25) and for heavy R (Gd,...) undergo a transition into a ferromagnetic state at temperatures below 37 K (see table 4.9). PrNi5 is a Van Vleck paramagnet which shows hyperfine enhanced nuclear spin ordering at 0.4 mK (Kubota et al. 1980). ZF and TF-#SR measurements on the nonmagnetic reference compound LaNi5 indicate that the #+ is immobile up to 150 K and most likely occupies the f-site (1/2, 0, 0) which is also found to be occupied by hydrogen in the a-phase of LaNisHx (Dalmas de R6otier et al. 1990c). In PrNi5 the i-site, located near the f-site, was unambiguously identified to be the #+ site from the angular dependence of the #+Knight shift [Feyerherm et al. (to be published), a previously claimed multiple site occupation in PrNi5 (Kaplan et al. 1989, Hitti et al. 1990a) could not be confirmed in subsequent studies on several new high quality samples]. As reviewed below, the magnetic properties as sensed by the #+ are largely determined by the crystalline electric field (CEF) split ground state multiplet of the 4f-electrons affecting both the static and dynamic behaviour.
)
) OU
~Ni ~AI
Fig. 4.25. Crystal structure of the hexagonal CaCu5 type. Indicatedare various possible #+-sites: b, f, h, o, m with multiplicities of 1, 3, 4, 12, 6 per unit cell, respectively. The i-site (not shown) is found along the c-axis above or below the f-site.
136
A. SCHENCK and EN. GYGAX
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.= o
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MUON SPIN ROTATIONSPECTROSCOPY
137
GdNis. Zero field measurements on a single crystalline sample with fi(0) perpendicular to the c-axis at 3.3 K, i.e. below Tc, revealed two spontaneous precession signals with Ul = 5.3 MHz and u2 = 220.9 MHz with an amplitude ratio al : a2 of ~ 3 : 2. Obviously two different #+ sites must be involved. If fi(0) is chosen parallel to the c-axis no oscillating components are seen (Gubbens et al. 1994a). These results imply that the spontaneous local field at the #+ site is oriented parallel to the c-axis and suggest further that the c-axis is the easy axis. This conclusion is inconsistent with magnetization measurements (Gignoux et al. 1976) but agrees with M6ssbauer data (e.g., Tomala et al. 1977). The ZF-relaxation ),ZF has been measured for fi(0)H c-axis from room temperature down to 0.2 K. The results are shown in fig. 4.26. At high temperature AzF is temperature independent as expected for a Heisenberg magnet, neglecting the Korringa mechanism (see also section 4.2.1). The sharp increase of AzF in the vicinity of Tc reflects the critical slowing down of the spin dynamics. Since the temperature reading was not very accurate these data cannot be used for the determination of critical exponents. Relaxation can also be seen below Tc, involving the full asymmetry, which, below ~ Tc/2, varies approximately like T 2 ln(T) (solid line in the insert of fig. 4.26). This behaviour points to a two magnon scattering process (Dalmas de Rdotier and Yaouanc, 1994b). Fitting with the appropriate function a spin wave stiffness constant of D = 4.2(2) meV ,~2 is deduced. Note that this analysis does not require knowledge of the #+-site (Gubbens et al. 1994a). I''''
I''''1''''1''''
.
....
i ....
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:
0.10 F 0,08 [-
4
.
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. . . .
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T e m p e r a t u r e (K) Fig. 4.26. Temperature dependence of the ZF-relaxation rate in GdNi 5 for P(0)llc-axis. The insert shows the data below Tc On an expanded scale. The solid line is a fit to a two magnon scattering process (from Gubbens et al. 1994a).
138
A. SCHENCK and EN. GYGAX
TbNi5. This compound displays a strong magnetocrystalline anisotropy and the ordered moments point along the a-axis. Information on the CEF-levels of Tb 3+ can be found in Gignoux and Rhyne (1986). ZF-#SR measurements on a single crystal sample were performed below and up to Tc (Dalmas de R6otier et al. 1992). A single spontaneous precession signal was observed the temperature dependence of which is displayed in fig. 4.27. According to section 2.2 /~
:
4~r
(4.13)
~ - ]~fs -}- Bdip -}- Bc
~: gj/ZB (3~f)
(4.14)
assuming that the contact hyperfine field/3c c~ (~f). As shown in section 3.1 this is not generally true, but may be a reasonable assumption here by noting that Tc << (90. The temperature dependence of {~f) was calculated in a mean field approximation taking into account the CEF splitting of the Tb 3+ ground state multiplet (Gignoux Illllllllllllll
IIlllllll
80
~" 6o 4O
g (~
20 0
TbNi~
30 rid
20
c E
10
+++
-
0 IlllJltq~ll,lllltllllll 5 10
0
15
20
Temperature(K) Fig. 4.27. Temperature dependence of the spontaneous precession frequency and associated relaxation rate below T c in TbNi5 (from Dalmas de R6otier et al. 1992).
MUON SPIN ROTATION SPECTROSCOPY J
t
~
v
uul~
n
t
i
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139 ;
t
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CPOo
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i
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t
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i
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i
i ill
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Temperature (K) Fig. 4.28. Log-log plot of the ZF relaxation rate versus temperature for P(0)llc-axis and/~(0)_Lc-axis, respectively in ErNi5. Data shown by filled (open) symbols were obtained at the ISIS facility of the Rutherford-Appleton Lab. (at the Paul Scherrer Institute) (from Gubbens et al. 1994a).
and Rhyne, 1986). It is represented by the solid line in fig. 4.28 and reproduces the data very well. The dashed line is a Brillouin function obtained by ignoring the CEF interactions. Obviously CEF-effects are important and cannot be ignored. However, choosing a different set of CEF parameters, one obtains about the same results as represented by the solid line (Dalmas de Rdotier et al. 1992). ZF relaxation rates measured above Tc (Dalmas de R6otier et al. 1990c) as well as the relaxation of the precession signal below Tc have not yet been explained but, at least for T > Tc, seem to be also significantly affected by the CEF-splitting.
DyNis. Gubbens et al. (1994a) report that their ZF-results on DyNi5 resemble basically those on TbNis.
ErNis. Like in TbNi5 a huge magneto crystalline anisotropy is found in ErNi5 which leads in the ordered state to an easy axis parallel to the c-axis below Tc = 9.2 K. ZF-/zSR measurements on sing~ crystals display strongly anisotropic features (Gubbens et al. 1992, 1994a) For P(0)±c-axis no signal is found below Tc. Above Tc the ZF signal is well described by a single exponentially damped component. The relaxation rate Az~c rises steeply with decreasing temperature and becomes so short below ~ 55 K that the signal is altogether lost (see fig. 4.28). For f(0)llc-axis a single exponentially damped signal is found above about 7 K while below 7 K two components are revealed, one of which is temperature dependent. However, already at around 12 K, the signal amplitude drops by ~- 25% indicating that a corresponding fractions of #+ are relaxed extremely fast, reflecting perhaps the on-set
140
A. SCHENCK and EN. GYGAX
of static spin correlations in part of the volume already at around 12 K. The temperature dependence of the relaxation rate ),lzl~ is displayed in fig. 4.28 too. It shows a maximum at around 12 K (!) and is much reduced from ,kzX~up to ,,~ 200 K. The observed anisotropy thus persists to temperatures T ~ 20Tc. Gubbens et al. 1992 could explain qualitatively the high temperature anisotropy in terms of a mean field picture including the CEF splitting in a very approximate way. For P(0)_Lc-axis an exponential temperature dependence of )~ZF at low temperatures is predicted while )~lzl~ is only weakly temperature dependent. According to a 166Er-MSssbauer study the spin fluctuations are very slow (quasi static) below 50 K (Gubbens 1989). This may be in line with the up turn of ) ~ below around the same temperature. The slow fluctuations are thought to arise from an indirect process between the two levels of the Kramers ground state doublet. The temperature dependence of ,klZlFbelow Tc is very well described by the expression A(T) = a ctg ( A / kBT) + bT 7
(4.15)
with a = 0.15 MHz, A/kB /> 5 K and b = 1.1 Hz/K 7 (solid line in fig. 4.28). This functional dependence is a clear signature for a phonon induced relaxation mechanism which is produced by the magnetoelastic coupling of the 4f spins to lattice vibrations. The first term corresponds to a one phonon process and the second to a two phonon process, respectively. The fitted parameters have not been quantitatively explained yet. TmNis. ZF-measurements on single crystal samples above Tc (Gubbens et al. 1994a) yield spin fluctuation rates which for both orientations/5(0)1 ]c-axis and/5(0)_Lc-axis show identical temperature dependencies and agree very well with 169TinM6ssbauer
lo
"t
=.E.
t ~''
.E
"4-'~_
°
.o
}+C~
1
4)0
;,2
bauer
TmNi s
o
0.1 I ....
0
I,,~
50
JL,~
JlT~,,I
....
100 150 200 Temperature (K)
I~,~L
250
Fig. 4.29. Temperature dependence of the Tm-4f moment fluctuation rates in ZF normalized to corresponding M/~ssbauer data in TmNi5 (from Gubbens et al. 1994a).
MUON SPIN ROTATIONSPECTROSCOPY
141
results. Figure 4.29 shows the temperature dependence of the corresponding correlation times "r (= reciprocal fluctuation rate). Since the #+ site and related coupling parameters to the Tm 3+ moments are not known fig. 4.29 shows essentially ~IzlF(T) and )~-~(T) normalized to the M6ssbauer results. The observed functional form of the temperature dependence has not been explained yet.
YbNis. YbNi5 has a very low ordering temperature of only ~ 0.5 K (Hodges and Bonville, unpublished results). ZF-#SR and M6ssbauer measurements on a polycrystalline sample were performed from 0.1 K up to room temperature (Bonville et al. 1994). The temperature dependence of the #+ relaxation rate agrees very well with the temperature dependence of the spin fluctuation correlation time "r extracted from the M6ssbauer data. It is found that the fluctuation rate increases linearly with temperature (i.e. AzF oc 1/T) pointing to a Korringa type mechanism as the driving force. Compared to ErNi5 and TmNi5 the relaxation rates are much larger and much less temperature dependent. It seems that CEF effects are less important in YbNi5 than in the two other compounds. PrNis. Somewhat out of order we will also briefly review some TF-#SR results on this singlet ground state compound which does not show electronic magnetic order. The previous discussion of results in TbNis, DyNis, ErNis, TmNi5 and YbNi5 rested to some extent on CEF-induced effects. It was hereby assumed that the implanted #+ does not modify the CEF-Hamiltonian governing the nearest neighbour rare earth ions. That this assumption may be grossly in error is demonstrated by #+ Knight shift measurements in monocrystalline PrNi5 where the #+ site is unambigeously identified with the interstitial i-site (Feyerherm et al. 1994b). It is found that while the Knight shift at high temperatures (i.e. above 50 K) scales very well with the bulk susceptibility this scaling is totally lost at lower temperatures. The result can 0.45
_~l
0.40 \
i
;¢y
I
I
i
i
I
I
!
. . . .
"5 0.35
y
0.25
T
.~ 0.20
=o_ o.15 0
0.10
m
0.05 0.00
0
20
40
60
80
1O0
Temperature (K) Fig. 4.30. Temperature dependence of the local susceptibility in the basal plane of PrNi 5 sensed and modified by the/z + via the Knight shift (dipolar and contact) for two different directions defined in the
insert (fromFeyerhermet al. 1994b).
142
A. SCHENCK and EN. GYGAX
PrNi 5 E( 1 )
5
48 K -
-
r6
39 K -
-
23 K - -
v4
o
p e r t u r b e d by IJ+
\
-
-
45K
-
-
37K 23 K
7.5K 0
Fig. 4.31. Crystal field splitting of the 3H4-ground state multiplet of Pr3+ in PrNi5 without (undisturbed) and with (disturbed) the/~+ at the interstitial i-site (only nearest neighbour Pr3+ are considered) (from Feyerherm et al. 1994b and private communication). be used to extract an effective local susceptibility which in the basal plane becomes anisotropic as shown in fig. 4.30. The solid lines represent a fit to a CEF-model in which the CEF parameters B2°,/322 and the exchange parameter A were allowed to vary independently. A best fit was obtained for B ° = 0.54 MeV (0.51 MeV) B 2 = 0.08 MeV (0 MeV) and A = 2.7 mole/emu (4.73 mole/emu). The values in parenthesis refer to bulk parameters as obtained from inelastic neutron scattering (Amato et al. 1992a). Figure 4.31 compares the CEF level schemes with and without the #+ induced perturbation. Of particular significance is the appreciable lowering of the first and second excited levels. Point charge model calculations failed to reproduce the fit results but it is clear that the #+ introduces an additional electric field gradient and destroys the local symmetry on the nn-Pr sites. The #+ induced perturbation may be particularly important in the case of singlet ground state ions but may be also non-negligible in other cases showing a CEF splitting. In GdNi5, however, no #+ induced effects would be expected (see also the discussion in section 3.2 and Campbell 1984, Schillaci et al. 1984).
4.2,5. Ternary compounds with tetragonal ThCr2Si2 structure Table 4.10 presents a list of investigated compounds. Two more compounds with the same structure are treated in section 4.2.6 on heavy fermion systems (see table 4.11). ZF-#SR measurements in the nonmagnetic compounds YCo2Si2 and LaPd2P2 served to get an idea on the #+-site. Possible #+-interstitial sites in the ThCr2Si2 type structure are indicated in fig. 4.32. The observed zero field Kubo-Toyabe signals point to an occupation of site No 2 (1/2, 0, 0) or site No 4 (1/2, 1/4, 0) (Dalmas de R6otier et al. 1990a). The question is, of course, whether in all compounds with ThCrzSi2 structure the same site is necessarily occupied (see also discussion on CeRuzSi2, section 4.2.6 and URu2Si2, section 4.3.4). #+ diffusion is seen to set in above ~ 130 K (Dalmas de R6otier, 1990a).
MUON SPIN ROTATION SPECTROSCOPY
143
TABLE 4.10 List of ternary compound with tetragonal ThCr2Si2 structure investigated by #SR (see also table 4.11). Compound Magnetic structure
TN, TC (K)
#SR
Samples
References Dalmas de R6otier et al. (1990a) Dalmas de R6otier et al. (1990a) Dalmas de R6otier et al. (1990a) Yaouanc et al. (1994) Matokawa et al. (1990), Nojiri et al. (1992) Gubbens et al. (1994b)
YCo2 Si2
-
-
ZF
sintered powder
LaPdzP2
-
-
ZF
sintered powder
~ 35
ZF
sintered powder
CeRhzSi2
AF:single ~',/7[[c-axis
PrRu2Si2 PrCo2Si2
FM,/Tile-axis ~ 15 ZF s.c. AF, 4 metamagnetic 30 (9,17) ZF s.c. transitions NdRhzSi 2 AF: single ~,/Tllc-axis 57 ZE LF s.c., sintered powder
~
)
#
6
#3 i
.#7
5
© o • Ce Cu Si Fig. 4.32. Crystalstructureof tetragonaltenarycompoundsof the ThCr2Si2 type. Starsindicatepossible interstitial/~+ locations.
CeRh2Si2. Z e r o field data confirm the onset o f m a g n e t i c order at ~ 35 K ( D a l m a s de R6otier et al. 1990d), p r e v i o u s l y identified b y neutron scattering (Quezel et al. 1984a). T h e onset o f o r d e r manifests itself b y a drastically increased relaxation rate with no loss in the signal amplitude. M e a s u r e m e n t s at 22.5 K reveal an additional p r e c e s s i o n signal c o r r e s p o n d i n g to a spontaneous field o f ~ 11 m T at the # + position. Since no m e a s u r e m e n t s were m a d e in the range 22.5 to 33 K no information is available on the e v o l u t i o n o f the precession c o m p o n e n t which, as far as the limited data can tell, is not present yet a c o u p l e o f degrees b e l o w TN. The a p p e a r a n c e o f two signals a s s o c i a t e d with zero net field and 11 mT, suggest the o c c u p a t i o n o f two different sites. In fact, using the m a g n e t i c structure o f Q u e z e l et al. (1984a, b), one calculates d i p o l a r fields o f zero and 13 m T at the sites No. 2 and No. 4, respectively.
144
A. S C H E N C K and E N . G Y G A X
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MUON SPIN ROTATION SPECTROSCOPY
145
c~
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146
A. SCHENCK and EN. GYGAX
PrRu2Si2. In contrast to the other compounds in table 4.10 PrRu2Si2 shows ferromagnetic order below Tc = 15 K and has a giant magnetic anisotropy (anisotropy field Ha = 400 T (Shigeoka et al. 1992)) which seems to be much larger than in any other 4f-electron system reported so far. CEF effect are certainly very important but cannot account exclusively for the magnetic properties of this compound. ZF-/~SR measurements below Tc yield a spontaneous precession signal if fi(O)±caxis and only an exponentially relaxing signal if P(0)l]c-axis (Yaouanc et al. 1994). It follows that the local field B~ at the #+ must be oriented parallel to the c-axis (at T = 4.5 K, Bu = 0.0393(2) T). The relaxation behaviour and rates obtained below and above Tc are partially very puzzling and have not yet found an adequate quantitative explanation.
PrCo2Si2. This compound orders antiferromagnetically below TN = 30 K and shows metamagnetic transitions at 1.2 T, 3.8 T, 6.7 T and at the saturation field 12.2 T if an external field is applied parallel to the c-axis. In zero field two more transitions in the AF-structure appear at 9 K and 17 K (Shigeoka et al. 1987, 1989a, 1989b, Nojiri et al. 1992). ZF and LF-#SR measurements on a monocrystalline sample with/5(0) and the applied field parallel to the c-axis were initiated with the goal to monitor changes in the #+ spin lattice relaxation rate at the 12.2 T metamagnetic transition, exploiting the possibility to combine pulsed magnetic fields with pulsed #SR-spectroscopy at the pulsed muon source at KEK (Tsukuba, Japan) (Motokawa et al. 1990, Nojiri et al. 1992). Indeed an enhanced (by a factor of ,.o 10) exponential relaxation rate (~ 0.5 #s -1) compared to ZF-results at 4.2 K and 12 K was observed for longitudinal fields varying from ,-~ 8 T to 13 T at effective temperatures < 12 K. However, in view of the very large error bars, +(30-50)%, on the relaxation rates and possible systematic uncertainties it is premature to draw some physics conclusions from these results. More reliable are ZF-results. From 50 K down to 4.2 K exponential relaxation is observed without any loss of asymmetry. The temperature dependence of the relaxation rate AzF is displayed in fig. 4.33. It shows a pronounced and rather wide 1.0
1
&-0.8 •
E++
0.6
0
cO
0.4
rr
o
0
X
0.2
oo i
0.0 0
10
t 20
i
i 30
I 40
50
T e m p e r a t u r e (K)
Fig. 4.33. Temperature dependence of ZF relaxation rate in PrCo2Si2. The three different transitions temperatures are indicated by the dashed vertical lines (from Nojiri et al. 1992).
MUON SPIN ROTATION SPECTROSCOPY
147
maximum at ,-~ 25 K with essentially no clear hints on the transitions at 9 K, 17 K and 30 K. In particular no divergent type of behaviour is visible at TN. Nojiri et al. (1992) speculate that this behaviour arises from strong spin fluctuations in the long period AF structures between 30 K and 9 K, which can be viewed as a soliton like motion of domain boundaries.
NdRh2Si2. Antiferromagnetic order sets in at 57 K and, differently from CeRh2Si2, ferromagnetic (001) planes are coupled antiferromagnetically along the c-axis. ZFand LF-#SR measurements on monocrystalline samples yield the following results I ....
%-- 0.06 -i- 0.05 0.04
m
÷,~~ 0+ I ' ' ' ' 1
....
I ' ' ' ' 1
....
I ....
I ' ' ' '
NdRhzSi2 ÷
0.03 ~s~
o. 0.02 E r~ 0.01
• 0 mT
÷~
0.00 0 I
e 200 mT 50
. . . .
100 150 200 250 300 Temperature (K)
I
. . . .
{ . . . .
I
. . . .
I
. . . .
I ' ' ' ' 1
l
NdRh2Si2
.
ZE
zero field
v
:
:
r" .m
E
~,s.
0.1
G
a
k~°°°
|o
•
•
•
S S S l L I S : I * I t ' * ' I , * * ' I * * * L I ' * ' * I
0
50
100 150 200 250 Temperature (K)
300
Fig. 4.34. Temperature dependence of the ZF relaxation rate in NdRh2Si2. The upper part refers to /5(0)llc-axis, the lower one to /5(0)_Lc-axis. The dashed line in the upper part below TN follows a T 2 In(T) dependence, pointing to a two magnon mechanism for the relaxation (from Gubbens et al. 1994b).
148
A. SCHENCKand EN. GYGAX
(Gubbens et al. 1994b): ff/3(0) and Bext is applied along the c-axis an exponentially relaxing, non oscillating signal is seen, the relaxation rate )H of which is essentially independent of [/3extl, implying a dynamical origin of the relaxation. The data are shown in the upper part of fig. 4.34. The temperature dependence of A1 below TN seems to follow a T 2 ln(T)-law which points to a two magnon (Raman) process (Dalmas de R6otier and Yaouanc 1994b) as already indicated in the weakly anisotropic ferromagnet GdNis (see section 4.2.4). However, no quantitative analysis of this behaviour has been presented so far. On the other hand if P(0) is perpendicular to the c-axis the #SR signal is lost below TN, probably because the limited time resolution at the pulsed muon source of ISIS prevented the observation of a fast oscillating precession component. Taken together with the nonvanishing, nonoscillating component for/3(0)llc-axis it can be concluded that the spontaneous field at the #+ is oriented parallel to the c-axis. The relaxation rate for fi(0)_l_c-axis above TN is displayed in the lower part of fig. 4.34. In contrast to the other orientation a strongly divergent behaviour is revealed which signals a slowing down of the spin dynamics as TN is approached. Note that the rate close to TN is about two orders of magnitude larger than for the other orientation. Combining the results from both orientations it can be concluded that the fluctuating components are also essentially only present along the c-axis pointing to longitudinal spin fluctuations along the same axis. Due to limited precision in the temperature control the precise form of the critical slowing down could not be determined.
4.2.6. Rare earth based heavy electron and related compounds Intermetallics treated in this section possess quite different compositions, crystal structures and magnetic properties but have in common certain low temperature properties by which they are classified as heavy electron or heavy fermion compounds (see, e.g., Steglich et al. 1993). Included are also some systems which show nearly heavy fermion or Kondo system behaviour. The study of magnetic properties by #SR spectroscopy has been reviewed in detail by Schenck (1993). Short reviews have been presented by Amato (1994) and Heffner (1993). Table 4.11 lists all rare earth based heavy electron and related compounds which have been studied by #SRspectroscopy up to date (1993). Quite unique information could be obtained which was not available from other techniques. The most important pieces of information are compiled in table 4.12. CeAl2. This CeA12 moderately heavy electron compound possesses a rather complex incommensurate and modulated antiferromagnetic structure to be described by a multiple 0~arrangement (Shapiro et al. 1979). Interestingly the transition temperature is found to vary for different samples and seems to cluster either around 3.4 K or 3.9 K, respectively (Gavilano et al. 1993) #SR measurements were performed on both monocrystalline and polycrystaltine (powder) samples (Hartmann et al. 1989, Ott et al. unpublished (1993)). TF-#SR measurements (Hext = 15 mT) on a single crystal served primarily the purpose to determine the #+-site in this cubic Laves phase compound which was identified as the (2-2) site (see fig. 4.7) as in the other rare earth aluminides (see section 4.2.1) (Hartmann et al. 1989). #+-diffusion was shown
M U O N SPIN ROTATION SPECTROSCOPY
149
.,--t
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=
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A. SCHENCK and EN. GYGAX £ O~
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MUON SPIN ROTATION SPECTROSCOPY I
'
i
L
n
151
I
0.20
ooo~O Z" "$ 0.15 E E < 0.10
°
°
oe
0.05
i
i
r
i
i
3
i
i
4
Temperature (K) Fig. 4.35. Temperature dependence of the paramagnetic and the magnetically ordered volume fractions in monocrystalline CeA12 as reflected by the amplitudes (asymmetries) of the two components in the TF-#SR signal below TN = 3.9 K (from Hartmann et al. 1989). not to be important below ~ 80 K. The same measurements revealed the appearance of a two component structure below 3.9 K one reflecting a paramagnetic behaviour, the other one showing a very rapid damping rate reaching ~ 40 #s -1 at ~ 3 K. The temperature dependence of the amplitudes of the two components is shown in fig. 4.35. The rapidly damped component reflects the evolution of a wide static field distribution, consistent with an incommensurate, modulated antiferromagnetic structure. But, as fig. 4.35 implies, this order does not involve at once the total volume of the sample, but the ordered volume grows gradually from zero at 3.9 K to ~ 80% of the total volume at ~ 3.2 K. Is this unexpected behaviour somehow related to the observation of two different transition temperatures? Zero field measurements on a powder sample yielded essentially the same picture (Ott et al. 1993). The latter sample was also investigated by 27A1-NQR (Gavilano et al. 1993). No mentioning of a two component behaviour is found in this paper. The two component structure of the #SR signal in CeA12 around TN is not unique but can be found in several other rare earth based heavy fermion compounds (e.g., CeA13, CeCu2Si2, YbBiPt etc.) giving the impression that it may be a characteristic feature of this class of materials.
CeA13. Long thought to be paramagnetic down to at least 60 m K (Murani et al. 1980) it came as a real surprise that this archetypical representative of fermion systems revealed the presence of an ordered state below ~ 1 #SR measurements (Barth et al. 1987, 1989a). Similar to CeA12 a two three) component structure developed below 1 K, but unlike in CeA12, the
the heavy K in ZF(or rather additional
152
A. SCHENCK and F.N. GYGAX 0.05 0.00
~\ + -f,,, , -...,/ - - : ~ - " ~ ' ~ - - ¢ ~ ' ~ " ~
-'--'--~"7
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-o15 a
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I
1.0
I
I
1.5 2.0 2.5 Time (psec)
I
I
3.0
3.5
0.05 0.00
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.. - - - 2 - ~
-0.05 E E -O.lO 69 ,< -0.15
b
-0.20 -0.25 0.0
I
I
I
I
I
I
I
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Time (psec)
Fig. 4.36. ZF-#SR signal in CeAI3 at 0.01 K (upper part) and at 0.2 K (lower part). It can be fitted by a sum of three components: one fast relaxing but nonoscillatingwith amplitude Af, one slowly relaxing and nonoscillating with amplitude As and an oscillating component with essentially a node near zero time (from Amato et al. 1994a). component displays a precession pattern corresponding to a local field of -,~ 22 mT rather than a wide field distribution with zero average. Figure 4.37 displays the temperature dependence of the amplitudes of the two signals, derived from more recent ZF-measurements (Amato et al. 1994a). To fit the data in fig. 4.36 actually a three component structure had to be adopted consisting of one oscillating, one very fast relaxing and one slowly relaxing component. The oscillating component showed an unphysically large phase shift (ignored in Barth et al. 1987, 1989a) which was later attributed to a precursor state manifest by the fast relaxing component (Amato et al. 1994a). It now seems that the sum of a fast relaxing and of a phase shifted oscillating components is under certain circumstances more representative of a spin density wave phenomenon (see Le et al. 1994, and section 7.1). The amplitude in fig. 4.37 associated with the ordered state signal represents the sum of the amplitude of the fast relaxing and of the oscillating components extrapolated to zero time. There is another important difference to CeA12. While the phase transition in CeA12 can also be monitored by the specific heat, which shows the characteristic cusp at TN, no such feature is seen in CeA13. Hence it seems that the magnetic order in CeA13 evolves in a non cooperative manner. This may be also indicated by the precession frequency which shows very little variation up to the temperature where the ordered volume vanishes (see fig. 4.38).
MUON SPIN ROTATION SPECTROSCOPY
153
25 ' 7 '
Amax
'
' /
20
'
//
/ /
15
"As
o:l
E E <
10
\
OI
0
0.1
I
I
I
0.2 0.3 0.4 Temperature (K)
I
0.5
0.6
Fig. 4.37. Temperature dependence of the zero time amplitudes (asymmetries) Af and As in CeAI3, Af reflects the volume fraction associated with magnetic order and As the (complementary) volume fraction remaining paramagnetic (from Amato et al. 1994a). 3.5 3.0 3-O-O -I- 2.5 2.0 'i1) 1.5 1.0 LI.
0.5 0.0 0.0
~
I
i
0.1
0.2 0.3 0.4 0.5 Temperature (K)
0.6
0.7
Fig. 4.38. Temperature dependence of the spontaneous precession frequency in CeA13. The solid line is intended to guide the eye only (from Amato et al. 1994a). S o m e o f the o b s e r v e d features are s a m p l e dependent. The first a p p e a r a n c e o f a m a g n e t i c a l l y o r d e r e d v o l u m e m a y vary f r o m 2 K d o w n to 0.6 K. In Barth et al. (1987, 1989a) it is shown that the m a g n e t i c order m a y be r a n d o m or spin glass like a b o v e 0.8 K up to 2 K, no such feature is seen in A m a t o et al. (1984a). A t the
154
A. SCHENCKand EN. GYGAX
lowest temperature Barth et al. (1987, 1989a) find nearly no persisting paramagnetic volume while Amato et al. report on a residual paramagnetic volume of ,,o 25% (see fig. 4.38). NMR-measurements have provided conflicting results on the presence or non-presence of magnetic order in CeA13 (Nakamura et al. 1988, Wong and Clark 1992). Later NMR studies by Ott et al. (1993) (priv. communication) seem to be consistent with the #SR results. From the local field of 22 mT at the #+, considering only dipolar fields and ignoring a possible contact hyperfine contribution, an upper limit of ~ 0.1 I#B was estimated for the ordered moment (Schenck 1993).
CePb3. TF-#SR measurements on a polycrystalline sample at 10 K revealed a split four-component signal with distinct Knight shifts ranging from -4200 ppm to +1000 ppm (Uemura et al 1986a). No further results are available. CeCus, Ce(Cul_xAIx)5, Ce(Cul_xGax)5. The system CeCu5 is not considered to be a heavy fermion compound according to a commonly adopted classification scheme, although its low temperature Sommerfeld constant 7 is nearly the same as for CeA12. Replacing some of the Cu by A1 or Ga (only the 3g-sites in the hexagonal CaCu5 structure are involved) the system seems to acquire heavy fermion properties as reflected by vastly increased 7 constants which seem to peak for z around 0.20 (Bauer 1991). Undoped CeCu5 orders antiferromagnetically below ,-~ 4 K (propagation vector ( = (0, 0, 1/2), ~orallc-axis), with rising z a suppression of TN is observed and for z > 0.2 long range order seems to be suppressed (Bauer 1991). The question was whether some type of short range or spin glass order could persist though. To answer this question ZF-#SR was applied to undoped CeCu5 and to doped compounds with z (A1, Ga) = 0.1 and 0.2 (all polycrystalline) (Wiesinger et al. 1994a, 1994b and priv. communication). In CeCu5 a spontaneous precession signal appeared below TN in an increasing part of the volume, however, never accounting for more than ~ 30% of the total volume, as can be deduced from the signal amplitude displayed in fig. 4.39 (insert). This figure shows also the temperature dependence of the spontaneous precession frequency. The non-oscillating component shows appreciable exponential relaxation down to the lowest temperatures (A _~ 2.2 #s -1 at 1 K). The observed behaviour seems to be incompatible with the magnetic structure indicated above, since for that structure only one signal is predicted with Bu = 0 for the #+ at the b-site, which site is deduced from the ZF Kubo-Toyabe signal observed above TN. The temperature dependence of the two signal amplitudes, moreover, suggest that two different kinds of magnetic domains could coexist like in CeA12 and CeA13. Preliminary data on the doped compounds show that the oscillating signal, which indicates long range order, has disappeared (or nearly disappeared in the sample with z = 0.1) and is replaced below ~ 2 K by a wide static field distribution of Gaussian shape, which now accounts for 75% of the total volume (Wiesinger et al. 1994b, priv. communication). The rms width of the field distribution amounts to ~ 23 mT which is about half the field resulting from the spontaneous precession frequency in CeCus. The data reveal clearly that indeed some spin glass like order is present even in compounds with z = 0.2. This raises the possibility that the enormous "),-values
MUON SPIN ROTATIONSPECTROSCOPY G
155
O
6 °
'
'
C 'e C u 5
o ~ 0
0 30
~ ° ~
4
,
,
,
i
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~
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o oc.c io~ oc ~ ,~
°°
o
q)
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i
i
i
1
2
3
Temperature
I ~V
4
5
(K)
Fig. 4.39. Temperature dependence of the spontaneous precession frequency in CeCu5. The insert shows the behaviour of the amplitudes. Open circles refer to the precessing component, closed circles to the nonprecessionbut rapidly relaxing (),ZF ~ 2.2 #s for T --+ 0 K) component(from Wiesinger et al. 1994a). observed around z = 0.2 are of magnetic origin and arise from a high density of excited states at small energies which are known to exist in spin glasses.
Cefu6. This is one of the few remaining heavy fermion compound which have not shown any hints for some type of order at low temperatures. ZF-#SR measurements performed on a single crystal down to 40 mK likewise did not reveal any indication for static magnetic order placing an upper limit of ~ 10-3#B on any ordered moment if such should exist (Amato et al. 1993c). CeB6. This cubic compound shows antiferroquadrupolar ordering below TQ = 3.2 K and antiferromagnetic order below TN = 2.3 K, described by a double 0" structure (ql = (1/4, 1/4, 1/2), 42 = ( 1 / 4 , - 1 / 4 , 1/2)) (Effantin et al. 1985). A possible temperature dependence was not studied. In the quadrupolar phase antiferromagnetic order can be induced by an external field. Concerning the structure of the induced order controversial results are obtained from UB-NMR (Takigawa et al. 1983a, Kawakami et al. 1982) and neutron scattering (Efffintin et al. 1985; Erkelens et al. 1987). TF-#SR measurements on monocrystalline samples above TQ proved unambiguously that the #+ is located at the site (1/2, 0, 0) (or equivalently at the sites (0, 1/2, 0) and (0, 0, 1/2)) (see fig. 4.40) (Feyerherm et al. 1994a). ZF-measurements below TN displayed a very complex signal with 8 different spontaneous precession frequencies ranging from ~ 2.3 MHz to ~ 77 MHz as can be seen from
156
A. SCHENCK and F.N. GYGAX
(~)Ce
0 B
Fig. 4.40. Crystal structure of cubic CeB6. The/z+-site is indicated.
a Fourier-transform of the ZF-#SR signal at 10 mK (fig. 4.41). The temperature dependencies of the spontaneous frequencies are shown in fig. 4.42. Their partially very strange behaviour could not be explained yet. It may point to a temperature dependent reorientation of some of the Ce-moments. On the basis of the magnetic structure suggested by Effantin et al. (1985) dipolar field calculations predict no more than seven different fields, associated with the sites (1/2, 0, 0), (0, 1/2, 0) and (0, 0, 1/2), out of which six appear as slightly splitted triplets (sites (1/2, 0, 0), (0, 1/2, 0)). The calculated fields (a contact contribution is included) range from 30 mT to 90 mT (or 4.06 MHz to 12.2 MHz), far lower than the maximum observed field of ,-~ 0.57 T (Feyerherm et al. (1994a) and to be published). In particular the high frequency components are principally not explainable if the ordered moment is as small as 0.28#B as claimed by Effantin et al. (1985). It must be concluded that the AF-magnetic structure in CeB6 as well as the size of the ordered moments are drastically different from the neutron scattering conclusions or that the pres-
100 "
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4
6
8
10
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60
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80
FREQUENCY (NHz) Fig. 4.41. Fourier power spectra of the ZF-/zSR signal in CeB6 below TN (from Feyerherm et al. 1994a).
MUON SPIN ROTATION SPECTROSCOPY
157
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10 O C CD D Cr CD
A
CeB 6 8.~<~
m
%,
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6
•
o
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spontaneous muon precession in zero magnetic field
@
•
~ m mt~u N D
~ O@0@0 O @
OO@
O
m D m ~ D
mmDmD
O
O0~
[] m D l ~ D
A A~i~ ....
0.0
, ,
0.5
. . . . . . . . . . .
1.0 1.5 Temperature (K)
*
2.0
2.5
Fig. 4.42. Temperature dependence of the eight spontaneous precession frequencies in CeB6 below TN. Open symbols: /5(0)11(1, 1, 0), filled symbols: /5(0)11(1, O, O) (from FeYerherm et al. 1994a).
ence of the #+ alters the magnetic structure locally. However, even when admitting the latter possibility, the appearance of more than seven frequencies is difficult to understand. Knight shift measurements in the quadrupolar phase are also at odds with the suggested induced AF-structure in this regime in that no further splitting of the two signals, seen above TQ, is observed below TQ. The observation of two signals above TQ reflects the fact that the three sites (1/2, 0, 0), (0, 1/2, 0) and (0, 0, 1/2) which are crystallographically equivalent, are magnetically inequivalent in the paramgnetic state (Feyerherm et al. 1994a). Despite considerable efforts to understand CeB6 it remains a mysterious system and is a challenge for further studies.
CeCu2Si2. This is probably the most famous and probably the most thoroughly investigated heavy fermion compound due to the fact that it was the first HF system displaying superconductivity. It was known that some kind of AF-magnetic order develops in nonsuperconducting Cu-deficient CeCuz_xSi2 or in Cel_~LaxCuzSi2, but no magnetic order was found in superconducting (Cu-enriched) CeCuz+xSi2 (Grewe and Steglich 1991). It therefore was a surprise when ZF-#SR measurements on a superconducting CeCu2.1Si2 sample revealed the onset of some random magnetic order below 0.8 K, i.e. at a temperature above the superconducting transition temperature
158
A. SCHENCK and EN. GYGAX
0.8 ~,
v__-~ "~x!
CeCu2 Si2
SC
"
-
0.4
"\ ~
"./ I"° 0
2
\
o
\"° 4 B (Tesla)
\
\" 6
8
Fig. 4.43. Magnetic and superconducting phase diagram of CeCu2Si 2. The solid lines represent He2 for HextHa-axis and llc-axis, respectively, the lower dashed curve reflects anomalies in the elastic constant Cll, the upper dashed curve separates a not well identified ordered magnet phase from the pararnagnetic phase (adapted from Steglich et al. 1991).
Tc ~ 0.6 K (Uemura et al. 1989). Since then NMR and other measurements have provided indications for a magnetic phase diagram in the temperature versus field representation as shown in fig. 4.43. For small applied fields the phase boundary is close to Tc somewhat inconsistent with the ZF-#SR result. An important question, never answered satisfactorily before, concernes the nature of the coexistence of magnetic order and superconductivity: is it carried by the same electrons, is it microscopic or macroscopic? ZF-measurements on a CeCu2.2Si2 sample (Luke et al. 1989b, 1994) and on a CeCu2.05Si2 sample (see Amato 1994, Feyerherm et al. 1995) seem to show that magnetic order and superconductivity do not coexist on a microscopic scale, that they are even mutually exclusive. The ZF-#SR signal starts to develop a two component structure as the temperature is lowered below ,-~ 1.2 K. Above this temperature relaxations is only induced by random dipolar fields from the Cu-nuclear moments (Kubo-Toyabe signal). One of the two components below 1.2 K shows a fast Gaussian decay with a strongly rising cr as the temperature decreases (fig. 4.44). The other component show basically the same behaviour as above 1.2 K with a somewhat enhanced relaxation rate at around To. The relaxation rate of the fast component corresponds to a static field spread of about 140 G at the lowest temperature. Assuming truly random order and considering all possible and reasonable interstitial sites an upper limit of 0.25#B is estimated for the ordered moment. The #+-site in CeCu2Si2 is not known. From the splitting of the TF-signal above 1.2 K in a polycrystalline sample it may be concluded that two different sites are involved (unpublished results). Most interesting is the behaviour of the amplitudes. As fig. 4.45 shows the ordered volume fraction, as measured by the amplitude of the fast signal, increases to about 70% at T~. Just below Tc it decreases again, signaling a depression in the ordered volume as superconductivity sets in. Superconductivity seems to be confined to the volume fraction not showing magnetic order, but this needs to be studied in more detail. There is essentially no difference
MUON SPIN ROTATIONSPECTROSCOPY 4
i
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i
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CeCu2osSi 2 ZF "
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lO I
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0
0.2
0.4
0.6
0.8 r (K)
t.0
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Fig. 4.44. Temperature dependence of the Gaussian decay constant of the fast relaxing component in CeCu2.05Si2 (from Amato 1994). 1.0
CeCu2.05Si2 0.8
pm
0.6 <E 0.4
0.0
i
0.0
i
0.2
i
i
i
i
i
i
0.4 0.6 0.8 Temperature (K)
i
1
1.0
i
1.2
Fig. 4.45. Temperature dependence of the amplitudes of the two components in the ZF-/zSR signal in CeCu2.osSi2. A1 (open symbols) and A2 (filled symbols) reflect the paramagnetic and the magnetically ordered volume fractions, respectively. The latter is identified by the fast Gaussian decay (fig. 4.44) (from Amato 1994). in the temperature dependence of the two amplitudes measured in CeCu2.2Si2 and CeCu2.05Si2. The appearance of two magnetically inequivalent domains in CeCu2Si2 resembles to a great extend the results obtained in CeAI2, CeA13, Ce(CUl_x(Ga, A1)=)5 as shown above. Once more one gets the impression that this behaviour is characteristic for this class of compounds.
160
A. SCHENCK and EN. GYGAX
CeRu2Si2. Conventional measurements did not reveal any hint for magnetic order in this compound. However, a metamagnetic like transition at Hext -~ 8 T for T < 10 K suggests that CeRu2Si2 is close to a magnetic instability (Haen et al. 1987). Inelastic neutron scattering show indeed (also for CeCu6 !) the evolution of intersite antiferromagnetic correlations below 60 K (Rossat-Mignod et al. 1988b). It is argued that quantum fluctuations prevent the thermal divergence of the correlation length thereby preventing long range static order. This picture was changed by ZF- and LF#SR measurements (Amato et al. 1993a, 1994b, Amato 1994). These measurements on two different monocrystalline samples revealed the onset of some static order at around 2 K (see fig. 4.46). The only other signature for a phase transition is seen in the thermoelectric power S which displays a minimum at ,-~ 2 K (see fig. 4.46). Ill,
I
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,
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i t'~'l'l
I
I
101
T (K) Fig. 4.46. Temperaturedependence of (a) the ZF-relaxationrate and (b) the thermoelectricpower S in CeRu2Si2 (from Amato 1994).
MUON SPIN ROTATION SPECTROSCOPY
161
This feature was previously attributed to the onset of a coherent regime in a Kondo lattice (opening of a pseudo gap (Martin 1982)) but this interpretation may now need revision. The width of the static internal field distribution at the #+ in the ordered state is extremely small and of the order of 0.02 mT. From this an ordered moment of I0-3#B is estimated (upper limit 0.7 x 10-3/ZB). This is the smallest moment ever encountered in an ordered state. The #+-site in CeRu2Si2 is known from the angular dependence of the Knight shift measured at higher temperatures in a transverse field (Amato, priv. communication and to be published). It is the (1/2, 1/2, 0) position (site No. 1 in fig. 4.32). Note that measurements in the non magnetic isostructural compounds Y(Co)2Si2 and LaPd2P2 did not favour this site. TF-field measurements in a very small applied field (7.4 mT) served to monitor the #+ spin lattice relaxation which is induced by the 4f-electron spin fluctuations (Amato, priv. communic.). The TF-relaxation rate A2 = l/T2 is mainly reflecting a 1/Tl-mechanism since static line broadening is practically absent due to the absence of sizable nuclear moments (a small correction for those is applied) and the small applied field. The relaxation time T2 is displayed in fig. 4.47 together with the onsite (Fss) and inter site (/]s) line width from inelastic neutron scattering (Fss is proportional to the single site fluctuation rate and /is to the correlated inter site fluctuation rate) (Regnault et al. 1990). Since the fluctuations are fast we have T2~- T1 oc F.
(4.16)
As can be seen T2 scales closely with /'ss as expected. The proportionality factor between T2 and /'ss can be used to extract a rough estimate on the size of the
3.5
~
3.0
C e R u 2 Si2
2.s "-"
L.-
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,
1
2.0 ~_~L,k_.,L-i,JS..~ '
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'
~
'
~
-
loo
I
~" .-.s
1.5
I--~
1.0
0.5
50 -is
-
0.0
,
0
I
20
i
I
,
40
1
60
i
I
80
i
0
100
T (K)
Fig. 4.47. Temperaturedependenceof the/z+ TF relaxation time 7"2(open circles) and the on site (Fss) and intersite (/]s) line width from inelasticneutron scatteringin CeRu2Si2 (from Schenck 1993).
162
A. SCHENCK and EN. GYGAX
fluctuating moment: ~ I#B. The ordered moment at low temperatures is extremely reduced compared to this value. Since such small moments are found in other heavy electron systems (UPt3, Ul_xThxBel3, UCus, see section 4.3.2) it seems that the establishment of very small moment magnetic order (random or long range) is another characteristic feature of heavy fermion systems. Note that generally almost all ordered moments are much reduced in comparison to the Hund's rule moment of Ce3+: # = 2.54#B. The system CeRu2Si2 shows more conventional AF-magnetic order when other elements are placed on the Ce, Ru or Si sites. For instance Ce(RUl_~Rhx)2Si2 has shown AF like transition for 0.05 < z < 0.3 by means of specific heat and susceptibility measurements (Sakakibara et al. 1992). For z = 0.15 a transition temperature of TN --~ 5.5 K is estimated. ZF-#SR measurements on polycrystalline Ce(Ru0.asRh0.15)2Si2 confirmed the onset of magnetic order below 5.5 K, which appears to be random in nature as deduced from the Gaussian character of the relaxation behaviour below 5.5 K (Murayama et al. 1993). However, as found in other systems only a fraction of the volume takes part in the order. From the static field spread of N 15 m T at 4 K the ordered moment is estimated to be ~ 0.2#B.
CeTSn (T = Ni, Pd, Pt). These orthorhombic crystallographically rather complex compounds are viewed as Kondo lattice systems with no heavy fermion properties. However substitution of a few % Cu for Ni transforms the system CeNiSn to a HE compound. CeNiSn is a Kondo semiconductor with as small pseudo gap ( ~ 14 K) at the Fermi surface which is thought to arise from AF-magnetic correlations between quasi particles. In high magnetic fields ( ~ 12 T) the semiconducting behaviour disappears and gap formation is suppressed (Takabatake et al. 1992). Various experimental results (see, e.g., NMR results of Kyogaku et al. 1992) hint at a magnetic phase transition at low temperatures (< 0.2 K) but an actual phase transition could not be established. In contrast CePdSn and CePtSn are Kondo metals which display antiferromagnetic order below N 8 K, which for both compounds shows an incommensurate, modulated structure according to neutron results (Kohgi et al. 1992, Kadowaki et al. 1993). TF-#SR measurements on monocrystalline CeNiSn reveal an unmeasurably small relaxation rate above 2.5 K. Below this temperature the relaxation rises in a pronounced manner but remains small (A2 "-~ 0.065 #s -1 at 33 mK). The observed temperature dependence, following a power law A2 e( T -1/3, is not untypical for a system approaching a phase transition but down to 33 mK no phase transition was encountered (Kratzer et al. 1992). It can be concluded that CeNiSn is at all temperatures (i.e. down to 33 inK) a fast spin fluctuator. This may be correlated with the other notion that CeNiSn is a valence fluctuating system, as has been deduced from susceptibility data (Takabatake et al. 1990). ZF measurements in CePdSn and CePtSn reveal the onset of spontaneous coherent spin precession below 7.5 K and 8.2 K, respectively (Kalvius et al. 1994). In CePdSn the #SR signal displays clearly two well resolved frequencies and the relaxation is relatively slow implying relatively narrow field distributions at the #+-sites. The latter are not known yet. This observation of narrow and distinct field distributions
MUON SPIN ROTATION SPECTROSCOPY
163
0.2 a
0.2
2.. ....
20G LF ,,,.
.........
-" . . . .
"'
'
" '~ '
t
-J
i
t
'"t
0.1
~ t
0.1
CePtSn 9K
0
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~a~ 0.2
CePtSn 7K 4
6
8
0
200G LF
~
0
lOG LF
o
i
0.4
~
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O. I
~
,
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b
CePtSn 8.2K
0.1
I
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I
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,
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~
-0.
2
I
I
o
i 0.5
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ZF I
t
I
Time (#s) Fig. 4.48. ZF-#SR signal in CePtSn at various temperatures reflecting the appearance of static random order (b) and coherent long range order (c and d). The static order at 8.2 K is verified by the decoupling in longitudinal fields (b) (from Kalvius et al. 1994).
appear to be inconsistent with an incommensurate modulated spin structure which is expected to produce rather wide field distributions. CePtSn displays a rather unexpected behaviour just above the temperature where coherent spin precession first appears. As can be seen from fig. 4.48 the ZF-signal changes from a weak decay above 8.5 K to a static Kubo-Toyabe behaviour below 8.5 K, reflecting the development of a random static field distribution with a width of about 45 G (Kalvius et al. 1994), followed by the appearance of the coherent spin precession pattern just below 8.2 K. Obviously long range order is preceeded by a precursor spin glass like state. It could imply that the fast paramagnetic fluctuations above 8.5 K are slowed down to rates below 1 MHz, creating a quasi static situation with respect to the #SR time window. A further change in the coherent precession pattern is observed below ~ 5 K (fig. 4.48d), indicating a transition to a different magnetic structure in agreement with neutron scattering results (Kadowaki et al. 1993). Again there is a problem to reconcile the appearance of distinct and relatively narrowly peaked frequency distributions with the claimed incommensurate structures (also below 5 K in CePtSn).
YbBiPt, Ybo.sYo.sBiPt. YbBiPt possesses a record high Sommerfeld constant of 7 -~ 8 J/(mol-Yb K 2) at low temperatures which has lead to quite some interest in this
164
A. SCHENCKand EN. GYGAX
cubic compound. Specific heat and susceptibility measurements suggest some kind of phase transition at ~ 0.4 K (Fisk et al. 1991). Recent resistivity measurements suggest a partial gapping of the Fermi surface at 0.4 K and the appearance of a spin density wave (SDW). The opening up of a gap can be suppressed in fields >0.3 T (Movshovich et al. 1994). ZF-, TF- and LF-#SR measurements were performed on crushed powder and crystalline samples (Amato et al. 1992b, Amato et al. 1993b, Heffner et al. 1994). The ZF-measurements identified the transition at 0.4 K to be a magnetic phase transition. Since no precession pattern was seen but only a wide Gaussian like distribution of fields (~ 8 mT) with zero average it was concluded that a spin glass like random order or some complicated incommensurate structure must be established again in a spatially inhomogeneous way. Some information on the #+ site was obtained from TF-measurements at higher temperature, which indicated that the #+ is located somewhat off center at the position (1/2, 1/2, 1/2) (Feyerherm, priv. communication). Adopting this site and the random order picture an ordered moment of ~ 0.1#B is estimated. This is much smaller than the moment following from the Curie behaviour of the susceptibility below 10 K (3.6#B). However, the small value of the ordered moment is consistent with the absence of a nuclear Schottky anomaly in the low temperature specific heat (Thompson et al. 1993). Like in other heavy fermion systems the ZF-signal showed a two component structure which developed already much above 0.4 K, i.e. below ~ 1.2 K. Above 0.4 K both components showed an exponential relaxation behaviour. At 0.4 K one of the two components changed abruptly to a Gaussian behaviour with a rapidly increasing decay rate, while the other component continued to show exponential relaxation (see fig. 4.49) just as in the paramagnetic phase. Interestingly the Gaussian component changed in appearance, below ~ 0.1 K, indicating a change in magnetic structure or spin dynamics (Heffner et al. 1994) consistent with similar evidence from susceptibility and specific heat data (Thompson et al. 1993). The Gaussian field distribution did not change in longitudinal fields up to 2 T. This is quite significant since it proves that the magnetic order, sensed by the #+, cannot be associated with the SDW carried by the conduction electrons, which is destroyed in fields above 0.3 T. It therefore seems that the magnetism in YbBiPt is of twofold origin: Yblocal moment order and a conduction electron SDW, implying that the electronic ground state is made up of rather independent electronic subsystems. In this respect there is a certain parallelity with the results from UPd2A13 and UCu5 (see section 4.3.2). ZF-measurements in Yb0.sYo.sBiPt lead to rather similar results. Interestingly, despite a 50% dilution of the Yb-moments, the phase transition or spin freezing temperature was very little reduced. The dilution effect was clearly seen in a corresponding decrease of the static field spread (Amato et al. 1993b).
Sm3Se4. Low temperature susceptibility measurements revealed a huge linear specific heat term with 3' = 0.79 J/(K 2 mol-Sm3+) despite the fact that Sm3Se4 shows semiconducting behaviour with no free carriers at low temperatures (Fraas et al. 1992). This system has been discussed within the context of "heavy electrons without free
MUON SPIN ROTATION SPECTROSCOPY 8
,
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165
7 6
4" s ,.~ 4
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c
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0.4 0.6 0.8 1.0 T (K)
I
1.2
Fig. 4.49. Temperature dependence of the amplitudes and the relaxation rates from a two component analysis of the ZF-/zSR signal in crystalline YbBiPt. The rapidly relaxing signal (Af, ¢rf, Af) changes from an exponential behaviour (Af) to a Gaussian behaviour 0rf) at 0.5 K. The slowly relaxing signal (As) displays an exponential behaviour with only a weakly temperature dependent ~,s (from Amato et al. 1993b).
carriers". Sm appears in this compound in the two valence states Sm2+ and Sm 3+ with a relative occupation of 1 : 2, and no charge ordering. Relatively slow valence fluctuations are observed above 100 K (Takagi et al. 1992, 1993). Nothing was known about the low temperature magnetic properties of this compound. ZF-#SR measurements on a polycrystalline sample revealed the development of static magnetic order below 20 K by the appearance of a fast damped Gaussian component, again in only part of the volume (see fig. 4.50). The low temperature static field spread seen by the #+ amounts to ~ 3.5 mT, from which, making some reasonable assumption on the #+ site, a randomly ordered moment of 0.05#B can be estimated (Takagi et al. 1993 and unpublished results). A spin glass type structure of randomly frozen moments (perhaps related to the statistical distribution of Sm 3+ ions
166
A. SCHENCK and EN. GYGAX
3.5 3.0~ + + + ~ =k v 2.5 I
i
illllh
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i
i
lll,,q
i
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tr tO
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o Gauss.
• Exp.
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m 1.0
rr
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oe'" i
.... %.
"if,
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10
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,,,,,,I
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iiiiiii
100
i
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i
iiiiill
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T (K) Fig. 4.50. Temperaturedependence of ZF relaxation rates (exponential, Gaussian) and amplitudes (asymmetries) from a two component analysis of the ZF-#SR signal in Sm3Se4 below ~ 20 K. Above 20 K only one component, decaying exponentially, is seen which is unchanged in a longitudinal field (from Takagi et al. 1993 and unpublished results). on the Sm sublattice) may lead to a high density of low energy magnetic excitations - as in a conventional spin glass - and could explain the large linear specific heat term, as discussed in the case of YbBiPt.
4.2.7. Ternary rhodium borides and chevrel phase compounds The interest in the ternary compounds RRh4B4 (R = rare earth) stems from their property to show superconductivity in coexistence with AF magnetic order as in SmRh4B4 or reentrant ferromagnetism as in HoRh4B 4 and ErRh4B 4 (see, e.g., Maple et al. 1982, Kakani and Upadhyaya 1988). The Chevrel phase systems RMo6S8 (RMo6Se8) show coexisting AF-magnetic order and superconductivity for R = Nd, Gd to Er, Yb (Fischer 1978). The situation in EuMo6S8 and EuMo6Se6 is controversial. Recent investigations claim the establishment of some complex order below 0.4 in EuMo6S8 and below 0.85 K in EuMo6S8 (Takabatake et al. 1984, Quezel et al. 1984b). A structural phase transition from rhombohedral at high temperatures to trictinic a low temperatures was detected at ~ 110 K in EuMo6S6 (Baillif et al. 1981). At the same temperature a change from a metallic to a nonmetallic behaviour was found in resistivity measurements (Meul et al. 1982). The system Eu]_~SnxMo6S8 (z > 0.2) shows again superconductivity. No structural phase tran-
MUON SPIN ROTATIONSPECTROSCOPY
167
sition is seen in this pseudo ternary compound and the rhombohedral structure is observed at all temperatures which is apparently a prerequisit for the development of superconductivity. It has attracted particular attention because of the observation of field induced superconductivity due to the Jaccarino-Peter effect (Meul et al. 1984). Rare earth rhodium borides. TF and ZF-#SR measurements on the nonmagnetic homologues LaRh4B 4 (Boekema et al. 1982) and YRh4B4 (Huang et al. 1983b) showed that the #+ is immobile up to about 200 K. Possible #+ sites were discussed in detail by Noakes et al. 1987. Measurements on the magnetic compounds yield the following results.
SmRh4B4, ErRh4B4. #+ relaxation
observed in ZF and TF displayed a pronounced temperature dependence (Noakes et al. 1987, 1985) from which the rare earth moment fluctuation rates could be determined. Although the Er 3+ moment is considerably larger than the Sm 3+ moment the fluctuation rates are very similar in their magnitudes and temperature dependencies (as an example see fig. 4.51). No effect of the superconducting transition on the fluctuation rates are seen. Since the #+ relaxation rates became excessively large in ErRh4B4 when lowering the temperature below 50 K the region around the onset of ferromagnetism could not be studied. ZF-measurements below TN in SmRh4B4 did not reveal any precession signal. Instead the data could be best fitted with two exponentially relaxing components, one .-(1) --~ 10 #S -1) and the other one of approxidisplaying a very fast relaxation rate (Zzv mately equal amplitude showing a rather slow relaxation (x(2) ~ 0.17 #s -1) (Huang ~-"ZF et al. 1983b). It is argued that this most likely reflects an occupation of different sites with rather different magnetic environments in the ordered state. In any case the absence of coherent spin precession and the appearance of exponentially damped I
I
I
I
6 o g"J 0
-~ rr
4
._o ¢3 II
0
0
I
I
i
I
50
1O0
150
200
250
Temperature (K) Fig. 4.51. Temperature dependence of the Sm 4f-moment fluctuationrate in SmRh4B4. The solid line is a fit to a model which includes the RKKY, the Korringa mechanism and phonon induced transitions between CEF levels (from Noakes et al. 1987).
168
A. SCHENCKand EN. GYGAX
signals points to a rather complicated antiferromagnetic structure such as has been seen in NdRh4B 4 and TmRh4B4 (Majkrzak et al. 1982, 1983). There is no other information on the AF structure in SmRh4B4. It also needs to be checked to what extend the #SR-data below TN still reflect dynamic features. The spin relaxation rates, shown in fig. 4.51, were explained in terms of phonon induced transitions between the CEF levels of both Er 3+, Sm 3+ and the RKKY- and the Korringa mechanism (Noakes et al. 1987). A fit of this model (solid line in fig. 4.51) leads to values for the RKKY exchange rate P'RKKY'the Korringa constant UKorr/T and the strength of the CEF related spin lattice relaxation which are in rough agreement with theoretical estimates for SmRh4B6 (Kumagai et al. 1981) (t,fi~K Y ,--o 1.2 x 10 s S- 1 , UfiKtorr/T~ 3.4 x 10 6 K - I s - l ) . For ErRh4g 4 the apparent RKKY rate and the Korringa rate are determined to be URKKynt~-- 3 X 10Ss -1 and U~torr/T -~ 4 x 105 K - i s -1, i.e. the RKKY-mechanism dominates the spin fluctuation rate below ~ 50 K and the Korringa mechanism is essentially absent. This is not understood in detail. Some excess slowing down in the spin fluctuation rate is seen in SmRh4B4 below ,-~ 4 K when approaching TN (Noakes et al. 1987).
HoxLul_xRh4B4 (x = 1, 0.7, 0.02, 0,005). The lowest state of the J = 8 518 Ho 3+ground state multiplet in HoRh4B4 is a degenerate nearly pure I + 8) doublet with no or only very small off-diagonal matrix elements of J, inhibiting or suppressing relaxation within this doublet at low temperatures by, e.g., the Korringa mechanism. In this respect HoRhaB4 is quite distinct from SmRh4B4 and ErRh4B 4 which both possess degenerate CEF ground-state level which are connected by IAmjI = 1 transitions. Consistent with the ground state properties of Ho 3+ in rhodium boride a severe slowing down of the spin fluctuations is observed in ZF- and LF-#SR measurements. In the system HoxLul_xRh4B4 this is seen for all concentrations x to the extent that even in the very dilute compounds with x = 0.02 and x = 0.005, which do not show magnetic order, a quasi static situation develops below T "-~ 9 K for x = 0.02 and below T _~ 6.5 K for x = 0.005 (described as an isolation of the ground state doublet). Since the fluctuation rates are essentially independent of x below ~ 10 K a single ion relaxation mechanism must prevail which points to the Korringa mechanism, although quite suppressed, as the responsible one (Heffner et al. 1985, 1984, MacLaughlin et al. 1983, Boekema et al. 1982). The onset of magnetic order in HoRh4B4 (Tc = 6.6 K) and in HO0.TLU0.3Rh4B4 (Tc = 4.1 K) is not reflected visibly in the ZF-#SR relaxation data. However, very similar to the dilute compounds, quasi static behaviour develops below (9-10) K (fluctuation rates < 1 MHz). Above ~ 10 K the fluctuation rates change to a thermally activated behaviour reflecting the transition from intra ground state doublet relaxation to a much faster activated behaviour involving excited CEF levels as in SmRh4B 4 and ErRh4B 4. The onset Of superconductivity in Hoo.TLuo.3Rh4B4 has no apparent effect on the fluctuation dynamics.
GdRh4B4. The spin dynamics in compounds such as SmRh4B4, ErRh4B4 and HoxLUl-xRh4B4 is obviously very much determined by the CEF-split ground state
MUON SPIN ROTATION SPECTROSCOPY
169
features. In contrast Gd 3+, which is in a pure spin s t a t e (857/2) , is unaffected by the CEF. This is clearly reflected in ZF- and LF-#SR data which reveal an essentially temperature independent spin fluctuation rate (~ 5 x 101° s -1, depending on the assumed site) down to the ferromagnetic ordering temperature (_~ 5.6 K). The temperature independence points to an RKKY exchange mechanism. In comparison to S m R h 4 B 4 and E r R h 4 B 4 the rate is enhanced by two orders of magnitude (MacLaughlin et al. 1983). No slowing down of the fluctuation rate close to Tc shows up when approaching Tc from above (the critical region may be very narrow) but the #+ relaxation rate decreases steeply below Tc reflecting the freezing of fluctuations in the ordered state (small amplitude fluctuations). The rather sharp break in the #+ relaxation rate at Tc is rounded off remarkably in a longitudinal field of 0.1 T. This feature has not been explained. No spontaneous coherent spin precession signal is seen below Tc. This together with the small relaxation rate at 2 K implies that the #+ resides at a site where, in the ordered state, the internal fields must cancel rather well.
EuMo6S7.5Seo.5, Euo.75Sno.25Mo6S7.6Seo.4.The first compound does not become superconducting but shows, as pointed out before, a structural phase transition at ~ 110 K. The second compound becomes superconducting below 5.15 K. The partial substitution of Se for S was chosen in order to create a particular phase diagram in the field
80 a ) ~
100
'~
I
I
I
I
I
60
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40 >
20
~ oo I I I I I I I f I ~ I I I I ] I I I I I L I I I I I I
0
50
100
i
80 '~
100 150 200 Temperature (K) i i i
I
250
300
I
b)
60
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~.~ 40 20 0
i
i
i
i
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50
i
i
i
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i
i
i
150
i
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i
i
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i
i
i
+ ~ i
250
i
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Temperature (K)
Fig. 4.52. Temperature dependence of the Eu-4f moments fluctuation rates u in (a) EuMo6S7.5Seo+5 and in (b) Euo.75Sno.25Mo6S7.6Seo.4 extracted from ZF-relaxation rates (from Birrer 1991).
170
A. SCHENCKand EN. GYGAX
induced superconducting state which, however, is of no relevance for the present discussion. ZF, LF and TF-measurements show consistently the presence of rather slow spin fluctuations in the range ~ (1-300) K and some kind of magnetic order below or around 1 K (Birrer et al. 1990, 1989b, Birrer 1991). The temperature dependence of the Eu-4f moment fluctuation rate u is shown in fig. 4.52 for both compounds. It was deduced from the muon spin relaxation rate AZF (= A1) by adopting a reasonable #+ site and assuming an Eu 3+ moment of # = 7.5#B (S = 7/2). The effect of the structural phase transition is clearly manifest in the data shown in fig. 4.52a. Interestingly u rises linearly with T in the metallic phase (also in Eu0.75Sn0.25Mo6Sv.6Se0.4 from 10 K up to at least 130 K, fig. 4.52b), indicating a Korringa mechanism, but is temperature independent in the non metallic phase down to 10 K. In both compounds a change in behaviour is observed below 10 K. While u in the Sn doped compound becomes now temperature independent at the same value as found in the non metallic phase, u in the undoped compound starts to rise down to ~ 0.8 K, where it saturates. However, LF measurements show that below 0.8 K in EuMo6S0.vSe0.5 and somewhere below 3.5 K, but above 1.4 K, in Eu0.75Sn0.25Mo6ST.6Se0.4static random fields are established signaling the onset of some magnetic order (Birrer 1991). Whether it is spin glass like or of a complex long range structure could not be determined. The fluctuation behavior displayed in fig. 4.52b, in particular also the linear temperature dependence below 130 K, agrees closely with M6ssbauer results in Eu0.25Sn0.75Mo6S8(Dunlap et al. 1979). The spin dynamics in Eu0.75Sn0.25Mo6S7.6Se0.4is unaffected by the superconducting transition at 5.15 K. 4.2.8.
R2Fel4B
This class of rare earth intermetallic compounds has found an important application in the construction of hard permanent magnets. Their usefulness in this respect derives from very large magneto-crystalline anisotropies which are related to CEF effects and strong spin-orbit interactions of the rare earth constituents (see, e.g., Buschow 1986) From a more fundamental point of view these compounds are interesting since both the R- and the Fe-sublattice display magnetic order which sets in below a common Curie temperature indicating a strong interplay of the localized 4f electrons and the more itinerant 3d electrons. The sublattice order is ferromagnetic for all compounds but the two sublattices couple ferromagnetically for the light rare earth up to Sm and antiferromagnetically for the heavy rare earth. In each case a collinear arrangement is found. In some compounds spin canting without destruction of the collinearity is observed. The crystal structure is quite complicated as shown in fig. 4.53. From studies of hydrided compounds with small hydrogen concentrations it was deduced that hydrogen occupies the so called tetrahedral 4e sites with two R and two Fe nearest neighbours (see fig. 4.53) (Ferreira et al. 1985). There are four crystallographically equivalent 4e sites within the unit cell. They are also magnetically equivalent as long as the ordered moments are parallel to the c-axis. It is reasonable to assume that also implanted #+ will reside at the 4e site. ZF-#SR measurements were under taken with the aim to gain additional information on the low temperature magnetic structure of the RzFex4B system (Yaouanc et al. 1987, Niedermayer et al. 1990).
MUON SPIN ROTATION SPECTROSCOPY
171
/,e site
[I
010~,
R2Fell.B Fig. 4.53. Crystal structure of tetragonal R2Fel4B (R = rare earth). Indicated is a tetrahedral 4e interstitial site which is known to be occupied by dissolved 'hydrogen (from Niedermayer et al. 1990).
In all investigated polycrystalline compounds (see table 4.14) a single spontaneous coherent spin precession signal was seen in ZF-measurements. In the compounds Y2Fe14B and Pr2Fel4B the spontaneous field Bu at the #+ site decreases smoothly with temperature with no further structure consistent with no spin canting in this two compounds. B,(T) scales roughly but not precisely with the macroscopic magnetization. Note that in Y2Fel4B Bu originates solely from the Fe-sublattice. The upper part of fig. 4.54 shows the temperature dependence of z~u in Nd2Fe14B together with the macroscopic M(T). Below 150 K, uu(T) decreases while M(T) continues to increase. The break in ut,(T) coincides with the start of the spin canting known from other experiments. Here the macroscopic magnetization changes continuously from an orientation parallel to the c-axis to an orientation parallel to the [110] axis. Interestingly uu(T) below 150 K scales with the magnetization component along the c-axis (dashed curve in fig. 4.54). The spin canting should lead to the appearance of two magnetically inequivalent types of 4e sites and one would expect to see two distinct precession signals. The absence of a splitting below 150 K and the scaling of u~(T) with the magnetization component along the c-axis points to some averaging mechanism by which planar internal fields are averaged to zero. It is suggested that /~+ diffusion, which must be fast in this complicated compound even at temperatures as low as 4.2 K, is responsible for this mechanism. However, in the absence of any strong temperature effect on the relaxation rate of the precession signal #+-diffusion
172
A. S C H E N C K and E N . G Y G A X
m
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~
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MUON SPIN ROTATION SPECTROSCOPY
173
tz~
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~ o o ~ ~ g~
o ©
ca
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::i.
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m
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174
A. SCHENCK and EN. GYGAX I
180
I
I
Nd2Fe14B
_
M (30M'~-~'f0) el"~e ~
"1'~ 170 o rI1}
"
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I
100
400
200
02Fe14 B
300
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,,--.
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300 0
f 100
I 200
T 12 300
Fig. 4.54. Temperature dependence of the spontaneous precession frequency and of the saturation magnetization M (solid line~ in Nd2Fe]4B (upper part) and in Ho2Fel4B (lower part). The dashed lines show the projection of M on the c-axis (from Yaouanc et al. 1987, Niedermayer et al. 1990).
appears somewhat unlikely and it rather seems as if some aspect of the magnetic structure in the spin canting regime is not properly understood. Very similar results are also observed in H o 2 F e l 4 B where again uu(T) shows a break at ~ 50 K below which temperature spin canting develops in this compound (see lower part of fig. 4.54). Interestingly in this compound the macroscopic magnetization decreases with temperature due to the AF coupling of the two sublattices, while u(T) increases till ~ 50 K because in this case the dipolar fields from the Fe- and Ho-moments add constructively at the 4e #+-site. Table 4.14 lists the low temperature (15 K) B~ and the difference B~ - BL (BL is calculated from the macroscopic saturation magnetization at low temperatures) which is given by +[/~c Figure 4.55 shows that B , - BE scales very well with the rare earth moment or its component along the c-axis, respectively. This figure teaches that the Fe-sublattice contribution to the microscopic local field at the #+ is rather independent of the rare earth element present.
+/~dipt-
MUON SPIN ROTATION SPECTROSCOPY I
I
I
I
175
1
I
I
I
I
I
I
I
3.5
3.0 2.5
D Tb y
2.0 i
m= 1.5 •
. . . . . . . . . . . . . . . . . . .
0.5 0
I
I
I
I
-10 -8 -6 -4 -2 0 2 4 gnE(~B)
Fig. 4.55. Linear correlation of (Bu - BL) (low temperature limits) with the value of the rare earth
moment (from Niedermayeret al. 1990).
4.3. IntermetalIic compounds containing actinide elements Some of the results to be discussed below have been reviewed before by Asch (1989, 1990) and Schenck (1993). Tables 4.15 and 4.16 list all the compounds studied so far by #SR spectroscopy.
4.3.1. Cubic laves phase compounds: UAI2, UMn2, NpAl2 UAI2. Some times considered to belong to the class of heavy fermion systems (7 = 90 mJ/mol K 2) UA12 seems to be a fast spin fluctuator (TSF ~ (25-30)K) down to the lowest temperatures with no disposition towards magnetic order. The importance of spin fluctuations is revealed by a T 3 In T behaviour of the low temperature specific heat. This picture is fully in line with ZF- and LF-#SR measurements on a polycrystalline sample (Kratzer et al. 1986, Asch et al. 1987). LF-measurements in particular reveal an extremely small relaxation rate ), ~< 0.05 #s -1 which translates into a U-5f electron spin fuctuation rate of 1/Tc > 1013 s -1, assuming the U-5f moment to be given by ~ 4#B, as deduced from the magnetic susceptibility above 100 K (see, e.g., Fournier et al. 1985). This rate estimate agrees well with results from a neutron scattering measurement of the dynamic susceptibility (Loong et al. 1986). UMn2. ZF- and LF-#SR measurements on a powder sample (Cywinski et al. 1994a) prove UMn2 to be a fast spin fluctuator like UAI2 and no indications for long range order involving either the 5f and for the 3d moments are seen in agreement with neutron diffraction measurements. This seems to rule out expectations that AF order could develop below ~ 240 K, somewhat above a structural transition in the range
176
A. SCHENCK and EN. GYGAX
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MUON SPIN ROTATION SPECTROSCOPY
177
o.q~
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178
A. SCHENCKand EN. GYGAX
(210-230) K in analogy to U F e 2 where a rhombohedral distortion coincides with a ferromagnetic transition at 165 K (see, e.g., Fournier et al. 1985).
NpAl2. NpA12 is a ferromagnet which orders below Tc = 56 K. Only prelimenary ZF-#SR results are so far available (Aggarwal et al. 1990). In contrast to all other cubic Laves phase compounds studied by ZF-#SR in the ordered state, NpA12 is the only system in which a spontaneous spin precession signal is seen with more than one precession frequency. Indeed if the #+ is placed at the (2-2) site, as found in CeA12 (see fig. 4.6, section 4.2.6) several distinct local fields should be visible, but a detailed analysis is as yet missing. TF-#SR measurements (0.02 T) show a strongly rising relaxation rate or a slowing down of the spin dynamics, respectively as Tc is approached from above, starting at ,-~ 75 K, which is typical for a second order phase transition.
4.3.2. Binary compounds with NaCl structure Like the rare earth monopnictides the corresponding U compounds show complex magnetic structures of multiple q spin arrangements. The U-monochalcogenides are ferromagnets (see table 4.15).
UAs. #SR-measurements in ZF, TF and LF on a mosaic of unoriented crystalline platelets mirror very nicely the different magnetic phases and provide some additional information (Asch et al. 1987, 1989, Kratzer et al. 1990). ZF-measurements below 62 K in the type IA, double 0"AF phase reveal spontaneous coherent spin precession involving two frequencies and one non-oscillating component (see fig. 4.56). The temperature dependence of the frequencies is displayed in fig. 4.57. Assuming the #+ to occupy the same site as in CeAs (see fig. 4.21) one calculates for the given AF structure a zero net dipolar field and by symmetry arguments also a zero contact hyperfine field. The fact that non-zero frequencies and a splitting is seen is a result of a tetragonal lattice distortion occuring at 62 K (c/a < 1) (also at 124 K (c/a > 1)). This distortion is a necessary prequisite for the establishment of the type IA double ~' spin structure (Sinha et al. 1981). It changes the point symmetry at the #+ site with the effect that crystallographically equivalent sites become magnetically inequivalent (--+ splitting of signal) and that the dipolar fields from the neighbouring U-moments do no longer cancel (--+ non zero frequencies). In fact the distortion explains the ratio of the signal amplitudes associated with the two oscillating and the one nonoscillating signal. Dipolar field calculations predict a ratio of x/2 for the two frequencies independent of the size of the distortion. The fact that at the lowest temperature a ratio of ~ 2 is observed points to additional contact hyperfine fields, which are also needed to account for the strange temperature dependence of the lower frequency in fig. 4.57. A detailed understanding, however, is lacking. It should be emphasized that neither neutron nor X-ray diffraction could detect the tetragonal distortion, providing only an upper limit of ]c/a - 11 < 2 x 10 -11 (Sinha et al. 1981, Knott et al. 1980). The #SR-results provide the only direct evidence for the distortion by the change of the point symmetry but no quantitative analysis was presented.
MUON SPIN ROTATION SPECTROSCOPY
179
0.15 0.10 0.05 0 -0.05 -$ E E
I
I
I
I
I
I
1
2
3
4
5
6
Time (gs)
(n
0.15 0.10 0.05 0 -0.05
I 0.5
I 1
Time (~s)
Fig. 4.56. ZF-/zSR signal in UAs below 62 K in the type IA, double ~"AF phase. The lower part shows an expanded early section of the signal (from Asch et al. 1987). I
12.0
o o
I
I
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03 O 0 o
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og
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0 0
or
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I
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10
20
30
40
50
60
Temperature (K)
Fig. 4.57. Temperature dependence of the two spontaneous precession frequencies in UAs in the type IA, double q AF phase below 62 K (from Asch et al. 1987).
Above 62 K the coherent spin precession signal vanishes abruptly and only a weakly damped Lorentzian Kubo-Toyabe signal is seen with no temperature dependence up to TN ----- 124 K. This is consistent with the prediction that even in the presence of a tetragonal distortion the type I single q" spin structure will not lead to
180
A. SCHENCK and EN. GYGAX
non-zero net dipolar (and contact) fields at the #+-site. The extremely small residual field spread of N 0.8 m T at the #+-site, following from the static Lorentzian K u b o Toyabe behaviour implies a very perfect and static spin structure in the vicinity of the #+ and that disturbances are dilute and more distant. Spin excitations do not seem to play a role. The transitions at TN = 124 K into the paramagnetic state shows up very markedly in W-measurements. The relaxation rate drops by more than a factor of two and the precession frequency displays a jump by more than +2500 ppm (Asch et al. 1987). The relaxation rate above 124 K is essentially temperature independent up to ,-~ 180 K, where another down jump to a very small rate is observed (see fig. 4.58). In particular no increase of the relaxation rate (no slowing down of spin fluctuations) is seen when approaching TN from above consistent with the notion of a first order phase transition (Sinha et al. 1981). The change at 180 K is accompanied by a transition from a Gaussian damping function above this temperature, reflecting the nuclear (75As) dipolar field distribution, to a more exponential one below this temperature (but still reflecting static features, Kratzer et al. 1990). The modified relaxation behaviour below 180 K is ascribed to the onset of a magnetic precursor state in which the 5f-moments no longer act as free paramagnetic spins. This is in accord with diffuse neutron scattering results slightly ( ~ 10 K) above TN which reveal strongly anisotropic spin fluctuations tending towards an incommensurate sinuoidally Tt
TN
°o
0.4
UAs
oo
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(a) O O
,
0 0.8
, ,
~ ....
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_~o~p o o o oo o
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91
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o ,,,I
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50
,o, ,o,, o, ,o,
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100
250
150
200
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Temperature (K)
Fig. 4.58. Temperaturedependence of TF-relaxation rates A2 in (a) UAs, (b) UP and (c) CeAs. The first order nature of the phase transition at TN in UAs and UP is manifest by the discontinuousjump of ),2- In contrast ),2 in CeAs reflects a critical slowing down of the spin dynamics near TN and signals a second order phase transition (from Asch 1989).
MUON SPIN ROTATION SPECTROSCOPY
181
moduled spin structure (Sinha et el. 1981). The #SR data show that the precursor state sets in already about 50 K above TN (Asch et el. 1989). USb. Like in UAs in the type I single q phase, ZF-measurements on USb do not exhibit any coherent spin precession below TN (the spin structure is of type I, triple q-) but display a Lorentzian Kubo-Toyabe behaviour with full amplitude. In contrast to UAs the internal fields acting on the #+ are not totally static below TN and both the static width A and the spin fluctuation rate u show a pronounced and very interesting temperature dependence (see fig. 4.59) (Asch et el. 1990). A displays a maximum at ~ 140 K at which temperature the fluctuation rate u starts to rise dramatically with increasing temperature. Neutron scattering measurements signal at ~ 140 K the collapse of spin waves, well resolved at lower temperatures, and the development of a broad inelastic peak centered at zero frequency (Hagen et el. 1988). The #SR results are interpreted in terms of a phase de-locking of the magnetic components in the triple ( structure just as in DyAg (see section 4.2). Phase de-locking, induced thermally, produces irregularities (defects) in the spin structure and hence increases the field inhomogenity sensed by the #+. This explains the rise of A with increasing temperature. At around 140 K a motionat narrowing effect sets in which arises from a slow diffusive motion of the thermally induced perturbances or defects in the spin structure and explains the step rise in u and - at least qualitatively - the decrease of A above 140 K. Note that the disturbances/defects are still quite dilute so that a Lorentzian Kubo-Toyabe picture is applicable. By comparison with other compounds it is found that a dynamic Lorentz-KuboToyabe behaviour with a temperature dependent A is typical for a multiple 0"structure which, in contrast to a single 0~structure, seems to be more easily distorted due to de-locking of the phases between the Fourier components of the moments (Asch et el. 1994). UP. This compound displays rather similar properties as UAs (see table 4.15). A subtle but important difference is that in the ordered phase, associated with the double
USb
9 i
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~ 1.1 1.0
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TN
Fig. 4.59. Temperature dependence of the width A and the spin fluctuation rate v from the dynamic Kubo-Toyabe signal seen in USb (from Asch et el. 1990).
182
A. SCHENCKand F.N. GYGAX
structure, the propagation vector is given by q = (0, 0, 1) (type I) while in UAs ~ = (0, 0, 1/2) (type IA). Only in the latter case one calculates non vanishing dipolar fields at the #+ site, if also a tetragonal distortion is present. Consequently in UP no coherent spin precession signal is seen in ZF-#SR measurements (Aggarwal et al. 1989). TF-measurements show abrupt changes in the relaxation rates at both transitions temperatures (see fig. 4.58b) but no indication for critical behaviour in line with the first order nature of the phase transitions. In contrast to UAs also no magnetic precursor state is seen in UP above TN = 122 K (Aggarwal et al. 1989).
UN. UN orders antiferromagnetically into the type I single q structure at 53 K. The transition is accompanied by a tetragonal distortion with c/a > 1. From the pressure dependence of TN and #u strong evidence for itinerant magnetism was deduced (Fournier et al. 1985). The phase transition is believed to be of second order. ZF-#SR measurements below TN do not reveal a spin precession signal but a static Lorentzian Kubo-Toyabe behaviour consistent with similar results in the single qphase in UAs and UP (Mtinch et al. 1993). TF-measurements (Mtinch et al. 1993) show a drastic increase of A2 at TN but no indications for a critical slowing down of the spin dynamics when approaching TN from above just like in UP (see fig. 4.58b). This is unexpected in view of the assumed second order nature of the phase transition. A2 above TN is in fact very small (~ 0.03 #s -l like in UP) and temperature independent and implies a very fast fluctuation of the U-moments. From the point of view of #SR there is no difference in the magnetic behaviour of UP and UN above and below TN (except that UP possesses another phase transition at lower temperatures). UTe. In contrast to the U-monopnictides this monochalcogenide shows ferromagnetic order below Tc = 104 K. ZF-#SR measurements below Tc could not detect any coherent spin precession signal, probably because of a too rapid relaxation due to a very wide field distribution associated with lattice irregularities (Aggarwal et al. 1989). TF-measurements (0.1 T) above Tc yield a frequency shift which scales very well with the susceptibility. The exact form of the temperature dependence of the TF-relaxation rate could not be extracted but its diverging trend when approaching Tc from above is consistent with the second order nature of the ferromagnetic phase transition. 4.3.3. Binary compounds with cubic AuCu3-structure: USn3, Uln3, U(Ino.5Sno.5)3 UIn3 shows antiferromagnetic order below TN = 88 K with a type I triple q spin structure. USn3 on the other side is a paramgnet exhibiting strong spin fluctuations. In the mixed system U(Sn~Inl_~)3 long range magnetic order is suppressed for x/> 0.4 (Zhou et al. 1985). Prelimenary #SR-measurements applying the ZF-, TFand LF-technique yielded results which generally confirmed the present picture on the magnetism of these compounds (Zwirner et al. 1993, Kratzer et al. 1994b, Asch et al. 1994). The results on USn3 imply indeed a very fast spin fluctuation of the order of 1013 s -1 or faster. The same is found in the paramagnetic state of UIn3. As in the other compounds with type I triple-~f spin structure (USb, DyAg) the ZF-#SR
MUON SPIN ROTATION SPECTROSCOPY
183
signal in UIn3 below TN = 88 K is well described by a dynamic Lorentz-KuboToyabe function. The temperature dependence of A and u resembles closely the results on USb displayed in fig. 4.59 and is discussed there. In the present case the dynamic range extends only for about 10 K below TN. A possible first-order nature of the phase transition is reflected by a temperature independent frequency shift and relaxation rate in TF-measurements when approaching TN from above. New information is gained on the mixed compound U(Sn0.sIn0.5)3 which is expected not to show long range magnetic order. AF- and TF-measurements reveal, however, the onset of spin glass order below ~ 30 K. This is evidenced by a change of the ZF-relaxation function from a Gaussian to a Lorentzian behaviour (well described by the spin glass relaxation function of Uemura et al. 1980) and a strong increase of the W-relaxation rate below 50 K. Previously it was found in U(Sn0.5In0.5)3 that the specific heat c(T)/T shows a slight up turn and the resistivity p(T) a break in slope and a weak decrease at or below 30 K (Lin et al. 1987). These features were not explained before but find now in the light of the #SR results a natural explanation.
4.3.4. Tenary compounds with tetragonal ThCr2Si2 or CaBe2Si2 structure URh2Si2. The antiferromagnetic local moment (#u = 1.95#B ) order in this compound is identical to the one in NdRh2Si2 (see table 4.10), yet ZF- and LF-#SR measurements on a polycrystalline sample display quite a different behaviour (Yaouanc et al. 1990, Dalmas de R6otier et al. 1990d, 1994c). Below TN a one frequency coherent spin precession signal is seen which at low temperatures implies a local field of 0.305 T. Obviously only one type of site is occupied by the #+. The site (1/4, 1/4, 1/4), No. 7 in fig. 4.32, can be excluded since it involves a zero net internal field). The corresponding information is missing for NdRh2Si2 due to the limited time resolution available at the ISIS facility. In CeRh2Si2, which has a
URh2Si2
-
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f
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Fig, 4.60. Temperature dependence of the relaxation rate ~ZF in URh2Si 2. Below TN )~ZFis really a )q (see text) (from Dalmas de R6otier et al. 1994c).
184
A. SCHENCK and F.N. GYGAX I
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Fig. 4.61. Dependence of the spin lattice relaxation rate -~1 on the strength of a longitudinally applied field (/~(0)llnext) below TN in URh2Si 2 (from Dalmas de R6otier et al. 1994c).
slightly different magnetic structure, two different internal fields were seen below TN, suggesting that the #+ is located at two different interstitial sites. Very different is the dynamic behaviour below TN in URh2Si2 (see fig. 4.60). The longitudinal relaxation rate )`1 (the relaxation function is well described by an exponential decay) revealed by those #+ whose spins happen to be parallel to the static internal field is essentially temperature independent while in NdRheSi2 a quadratic temperature dependence is seen for P(0)llc-axis (see fig. 4.34). Moreover, again in contrast to NdRh2Si2, )`1 below TN is dependent on the strength of a longitudinally applied field (see fig. 4.61). This feature is not understood at present. Above TN, ),1 drops quickly with rising temperature similarly to what is seen in NdRh2Si2 for fi~(0)_Lc-axis or in GdNi5 (see figs 4.34, 4.26), reflecting some slowing down of the spin fluctuations as TN is approached from above. A more quantitative analysis of the data is as yet missing.
U(Rho.35Ruo.65)2S@ While URh2Si2 is characterized as a local moment (# _~ 1.4#~) antiferromagnet URu2Si2 is a magnetic heavy fermion superconductor exhibiting ultra small moment (# _~ 0.02#B ) magnetic order below 17 K (see section 4.3.5). It is of considerable interest to study the transition from one type of behaviour to the other one by investigating the mixed compounds U(Rh~Rul_=)2Si2. ZF- and LF-#SR measurements were conducted on the compound U(Rh0.35Ru0.65)2Si2 [polycrystalline sample for which the magnetic structure is not known (Yaouanc et al. 1990, Dalmas de R6otier et al. 1990d)]. The ZF-results are shown in fig. 4.62. A single exponentially damped signal is observed. Its amplitude starts to drop smoothly at about 150 K to 1/3 of its initial value below ~ 40 K. This drop signals the development of a very fast relaxing (or precessing) component which, since these measurements were performed at the pulsed muon source of ISIS, could not be resolved. In any case the low temperature value of the amplitude reveals unambigeously that the #+ are exposed to a very wide static field distribution or, alternatively, to a rather high
MUON SPIN ROTATIONSPECTROSCOPY [
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100 200 Temperature (K) Fig. 4.62. Temperaturedependence of the ZF-~SR signal amplitude (asymmetry) and relaxation rate AZF in U(Rho.35Ruo.65)zSi2. Note the loss of amplitude between ~ 150 K and ~ 42 K, indicating the transition into a magnetically ordered state (from Dalmas de Rdotier et al. 1990d). local field leading to a rapid coherent spin precession, too rapid to be resolved. In other words magnetic order is established in this compound somewhere below ,-~ 40 K. Whether it is long range or short range (e.g., spin glass like) cannot be deduced from the present #SR data. The drop in the amplitude could indicate that the development of magnet order proceeds in a spatially inhomogeneous fashion, a not uncommon feature in heavy electron systems (see sections 4.2.6, 4.3.5). Very interesting is also the temperature dependence of the ZF-relaxation rate AzF (see fig. 4.62). LF-measurements prove that AZF (= At) is more or less entirely of dynamic origin in the whole temperature region studied. AzF peaks sharply at ~ 42 K, similar to what is seen in polycrystalline NdRh2Si2 (Dalmas de Rtotier, 1990d) and is a clear signature for a magnetic phase transition. Note that AzF is generally quite small implying that above TN --~ 42 K spin fluctuations must be rather fast. The relaxation rate below TN is independent of a longitudinally applied field, therefore reflecting still some dynamics as in NdRh2Si2 and UPt2Si2, quite in contrast to the field dependence seen below TN in URh2Si2. In summary magnetic order is seen in U(Rho.35Ruo.65)2Si2 below ~ 40 K but the dynamical behaviour in the ordered state is different from the one in the parent compound URh2Si2.
186
A. SCHENCK and EN. GYGAX '
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UCo2Si2. Some preliminary ZF-#SR measurements imply very fast spin dynamics above the ordering temperature TN = 85 K. No slowing down of the dynamics is seen on approaching TN from above. Below TN 2/3 of the signal is lost as is expected for a polycrystalline sample, given the limited time resolution at the ISIS facility (Dalmas de Rdotier et al. 1994c). UPt2Si2. Again only preliminary ZF- and LF-#SR data are available (Dalmas de R6otier et al. 1994c). The observed temperature dependence of AzF and A1 is displayed in fig. 4.63. The small field dependence is ascribed to a decoupling from the Pt-nuclear dipole moments. The data are quite similar to the results in U(Rh0.36Ru0.35)2Sia and other isostructural rare earth compounds. They reflect mostly the dynamics of the spin system and indicate a certain slowing down, which starts already much above TN. 4.3.5. Actinide based heavy electron and related compounds All systems investigated by #SR are listed in table 4.16. For a more detailed discussion of the #SR results see Schenck (1993). A compilation of some of the most important #SR results is presented in table 4.17.
UPt3. The heavy fermion superconductor UPt3 is certainly one of the most fascinating compounds among all heavy fermion systems possessing a rather intriguing low temperature phase diagram (for a recent status see de Visser et al. 1993). First indications for magnetic order at ~ 5 K, preceeding the superconducting transition at Tc ~ 0.5 K were provided by ZF- and TF-#SR measurements on a polycrystalline sample (Heffner et al. 1987, 1989a, Cooke et al. 1986). Figure 4.64 displays the measured ZF-relaxation rate AZF which exhibits a significant increase below 5 K. LF-measurements proved that this - sample dependent - increase is associated with the development of small static fields of order 2 G at the #+ site or sites. Subsequent neutron diffraction measurements confirmed the onset of an ordered state involving
MUON SPIN ROTATION SPECTROSCOPY
187
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A. SCHENCK and EN. GYGAX
UPt 3 Gaussian relaxation 0.20
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tiny moments of the order of 0.02#B (Aeppli et al. 1988). Taking the #SR-and neutron results together it follows that the /~+ must be located at a site at which the dipolar fields from the ordered U-moments, assuming the structure suggested by Aeppli et al. (1988), cancel perfectly for a perfect stoichiometric and defect free lattice (Schenck 1993). Note that no anomaly in the specific heat is seen at 5 K. Prior to the discovery of magnetic order in UPt3 antiferromagnetic order had already been found in the doped compounds Ua.95Th0.05Pt3 and U(Ph_=Pd~)3 (0.02 ~< :c ~< 0.07) (Goldman et al. 1986, Frings et al. 1987). Interestingly the magnetic structure is the same as in undoped UPt3 with TN also of the same magnitude (TN ~ (3.5-6.5) K) but the ordered moment is much larger (,-~ 0.5#~) and the magnetic phase transition can also be seen in transport and thermodynamic data (Ramirez et al. 1986). A few low statistics ZF-#SR measurements on the compound U1.95Th0.05Pt3 confirmed the onset of magnetic order at TN -- 6.5 K (Heffner et al. 1989a): below this temperature a two component precession signal appears reflecting spontaneous local fields of 0.06 T and ~ 0.009 T. However, the total amplitude of the two components accounts for only 20% of the implanted ~+ implying either a severe loss of polarization due to an extremely inhomogeneous distribution of internal fields in most of the sample volume or a zero field site for most of the implanted #+. Since the two spontaneous fields are also associated with a large field spread of ~ 0.007 T it seems that AF-order in the investigated polycrystalline specimen is not so well developed, probably as a result of poor sample quality. Nevertheless the appearance of well resolved precession signals in U1.95Th0.osPt3 and the absence of any precession signal in pure UPt3 is somewhat of a mystery given the belief that the AF-structure for both compounds is identical (e.g. scaling the field of 0.06 T
MUON SPIN ROTATIONSPECTROSCOPY
189
down by the moment ratio 0.02/0.5 _~ 0.04 one should have seen a local field of 24 G instead of the 2 G mentioned above). ZF- and W-measurements on high quality mono- and polycrystalline UPt3 samples revealed another increase in relaxation rate starting at 490 mK, i.e. near the temperature at which a second phase transition is seen in specific heat data some 60 mK below the transition into the superconducting state (see fig. 4.65) (Luke et al. 1993a, b). Obviously the lower of the double transition around 0.5 K is associated with a further increase in the static field spread ( ~ 0.01 mT). Judging from TF-measurements at 0.18 T the field spread is rather isotropic. The appearance of a split transition into the superconducting state is believed by many investigators to be a consequence of the antiferromagnetic state below 5 K which provides a symmetry breaking field. This couples to the superconducting order parameter and splits the transition into an otherwise degenerate ground state. A coupling between the magnetic and the superconducting order parameter seems also to be indicated by neutron scattering data (Broholm 1989). Blount et al. (1990) have suggested that the neutron data below Tc could be explained by a reorientation of the small antiferromagnetic moments. Luke et al. (1993b) showed that a rotation of the moments in the basal plane by ~- 30 ° could reproduce the increase in local fields below 490 mK. Other explanations, based on the speculation that the lower transition leads to a time reversal invariance violating state, are discussed in Luke et al. (1993b). The low temperature features seen by ZF-#SR in UPt3 are similar to results obtained in U1L=Th~Be13, in which also a double transition is seen for 0.019 ~< z ~< 0.043. However, in the latter case no magnetic ordering seems to precede the transition into the superconducting state (see below) and the idea of a symmetry breaking
0.065
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190
A. SCHENCK and EN. GYGAX
field responsible for a split transition may not be applicable. The occurence of ultra small ordered moments in other nonsuperconducting HF-compounds (see, e.g., CeRu2Si2, UCus) moreover may suggest that the small moment magnetic order is perhaps a phenomenon unrelated to superconductivity.
UCus. This moderately heavy electron compound orders antiferromagnetically below TN = (15-16) K. The magnetic structure has been studied by neutron diffraction and NMR spectroscopy. The data were interpreted in terms of two different structures. Murasik et al. (1974) (also Schenck et al. 1990b) explain their data in terms o f ferromagnetic (1, 1, 1) planes and an antiferromagnetic coupling between neighbouring planes (single q structure) while Nakamura et al. (1990) on the basis of NMR data propose a quadruple q structure. Specific heat and resistivity measurements reveal a second phase transition with hysteretic features at ~ 1 K (Ott et al. 1985). #SR-measurements were aimed in particular at a better characterization of the 1 K transition. The studies started on a sample which did not show the 1 K phase transition. ZF-measurements revealed the onset of three different signals below TN, one associated with zero average field, but non-zero static field spread, the other two displaying coherent spin precession corresponding to low temperature local fields of 0.146 T and 0.1 T, respectively (Barth et al. 1986b, 1988). Figure 4.66 shows the temperature dependence of the spontaneous precession frequencies. The solid lines in fig. 4.66 represent the temperature dependence of the ordered moment deduced from neutron diffraction experiments (P. B6ni, priv. communication, Schenck et al. 1990b). As can be seen, only the 0.146 T signal scales with the order parameter. The crystal structure of UCu5 is displayed in fig. 4.67. The two possible #+ interstitial sites are indicated. Dipolar field calculations (#ord = 1.55#B) show that irrespective of whether the single-q or the quadruple-0" structure is adopted, Baip at the site (1/2, 1/2, 1/2) is zero. For the single-0'structure one finds Bdip = 0.23 T at all equivalent sites (3/4, 3/4, 3/4), while for the quadruple-q structure one finds t3di p = 0 T 2O
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MUON SPIN ROTATIONSPECTROSCOPY
UCu 5
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191
u Cu
I
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I
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w
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Fig. 4.67. Crystal structure of the cubic AuBe5 type. Two likely #+ interstitial sites are indicated. at site (3/4, 3/4, 3/4) and B d i p = 0.27 T at sites (3/4, 1/4, 1/4), (1/4, 1/4, 3/4), (1/4, 3/4, 1/4), respectively. The occurence of two precession frequencies cannot be explained by either structures. Also the signal amplitude ratios (A(0.146 T) : A(0.1 T) : A(0 T) _~ 3 : 2 : 2) do not correspond to the relative site populations. Since for each signal the damping rate is found to be quite small and could be explained more or less by just the random Cu nuclear dipole fields the local fields are quite narrow and would point to a rather perfect commensurate structure. These results together with the strange temperature dependence of the 0.1 T signal could indicate that the magnetic structure is still more complex than a single-q or a quadruple-q structure or that the #+ is found also at defect sites or changes by its presence the magnetic structure locally. In view of the fact that basically the same results are also obtained in a second high quality sample, which showed the 1-K-phase transition, and that all the lines are rather narrow ( ~ 0.5 mT) we rather tend to believe that what is seen reflects intrinsic properties. The first sample investigated showed, as pointed out before, rather small damping rates which were temperature independent from 3/4 TN down to some 10 mK. ZFmeasurements (limited to T < 2 K) on a second sample, which showed the 1 K phase transition, produced the same temperature dependence of the spontaneous frequencies with no break at ~ 1 K. In contrast the relaxation rates for both the zero frequency signal and the 0.1 T and 0.145 T signals showed a dramatic increase
192
A. SCHENCK and EN. GYGAX 3.0
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T e m p e r a t u r e (K) Fig. 4.68. Temperature dependence of the relaxation rates associated with the 0.145 T signal (~z, o1), the 0.1 T signal (,X2,o'2) and the 0 T signal (,~4, o.4) in UCu5. Around 1.1 K the relaxation function changes from Gaussian (o-) above 1.1 K to exponential (X) below. A further signal with approximately the same frequency as the 0.145 T signal but an order of magnitude larger relaxation rate ,~s, also above 1.1 K, is attributed to disturbed magnetic domains (from Schenck et al. 1990d).
M U O N SPIN ROTATION SPECTROSCOPY
193
at ~ 1.1 K, as shown in fig. 4.68 (Schenck et al. 1990a, b). In parallel neutron diffraction showed neither a change in the nuclear nor in the magnetic Bragg peaks when changing the temperature across the 1 K-transition (Schenck et al. 1990b). Obviously the antiferromagnetic structure is unchanged by the 1 K-transition, but the local fields at the #+ sites show a pronounced broadening (NMR results point to the opening up of a gap in the spin excitation spectrum at ,-~ 1 K, Nakamura et al. 1990). The specific heat jump at ~ 1 K suggests that the 1 K phase transition is associated with the heavy electrons. The appearance of obviously quasi random static fields below 1.1 K may than be linked to the heavy electrons as well and it is suggested that these electrons enter into some ordered state (random or in form of a spin density wave) coexisting with the antiferromagnetic order established below 16 K and that these electrons or quasi particles must be distinct from those electrons responsible for the 'conventional' antiferromagnetic order below TN. In other words it is suggested that the low temperature behaviour of UCu5 is determined by the presence of two rather independent electronic substates in the ground state ('heavy' and 'light' mass states, involving different sections of the Fermi surface?) (Schenck et al. 1990b). The idea that more than one kind of electrons has to be considered has come up also for other compounds (see, e.g., Caspary et al. 1993, Feyerherm et al. 1994c). Assuming a random picture the ordered moment of the heavy quasi particles in UCu5 has been estimated to be ,-~ 0.01/zB. Subsequently Nakamura et al. (1994), on the basis of NMR results, have suggested that the 1 K transition reflects a transition from the quadruple c7structure above 1 K to the single q structure below 1 K. This interpretation is clearly inconsistent with the #SR results.
UCd11. This nonsuperconducting HF compound orders antiferromagnetically below 5 K but the magnetic structure is not known. Neutron scattering investigations place an upper limit of ~ 1.5#B on the ordered moment (Thompson et al. 1988). In fact the only direct information on the development of magnetic order at 5 K stems from #SR-measurements on a polycrystalline sample (Barth et al. 1986c, Barth 1988). ZF-, TF- and LF-measurements reveal a loss of the signal below 5 K which indicates the onset of a very wide static field distribution exceeding several 0.01 T. UCd11 crystalize in the cubic BaHgll-structure which is rather complex and provides a large number of magnetically inequivalent possible sites for the #+. In any case the ordered moment must be of the order of lPB in order to produce a field spread of several 0.01 T. Of interest is the LF-relaxation behaviour above TN. As fig. 4.69 shows a field independent #+ spin lattice relaxation is observed which follows a power law and indicates a 5f-spin fluctuation rate of l]5f O( ( T - T N ) 0"4+0"1 o(
v/-T,
T > TN.
(4.17)
This dependence is typical for a system with Kondo resonance behaviour and is consistent with the theory of Cox et al. (1985). A fluctuation rate of usf ~ 10 l° s -1 is estimated for T = 2TN. No such behaviour is seen in the other heavy electron U-compounds. The fact that spin fluctuation become manifest in #SR-measurements in UCdll is probably related to a relatively small distance between the p+ and a nearest U-neighbour providing a strong hyperfine coupling (Schenck 1993).
194
A. SCHENCKand EN. GYGAX I
I
I
I
I
UCdll
longi1'udinolfield
4 -r 5
I000 G o 2000 G
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v
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0
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I
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I
2
5
4
5 T/T N
6
7
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Fig. 4.69. Temperature dependence of the spin lattice relaxation rate )~1 = T11 in UCdll. Note that )~1 is independent of the applied field. The solid line represents a fit of eq. (4.17) to the data (from Barth et al. 1986c).
U2Znl7. Neutron diffraction shows the onset of a rather simple antiferromagnetic structure in U2Znl7 below 9.7 K (Cox et al. 1986). Nearest neighbour U-moments both in the basal plane and along the c-direction in this rhombohedral structure of the ThEZn17 type are coupled antiferromagnetically and are oriented parallel to the basal plane. On the basis of this structure one calculates vanishing dipolar fields at the two high symmetry interstitial sites available to the #+. From the splitting of the TF-#SR signal in the paramagnetic state, using a single crystal sample, and from the angular dependence of the frequency shifts it seems that both sites are indeed occupied (Barth et al. 1986b, 1989b, and unpublished results). However, when cooling the sample through TN both ZF- and TF-measurements show a partial (~ 25%) loss of the signal implying that in part of the sample volume a large static internal field spread develops below TN. This is found in both a polycrystalline and a monocrystalline sample. From LF decoupling measurements it is deduced that the with of the field spread amounts to -,~ 0.1 T (Barth et al. 1986b). Interestingly the fraction of implanted #+ exposed to the large field spread below TN shows also a highly peculiar behaviour above TN. In TF-measurements on a single crystal above TN this fraction is associated with two (or even four) components distinct by their different frequency (Knight) shifts and by a highly unusual angular dependence of the shifts (Schenck et al. 1992, and unpublished results). The angular dependence involves higher order (> 2) Legendre polynomials and is at present not understood at all. It is speculated that the mysterious behaviour of the 25% fraction is a result of competing interactions which could also explain the development of same sort of random order in part of the volume. The question o~f course is what makes this 25%-fraction of the sample volume so different from the rest both in the ordered and in the paramagnetic regime. It does not seem to be sample dependent, more-over its size renders it unlikely
MUON SPIN ROTATION SPECTROSCOPY
195
that crystal defects or the presence of foreign phases are responsible. The onset of the random order coincides precisely with the independently determined N6el temperature. In view of all this it seems as if the inhomogeneous magnetic features seen by #SR in U2Znl7 are an intrinsic property.
UBel3, Ul_~Th~Be13, U1_~Th~Be13_vBv. UBe13 is one of the few remaining U-based heavy electron systems which have not shown signs for a magnetically ordered state. Rumors that a transition occurs at ,-~ 9 K could not be substantiated in later studies. In particular ZF-#SR on UBe13 did not reveal any evidence for a magnetic state with ordered moments > 10-3#B (Luke et al. 1991b, Heffner et al. 1990). If more than 1.9% of U is replaced by Th (but less than 4.3%) a second phase transition at Tc2 somewhat below the superconducting transition temperature Tel is observed. The actual phase diagram is shown in fig. 4.70. It is argued that below Tc2 a different type of superconducting phase could be entered (see, e.g., Sigrist and Rice 1989, Sigrist and Ueda 1991). ZF-#SR measurements established that the phase below To2 is associated with the development of static random intemal fields of electronic origin (~ 0.18 roT) (Heffner et al. 1987, 1989a, 1989b, 1990). This follows from an increased damping rate A of the ZF-signal (given by a static Gaussian Kubo-Toyabe function) below Tc2. As an example see fig. 4.71, which collects results from specific heat, ac susceptibility Xae and ZF-#SR measurements on a U0.965Th0.035Bea3 sample. Clearly visible is the rise of ,4 at Tc2, which is determined from the strong anomaly in the specific heat. Tel is determined by the diamagnetic response of Xac. The rise of ,4 below Tc2 is well described by a spin 1/2 Brillouin function. Assuming a random moment order and making some educated I
I
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Ul"xThxBe13
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h
f 0.0 0.I 0
MAGNETIC I
2.0
~
4.I 0
I
I
6.0
x (%)
Fig. 4.70. Phase diagram of U1_xThxBe13 (from Heffner et al. 1990).
196
A. SCHENCK and EN. GYGAX 0.30
a) l
I
-! ::L
I
I
I
I
S" 0')
I
I
I
I
U 0.965 T h 0.035 B e 13 -
0.28
Ho = 0
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0.24 Y
& -6
I
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I
1
1
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I
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b)
,
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-
0 o3
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c) U
-2
-
-4
-
-6
--
"8
•e.~t~l
k
m
- -
-lO
I 0
I 0.2
I
1• 0.4
I
I
I
0.6
TEMPERATURE
l 0.8
t 1.0
(K)
Fig. 4.71. Temperature dependence of # + ZF relaxation rate O'KT, specific heat cp and ac susceptibility X~c in Uo.965Th0.035BeI3 (from Heffner et al. 1989b).
guess on the #+-site the ordered moment is estimated to amount to ~ 5 x 10-3/ZB (Schenck 1993). As we have seen a similar behaviour was also observed in UPt3. But ultra-small moment ordering is also seen in non superconducting heavy electron systems (e.g., CeRuzSie). The question is then whether different mechanisms have to be involved to explain these results. In the superconducting systems it has been suggested that the phase below Tc2 (in UPt3 and UI_=Th=Bel3) could violate time reversal invariance and would be associated with spontaneously appearing magnetic fields (Sigrist and Ueda 1991, Heffner et al. 1990). Alternatively the small moment
MUON SPIN ROTATION SPECTROSCOPY
197
magnetism is unrelated to superconductivity and is a phenomenon not uncommon for a wider class of heavy-electron systems. Finally we mention that substitution of B for Be, although it has an effect on the entropy released at Tel, does not interfere with the small moment order induced by Th doping (Heffner et al. 1991).
URu2Si2. Also this moderately heavy fermion superconductor displays small moment magnetic order below TN = 17.5 K. The phase transition is accompanied by a relatively huge jump in the specific heat but the ordered moment amounts to only 0.04#B as determined by neutron and X-ray diffraction measurements. (Broholm et al. 1987, Mason et al. 1990, Isaacs et al. 1990). The same studies revealed an antiferromagnetic structure of type I with the AF propagation vector given by ( = (0, 0, 1) and the static moment aligned along the c-axis. ZF-#SR measurements reflect clearly the transition into the ordered state (McLaughlin et al. 1988, Luke et al. 1990c, Knetsch et al. 1993). Figure 4.72 displays results on the ZF-relaxation rate in a monocrystalline sample for P(0)±c-axis. At TN the relaxation rate rises steeply within a few degrees followed by a much weaker increase as the temperature is reduced further. This temperature dependence does not follow the temperature dependence of the ordered moment as measured by neutron scattering (Broholm 1989, Mason et al. 1990) a feature not understood at present. Adopting the proposed antiferromagnetic structure one calculates dipolar fields of the order of 5 mT, which are parallel to the c-axis. Only at the site (1/4, 1/4, 1/4) one finds Bdi p ~ 0. The internal fields should thus be perpendicular to/5(0) and, except for the (1/4, 1/4, 1/4)-site one expects to see a clear spin precession signal for P(0)±c-axis. However, no such signal is observed. If the slow relaxation seen instead is interpreted as the beginning of a cos oJr modulation on extracts B , _~ 0.2 mT. The neutron scattering data and 0.20
"'I"
l""l";'l~"'l""l't"l
'''
URu2Si 2
0.16
-.>
ZF, P I ~ 09
0.12
TN
tO
0.08 ¢1
n" 0.04
¢~
¢ 0.00
,,,I,, 0
5
l,,,,l,,,,l,t,,l,,,,l,,,,~P,,, 10
15
20
25
30
35
40
T (K) Fig. 4.72. Temperature dependence of the ZF-relaxation rate ),ZF in URu2Si 2. Note the discontinuity at TN (from Knetsch et al. 1993).
198
A. SCHENCK and F.N. GYGAX
the #SR-data, therefore, appear totally inconsistent. Several possibilities are implied by this inconsistency: (i) the #+ resides at the site (1/4, 1/4, 1/4) where B~ip = 0: this possibility is questionable in view of the results in URh2Si2, which clearly rule out the site (1/4, 1/4, 1/4) in this homologous compound (see section 4.3.4); (ii) the #+ quenches somehow the 5f-moments at the nearest neighbour U-sites (MacLaughlin et al. 1988); again this possibility is not supported by the #SR results in URh2Si2 which seem to be fully determined by the known AF-structure; (iii) magnetic structure and the magnitude of the ordered moments are not determined correctly by the neutron and X-ray scattering experiments. Also this is not a very likely possibility. Hence the #SR-results provide an unsettled problem. It should be noted that the small moment magnetic order is embedded in a strong paramagnetic background as evidenced by the magnetic susceptibility and the #+ Knight shift below TN (Knetsch et al. 1993, and unpublished results).
UNi2AI3. Similar to UPt3 and URu2Si2 this heavy electron system orders first magnetically below ,-~ 5 K and becomes superconducting inside the antiferromagnetic phase below ~ 1 K. ZF-#SR-measurements were the first to demonstrate that indeed magnetic order was established and that it was unaffected by the transition into the superconducting phase. (Amato et al. 1992c). The same study provided an estimate of the ordered moment of --~ 0.1#B. A typical ZF-signal is shown in fig. 4.73. This signal was interpreted in terms of a multisite occupancy and a simple antiferromagnetic structure with the moments aligned parallel to the c-axis of this hexagonal system of the same type as the RNi5 compounds. Alternatively Uemura et al. (1993) proposed that the #SR-data could also reflect an incommensurate spin
0.0
c.O m
-10.
N
Q_
-20.
r 0
I 1
i
I 2
i
I 3 Time
r
I 4
= 5
(l.~sec)
Fig. 4.73. ZF-/zSR signal in polycrystalline UNi2A13 at 0.3 K (from Amato et al. 1992c).
6
MUON SPIN ROTATIONSPECTROSCOPY
199
density wave order. Indeed later neutron scattering measurements revealed a long range incommensurate AF-order with a wave vector 0'= (1/2 + 3, 0, 1/2) (3 = 0.11) and a maximum ordered moment of # ~_ 0.24#B (Lussier et al. 1994). Whether the #SR-data and the neutron results are consistent with each other has to await a better understanding of the #+ site in this system.
UPdzAI3. Among all heavy electron superconductors this system is special in that it displays the highest superconducting transition temperature (~ 2 K) in coexistence with the largest ordered moment (,-~ 0.85#B ). The magnetic structure has been determined by neutron scattering (Krimmel et al. 1992). ZF-#SR measurements imply that superconductivity and magnetic order coexist microscopically (Amato et al. 1992d, Feyerherm et al. 1994c). However, no information on the magnetic structure could be determined from #SR-measurements due to the fact that the #+ resides at the high symmetry b-site (see fig. 4.25) at which the net internal field in the ordered state is zero. The #+-site has been determined unambigeously from the angular dependence at the #+ Knight shift and the A1 nuclear dipole field induced relaxation rate (Feyerherm et al. 1994c). 5. Review of results in magnetic insulators In contrast to the #+ in a metal, a positive muon implanted into an insulator represents a more complex system. Not only is it possible to encounter the formation of muonium and the concomitant - more complex - #SR signal (or the corresponding missing fraction), but other chemical effects may be of particular importance and influence the #+ in its localization and its coupling to the environment. For detailed descriptions of the situation see, e.g., Schenck (1985) and Patterson (1988). A reference list and an overview of the magnetic insulator systems studied by #SR spectroscopy is presented in table 5.1. (This table and the present chapter do not embrace the substances related to high-temperature superconductors, which are the subject of chapter 6.) Because the #SR studies are more complicated for magnetic insulators, they are also more fragmentary and less systematic than the ones on elemental metals. Most of the examined substances are oxides, and we divide these schematically in crystals with corundum-type structures, rare-earth orthoferrites with perovskite-type structures and rare-earth (R) perovskites RNiO3, CuO or related compounds, and MnO. The studied non-oxide magnetic insulators are fluorides and the COC12.2H20 compound. Finally the case of the antiferromagnetic molecular crystal a-O2 is also presented. Disregarding perhaps Cr203 and MnO, which have not been particularly well studied in this respect, it seems established that for all other oxides below approximately 500 K the occurrence of oxygen-muon bonds ('muoxyle bridges') plays an essential role in the localization of the positive muons - see, e.g., Boekema (1984), Boekema et al. (1985), Chan et al. (1986) and Lin et al. (1986).
5.1. Oxides with corundum-type structure ~-Fe203. In this compound a spontaneous #SR signal has been observed for the first time in an antiferromagnet (Graf et al. 1978). Consecutively the same research
200
A. SCHENCK and EN. G Y G A X
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MUON SPIN ROTATION SPECTROSCOPY
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8
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MUON SPIN ROTATION SPECTROSCOPY
203
group (Rtiegg et al. 1981) noticed that below 120 K the spontaneous signal was in fact split into three components - see fig. 5.1. Between 120 and 500 K a single frequency signal remains and the corresponding Bu follows the magnetization curve. At the Morin temperature, TM = 263 K, the signal shows that the local field at the #+ changes by a factor 2.15, due to the iron spin reorientation in the host, but the signal shows no discontinuity in the relaxation rate. The collapse of the three lines into one at about 120 K seems to correspond to a transition of three distinct muon states into a single one. This could be an indication for the onset of jumps between different potential minima for the muon in the unit cell. Potential energy calculations in c~-Fe203 (and in the non-magnetic compound c~A1203) favour particular sites for the #+, all located about 1 A away from their nearest neighbour, an oxygen ion. In such an oxygen-muon bond configuration the contact hyperfine field at the #+ may not only result from a direct overlap of the wavefunction tails of the magnetic electron and the #+, but supertransfer of hyperfine fields from a magnetic cation via the oxygen anion to the #+ can take place, depending on the geometry and the wave functions of the ions. This field/3c will add to the dipolar field to produce the local field/31oc acting on the #+: (5.1)
Bloc = /~c + J~dip.
/~dip@*/~) has to be calculated, e.g., as described by Denison et al. (1979) (notice that for an antiferromagnetic sample J~dip = /~dip)" Thus, a comparison of the results of hyperfine field calculations in this covalency-effect scheme, assuming the various proposed/z + sites as starting guides, will help to find the #+ states by requiring overall consistency (Boekema 1984). So far, however, the data allow more than one unique interpretation for the #+ localization. 250
'
'
'
1230'
200 ~
'
'
220
15 16
~"
150 -
I,..-,,-,.'4,. 50 100
1 2 1 0
150 200 :::L m
>=- 100
50
TM
0
I 0
I 200
,,\T~
i
I 400
i
I 600
I
..... 3 "I- -I--800
0
Temperature (K) Fig. 5.1. Temperature dependence of the zero-field /zSR frequencies and the local fields measured in single-crystal a-Fe203. The low temperature data are expanded in the insert (Rtiegg et al. 1981).
204
A. SCHENCK and EN. GYGAX
The direction of the local field/31oc with respect to the crystalline axes was determined by applying an external field with various orientations relative to the crystal and measuring IB, I. Since the antiferromagnetic structure is not destroyed if the applied field is not too strong, the demagnetization field remains zero and the/z + sees a field given by the vector equation /~/z ~-~ /~loc 4- /~ext.
(5.2)
With the correct assumption for the orientation of/31oc relative to ]~ext the absolute value deduced from eq. (5.2) will match the experimental value. Below the Morin temperature it was observed that each frequency splits into two according to
I~.1
IS~l =
Bext 4-
IB~o~l
(5.3)
for/~ext parallel to the c-axis, showing the alinement of/~lo~ along the c-axis. At room temperature, well above TM, B]o~ is found to be perpendicular to the c-axis, probably parallel to the crystalline a-axis. The disappearance of the remaining spontaneous signal at 500 K and the reappearance of a signal when applying an external field around 750 K is explained by means of #+ diffusion (Rtiegg et al. 1981). Examining the scheme for supertransfer of hyperfine fields it appears that Bo is parallel to the 3d-moments and that in contrast to Bdip the field/3c is not changing its value at the Morin temperature (for a discussion see Boekema 1984 and references therein).
Cr203. In zero field two #SR frequencies are observed at low temperature, one of them disappears around 150 K and the other is present up to TN. Both follow approximatively the behaviour of the lattice magnetization (fig. 5.2). Part of the ~ i I8 • Single crystal _ o Powder
1 O0 80
g
-
6
60 4 m= 4o
2
20 0
I 0
I 1 O0
I
I 200
I
I
0
300
T e m p e r a t u r e (K)
Fig. 5.2. Temperature dependence of the zero-field /~SR frequencies and the local fields measured in Cr203. The powder-sample data scatter more than the single-crystaldata (Rilegg 1981).
MUON SPIN ROTATION SPECTROSCOPY '
I
i
I
t
I
'
I
i
I
i
I
I
205
I
120 110 ~.100 9o
80 70 60 i
1
2
3
I
i
4
Bext (kG)
Fig. 5.3. Field dependence of the transverse-field /zSR frequencies measured in single-crystal Cr203 at 130 K. /3ext is applied parallel to the crystalline c-axis. The solid lines are results of calculations assuming various values for the angle a between/31oc and the basal plane. The lines correspond (from top to bottom) to values a = +9 °, +1 ° and - 9 ° for the upper triplet, and a = +24 ° and -24 ° for the lower doublet (Rilegg 1981). muons observe a vanishing local field (see Rtiegg et al. 1979). The Cr203 /zSRsignals differ sensibly from those observed in c~-Fe203: in the former system they are weaker - with smaller asymmetries and higher relaxation rates. Due among other things to the different spin structures of Cr203 and ~-Fe203, the local fields at the #+ sites have different orientations. Transverse field #SR measurements in Cr203 (see, e.g., fig. 5.3) show that/31oc is at an angle o~ with respect to the basal plane. This angle amounts to ± 2 4 ° for the lower frequency line, and to + 9 °, +1 ° and - 9 ° for the upper one (see the splitting of the two lines showing up when/3ext is applied parallel to the c-axis). The azimuthal orientations of Blo~ are also determined for the two frequencies and the various values of the angle ~ (Rtiegg 1981). As for c~-Fe203, the question of the muon site is not solved in a unique way. Also #+ trapping at a defect site cannot be ruled out - the lower #SR frequency in Cr203, e.g., can best be reproduced assuming a trapped muon near an non-magnetic A13+ ion substituting a Cr 3+ ion (Rtiegg 1981).
FeTi03. Transverse-field #SR measurements (Boekema et al. 1983) showed that above TN free muon-like behaviour was observed, whereas below TN the muons are experiencing local internal fields. Zero-field measurements below TN showed two weak but observable signals (fig. 5.4), following approximatively the magnetization curves for the Fe z+ ions. The values extrapolated to T = 0 K of the internal fields amount to 2.0 and 3.4 T respectively. Relatively large covalent contributions are
206
A. SCHENCKand EN. GYGAX i
500
.~- . . . .
400 ~" 300
i
i
i
i
i
i
@
, O____O_O...._.
O',,,,
%" 200
•
~'.~% %%
100 0
I
I
I
I
10
20
30
40
I "~
50
I
I
60
70
Temperature (K) Fig. 5.4. The frequenciesof the zero-field#SR signal in FeTiO3 at low temperature. For comparison, calculated magnetizationcurves for Fe2+ ions are drawn(Boekemaet al. 1983). expected and a rough estimate, taking also dipolar contributions into account, yields a field interval corresponding to #SR frequencies extending from 200 to 500 MHz, in agreement with the measurements (Boekema et al. 1983). Precise calculations were found difficult because possible effects of local #+ motion occurring at low temperature.
Fe304. This is a ferrimagnetic oxide (TFN = 858 K) that undergoes a semimetal-toinsulator transition at the Verwey temperature (Tv) near 121 K. In the course of a series of #SR studies (Boekema 1980, Boekema et al. 1985 and 1986) an anomalous change in local field and depolarization rate was observed at 247 K. The temperature dependences of the zero field data (spontaneous frequency and relaxation rate) are shown in fig. 5.5. The frequency follows essentially the bulk magnetization, but a small offset is clearly visible for the interval starting at Tv and ending at about 247 K. The local field is observed to be directed along the (111) direction, which is the easy axis of magnetization. The experiments performed with an external field greater than the demagnetization field and applied along the (110) direction (Boekema et al. 1986) showed that as the temperature is decreased below 247 K, the #SR frequency line splits, indicating the onset of two local fields, i.e. two magnetic inequivalent sites. This supports the model of a phase transition involving the onset of a short-range order already nearly 130 K above the well known Verwey transition. In that sense the anomaly at 247 K can be viewed as a precursor of the semimetal-to-insulator transition. V203. This oxide, which possesses interesting electronic properties, has been the latest member of the group of the corundum structured sesquioxides studied by #SR. Although V203 has the basic corundum structure in the high temperature phase where it is a paramagnetic metal, it undergoes a combined structural, magnetic and electrical phase transition below 155 K to a monoclinic antiferromagnetic insulating phase. At low temperature the V 3+ moments are aligned at +71 ° with the corundum c-axis, in alternating ferromagnetic planes normal to the monoclinic [0 1 0] or hexagonal [1 1 0]
MUON SPIN ROTATION SPECTROSCOPY 40
i
I
I
I
i
I
207
i
(a) 30
70 ,.(
60
O "O.~ '"'"~ to
50
20
40
|%.
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|
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10
30
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""lit,.. _
0
I
0
200
400
20
"'
"O,,
I
I
600
-1-
10
"... I.
800
I
0 1000
Temperature (K)
70
I
I
i
(b)
65 -1-
I
4.5
60
(.9 v :=L 1213
55
~4.0
rv 50
5.0
I
50
I ~ 100
I
I
I
150
200
250
Temperature (K)
Fig. 5.5. Temperature dependence of the frequency and the relaxation rate of the zero-field /~SR signal observed in Fe304 single crystals (a), and detailed frequency data for the Verwey-phase-transition temperature region (b) - from Boekema et al. (1985). direction. In V2O 3 one can ignore the covalent contributions to the field observed by a muon bonded to an oxygen and treat the internal field as purely dipolar to a very good approximation (Chart et al. 1986). Zero-field #SR data were obtained first by Uemura et al. (1984) and then by Denison et al. (1985). Below TN one oscillating signal following the trend of the magnetization curve appears in addition to the signal continuing to have a zero frequency (fig. 5.6). Data taken (Denison et al. 1985) with an external field applied along the corundum c-axis show that the oscillating signal splits into four, corresponding to orientations of the internal field at 7 °, 66 °, 116 ° and 174 ° (±5 °) with respect to the c-axis in the absence of an applied field (fig. 5.7). The magnitude of this internal field is about 0.11 T. The measured relaxation rates clearly indicate the absence of diffusion, even above
208
A. SCHENCK and EN. GYGAX 20.0
i
i
i
i
100.0
150.0
200.0
15.0 "° "o'-'@-O..o4...i,~
g 10.0
5.0
0.0
50.0
Temperature (K)
Fig. 5.6. Temperature dependence of the zero-field #SR frequencies measured in V203. Note signals at zero frequency below the transition temperature at 134 K. This transition temperature shows a well known hysteresis, not marked on this figure (Denison et al. 1985). 32.0 '
i
i
i
i /
.o_
S /
24.0 -
g 200 16.0 12.0 8.0 4.0 0.0 0.0
I
I
I
I
I
0.25
0.50
0.75
1.00
1.25
.50
Bext (kG)
Fig. 5.7. Transverse-field /zSR frequencies measured as function of Bext applied along the hexagonal e-axis of a V203 single crystal at 65 K. The solid lines represent the calculated frequencies for the net field I#~1, where 0 is the angle between the original/3]oc and the c-axis (Denison et al. 1985). the transition temperature of 134 K. Let's mention at that point that the transition temperature around 150 K shows a well k n o w n hysteresis, observed also in the # S R signal ( U e m u r a et al. 1984). In V203 only a subset o f the expected #+ sites in the c o r u n d u m structured oxides is occupied ( B o e k e m a et al. 1986). This is viewed as a signature for the vanadium pairing interaction suggested by G o o d e n o u g h (1963) as the mechanism responsible
MUON SPIN ROTATIONSPECTROSCOPY
209
for the structural, magnetic, and electrical phase transition in V203. In this picture the #+ cannot occupy the interstitial sites of reduced volume resulting from the V 3+ ion displacement in the corundum to monoclinic structural transition. Hence, #SR provides corroborative evidence for the mentioned phase-transition model.
5.2. Orthoferrites and RNi03 perovskites The rare-earth (R) orthoferrites (RFeO3) and the RNiO3 compounds crystallize all with the perovskite-type orthorhombic Pbnm (D 16) structure. The sublattice of the Fe or Ni ions, octahedrally surrounded by oxygen ions, is nearly cubic. Though crystallographically similar, the orthoferrites show a rich variety of magnetic properties (White 1969). The iron spins are coupled essentially antiferromagnetically, with Ntel temperatures in the range 740-620 K, whereas the spins of the rare-earth ions remain unordered down to typically 4 K. Due to a small spin canting, these compounds behave as weak ferromagnets. A systematic #SR study has been performed in six different orthoferrites (table 5.1) and reported by Holzschuh et al. (1980, 1981), and in the comprehensive article by I
I
I'
100 F ~ " SmFeO
50 25 0
-
1"2"41-]74
i
=
I
I
• --~1~--~0~0--
Cor "
I
,,-,._,,_.,
=
25
3
I
I
IQ---O-'O'-[ "~
EuFe03 (F4) 4
I
}-£4 " - * " " ~ "
I
I
I
I
DyFe03
2 5 I }-F4 1 I I I I t I 0 >=. 50 _ . _ ~ .~ . _ . YFeO 3 (F4) 25 I I I I I 0 50 HoFeO 3 25 Fr4 I I I I I O. 100" ErFeO a 75 50 25 r2~4Fr4 I I I l I 0 100 200 300 400 500 600 0 Temperature (K) Fig. 5.8. Measuredzero-field/~SRfrequenciesfor the rare-earth orthoferriteseries. The solidlines only connect the data points. Fe-spin configurationsare indicated(Holzschuhet al. 1983).
210
A. SCHENCK and EN. GYGAX
Holzschuh et al. (1983). In fig. 5.8 the temperature dependences of the zero-field #SR frequencies are summarized. At room temperature only one signal is observed, whereas at low temperature two or three signals are seen - except for SmFeO3 and DyFeO3. As in the case of a-Fe203, and possibly as in Cr203 and FeTiO3, this suggests that different sites in the unit cell will be occupied by the muon at 0 K. At higher temperature local #+ motion or hopping between these sites occurs. The Fe spins of the studied orthoferrites are at the higher temperatures in the so-called F4 configuration (notation of Bertaut 1963), i.e. basically aligned along the crystalline -t-z-direction, disregarding small canting angles of the order of 0.5 ° . At the lower temperatures the spin configuration is different, except for EuFeO3 and YFeO3. There, for SmFeO3 and ErFeO3 the 1"2 configuration is encountered, with now spins parallel to the -t-z-direction, however again with small canting angles. The temperature domains characterized by/"2 and/"4 configurations are marked in fig. 5.8. The discontinuities in the #SR frequencies in SmFeO3 and ErFeO3 are obviously related to the/"2-/"4 transition. In the other compounds the disappearance of the higher frequency components at certain temperature cannot be related to any of the known properties of the substances. Holzschuh et al. (1983) state that the higher frequency lines are associated with metastable #+ states, which decay with raising temperature to a ground state configuration associated with the lower frequency line. For this latter state a #+ site has been determined. This was done comparing the results of refined dipolar field calculations with a thorough set of zero-field as well as transverse-field #SR data, including the measurement of field and single-crystal orientation dependences - see, e.g., fig. 5.9. This most stable #+ site is located in the rare-earth-oxygen plane (z = 1/4 mirror plane), at 1 A of the O-ion, practically at the center of the slightly distorted square formed by the rare-earth ions. The distance to the O-ion corresponds to the bond length in the (OH)- molecule, 271oc is only of dipolar origin, Bc and hence the supertransfer of hyperfine fields can be neglected.
66 t
0
I I I YFeO3 Bext = 4kG T = 296 K
I
60
120
CI
I
180
I
I Bext
t
240
Angle ~ (deg.) Fig. 5.9. Measured orientation dependence of the transverse-field/zSR frequencies for YFeO 3 with an applied field of 0.4 T in the a-b plane. The solid lines are from a fit of a field-induced canting model. The results are used for the/*+-site determination (Holzschuh et al. 1983).
MUON SPIN ROTATION SPECTROSCOPY
211
Lin et al. (1986) have re-evaluated the data in these compounds (Holzschuh et al. 1983) and pushed further the muon site search. They first confirm the findings of Holzschuh et al. (1983) concerning the most stable site. They observe, however, that the proposed site splits into two different subsites (in terms of magnetic structure), leading to the same frequencies in SmFeO3 and ErFeO3, but to the two slightly different frequencies in YFeO3 and HoFeO3 (the sites are now called 1 for the ground state and 2 for the first metastable state). In addition Lin et al. (1986) find a new site candidate, corresponding to the remaining unaccountable frequency line in EuFeO3, YFeO3, and ErFeO3. This site ~site 3) lies symmetrically, approximatively above and below site 2, at the usual 1 A bond distance of the O-ion also bonded to site 2. New for site 3 is the observation that neglecting supertransfer, effects is not nearly as good as for sites 1 and 2, situated in the mirror plane. A precise re-evaluation including this covalent hyperfine field has not yet been performed. Torrance et al. (1992) have performed a systematic study of the insulator-metal and the magnetic transitions in the perovskites RNi03 (R = Pr, Nd, Sm, Eu) - fig. 5.10.
Rare Earth Ionic Radius (angstr6ms)
1.10 ~ O Eu
.00 i i Transitions in
500
Mago:
.-.
~- 4 0 0 - h , k (Z) •¢ [-],m (n-soatt.) 'm
i _ ~ ~ ~ \
1.20 i
t@Srn " ~ ~ r ~ ( ~ / ~ _ ~ O1~(~)~
¢~ 3 0 0 {3..
INSULATOR c
.o
. ~ " ~"J- ~'~ I~ Nd
"
2OO -L
y
/
METAL
Eu
-
o0 ¢-
r
,~ 100 0 0.86
ANTIFERROMAGN. INSULATOR 0.88
~ 0.90
~ 1
I 0.92
\
I 0.94
Tolerance Factor Fig. 5.10, Insulator-metal-antiferromagnetic phase diagram for RNiO3 as a function of the tolerance factor and (equivalently) the ionic radius of the rare earth (R). The observed insulator-metal transitions (resistivity or differential calorimetry measurements) are indicated by large open symbols, whereas the magnetic transitions are represented by three different solid symbols, according to the used method: susceptibility, n-scattering or /xSR measurements (left inset). Additional ~SR measurements of the AF-metal transition (not shown) are in excellent agreement with those from conductivity and neutron measurements. The structure of the RNiO3 compounds is shown schematically in the right inset - see text (from Torrance et al. 1992).
212
A. SCHENCKand EN. GYGAX
For the Eu and Sm compounds as well as for the solid solutions Sml_xNdxNiO3 the antiferromagnetic ordering-temperature data are obtained from TF-#SR measurements only. For the Nd and Pr compounds and for the solid solutions Ndl_xLa~NiO3 and Prl_~La~NiO3 the transition temperatures obtained from #SR and neutron scattering or conductivity measurements are in perfect agreement. The GdFeO3 structure of the RNiO3 compounds (Demazeau et al. 1971, Lacorre et al. 1991) is shown schematically in the inset of fig. 5.10. Regular NiO6 octahedra share comers to form a three-dimensional array, with the R ions occupying the space between these octahedra. In this structure the Ni-O-Ni bond angle, 0, plays an important role, since the electronic bandwidth and the magnetic exchange interaction are closely related to cos 0 (see, e.g., Sawatzky et al. 1976). This angle is generally less than 180 ° because of the orthorhombic distortion, which is conventionally discussed in terms of the tolerance factor, defined as t =_(dR-o)/X/~(dNi-O). If the rare-earth ions were large enough to give t = 1, the rare-earth-oxygen bond lengths (dR-o) and nickel-oxygen bond lengths (dNi-o) would be compatible with the ideal cubic perovskite structure, i.e with 0 = 180 °. Since the rare-earth ions are too small to satisfy this criterion, the structure becomes distorted as the NiO6 octahedra tilt and rotate in order to fill the extra space otherwise present around the rare-earth ion. The distortion tends to be slightly reduced as the temperature is increased. Torrance et al. (1992) draw the general phase diagram (fig. 5.10) for the RNiO3 series as function of the tolerance factor t. It appears clearly that the transitions observed form a coherent pattern. These transitions separate three distinct regimes: an antiferromagnetic insulator, a paramagnetic insulator and a metal. The observed insulator-metal transition depends strongly on R. For small R it occurs a at higher temperature than the antiferromagnetic ordering. The observations are discussed in the framework of a picture developed by Zaanen et al. (1985) and (1990), according to which there are two general types of band gaps possible: the Mott-Hubbard gap due to the Coulomb correlation energy U and the charge-transfer gap associated with an energy A. The insulator-metal transition in RNiO3 is most probably caused by the closing of the charge-transfer gap, induced by an increase in the electronic bandwidth either as a function of increasing temperature or ionic radius of R.
5.3. Miscellaneous mostly Cu-based and layered oxides Various #SR studies have been undertaken on CuO and other copper-oxide compounds related to high-To superconductors. The review concerning this latter class of materials is however mainly included in chapter 6.
CuO, BaCu02, BaY2Cu05. (See also BaCuO2 and BaY2CuO5 in section 6.2.6.) Weidinger et al. (1988) have found magnetic ordering in CuO, BaCuO2 and BaYzCuO5 ('green phase' of Y-Ba-Cu-O) indicated by well defined muon spin precession frequencies in zero-field measurements. A single precession frequency was observed in BaCuO2, whereas 5 frequencies were seen in both CuO and BaYeCuOs, corresponding to different muon stopping sites. A TN of 226 K was found in CuO,
MUON SPIN ROTATIONSPECTROSCOPY 0
213
Frequency (MHz) 10 2O 30 i
(a) 0 O_ .r0 I.t_
250
(b)
30 200 1-
"r"
15o E
~v20
e
>,.,, ,o ,t"-
rrl
100
0"
~10
t.l_
50 ,, ', ~ Ii ; ', ', ', Ii ~ ', ~ ', I ', ,,,I, .....
(c)
[
I ....
I,,
...... i 6 o 200 Temperature (K) Fig. 5.11. Zero-field #SR measurements in CuO: (a) typical Fourier-transform spectrum at 43 K; (b) temperature dependence of spontaneous frequencies compared with S = 1/2 molecular-field model; (c) muon depolarization rates. The five distinct lines, characterized by five corresponding point symbols in (b) and (c), originate from different muon sites (from Niedermayer et al. 1988).
whereas ordering temperatures of only 11 K for BaCuO2 and 15 K for BaY2CuO5 were observed. A more complete report on the magnetic properties of CuO, studied by #SR as well as 57Fe M~3ssbauer-source spectroscopy (MS) and l°°Rh perturbed angular
214
A. SCHENCK and EN. GYGAX
correlation (PAC), is given by Niedermayer et al. (1988). For the interpretation of the zero-field #SR results in magnetically ordered CuO, it is assumed that the fields at the muon sites are due to a sum of dipolar fields and supertransferred hyperfine interactions via the # + - 0 2 - bond, as, e.g., in c~-Fe203 (see section 5.1). As shown in fig. 5.11, below 60 K four distinct signals are seen, two disappearing at 60-80 K, and above 100 K, an additional signal is populated. The various components of the signal sum to the full original muon polarization, indicating that the precession of all implanted muons is observed. Clearly, antiferromagnetic order is detected by #SR below TN ,-~ 226 K; this is also indicated by MS and PAC. The muon-depolarization anomalies detected below TN (fig. 5.11c) are interpreted as indicating a change in muon localization produced by diffusion from metastable traps at low temperature to stable traps at higher temperature. The #SR fields that survive to TN are reasonably well approximated by a S = 1/2 molecular-field model. A high-quality polycrystalline CuO sample has also been studied with transverseand zero-field #SR by Duginov et al. (1994a). The data confirm most of the zero-field features reported by Niedermayer et al. (1988). However, the highest frequency line observed by Niedermayer et al. (1988) above 100 K is not seen and Duginov et al. (1994a) claim that no #+ polarization is missing in the signals they observe. In the temperature region of the incommensurate antiferromagnetic structure detected with neutron diffraction measurements by Forsyth et al. (1988), between 213 K and TN, no spontaneous #+ precession is seen. A peak in the relaxation rate of the slowly relaxing component of the zero-field signal at 219 K is supposed to be connected with the strong development of dynamic correlations near the incommensurate-commensurate transition.
Cao.86Sro.14Cu02, Sr2Cu03, La2fu04_ v, Sr2fbt02Cl2. The infinite-layer compound infinite-chain compound Sr2CuO3 have been studied by #SR by Keren et al. (1993) and compared to the La2CuO4_y and Sr2CuO2C12 systems (section 6.1). In Cao.86Sr0.14CuO 2 spin precession is observed below 360 K above that temperature a rapid #+ depolarization due to the onset of #+ diffusion occurs. The measured #SR frequency permits to extend nicely the sublatticemagnetization curve observed with neutron scattering to lower temperature. Below 225 K the frequency curve splits into two lines approaching 17.9 MHz and 14.3 MHz respectively for T --+ 0, and Keren et al. (1993) discuss also the possible corresponding #+ sites. The sublattice magnetization Ms shows a slower decay with increasing temperature in Cao.86Sr0.14CuO2, compared with that observed in La2CuO4_u and Sr2CuO2C12 (see fig. 6.19 in section 6), indicating that a wider CuQ-layer separation results in more two-dimensional magnetic behavior. Calculations show that Cao.86Sr0.14CuO 2 (dcu O = 3.20 A) is more appropriately described by a 3D model whereas Sr2CuO2C12 (dcuo = 7.76 A) is a very good example of a quasi-2D Heisenberg system. In SrzCuO3 ZF #SR oscillations were seen below 4.15 K, and the Ntel temperature determined as 4.15K < TN < 6 K; the sublattice magnetization was followed down to ,-~ 10 mK (Keren et al. 1993). Again two frequencies are present. The exchange interaction, inferred from susceptibility measurements, is of the order of J = 103 K, Cao.86Sr0.14CuO2 and the
-
MUON SPIN ROTATIONSPECTROSCOPY
215
implying a remarkable suppression of the ordering temperature with kBTN/J ~ 0.01 in SrzCuO3. The result demonstrates a clear signature of low-dimensional magnetic behavior in the CuO chains. For further discussion see also Uemura et al. (1994).
Y2Cu205. Duginov et al. (1994b) have performed ZF and TF #SR measurements in Y2Cu205 ('blue phase' in the Y-Ba-Cu-O family). In ZF the temperature dependence of Bu has been measured. In addition to the well established AF ordering of the Cu 2+ moments at TN1 = 13 K the authors find the indication of a second transition at TN2 = 7.5 K. This can be interpreted as a steady change in orientation of the magnetic copper moments with decreasing temperature, starting at 7.5 K. c~-Bi203. NQR and #SR measurements have been performed in c~-Bi203 by Duginov et al. (1994c). ~-Bi203 is usually considered as diamagnetic, but a splitting of the NQR spectral lines and the internal fields observed by #SR can be explained by the bonds in c~-Bi203 being of partially covalent nature. According to this explication not only 6s- and 6p-electrons but also 5d-electrons take part in the bond formation, hence the electronic shell can get a small magnetic moment of the order of 0.1#B, producing the observed field at a temperature of 135 K. SrCrsGa4019 (Kagomd lattice). The layered oxide SrCrsGa4019 (frustrated Kagomrlattice system) has been examined by LF #+ spin relaxation technique by Keren et al. (1994a). The results have been discussed by Uemura et al. (1994) in the context of frustrated and/or low-dimensional spin systems. SrCraGanO19 shows an unconventional spin-glass like behavior with very strong dynamical spin fluctuations persisting for T/Tg --+ O.
5.4. MnO Muon spin precession was observed in zero field in the ordered state of MnO by Uemura et al. (1984). The single component #SR signal found below TN underlines the fact that the sublattice magnetization Ms, proportional to B,, deviates quite noticeably from a S = 5/2 Brillouin function expected for conventional antiferromagnets. Such an anomalous behaviour of Ms was also observed in neutron scattering (Shull et al. 1951) and ESR (Sievers and Thinkham 1963) measurements. The #SR data, however, provide much more accurate information, especially near TN; the internal field of 0.68 T at T = 117 K suddenly disappears at T = 119 K. B~, extrapolated to T = 0 K (1.14 T) is reasonably well understood assuming a #+ placed at the body centered interstitial site of the simple cubic MnO lattice.
5.5. Magnetic fluorides Several papers have been published on #+ in magnetic fluorides. First, De Renzi et al. (1984a) and (1984b) intended to use the magnetically well known CoF2 and MnF2 insulators as a test case for #SR. In their extended reports they present a strong indication for an octahedrallike #+ location in CoF2, for which they could observe a spontaneous /~+ frequency in the antiferromagnetic state (fig. 5.12). However,
216
A. SCHENCK and EN. GYGAX
Fig. 5.12. Summary of measured angular dependences of the #SR frequency shifts in CoF2 at 41 K (circles and triangles) and at 13 K (squares). The crystal was rotated such that the external field of 0.3 T scanned the a--c plane (left side of the vertical axis on the figure) or the a-b plane (right side of the vertical axis). The solid lines are from calculationsfor the octahedral #+ site (De Renzi et al. 1984b). in both fluorides only a limited fraction of #+ contribute to the #SR signals. This was especially unfavorable for the MnF2 case - with no signal observed in the antiferromagnetic phase - resulting in an uncertain #+ localization. Nevertheless, De Renzi et al. (1984b) present several conclusions on the host magnetism, particularly for the CoF2 sample. The occurrence of a muonium signal in MnF2 and in site-diluted (Mn0.sZn0.5)F2 was discovered by Uemura et al. (1986b) (fig. 5.13). The formation of a F - : #+ : F 'hydrogen'-bonded center was considered for MnF2 by Kiefl et al. (1987), in analogy to the clearly established muon-fluorine bonds in various non-magnetic fluorides studied by Brewer et al. (1986) (such a location for the muon is compatible with the octahedrallike site favoured by De Renzi et al. (1984b) in CoF2); this type of state is now generally considered for #+ in fluorides - Noakes et al. (1993) and references therein. Thus, the #+ situation in fluorides is somewhat complicated, since the muons can appear in 3 different electronic states: (i) as (partly screened?) bare #+, (ii) in muonium form and/or (iii) as part of a ( F - # + F - ) - ion. This latter state especially has a rather noticeable effect on the host: by pulling two F - together (e.g., in MnF2 the nominal distance of 1.76 A between the two fluorine ions is reduced to 1.21 A by the intercalate #+ - Kiefl et al. (1987)) the crystal structure is quite affected in the #+ vicinity. Also in the (F#+F) - ion the #+ interaction with the quite close 19F nuclear moments will compete with the interaction between #+ and the possibly much larger anion moments, but also more distantly situated (Noakes et al. 1993). To add to the complexity, it is observed that the occupation of the three #+ states is a function of temperature (Noakes et al. 1993). Luckily the observation of a single
MUON SPIN ROTATION SPECTROSCOPY 1.0
A
217
A
•
O
O
~ I-
0.5
• v ( 0 ) = 153 MHz o v ( 0 ) = 1.3 GHz 0.0 0.0
I
I
I
I
I
d.5
I
I
I
.0
v/v N
Fig. 5.13. Temperature dependence of the zero-field #SR frequencies measured in MnF2 below TN = 67 K; a low frequencymuon signal and a high frequencymuoniumsignal are observed (Uemura et al. 1986b). The low frequency signal originatesfrom a (F/~+F)- ion, as proposed by Kiefl et al. (1987). spontaneous non-zero #+ frequency (other than a muonium frequency) in zero-field measurements in the antiferromagnetic phase (MnF2, Uemura et al. (1986b), CoF2, De Renzi et al. (1984b)) or of the characteristic oscillating zero-field muon spin relaxation signal generated in (F#+F) - above the N6el temperature (MnF3, CuF2, Noakes et al. (1993)) indicate a static behaviour of the muon in all studied fluorides, at least certainly for T ~< TN. So far the following informations on the magnetism of fluorides was deduced from #SR measurements:
CoF2 (De Renzi et al. 1984b). In the zero field #SR experiment the spontaneous field B u is proportional to the sublattice magnetization. The temperature dependence of B~, reflects the presence of the strong magnetic anisotropy. In particular at the lower temperature the behaviour follows the predictions of the spin-wave theory, while on approaching TN the observed simple power-law dependence agrees with the three-dimensional Ising model. MnF2 and site-diluted (Mno.sZno.5)F2. The/z-spin relaxation rates 1/T1 measured in zero field in both muonium and (F#+F) - states decrease rapidly with decreasing temperature below TN (Uemura et al. 1986b). The mechanism of the spin relaxation is explained above TN by the exchange fluctuations of the Mn moments, and below TN by the Raman scattering of spin waves. With the magnetic Mn atoms of MnF2 randomly substituted by the non-magnetic Zn atoms, the diluted antiferromagnet (Mn~Znl_~)F2 system can be used to study the effect of randomness on the spin fluctuation and ordering. The rate 1/T1 for the diluted (Mn0.sZn0.5)F2 is significantly
218
A. SCHENCK and EN. GYGAX
I 0.001
I
I
I
T= 20K
,L~
"
I
0 T = 33K
b "6 E E
<
,I ....
0
I,. II " --~ -,i~"ll.r-WW'-l~
T = 48K ~ l l
i,ll
0
"8 0.002 0.001 C3
0
i I '
-0.001
~
Illl T= 6511~1 1
I
-0.002 0
I
I
I
I
0.1
0.2
0.3
0.4
0.5
Longitudinal Magnetic Field (T) Fig. 5.14. The muonA9F level-crossing spectra in MnF2 as a function of temperature below TN = 67 K. The upper (A = 1) resonance is off scale at lower temperatures. The curves are fits of a theoretical difference signal; the positions of the resonances scale approximativelywith the sublattice magnetization (from Kiefl et al. 1987). larger than the corresponding values for pure MnF2 at the same normalized temperature (Uemura et al. 1986b). The difference between pure and dilute systems is related to the large spectral weight of low-energy magnons in (Mn0.sZn0.5)F2 found by neutron scattering (Uemura and Birgeneau 1986c). A model for #+ spin-lattice relaxation in an antiferromagnet is presented by Keren (1994) and used successfully by Keren et al. (1994b) to describe the 1/Ta measurements in MnF2. The observation of muon-nuclear level-crossing resonance (LCR) in the antiferromagnetic state of MnF2 (Kiefl et al. 1987) demonstrates that this technique can be used to obtain informations both on the local field at the muon and at neighboring nuclear spins in magnetically ordered systems (fig. 5.14). The observed shift of the local field at the 19F nuclei next to the #+ (with respect to 19F NMR data in MnF2) , is attributed to the disturbing influence of the muon.
MnF3 (Noakes et al. 1993). Below TN no fast oscillation can be detected in the zero-field measurements. At 10 K a large #+ spin-relaxation rate is observed for the major fraction of the signal, indicating a distribution of local fields at the (F#F) sites with a width of 0.1 T or more. Such apparent local magnetic disorder in a relatively simple magnetic structure may be due to the complicated crystal structure. With 12 formula units per monoclinic unit cell, the muons in the (F#F)- ions may be placed at a large number of slightly different positions with respect to the magnetic structure.
MUON SPIN ROTATION SPECTROSCOPY
219
CuF2 (Noakes et aL 1993). In the antiferromagnetic phase, the relatively low spontaneous frequency (corresponding to a local field of 0.15 T at low temperature) and the relatively low #+ depolarization rates of the signals indicate that the host is a rather weak-field magnet. The large bulk susceptibility above TN (Fischer et al. 1974) is interpreted as indicating substantial short range order. The muons as local probes can be sensitive to local ordering, so the coherent frequency need not necessarily go to zero at TN in this case. Unfortunately, the lowest temperature paramagnetic-state data obtained so far in CuF2 were taken well above TN, at 100 K, and no evidence for ordered moments was seen. 5.6. CoCl2.2H20 This compound has been comprehensively studied by proton NMR in its antiferromagnetic phase (Narath 1969). A unique magnetic field at the proton site in the water molecule has been found, indicating that all proton sites are magnetically equivalent. The field at the proton amounts to 0.42 T at the T = 0 K limit, and follows over a wide temperature range a power law of the form {Bp(0) -- B p ( r ) } oc T 6'5.
I
/
I
1.0
o
Vl0wer
x
Vupper
/
0.5 I-
'2. 0 v
:=L
T 4 . law
0 ._1
-0.5
-1.0 I
0.7
X
I
I
I
0.9
1.1
1.3
Log (T)
Fig, 5.15. Double logarithmic plot of the temperature dependence of the frequency shifts for the two zero-field/zSR signals in antiferromagnetic COC12-2H20 - Brewer et al. (1981).
220
A. SCHENCK and EN. GYGAX
One expected to find the #+ at one of the proton sites, but the zero-field #SR measurements (Brewer et al. 1981) showed surprising results: t w o frequencies are found, corresponding to internal fields of 0.273 T and 0.283 T at the T = 0 K limit, and both fields follow over the studied temperature range (from 4 to 17 K) a power law with a quite different exponent: {B#(0) - B~(T)} o( T 4"0. This temperature dependence, plotted in fig. 5.15, is totally different from the behaviour in the other antiferromagnetic insulators, where generally Bloc follows the sublattice magnetization. No explanation of the results is available so far. 5. 7. Solid oxygen
Storchak et al. (1994) present a ZF #+SR study of a-O2 (AF phase of solid oxygen) in the temperature range 10-24 K. Solid oxygen is one of the most unusual molecular crystal, as the 02 molecule possesses an electronic spin S = 1 in the ground state. Strong direct coupling of the 02 molecules' 7r-orbitals is realized on the background of the weak intermolecular Van der Waals interaction, closely connecting magnetic and lattice properties. At equilibrium vapor pressure solid oxygen exists in three crystalline structures; the low-temperature a-phase is known to be antiferromagnetic. Informations on the/z+-solid oxygen complex is given by Storchak et al. (1992). Below the a - f l transition temperature (T~-~ = 23.8 K) Storchak et al. (1994) observe long-lived #+ spin oscillations in ZF, manifesting the existence of an ordered state. Figure 5.16 shows the local magnetic field at the muon as function of temperature. For a comparison the normalized Brillouin curves for TN = T~-~ and TN = 40 K (about the estimate given by Bhandari and Falicov (1973) and Slyusarev et al. (1979)), respectively, are displayed. The abrupt drop of B~ in the vicinity of T~-~ shows that the ordinary second order phase transition does not occur in solid 1.6
I
I
I
I
1.2 (..9 v
0.8 'l I
0.4
0.0
I
5
10
I
I
15 20 Temperature (K)
I
25
30
Fig. 5.16. Temperature dependence of the magnetic field at the /~+ in c~-O2; circles: experimental points. Brillouin curves for spin S = 1, B0 = 1.27 kG, TN = Ta_;~ (dash-dotted line) and TN = 40 K (dashed line), respectively. The solid line is a fit of a 2D-Heisenbergmodel with an anisotropyparameter c~~ 10-2 - see text (from Storchak et al. 1994).
MUON SPIN ROTATIONSPECTROSCOPY
221
oxygen. Storchak et al. (1994) fit their data with the phenomenological model presented by Le et al. (1990a) for a 2D-Heisenberg spin-1 system with TN ----40 K and the anisotropy parameter c~ = 0.01; a good agreement is obtained up to T = 23 K (solid line in fig. 5.16). The behavior is similar to that found for Sr2CuOzC12 by Le et al. (1990a) (see section 6.1). It is known that in the/3-phase of solid oxygen a magnetic order, at least of short range nature, is present (Stephens and Majkrzak 1986). Storchak et al. (1994), however, do not observe the presence of a magnetic order above T~-~. 6. Review of results in layered cuprate (high To) compounds #SR spectroscopy has contributed significantly to our knowledge of the magnetic properties of the high temperature oxide superconductors and their magnetic parent and related compounds. First evidence for magnetic order in the (123)- and the (2212)-families and in NdzCuO4 (the parent compound of the electron high Tc superconductors) was in fact provided by #SR (Nishida et al. 1987a, b, De Renzi et al. 1989, Luke et al. 1989a). The potential of #SR to detect short range and random order has been particularly of value and helped in the elucidation of phase diagrams. Some of the work has been reviewed by Budnick et al. (1990a), Nishida (1992a, b) and De Renzi (1992).
6.1. La2Cu04 and related compounds Table 6.1 presents a list of the (214) cuprates and related compounds studied so far by #SR. The possible #+ site or sites were considered in several papers (Le et al. 1990a, Hitti et al. 1990b, Torikai et al. 1993a). According to the most recent and detailed investigations by Torikai et al. (1993a) possible #+ sites are restricted to small areas on the (100)- or (011)- and the (ll0)-plane near to an apical oxygen at a distance of ,-~ 1 A as shown in fig. 6.1. The site proposed by Hitti et al. (1990b) is close to the 'a' area. The 'a' area is also close to a theoretical prediction by Sulaiman et al. (1993). As in other oxide materials (see section 5) the #+ seems to bind to an oxygen ion forming a kind of an O-H bond (see also Boekema 1988).
La2Cu04. The appearance of antiferromagnetic order in La2CuO4+6 depends very sensitively on the exact oxygen content. Some oxygen deficiency (~ < 0) stabilizes the antiferromagnetic state (e.g., ~ = -0.3 --+ TN --~ 300 K), while an oxygen excess (~ > 0) (introduction of holes into the system) suppresses the antiferromagnetic order and eventually leads also to superconductivity with critical temperatures nearly as high as in the Sr-doped compounds. The presence of antiferromagnetic order in LazCuO4_6 is readily detected by #SR by the appearance of a spontaneous precession signal below TN in a ZF-experiment. It is found that the spontaneous field at the #+ extrapolated to zero temperature falls within a rather narrow range of B u _~ (38.0-43.0) mT independent of TN or the oxygen deficiency, respectively. Also the exact La/Cu ratio seems to be of no effect.
222
A. SCHENCK and EN. GYGAX
TABLE 6.1 List of La(214)-cuprates and related compounds studied by /~+SR (and #-SR). For references see table 6.2. Compound
Crystal struct,
Mag. struct.
TN (K)
Tc (K)
/~+ SR
La2_eCuO4_ ~
orthorhombic for T < 530 K orthorhombic for T < 530 K orthorhombic for T < 530 K orthorhombic for T < 530 K
AF
<290 6-dep. ~<260
-
ZF (#-SR) ZE ZF, LF
La2(CUl_~Zn~)O4 0 ~< :c ~< 0.10 La2(CUl_x Coz)O4+ 6 La2_zSr~CuO4_6 0 ~ x ~< 0.15 Lal.875Bao.125CuO4 Lal.875Bao.075Sro,050Cu04 La2_~_ySr~NdyCuO4 La2NiO4+6 Nd2CuO4_6 Pr2CuO4_ 6
Sm2CuO4_, Nd2_~CezCuO4_ ~ 0 ~< x ~< 0.17 Nd2_xSrxCuO4_6 0~<x ~<0.20 Lal.2Tbo.sCuO4
Sr2CuO2C12 La2MCu206+ 6 M = Ca, Sr
Lal.9Y0.tCaCuO6+6
tetragonal tetragonal tetragonal tetragonal, T~ tetragonal, tetragonal, tetragonal, tetragonal,
T~ T~ T' T~
tetragonal, T t
AF, random SG
ZF
AF (x ~< 0.05) SG (x ~ 0.13) AF AF AF AF, different from La2CuO4 AF (La2NiO4) AF (La2NiO4) AF (La2NiO4) AF(x ~ 0.14)
38 <50 < 30 320 ~ 245-275 ~ 250 ~ 250 ~<250
AF(x ~< 0.10)
<280
AF(La2CuO4) /~ = 0.46#B random tetragonal (KzNiF4) AF 2 layer perovskite AF
~- 170 <280
tetragonal, T*
2 layer perovskite
-
AF
> 0 for x/>0.6 0 20.5 -
ZF, LF, TF (#-SR) ZF ZF, TF ZF ZF
~< 24 (x > 0.14) -
ZF ZF ZF ZF, TF
-
ZF
260 >300 <45 for (M = Sr) 250 for (M = Ca) ~ 250
ZF
ZF ZF, TF
ZF
A c o m p i l a t i o n o f results is p r e s e n t e d in table 6.2. T h e temperature d e p e n d e n c e o f Bu is d i s p l a y e d in fig. 6.2 for various 5. It can be r e p r o d u c e d b y adopting a 2DH e i s e n b e r g m o d e l with a small anisotropy to allow for 3D long range o r d e r (Le et al. 1990a, b). A n i m p o r t a n t p a r a m e t e r is g i v e n b y A = gpBHA/4JMs w h e r e HA is the a n i s o t r o p y field, J the H e i s e n b e r g e x c h a n g e p a r a m e t e r and Ms the sublattice m a g n e t i z a t i o n in a p p r o p r i a t e units. In order to reproduce, Bu(T ) o(Ms(T), e.g., for = 0.03, o n e finds A _~ 10 . 3 ( L e e t al. 1990a, b). T h e n e a r l y constant B u ( 0 K ) in all the different L a 2 C u O 4 - s a m p l e s i n v e s t i g a t e d is in m a r k e d c o n t r a s t to results f r o m neutron scattering. F i g u r e 6.3 shows the sublattice m a g n e t i z a t i o n d e r i v e d from the m a g n e t i c B r a g g p e a k intensity o f three different m o n o c r y s t a l l i n e s a m p l e s with different TN ( Y a m a d a et al. 1987). A s can b e seen the sublattice m a g n e t i z a t i o n Ms for T --+ 0 K drops significantly with TN. It c o u l d be s h o w n that the r e d u c e d Ms(0 K) does not arise f r o m only partial m a g n e t i c order in
MUON SPIN ROTATION SPECTROSCOPY
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(c)
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in Zn substituted compounds Laz(Cul-=Zn=)O4 (Lichti et al. 1991b). The idea was to study the effect of Zn substitution on the magnetic properties in a system where the substitution takes place only at known Cu-sites. Since La2CuO4 only
228
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0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 Zn Concentration (x) Fig. 6.4. Magneticphase diagramof La2Cul_zznxO4. Opensymbolsare from/~SRmeasurementsand closed symbolsare from dx/dt and Xmaxdata (fromLichtiet al. 1991b). possesses CuO2-planes Zn substitution can only take place there, quite in contrast to the case in YBazCu3Oz. The substitution of Zn 2+ creates a spin hole (3d-shell is filled up in Zn) and removes a 3d charge hole from the planar network and disrupts locally the Cu-O hybridization. It suppresses not only the magnetic order but also superconductivity in the Sr-doped compounds. The ZF-#SR shows the presence of an ordered phase in all samples with 0 ~< x ~< 0.10. However, just below TN the magnetic order appeared random or of very short range only as evidenced by a fast decaying but nonoscillating PzF(t). Only at significantly lower temperatures, T ~, was a spin precession signal observed indicating the evolution of also 'long range' order. The results allow to construct a phase diagram as shown in fig. 6.4. It suggests a total suppression of magnetic order for z /> 0.11. The 'flat' part extrapolates to an x value which is quite close to 0.41, the site percolation threshold for Zn substituted sites. This could suggest that simple dilution controls this part of the phase diagram. The faster decrease of TN and T p for small x may point to additional frustration involving the coupling beyond the nearest neighbors. Quite remarkable is also the observation that the development of first the random order and then the 'long range' order is restricted to a fraction of the volume which grows from zero just below TN to essentially 100% at the lowest temperature. The remaining volume stays paramagnetic. This behaviour is reminiscent of what has been observed, e.g., in CeA13 and also in HoBazCu307 (see later). Whether, in the present sample, it could reflect a very inhomogeneous distribution of the substituted Zn, implying a wide distribution of local TN or T p, or an evolution of magnetic order through a percolative mechanism or something else remains to be seen. A comparison with results on YBa2(Cul_~Zn=)Ox will be presented below.
La2_xSrxCu04. Doping La2CuO4 with Sr (i.e. substituting Sr2+ for La 3+) introduces holes into the CuOz-planes just like in the case of an excess oxygen content. The additional spin carrying holes, probably located at the oxygen sites, are believed
MUON SPIN ROTATION SPECTROSCOPY
229
to be coupled ferromagnetically to the neighboring Cu-moments and thus interfere with the antiferromagnetic coupling of the Cu-moments, causing frustration and eventually a suppression of the Cu-moment order. At higher concentrations the holes will become the carriers responsible for superconductivity. It is suspected that the mechanism leading to Cooper pair formation may be magnetic in nature. This possibility has triggered quite some research into the question whether magnetic order and superconductivity can coexsist on a microscopic scale or whether they are mutually exclusive. One important model in this respect has been suggested by Aharony et al. (1988) which predicts a spin glass type of state as a result of magnetic frustrations. The #SR-results on La2_xSr~CuO4_6 for x < 0.5 resemble very much the results obtained in the pure La2CuO4_6 system when varying ~. In the ordered state the low temperature spontaneous field at the /~+, B~ (~ 0 K), is rather independent of x although TN drops quickly with increasing x. Also the width of the local field, AB (~ 0 K), increases with increasing x and thus reflects nicely the disorder introduced by the hole doping induced frustration (see table 6.2). The #SR results on poly as well as monocrystalline samples show that long range antiferromagnetic order is lost for a critical xc > 0.5 (since ~ is usually not determined the Xc-values from different investigations vary somewhat) (Kitazawa et al. 1988, Weidinger et al. 1989, Grebinnik et al. 1990a, Torikai et al. 1993a). However, this does not mean that no magnetic order is present at all. Rather a different type with spin glass like properties emerges which can be observed up to z _~ 0.15 (Weidinger et al. 1989). Although this is still somewhat controversial (see the comments by Harshman et al. 1989 and Heffner and Cox 1989 to Weidinger et al. 1989, and also the zero result by Kiefl et al. 1989) there is mounting evidence that at least up to x = 0.13 random static order can be observed. The evidence is the following. (i) The phenomenon is observed in high quality single crystals, (ii) the whole sample volume participates, (iii) the typical features of #+-relaxation in a classical spin glass are seen. As an example fig. 6.5 shows the ZF-#SR signal in a single crystal with x = 0.11 (Torikai et al. 1993c). At 20 K a Gaussian damping is observed which is induced by the random dipolar fields from the Cu- and La-nuclei. At a slightly lower temperature (To) the Gaussian decay is changed to an exponential one signaling a sudden influence of the Cu-3d moments as a result of the onset of correlations and possibly a slowing down of their dynamics. Below 8 K (= Tf) static random order is indicated by the development of a Kubo-Toyabe signal. Very similar results have been obtained by Sternlieb et al. (1990) who also demonstrated the static nature of the random field distribution at low temperatures in LF-decoupling measurements. There is another distinct difference between samples displaying long range magnetic order (x < 0.1) and samples with random order (0.1 < x < 0.13). While in the former samples above TN the 3dspin dynamics is so fast as to be ineffective in inducing #+ spin lattice relaxation (--+ 3d-spin fluctuation rate ~> 1012 s - l ) the dynamics is much slower in the latter samples and seems to freeze out smoothly on approaching the freezing temperature. Grebinnik et al. (1990a) find for a polycrystalline sample with x = 0.05 that PzF(t) above the freezing temperature Tf ~ 4 K is well described by eq. (2.18), i.e. PzF(t) = Po exp ( - (At)~).
(6.1)
230
A. SCHENCK and F.N. GYGAX
0.15 20K 0.10 EE <
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Time (IJS) Fig. 6.5. ZF-#SR signals in La1.89Sr0.11CuO4 for different temperatures. Note the appearance of a nearly static Kubo-Toyabe signal at 3.5 K (from Torikai et al. 1993c).
Corresponding fit results are displayed in fig. 6.6. A displays a divergent type of behaviour, and the exponent changes from 1 to 1/3 near Tf. This is a typical behaviour for a not so dilute spin glass (see, e.g., Campbell et al. 1994) and has also been seen in a Co substituted (214)-compound: La2Cu0.25Co0.7504. (Lappas et al., to be published.) Figure 6.7 presents a phase diagram for monocrystalline La2_=Sr=CuO4 proposed by Torikai et al. (1990, 1993a) on the basis of their #SR-data. As is evident the spin glass type of phase overlaps more or less completely with the superconducting phase. However, long range order just disappears approximately where superconductivity first shows up. It is also very interesting to note that Tf and To assume a maximum at an z-value which corresponds to the concentration where the low temperature tetragonal (LTT) phase is observed in polycrystalline samples. However, in the present case the sample with z = 0.11 shows 100% bulk superconductivity (Torikai et al. 1993c). The fact that both Tf and To tend to zero when z approaches 0.15 has led Torikai et al. (1993c) to suggest that a phase boundary exists at z corresponding to the maximum To and that the spin state above that z is qualitatively different from conventional antiferromagnetic or spin glass order. Finally we mention that also TF-#-SR-spectroscopy has been applied to the system La2_=Sr=CuO4. Quite visible and distinguishable are two components arising from # - captured by the planar and apical oxygen (Nishiyama et al. 1993, Torikai et al. 1993b). From these measurements the temperature and angular dependence of the /z--Knight shift in the lowest muonic Bohr orbital in oxygen has been determined. One expects that the results should correspond to equivalent data from t70-NMR insofar as the same site is probed. This is not the case and also the assignment
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Fig. 6.7. Magnetic and superconducting phase diagram of La2_=Sr=CuO4. Closed circles indicate the onset temperature, To, for short range correlations and closed squares the temperature, Tf or TN, at which static magnetic order is established (spin glass like for x > 0.05, and coherent long range for x < 0.5) in monocrystalline samples. Results on Tf, TN for polycrystalline samples are indicated by the dashed line. Superconducting transition temperatures, Te, in the single crystals are indicated by triangles (from /~SR) and crosses (from ac - X), and in polycrytalline material by the dot-dashed curve (from Torikai et al. 1993c).
232
A. SCHENCK and EN. GYGAX
of the two # - S R components to the two oxygen sites is not clear. The difference between the 170-NMR (Ishida and Kitaoka 1991) and the (O#-)-SR results may arise from the fact that (O#-) z-1 corresponds to nitrogen, thus being an impurity ion in the lattice, or that the oxygen (or nitrogen) electronic shell modified during the #--cascade to the lowest Bohr orbital is left in an unrelaxed paramagnetic state.
La2_:~(Sr,Ba)~Cu04. The system La2_~Ba~CuO~ displays a rather similar phase diagram as La2_~Sr~CuO4, except in the vicinity of z = 0.125 where superconductivity was found to be almost completely suppressed (Moodenbaugh et al. 1988). This appears to be correlated with an additional structural phase transition at To ,-~ 60 K which changes the system from the low temperature orthorhombic (LTO) phase to a low temperature tetragonal (LTT) phase and which is only seen in the Ba doped compounds (Axe et al. 1989). At much higher temperatures La2_~Ba~CuO4 like La2_~Sr~CuO4 undergoes a structural transition from a high temperature tetragonal (HTT) phase to the LTO phase. The structural phase diagram is shown in fig. 6.8. The question that arose immediately was, of course, whether the disappearance of superconductivity was accompanied by the appearance of magnetic order. ZF-#SR measurements on polycrystalline samples with z in the vicinity of 0.125 revealed indeed the presence of spontaneous #+ spin precession as can be seen from fig. 6.9 (Luke et al. 1991a). The low temperature spontaneous B~,(,,~ 0 K) amounts to 0.025 T which is considerably reduced from the maximum value of ~ 0.043 T found in La2CuO4_& Assuming that the antiferromagnetic structure is the same as 500
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in the parent compound the reduced Bu(,~ 0 K) can be used to estimate the magnitude of the ordered moment to be about 0.3#B. This value is in good agreement with estimates resulting from heat capacity measurements near z = 0.12 (Wada et al. 1990). B~,(~ 0 K) turns out to be rather independent of the exact value of z (see table 6.2). Following the temperature dependence of B~,(T) the transition temperatures TN could be determined. The results are also plotted in fig. 6.8. It is seen that To and TN follow the same z-dependence (Kumagai et al. 1993). The LTO-LTr transition was also found in the compound La2_~_vSr=NdyCuO4. Again magnetic order could be detected by ZF-#SR in a sample of composition Lal.775Sr0.125Nd0ACuO4 with B,(0 K) ~ 0.025 T (Kumagai et al. 1993). The results indicate that (at least long range) magnetic order and superconductivity are mutually exclusive. The role of the LTO-LTT transition is not yet clear (new #SR studies of the system Laz_=Sr=CuO4 have also revealed a long range ordered AF-state in the range z = 0.105 - 0 . 1 2 without a transition to the LTT phase (Watanabe et al. 1994)). It may involve a reduction in hole concentration in the CuO2-planes, shifting the system closer to the Lal.sSr0.aCuO4-situation. On the other hand the reduced value in the ordered moment needs to be explained as well. The latter suggests a change in the electronic structure within the CuOz-plane not just a dilution of the hole concentration. To study these problems further investigations of the mixed system La2_=(Sr, Ba)=CuO4 have been started. Neutron diffraction and TF- and ZF #SR measurements were performed on a Lal.a79Bao.075Sr0.050CuO4 sample (Lappas et al. 1994a, Lappas 1993, and unpublished results). This sample revealed clearly the presence of a superconducting transition at Tc - 22 K, detected by resistivity and magnetization measurements. The neutron measurements showed a gradual increase of the LTI" phase out of the LTO-phase below about 40 K, saturating at about 80% of the sample volume below about 25 K. TF-#SR measurements revealed two signals: one with a
234
A. SCHENCK and EN. GYGAX 100 • Neutron e /J, +SR
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Fig. 6.10. Temperature dependence of the volume fraction in Lal.875Bao.075Sro.05CuO4 showing the LTT-phase (from neutron scattering) or magnetic order (from TF-/zSR-data) (from Lappas et al. 1994). 4.0
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MUON SPIN ROTATION SPECTROSCOPY
235
displayed spontaneous spin precession with B , 000(~ 0 K) _~ 0.024 T. Interestingly the onset of the spin precession signal, implying some 'long range' order, took place only below N 27 K while the W-measurements imply an onset temperature of 50 K (compare figs 6.10 and 6.11). In any case the #SR-measurements together with the neutron results prove that the occurence of superconductivity is restricted to the LTO-phase, while magnetism is associated with only the LTr phase. These findings are tentatively explained in terms of coexsisting Sr-rich and Ba-rich microdomains. The temperature dependence of the relative fractions remains unexplained. La2NiO 4. Very similar in structure to La2CuO4 this system has attracted attention with
respect to the possibility that it may show superconductivity like its Cu counterpart. Although no superconductivity was unambiguously found, magnetically it behaves very similar to La2CuO4. In stoichiometric La2NiO4 long range 3D antiferromagnetic order is observed below TN =320 K by neutron diffraction (Rodriguez-Carvajal et al. 1992). Its magnetic structure can be derived from the one in La2CuO4 by flipping the spin of the center Cu atom in fig. 6.13(b). This is confirmed by ZF-#SR which shows the presence of spontaneous spin precession below room temperature (Martinez et al. 1992). In contrast to La2CuO4_a two frequencies are identified corresponding to low temperature local fields of B(~I)(0 K) _~ 0.26 T and/3(2)(0 K)= 0.015 T, respectively. O ' O O qrl) • N
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(R = Nd, Pr, Sm). Also these compounds have a crystal structure similar to La2CuO4. In contrast to La2CuO4 they remain tetragonal at all temperatures (the R2CuO 4
MUON SPIN ROTATION SPECTROSCOPY 5
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237
2
AC~A¢~A
1
g.ie
00
o AO A -->
B~_L~
I
I
I
25
50
75
I
100
o4 125
Temperature (K) Fig. 6.14. Temperature dependence of the spontaneous/z + spin precession frequency and the direction of/~u in Nd2CuO 4. Clearly manifest are the spin reorientation transitions at 35 K and at 75 K (from Luke et al. 1990a).
phase is called T') and the Cu-ions are only four fold coordinated (there is no apical oxygen) (see fig. 6.13c). They are the parent compounds of the electron doped (214) superconductors. ZF-#SR spectroscopy was first (Luke et al. 1989a) to demonstrate that all these compounds show Cu-moment magnetic order below typically 250 K (see table 6.2). However, the magnetic structure appeared more complex as a function of temperature, as is best seen from the results on a Nd2CuO4_6 single crystal sample. The ZF-spontaneous #+ precession frequency from this crystal is shown in fig. 6.14 as a function of temperature. As can be seen/3t,(T) changes not only its value but also its direction abruptly at certain temperatures. In accordance with neutron diffraction results (Endoh et al. 1989) this is traced back to spin reorientation transitions at 35 K and 75 K, respectively. Above 75 K the antiferromagnetic structure is the same as in La2NiO4, it changes between 35 K and 75 K to the magnetic structure established in La2CuO4_~ and reverts back to the La2NiO4 structure below 35 K. The ordered moment amounts to generally ~ 0.5#B. The reduced value of Bu(O K) as compared to Bu(OK) in La2CuO4 is a consequence of the different magnetic structure. Note that B , (0 K) is of similar order of magnitude as the lower field B(~2) in La2NiO4 (see table 6.2). A spin reorientation transition has also been observed by/zSR in Pr2CuO4 at ~ 40 K (Akimitsu et al. 1994).
Nd2_zCe=CuO4_a. Replacing
some of the trivalent Nd 3+ (or Pr 3+) by tetravalent Ce4+ mobile electrons are introduced into the Cu-O planes. For a critical concentration z ~> 0.14 superconductivity is observed with Tc,m~x~- 24 K (up to z ~- 0.18). Another necessary condition for superconductivity seems to be a certain oxygen deficiency (6 > 0.01) (Takagi et al. 1989). Thus electron doping has the same effect as hole doping in the La2CuO4-system. The question then was whether also the magnetic order, present in the undoped parent compounds, is affected in the same
238
A. SCHENCK and EN. GYGAX
300 250
i
La2.xSr,Cu04
Nd2.,CexCuO4
-~ 200 AFM
(11 n
E 150 cO
,*2-100 ffJ t'-
AFM
SC
0 0.2
~C
I
0.( 0.1 DopantConcentration
0.1
0.2
Fig. 6.15. Magnetic and superconducting phase diagram of hole doped La2_=Sr=CuO4 and electron doped Ndz_=CexCuO4. Solid symbols are deduced from/~SR-data (from Luke et al. 1990b).
way by electron - as by hole doping. #SR spectroscopy on Ce-doped Nd2CuO4 and Pr2CuO4 found indeed a rather abrupt suppression of Cu-magnetic order for z > 0.14 (Luke et al. 1989a, 1990a, b, Davis et al. 1990, Akimitsu et al. 1994) in agreement with later neutron diffraction work (Rosseinsky et al. 1989, 1991a). These measurements served to track the ordering temperature as a function of :c. The results are displayed in a phase diagram, combining the systems Lae_~Sr~CuO4 and Ndz_=CexCuO4 (fig. 6.15). It is again found that magnetic order is not established at once in the whole sample volume. A sizable paramagnetic fraction survives to temperatures much below the ordering temperature TN. It is also found that a very wide field distribution is sensed by the #+ - rather than a unique field, indicating that the magnetic order is disturbed and probably not of very long range nature. Figure 6.15 shows that TN declines much more rapidly with rising electron doping than with rising hole doping. This is understood in the following way: electron doping will change Cu 2+ to Cu 1+, the latter being nonmagnetic like a Zn ion substitute, diluting effectively the Cu-moment system. In contrast holes are mainly located at the oxygen ions, changing O -2 to O-, the latter carrying spin and inducing effectively a ferromagnetic coupling between Cu-moments and hence introducing frustration into the antiferromagnetic order. Frustration is known to have a much stronger effect than dilution on the suppression of magnetic order. On the other hand the maximum of Tc appears at approximately the same level of hole or electron doping. In contrast to the LazCuO4-system no intermediate doping regime is found where superconductivity and magnetic order of spin glass type coexist. Rather there seems to be a common sharp boundary separating the superconducting and nonmagnetic phase from the magnetic and semiconducting phase.
MUON SPIN ROTATIONSPECTROSCOPY
239
Nd2_~SrxCu04_6. It is also possible to introduce holes into the T~-phase Nd2CuO4 by substituting Sr2+ for Nd 3+ (Rosseinsky et al. 1992). Due to a slight oxygen deficiency (3 >t 0.03) holes were only created for x/> 0.1. ZF-#SR measurements showed indeed a magnetic behaviour for x <~ 0.06 which was little changed from the undoped parent compound. For a sample with x = 0.06, TN dropped to 240 K. Also the spin reorientation transitions where hardly affected in this doping regime (Rosseinsky et al. 1991b, 1992). However, for x = 0.10 (formal Cu-ionic charge: +2.02) the #SR data revealed a drop of TN to 60 K and no signs for the spin reorientation transitions were any longer visible. Also the decay rate of the #+ spin precession signal was considerably faster than in the samples with smaller x, implying a certain amount of disorder. Nevertheless over all long-range-order seemed to prevail (at least in part of the volume) as in the other samples, as was evident from the observation of magnetic Bragg peaks in neutron scattering (Rosseinsky et al. 1991b). Increasing x to 0.20 (formal Cu-ionic charge: 2.04) no precession signal could be found any more and no Cu-moment could be detected at 1.5 K by powder neutron diffraction. Obviously long range magnetic order was now suppressed. But the ZF#SR signal still displayed the presence of a wide static field distribution with zero average typical for a spin glass, which starts to develop below ~ 100 K in part of the sample volume. Both in the x -- 0.01 and the x = 0.02 sample pronounced relaxation was also visible in the paramagnetic regime indicating a much slowed down Cumoment dynamics in comparison to the hole free samples. The phenomenology of magnetism and its dependence on hole doping in Ndz_xSr~CuO4_6 has thus very much in common with the magnetic behaviour in the La2_xSrxCuO4_6 system. However, no superconductivity was observed in Ndz-xSrxCuO4. Suppression of magnetism by hole doping is thus not necessarily followed by a superconducting or even a metallic phase. L a 2 _ x T b x C u O 4 (x -~ 0.8). The tetragonal crystal structure of this compound is shown
in fig. 6.16. It arises from a fusion of half the T' (Nd2CuO4) and half the O/T (La2CuO4)-unit cells, forming the so called T*-phase in which Cu is five fold coordinated. Lal.zTh0.8CuO4 is a parent compound of yet another system which becomes superconducting upon hole doping (Sawa et al. 1989). Little is known sofar about the phase diagram of this system. ZF-pSR spectroscopy was first to reveal the presence of magnetic order in the parent material of the T*-phase (Lappas 1993). Subsequently the strength of the staggered Cu-moment (= 0.46(6)/zB) and the antiferromagnetic structure could be determined by neutron scattering. The magnetic structure was found to be identical to the one in La2CuO4 (Lappas and Prassides, to be published). High resolution ZF-#SR spectroscopy displayed the onset of a spontaneous spin precession signal below ~ 170 K, but already below ~ 220 K evidence for some sort of random static order appeared as evidenced by a strong relaxation. Static random order may have even survived in a small fraction (_~ 15%) of the sample volume up to room temperature (AB, _ 2.3 mT). Below 220 K one notices a steady increase of the magnetically ordered volume fraction which levels off around 80% below 100 K. The temperature dependence of the spontaneous
240
A. SCHENCKand EN. GYGAX
T
@
Fig. 6.16. Crystal structure of T*-phase (La, Tb)2CuO4. Cu is fivefoldcoordinatedby oxygen. B u is displayed in fig. 6.17. law:
B.(T) = B,(O) [1 - -T-~N] ~
It can be fitted below 150 K by a simple power
(6.2)
The parameters TN and /3 depend on the temperature range covered by the fit. Two best fit curves are indicated in fig. 6.18 with/3 = 0.36(3), TN = 130(1) K and /3 = 0.49(4), TN = 146(1) K, respectively. The persistence of magnetic order above these temperatures could point to the appearance of a different magnetic phase in part of the sample volume. An exponent of/3 = 0.36 is in close agreement with the prediction (/3 = 0.367) for a 3D S=1/2 Heisenberg antiferromagnet. An exponent of /3 = 0.5 would better correspond to a mean field model. A transition temperature closer to 130 K is also indicated by the exponential relaxation behaviour ()~zF(T)) in the paramagnetic volume fraction. It shows a pronounced divergence at around 120 K (see fig. 6.18), a temperature at which about 50% of the sample is still in the paramagnetic phase. This feature signals a considerable slowing down of the spin dynamics in the paramagnetic volume at ~ 120 K. Strangely below this temperature the dynamics appears to speed up again. The decay of the spin precession signal does not show any anomaly at ~ 110 K and seems to arise only from the spread in static local fields. The temperature dependence of ~ZF follows an Arrhenius behaviour between 120 and 170 K yielding an activation energy of ~-, 0.06 eV. From the value
MUON SPIN ROTATION SPECTROSCOPY
350 j , , "'-...'~. | 300 - -,r~.~.
,
241
, , , , ...... b = 0.36(3) -b = 0.49(4)
250 E. ~ . . "'"'" I ''"~.,., ~,~"" 200
i N~el
m= 1 5 0 .
""",.
'°°t 50
Oil
i
I
0
50
i
I
=
I
=
100 150 Temperature (K)
200
Fig. 6.17. Temperature dependence of the spontaneous B# in Lal.2Tb0.sCuO4. The dashed and solid lines represent fits of eq. (6.2) to the data, see text (from Lappas 1993).
3.0
I
I
I
i
2.5 if)
2.0 tO
1.5 1.0
CC
0.5 0
0.0
I
0
50
I
100 150 200 Temperature (K)
-O-
0
i
250
300
Fig. 6.18. Temperature dependence of the ZF-relaxation rate in the paramagnetic volume fraction of La]2Tb0.8CuO4. The sharp cusp seems to coincide with TN, determined from B#(T) (see fig. 6.17) (from Lappas 1993, Lappas et al. 1994b). o f AZF at 20 K a fluctuation rate o f u ~ 109 s -1 can be estimated ( L a p p a s 1993, L a p p a s et al. 1994b). O n s e t o f m a g n e t i c o r d e r o f the Tb 3+ 4 f - m o m e n t s is o b s e r v e d b e l o w 20 K b y a drastic i n c r e a s e o f the d e p o l a r i z a t i o n rate o f the spin precession signal ( L a p p a s et al. 1994b).
242
A. SCHENCK and EN, GYGAX
Sr2Cu02Cl 2. Also this compound is a layered perovskite with the tetragonal K2NiF4
structure. Compared to La2CuO4 all apical oxygen ions are replaced by CMons (see fig. 6.13a). This leads to an increase of the unit cell along the c-axis by 20%. The Cu-O coordination is thus four fold and in this sense Sr2CuO2CI2 resembles the T'-phase (Nd2CuO4). Neutron scattering and magnetic susceptibility measurements have revealed that SrzCuOzCI2 orders antiferromagnetically like La2CuO4 (Vaknin et al. 1990). Magnetic order has been also established by ZF-#SR measurements on a single crystal sample (Le et al. 1990a, b). A spontaneous spin precession signal was found which disappears sharply at 260 K (see fig. 6.19). It consist of one frequency down to 60 K and splits into two components with equal weight below 60 K. By using different orientations of the single crystal sample with respect to fi(0) it was determined that the spontaneous fields are directed parallel to the a - b plane. Note that in La2CuO4 Btz is pointing out of the plane. The low temperature frequency average (N 16 MHz) corresponds to a field of 0.12 T which is much larger than B u (0 K) in La2CuO4. These differences are ascribed to a different #+-site which, since there is no @ical oxygen, must be located near an oxygen in the CuO2 plane. The splitting of Bu for T < 60 K is believed to be of intrinsic origin since there is also a peak in the magnetization near 50 K when the external field is applied parallel to the c-axis. The splitting may arise from a possible spin reorientation transition not seen so far in any neutron scattering work. The temperature dependence of B~, resembles the results obtained in La2CuO4. As in the latter compound it has been explained on the basis of a 2D-Heisenberg model with A -~ 10 -5 (see section 6.1). The much smaller value of A in the present case implies a very weak anisotropy field as a consequence of the tetragonal structure (Le et al. 1990a). 20
I
I
I
I
I
61: ..... H I I c '= N
z
15
~2
~Lm~ ~ Aax LX
o c-
10
I
5 _
I
i
I
I
T"--r
O 50 100 150200250300 Zk Temperature (K) "-'
o P# I l c a x i s
12r
u_
0/
Z~
~LX A
zx P # / caxis
Zk
0
0
I
I
I
I
I
50
100
150
200
250
300
Temperature (K) Fig. 6.19. Temperature dependence of the spontaneous /z+ spin precession frequency (or frequencies) in monocrystalline Sr2CuO2C12. A splitting develops around 50 K which correlates with a peak in the magnetic susceptibility (see insert) (from Le et al. 1990a).
MUON SPIN ROTATION SPECTROSCOPY
243
La2MCu206+6 (M = Ca, Sr). The hole-doped double-layer system La2MCu206+6 (see, e.g., Fuertes et al. 1990) has shown superconductivity for M = Ca and for Sr doped La2_xSr~CaCuO6+6 but not for the compound with M = Sr. Prior to #SR measurements no magnetic order in the parent material had been identified. But ZF-#SR spectroscopy (Ansaldo et al. 1991, 1992) proved again the presence of magnetic order by the appearance of a spontaneous spin precession signal allowing also to determine the transition temperature TN. In the system La2SrCu206+6 it was found that TN decreases from more than 300 K for a sample with 6 < 0.06 to ,-, 250 K for a sample with 6 = 0.2. A TN -~ 250 K was measured in a La2CaCu206+~ with 6 -~ 0.037. Common for all samples was a two frequency precession at low temperatures corresponding to local fields of B~, (0 K) = 0.036 T (main signal) and B~ (0 K) = 0.13 T. The lower field is probably associated with #+ bound to an apical oxygen while the high field is associated with #+ near a CuQ-plane. Note that B~ (0 K) = 0.13 T is close to the corresponding value in Sr2CuO2C12 (see table 6.2). The high frequency component becomes blurred above ~ 250 K. Very peculiar is the temperature dependence of Bu(T) in the LaaCaCu206+6 sample (see fig. 6.20). In contrast to the M = Sr samples both B~, drop by roughly a factor of 1.75 when going from the lowest temperatures up to ~ 30 K (Ansaldo et al. 1991, 1992). The authors suggest that this drop may be associated with the onset of superconductivity due to the mobility and segregation of the excess oxygen intercalated in a Ca(La) layer between two CuO2-1ayers. As the temperature is lowered the excess oxygen may cluster into domains producing locally a high enough hole concentration to facilitate superconductivity and depleting other regions from holes thereby stabilizing the antiferromagnetic order there and restoring the moments to their full staggered value. The presence of superconductivity below 45 K in about 15% of the sample volume was indeed interfered from weak W-measurements (Ansaldo et al. 1992).
18
I
I
I
I
I
I
I
I
16 14 1
12 10
¢.-
Ill•
8
6 LL
4
0
2 0
I
0
I
i
0 I
I
0 I
I
100
I
I
0
I
200
Temperature (K)
Fig. 6.20. Temperaturedependence of the two spontaneous/z+ spin precession frequencies in La2CaCu206.037. The pronounced increase of both frequenciesbelow (20-30) K is attributed to a segregation into oxygen (hole) rich and oxygen depleteddomains (from Ansaldoet al. 1992).
244
A. SCHENCK and EN. GYGAX
6.2. YBa2Cu30x and related compounds A list of compounds studied by #SR spectroscopy is given in table 6.3. Possible #+-sites have been considered in a number of papers. Theoretical work has been presented by Boekema (1988), Dawson et al. (1988), Li and Brewer (1990), Halim et al. (1990), Lichti et al. (1990a, b) and experimental work has been discussed by Dawson et al. (1990, 1991a), Nishida et al. (1990a), Brewer et al. (1990) and Weber et al. (1990). There is a general consensus that, like in the L a 2 C u O 4 system, the #+ will be bound to an oxygen, forming a kind of an O - H bond with a bond length of ~ 1 ,~. More specifically, in the fully oxygenated (123)-system (x = 7) the #+ is preferentially found near a chain oxygen at a position (0.14, 044, 0.071) (Weber et al. 1990, see fig. 6.21). The same site is also taken by hydrogen in hydrogenated YBa2Cu307 (Weidinger et al. 1994). With less probability the #+ is also found near an oxygen in the CuO2-plane. This position is not very precisely known. In the oxygen depleted (x = 6) system all the chain oxygen is absent and the #+ is now found near an apical oxygen.
6.2.1. YBa2Cu30~ The very first indication for magnetic order in an unspecified member of the superconducting YBaCuO-family was provided by Nishida et al. (1987a), using ZF-#SR. Subsequently the same group (Nishida et al. 1987b) was first to prove the existence of long range magnetic order in the tetragonal phase of YBa2Cu3Ox, the parent
b/
1',
r. sa
/
___k
Fig. 6.21. Lower part of the crystallographic unit cell of YBa2Cu3Oz with possible/z + sites indicated by olden circles and filled circles. The cluster of points to the right (center is at (0.14, 0.44, 0.071) about 1.0 A away from the chain oxygen 0(4)) and equivalent positions is found for x ----7, the more spread out distribution of sites close to the apical oxygen O(1) (distance is again of the order of 1.0 ,~) and equivalent positions for x -- 6 (from Weber et al. 1990).
MUON SPIN ROTATION SPECTROSCOPY
245
[.. F
c~
d ,,d V
v~
o
v~ ,,,.4,
v~
I
+
~ ~ v~
e- c4 ~: II II II
~t
::::1.
=L&:&
0
<~ 0 o
~ tl u u q~ tt~
N
~v
#
c5 II
"~
o--
o
N ? ~ A ~ V
o
t~
0
v~v/~v/~v/v~V/V ~v/
~ o~
v/Zv/ ~v/av/vav/~/~.v/
~¢~
246
A. SCHENCKand EN. GYGAX 500
I
I
i
I
I
I
f
I
I
I
YBa2Cu3Ox gSR
400
[2] quenched [2] annealed
n.s. 300
[41 [51
I
g AFM
~
[]
!
200
100
~
~ellj~ annealed~ I
Ortho-I
I 'l
Ortho.ii r ~ )O00"-
i~
i
i
i
i
7.0 X Fig. 6.22. Magnetic and superconductingphase diagram of YBa2Cu30=. The magnetic part stems from/zSR and neutron scattering measurements: (1) Nishida et al. (1988b), (2) Brewer et al. (1988), (3) Tranquada et al. (1988), (4) Rossat-Mignodet al. (1990), (5) Rebelsky et al. (1989) (from Nishida 1992b).
6.0
6.5
material for the high temperature superconductor YBa2Cu307. Long range antiferromagnetic order was confirmed shortly after by neutron diffraction measurements on an oriented powder sample (Tranquada et al. 1988). Since then #SR experiments on the YBazCu30= system investigated the dependence of magnetic order on the oxygen content and in particular tried to verify a possible coexistence of magnetic order and superconductivity in a certain range of z like in the La2CuO4-system (see table 6.3). Results on the transition temperatures following from these experiments are summarized in fig. 6.22, including data from neutron scattering (Rossat-Mignod et al. 1990, Rebelsky et al. 1989, Tranquada et al. 1988) and superconducting transition temperatures (Nishida 1992a, b), As in the LazCuO4 system TN decreases with the hole concentration (oxygen content), most rapidly in the range z = 6.2-6.4, depending on the sample preparation method: samples prepared by an annealing procedure show a drop of TN at smaller z-values while in samples quenched from high temperatures the drop of TN is shifted to slightly larger z-values (Brewer et
MUON SPIN ROTATION SPECTROSCOPY
247
al. 1988). Weidinger et al. (1990) even found TN _~ 60 K in a quenched sample with z = 0.5. The difference in behavior is ascribed to differences in oxygen ordering in the Cu-O chain planes for nonstoichiometric oxygen concentrations. By very slow and careful annealing the orthorhombic phase can be stabilized down to z = 6.2. For quenched samples the tetragonal phase is observed which converts to the orthorhombic phase at higher x-values (for a detailed discussion and references see Nishida 1992b). Independent of preparation technique TN is rather constant up to z = 6.2. It is argued that the addition of oxygen into the chain position up to z = 6.2 does not introduce holes into the CuO2-planes and thus cannot disturb the intra plane antiferromagnetic exchange coupling (Rossat-Mignod et al. 1990). Figure 6.22 shows that magnetic order (not necessarily of long range nature) and superconductivity seem to coexist around and below z = 6.5. Actually all available data show that magnetism and superconductivity exist in the same sample, if Tc is below approximately 50 K (see Weidinger et al. 1990). Again the question arises on what scale this coexistence takes place. A macroscopic separation into a magnetic and a superconducting phase can be ruled out since TN and Tc vary in a continuous way with the oxygen content. Although the fraction of #+ sensing magnetism declines with rising z or Tc, respectively, the corresponding volume fraction is not 100 90
80
70
o~ 60 t-
0.57
O
50 .2 '$
\7
tt~
40
3;
0.67
30 20
\
YBa2Cu306+x
\ \ \
10
\ \
0
I
10
I
}
20 30 Tcrnidp°int (K)
I
I
40
50
60
Fig. 6.23. Fraction of magnetically ordered volume in YBa2Cu306+= as a function of z. The fraction is obtained from the amplitude of the corresponding/~SR-signal (from Weidinger et al. 1990).
248
A. SCHENCKand EN. GYGAX 320
I
I
c I P.
300
I
I
Site#1
280 L9 260 .._= o~ C 0
240
i
I
[-
I
,ev ~
1300 0 ._J
I
8 MHz
1260 1220 1180
ii 0
i 50
l
i~~
1O0 150 Temperature (K)
200
Fig. 6.24. Temperature dependence of the two spontaneous /z+ precession frequencies in an oriented powder sample of YBa2Cu306.0 (from Brewer et al. 1989). associated with a constant TN, as one may suspect if macroscopic magnetic domains would be present. The #SR data also show that the spontaneous static internal fields at the #+ decrease very rapidly when the superconducting phase is entered (Weidinger et al. 1990, Brewer et al. 1989). Also this is inconsistent with a macroscopic phase separation picture. However, one cannot exclude the coexistence of microdomains of orthorhombic and tetragonal structure which are so small that they will influence each other, explaining the continuous variation of TN and To. The presence of a spontaneous #+ spin precession signal or of at least coherent short range magnetic order places a lower limit on the tetragonal domain size of ~ 50 .~. This is still small enough to not inhibit superconductivity~ due to a proximity effect vis-a-vis a superconducting coherence length of (20-30) A. Of course the amplitude of the spin precession signal must be reduced (as is observed, see fig. 6.23) and #+ in the orthorhombic domains will still feel some random fields, spilling over from the tetragonal domains, causing depolarization (as is also observed). It has been also suggested that an electronic phase separation could produce hole rich and hole depleted microdomains (Emery et al. 1990). The general picture provided by #SR on the phase diagram of YBa2Cu30~ fits well with other results, notably from neutron scattering experiments. We now discuss some more specific #SR results. ZF-#SR in the ordered state displayed the presence of clearly two frequencies (Brewer et al. 1989, Budnick et al. 1990a, Barsov et al. 1994). The dominant frequency (B, (0 K) ~_ 0.03 T) is seen
MUON SPIN ROTATION SPECTROSCOPY
18
~illl
249
YBa2Cu30x
•
17
il
16
+ ~ Q x
g
LL
• x 0 •
2
I
II~
I
I
•
~OAcL °
6.08 8.16 6.31 6.32
40
~'
+
4~ (~
I
I
I
I
I
I
I
l
I
I
80 120 160 200 240 280
• 6.08 × 6.16
4
a
/i /~jt J
-- 2
b
n- 1
0
I
t
I
I
I
I
I
I
I
I
1
I
I
I
I
40 80 120 160 200 240 280 Temperature(K)
Fig. 6.25. Temperature dependence of (a) spontaneous /~+ precession frequencies and (b) associated relaxation rates in samples with various oxygen concentrations (from Barsov et al. 1994).
for :c up to 6.5 (depending on the preparation procedure). A second high frequency component ( B , (0 K) = 0.13 T II c-axis) is only seen in samples with x < 6.3. Occasionally a third frequency is seen corresponding to a Bu (0 K) -- (0.0080.015) T (Nishida et al. 1990a). The three frequencies correspond to the three sites discussed above and are consistent with the antiferromagnetic structure determined by neutron diffraction measurements (Tranquada et al. 1988). The dominating B , (0 K) is rather insensitive to the oxygen concentration for z < 6.2-6.32 (Kiefl et al. 1989, Weidinger et al. 1990, Barsov et al. 1994). In contrast and analogous to the La2CuO4-case neutron scattering showed a pronounced decrease of the magnetic Bragg peak intensity when z was changed from 0.15 to 0.38 (Rossat-Mignod et al. 1990). The temperature dependence at B~ = 0.03 T and B~ = 0.13 T in an oriented z ~_ 6.0 powder is displayed in fig. 6.24 (Brewer et al. 1989). Very peculiar is the rise of Bu below ~ 80 K (T/TN ~- 0.2) which is more pronounced for the dominant 0.03 T-signal which arises from ~+ located near the apical oxygen. This
250
A. SCHENCK and EN. GYGAX
anomaly is also found in sample with z -- 6.08-6.32 (Nishida et al. 1988b, Barsov et al. 1994). Interestingly a similar anomaly at T/TN ~- 0.2 is also found in the (2212)-family (see below). At 10 K another anomaly shows up in that Bu(T ) drops sharply for the 0.13 T-signal and slightly for the 0.03 T-signal. This drop has not been seen in the data of Nishida et al. 1988b (z _~ 6.2) and of Barsov et al. 1994 (z = 6.08-6.32, see fig. 6.25a). Its origin in the z = 6.0 oriented powder sample is not explained. The 80 K anomaly shows also up in the staggered magnetization determined from the intensity of the magnetic Bragg peaks in neutron scattering for samples with z > 6.2 but apparently not in samples with z < 6.20 (Rossat-Mignod et al. 1990). In contrast to the #SR results the magnetization decreases below ~ 80 K. Interestingly also the spread ABe(T) of the local field B,(T) increases below 80 K (Barsov et al. 1994, see fig. 6.25b). Taken together it seems that long range order gets disturbed below 80 K (at least in samples with z > 6.08) with the effect that the Bragg peak intensity decreases and the field spread at the #+ site is increased. That also Bu(T) increases more rapidly below 80 K may be a subtle result of forming the vector sum of dipolar fields at the #+ position (the position near an apical oxygen may be particularly sensitive to slight changes in the moment order since it is situated almost half way between the CuO2-planes). The appearance of a certain disorder below 80 K may be associated with a freezing of holes at the oxygen sites. Finally it has to be emphasized strongly that from the perspective of the implanted #+ the onset of magnetic order never involves the total sample volume at once. Depending on the sample preparation magnetic order in most of the sample volume may only be obtained at temperatures significantly below TN. This may be explained in terms of a distribution of transition temperatures due to an inhomogeneous distribution of the chain oxygen ions, but this explanation cannot very well be applied to samples with z ~< 6.2, where TN varies only little. Exploratory TF-#-SR-spectroscopy on YBa2Cu30~ (z = 6,6.5,7) has been reported by Nishida et al. 1991, Nishida 1993).
6.2.2. Yl_vPrvBa2Cu30~ (x = 6,7) Replacing Y in Y B a 2 C u 3 0 7 by other rare earth atoms the superconducting properties of the (123)-O7 system are hardly effected. A notable exception is a replacement by Pr which - in contrast to Y or other rare earth substitutes - is believed to have an ionic charge of ~ 4 + instead of 3 + and hence donates electrons 6. Therefore one may expect that Pr-substitution has a similar effect on the hole concentration in the CuO2planes as removing oxygen. Indeed PrBa2Cu307 does not show superconductivity but antiferromagnetic order of the Cu-moments in the CuO2-planes instead (Felner et al. 1989). A remarkable difference to YBa2Cu306 is the fact that PrBazCu307 retains the orthorhombic structure. ZF-#SR measurements on polycrystalline samples served to determine the phase diagram of Yl_vPrvBa2Cu307 (Cooke et al. 1990a-d). Long range antiferromagnetic order, again in evidence via a spontaneous 6 This view is challenged by X-ray absorption (XANES) results which show that Pr in the (123)compounds is in the trivalent state (Pr 3+) (U. Staub, priv. communication). The appearance of Cu 2+moment order for y > 0.5 and the destruction of superconductivity must, nevertheless, imply that the holes in the CuO2-planes are removed and instead are probably located close to the pr3+-ions.
MUON SPIN ROTATIONSPECTROSCOPY
251
spin precession signal, was observed for 0.5 < y ~< 1. The temperature dependence of the spontaneous frequency u~ is displayed in fig. 6.26 for various y. The abrupt drop in u, below 20 K for y = 1 and below 6.5 K for y = 0.8 is probably arising from the onset of magnetic order of the pr4+-moments. This phase transition at TN2 has also been seen in susceptibility, specific heat and neutron scattering measurements. It seems, however, that pr4+-moment ordering alone is not sufficient to explain the drop of ur, satisfactorily. Rather it appears necessary to invoke in addition a small (0.02#B) ordered moment on the Cu-chain sites (Dawson et al. 1991b). Such a small moment may have escaped detection in NMR/NQR measurements (Ltitgemeier 1989). The spontaneous field at the #+, extrapolating the values above 20 K to zero temperature, B~ (0 K) = 0.016 T, is clearly smaller than the corresponding value in YBa2Cu306 (see table 6.4). The difference arises from the different sites that are taken by the #+ in the 06- and the O7-compounds and is not the result of different values of the ordered Cu-moments. The value of 0.016 T is close to what is found in hydrogenated YBa2Cu307 (see below) and occasionally in YBa2Cu306+6 (5 < 0.5) and confirms a #+-site assignment close to a chain oxygen. As before in YBa2Cu306+~, B~(0 K) seems to be rather independent of the Pr-content y or the hole concentration, respectively. At y = 0.5 no long range magnetic order could be detected. Instead a fast relaxing signal was seen which could be well described by a function typical for spin glasses with nearly static features (Cooke et al. 1990d). From the temperature dependence of B~ for y > 0.5 and of the relaxation rate for y = 0.5 the N6el temperatures or a spin freezing temperature TN1 could be determined which are displayed in fig. 6.27 as a function of y. Included are also superconducting transition temperatures Tc for compounds with y < 0.6 as well as the additional magnetic transition temperatures TN2 at low temperatures. The resulting phase diagram is very similar to the YBa2Cu306+6-phase diagram including a narrow regime of coexisting superconductivity and spin glass order. This feature has to be commented in the same way as for YBa2Cu306+6. i
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252
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In PrBa2Cu306 two spontaneous frequencies showed up, one corresponding to the frequency seen in PrBa2Cu307 the other one being close to (in fact 16% larger than) the value seen in YBa2Cu306+6. This points to the presence of an appreciable amount of chain oxygen ions so that #+ can be found both near chain oxygen and apical oxygen sites, respectively.
6.2.3. HzYBa2Cu307_6 Doping YBa2Cu307 with hydrogen has the same effect as replacing y3+ by Pr 4+ ions, namely it donates electrons to the CuO2-planes and reduces the hole concentration. This conjecture was first fully proved by ZF-#SR-measurements which showed the presence of long range antiferromagnetic order in HzYBa2CuaO7 for z > 0.5 (GliJckler et al. 1989, 1990a, 1990b, Niedermayer et al. 1989), following a first indication for some sort of local magnetic order by NMR (Goren et al. 1989). Persistence of superconductivity up to hydrogen concentrations of z = 0.2 was observed before by Reilly et al. (1987). The ZF-#SR results revealed two spontaneous precession signals corresponding to B (1) (0 K) = 0.015 T and _/~R (1) (0 K) -- 0.03 T. The temperature dependence of R (i) for a sample with z = 0.9 (6 = 0) is reproduced in fig. 6.28. The higher frequency signal appeared only weakly while in oxygen deficient samples it was the dominant component. This fact indicates that the low frequency signal is associated with #+ bound to the chain oxygen and the high frequency signal with #+ bound to the apical oxygen site. The near perfect agreement of the frequency values with the corresponding values in YBa2Cu306 and Y l _ y P r y C u 3 0 7 (see table 6.4) proves that the antiferromagnetic structure of the ordered Cu-moments in the CuO2-planes as well as the moment value is not affected to any significant degree by H- or Pr-doping. The ZF-#SR measurements show that, depending on the level of hydrogen doping, only a fraction of the sample volume contributes to the spontaneous precession
MUON SPIN ROTATION SPECTROSCOPY 5
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50
i 100 150 200 250 300 350 400 Temperature (K)
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30 25 o~ 20
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Fig. 6.29. Fraction of the magnetically ordered volume in YBa2Cu3OTHz as a function of z. The fraction is determined from the amplitude of the spontaneous spin precession signal (from Niedermayer et al. 1989).
signals. As fig. 6.29 reveals this fraction is zero below z = 0.5 and saturates at about 20% above z ~_ 1.5. The data show that the remaining volume fraction is associated with a nonoscillating, slowly and exponentially decaying signal, reflecting random internal fields of a few 0.1 roT. Niedermayer et al. (1989) speculate that this signal could be associated with a third site with very small residual fields in the ordered state. More likely may be an explanation in terms of a non random distribution of the dissolved hydrogen atoms (e.g., a phase separation into a hydride phase and a largely hydrogen free (z < 0.13) phase; Reilly et al. 1987) leaving a large part of
258
A. SCHENCKand EN. GYGAX
the sample volume in a non magnetic but also non superconducting state since no superconductivity is indicated for z > 0.8, as follows from TF-#SR-measurements (Gltickler et al. 1990a, b). Consistent with the picture of hydrogen as an electron donor, compensating holes in the CuOz-planes, is the observation that magnetic order becomes manifest already at smaller z-values in oxygen deficient compounds (see table 6.4) (Gltickler et al. 1989). 6.2.4.
YBa2(Cul_vTy)3Ox,T
= Zn, Fe
The replacement of Cu by trivalent ions, such as Fe 3+, mainly involves the Cu chain sites while divalent Zn 2+ substitutes preferentially for Cu in the CuO2-planes. Both types of substitutions reduce Tc and eventually suppress superconductivity altogether. In this respect the 'nonmagnetic' Zn is much more effective than even the magnetic substituents Co, Ni and Fe. Zn substitution does not alter the orthorhombic structure, the oxygen stoichiometry and the hole concentration while in the case of Fe substitution the hole concentration is reduced and the orthorhombic structure changes to the tetragonal one for y/> 0.04. This structural change can be avoided by employing a special thermal treatment (Katsuyama et al. 1990). The interest in studying the effects of substitutions on the Cu sites is motivated by the expectation to learn more about the possible role of magnetic interactions in the pairing mechanism. While the effects of substitutions on the superconducting properties have been studied in some detail much less is known about the magnetic features induced by the substitutions. #SR-spectroscopy was applied to gain more information in this respect. Zn-substituted compounds were studied by Garcia-Munoz et al. (1991) and Mendels et al. (1994) with respect to magnetic properties. Superconducting properties were studied by #SR by Albanese et al. (1992). Zero field #SR and neutron polarization analysis were applied in a search for localized moments in a YBa2 (Cu0.96Zn0.04)306.95-sample. No evidence for static or slowly fluctuating local atomic spins were detected. However, Tc was reduced to ,-~ 47 K. More extended ZF and TF-#SR measurements by Mendels et al. (1994) on samples with y = 0.04 and varying oxygen deficiencies allowed to draw a complete phase diagram which is shown in fig. 6.30. The interesting part of it is found in the range 6.4 < z ~< 6.67 where a disordered magnetic structure is clearly revealed by the ZF-data which extends right up to the metallic threshold but does not seem to overlap with the superconducting phase. Note the difference to pure YBazCu3Oz. Obviously Zn-doping has a destructive effect on long range magnetic order but stabilizes a random magnetic order to a higher level of hole doping. The latter is ascribed to the effect of Zn-doping on the hole dynamics which is slowed down as the missing Cu ions limit the spatial extension of the wave function of the holes. Comparing Zn-doped YBazCu307 with Zn-doped La2CuO4 it appears as if Zn-doping interferes differently with the magnetic order in the two systems. One reason may be that, although to a lesser extend, Zn replaces also Cu in the Cu-O chains. Another remarkable result of Mendels et al. (1994) is the observation of a Curie behaviour of the transverse field relaxation rate in the paramagnetic regime for 6.43 ~< z ~< 6.88. This points strongly to the presence of local moments also in the paramagnetic phase.
MUON SPIN ROTATIONSPECTROSCOPY i.-- i-.--'
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Fig. 6.30. Magnetic and superconducting phase diagram of YBa2(Cu0.96Zno.04)30=. Magnetic critical temperature TN and Tf are determined from NMR- and/zSR-data. For comparison the phase diagram of pure YBa2Cu30= is also schematically shown (from Mendels et al. 1994). These moments must be created due to the presence of the Zn-substituents. Again this may be a consequence of a modified hole dynamics. Fe-substituted compounds were studied by Matsui et al. (1990), Okuma et al. (1990), Kossler et al. (1990) and Baggio-Saitovitch et al. (1990). Previously MSssbauer spectroscopy (for a list of references see Okuma et al. (1990) and Matsui et al. (1990)) and neutron time of flight measurements (Mirabeau et al. 1989) had already provided evidence for a freezing of the Fe-moments, the latter experiment suggesting a type of spin glass order in an y = 0.06 sample below 18 K in coexistence with superconductivity. In contrast MSssbauer data obtained by Baggio-Saitovitch et al. (1990) seem to indicate some non random but probably very short range order in a semiconducting sample with g = 0.05. All #SR-data, mostly taken in the zero field configuration, are consistent with a completely random order of the Fe-moments: PZF(t) did not show any oscillation in samples with y >/0.04 but was well described by a stretched exponential function (see eq. (2.22)) above the spin freezing temperature Tf and by a modified spin glass Kubo-Toyabe function below Tf (Okuma et al. 1990). The spin glass order below Tf was not completely static but showed a fluctuation rate of the Fe-moments of uFe ~-- 2 x 105 s -1 at 4 K in a tetragonal sample with y = 0.08 (Okuma et al. 1990). The ZF-#SR data allowed to determine the freezing temperature Tf with some precision. Figure 6.31 displays a phase diagram of YBa2(Cu~_uFeu)30= which includes M6ssbauer, susceptibility and /zSR data, and shows nicely the over all consistency on the spin freezing temperatures (Matsui et al. 1990) (see also table 6.4). As mentioned above, by a proper heat treatment YBa2(CUl_uFey)307 can be prepared to remain in the orthorhombic phase for y > 0.04. Such an 'ortho' sample with y = 0.08 was also investigated by Okuma et al. (1990). It was found from TF-/zSR measurement that about 1/3 (increasing to about ~ 45% at ~ 25 K and decreasing again to ~ 20% at ,,~ 4 K) of the volume
260
A. SCHENCKand EN. GYGAX t
t
t2
YBa2(CUl_y Fey)30x 0 Tc (Meissnereffect " ~ _ N(CW) x Tg susceptibility x 4 . . • ~+sR Z~ Nasuet al g 50 S U~BTamakietal O % F-100
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Y (Fe) Fig. 6.31. Magnetic and superconducting phase diagram of YBa2(Cul_yFe#)30= (from Matsui et al. 1990). remained superconducting with Tc = 90 K and no signs of magnetic order, while the remaining volume fraction displayed random magnetic order below ~ 33 K. These observations are explained in terms of the formation of Fe-rich domains, which enter into a spin glass phase at low temperatures, and almost Fe-free domains which become superconducting below 90 K by forming a percolative network. The observed complementary temperature dependencies of the two volume fractions are not explained.
6.2.5. Lanthanide substituted (123)-compounds As mentioned in section 6.2.2 the full replacement of Y by lanthanide ions, with the exception of Ce, Pr, Tb and Pm, does not affect superconductivity in the (123)-system with Tc staying close to 90 K in fully oxydized samples. At low temperatures antiferromagnetic ordering of the lanthanide 4f-moments is observed without any adverse effect on the superconductivity, although the lanthanide moments are sandwiched by the superconducting CuO2-planes. Apparently the superconducting electrons are very narrowly confined to the CuO2-planes, as also evidenced by the extremely short coherence length along the crystallographic c-axis (~c -~ 3 A), and do not overlap with the local 4f-electrons. The absence of conduction electrons at the rare earth sites is also implied by M6ssbauer data (Alp et al. 1987, Smit et al. 1987). In view of these features it is not so clear by what mechanism the observed 3D magnetic order is driven. It is argued that dipole-dipole interactions may be responsible (Felsteiner 1989). Nevertheless, it is found that the amount of oxygen deficiency can have a pronounced effect on the magnetic structure of the 4f-moments. For example, in ErBa2Cu30= the antiferromagnetic structure changes from 2D for x < 6.5 to 3D for z > 6.5 (Maletta et al. 1990a). Also #SR-measurements show that the 4fspin dynamics is strongly affected by the amount of oxygen deficiency (see below). These results indicate that at least the coupling between the rare earth-planes is of the super exchange type involving the chain oxygen ions and then probably also
MUON SPIN ROTATION SPECTROSCOPY
261
oxygen ions in the CuO2-planes without inducing any pair breaking. The system HoBa2Cu30~ is special in that Ho 3+ possesses a non magnetic singlet ground state level and the observed magnetic order requires the formation of moments out of this singlet ground state by either overcritical exchange or nuclear hyperfine effects (Roessli et al. 1993).
GdBa2Cu30:~. Zero field/zSR measurements on two GdBa2Cu307_a samples with Tc = 60 and 90 K revealed two spontaneous spin precession signals below TN = 2.3 K, confirming the onset of antiferromagnetic order of the Gd-4f moments (Golnik et al. 1987). The temperature dependence of these frequency is shown in fig. 6.32. The higher frequency in only marginally visible in the 90 K-sample, but is well developed in the 60 K-sample. Both frequencies can be consistently accounted for by considering the antiferromagnetic structure of the Gd-sublattice and assigning the #+ to the apical oxygen site (high frequency component) and to the chain oxygen site (low frequency component). Very interesting is the observation of/z+-relaxation (see fig. 6.33) above TN in the 60 K-sample as well as in a z = 6.2 sample, indicating some slowing down of the Gd-4f spin dynamics but not in the 90 K sample (Budnick et al. 1990a, Niedermayer et al. 1993). This implies that the spin dynamics in the 90 K sample is much faster than in the 60 K-sample. This phenomenon is particularly intriguing because the N6el temperature seems to be rather independent of the oxygen deficiency. It will be interesting to study these features in more detail. A possible interaction between the Cu(II)-sublattice order and the Gd-sublattice order was investigated by ZF-fSR in a GdBa2Cu306.3 sample (Niedermayer et al.
Gd BCl2 Cu 30T_v 7 6
C"
~3
0
1 2 3 Temperature (K)
Fig. 6.32. Temperature dependence of the two spontaneous precession frequencies in GdBa2Cu3OT_~. The circles are from a Tc = 60 K sample and the squares from a Tc = 90 K sample. Lines are guides for the eye (from Golnik et al. 1987).
262
A. SCHENCK and EN. GYGAX
15 I
7-
t/\,
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_ 10 0
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100
Temperature (K) Fig. 6.33. Temperature dependence of the ZF-relaxation rate in three different GdBa2Cu306_ = samples
above TN of the Gd-sublattice (z = I, Te -~ 90 K; z = 0.7, Tc = 60 K; ~c= 0.2, not superconducting) (from Budnick et al. 1990a).
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GdBa2Cu306.3
1993). A single spin precession signal was found below ~ 300 K, the temperature dependence of the frequency u~, is displayed in fig. 6.34. Analysis of these data show that below the Gd-sublattice ordering temperature T~ d = 2.3 K the measured frequency can be understood by simply considering the vector sum of dipolar fields originating from the ordered Cu(II)-sublattice and the ordered Gd-sublattice, employing for the magnetic structures the information gained from neutron scattering work
MUON SPIN ROTATIONSPECTROSCOPY
263
(McK. Paul et al. 1988, Mook et al. 1988, Rossat-Mignod et al. 1988a). Hence it seems that below TN Ga the two magnetic sublattices are not affected by the presence of the other one. At high temperatures, i.e. above --, 150 K, u,(T) follows closely the behaviour seen in YBa2Cu306.3 (see fig. 6.34) indicating that also in this temperature range the magnetic structure of the Cu(II)-sublattice is not modified due the presence of Gd-moments. Quite a different behaviour is observed in the intermediate range TN Gd < T < 150 K. Clearly the Cu(II)-magnetic sublattice is now drastically affected by the Gd-4f moments. Whether this is a result of the development of static correlations among the 4f-spins, induced by and perhaps also modifying the Cu(II)-magnetic sublattice, or of the slowed down Gd-4f-spin dynamics in oxygen deficient material, destabilizing to a certain degree also the Cu(II)-moment ordering, is not known. It should be noted that again TN Gd and TCu(II) are not affected to any noticeable degree.
DyBa2Cu307_6. Attempts to measure a Dy-4f moment induced #+-Knight shift above Tc produced a zero result within the achieved precision (Schenck et al. 1990a). No studies at low temperatures have been performed so far.
HoBa2Cu3Ox. This system has been repeatedly investigated by #SR-spectroscopy. Generally it was observed in ZF-#SR measurements that the /z+ relaxation rate increases drastically below 10 K and saturates below ~ 2 K (Nishida et al. 1988a, Kuno et al. 1988, Birrer et al. 1989a, Grebinnik et al. 1990c). The low temperature relaxation rate in samples with z ~ 7, if interpreted as dephasing, would correspond to an internal field spread of (5-13) mT, pointing to a random freezing of the Ho4f moments already around 2 K, while specific heat and neutron diffraction data indicate a transition to long range antiferromagnetic order around (140-190) mK (Dunlap et al. 1987, Fischer et al. 1988, Roessli et al. 1993). More detailed ZF/~SR measurements by Birrer et al. (1989a), extending down to 40 mK, revealed also some perhaps restricted, long range order starting already below 5 K in a small fraction Of the polycrystalline sample volume. Their data can be analyzed in terms of a two component structure of the ZF-#SR-signal, which develops below ,-~ 50 K. In the range 50 K to 5 K random order appears in a fraction of the sample volume growing from ~ 0% at 50 K to ~ 30% at 5 K, the remaining volume staying paramagnetic. Below 5 K the random order transforms to some coherent, but short range order, as evidenced by the emergence of an oscillating but heavily damped signal. The temperature dependence of the corresponding frequency u, is displayed in fig. 6.35. In parallel, the ordered volume fraction grows at the expense of the paramagnetic fraction and reaches essentially 100% around 2 K. The oscillating signal shows a pronounced and rather temperature independent Gaussian relaxation, implying a static field spread of 8.2 roT, which explains why the oscillating behaviour has been overlooked in the earlier work. A clear oscillation is only directly evident at the lowest temperatures (see insert in fig. 6.35). As fig. 6.35 shows ut, changes rather abruptly at ~ 100 inK. This change was attributed to a spin reorientation transition from fiHo being parallel to the e-axis below 100 mK (also predicted theoretically by Misra et al. 1992) to being parallel to the e-axis above 100 inK. The ordered
264
A. SCHENCK and EN. G Y G A X
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I
I I I
III
10 2
Temperature (K) Fig. 6.35. Temperature dependence of the spontaneous # + precession frequency in HoBa2Cu307_~. The insert in the upper right corner shows the same on a linear temperature scale. The insert in the lower left corner shows the ZF-/~SR signal at 39 mK (from Birrer et al. 1989a).
moment was estimated to be #Ho ~- 2"6#B" The most remarkable feature of the #SRresults is the absence of a clear cut cooperative phase transition which is inconsistent with both the specific heat and neutron results. In view of this one is tempted to associate the anomaly in uu at 100 mK with the true phase transition to long range antiferromagnetic order (implying that the temperature calibration was in error) and to interpret the results above "100 inK" as an extremely short range precursor phenomenon. More recent neutron diffraction measurements revealed a clear onset of long range antiferromagnetic order at (190 4- 10) mK with a propagation vector q = (0, 1/2, 1/2) and #Ho = 2.8#B aligned parallel to the c-axis (Roessli et al. 1993). The long range order is limited to a correlation length of ~ 30 A along the c-axis due to the occurence of stacking faults along this direction. It was further established that the nuclear hyperfine interaction is the driving force in the long range magnetic order of the Ho3+-moments which evolves out of a singlet level of the Ho3+-518 ground state multiplet. The magnetic structure proposed by Roessli et al. (1993) is in marked disagreement with the #SR-results. On the basis of this structure one calculates a net dipolar field of 0.64 mT at the #+-site while the #SRmeasurements reveal a field of 18.5 roT. It is impossible to explain the difference in terms of an additional contact hyperfine field in view of the zero Knight shift result in the paramagnetic phase (see below). The unique and indisputable information provided by the #SR results is the random freezing of the Ho-moments already far above the Nrel temperature. With respect to this several interestingquestions can be asked: what causes frustration; which mechanism is responsible for the coupling of
MUON SPIN ROTATIONSPECTROSCOPY
265
the moments (dipole-dipole, super exchange); which mechanism is responsible for the formation of a local moment out of the singlet ground state level also at higher temperatures (nuclear hyperfine, overcritical exchange, population of higher excited levels); etc? Answers to these questions are not yet available. Also, the oxygen content seems again to be of importance since the freezing of the Ho-moments is less visible in a HoBaeCu306.2 sarnple (Kuno et al. 1988). Dilution of Ho by Y has also a negative influence on the freezing process (Grebinnik et al. 1990c). TF-#SR measurements on a HoBa2Cu307_~ (To = 90 K)-sample produced no visible Ho-induced #+-Knight shift (Weber 1991). Earlier claims (Schenck et al. 1990a,c, Maletta et al. 1990b) to have seen a very sizable Knight shift in HoBa2Cu307 are incorrect and resulted from neglecting effects due to powder broadening.
ErBa2Cu30~. ZF-#SR investigations in a series of ErBa2Cu3Ou-compounds with different z (see table 6.5) yielded in all cases a spontaneous spin precession signal below the respective Ntel temperatures (Maletta et al. 1990c). Of course, for z /> 6.6, only the Er-sublattice enters into a (3D) antiferromagnetic phase below TN = 0.6 K (Maletta et al. 1990a). The corresponding #SR-signal displayed a very small single frequency v~, the temperature dependence of which is shown in fig. 6.36. Interestingly the precession pattern appeared to persist up to temperatures of at least 1.2 K. At the transition temperature TN a significant increase of v~ is observed, which is more pronounced in the z = 6.6 sample. The shift of TN and of v~ (~ 0 K) with the oxygen content z is well in line with neutron diffraction experiments on the same samples (Maletta et al. 1990a). In fact using the magnetic structure and #Zr = 4"4#B (1[b'axis) derived from the neutron work one predicts a field of ~ 0.6 mT at the/z + position near a chain oxygen in excellent agreement with the experiment. The persistence of a precession signal above TN is also well in line with neutron results which reveal short range magnetic correlations up to ,,o 1 K. Unfortunately the #SR-measurements did not extend beyond ,-~ 1.2 K. (But see also Grebinnik et al. 1990b, c.) In the whole covered temperature range the damping of the precession signal is very small (and temperature independent below TN) (compare with the case in HoBa2Cu3Ox !) but this has not to be taken as evidence for a very perfect long range magnetic structure. It merely reflects the fact that the net dipolar field at the #+ site is close to zero (this is a consequence of fiZr being aligned along the b-axis). The difference in the relaxation behaviour (see fig. 6.36) between the z = 7.0 and z -- 6.6 sample below 1 K is puzzling and not explained yet. For samples with x ~< 6.4 the onset of magnetic order of the Cu(II) sublattice is seen again by the appearance of spontaneous spin precession in the ZF-#SR signal. No such signal was seen in a compound with z = 6.53 down to 3 K. The temperature dependence of the single frequency v~,, seen in compounds with z -- 6.11, 6.34 and 6.40, is displayed in fig. 6.37. In particular the data from the x -- 6.34 sample indicate that, if it were not for the presence of the Er-moments, v~ would approach ~ 4 MHz as in YBa2Cu306. A sample with z = 6.20 was also investigated below 1 K. No evidence for magnetic order of the Er moments was found. The anomalous increase of u~, below 10 K, particularly in the z = 6.34 sample, is somewhat reminiscent of a similar behaviour in GdBa2Cu306+~
266
A. S C H E N C K and EN. G Y G A X
0
,--Z
0 ~,
0
i"
t",l o
+ o
=
•
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8
~ = ~ o 0
~ o
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MUON SPIN ROTATION SPECTROSCOPY
267
v~vvv~
0
,.,.,
~o
~,~ ~ ~
o
~ o o
<~ on
~
V
on
A
oc
C o
..... ~
o
r',!,,.q.
o,..o
268
A. SCHENCK and F.N. GYGAX
ErBa2Cu30 x 0.09 o,.,o
-1-
0.06 g~a 0.03 ¢._ U_
0.00
"7
I
I
I
I
I
I
I
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I
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!
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::L
0.30 1:3 I._.
0.20 .$... X
0.10 C~
0.00
I
I
I
I
f
f
I
|
[
0.5 1.0 Temperature (K)
Fig. 6.36. Temperature dependence of the spontaneous /z+ precession frequencies and the associated relaxation rates in two superconducting ErBa2Cu30= samples (z = 6.6, 7.0) (from Maletta et al. 1990c).
(Niedermayer et al. 1993) and reflects clearly some effect of the Er-moments on the Cu(II)-magnetic ordering. Neutron diffraction measurements on the same samples showed the onset of magnetic correlations among the Er-moments in the a-b plane below 1 K which essentially saturate below 230 mK without the formation of a 3D long range antiferromagnetic structure (Maletta et al. 1990a). Since the Er-moments do not display a 3D-antiferromagnetic order the increase of uu below ,-~ 10 K cannot be understood in the same way as in GdBa2Cu306+6. It rather seems that the Cu(II) magnetic sublattice is somehow modified in an as yet undetermined fashion. It has to be emphasized that the Cu(II)-long range magnetic order is again not seen in the full sample volume. Particularly in the z = 6.4 sample quite a fraction of it is associated with a very rapidly but nonoscillating signal. This fraction decreases with increasing temperature and disappears at around 300 K. It seems to reflect spin glass behaviour in part of the sample. Whether this behaviour reflects a nonhomogeneous oxygen distribution or is induced by the Er-moments remains to be seen. It is not known whether this sample could become superconducting. ZF-#SR measurements on a ErBa2Cu306.2 sample by Lichti et al. (1990b) revealed two frequencies in the spin precession signal appearing below ,-~ 300 K. In addition
MUON SPIN ROTATION SPECTROSCOPY
269
o 6.11
_ ~.#...... o ~ _ _ e"..........-,,, ~ ~
,.~
-r "
e'O-~
"
3
~
•
-
• 6.34 ,', 6.40
"'......~ _
~
°.
2
i I 0
I
I
I
I
I
I1[
t
I
I
101
I
I
I
I I
I
10 2
T e m p e r a t u r e (K) Fig. 6.37. Temperature dependence of the spontaneous/z + precession frequencies in ErBa2Cu30= with x = 6.11 (tetragonal), 6.34 (orthorhombic) and 6.40, The latter sample shows a weak superconducting response below 32 K (from Maletta et al. 1990c).
to the familiar 0.036 T-component a second frequency corresponding to a field of 0.055 T was seen. The latter may be associated with a site near the CuOz-plane and could correspond to the 0.13 T signal seen in YBazCu306+~ (5 < 0.3) by Brewer et al. (1989) (see table 6.4). The same authors performed also TF-#SR measurements. From an anomaly in the W-relaxation rate, seen at 65 K, they conclude that a second magnetic phase transition may be present (Lichti et al. 1990b). A search for a Er induced #+ Knight shift in samples with z = 6.53 and z = 7 (T > To) produced again a zero result (Schenck et al. 1990a). Earlier reports to the contrary (Schenck et al. 1990c, Maletta et al. 1990b) are again unsubstantiated. Knight shift results below Tc are discussed by Lichti et al. (1991a).
6.2.6. Other compounds Long range antiferromagnetic order was detected for the first time by ZF-#SR in the compounds BaCuO2 and BaYzCuO5 (green phase of YBaCuO). From these data the transition temperatures could be determined (see table 6.3) (Weidinger et al. 1988).
6.3. Bi-based (2212)-compounds For an overview of investigated compounds (all have an orthorhombic crystal structure) see table 6.6. In fact magnetic order in insulating or semiconducting members of the (2212)-family7 was first demonstrated in #SR experiments almost simultane7 Substituting trivalent y3+ for divalent Ca2+ or Sr2+ the carrier (hole) concentration is reduced (Tamegai et al. 1988). BizSr2YCu208 and BizSrCaYCu208 are insulators. Holes are primarily introduced by some oxygen excess 5 > 0.
270
A. S C H E N C K
and EN. GYGAX
oo
~o
oo
"G ©
0 :t
r~
~o P~
p~
p~
O
r~
+
0
~
~
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r~
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:~
d d d d
O
(-q
c5
c5
e
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b..,
[..-,
t"q
t'q t'q
.1
© )
r..) e.i
eq
t..)
~1
M U O N SPIN ROTATION SPECTROSCOPY
271
0
O
© o ;~ ee3 o
~
~
rm o o
~n
O
~.
0
¢xl e q
¢¢3
II
II
O o
A~ [.r.. N
r.~ N
u
O
[q
© o
0 0
272
A. SCHENCK and EN. GYGAX
ously by Yang et al. (1989), Nishida et al. (1988c) and De Renzi et al. (1989). ZF-measurements at ~ 5 K in compounds Bi2Sr2YI_~Ca~Cu20~8 with z ~< 0.2 revealed three oscillating components (see table 6.6) in addition to a nonoscillating one. The temperature dependencies of the three frequencies or local fields in a Bi2Sr2YCu20~8 sample are displayed in fig. 6.38 together with the relaxation rate of the low field (0.4 MHz) component (Nishida et al. 1990b). As can be seen, the 0.027-T-component disappears at 80 K. At the same temperature ~r drops abruptly by a factor of ,.o 3. These features are not understood at present. In Bi2Sr2YCu20~8 a fourth high frequency component was seen with, however, an extremely fast relaxation rate (,.o 10 7 s - l ) . The appearance of several components may not be a surprise in these more complicated compounds and points to the existence of several #+-sites. Possible #+-sites have not yet been considered in detail but the pair of signals centered at 0.03 T may indicate sites near an apical oxygen similar as in YBa2Cu306. The high frequency signal may correspond to the 0.12 T signal in YBa2Cu306+6, i.e. a site close to a CuO2-plane may be occupied. The low frequency signal may be associated with a Bi2Sr2YCu20Y i i
0.4 bo 0.3 -
~mo
• •
:b o (Pa
0.2 o.1 Im-,nlliIRm-, mm
m mmm
0
l
t
m[
1.0
j
i
i b
0.8 ~m
0.6 F WI i 0.4
¢,... .'¢ 0 0
,
I
I
I
1 O0
200
300
400
T (K) Fig. 6.38. Temperature dependence of (a) the 3 spontaneous local fields at the /~+ observed in BizSr2YCu20~ 8. The 0.027 T local field disappears above ~ 80 K. Below the same temperature the relaxation rate (b) associated with the lowest local field signal increases abruptly (from Nishida et al. 1990b).
MUON SPIN ROTATION SPECTROSCOPY
273
site near an oxygen in the Bi-O plane, which has no counterpart in the (123)-system. In any case the close correspondence of some of the frequencies with observed frequencies in the (123)- and the LaCuO-systems indicates that the Cu-moment order must be quite similar in all the cuprate layered compounds. In particular the magnitudes of the Cu-moments must be quite comparable. The ZF-#SR data obtained in Bi2Sr2Y0.6Cao.4Cu208, Bi2Sr2.5Y0.5Cu20~8 and Bi2SrCaYCu2Os+6 also show the presence of magnetic order but it is now of a random (spin glass like) structure. This phase is followed, when further decreasing the Y-content, by the appearance of superconductivity (see fig. 6.39). Like in the (123)- and the LaCuO-families the development of magnetic order starts first in only a tiny fraction of the sample volume and even at very low temperatures may not involve all of the sample volume. Figure 6.40 presents an example for how the paramagnetic fraction of the sample volume decreases with decreasing temperature in compounds BizSr2Yt_xCa~Cu208 with z = 0, 0.1, 0.2 and 0.3. These data are obtained from TF-#SR-measurements which allow to identify the 400
I
Bi2 Sr2Y1 -x CaxCu2Oy
3O0
b-
+
2OO
100 [] AF
FIND
SG
SC D
0 0.0
i
I
I
I
I
I
I
0.5
I
I
1.0
X
Fig. 6.39. Magnetic and superconducting phase diagram of Bi2Sr2_xY~Cu208. The magnetic part is deduced from/~SR-data showing AF-order for x<0.3 and spin glass like order for 0.5 > z > 0.3. The arrow for z = 0 indicates that TN is above the instrumental T limit (from Nishida et al. 1990b).
274
A. SCHENCK and EN. GYGAX
10 gO.8
."-~ _u
~-0.6
~
Bi2 Sr2Yl_xCax Cu20, i i ~'x:o.3
~ ,~
0.4
x:o-2 I
-
~X:0.1
f •
o
-
a_ 0.2 0(3 0
t
I
100
200 T (K)
300
400
Fig. 6.40. Fraction of paramagnetic volume in various Bi2Sr2Yl_~CaxCu20~t samples as a function of temperature. The fraction is determined from TF-/~SR measurements (from Nishida et al. 1990b).
fraction of #+ in a paramagnetic environment. It can be seen that, e.g., in a sample with z = 0.2 magnetic order sets in at around 300 K but at ~ 250 K more than half of the volume is still paramagnetic and this fraction does not drop below 30% at the lowest temperatures. Even for a more or less stoichiometric sample with z -- 0 magnetic order develops in a spatially inhomogeneous fashion. The latter result, assuming that the oxygen content is close to 8 per unit formula, could suggest that the inhomogeneous magnetic ordering is an intrinsic property of these layered systems. #SR-spectroscopy should be in a position to explore this property in a more systematic way. Interpreting the onset temperatures of magnetic order as N6el or freezing temperatures a phase diagram can be drawn as shown in fig. 6.39 (Nishida et al. 1990b). By comparison with fig. 6.22 it is seen that all layered cuprate families behave in the same way. In the insulating or semiconducting phase the CuO2-1ayers show antiferromagnetic order. With the introduction of holes into the CuOz-planes magnetic order becomes frustrated and eventually a spin glass phase is entered. On further increasing the hole concentration magnetism is lost altogether and a superconducting phase evolves. Whether a small region exists where spin glass order and superconductivity coexist in a truly microscopic manner is still a disputed matter.
7. Study of magnetic order in organic compounds All compounds studied are listed in table 7.1.
7.1. (TMTSF)2X The family of the tetramethyl-tetraselena-fulvalene (TMTSF)2-X compounds displays many intriguing properties such as superconductivity, anion ordering, quantum Hall effect, spin density wave (SDW) ordering and field induced spin density waves
M U O N SPIN ROTATION SPECTROSCOPY
eee
~
e
+ d
¢q ¢q
¢q
,,~
~
a
a
c~
c~
~c;~ z r..)
275
276
A. SCHENCK and EN. GYGAX
owing to their highly anisotropic electronic structure (low dimensionality) (J6rome and Schulz 1982, Ishiguro and Yamaji 1990). The spin density wave properties have been studied by a variety of techniques but many detailed features, e.g., elementary excitations, sublattice magnetization, SDW wave vector and the order of the transition are not too well determined. The usefulness of #SR-spectroscopy in addressing some of these problems rests again in the possibility to perform the experiments in zero applied field.
(TMTSF)zPF6. Antiferromagnetic SDW order is observed in this compound at ambient pressure below TN = 122 K. The anion PF6 is located in a centrosymmetric position. ZF and LF-#SR measurements were aimed at a determination of the exact SDW structure (commensurate versus incommensurate) and the order of the phase transition (Le et al. 1991, Le et al. 1994). Previous NMR measurements (Takahashi 0.14 ~N~" ~ 0.14 ~ b 0.14: ~ 0.12
~ .
%
(TMTSF)2PF 6 H =0 ~,xt "~ " ~ ' ~
I
12.25K
% E 0
(a)
'
,? ?' '
oo,
0.00
0
I
I
I
2
4
6
Time (/zs)
(b) 13_
2.0
E .<
1.0 n-0.0
I
0.0
I
0.2 0.4 0.6 Frequency (MHz)
/~
0.8
Fig. 7.1. (a) ZF-/~SR signals in (TMTSF)2PF 6 for various temperatures (b) Fourier transform of the signal taken at 3.7 K (from Le et al. 1994).
MUON SPIN ROTATION SPECTROSCOPY
277
et al. 1986, Delrieu et al. 1986a, b) had detected the SDW-state, but the applied field was rather high and the system was in the spin-flop state. Figure 7.1a displays some typical ZF-#SR spectra around the transition temperature. As can be seen below 12.2 K a precessional pattern develops but the actual frequency spectrum, as revealed by Fourier transforming the signal, is quite broad, showing a shoulder on the low frequency side and a peak at a frequency of ~ 0.55 MHz, corresponding to an internal field of 0.004 T (see fig. 7.1b). This distribution appears incompatible with a commensurate structure (provided only one type of site is occupied by the #+) but can be well reproduced by a distribution of dipolar fields arising from an incommensurate sinusoidally modulated intermolecular spin density wave with wave vector ~) = (0.5, 0.24, -0.06) and maximum amplitude of 0.1#B/molecule (Takahashi et al. 1986). The shape of the frequency spectrum does not depend very much on the assumed #+ site and also not on the exact value of Q as long as the modulation is incommensurate. In this picture the peak frequency uu,p (see fig. 7.1b) provides a good measure of the SDW amplitude M or the order parameter. The temperature dependence of Uu,p is displayed in fig. 7.2 together with the corresponding results on the two other (TMTSF)2-X compounds with X = NO3 and X = C104. The data show little temperature dependence below TN/2 and quite an abrupt change at TN. The latter is taken as evidence for a first order phase transition. It may be ascribed to a cross over from a 1D to a 3D behaviour whereby the already existing, albeit fluctuating order parameter in the 1D-regime is frozen out at a finite value at the transition temperature. The temperature dependence of Uu,p below ~ TN/2 is, although weak, much stronger than one would expect from a mean field treatment of the SDW transition 0.7
(TMTSF)2-X 0.6
"T-
Hext=O
0.5
',
0.4 >, 0 c
~"4 p;6"~
NO 3
Ci04
0.3
4
"
E)a) 0.2 t, k_
0.1 o.o
0
t ,
5
I
I0
15
Temperature (K) Fig. 7.2. Temperature dependencies of the spontaneous iz+ precession frequencies in (TMTSR)2-X with X = C104, NO3, PF6. The solid lines are guides to the eye (from Le et al. 1994).
278
A. SCHENCKand EN. GYGAX 1.02
I
i
i
i
1.00 0o0 0.98 0
0.96
I.-- 0.94 0.92 0.90
Heisenberg (NN)
0.88
1
0
2
I
I
4 6 Temperature
I
8
10
(K)
Fig. 7.3. Temperature dependence of uj,(T)/u~(O) = M(T)/M(O) in (TMTSF)2PF6 below TN/2 and various model predictions. The data are very well described by a 2D-spin wave excitationmodel (from Le et al. 1994). (Yamaji 1982). The opening up of an energy gap A should largely suppress single particle excitations and consequently the magnetization or Uu,p should be largely temperature independent below ,,~ TN/2. It is therefore argued (Le et al. 1994) that the variation of U~,p or M at low temperature is determined by collective spin wave excitations. Indeed the temperature dependence of tJ~,p(T)/u#,p(0) = M(T)/M(O) can be very well accounted for by such an approach (solid line in fig. 7.3) leading to an average spin wave stiffness constant of 13 = 200 K. This value is much larger (by a factor 3-5) than what is expected from a local moment nearest neighbour Heisenberg model. However, the large value can be understood, at least qualitatively, on the basis of an itinerant electron model (Le et al. 1994).
(TMTSF)2N03, (TMTSF)2CI04. In these compounds the anions NO3 or C104 are located at non-centrosymmetric positions with the consequence that an anion ordering transition is found at temperature TAo (= 41 K in the NO3-compound). The ground state of these systems depends on the degree of anion order-disorder produced by the cooling rate through TAO. In the NO3-compound a SDW state below 12 K can be obtained by slow cooling, while in the C104-compound a SDW state is achieved below ~ 4 K by very rapid cooling (quenching). ZF-#SR measurements revealed spectra very similar to the ones found in the PF6compound indicating an incommensurate spin density wave state in each case (Le et al. 1994). The temperature dependence of the peak frequency Uu,p for both compounds is included in fig. 7.2. As can be seen the low temperature u~,v (or the spin density wave amplitude M) is essentially the same in all three compounds despite the fact
MUON SPIN ROTATION SPECTROSCOPY
279
that rather different transition temperatures are observed. This behaviour is taken as support for a nesting model for the SDW condensation (Takahashi et al. 1989). According to this model the SDW gap ,4 and the order parameter M are mainly determined by the on site Coulomb energy U and the on-chain coupling t, which are independent of the anion X. The decrease of the transition temperature, on the other hand is a result of the loss of perfect nesting as the dimensionality of the systems increases (i.e. becoming more 2D), e.g., as a function of pressure or type of anion, but this has no effect on M as long as the SDW ground state is established.
7.2. Ni2(C2H8N2)2N02(CI04) (NENP) NENP is a nearly ideal realization of a spin-1 linear-chain Heisenberg antiferromagnet. For such a system Haldane (1983) has predicted the existence of a quantum energy gap between the nonmagnetic singlet ground state and the lowest triplet excited state. No such gap occurs for half integer spin systems. Admitting also some inter chain coupling above a certain critical value long range magnetic order may be expected (Affleck 1989). However, the inter chain coupling in the NENP system appears too weak to allow for the development of long range magnetic order. In fact magnetization measurements place an upper limit of 1.2 K on the transition temperature to an ordered magnetic phase (Renard et al. 1987). Nevertheless the low temperature properties of NENP remain an important issue. ZF- and LF-#SR measurements on a polycrystalline specimen reveal indeed interesting new information which indicates that NENP could be very close to static magnetic order (Sternlieb et al. 1992). Applying a small (0.01 T) longitudinal field in order to decouple the #+ spin from nuclear dipolar fields the LF-relaxation follows well a stretched exponential (exp(-iv/~-/at)) which is indicative for a broad fluctuating local field distribution. Figure 7.4 displays the temperature dependence of ),1. As can be seen ),1 rises steeply between 3 K and 2 K followed by a saturation down to 20 mK. The fast rise of ),1 below 3 K points to a slowing down of the spin dynamics. However, no static limit is reached. This follows from a persisting field 1.4 ,~
1,2
I
p
o
I
I
I
I
o 0
~7 1.o
I
NENP LF=IOOG
_
o.8
~O
0
0.6 0.4
rr
O
0.2 0.0 0
O
O
I
~
t
I
I
2
3
4
5
6
7
Temperature (K) Fig. 7.4. Temperature dependence of A1 (measured in an external field of 0.01 T) in NENR Note the rapid rise below 3 K (from Sternlieb et al. 1992).
280
A. SCHENCK and EN. GYGAX
dependence, even at 20 mK, which is roughly described by ALF O( 1/co~ and implies very small fluctuation rates of the order of 40 MHz at 20 mK. The local fields are of the order of Bloc ~ 90 G. The latter value is too large to be caused by loose chain ends or impurities but, on the other hand, too small to be representative of all Ni-moments. Therefore, if A1 and Bloc are reflecting a truly intrinsic behaviour, it must be concluded that only a limited portion of the Ni-spin fluctuation-spectrum is affected by a slowing down of the spin dynamics (Sternlieb et al. 1992).
7.3. p-NPNN p-NPNN (p-nitrophenyl nitronyl nitroxide, C13H16N304) is a chemical radical which has been identified to show ferromagnetic order (Awaga et al. 1989, Takahashi et al. 1991). Although various techniques have been used in the study of this system the most fundamental parameter, namely the spontaneous magnetization has remained uninvestigated, but has later been measured in a ZF-#SR experiment on t-phase monocrystalline material (Le et al. 1993). The onset of magnetic order below 0.7 K is clearly reflected in the appearance of a long lived spontaneous coherent spin precession signal with only one frequency uu implying a unique #+ site in this complex system. The temperature dependence of uu, which is proportional to the spontaneous magnetization M is displayed in fig. 7.5. The Curie temperature following from this plot is 0.67 K and indicates by comparison with other samples a slight sample dependence. The magnetization has been previously measured at 0.44 K with the result M = 0.5#B/molecule (Tamura et al. 1991). Rescaling this value with the present u(T) one gets M(0 K)= 0.6#B/molecule. Expected is M = l#B/molecule. The difference is ascribed to systenaatic uncertainties in the magnetization measurements. The #SR data indicate that the internal spontaneous field is nearly parallel to the crystalline b-axis. 2.5
I
I
I
I
I
I
I
H,~=0 "1-
2.0-
> ",
4.5
a~
1.0
u_
0.5
0.0
I
0
i
w
I
J
I
T i
100 200 300 400 500 600 700 800 Temperature (mK)
Fig. 7.5. Temperature dependence of the spontaneous /~+ precession frequency in p-NPNN. The solid line represents a fit of eq. (7.1) to the data (from Le et al. 1993).
MUON SPIN ROTATION SPECTROSCOPY
281
The temperature dependence of uu c( M is very well fitted (solid line in fig. 7.5) by the expression M ( T ) oc (1 - (T/Tc)'~) ~
(7.1)
with c~ = 1.86 and/3 = 0.32. The low temperature behaviour can be expressed as (M(0) - M ( T ) ) c< T '~ which is close to the magnon induced temperature dependence in a 3D system with ~ = 1.5. Near Tc one has M ( T ) ~x (Te - T ) ~ which, with /3 = 0.32, is in excellent agreement with the value /3 = 1/3 expected for a 3D Heisenberg ferromagnet. The behaviour of/3-phase p-NPNN is thus consistent with that of a 3D Heisenberg system. This is in contrast to susceptibility and magnetization measurements in the ?-phase of p-NPNN which could be well explained in terms of a quasi 1D-ferromagnet (Takahashi et al. 1991). Acknowledgements We are indebted to the many colleagues who have sent us re- and preprints, who responded quickly to questions and even provided us with high quality figures. Many thanks go to Dr. Alex Amato who read carefully the manuscript and was patient enough to provide advice and help whenever needed. Finally we have to thank Mrs. M. Sekolec and Mrs. R. Bachli for preparing skilfully the typed manuscript and Mrs. I. Kusar of PSI for drawing or redrawing a major fraction of the figures. List of some of the used abbreviations and symbols ABBREVIATIONS (#)LCR #SR AF anneal bcc CAF cor
fcc FI FM hcp hex ins LCR LF-pSR LIAF met mon
(muon) level crossing resonance muon spin rotation, relaxation and resonance antiferromagnetic annealing body centered cubic commensurate spin density wave corundum face centered cubic ferrimagnetic ferromagnetic hexagonal close-packed hexagonal insulator level crossing resonance longitudinal field #SR longitudinal incommensurate spin density wave metal monoclinic
282
A. SCHENCK and EN. GYGAX
Mu
n-irrad O, oct OPC orth P PC per p-irrad rut SC, s.c. scu
SDW sem
SF SG T T± TF-#SR TIAF USC WA WF ZF-#SR
muonium (#+e-) neutron irradiated octahedral oriented polycrystals orthorhombic paramagnetic polycrystalline, polycrystal perovskite proton irradiated rutile single crystal simple cubic spin density wave semimetal spin fluctuations spin glass tetrahedral tetrahedral with tetragonal axis perpendicular to [100] direction transverse field #SR transverse incommensurate spin density wave state unoriented single crystals weak antiferromagnetic weak ferromagnetic zero field #SR SYMBOLS
F,A /~ % z~ 2 AB u 0
~1 = 1/TI /~2 = 1/T2 AZF /./ uu - u x u u (= w u / 2 7 r ) o
~-c
(= 1/.)
muon depolarization or dephasing rate, general #+ depolarization - several components muon gyromagnetic ratio (see table 2.1) second moment of one cartesian field component in ZF rms width of local field distribution strain orientation or angle between field and c-axis spin lattice relaxation rate spin lattice relaxation rate in ZF transverse relaxation rate ZF-relaxation rate from exponential decay magnetic moment fluctuation rate level crossing resonance frequency muon - nucleon X muon Larmor or precession frequency Gaussian depolarization rate (cr2 = M2) correlation time orientation or angle between field projection on the basal a-b plane and the a-axis
MUON SPIN ROTATIONSPECTROSCOPY
283
X Xat A Ac
susceptibility tensor (usually in emu/mol) atomic susceptibility tensor (emu/atom) amplitude or asymmetry of #SR signal contact hyperfine coupling constant
Adip Ai AB u B~
dipole coupling tensor amplitude or asymmetry of i-th component of #SR signal rms width of local field distribution total local magnetic field at the muon field at the muon - several components or sites (contact) hyperfine field at the muon demagnetization field dipolar field applied magnetic flux density Lorentz field field at the #+ in the Mu-state Kubo-Toyabe relaxation function for Gaussian field distribution Kubo-Toyabe relaxation function for Lorentzian field distribution depolarization function in transverse field applied magnetic field muon Knight shift second moment of field distribution (usually in MHz2), related to AB~
Bc Bdem Bdip Bext BL BMu
a~T
% GTF Hext
K. M2 4-4
N p, press
P(t) PLF(t) PTF(t)
PZF(t) T
T1 T2 Tc TFN TM TN Tv G Tf
demagnetization tensor (factor) pressure time dependence of muon spin polarization, projected on P(t = 0) P(t) measured in longitudinal field (/~ext]lfi(0)) P(t) measured in transverse field (/lext±/3(0)) P(t) measured in zero field temperature longitudinal spin-lattice relaxation time transverse (spin-spin) relaxation time Curie temperature ferrimagnetic ordering temperature Morin temperature N6el temperature Verwey temperature superconducting transition temperature freezing temperature in a spin glass-like system
284
A. SCHENCK and EN. GYGAX
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chapter 3 INTERSTITIALLY MODIFIED INTERMETALLICS OF RARE EARTH AND 3D ELEMENTS
HIRONOBU FUJII Faculty of Integrated Arts and Sciences Hiroshima University Higashi-Hiroshima 739 Japan
and
HONG SUN Materials Science Research Department Research and Development Center Sumitomo Metal Industries, Amagasaki 660 Japan
Handbook of Magnetic Materials, Vol. 9 Edited by K. H.J. Buschow 01995 Elsevier Science B.V. All rights reserved 303
CONTENTS 1. Introduction
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2. Formation of the interstitially modified intermetallic compounds . . . . . . . . . . . . . . . . . . . . . . . 2.1. Arc-melting method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Melt-spinning method
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305 307 308 309
2.3. Gas-phase interstitial modification method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
310
2.4. Solid-solid (or liquid) reaction and plasma nitriding methods
314
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2.5. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3. Interstitial compounds of the 2:17-type structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Crystallographic structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
314 315 315
3.2. Curie temperature and exchange interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
328
3.3. Magnetic anisotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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3.4. M6ssbauer and NMR studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
341
3.5. Substitution effect
349
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4. Interstitial compounds of the l:12-type structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
353
4.1. Location of N atoms in the tetragonal structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
354
4.2. Structural and intrinsic magnetic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
356
4.3. Substitution studies
364
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4.4. Interstitial modification study on compounds with various structures . . . . . . . . . . . . . . . . 5. Electronic band structure calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
364 367
5.1. Calculations of the 2:17-type interstitial compounds R2Fel7Z3 ( Z = N or C) . . . . . . . . . .
367
5.2. Calculations of the l:12-type interstitial compounds RFe12_~TzZ u ( Z = N or C) . . . . . .
375
5.3. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6. Applications
.................................................................
380 382
6.1. Improvement of the thermal stability
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382
6.2. Development of permanent magnets
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383
7. Prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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1. Introduction
One of the methods for fabricating new magnetic materials is to interstitially introduce non-metallic atoms like H, B, C or N with small atomic-radius into host metals or compounds. As interstitially modified compounds, hydrides have been well known since 1960s and the magnetism has been covered in chapter 6 of volume VI in this series (Wiesinger and Hilscher 1991). Generally speaking, no significant change in the magnetism was observed upon hydrogenation. On the other hand, the possibility of dramatic improvement of magnetic properties was pointed out in the nitride FeI6N2 twenty years ago, which had been accidently found in the Fe-N thin films formed by evaporating Fe in a Nz-gas atmosphere (Kim and Takahashi 1972). This compound is regarded to be one of the interstitially modified compounds. The deduced Fe moment was reported to be 2.9#B, named 'giant magnetic moment'. Metallic iron crystallizes in the body centered cubic structure below 912°C and has an atomic moment of 2.2#u at 0 K, which is smaller than 3#B/Fe-atom expected for a localized d-state in an Fe atom with seven 3d-electrons. This moment reduction is due to the hybridization of the 3d-3d electron states or the overlap between the 3d-electron wave functions. If the hybridization or overlap is reduced or removed by lattice expansion due to interstitial modification, we can expect an increase of the moment per Fe atom. Since a confirmation of the 'giant moment' (~3.0/zB/Fe-atom) was made by Sugita et al. (1991) in a single crystalline Fex6N2 thin firm, much attention has been paid to developing Fel6N2 in bulk form, which is technically promising material for the applications as magnetic medium in high performance metal recording tapes or as soft magnetic materials. However, data of the magnetic properties of Fel6N2 phase widely scatters, and there are still controversies as to whether the giant moment exists in the Fel6N2 compound or not. Under these circumstances, it is very interesting to apply the interstitial modification technique to rare earth (R) transition metal (TM) intermetallic compounds for searching new promising magnetic materials. Before introducing the magnetism on interstitially modified R-TM intermetallic compounds which have been discovered in recent years, we will briefly trace the historical background of rare earth permanent magnets. Until now, the intermetallics composed of rare earth and 3d elements have been mainly developed as high-performance permanent magnets. In the 1960s, hexagonal SmCo5 compound with the CaCu5-type structure appeared on the stage as the 305
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H. FUJII and H. SUN
first rare earth high-performance magnet. The compound has quite favorable magnetic properties as permanent magnets, especially, (1) the extremely large uniaxialmagnetocrystalline anisotropy (#0Ha "~ 28 T) originating from the single-ion anisotropy of the Sm sublattice, (2) the relatively large saturation magnetization due to ferromagnetic coupling between Sm and Co moments (Ms '-~ 1.14 T) and (3) the high Curie temperature (To = 1000 K) (Strnat 1967). The development of the liquid-phase sintering technique made fully dense and stable SmCo5 magnet possible (Das 1969, Benz and Martin 1970). In alloys of Sm with Co, the saturation magnetization of Sm2Co17 (Ms N 1.25 T) is larger than that of SmCo5 and the Curie temperature (Tc = 1193 K) is also higher. Although the uniaxial anisotropy field of Sm2Co17 is only 7 T which is smaller than that of SmCos, Sm2Co17 has the possibility of leading to better permanent magnets than SmCo5 magnet. As a result of much effort, a nice combination between the high saturation magnetization of Sm2Co17 and the high magnetic hardness of SmCo5 was realized by controlling the kinetics of the precipitation reaction in a system with the approximate composition SmCo7.4, in which some of the Co was replaced by Fe and small amounts of Cu and Zr (Ojima et al. 1977, Yoneyama et al. 1978). The highest energy product which has been achieved is more than 240 kJ/m 3 (Mishra et al. 1981). As the main components Sm and Co are particularly expensive, it is desirable to use iron-based compounds in place of cobalt-based compounds. Unfortunately, the rare earth iron compounds with the CaCus-type structure do not exist. The R2Fe~7type compounds which are isomorphous to R2Co17 exist, but the Curie temperature is too low to be used as permanent magnets and the magnetic anisotropy at room temperature is not uniaxial which is not suitable for permanent magnets. In the 1980s, scientific research on rare earth iron compounds containing a small amount of non-metallic elements had been done quite intensively. As a result of continuing efforts, a novel type of permanent magnet material was discovered in 1984, which was based on the ternary compound Nd2Fel4B with the tetragonal structure (Sagawa et al. 1984, Croat et al. 1984). The magnetic characteristics of Nd2Fe14B are Ms = 1.60 T, #0Ha = 7 T at room temperature and Tc = 588 K. The achieved energy product was 360 kJ/m 3, which significantly exceeded all previous values. Because of its lower cost and superior properties, the Nd-Fe-B magnets have rapidly replaced the Sm-Co magnets and the spectrum of applications has continuously expanded. The main problem of the Nd-Fe-B magnets is the poor temperature stability due to the relatively low Tc which leads to a practical temperature limit of 150°C. Also their corrosion resistance is weak. Thus it is still necessary looking for new magnetic materials with better thermal and magnetic properties. Here, it should be noted that B is not an interstitial atom in the tetragonal structure and NdzFel4B does not belong to the interstitially modified compounds. In 1990, the interstitially modified compound Sm2Fea7N3 was discovered by applying the gas-phase interstitial modification technique to Sm2Fel7 (Coey and Sun 1990). This interstitial nitride was prepared by heating SmzFea7 at 450-500°C under a nitrogen or ammonia gas atmosphere. The crystal lattice of Sm2Fe17 expands more than 6% to accommodate three nitrogen atoms at the interstitial sites. The Curie temperature Tc increases dramatically from 398 K to 752 K. The saturation
INTERSTITIALLYMODIFIED INTERMETALLICS
307
magnetization of Sm2Fel7N3 (Ms = 1.54 T) is comparable to that of NdzFel4B and the uniaxial magnetic anisotropy (#0Ha = 26 T) is three times as strong as that of NdzFel4B. By applying a similar method, the nitrides of Nd(Fel_zTz)lzN with T = Ti, V and Mo, which crystallize in the tetragonal ThMnlz-type structure, were also successfully formed (Yang Y.C. et al. 1991, Anagnostou et al. 1991a, Wang and Hadjipanayis 1991). The Curie temperature and uniaxial anisotropy field of these Nd-containing 1:12 nitrides are comparable with those of NdzFel4B, but the magnetizations are somewhat lower. Similarly to the R-TM intermetallics with the 2:17-type and l:12-type structures, many other structure type compounds can also be interstitially modified, and the structural and magnetic properties can be drastically altered. Hydrocarbon gas can be substituted for nitrogen to make interstitial carbides. Therefore interstitial modification has opened a wide field for scientific research besides the generation of great technical interest in the application of SmzFe17 interstitial nitride or carbide as permanent magnets. Since the first scientific publication of the discovery of the 2:17-type nitrides in early 1990 (Coey and Sun 1990), world wide efforts have been made and are still being devoted to the study of interstitial modifications of various kinds of R-TM intermetallic compounds. The study covers not only every aspect of the structural and intrinsic magnetic properties, but also the development of the promising interstitial compounds into hard magnets. In addition, much attention has been paid to the study of the gas-phase interstitial modification (GIM) process itself. In this chapter, we will review the studies of the interstitially modified intermetallic compounds in the following order: the study of the GIM process; the effects of interstitial modifications on the structural and magnetic properties of the 2:17-type compounds, l:12-type compounds and also compounds of other structure types; the electronic band structure calculations of the interstitial compounds and finally the research aimed at applications of the interstitial compounds as permanent magnets. The emphasis is on the 2:17-type and 1:12-type interstitial nitrides and carbides.
2. Formation of the interstitially modified intermetallic compounds Hydrogen, nitrogen and carbon are the well known elements that have been successfully used for interstitial modifications. The interstitial hydrides have been known for a fairly long time (see the review of Wiesinger and Hilscher 1991). In the field of magnetism, besides the improvement of magnetic properties (mainly the Curie temperature) by hydrogenation, the HDDR (Hydrogenation-DecompositionDesorption-Recombination) process has been used as a novel technique for the production of permanent magnets. Another field where the hydrides are of great interest is their applications as hydrogen storage and hydrogen purification materials, and furthermore as hydrogen batteries. The interstitial carbides and nitrides were discovered and developed in recent years. C and N were found to have much stronger effects than H on the magnetic properties. While the hydrides and nitrides can only be produced by the Gas-phase Interstitial Modification methods (GIM), the carbides
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H. FUJII and H. SUN
can also be made by arc-melting and melt-spinning in addition to the GIM process. In this section, various kinds of processing methods for producing the interstitially modified materials will be described. The emphasis is on the GIM method.
2.1. Arc-melting method Detailed investigations on the conditions under which the tetragonal R2Fel4C phase is formed have shown that the corresponding ternary systems contain another new phase with the composition RzFea7Cy (Liu N.C. et al. 1987, Gueramian et al. 1987, de Mooij and Buschow 1988), which is the interstitial modified 2:17 phase. As shown in fig. 2.1, the solid line defines temperature regions below which the tetragonal R2Fe14C phase is stable and above which the hexagonal or rhombohedral R 2 F e l 7 C v phase is stable. Because of the high melting point of carbon, Fe3C is made first by arc-melting. Then it is mixed together with appropriate amount of R and Fe and melted again to form the as-melted ingot. High temperature and long time (above 1000°C for a few weeks) annealing is necessary for forming the R2Fe17C u phase. In order to avoid the phase transition into R2Fel4C during cooling (fig. 2.1), samples have to be quenched into water from the annealing temperature. The carbon content y is continuously, variable, but the maximum amount is less than 1.6 for heavy rare earths and less than 1.0 for light rare earths. Both the maximum contents are much less than 3, which is the available interstitial sites in the hexagonal or rhombohedral structures (Sun et al. 1990a, Coene et al. 1990, Zhong et al. 1990). The substitution of Ga for Fe can stabilize the 2:17 structure with higher interstitial carbon content. Carbon concentration as high as 2.5 was achieved in R2Fe17_zGazCy(z = 2 and 3, 0 ~< y ~< 2.5) by arc-melting (Shen et al. 1993, I
I
I
I
I
I
!
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12oo
R2Fe17Cy~ ~ v
t--- lOOO R2Fe14 C
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I
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I
[
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LaCe Pr NdPmSmEuGd.TbDyHoEr Fig. 2.1. Transformation temperature Tt of the R-Fe-C systems. The R2FelTCv phase is stable above the solid line and the RzFel4C phase is stable below the solid line. The broken line indicates the temperature range in which the reaction rate is too low for formation of the R2Fel4C phase from the non-equilibrium phases of the as-cast melt. Replotted from de Mooij and Buschow (1988).
INTERSTITIALLYMODIFIEDINTERMETALLICS I
309
I
#_ Sm2Fe1702.0
r"
Sm2Fe14Ga3C2.0 o 1~
30
[
1
40
50
60
20 ( degree ) Fig. 2.2. X-raydiffractionpatterns of Sm2FelTC2.0and Sm2FeI4Ga3C2.0. The compoundswereprepared by arc-meltingand annealedin vacuumat 1270 K for 12 hours (after Shen et al. 1993). 1993b). Shen et al. also reported similar stabilization effects by the substitutions of Si or A1 for Fe. Annealing at temperatures higher than 1000°C is still necessary, but the time period requested is reduced to less than 24 hours. The effect of Ga can be clearly seen in the X-ray diffraction patterns of Sm2FelTCz0 and SmzFe14Ga3C2.0 in fig. 2.2. While the later compound is of nearly pure 2:17 phase with the ThzZn17 rhombohedral structure, the former one is a mixture of a-Fe and probably the 2:17 phase.
2.2. Melt-spinning method Interstitial compounds R2Fe17Cv with y = 0-2.8 can be prepared by arc-melting and subsequent melt-spinning (Shen et al. 1992, Kong et al. 1992, 1993a, b, Cat et al. 1992a, b, 1993a, b). The alloys with the corresponding stoichiometric compositions were first arc-melted, and then by using a suitable quenching rate (1020 m/s for Y and Tb), almost pure 2:17 phases were obtained. The maximum carbon content y increases as the rare earth atomic radius decreases (or as the atomic number increases). Only the preparation of carbides containing heavy rare earths has been reported. Common features of the arc-melted and melt-spun interstitial carbides are their high temperature stability (contrary to the metastability of the gas-phase interstitially modified interstitial materials) and the structure transition from the hexagonal Th2Ni17-type structure to the rhombohedral Th2ZnlT-type structure with the increasing carbon content for heavy rare earth compounds. For interstitial compounds made by the GIM process, no such structure transformation has been reported. These features will be discussed later.
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H. FUJII and H. SUN
2.3. Gas-phase interstitial modification method 2.3.1. Gas-phase interstitial modification process It has been known for long that rare earth-iron intermetallics can absorb prodigious quantifies of hydrogen, and that their magnetic properties are altered (Wallace 1978, Buschow et al. 1982). This idea was extended to nitrogen and carbon absorptions by using gasses containing N or C (Coey and Sun 1990, Coey et al. 1991a, b, Sun et al. 1990b and 1992). The gas absorption characteristics were studied by the latter authors using a thermopiezic analyzer (TPA), which involved the measurement of the gas pressure variation as a function of temperature. The basic principle is that when a sample which absorbs or desorbs gas is heated in a closed volume at a constant rate, the pressure-temperature curve p(T) and its derivative dp(T)/dT provide a fingerprint of the material, and allow the amount of gas-envolving or gas-absorbing phase to be determined. The TPA traces of Y2Fel7 in H2, N2, NH3 and Chill0 are shown in fig. 2.3. Y2Fel7 acts as a catalyst and it induces breaking of the strong N -= N bond even at temperature as low as 400°C. When making carbides using this method, normally a hydrocarbon gas is used. At the same time of the formation of the carbides, hydrogen gas also forms, which has to be pumped out at temperatures around 500°C in order to avoid the formation of hydrides during cooling to room temperature. As can be seen from the TPA trace of Y2Fe]7 in H2 shown in fig. 2.3, the H2 gas pressure at about 500°C is roughly the same as at room temperature, which indicates that nearly no hydrogen remains in the compound. Therefore, the hydrogen content in the carbides is negligible. The gas-phase interstitial modification process can be carried out using fixed or flow gas atmospheres (nitrogen or ammonia for nitrogenation, and hydrocarbon gasses for carbonation) in conventional furnaces. Sometimes a certain fraction of hydrogen gas is added in order to activate nitrogenation or carbonation by hydrogenation which occurs at lower temperatures (fig. 2.3). Liu J.P. et al. (1991) interpreted '
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Fig. 2.3. Thermopiezicanalysisof Y2Fe17 heatedin H2, NH3, N2 and C4H10at 10 K/min.
INTERSTITIALLYMODIFIEDINTERMETALLICS
311
the nitrogenation reaction process using the same model as for the ternary hydrides by considering the reaction enthalpy (AHf) of the following two transformations, 2R2Fe17 + 3N2 --+ 2R2Fe17N3,
(2.1)
R2Fe17 + N2 -+ 2RN + 17Fe.
(2.2)
and
The reaction enthalpy AH~ of the interstitial nitride formation process is sufficiently negative, which makes the formation of the 2:17 nitrides possible, once the temperature has been raised high enough to overcome the activation energy for the absorption process. Although the enthalpy change AH~ of the decomposition process is more negative, the activation energy is also much higher. Thus the nitride phase can be formed in a limited temperature range as a metastable phase. If the nitrogenation process is performed at too high temperatures or for too long times, degradation takes place and the harmful impurity phases appear in the nitrides. By carefully controlling the nitrogenation condition, the decomposition process can be depressed, but it can not be completely eliminated. Many studies have been devoted to the preparation of high quality nitrides. High pressure nitrogenation, pre-hydrogenation treatment etc. have been found to be helpful. Fujii et al. (1992a, b) have claimed that one of the reasons for the decomposition of the nitride phase into SmN and ~-Fe is that the temperature at the surface of the Sm2Fe17 particles increases as a result of the heat formation during the reaction process and might exceed the decomposition temperature. Thus, the relative better thermal conductivity of the high pressure (up to 100 atm.) N2 gas could help to reduce the particle surface temperature and depress the decomposition process. Fukuno et al. (1991, 1992a) reported that hydrogen treatment before nitrogenation significantly increased the gas-solid reaction area by inducing many cracks in the Sm2Fe17 particles. This hydrogenation process thus promoted nitrogenation at a lower temperature and the formation of impurity phases could be minimized. Lower temperature and longer nitrogenation time is preferred in order to obtain high quality nitrides. 2.3.2. Reaction mechanism
The nitrogenation process has been observed and studied by many different experimental techniques, which include the Kerr microscopy observations by Mukai and Fujimoto (1992), in situ neutron powder diffraction studies by Isnard et al. (1992a), micrograph studies applying metallography and EPMA techniques by Colucci et al. (1992, 1993a, b) and Fujii et al. (1994b). The nitrogenation process is understood to proceed preferentially through extended defects such as phase and grain boundaries, dislocations and dislocation arrays. Nitrogen diffuses into the particles along one such path and then bulk diffusion occurs perpendicular to this path inside the particle. The bulk diffusion coefficient is very small compared with the short circuit diffusion through defects.
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H. FUJII and H. SUN
The reaction between the gas phase and the rare earth intermetallics was studied by Skomski and Coey using the lattice gas model (Coey et al. 1992, Skomski and Coey 1993a). The net reaction energy U0 consists of three parts; the energies which are necessary to dissociate the gas molecules, the energy for expanding the lattice and the energy gain due to the gas-lattice interaction. For the Sm2Fel7N v system, it was estimated that U0 = - 5 7 + 5 kJ/mol, and the diffusion parameters Do = 1.02 mmZ/s, Ea = 133 kJ/mol. Diffusion constant at a certain temperature T can be calculated by the expression DT = Do exp(-Ea/kT). The reaction kinetics of N2 absorption by Sm2Fel7 were experimentally investigated using volumetric and gravimetric measurements by Uchida H.-H. et al. (1993) and they found that Ea was in the range 100-163 kJ/mol, in agreement with Skomski and Coey (1993a). Skomski and Coey (1993a) also investigated the stress and strain in the inhomogeneously nitrogenated grains in the linear elastic approximation. The nitrogen diffusion progresses from the grain surface into the center. At the initial stage of nitrogenation or in the case of not fully nitrided materials, the stress and strain lead to an expanded nitrogen-free particle center with an increased Curie temperature but negative anisotropy constant/(1. This soft center could act as a nucleation center for domain walls and destroy coercivity. Fujii et al. (1994b) studied the nitrogen absorption process in SmzFel7 particles at 733 K under various Nz-gas pressures. The observation of EPMA-line profiles of the N-element in the grains led these authors to claim that nitrogenation process consists of the following two mechanisms: The nitrogen diffusion process and the phase transformation from the nitrogen poor Sm2Fel7Nx to the fully nitrided Sm2Fel7N3. Both mechanisms progress concurrently under Nz-gas pressures above 0.1 MPa. However, the diffusion process becomes dominant under low N2-gas pressures below 0.05 MPa and at this pressure a homogeneous phase with any value of z is stabilized, suggesting that the SmzFeI7-N solid solution exists above 733 K. 2.3.3. Nitrides with intermediate nitrogenation content It has been an open question whether the metastable nitride is a simple gas-solid solution with continuous range of intermediate nitrogen contents or whether it is a two-phase mixture of nitrogen-poor and nitrogen-rich phases. The attractive interatomic long-range interaction energy arising from the lattice deformation around the interstitial site is important for answering this question (Coey et al. 1992). Below a critical temperature Tcri, the attractive interaction dominates and the interstitial atoms form macroscopic clusters, and consequently a two-phase mixture is formed. If the nitrogenation is carried out above Tcri, then a solid solution phase should be formed. For Sm2FeavNv, Tcn was estimated to be about room temperature. As the nitrogenation is usually performed at temperatures much higher than room temperature, the nitrides should be present as a gas-solid solution phase with a continuous range of intermediate nitrogen contents, according to the estimation by Coey et al. (1992). However, not all the experimental results support this conclusion. Katter et al. (1992a) reported that the Sm2Fel7 nitrides existed over the whole concentration range of 0 ~< y ~< 3. SmzFel7Nu with intermediate nitrogen contents (0 ~< y ~< 2.94) was successfully prepared and the nitrogen content dependence of the
INTERSTITIALLYMODIFIEDINTERMETALLICS
313
unit cell volume, the Curie temperature, the saturation polarization, the anisotropy field and the thermal stability was examined. All these properties showed a continuous increase with increasing nitrogen content y. Christodoulou and Takeshita (1993e) also reported that the Sm2Fe17 nitride is not a line compound but exhibits a large solubility of nitrogen. However, it was difficult to form homogeneous interstitial compounds with y between 0 and 3, which requires either partial nitrogenation followed by long time heat treatment in argon atmosphere or nitrogenation in a predetermined amount of nitrogen. Mukai and Fujimoto (1992) observed the domain patterns of SmzFelyNy and concluded that nitrides with an intermediate nitrogen content exist. They found that the magnetic domain patterns were sensitive to the nitrogen content and the domain width became narrower as the nitrogen content decreased. The possibility of the existence of an intermediate nitrides was also suggested by Uchida H. et al. (1992) by measuring volumetrically the pressure-composition isotherm of the SmzFelv-N system at 823 K. No plateau region was observed in the P - C - T curve at nitrogenation concentrations lower than 3, which was taken as an indication of the existence of solid solutions between Sm2Fe17 and N. On the other hand, there are many publications in which it is reported that nitrides with intermediate nitrogen content do not exist. By X-ray diffraction experiments, Coey et al. (1991a) examined the reaction products after heating YzFe17 in the TPA to temperatures ranging from 300 to 850°C. The results showed that at temperatures lower than the temperature at which fully nitrided sample could be formed (600°C), the products were always mixtures of the pure 2:17 phase and the fully nitrided phase. Isnard et al. (1992a) reached the same conclusion by in situ neutron powder diffraction study of the nitrogenation process of NdzFel7. They found that even at the beginning of the reaction, the nitride was a highly charged interstitial phase, no progressive filling of the interstitial site was observed and only the ratio of the nitride phase increased as nitrogenation progressed. Similar results were obtained in a metallography study of the nitrogen diffusion patterns in Nd2Fe17 by Colucci et al. (1993b). No formation of a nitrogen solid solution phase was observed, and the fully nitrided phase precipitated directly from the phase free of nitrogen.
2.3.4. Formation of carbonitrides and other multiple interstitial compounds of H, C and N Carbonitrides were formed by subsequent nitrogenation of the arc-melted carbides (Coey and Sun 1990, Nagata and Fujii 1991, Kou et al. 1991a, b, Yang Y.C. et al. 1992a). This is a combined arc-melting and GIM process. Altounian et al. (1993) and Chen et al. (1993a, b) made the carbonitrides by the GIM process only. The carbonitriding process can be done either using mixtures of N2 gas and hydrocarbons or sequentially one followed by another. A mixed gas of nitrogen and methane proved to be successful for obtaining carbonitrides of R-Fe intermetallics with various nitrogen to carbon ratios. The reaction was written as follows, 1
yN2 + zCH4 + R2Fe17 ~ R2Fe17CxN v + 2xH2.
(2.3)
Similarly to the preparation of carbides by the GIM process, H2 should be pumped out to avoid the formation of the undesired hydrides. For the sequential process, it was
314
H. FUJII and H. SUN
found that nitrogenation should be done first, followed by the carbiding reaction. If carbonation was followed by nitrogenation, then only carbides were produced because the carbon layer formed on the surface of the particles prevented nitrogen atoms from entering into the particles. Christodoulou and Takeshita (1993f) reported the preparation of SmzFelv-carbonitildes, carbonhydrides, nitrohydrides and carbonitrohydrides. The carbide was made first, by direct melting or gas phase carbonation, then it was nitrogenated and finally hydrogenated. The nitrohydride can be produced directly by nitrohydrogenation in a mixture of N2 + H2 or N}-I3 gasses. The SmzFely-carbonitrohydrides can also be prepared by gas phase reaction of Sm2Fel7 powders with a mixture of hydrocarbon, N2 and H2 gasses.
2.4. Solid-solid (or liquid) reaction and plasma nitriding methods A new route for the synthesis of metalloids interstitials is solid-solid (or liquid) reactions. This has been tried for synthesizing carbides using heavy hydrocarbon organic compounds, such as benzene (C6H6) and toluene (C7H8) etc. (Fruchart et al. 1994). Interstitial modifications of Y2Fel7 by reaction with solid boron, silicon and sulfur were tested by Skomski et al. (1993), but were not very successful. Compared to the gas-phase interstitial modification, the solid-solid reaction has the following advantages; (1) it can be conducted at relative low temperatures and thus the decomposition process could be depressed, and (2) liquid and solid materials are easier for handling. In order to avoid the formation of hydrides, the reaction should be conducted at temperatures higher than 400°C. For this purpose, Fruchart et al. (1994) suggested to use hydrocarbon (and hydrocarbonitrogen) materials of heavier formula weight, which have both a higher thermal stability and a lower H/C(N) ratio. Plasma nitriding of SmzFe~7 was done by Machida et al. (1993). It was performed by glow-discharge between the electrodes under a differential pumping condition at 2 Torr of a N2-H2 mixed gas with a molar ratio of 1:2. The advantage is that the reaction temperature was only 423 K, which is much lower than the conventional thermal gas-solid or solid-solid reaction.
2.5. Summary Sm2Fe17nitride is a most interesting material for permanent magnet applications. For making the nitride, GIM is the most suitable way. High quality (fully nitrided and free from impurity phases) nitrided material is essential for making the final magnet products with useful magnetic properties. The nitrogenation process is a relative complicated process which is not only affected by the nitrogenation conditions, such as the temperature, reaction period, gas pressure and composition of gasses, but is also affected by the initial Sm2Fel7 particle size and surface condition. The basic features and diffusion patterns of the GIM process have been fairly well understood. However, further studies are necessary for improvement and better controlling of the GIM process.
INTERSTITIALLYMODIFIEDINTERMETALLICS
315
3. Interstitial compounds of the 2:17-type structure Among binary rare earth iron intermetallics, compounds with the 2:17-type structure are the most iron rich ones and they are particularly stable. The R2Fel7 compounds exist across the whole lanthanide series, from Ce to Lu, except for La itself. The magnetic properties of the series have been studied in great detail (Buschow 1977, Wallace 1985). The magnetization is fairly high because of the high iron content. However, none of these compounds exhibits an easy-axis anisotropy at room temperature, and only Tm2Felv does so in the liquid nitrogen temperature range. Furthermore, the Curie temperatures are surprisingly low (240-480 K) for compounds containing so much iron. Therefore the R2Fe17 compounds have been disregarded as potential permanent magnet materials. It has been found that elements with small atomic radius can occupy interstitial sites of the R2Fel7 host lattice. These interstitial atoms cause displacements of the metal atoms from their regular sites, and the resulting crystal lattice distortions give rise to various kinds of changes in physical properties which are interesting from both fundamental and applied points of view. Interstitial modifications by H, C and N have been studied intensively and proved to be successful for improving the magnetic properties of R2Fe17. In this section, various studies of the structural and magnetic properties of interstitial R2Fe17 carbides and nitrides will be summarized. Studies of the R2Fe17-hydrides have been already reviewed by Wiesinger and Hilscher (1991). For this reason we will omit them here. 3.1. Crystallographic structures The RzFe17 compounds crystallize in the rhombohedral ThzZn17-type structure (space group R3m) for rare earths lighter than Gd and in the hexagonal ThzNily-type structure (space group P6/mmc) for rare earths heavier than Tb. The compounds with R = Gd, Tb and Y can exist in both forms depending on the high temperature annealing condition. Hexagonal form of Ce2Fel7 has also been reported to coexist with the rhombohedral one (Buschow and van Wieringen 1970). Both of the structures are derived from the CaCus-type structure by the ordered substitution with a (dumbbell) pair of Fe atoms for each third rare earth atom in the basal plane (Florio et al. 1956, Zarechnyuk and Kripyakevich 1962). When these substituted layers are stacked in the sequence abcabc, the Th2Zna7-type rhombohedral structure is realized. If the stacking sequence is, instead, ababab, then the ThzNi17-type hexagonal structure is formed. The structures are illustrated in fig. 3.1, both of which are represented by hexagonal cells with two and three RzFe17 formulas for the hexagonal and rhombohedral structures, respectively. 3. I.I. Structure modification by the GIM process The modification of the R2Fe17 structures by interstitial nitrogen and carbon atoms introduced by the GIM process is essentially to expand the unit cells, without changing the rhombohedral or hexagonal symmetry of the parent compounds. This retaining of the crystallographic symmetry is the main difference when compared to the arcmelted carbides, where a structure transition from the hexagonal symmetry to the
316
H. FUJII and H. SUN
v
v
v
_
I
C
a v
v
a
v
R 06C
R (~)2d 02b
Fe
~6c
~gd
Z
•
o18g
9e
Th2Znl7
(~)18f
O18h
Fe ~ 4 f
@6g
Z
0121
•
6h
@12J
4D12k
Th2Nl17
Fig. 3.1. Crystal structuresof R2Fe17,left: rhombohedralTh2ZnlT-type;right: hexagonalTh2Ni17-type, showing the rare earth sites (R), iron sites (Fe) and the interstitialsites (Z). rhombohedral symmetry was observed with increasing carbon content (for detail see the following section). Lattice parameters of nitrides and carbides of all the RzFel7 compounds are collected in table 3.1, in which also included are the carbonitrides and carbonitrohydrides for some of the rare earths. As shown in table 3.1, the total number of nitrogen and carbon atoms per formula unit is close to or slightly less than 3 in nearly all the interstitials. The expansion of the cell volume upon nitrogenation or carbonation, or the combination of them, is 6-7% for all the R2Fea7 compounds except for Ce, where the volume increase is more than 8%. It is also noticeable that nitrides have a slightly larger volume than carbides in general. Figure 3.2 compares the lattice parameters of the GIM nitrides R2Fel7N v and carbides R2Fel7Cv, the arcmelted carbides R2FeivC and the host R2Fel7 compounds (2/3e and 2/3V for the rhombohedral compounds are plotted). The normal variation in lattice parameters associated with the lanthanide contraction is shown excepting the Ce compounds. The anomalous position of Ce suggests a near tetravalent (4f°) configuration for Ce in CezFe17, which changes to an intermediate valence configuration between 4f ° and 4f I in the nitrides and carbides.
3.1.2. Structure studies of the arc-melted and melt-spun carbides The expansion effect of the unit cell volume due to interstitial carbon atoms introduced by the arc-melting method is similar to those introduced by the GIM method,
INTERSTITIALLY MODIFIED INTERMETALLICS
317
TABLE 3.1 Crystallographic structure data and magnetic properties of R2Fel7 and their interstitial compounds. V is the crystal cell volume calculated from V =
-~a2c. Saturation magnetization as at room temperature
and 4.2 K are expressed in the unit of/zB/formula. Compound
a (]k)
C (/k)
V (•3)
AV/V (%) Tc (K)
as (#B/f.u.) RT
Ce2Fel7 Ce2Fe17N2.8 Ce2FelvN2.5 Ce2FeI7N25 Ce2FeI7N3. 6 Ce2FelTCu CezFe17C2.8 Ce2Fe17C2.5 Ce2Fel7C2 Ce2FeI7CxN/,
8.48 8.73 8.743 8.743 8.73 8.73 8.74 8.73 8.72 8.73
12.38 12.65 12.673 12.688 12.81 12.56 12.65 12.58 12.64 12.68
773.5 834 838.9 847.9 845.5 829.5 836 830
8.8 8.24 9.43 9.3 8.3 8.0 8.2
Pr2Fel7 Pr2Fel7N2. 5 Pr2FelvN25 Pr2FelTN2.86 PrzFelTCy Pr2Fel7C2. 7 PrzFel7C2. 5 Pr2Fel7C 2 PrzFelvCxNu
8.574 8.77 8.794 8.795 8.80 8.79 8.85 8.78 8.79
12.324 12.64 12.668 12.659 12.59 12.63 12.61 12.65 12.66
790.7 841.8 848.4 847.9 843.3 845 855
6.5 6.65 6.68 6.7 6.8 8.3
Nd2Fel7 Nd2Fel7N2.3 Nd2Fel7N2.5 Nd2Fel7N2. 4 Nd2FelvCu NdzFel7C2.2 NdzFel7C2.5 Nd2Fel7C2 NdzFel7CxN u
8.563 8.76 8.783 8.776 8.79 8.76 8.80 8.76 8.76
12.444 12.63 12.663 12.661 12.60 12.62 12.60 12.64 12.65
790.2 838.8 845.5 844.5 842.1 839 845
6.2 6.45 5.85 6.6 5.9 6.7
Sm2Fel7 Sm2Fe17N2.3 SmzFeI7N2. 5 Sm2FelTN2. 2 Sm2Fel7N2 SmzFe17N3.1 SmzFel7N2. 9 Sm2FelTN3.o Sm2Fe17N2.7 Sm2Fel7Ns.2 SmzFelvN2.9 SmzFeI7N2. 6 Sm2Fel7 N2.94
8.55 8.73 8.741 8.730 8.732 8.74 8.76 8.728 8.778 8.838 8.743 8.71 8.7425
12.43 12.64 12.666 12.630 12.631 12.65 12.76 12.638 12.74 12.82 12.703 12.61 12.659
786.9 833.7 838.2 834.1 834.1
6.3 6.36 6.01 6.2
833.73
837.9
6.2
210 713 700 712 589 716 608 589 721 290 728 720
4.2 K 29.3
36.4 32.2
36.3
31.6
39.9 33.8
25.1
30.0
18.1 37.9 36.5
653 735 690 654 737
27.0
330 732 740
17.1 40.5 34.9
41.3 34.5 30.8
43.9
659 739 662 658 740
29.0
31.8
389 749 750
22.4 31.9 32.2
34.1
745 752
35.1 34.0
748
35.7
740
34.3 35.5 36.2
746
Ref.
35.1
38.2
38.1
35.0
[13, 24] [1] [2, 3] [4] [13, 24] [7] [21] [22] [8, 9] [8, 9] [1] [1] [2, 3] [4] [7] [21] [22] [8, 9] [8, 9] [1] [1] [2, 3] [4] [7] [21] [22] [8, 9] [8, 9] [13, 24] [1] [2, 3] [4] [5] [13, 24] [14] [15] [16] [16] [17] [18] [19]
318
H. FUJII and H. SUN TABLE 3.1 (Continued)
Compound
a (,~)
c (-~)
V (,~3) AV/V (%) Tc (K)
Sm2Fel7Cy Sm2Fel7C 2 Sm2Fe17C2.5 Sm2FelvC2.5 Sm2Fe17C2 Sm2Fel7C:rNy Sm2Fe17CN u Sm2Fe17Ny Sm2Fe17Co.4Ny Sm2FelTCo.TN u Sm2FelTCo.9N u Sm2Fel7N3.oHo.8 Sm2FelTCo.sN2. 4 Sm2FelTCo.5N2.4Ho.8 Sm2FeÂTC2.6 Sm2FeI7C2.6H1.1 Sm2Fel7 C2.6No.1 Sm2FelTC2.6NoA HI.O
8.75 8.749 8.73 8.77 8.73 8.75 8.712 8.742 8.736 8.742 8.765 8.739 8.742 8.735 8.744 8.753 8.747 8.754
12.57 12.595 12.67 12.61 12.65 12.65 12.604 12.651 12.650 12.633 12.683 12.733 12.652 12.715 12.572 12.622 12.584 12.634
833.0
Gd2Fel7 Gd2Fel7N2. 4 Gd2Fe17N2.5 Gd2Fe17N2.5 Gd2Fe17C u Gd2FelTC2.5 Gd2Fe17C2 Gd2FeI7CzN u Gd2FelTCNy
8.508 8.69 8.713 8.715 8.70 8.68 8.68 8.70 8.695
12.432 12.66 12.652 12.653 12.61 12.69 12.66 12.67 12.603
779.4 827.6 831.8 832.3 825.8 828
Tb2Fe17 Tb2Fe17N2.3 Tb2Fe17N2.5 Tb2Fel7Cy Tb2Fe17C2 Tb2FelTCxNy Tb2Fel7CNy
8.484 8.66 8.683 8.67 8.65 8.65 8.678
12.410 12.66 12.666 12.64 12.66 12.71 12.602
773.6 823.1 827.0 823.2
Dy2Fel7 Dy2Fe17N2.8 Dy2Fe17N2.5 Dy2Fel7Cy Dy2FelTC2. 7 Dy2Fe17C2.5 Dy2Fel7C 2 Dy2FelTCxNu Dy2Fe17CNv
8.445 8.64 8.670 8.65 8.63 8.69 8.63 8.66 8.643
8.304 8.45 12.666 8.42 8.42 8.46 8.42 8.45 8.461
512.9 545.9 824.5 545.2 543 553
836 840
828.5 837.3 836.0 836.0 843.8 842.12 837.34 840.14 832.48 837.49 833.85 838.54
6.2 5.9 6.5 7.1
6.2
6.2 6.89 6.01 5.9 5.9
825.2
6.4 6.54 6.4
821.9
547.4
6.4 6.52 6.3 6.1 8.5
668 670 760 679 680 758 778 753 759 753 760 748 752 752 673 674 678 678 477 758 740
~s (/zB/f.u.) RT
4.2 K
26.6
34.5 30.1
26.2
29.2
31.2 32.3
35.1
Ref.
[7] [20] [21] [22] [8, 9] [8, 9]
[lO] [11, [11, [11, [i1, [15] [15] [15]
36.3 36.3 35.0 35.2 29.3
12] 12] 12] 12, 15]
[15] [15] [15] [15]
10.4 26.7 17.9
711 763 712 764 813
27.3 20.1
28.1
404 733 730 680 680 748 778
11.6 22.4 23.6
367 725 720 674 733 681 683 724 758
11.4 27.1 25.6
25.0 21.3
24.3
17.9
23.0 17.1 14.2
23.1
[1] [1] [2, 3] [4] [7] [21] [8, 9] [8, 9] [lO] [1] [11 [2, 3] [7] [8, 9] [8, 9] [10] [1] [1] [2, 3] [7] [21] [22] [8, 9] [8, 9] [10]
INTERSTITIALLY MODIFIED INTERMETALLICS
319
TABLE 3.1 (Continued) Compound
a (A)
e (.A)
V (A 3)
AV/V (%) Tc (K)
as (#B/f.u.) RT
Ho2Fel7 Ho2FelTN3.0 Ho2Fe17N2.5 Ho2Fel7N2.1 Ho2Fel7Cy
8.439 8.62 8.632 8.609 8.61
8.280 8.45 8.472 8.480 8.43
510.7 543.8 546.7 544.3 540.8
Er2Fel7 Er2Fel7N2.7 Er2FelTN2.5 Er2Fe17N2.45 Er2Fel7C u
8.272 8.46 8.476 8.469 8.41 8.438 8.44 8.46 8.44 8.49 8.460 8.472 8.469 8.469 8.480 8.478 12.628
508.0 542.8 544.9 540.5 538.5
Er2Fel7 C2.4 Er2FelTC2.5 Er2FelTCy Er2FelTCxN u Er2FelTCNy Er2Fel7Ny Er2Fel7Co.4Ny Er2Fel7Co.6Ny Er2FelTCo.sNy Er2Fe17Cl.0Ny Er2Fel7Cl.sNy
8.421 8.61 8.622 8.584 8.60 8.630 8.61 8.68 8.63 8.63 8.615 8.633 8.643 8.643 8.651 8.647 8.652
543.8 546.8 547.9 547.8 549.6 549.0 818.6
Tm2Fel7 Tm2Fel7 N2.7 Tm2FeI7N2.5 Tm2Fel7C u Tm2Fel7Ny TmzFel7Co.zNy TmzFeI7Co.4Nu Tm2Fe17 Co.6Ny Tm2Fel7Co.8Nv TmzFel 7C 1.oNy
8.397 8.58 8.583 8.60 8.569 8.584 8.590 8.586 8.586 8.584
8.276 8.47 8.482 8.43 8.481 8.486 8.478 8.485 8.484 8.485
505.4 540.6 541.1 539.6 539.3 541.5 541.8 541.7 541.6 541.4
Yb2Fe17 Yb2Fel7N2.8
8.414 8.5701
8.249 8.495
505.7 540.0
6.48
280 675
Lu2Fel7 Lu2Fe17N2.7 Lu2Fe17N2.5 Lu2FelTCy
8.390 8.57 8.576 8.57
8.249 8.48 8.475 8.42
502.9 539.4 539.8 535.4
7.1 6.68 6.3
255 678 675 657
Y2Fel7 Y2Fel7
8.477 8.51
8.264 12.38
514.3 776.4
Er2Fe17C2
541 553
6.5 6.56 6.27 5.9
6.9 6.78 5.84 6.0 6.7 6.5 7.3
7.2
7.0 6.59 6.8 6.3
327 709 710
11.2 27.2 25.2
672 296 697 690 663 675 708 671 675 700 723 683 712 706 709 701 698 260 690 690 656 700 701 703 705 701 703
325 300
24.5 17.5
7.4 31.7 27.4
20.5 17.9
22.0
12.8
27.4
32.5 32.9
30.2 21.2
[1] [1] [2, 3] [4] [7]
[1] [1] [2, 3] [4] [7] [20] [21] [22] [8, 9] [8, 9] [10[ [11] [11] [11] [111 [111 [11] [11 [1] [2, 31 [7] [11] [11] [111 [11] [11] [11] [23] [2, 31
34.2
39.0 36.4
[11 [11 [2, 31 [71
32.8 34.0
[1] [24]
35.2
18.6
Ref.
4.2 K
320
H. FUJII and H. SUN TABLE 3.1 (Continued) c (A)
V (~3)
AV/V (%) Tc (K)
O's (p,B/f.u.)
8.44 8.465 8.484 12.69 8.40 8.414 8.46 8.40 8.40 8.48 8.415 8.488 12.606
6.4
34.2
YzFelvN3.1 YzFeI7Cy Y2FeITC2 Y2Fel7C2.8 Y2FelTC2.5 Y2FelTC2 Y2Fel7CzN u YzFel7CNy Y2Fel7Co.6Ny YzFe17C1.2Ny
8.65 8.637 8.646 8.67 8.66 8.689 8.64 8.65 8.67 8.66 8.635 8.634 8.673
547.3
543.4 547.9 821.2
701 668 673 722 678 668 717 723 722 724
Th2Fel7 Th2Fe17Nu
8.572 8.798
I2.472 12.703
794 853
320 747
Compound
a (h)
RT YzFeI7N2.6
Y2Fe17N2.7 Y2FeI7N2.8
References: [1] Sun et al. (1990b) [2] Buschow et al. (1990) [3] Liu J.P. et al. (1991) [4] Isnard et al. (1992d) [5] Katter et al. (1990) [6] Jacobs et al. (1991) [7] Sun et al. (1992) [8] Altounian et al. (1993) [9] Chen et al. (1993) [10] Yang Y.C. et al. (1992a) [11] Kou et al. (1991a) [12] Kou et al. (1991b)
549.2 826.1 546.1 547 544
6.70 6.4 6.2 6.8 6.6 6.2
694 690
Ref.
4.2 K 38.5
28.9
39.8 35.8 34.1
27.9
32.5
35.8
30.4 38.1
[11 [3] [4] [24] [7] [20] [21] [22] [8, 9] [8, 9] [10] [11] [11] [6] [6]
[13] Fujii et al. (1992) [14] Machida et al. (1993) [15] Christodoulou and Takeshita (1993f) [16] Uchida H. et al. (1992) [17] Wei et al. (1993) [18] Mukai and Fujimoto (1992) [19] Katter et al. (1992a) [20] Hu and Liu (1991) [21] Liao et al. (1992) [22] Tang et al. (1992) [23] Buschow (1972) [24] Fujii et al. (1995a)
but the overall expansion is much less in the arc-melted carbides (table 3.2), which is obviously associated with the smaller amount of carbon atoms introduced in. As mentioned in section 2, the solubility y of carbon in R 2 F e l T C v obtained from the melt and subsequent high temperature annealing is limited to y ~< 1.6 for heavy rare earths and y ~< 1.0 for light rare earths. From the study of the dependence of the unit cell volume V on carbon content y for R = Sm (Popov et al. 1990, Gr6ssinger et al. 1991, Wang and Hadjipanayis 1991a), Gd (Dirken et al. 1989), Ho (Haije et al. 1990), Tm (Gubbens et al. 1989, Gr6ssinger et al. 1991), Er (Kou et al. 1991c), Y (Coene et al. 1990, Sun et al. 1990a) and Th (Isnard et al. 1992e, Jacobs et al. 1991), a linear relationship between V and y was found until y ~ 1. In the case where the host R2Fe17 takes the Th2Ni17 structure, there is a structure transition from the hexagonal to the rhombohedral structure with increasing carbon concentration (Sun et al. 1990a, Coene et al. 1990, Haije et al. 1990, Kou et al. 1991c). This structure transformation is reminiscent of the structural transformation
INTERSTITIALLY MODIFIED INTERMETALLICS
321
8.7
,< ._... 8 . 6 - o
r~
R ~ ~'~
.-~...~ ~ ~...~, ~o
/ 0 - - 0 ~'
'~'o.~ ~0~
8.4 ~
+
~ D
~
8.5A
o
8.3
o , . n l o ° . . . o°
o\/
8.2
,..
°
-o
o
_li-i~_,
560 "-" 540
""~
>
O~C[/ - 0 ~ ° ~
520
o°--o° o°__~o oo-
~L~....~,,,~.~,,,~.
0... / 0
o... 0"-0
[]~ 0
~o
~0~
°-°'-'-°
500 Y
Pr Ce
Nd
Pm Eu Tb Ho Tm t u Sm Gd Dy Er Yb
Fig. 3.2. Lattice parameters and cell volumes of R2FeI7, the arc-melted R2FelTC, the GIM R2FelTCy and R2Fel7Ny (after Sun et al. 1990b and Zhong et al. 1990).
observed in R2Fel7 when passing in the opposite direction through the lanthanide series (from Lu to Pr). In both sequences the hexagonal structure is observed for relatively small lattice constants and the rhombohedral structure for relatively large lattice constants. The lattice parameters as a function of carbon concentration y for Y2FelTC v are shown in fig. 3.3, where a discontinuity in the lattice constants near the transformation point can be seen. It is also clear that the change in crystal structure is accompanied by an expansion and contraction of the lattice in the a and c directions, respectively, with ahex < arhomb, but Chex > Crhomb at the transition point. It should be noted that the value of y at which the transformation occurs was found to be different by different authors. This is due to differences in heat treatment condition and difficulties in the accurate controlling of the carbon content in the 2:17 structures. The structural and magnetic properties are very sensitive to the heat treatment condition because the dissolution of carbon in the matrix depends strongly on the annealing temperature and time (Sun et al. 1990a, Wang and Hadjipanayis
322
H. FUJII and H. SUN
TABLE 3.2 Crystallographic structure data and magnetic properties of the arc-melted carbides R2FeI7C. V is the crystal cell volume calculated from V = '/~aZc. Saturation magnetization ~s at room temperature and 2 4.2 K are expressed in the unit of ~B/formula. Compound
a (A)
c (,~)
V (,~3) AV/V (%) Tc (K)
Ce2FeI7C Pr2FeI7C Nd2FeI7C Nd2Fe17C Sm2Fel7C Sm2Fe17C Sm2Fe17C Gd2Fe17C Tb2Fe17C Dy2Fe17C Ho2Fe17C Er2Fe17C TmzFelvC Lu2Fel7C Y2Fe17C ThzFel7C1.2 Th2Fel7C1.2
8.540 8.604 8.630 8.6299 8.644 8.6297 8.624 8.627 8.602 8.585 8.572 8.538 8.524 8.487 8.589 8.697 8.694
12.424 12.466 12.474 12.4739 12.476 12.4614 12.459 12.470 12.462 12.454 12.453 8.331 8.321 8.321 12.448 12.518 12.509
784.5 799.5 804 804.5 807 803.7
2.3 1.1 1.7
804 798 795 792 526 524 519 795 820 819
3.1 3.1 3.3 3.3 3.5 3.8 3.0 3.1 3.1
as (/zB/f.u.) RT
References: [1] Zhong et al. (1990) [2] Weitzer et al. (1990) [3] Weitzer et al. (1991)
2.9
297 370 449 435 552 495 516 582 537 515 504 488 498 490 502
24.8 462
4.2 K 32.8
31.0
Ref.
40.6 36.5 34.0 35.0 35.1 23.6 19.0 17.0 17.4 18.8 24.4 35.2 35.5 35.8 34.5
[1] [1] [1] [2] [1] [2, 3] [4] [1] [1] [1] [1] [1] [1] [1] [1] [5] ND [6]
[4] Popov et al. (1990) [5] Isnard et al. (1992e) [6] Jacobs et al. (1991)
1991a, b). In the R2Fe17C series, the stability range o f the rhombohedral structure extends towards the Lu end and the structure transformation from ThzZnl7 to Th2Nil7 takes place at Er, instead o f at Gd in the pure R2Fel7 c o m p o u n d s (Zhong et al. 1990). A novel type o f stacking, in which h o m o g e n e o u s sheets o f dumbbell pairs o f iron atoms and h o m o g e n e o u s sheets o f rare earth atoms along particular ordering planes are stacked at random, has been reported for Y2FeI7Cy when y is close to 0.6 at which t h e structure transition occurs (Coene et al. 1990). These stacking faults can locally change the R site s y m m e t r y (Gubbens et al. 1989) and m a y also form an intrinsic barrier in these materials for the attainment o f high coercive forces (Buschow et al. 1990). With increasing o f carbon content, a similar structure transformation from the hexagonal to the rhombohedral symmetry was also found in the interstitial carbides prepared by the melt-spinning method (see for example Cao et al. 1993a). On the other hand such a phase transition was not observed in the G I M interstitial carbides and nitrides because o f the low reaction temperature. For R2Fe17 with the ThzZnl7 structure (R = Sin, Gd and Th), the expansion o f the cell in the a-axis direction upon carbonation is much larger than that in the c-axis direction, which could be related with the crystallographic site occupation o f the interstitial atoms. In ThzFe17Cv, when y > 1.2, the appearance o f a BaCdal type
INTERSTITIALLY MODIFIED INTERMETALLICS
0
323
8.8 I I I (a/ 8.7 a 8.6 8.5 o ~° ~ ° ~°/°-°-°-°-° 8.4' 8.3 - - ° ~ ° ~ ' ~ ° " ° - ° - ° - ° ' ° 8.2 c 8.1 8.0 550
I
I
I
(b)
600 Tc
oso-o--o-
54O
o
o
550 50O
53O
450 ,.t
520
4O0
>
350
51C 0.0
I
I
I
0.5
1.0
1.5
30O 2.0
Carbon Content, y Fig. 3.3. Carbon concentration dependence of (a) the lattice parameters and (b) Curie temperatures and cell volumes of Y2FelTCv (after Sun et al. 1990a).
phase was reported and the fraction of this new phase was found to increase with increasing carbon content (Jacobs et al. 1991).
3.1.3. Structure properties of the nitrides with intermediate nitrogen content Unlike in the arc-melted carbides, a continuous variation of the nitrogen content in the GIM nitrides was first reported not to be possible. However, more detailed studies have later demonstrated that nitrides with nitrogen content in between 0 and 3 do exist (see section 2.3.3 and the references cited there in). There are a few reports that the nitrogen content y can be as high as 6 or 8 in Sm2Fe17Nv (Iriyama et al. 1992, Wei et al. 1993), where the best magnetic properties can be obtained at y -- 3. Structural and magnetic properties of SmzFelTNu as a function of y have been investigated by Katter et al. (1992a) and they found that the SmzFel7 nitrides existed over the whole concentration range 0 ~< y ~< 3. The lattice parameters and cell volume dependences on the nitrogen content y are redrawn in fig. 3.4. The unit cell volume has increased by 6.2% at y = 3.0, but most of the expansion has occurred at y < 1.99. The gas-phase interstitial modification process can be simulated by the lattice-gas model which has been considered to bear strong resemblances to the magnetic Ising model (Skomski and Coey 1993a). The corresponding parameters are the critical temperature Tcrit in the lattice-gas system and the magnetic ordering temperature Tc in the Ising system. Terit describes a second-order phase transition; below Tcrit there is the possibility of two coexisting phases, the nitrogen-poor a-phase and the
324
H. FUJII and H. SUN 8.80
,<
,
~
8.70
~
,
/ f ' f
,
......
"
8.60 i , / i
8.5o
I
I
12.60
/
,,< v 0
12.50
820840[-F >
I
I
,~"-"-*"-*~
~,....~,/"
12.40
v
I
I
I
I
1
I
I 2.0
I 2.5
j./.~*~'-'--
800~....~ . . . . 780[760~I I 0.0 0.5 1.0
I 1.5
3.0
Nitrogen Content, y Fig. 3.4. Nitrogen concentrationy dependenceof lattice parameters a and c, and the unit cell volume V for Sm2Fe]7Ny (after Katter et al. 1992a). nitrogen-rich/3-phase. For Sm2Fel7Ny, Tcrit is not yet known, but it does not depend on the gas pressure and there are strong evidences indicating that Terit < 400°C (Fujii et al. 1994c). This indicates that above 400°C, Sm2FelvNy forms a gas-solid solution phase rather than a two-phase mixture of a and/3 nitrides. The lattice-gas model provides theoretical support for the existence of the nitrides with intermediate nitrogen concentration. 3.1.4. Location of interstitial atoms The expansion of the cell volume due to nitrogen or carbon additions has led to the conclusion that the added atoms occupy interstitial hole sites in the 2:17 structure. In order to understand the drastic changes of structural and magnetic properties accompanied by interstitial modifications, various crystallographic studies have been conducted. The interstitial carbides were studied first and later work was focused on the nitrides after they had been discovered. By X-ray and neutron diffraction studies, carbon atoms in the arc-melted carbides RzFelvCy were first reported to be located on the 3a site, which is in between the dumbbell iron atoms and which is too small to accommodate one carbon atom (Luo et al. 1987a, b). It was later established by neutron diffraction studies that the carbon atoms fill voids of nearly octahedral shape formed by a rectangle of Fe atoms and two rare earth atoms at opposite comers (Helmholdt and Buschow 1989, Haije et al. 1990), which are the 9e sites in the ThzZnl7-type structure in fig. 3.1. Similar conclusions had been drawn earlier by Block and Jeitschko (1986 and 1987 ) from
INTERSTITIALLY MODIFIED INTERMETALLICS
325
the structure refinement of X-ray data on single crystal of R2Mn17C3_y. While full occupation of the 9e (6h for the Th2Ni~7-type structure) sites by carbon atoms corresponds to the formula R2Fel7C3, only less than half of the full occupancy has been achieved in the arc-melted carbides. Neutron diffraction results on the crystallographic position and occupancy of nitrogen atoms in the interstitial nitrides R2Fe~7Ny for various rare earths are summarized in tables 3.3a and b. Nitrogen has a large neutron scattering length pi = TABLE 3.3 The occupancy factor n and the atomic position parameter x of the interstitial sites occupied by interstitial nitrogen atoms in (a) the rhombohedral Th2ZnlT-type R2FelTNy (R = Ce, Pr, Nd and Th) and (b) the hexagonal Th2Ni~7-type Y2FelTNy compounds. a 9e (0.5, 0, 0)
18g (x, 0, 0.5)
Compound
n
z
Nd2Fel7N2. 6 Nd2Fe17N2.56 Nd2FelvN2.52 NdzFe17Nk26 NdzFe17Nv NdiFe17N3 NdzFelvN2.85 NdzFel7N2.91 NdzFelTN4.5
0.86(2) 0.85 0.60(2) 0.14(5) 0.860(8) 0.984(8) 0.95(4) 0.95(4) 0.8
Ce2Fe17N3 Pr2Fe17N2.9 ThzFelvN3
0.992(12) 0.972 0.988(4)
0.806(6) 0.805
0.12(1) 0.14(5)
0.811(57) 0.854
0.01(2) 0.35
References: [1] Ibberson et al. (1991) [2] Yang Y.C. et al. (1991a) [3] Jaswal et al. (1991) [4] Yelon and Hadjipanayis (1992) [5] Miraglia et al. (1991)
Compound Y2Fe16.5N2.9 Y2FelTN2.5 Y2Fe18N2 YzFels.sN2
n
[6] [7] [8] [9] [10]
12i (x, 0, 0)
x
X
0.8329(5) 0.833 0.8319 0.8292(13)
References: [1] Ibberson et al. (1991) [2] Yang Y.C. et al. (1991a)
0.77(1) 0.83 0.67(2) 0.56(3)
e (A)
Ref.
8.7760(1) 8.762 8.763(1) 8.629(1) 8.776(1) 8.786(1) 8.7746(5) 8.7773(4) 8.763
12.6366(8) 12.631 12.644(2) 12.512(2) 12.661(1) 12.676(1) 12.6570(6) 12.6602(5) 12.688
[1] [2] [3, 41 [3, 4] [5] [6] [7] [7] [8]
8.737(1) 8.771(1) 8.8020
12.702(1) 12.629(1) 12.737
[6] [9] [10]
Isnard et al. (1992b) Kajitani et al. (1993) Yan et al. (1993) Isnard et al. (1992c) Isnard et al. (1993)
6h (x, 2x, 0.25) n
a (,~)
0.1465(19)
n
a (h)
c (£)
Ref.
0.10(1)
8.6393(1) 8.653
8.4749(2) 8.451
8.6622(11)
8.4702(13)
[11 [2] [3] [4]
[3] Jaswal et al. (1991) [4] Yelon and Hadjipanayis (1992)
326
H. FUJII and H. SUN
0.930 x 10 -12 cm which makes it easy to determine the location of nitrogen accurately. All the studies indicate that nitrogen predominantly occupies the 9e(6h) octahedral sites and the best fits have been obtained with exclusive occupancy of these sites in Pr2Fe17N2.9 (Isnard et al. 1992c). For Nd2Fe17, some authors also suggested a partial occupation of a second interstitial site, the 18g sites (see table 3.3a). Jaswal et al. (1991) have reported that nitrogen fills the 18g site first, to its occupancy limit n = 1/6 and then fills the 9e site to its limit n = 2/3. They also found that the cell volume increased almost linearly with increasing 9e site occupancy, but not with the total N content. In fitting the neutron diffraction spectra, Kajitani et al. (1993a, b) positioned a small amount of nitrogen atoms on the 18g site. However, they suspected that these 18g-site interstitial atoms might be hydrogen instead of nitrogen, since some hydrogen atoms coexisted with nitrogen in the samples because the nitrogenation was performed in a NH3-H2 gas mixture. A different model was given by Yan et al. (1993) who reported a nitrogen content as high as 4.5 atoms per formula of Nd2Fe17. From their structural analysis these authors concluded that nitrogen filled the 9e and 18g sites simultaneously and achieved a final occupancy of 0.80 and 0.35, respectively. The occupancy of nitrogen on the 18g site was limited to 50% of the nitrogen hexagon at alternating vertexes and consequently a full occupation of 6 nitrogen atoms per formula was suggested in the model. From the abnormally large thermal factor of nitrogen on the 18g sites, the authors concluded that vibrating ellipsoids of nearest neighbors overlapped, so that the nitrogen atoms should be able to move freely from one site to another nearest-neighbour site. The cluster consisting of the nitrogen hexagon at 18g sites and two rare earth atoms at 6c sites above and below the nitrogen hexagon was considered to be responsible for the metastability of the nitride, because the nitrogen atoms at the 18g sites would have sufficient kinetic energy to move to other sites at high temperatures. For the Y2Fel7 compound, Jaswal et al. (1991) reported that the hexagonal host compound showed considerable compositional variation as well as disorder associated with less than complete dumbbell substitution of one-third of the rare earth sites. These features remained after nitrogenation and complicated the structure refinement of Y2Fel7Ny. Nevertheless, N atoms were located at the 6h octahedral sites with 2/3 occupancy and a final composition of Y2Fe18N2. Another type of partial disorder consisting of the replacement of some of the rare earth atoms at the 2b site by a pair of Fe 4e atoms in the host Y2Fe17 was taken into account by Ibberson et al. (1991). In the nitride, they placed 12% of the N atoms on the 12i site and this led to a final formula of Y2Fe16.sN2.9 was deduced. Neutron diffraction studies of the Sm compounds are not possible because of the large absorption cross section of Sm atoms. The site occupancy of nitrogen atoms in SmzFeITN u was studied by EXAFS experiments using the SmLni edge (~ = 0.184 nm) (Coey et al. 1991a, Capehart et al. 1991). The magnitude of the Fourier transformation of the EXAFS is shown in fig. 3.5(a) and (b), where the experimental (solid line) and calculated (dashed line) radial distribution of atoms surrounding the Sm atom, before and after nitrogenation, were plotted. Figure 3.5(a) shows only the first shell of iron neighbors with 7(2) atoms at a distance of 0.310(3) nm.
INTERSTITIALLY MODIFIED INTERMETALLICS
327
(a)
N c
_c
0.0 Fig. 3.5.
0.2
0.4 0.6 0.8 Radlal dlstance (nm)
1.0
Radial distribution functions deduced from Sm2FelTLIn edge EXAFS of (a) before and (b) after nitrogenation (after Coeyet al. |991a).
" 18,-Fo
/~
9e-z / / O~c-R ,~__ ~ •
,~
"
~,
/,,°/
~(
o
/,,, O 18h-Fe / 9d-Fe /
•
~/ ~/
,~____¢
//
zo0 p~''Q''..
/
/
/- """". " '("o---3'/ Fig. 3.6. Atomic site position of z = 0 and z = 1/6 planes of the Th2Zn17 unit cell, where the interstitial 9e and 18g sites are showed.
328
H. FUJII and H. SUN
In fig. 3.5(b), the R-Fe distance has expanded to 0.316(3) nm, and another closer shell appears, corresponding to 2(1) nitrogen atoms at 0.252(2) nm. This distance, which equals to the sum of the samarium metallic radius (0.180 nm) and the nitrogen single bond radius (0.074 nm), allows the nitrogen atoms on the 9e octahedral interstitial site to be located. Yang C.J. et al. (1993) reported a detailed X-ray diffraction study of the Sm2FelTnitride made by nitrogenation of the melt-spun Sm2Fel7 compound. The site occupancy by nitrogen atoms were found to be the same as those derived from neutron diffraction and EXAFS experiments. However, they reported that the volume expansion was less for the rapid quenched compound than the cast compound. Figure 3.6 shows the atomic site position of the z = 0 and z = 1/6 planes of the rhombohedral unit cell, where the interstitial 9e and 18g sites are included. As the 9e sites are in the same e-plane with rare earth sites and have the rare earth sites as the nearest neighbors, the electronic environment of the rare earth atoms will be modified severely upon introducing N and/or C atoms into the 2:17 structure and the magnetocrystalline anisotropy is expected to be changed drastically.
3.2. Curie temperature and exchange interactions The magnetic ordering temperature Tc (Curie temperature) is governed by three kinds of exchange interactions: (1) the 3d-3d exchange interactions, which are the direct exchange interaction due to overlapping of the 3d-electron wave functions and these are strong enough to dominate Tc of the 3d rich intermetallic compounds; (2) the 3d-4f exchange interactions, which couple the 3d and 4f moments; and (3) the interactions between the rare earth spins, which are assumed to be weak and negligible in comparison with the interactions mentioned above. Exchange interactions in the R2Fe17 compounds are weak compared to those in the elemental Fe. The Curie temperatures are around room temperature for R2Fel7, whereas Tc for Fe is about 1043 K. This has been assumed to be due to the very short Fe-Fe interatomic distances at the dumbbell sites (Givord and Lemaire 1974). It is well known (the N6el-Slater curve) that 3d transition metal atoms interact with each other positively, i.e. couple ferromagnetically, at large interatomic distances, but that at too short distances they interact negatively or couple antiferromagnetically. In the RzFel7 compounds the Fe-Fe distance at the dumbbell 4f or 6c sites is typically about 2.4 A, which is shorter than 2.42 A below which negative exchange interaction occurs. This weakens the overall positive exchange interactions and lowers the Curie temperature. As a direct effect of the volume expansion by interstitial modifications, the Fe-Fe interatomic distances increase, which induces the enhancement of the exchange interactions and thus the Curie temperature increases enormously. Using the mean field model, Anagnostou et al. (1994) fitted the temperature dependence of the reduced magnetizations obtained from the M6ssbauer hyperfine fields and estimated the exchange interactions between the four different Fe sites in YzFe17 and Y2Fe17Nu. The results have shown that the exchange interaction between the 4f sites is strongly negative (antiferromagnetic) in Y2Fel7, and it increases and becomes
INTERSTITIALLY MODIFIED INTERMETALLICS I
I
i
I
I
I
329
I
800 e ~ . e .~ ,b..~ e - - ' " - " e " - - ' - " e ~ e . ~ ,
R2Fel7Ny
\/
600
..Fe,.C,
•
v
nn~ n""~" ran...,m~,..~_~.__ nn
O
"..........
400
R2Fel7
200
Y
Pr Ce
Prn Nd
Eu Sm
Tb Gd
Ho Dy
Tm Er
Lu Yb
Fig. 3.7. Curie temperature of R2Fel7, the arc-melted R2FelTC, the GIM R2Fe17Cy and R2Fe17N u (after Sun et al. 1990b and Zhong et al. 1990) through the rare earth series.
120
-
I
'
'
'
I
'
'
I
'
'
'
I
•
100
/,
'-
O
A N
80 v
u
60
o
U F'-
<1
0
40
•
I ~
0
20
o.-" -
Y2Fel7Zy
#
#
I 0
l
l
l
l
l
l
,
l
l
2
l 4
t
l
l 6
A V I V (%) Fig. 3.8. ATc/Tc as a function of AV/V for Y2Fel7 and its hydrides, carbides and nitride. The dashed line was calculated from the pressure dependence of the Curie temperature d(Tc)/dp = - 4 7 K/GPa (Nikitin et al. 1991) and the bulk modulus 13 = 128 GPa (Beuerle et al. 1991).
330
H. FUJII and H. SUN
weakly negative in Y 2 F e l 7 N v. Data on Curie R2Fel7C, the RzFelTNy are listed in table 3.1 and 3.2 and hancement of Tc are 150 K, 332 K and 386 K carbides and nitrides, respectively.
R2Fel7, the arc-melted carbides
temperatures for the host compounds GIM carbides R 2 F e l 7 C u and nitrides plotted in fig. 3.7. The average enfor the arc-melted R2Fe17C, the GIM
3.2.1. Relation between Curie temperature and the unit cell volume The volume-dependence of Te for hydrides, carbides and nitrides of Y2Fel7 is plotted in fig. 3.8. The dashed line was calculated by using the pressure dependence of Curie temperature d(Tc)/dp = - 4 7 K/GPa (Nikitin et al. 1991) and the bulk modulus B = 128 GPa (Beuerle et al. 1991). The common trend indicates that the volume effect on Tc outweighs the chemical particularities of the individual interstitials. Figure 3.9 plots Tc versus the corresponding unit cell volume for various interstitials of Sm2Fe17, which includes the data obtained by Katter et al. (1992a) for the intermediate nitrogen content interstitials Sm2Fe17N u (0 ~< y ~< 2.94), and data obtained by Christodoulou and Takeshita (1993f) for hydrides, carbides, nitrides and the combinations of them. Here a linear relationship between the two quantities is demonstrated again. Data by Fujii and coworkers (Nagata and Fujii 1991, Fujii et al. 1995a) have shown that the increase of Tc in the interstitial compounds is related linearly to the increase of the lattice constant a rather than to the unit cell volume V. The a-axis expansion induces a reduction of the hybridization between the Fe 3d and R 5d electron states. This in turn reduces the density of states of the 3d-electron at the Fermi energy and leads to the increase in Te according to the spin fluctuation theory (Mohn and Wohlfarth 1987). Most of the published results agree that the maximum interstitial nitrogen solubility in RzFe17 is 3 nitrogen atoms per formula unit and that the occupancy is exclusively on the 9e sites (Isnard et al. 1994). In this interstitial range (0 ~< y ~< 3), the Curie 600
,
,
,
800
820
840
5OO 40O ,,t 1v (.~
300 20O 100
780
Cell Volume V ( A3)
Fig. 3.9. Relationship between the Curie temperature Tc and the crystal cell volume V for the Sm2Fel7 nitrides, carbides, hydrides, carbonitrides, carbonhydrides, nitrohydrides and carbonitrohydrides. Data were taken from Katter et al. (1992a) and Christodoulou and Takeshita (19931").
INTERSTITIALLY MODIFIED INTERMETALLICS
331
temperature increase can be well explained by the magnetovolume effect, as shown in figs 3.8 and 3.9. However there are publications which claim that y could be as high as 8, but the relation between Curie temperature and volume breaks down for y > 3. Wei et al. (1993) reported that the strength of exchange interactions reaches a maximum at y = 3 and then T~ decreased with further increase of y.
3.2.2. Estimation of the strength of exchange interactions The exchange interactions can be analyzed by the molecular field model, which is commonly used to describe the variation of the Curie temperature in the R-Fe intermetallic series, under the assumption that the localized 3d-electron model is applicable. The exchange interactions take place between all unpaired spins in the 3d-4f system and they are generally considered to be of the Heisenberg type. Applying the two-sublattice molecular field model to the paramagnetic state (Belorizky et al. 1987), the following expression can be obtained,
To=1 [TFe + TR -k- i ( T F e -
TR)2 -I- 4T2Fe],
(3.1)
where
rFe = nFeFeCFe,
(3.2)
TR = ~2nRRCR,
(3.3)
and
TRFe = I ' Y [ n R F e ~
: V/(Tc -- TFe)(Tc - TR).
(3.4)
Here nij are the molecular field coefficients (with the same dimension as #o),
CR = NRg2j(j + 1)/~2/3kB, NR is the number of rare earth atoms per unit volume, CFe = NFe4SFe(SFe + 1)#2/3kB, NFe is the number of Fe atoms per unit volume and 3' = 2(9 - 1)/9. Taking SFe = 1 and neglecting TR, Tc is given by,
Tc=1 (TFe q- V/T2e + 4rR2Fe)
(3.5)
and, nFeFe and nRFe can be calculated from
TFe nFeFe = CFe
(3.6)
and
1 /Tc(Tc - TFe),
nRpe--I'Y~V ~C~e respectively.
(3.7)
H. FUJII and H. SUN
332
TABLE 3.4 Molecular field coefficients n ~ e and nFeFe of R2Fel7, R2FeI7Ny and R2Fel7Cv with y ,,~ 2 to 3.
Compound
np,Fe (/z0) Ce Pr
R2Fe17 R2Fe17Nv
---
R2Fel7Cy
--
345 695 --
nFeFe (#0)
Nd
Sm
Gd
Tb
Dy
Ho
Er
Tm
355 476 87
328 352 131
251 199 158
227 197 123
227 220 127
215 221 149
204 227 124
----
181 515 496
Taking the Curie temperature of the Lu compounds as Tve, nFeFe can be deduced and then nRFe can be obtained by substituting the appropriate Tc data of each rare earth into eqs (3.5), (3.6) and (3.7). Values of nFeFe and nRFe for R z F e I 7 and their carbides and nitrides are listed in table 3.4. As can be seen from the table, the Fe-Fe interaction is more than doubled for the nitrides and carbides compared with the parent compounds, whereas the R-Fe interaction nRFe is slightly weakened for the nitrides on average and is more signifcantly reduced in the case of carbides. This feature is reflected in fig. 3.7, in which the Tc curve of R 2 F e l 7 C y is much flatter than that of R2Fel7. Another method for the estimation of nRFe is by high-field magnetization studies (Liu J.E et al. 1991). At a critical field strength Beri, the antiparallel configuration between the R-sublattice magnetization and the Fe-sublattice magnetization in the heavy rare earth compounds is broken and the two sublattice moments start to bend towards the parallel direction with each other. In this situation the quantity nRFe can be derived from the slope of the M versus B curve above Bcri. Conclusions achieved by this method are similar to those obtained by the molecular field method. The reduction of the magnetic intersublattice coupling strength has also been concluded from the inelastic neutron scattering study of Gd2Fel7 and its nitride , Gd2FelTNu (Loewenhaupt et al. 1994), from the fitting of the temperature dependence of 166Er and 169Tin hyperfine fields in Er2Fe17C and Tm2FeayC (Gubbens et al. 1994) and from the fitting of the spin reorientation temperatures of Tm2FelvCy in terms of the crystal field and the T m - F e exchange interactions (Zhao et al. 1993).
3.3. Magnetic anisotropy In hard magnetic materials, the anisotropy energy originates from both the rare earth and 3d sublattices. The 3d anisotropy can be deduced from compounds with nonmagnetic rare earth elements. The rare earth contribution to the magnetocrystalline anisotropy is dominant at low temperatures whenever the 4f ions have non-zero orbital moments, but it rapidly decreases with increasing temperature. In the case when there are competitions between the rare earth and the 3d sublattice anisotropies, temperature-induced spin reorientation phenomena can occur as a consequence of the cancellation of the anisotropy contributions from the 4f and 3d sublattices. The easy magnetization direction of the R 2 F e l 7 compounds lies in the basal plane in the whole temperature range except for Tm2Fe17, where a change of the easy magnetization direction from basal plane to e-axis occurred at around 80 K with
INTERSTITIALLYMODIFIEDINTERMETALLICS
333
decreasing temperature (Givord and Lemaire 1974, Gubbens et al. 1976). This has been understood as the result of a competition between the easy-plane Fe and the easy-axis Tm sublattices anisotropies. Interstitial modification by nitrogen or carbon has led to a radical change of the magnetic anisotropy. In the interstitially modified compounds, spin reorientation phenomena were observed not only for R = Tm, but also for R = Er. In the case of Sm compounds, the room temperature anisotropy was found to be of strongly uniaxial character instead of planar, as in the host SmzFea7. This strong easy axis anisotropy combined with the reasonable high Curie temperature and high magnetization, makes the Sm2Fea7 interstitials to be very promising candidates for permanent magnet applications.
3.3.1. Theoretical background The main contribution to the magnetic anisotropy in permanent magnet materials is the crystal-field induced single-ion anisotropy on the magnetic rare earth-atoms. The 4f moment of the rare-earth atoms will prefer a certain magnetization direction which is determined by the properties of the rare-earth atoms themselves and the crystal electric field at the particular crystallographic sites. In compounds consisting of rare-earth and 3d metals, the easy magnetization direction is controlled by the 4f sublattice magnetic anisotropy owing to the strong exchange interaction between 3d and 4f moments. The macroscopic anisotropy energy can be expanded phenomenologically as EA : E E K~ sin~ 0 cos m ¢, n
(3.8)
m
where 0 and ¢ are the polar and azimuthal angles of the magnetization with respect to the [001] and [100] crystallographic directions, respectively. Considering the lowest order term only, the above equation can be expressed as EA = KI sin 2 0. In the absence of an external field, the spontaneous magnetization direction favours the crystallographic c-axis when satisfying the following condition: ~EA/~O = 0 and O2EA/O02 > 0, at 0 = 0. This means that a positive value of K1 will lead to an easy-axis anisotropy. On the other hand, within the ground state multiplet, the crystal field Hamiltonian on the rare earth atom is written as
HCF = E E B'~Om~(J)'
(3.9)
m
where the parameters Og~ are Stevens equivalent operators (Hutchings 1964) and B ~ are the crystal-field parameters. The thermal averages of O~ vary initially as a power n(n+ 1)/2 of the rare earth magnetization (Callen and Callen 1966). Hence the higher the order of the anisotropy, the lower its contribution at higher temperature. B ~ can be separated into terms related to the surrounding charges (A~) and terms related to the 4f ions only (On(r~)),
B'~ = O~{rn)A~,
(3.10)
334
H. FUJI1 and H. SUN
where A T are known as the crystal field coefficients, 0n is a constant depending on the rare earth known as the Stevens factor (c~j,/3j, 7J for n = 2, 4, 6, respectively) (Stevens 1952), and (r n) is the mean of the nth power of the 4f radius, which has been calculated on the basis of Dirac-Fock studies of the electronic properties of the trivalent rare earth ions (Freeman and Desclaux 1979). The second order Stevens factor a j has a fixed value for a given rare earth; the sign is related to the asymmetry of the charge cloud of the 4f electrons. The shape of these charge clouds could be either like a pancake (o~j < 0, Ce, Pr, Nd, Tb, Dy, Ho) or like a cigar (c~j > 0, Sin, Tm and Er). In the case of Gd, aa = 0, because the 4f charge cloud has spherical symmetry. For both the hexagonal and rhombohedral symmetries, the relation between the macroscopic anisotropy parameter K1 and the crystal field-related parameters can be given as (Lindgard and Danielsen 1975), K
(T = O) = - 3
d(r2)(2j2
j)AO '
(3.11)
considering only the ground state multiplet, which is usually a good approximation for most of the rare earths. However Sm is a typical exception, where the involvement of higher multiplets in the calculation is necessary (Sankar et al. 1975). The above equation means that a positive value of K1k requires that aj and A° are of opposite sign. A ° represents the lowest order deviation from sphericity of the electrostatic potential and it can be split into two terms; the contribution from the charges on other atoms in the lattice, A°(lat), and the contribution from the charges of the valence electron of the rare earth atoms themselves, A°2(val). Recent band structure calculations of crystal field parameters for rare earth intermetallic compounds have showed that the asphericity of the valence electron charge density of the rare earth itself forms the dominant contribution to the lowest order crystal field parameter A° (Zhong and Ching 1989, Coehoorn et al. 1990). The sign of A ° is negative in the pure 2:17 compounds. In the nitrides and carbides, N and C atoms occupy the interstitial sites around rare earth atoms within the basal plane (fig. 3.6), which causes the increase of the rare earth valence electron charge density in the plane in order to match those of the interstitial atoms, and A° decreases to more negative values (Coehoorn 1991). Consequently, for rare earths whose a j are positive (Sm, Er and Tm), the easy axis anisotropy of the rare earth sublattice is enhanced by interstitial modification. For the Sm interstitial compounds, the easy axis Sm sublattice anisotropy predominates that of iron even above room temperature. In the case of Er and Tm, the easy plane iron sublattice anisotropy is still dominant at high temperatures, but the spin reorientation temperature increases upon interstitial introduction.
3.3.2. Summary of experimental data The easy magnetization direction at room temperature for all compounds in the RzFe17 series lies in the basal plane. The easy magnetization direction at room
INTERSTITIALLY MODIFIED INTERMETALLICS
335
temperature can be deduced from X-ray diffraction patterns of magnetically-aligned powders (fig. 3.10). When the alignment direction is parallel to the the scattering vector of the X-ray beam, the enhanced (001) or (hk0) reflections indicate that the easy magnetization direction is parallel and perpendicular to the crystallographic c-axis, respectively. As shown in fig. 3.10, the Fe sublattice anisotropy retains the same sign of the host R2Fe17 compounds in nitrides and carbides, in which the easy magnetization direction lies in the basal plane in the whole magnetically ordered regime. The Sm compounds are the only members in the interstitial nitrides or carbides which exhibit easy e-axis anisotropy at room temperature. There are many studies on the magnetic anisotropy of the SmzFcI7 nitrides and carbides. In the arc-melted carbide Sm2FelvCv, the easy c-axis anisotropy at room temperature was observed when y ~> 0.4 by X-ray diffraction studies on magnetically aligned powder (GrSssinger et al. 1991), by magnetic measurements (Zhong et al. 1990, Popov et al. 1990) and by 57Fe MOssbauer measurement (Ding and Rosenberg 1991). When y < 0.3, SmzFe17Cv has easy plane anisotropy and when 0.3 < y < 0.45 it exhibits easy cone anisotropy (Popov et al. 1990). The room temperature anisotropy field yoHa was found to be 5.3 T for y = 1.0 (Kou et al. 1990). In the nitrides Sm2FelvN v, #oHa is also strongly related to the nitrogen content y (Katter et al. 1992a). Due to different measuring methods and different maximum nitrogen content attained by different authors, #0Ha at room temperature has been reported to be in a wide range between 11 and 26 T. By fitting the magnetization '
~oo I i~20'
'
I
I
'
'
$m2Fe 17
Y2Fel7
600
600
440
olo61-7--T ---T-v T-v-r---r$m2Fe17N2,3
Y2Fe17N2,6
5" c
3O0
,,-4,,
?7 600
;-i
440
003
V
i
L ,
,
] '
OO6
, '
, '
I I
(pog, ' '
"
I I
:
I0012 ~,--
Sm2Fe 17C2,2
Y2Fe17C2.2
30O .
.
.
.
.
.
600 I
40
60
2e (')
BO
00.3 , I
, .1_
.~_
I
....
,.009,
I
,
,
I
40
60 2e
BO
(')
Fig. 3.10. X-ray diffraction patterns of magnetically aligned Y2Fe]7, Sm2Fel 7 and their nitrides and carbides. Sm2Fel7 and all the Y compounds show easy-plane anisotropy, while SmzFelvN2.3 and Sm2Fel7C2. 2 show easy-axis anisotropy.
336
H. FUJII and H. SUN
curves of magnetically aligned powders, Katter et al. (1992a) estimated the total anisotropy constants K1 and K2 for the Sm2FelTNu series. Nitrogen concentration dependences of #0Ha, K1 and K2 are shown in fig. 3.11. It can be seen that K1 increases almost linearly with nitrogen content y, whereas K2 is not much affected when y > 0.8. The nitrogen concentration at which the easy magnetization direction reaches the c-axis can be estimated from the change of the sign of K1, the value of which has been found to be y = 0.55. An easy-cone concentration range was found at y ,-~ 0.4. In a study of the magnetic properties of Sm2Fe~7C=N v (x = 0, 0.4, 0.7 and 0.9, x + y ,-~ 3), Kou et al. (1991a) reported that the anisotropy fields were higher for x = 0.4, 0.7 and 0.9 than for x = 0, and they concluded that the effect of carbon on the crystal electric field acting on the Sm ion was slightly higher than that of nitrogen. On the other hand, Chen et al. (1993a, b) claimed that the effects of nitrogen and carbon were almost the same. Most of the reported #0Ha values at room temperature for the GIM carbides, carbonitrides and carbonitrohydrides were around 15 T (Christodoulou and Takeshita 1993f, Wei et al. 1993, Sun et al. 1992, Hu and Liu 1991). The temperature dependence of the anisotropy field for the Sm interstitial compounds has been studied by Kou et al. (1990), Katter et al. (1990), Chen et al. (1993a, b), Miraglia et al. (1991). The easy magnetization direction (EMD) remains parallel to the c-axis up to the Curie temperature and #oHa increases with decreasing temperature. From high field magnetization data, Liu J.P. et al. (1991) derived that 30
~ . . @ f
20
.j.jo.--'~"~"
"-r"
i
°
10
J
j" 0
¢ I
I
t
I,,,,
[
I
I
I
8 co
KI~ 6
J
,=J
.J
4 x,'o J
"
I
2
K2
.J ....
j ' ~ : 7
°
e - - e ~ ,
o
.2, r ~
• ,
0
,
,
,
I
1
,
,
,
,
I
2
Nitrogen Content, y
Fig. 3.11. Nitrogen concentration dependences of the anisotropy field/z0Ha , anisotropy constants K] and K2 at room temperature for Sm2FelTN u (after Katter et al. 1992a).
INTERSTITIALLY MODIFIED INTERMETALLICS
337
#oHa at 4.2 K is larger than 35 T in Sm2FelTN2.7. In a fitting of the high field magnetization processes by Kato et al. (1993), #0Ha of Sm2Fe17N3.o at 4.2 K was found to be extremely large and the field of saturation along the magnetic hard direction was estimated to be higher than 70 T. By using the singular point detection (SPD) technique, Chen et al. (1993a, b) measured #0Ha of Sm2Fe17N2.3 and Sm2Fe17C2, and Sm2Fe17C~Nv made by two different methods, in the temperature range from 370 K to 670 K. The data for the carbides and nitrides are replotted in fig. 3.12. The other two members in the 2:17 series which are interesting for the study of magnetic anisotropic properties are the compounds with R = Er and Tm, which show spin reorientation phenomena. At low temperatures, the anisotropic properties are dominated by the rare earth sublattice and the magnetization lies along the c-axis direction. At higher temperatures, the iron sublattice anisotropy dominates and the magnetization lies in the basal plane. The temperature at which the easy magnetization direction turns from the c-axis to the basal plane is the spin reorientation temperature Tsr. It is often measured by thermomagnetic scan in a low magnetic field, or by the temperature dependence of the a.c. susceptibility. It can also be deduced from analyzing the 57Fe M6ssbauer spectrum as will be described in section 3.4.2. Spin reorientation studies of various compounds made by different methods are listed in table 3.5. Some of the data taken from table 3.5 are plotted in fig. 3.13. In the arc-melted ErzFe17C v system, spin reorientation occurs when y >/0.8 and Tsr increases with increasing y (see the references in table 3.5). Two spin reorien12
10
I
[
I
oil
I
Sm2Fe,~TN2.3
kv
Sm2Fe1702
2 300
I
I
I
400
500
600
700
T (K) Fig. 3.12. Anisotropy field/~0Ha as a function of temperature for the GIM Sm2Fel7C2 and Sm2FelTN2.3. The values were obtained by the SPD technique and have not been corrected for the demagnetizing field (after Chen et al. 1993a, b).
338
H. FUJII and H. SUN
TABLE 3.5 Investigation of the magnetic spin reorientation properties of the interstitially modified R2Fel7 (R = Er and Tin) carbides and nitrides by various experimental techniques. M-T is the magnetization versus temperature curve. Compound
Method
Ref.
M/3ssbauer M-T a.c. susceptibility M-T, M6ssbauer
[1] [4] [11] [2, 3]
TmzFel7 Cu (0 ~< y ~ 1.4), arc-melted Tm2FelvCv (0 ~< y ~ 1.0), arc-melted TmzFel7Cv (0 ~< y ~< 1.4), arc-melted
M-T M-T a.c. susceptibility
[4] [5] [12]
Er2Fel7N2.7, GIM Er2Fel7N2. 7, GIM Er2Fel7N2.7, GIM
Mtissbauer M-T, MOssbauer a.c. susceptibility
[6, 7] [8] [9]
Tm2Fel7N2.7, GIM Tm2Fel7N2.7, GIM
M-T, M0ssbauer a.c. susceptibility
[8] [9]
Er2Fel7C2.2, GIM Er2Fel7C2, GIM TmzFeI7C2.2, GIM
M-T, M0ssbauer a.c. susceptibility M-T, Mtissbauer
[10] [14] [10]
Er2Fel7CxNy (0 ~ x ~ 1.5) Tm2Fel7CxN u (0 ~ x ~ 1.0)
a.c susceptibility a.c. susceptibility
[13] [13]
Er2Fel7Cy (0 ~ y Er2Fel7Cy (0 ~ y Er2Fe17Cu (0 ~ y Er2Fe17Cy (0 ~< y
~ 1.5), arc-melted ~ 2.0), arc-melted ~< 1.5), arc-melted ~ 3.0), melt-spun
References: [1] Zhou R.J. et al. (1992) [2] Kong et al. (1992) [3] Kong et al. (1993c) [4] Ohno et al. (1993) [5] Gubbens et al. (1989) [6] Gubbens et al. (1991) [7] Gubbens et al. (1992)
[8] Hu B.E et al. (1990) [9] Liu J.P, et al. (1991) [10] Qi et al. (1992) [11] Kou et al. (1991c) [12] Grtissinger et al. (1991) [13] Kou et al. (1991a) [14] Hu B.E and Liu (1991)
tation temperatures were observed when y /> 1.0 due to the existence of both the rhombohedral and hexagonal modifications in the specimen (Kou et al. 1991c). It was found that Tsr(hex) > Tsr(rhomb), as the hexagonal form is more contracted in the a-direction than the rhombohedral form. As can be seen from fig. 3.13, data obtained by different researchers are quite scattered, which could be due to the difficulty in the accurate determination of the concentration of the interstitial atoms.
3.3.3. Estimation of A ° of Sm2Fel7Ny By fitting the experimental magnetic anisotropy field data on the basis o f a twosublattice model including the exchange and crystal-electric-field (CEF), the values of the crystal field parameters A T can be deduced. Data obtained in this way for the SmzFel7 interstitials are listed in table 3.6. All the calculations included not only the ground state J = 5/2, but also the first and second excited states J = 7 / 2 and 9/2.
INTERSTITIALLY MODIFIED INTERMETALLICS 200
'
'
'
I
. . . .
I
'
'
'
339
'
Er2FeleCy 150 w
._..L---~.
,¢,
/:
100 I.-,-
50 ~'} ErzFe~TN2.7 I I j I Tm2Fe17Cy 200
~'~~ t---
150
I
I
I
I
t
O
~
A
I
I
I
I
I II
•
°
~ ) Tm2Fel7N2.7
:/1
IO0
50 0
I
i
i
]
I
i
i
i
i
2
Carbon Content, y Fig. 3.13. The spin reorientation temperature TSR as a function of carbon concentration y for Er2Fel7Cy and Tm2FelTCy. Data were taken from references in table 3.5. Values for Er2Fe17 and TmzFe17 nitrides are also included. TABLE 3.6 Crystal field parameters A~m of the Sm2Fel7 nitrides and carbides. /z0Ha (in unit of Tesla) is the experimentally measured anisotropy field at room temperature and 0 K. Compound
A20 (Kao 2)
SmzFe]TNa.94 Sm2FelTNu SmzFelTNv SmaFelTN3 Sm2Fe17C2.2
-242 - 160 :t: 5 -340 -600 -134 :k 20
A40 (Kao 4)
A°6 (Kao 4)
#oHa (T) RT
References: [1] Li and Cadogan (1991) [2] Li and Coey (1992) [3] Li and Cadogan (1992a)
8.0 + 1.0 200 -20 18.0 + 5.0
-3.0 + 1.0 - 4 4- 2.0
22 14 13.7 26.0 13.5
Ref. OK
31.2 > 70
[1, 2] [3] [4] [5] [6]
[4] Zhao et al. (1991) [5] Kato et al. (1993) [6] Li and Cadogan (1992b)
Different values c a l c u l a t e d b y different authors can at least partially be attributed to the fitting o f different e x p e r i m e n t a l data. M a g n e t i z a t i o n curves o f m a g n e t i c a l l y a l i g n e d Sm2Fe17N3.0 parallel and p e r p e n d i c u l a r to the easy m a g n e t i z a t i o n direction at 4.2 K and 296 K are replotted in fig. 3.14, together with the fits, w h e r e the i m p o r t a n c e o f the inclusion o f the excited J multiplets is d e m o n s t r a t e d (Kato et al. 1993).
340
H. FUJII and H. SUN I
!
40
i
I
(c) talc. 4.2K
(a) obs. 4.2K
H//HaJ~n
__
H//c-axis....,.......-"k~.~q/
/ ~ ~ / \
H _Lc-axis
--t
20 ' ~
0
2~)0
--
}
I
i
0
200
400
i 600
800
i
I
(d) calc. 296K
(b) obs. 296K 40
20 /
i;rCol~:i2gm:~;i:td2~;tiplets
/..,.
HJ-Ha~ign
A
.......
..,,,
%=88o HJ.c-axis
I 200
O~
H (kOe)
,, i
I
200 H ( kOe )
Fig. 3.14. Observed and calculated magnetization curves of Sm2Fel7N3. 0. Solid lined in (c) and (d) represent the results in which ground, first excited, and second excited J multiplets are taken into account, while broken lines are those including the ground J mulfiplet only. The thinner solid line in (d) denotes the case when the angle 0/~ between the c-axis and the field direction is 88°, simulating a situation of incomplete alignment (after Kato et al. 1993). The saturation magnetization of the hard direction was found to be lower than that of the easy direction. This anisotropy resulted from the ferrimagnetic coupling of the Sm and Fe moment when the external field was applied along the hard direction, whereas they coupled ferromagnetically when the field was in the magnetic easy direction (Kato et al. 1993, Zhao et al. 1991, Li and Cadogan 1991). The reason for this field induced ferrimagnetism has been explained by the intermultiplet mixing which originated primarily from the molecular field interaction rather than the CEF interaction. As the relative contribution from the molecular field becomes larger than that from the CEF at elevated temperatures, this ferrimagnetic coupling is more pronounced at 296 K than at 4.2 K. Xu et al. (1993) analyzed the data obtained by Iriyama et al. (1992) for Sm2Fe]7N v (0 < y < 6) and estimated the effect of different interstitial nitrogen sites on A T. They concluded that nitrogen atoms on the 9e site had a negative contribution to A °, and hypothetical nitrogen atoms on the 3b and 18g sites contributed a positive value to A ° and reduced the easy-axis anisotropy, which was reported to be in agreement with the experimental data. The observed spin reorientation temperatures of Tm2Fe]7Cv (0 ~< y ~ 2.2) was fitted by Zhao et al. (1993) and the average A ° value of the two Tm sites was derived (fig. 3.15). The absolute value of the average A ° increases with increasing carbon content in a nearly linear relationship. Similar results have been obtained by Li and Cadogan (1992b) for Sm2Fe]7C v and Sm2Fel7Ny.
INTERSTITIALLYMODIFIED INTERMETALLICS 500
. . . .
,
. . . .
341
,
Tm2FelTCy 400
,~" ,/ /
J"
300
200
/
/ /"
1oo
O0
,
,
,
,
I
I
,
,
,
,
I
2
,
Carbon Content, y
Fig. 3.15. Carbon concentration dependence of the average second-order CEF parameter A° for Tm2Fe17Cy (after Zhao et al. 1993). A0 was obtained by fitting the data of the spin reorientation temperatures.
3.4. MSssbauer and NMR studies MSssbauer spectroscopy is an effective experimental technique for obtaining information of the magnetic properties on an atomic scale. Both the 57Fe M6ssbauer and some of the rare earth M6ssbauer effects have been studied for the interstitially modified compounds.
3.4.1. 57Fe MOssbauer studies As there are four different crystallographic sites for iron in both the hexagonal and the rhombohedral-type R2Fe17 compounds, the observed spectrum must be a superposition of at least four sextets. Point charge calculations showed that under the combined effect of the dipolar field and quadrupole interaction, only the dumbbell 4f(6c) sites remain equivalent (Steiner and Haferl 1977). When the magnetization direction is along the c-axis, the angle between the hyperfine field and the electric field gradient is the same for all crystallographic equivalent sites so that there is no additional splitting and the sites remain equivalent for both the structures. When the magnetization direction is in the basal plane, for the rhombohedral structure, the 9d, 18h and 18f sites each splits into two groups with an intensity ratio 2:1, while in the hexagonal structure the 6g and 12k sites split into two groups with an intensity ratio 2:1, and the 12j site splits into three groups with an intensity ratio 1:1:1. Since the dipolar fields at two of the three groups of the 12j sites are very close, they can be treated in the same way as the 18f site in the rhombohedral compounds by splitting them into two groups with an intensity ratio 2:1. Thus the spectra of all the RzFelv compounds can be fitted to seven independent sextets.
342
H. FUJII and H. SUN
In the case of the interstitial modified carbides and nitrides, it is possible that the interstitial sites are not fully occupied. Then the 12j(18f) and 12k(18h) iron sites, which have one neighboring octahedral interstitial site, can have either one or zero interstitial neighbor. For most of the nitrides, as the occupancy of the interstitial sites is nearly full, the probability for one neighbor is much higher than that for zero neighbor. Hence it is reasonable to fit the spectra in the same way as for the host compounds and the variation in their near-neighbor environments may be considered as the reason for the broadening of the absorption lines. Ten subspectra were used by Long et al. (1994) in the fitting of the Th2FelTN2.6 spectra because the easy axis of magnetization was found to be in a general basal direction and not oriented along one of the basal axes. For much lower interstitial content, especially in the case of the arc-melted carbides, a further splitting of the subspectra arising from the influence of the substoichiometric concentration has to be taken into account, which complicated the fitting procedure. Some authors simply ignored this influences or derived the parameters of the overall averaged hyperfine field and the distinctly separate hyperfine field of the 4f(6c) dumbbell sites only (Zhou R.J. et al. 1991 and 1992). As to the site assignment of the spectra, most of the analyses were based on the hyperfine field and intensity considerations. The idea is that the strength of the hyperfine field on each site is predominantly determined by the number of iron and rare earth near-neighbours of the site. The higher the number of iron-neighbours, the larger is the hyperfine field, whereas the higher the number of rare earth neighbors, the smaller is the hyperfine field. According to the above considerations, Hu B.P. et al. (1991) decided that the hyperfine fields were in the order of 4f(6c)> 6g(9d)> 12j(18f)> 12k(18h), which agreed with by many other studies, while Kong et al. (1993c) fitted their spectra in a different order of 4f(6c)>12k(18h)>12j(18f)> 6g(9d). Another way of spectra assignment has been used by Long et al. (1992), who took isomer shift as a main clue for the assignment. The model was based on the Wigner-Seitz size cell environment of each iron site and they also considered the orientation of the magnetization and the magnetic moments as determined from either neutron-diffraction measurements or band structure calculations. The data of 57Fe Mrssbauer hyperfine fields are summarized in table 3.7, where data for the 6g(9d), 12j(18h) and 12k(18f) sites are the weighted averages. It can be seen that although the fitting and assignment procedures are different, the values of the overall averaged hyperfine field (Bhf) does not differ too much. However, the individual hyperfine field values at the various sites scatter a lot. The overall average hyperfine field of RzFel7, RzFelvN v and R2Fel7Cy at 15 K are plotted in fig. 3.16. The general feature is that the average hyperfine field (Bhf) across the series increases by about 4 T in the nitrides, but it decreases slightly in the carbides. These results could be understood by considering the different polarization effects on Fe atoms by their nitrogen and carbon neighbors. The hyperfine field in metals is largely due to the Fermi contact term Bs, which is proportional to the unpaired spin density at the nucleus. The increase of the hyperfine field indicates a larger polarization of s electrons. It is considered that the 4s band of Fe is more highly polarized by nitrogen atoms in nitrides than by carbon atoms in carbides,
INTERSTITIALLY MODIFIED INTERMETALLICS
343
TABLE 3.7 57Fe M0ssbauer hyperfine field (in units of Tesla) of each crystallographic site (averaged over subspectra) and the overall weighted average (Bhf) for the RzFe17 interstitial compounds at various temperatures. The superscripts a, b and c correspond to different methods of making the carbonitrides as described in section 2.3.4. Compound
6g(9d)
12k(18h)
12j(18f)
4f(6c)
(Bhf)
T (K)
Ref.
Ce.2FelTNu Ce2FeI7C v PrzFelvN u Pr2Fe17Cv Nd2Fe17Nv Nd2Fe17Cy Sm2Fel7N v SmzFet7Cy SmzFe17 SmzFelyNo.4o SmzFelvNo.81 Sm2Fe17N1.2o Sm2Fe|7N1.99 Gd2Fe17Ny Gd2Fe17C v Gd2Fe17C2.o GdzFe17 Gd2Fe17Co.5 Gd2FelvC1. 0 Gd2Fel7C1.5 Tb2Fe17Ny Tb2Fe17C v DyzFe17N u Dy2Fel7C u Ho2Fel7Nv HozFe17Cy Er2Fe17N v ErzFe17C v Er2Fel7C2.5 Er2Fel7 ErzFelvCo.5 Er2FeI7Co.8 Er2Fel7Cl.o Er2Fe17C1.2 Er2Fe17C1.4
36.7 30.7 35.6 33.5 36.1 33.7 39.4 36.2 32.2 34.3 37.4 38.2 39.5 36.7 34.3 25.5 26.6 27.4 26.2 26.0 37.2 34.9 37.3 34.8 36.8 35.1 40.7 36.5 24.7
31.4 25.4 30.8 25.1 30.5 25.1 31.1 26.2 27.4 28.7 30.3 31.4 31.8 31.5 25.5 31.1 30.0 31.2 32.0 31.5 31.6 26.0 32.6 26.4 32.3 26.4 33.5 26.1 28.4
34.2 31.6 33.3 28.5 33.3 29.0 35.6 30.2 30.1 31.4 34.1 35.4 35.7 34.8 29.3 32.1 32.0 32.8 33.0 32.5 34.6 31.4 35.3 31.3 35.8 30.9 35.9 30.7 35.4
39.9 36.4 37.1 34.5 36.8 34.7 32.9
33.1 25.3 31.7 25.5 31.6 26.2 28.2
35.3 31.1 35.5 30.0 35.2 30.7 29.7
38.3 34.7 37.7 35.4 38.8 35.2 41.6 36.5 36.1 37.6 41.9 42.3 42.1 38.8 36.5 36.7 36.9 37.0 37.1 36.6 39.5 37.3 40.1 36.6 40.7 36.5 42.5 37.4 38.0 37.4 37.5 41.4 40.9 40.9 39.7 40.0 41.7 37.4 40.4 36.8 40.2 36.2 34.6
34.1 29.7 33.3 29.0 33.5 29.2 35.4 30.6 30.3 31.7 34.3 35.3 35.7 34.5 29.7 31.1 30.9 31.8 31.9 31.4 34.6 30.8 35.3 30.8 35.3 30.7 36.8 30.9 31.4 31.6 32.3 33.0 32.9 32.7 32.4 32.6 36.2 30.7 35.0 30.0 34.8 30.5 30.3
15 15 15 15 15 15 15 15 4.2 4.2 4.2 4.2 4.2 15 15 12 12 12 12 12 15 15 15 15 15 15 15 15 12 4.2 4.2 4.2 4.2 4.2 4.2 4.2 15 15 15 15 15 15 15
[1] [2] [1] [2] [1] [2] [1, 3, 4, 6] [2] [3] [3] [3] [3] [3] [1] [2] [15] [15] [15] [15] [15] [1] [2] [1] [2] [1] [2] [1] [2] [14] [13] [13] [13] [13] [13] [13] [13] [1] [2] [1, 6] [2] [1, 4, 5] [2, 5] [5]
Er2Fe17C1.5 TmzFe17N u Tm2FelvCu LuzFe17Ny Lu2Fe17Cy YzFe17Nv YzFelvCy YzFelTH2.7
344
H. FUJII and H. SUN TABLE 3.7 (Continued)
Compound
6g(9d)
12k(18h)
12j(18f)
4f(6c)
(Bhf)
~/~(K)
Ref.
Pr2Fel7N2. 6 Nd2Fel7N2. 6 SmzFelvNv Sm2Fel7 C:~N,~ Sm2FelTC~Nv~ Sm2FelTCxN~ Sm2Fe17C2 Sm2Fe17H3.7 Er2Fel7C2.5 Lu2FelTNu Y2FelTN2.3 Y2FelTC2 Y2FelTC~N~ Y2Fel7CxNub YzFelvC~N~ Th2FeI7N2. 6 Th2FelTN2. 6
37.4 37.6 39.7 33.7 33.2 38.9 33.2 32.1 24.6 36.9 35.3 29.8 31.3 32.5 34.9 35.4 30.3
31.5 32.8 31.1 26.7 28.2 30.4 25.7 29.1 28.2 31.7 31.4 25.9 27.5 28.7 30.8 33.1 32.6
31.8 30.4 35.7 28.9 31.6 34.9 27.9 30.7 35.1 34.5 34.9 28.4 30.4 31.6 33.8 32.7 35.9
35.9 36.0 41.7 36.7 39.5 41.2 37.6 34.0 37.5 39.7 40.1 35.9 36.3 37.6 39.2 35.7 35.8
33.2 33.3 35.5 29.9 31.6 34.8 29.2 30.8 31.1 34.3 28.6 30.2 31.4 33.6 33.7 33.8
85 78 77 77 77 77 77 77 70 77.4 77 77 77 77 77 85 78
[10] [8, 9] [4, 6, 7] [7] [7] [7] [7] [7] [14] [6] [7] [7] [7] [7] [7] [11] [12]
Ce2FelTNy Ce2Fel7Cy Pr2FelTNy PrzFelvN2.6 PrzFelTCy NdzFe17N u Nd2Fel7N2. 6 NdzFe17Cu SmzFel7N~ Sm2Fe17 SmzFe17No.4o Sm2FelTNo.81 Sm2Fe17Nl.20
33.6 29.7 34.2 35.5 31.2 34.1 35.9 30.8 37.3 23.0 26.5 30.6 33.6 36.8 32.8 34.6 32.7 23.8 22.7 24.1 24.5 23.9 34.6 32.8 33.8 31.7 33.8 31.7 33.5 30.4
28.9 20.7 29.2 30.2 22.8 28.7 31.4 22.8 29.5 19.5 21.4 23.9 26.3 29.0 24.1 29.6 24.0 26.9 24.3 26.0 27.0 27.0 29.2 23.7 29.2 23.8 29.0 23.5 28.5 22.8
31.9 26.1 31.3 29.9 26.5 31.2 29.0 24.1 33.3 21.9 24.2 27.6 30.7 32.9 25.0 32.0 26.8 30.3 25.6 27.6 29.0 29.5 32.3 28.4 32.6 28.4 32.2 28.4 31.9 26.9
35.9 33.5 36.6 34.2 33.0 36.9 34.3 31.8 39.0 26.4 29.1 36.7 37.7 38.9 34.1 36.7 32.9 33.6 30.2 32.0 32.7 32.8 37.2 32.8 37.3 33.7 37.2 33.0 37.0 32.6
31.6 25.7 31.7 31.5 26.8 31.5 31.7 25.7 33.3 21.8 24.2 27.9 30.5 32.9 27.1 32.2 27.6 28.3 25.2 26.9 28.0 28.1 32.2 28.1 32.2 28.0 31.9 27.8 31.6 26.7
293 293 293 295 293 293 295 293 293 RT RT RT RT RT 293 293 293 293 293 293 293 293 293 293 293 293 293 293 293 293
[1] [2] [1] [10] [2] [1] [8, 9] [2] [1, 3, 4, 6] [3] [3] [3] [3] [3] [2] [1] [2] [15] [15] [15] [15] [15] [1] [2] [1] [2] [1] [2] [1] [2]
Sm2FelvN1.99 Sm2FelvCu Gd2FelTNy Gd2Fe17C u Gd2Fe17C2.o Gd2Fel7 Gd2Fe17Co.5 Gd2Fe17Cl.o Gd2Fe17Cl.5 Tb2Fel7N u TbzFe17Cy DyzFe17Ny DyzFel7C u Ho2FelTNu Ho2Fe17Cy Er2FelTNy Er2Fel7Cy
INTERSTITIALLY MODIFIED INTERMETALLICS
345
TABLE 3.7 (Continued) Compound
6g(9d)
12k(18h)
12j(18f)
4f(6c)
(Bhf)
T (K)
Ref.
Er2Fe17C2.5 Tm2FelTNu Tm2FelTCy Lu2Fe]7N u Lu2Fe17N u Lu2FezTC v Y2Fe]7Ny Y2Fe17Cu Y2Fe17H2.7 Th2FeITN2. 6
22.2 34.5 31.2 34.2 32.7 31.8 34.0 30.5 14.8 33.0
24.0 28.7 23.3 28.4 28.1 23.2 28.5 23.1 3.0 30.8
29.9 32.0 26.9 31.9 31.3 27.5 32.2 26.1 10.8 30.7
33.1 36.5 33.2 36.6 35.5 33.5 36.9 33.3 18.5 33.7
26.8 31.8 27.1 31.6
300 293 293 293 300 293 293 293 293 295
[14] [1] [2] [1] [6] [2] [1, 5] [2, 5] [5] [11]
References: [1] Hu B.R et al. (1991) [2] Qi et al. (1991) [3] Zhou R.J. et al. (1993) [4] Kapusta et al. (1992) [5] Qi et al. (1992b) [6] Zouganelis et al. (1991) [7] Chen et al. (1993b) [8] Long et al. (1992)
[9] [10] [11] [12] [13] [14] [15]
. o. R2Fel . . 7 I x R2Fel7CY • R2Fel7Ny
38 - 36
27.4 31.8 26.7 9.7 31.5
Pringle et al. (1992) Long et al. (1993) Long et al. (1994) Jacobs et al. (1991) Zhou R.J. et al. (1992) Kong et al. (1993c) Kong et al. (1993d)
. . . .
I
. . . . •
~- 3 4
• o
~-32 m 30
28 26 --o
(a)
I!l!l o R2FeI7 x R2Fel7Cy
(b)
• R2Fel7NY
0.1
Q
E E v
x
0.0
X X x N x x oo
x oo
X--.
o o
-0.1
~ l l l l
CePrNd
I l l l ~ l l l Sm
Gd Tb Dy Ho Er Tm
Lu
Fig. 3.16. Overall average (a) hyperfine fields and (b) isomer shifts of R2Fe]7, R2Fe17N u and R2FelTCy at 15 K (after Hu B.R et al. 1991, Qi et al. 1991).
346
H. FUJII and H. SUN
and consequently the magnetic hyperfine field is higher in nitrides than in carbides. Qi et al. (1992b) have attributed the difference of the hyperfine field for nitrides and carbides to the transferred hyperfine field from interaction with neighboring atoms, which is sensitive to the chemical nature of the interstitial impurity. The importance of this transferred hyperfine field can also be seen from the fact that the proportionality of the incremental moment and hyperfine field is not valid in interstitially modified intermetallics. 57Fe Mrssbauer studies of interstitial compounds with intermediate interstitial concentration have been carried out for the arc-melted ErzFel7Cy (0 ~< y ~< 1.5) by Zhou R.J. et al. (1992), for the arc-melted and melt-spun Gd2Fe17Cu by Kong et al. (0 ~< y ~ 2.0) and for Sm2Fe17Nv (0 <~ y ~< 2.94) by Zhou R.J. et al. (1993). Hyperfine field data for the above three series of compounds are included in table 3.7 and the data for Sm2Fe17Nv at 4.2 K are replotted in fig. 3.17. Also listed in table 3.7 are the 77 K magnetic hyperfine fields of the carbonitrides of Y and Sm compound made by Chen et al. (1993b), where the superscript a, b and c indicate the different synthesizing routes, for detail see ref. [7] of table 3.7. There is a general increase in the overall isomer shifts for the interstitially modified R2Fe17 compounds. The increase is 0.12 mm/s in the nitrides, which is higher than the value if considering the volume effect only. The situation in the carbides is the opposite, the 0.05 mm/s increase in the average isomer shift is lower than the contribution from the cell volume increase. This suggests that the interband charge
45
40
I-~'~
'
f
~
~
I-•
6c
9d
_
t
18f
35
m=
18h
~
30
~
25
~
-
~
I
~------------
I
< Bhf >
I-
35
rn V
30
"'
A
0
I
1
°
I
2
3
N i t r o g e n Content, y
Fig. 3.17. Dependence of the hyperfine field at the four Fe sites and the average hyperfine field (Bhf) on the N concentration for Sm2Fe17Ny at 4.2 K (after Rosenberg et al. 1993).
INTERSTITIALLY MODIFIED INTERMETALLICS
347
transfer occurs in the opposite sense in nitrides and carbides. As the isomer shift increases with decreasing 4s occupation, the increase of 3d occupation will also increase the isomer shift because the 4s electron density at the nucleus will be reduced owing to the expansion of the 3d shell. Thus it was suggested (Qi et al. 1991) that there could be a 4s-+3d transfer in the nitrides and a smaller 3d--+4s transfer in the carbides, which is consistent with the consideration of the average electron density at the boundary of the Wigner-Seitz cell. The other possibility is a greater 4s-+2p interatomic charge transfer in the nitrides, on account of the greater electro-negativity of nitrogen than carbon. However, definite conclusion can not be drawn from the M6ssbauer data alone.
3.4.2. Spin reorientation studies by 57Fe M6ssbauer measurements Besides the Fermi contact term Bs, the magnetic hyperfine field Bhf also contains an anisotropic orbital contribution Bo created by the electronic current around the nucleus. When there is a temperat
