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Over the last few decades magnetism has seen an enormous expansion into a variety of different areas of research, notably the magnetism of several classes of novel materials that share with truly ferromagnetic materials only the presence of magnetic moments.
Volume 21 of the Handbook of Magnetic Materials, like the preceding volumes, has a dual purpose. With contributions from leading authorities in the field, it includes a variety of topics which are intended as self-contained introductions to a given area in the field of magnetism without requiring recourse to the published literature. It is also intended as a reference for scientists active in magnetism research, providing readers with novel trends and achievements in magnetism. Volume 21 comprises topical review articles covering Heusler compounds, quasicrystalline solids,bulk amorphous alloys and nanocrystalline soft-magnetic alloys. 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 within the framework of physics, chemistry and material science.
Composed of topical review articles written by leading authorities Introduces given topics in the field of magnetism Provides the reader with novel trends and achievements in magnetismAcțiuni carte
Începeți să citițiInformații despre carte
Handbook of Magnetic Materials
Până la Elsevier Science
Descriere
Over the last few decades magnetism has seen an enormous expansion into a variety of different areas of research, notably the magnetism of several classes of novel materials that share with truly ferromagnetic materials only the presence of magnetic moments.
Volume 21 of the Handbook of Magnetic Materials, like the preceding volumes, has a dual purpose. With contributions from leading authorities in the field, it includes a variety of topics which are intended as self-contained introductions to a given area in the field of magnetism without requiring recourse to the published literature. It is also intended as a reference for scientists active in magnetism research, providing readers with novel trends and achievements in magnetism. Volume 21 comprises topical review articles covering Heusler compounds, quasicrystalline solids,bulk amorphous alloys and nanocrystalline soft-magnetic alloys. 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 within the framework of physics, chemistry and material science.
Composed of topical review articles written by leading authorities Introduces given topics in the field of magnetism Provides the reader with novel trends and achievements in magnetismMostră carte
Handbook of Magnetic Materials
Table of Contents
Cover image
Title page
Copyright
Preface to Volume 21
Contents of Volumes 1–20
Contributors
Chapter One. Magnetic Heusler Compounds
1. Introduction
2. Crystal Structure and Atomic Ordering
3. Semiconductors
4. The Slater–Pauling Rule
5. Half-Metallic Ferromagnets
6. Heusler Compounds in Devices for Spintronic Applications
7. Tetragonal Heusler Compounds
8. Summary and Outlook
References
Chapter Two. Magnetic Properties of Quasicrystals and Their Approximants
1. Introduction
2. Magnetism in QCs
3. Al-Based QCs and APs
4. QCs and APs Not Based on Al
5. Summary
References
Chapter Three. Bulk Metallic Glasses
1. Introduction
2. Glass-Forming Ability and Formation Mechanisms
3. Features of Glassy Structures
4. Thermal Stability
5. Mechanical Properties
6. Magnetic Properties
7. Corrosion Resistance
8. Applications
9. Future Prospects
References
Chapter Four. Nanocrystalline Soft Magnetic Alloys Two Decades of Progress
Abbreviations
1. Introduction
2. Alloy Processing
3. Alloy Design Considerations
4. Phase Transformations, Kinetics, and Thermodynamics
5. Structural and Microstructural Characterization
6. Magnetic Property Characterization
7. Other Physical Properties
8. Conclusions
References
Further Reading
Author Index
Subject Index
Materials Index
Copyright
North-Holland is an imprint of Elsevier
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First edition 2013
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ISBN: 978-0-444-59593-5
ISSN: 1567-2719
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Printed and bound in Great Britain
13 14 15 10 9 8 7 6 5 4 3 2 1
Preface to Volume 21
The Handbook of Magnetic Materials series is a continuation of the Handbook of Ferromagnetic Materials series. When Peter Wohlfarth started the latter series, his original aim 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 the title for the handbook series, although the latter aimed at giving a more complete cross section of magnetism than Bozorth’s book. In the past few decades, magnetism has seen an enormous expansion into a variety of different areas of research, 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 to Magnetic Materials. It is with much pleasure that I can now introduce to you Volume 21 of this handbook series.
In Chapter 1 of Volume 21 of this handbook, recent achievements on Heusler compounds are presented. The Heusler compounds form a fairly large class of ternary intermetallics that can be subdivided into two categories. The compounds in the first category have the stoichiometric composition X2YZ where X and Y are transition metals and Z is mostly a main group element. The compounds belonging to the second category have the stoichiometric composition XYZ and are often indicated as half-Heusler compounds. Both types of Heusler compounds adopt an ordered fcc-based crystal structure. Although Heusler alloys have already been known for more than a century, they have attracted considerable attention more recently because some of its members were found to exhibit some unusual physical properties in the form of half-metallic ferromagnets or ferromagnetic semiconductors with Curie temperatures above room temperature. Especially, the half-metallic ferromagnets have intriguing properties because they can be considered as half-metals defined as solids with metallic properties for one of the twospin directions only. The reason for this is the occurrence of a band gap for the other spin direction. As a consequence, the electrical conduction takes exclusively place for one spin direction. Needless to say, this has attracted much interest in a quite new research field, the so-called spintronics. Apart from the cubic Heusler compounds, there exist also Heusler compounds of tetragonal symmetry. These compounds have attracted attention due to their interesting shape-memory and magnetocaloric properties. Generally, it can be said that the large number of Heusler compounds form a large reservoir of materials ideally suited for testing how properties and structures interrelate. New developments in this research field are reported from the point of view of material scientists. The authors emphasize that for designing new materials that show desired features, it is imperative to reach a deep understanding of the interrelationships between properties and structures. In this light, they present a comprehensive review of recent achievements in this field including computational simulations.
Chapter 2 deals with quasicrystalline solids. Conventionally, solids can be divided into two groups, namely, crystalline and amorphous solids. The discovery of an icosahedral Al-Mn alloy by Shechtman et al. in 1984 showed that such a dichotomous division is no longer realistic and that it has to be complemented by a third group, namely, the quasicrystalline solids. The latter solids exhibit a long-range orientational order that is incompatible with periodic crystallographic packing in three dimensions, which tolerates only twofold, threefold, fourfold, and sixfold rotations. In fact, quasicrystalline solids display a novel type of long-range translational order, quasiperiodicity, and noncrystallographic orientational order accompanied by the crystallographically forbidden fivefold, eightfold, 10-fold, and 12-fold symmetry axes. Over the years, quasicrystals have been discovered in more than a hundred ternary and binary alloys. The majority of them are metastable and can only be prepared by rapid solidification techniques. According to their diffraction symmetry, all known quasicrystals can be divided into two classes. The first class consists of polygonal (octagonal, decagonal, dodecagonal) quasicrystals that are periodic along one direction. The second class, being the larger one, consists of icosahedral quasicrystals that have no periodicity along any direction. Whereas crystalline solids are packed with identical unit cells in three-dimensional space, quasicrystalline solids lack such identical units. Their structure can be described using higher dimensional crystallography. Approximants are a group of crystalline solids in which the atomic arrangements within their unit cells closely approximate the local atomic structures found in quasicrystals. This means that also for these approximants the structure requires a higher dimensional description. An extensive review of the magnetic properties of quasicrystals appeared in Volume 6 of this handbook, covering the literature up to 1989. Here, a review of the literature from 1990 to 2011 is presented.
Chapter 3 is devoted to bulk amorphous alloys. Amorphous materials are noncrystalline solids and are generally defined as phases lacking long-range three-dimensional atomic periodicity. Amorphous materials can be formed from oxides, ionic compounds, polymers, and alloys. For amorphous alloys, two fundamentally different ways of preparation are known. One of these methods is liquid quenching. Here a molten alloy is cooled sufficiently rapidly so that no time is available for nucleation and growth of crystallites. The other method involves vapor quenching where the metal atoms of a gas mixture impinge on the surface of a cold substrate. In this process also, there is not enough time left for the atoms to arrange themselves in an atomically ordered manner. It has become common practice to label the alloys produced by the former method as metallic glasses although amorphous alloys prepared by the second method can be identical to corresponding glasses in structure and properties. Rapid quenching of liquid alloys by melt spinning appears to be the most common preparation method for obtaining metallic glasses, the critical cooling rates being typically rather high, of the order of 10− 3 K s− 1. Glasses prepared by this method are usually obtained in the form of thin ribbons of variable width and lengths. Owing to their unique atomic scale structure, metallic glasses were found to have mechanical, electrical, or magnetic properties that can be superior when compared to their crystalline counterparts. However, the fact that the shape of these glasses is restricted to thin ribbons has mostly limited their practical application. Extensive research on a global scale during several decades has shown that, for some alloys, such high cooling rates are not required for reaching the glassy state. It holds especially for multicomponent alloys, for instance, based on Zr and Ti, that can have critical cooling rates for glass formation of the order of 1 K s− 1 only. This has offered casting of commercial metallic alloys to a fully glassy state in cross sections of several centimeters by employing conventional chill molds. In fact, the past decade has seen the production of a large number of such bulk glassy alloys (also termed bulk metallic glasses) arbitrarily defined as three-dimensional massive glassy pieces having a size of not less than 1 mm in any dimension. These bulk metallic glasses have attracted substantial interest of the materials research community, and their outstanding magnetic and mechanical properties are described here.
Chapter 4 addresses nanocrystalline soft-magnetic alloys. Innovative steps in materials design are commonly accompanied by the discovery of novel compounds, special microstructures, or advancements in processing which result in improved properties. This has been particularly true for soft-magnetic materials where the formation of new types of nanocrystalline microstructures has opened the possibility for the production of smaller, lighter, and more efficient materials for many power-oriented applications. This advancement in the field of soft-magnetic materials started with the advent of magnetic amorphous alloys. As described in Chapter 3 of this volume, amorphous magnetic alloys enabled the manufacturing of a new class of low-loss materials. The origin of their favorable magnetic properties stems from the fact that their anisotropies are much lower than in crystalline alloys due to the absence of long-range atomic order. It is well known that uncontrolled crystallization of amorphous materials results in anisotropy enlargement which reduces their favorable soft-magnetic properties because the newly formed devitrified material appears in too large crystallites. Initially, this has led to the conception that devitrification of amorphous precursors has to be avoided. But later it was discovered that by carefully controlled devitrification, magnetic alloys could be obtained that possessed really outstanding properties due to their nanocomposite microstructure. These outstanding properties showed up when the grain sizes were kept below sufficiently small dimensions and when there existed a strong enough exchange coupling between grains. The novel type of nanoscale microstructure enabling these beneficial properties was necessarily two phase, and its formation was only realized due to new concepts in alloy design, as partly described already in Chapter 3 of Volume 10. More recently, continued research in this field has led to a wide variety of compositions that lend themselves to the generation of similar nanocomposite microstructure, providing a large reservoir of soft-magnetic alloys with improved properties for various types of applications. In Chapter 4 of this volume, an updated account is presented of the progress achieved in this field, including descriptions of alloy design, synthesis, structure, and performance, all placed in the proper theoretical background of metallurgy and magnetism.
Volume 21, like 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 21 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 North Holland Physics Division of Elsevier B.V.
K.H.J. Buschow
Van der Waals-Zeeman Institute, University of Amsterdam
Contents of Volumes 1–20
Volume 1
1. Iron, Cobalt and Nickel, by E.P. Wohlfarth
2. Dilute Transition Metal Alloys: Spin Glasses, by J.A. Mydosh and G.J. Nieuwenhuys
3. Rare Earth Metals and Alloys, by S. Legvold
4. Rare Earth Compounds, by K.H.J. Buschow
5. Actinide Elements and Compounds, by W. Trzebiatowski
6. Amorphous Ferromagnets, by F.E. Luborsky
7. Magnetostrictive Rare Earth–Fe2 Compounds, by A.E. Clark
Volume 2
1. Ferromagnetic Insulators: Garnets, by M.A. Gilleo
2. Soft Magnetic Metallic Materials, by G.Y. Chin and J.H. Wernick
3. Ferrites for Non-Microwave Applications, by P.I. SlickS
4. Microwave Ferrites, by J. Nicolas
5. Crystalline Films for Bubbles, by A.H. Eschenfelder
6. Amorphous Films for Bubbles, by A.H. Eschenfelder.
7. Recording Materials, by G. Bate
8. Ferromagnetic Liquids, by S.W. Charles and J. Popplewell
Volume 3
1. Magnetism and Magnetic Materials: Historical Developments and Present Role in Industry and Technology, by U. Enz
2. Permanent Magnets; Theory, by H. Zijlstra
3. The Structure and Properties of Alnico Permanent Magnet Alloys, by R.A. McCurrie
4. Oxide Spinels, by S. Krupička and P.Novák
5. Fundamental Properties of Hexagonal Ferrites with Magnetoplumbite Structure, by H.Kojima
6. Properties of Ferroxplana-Type Hexagonal Ferrites, by M.Sugimoto
7. Hard Ferrites and Plastoferrites, by H.Stäblein
8. Sulphospinels, by R.P. vanStapele
9. Transport Properties of Ferromagnets, by I.A. Campbell and A. Fert
Volume 4
1. Permanent Magnet Materials Based on 3d-rich Ternary Compounds, by K.H.J. Buschow
2. Rare Earth–Cobalt Permanent Magnets, by K.J. Strnat
3. Ferromagnetic Transition Metal Intermetallic Compounds, by J.G. Booth
4. Intermetallic Compounds of Actinides, by V. Sechovský and L. Havela
5. Magneto-Optical Properties of Alloys and Intermetallic Compounds, by K.H. J. Buschow
Volume 5
1. Quadrupolar Interactions and Magneto-Elastic Effects in Rare-Earth Intermetallic Compounds, by P. Morin and D. Schmitt
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.F. 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 Ø. Fischer
Volume 6
1. Magnetic Properties of Ternary Rare-Earth Transition-Metal Compounds, by H.-S. Li and J.M.D. Coey
2. Magnetic Properties of Ternary Intermetallic Rare-Earth Compounds, by A. Szytula
3. Compounds of Transition Elements with Nonmetals, by O. Beckman and L. Lundgren
4. Magnetic Amorphous Alloys, by P. Hansen
5. Magnetism and Quasicrystals, by R.C. O’Handley, R.A. Dunlap and M.E. McHenry
6. Magnetism of Hydrides, by G. Wiesinger and G. Hilscher
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 M.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. Radwa’nski .
6. Neutron Scattering on Heavy Fermion and Valence Fluctuation 4f-systems, by M. Loewenhaupt and K.H. Fischer
Volume 8
1. Magnetism in Artificial Metallic Superlattices of Rare Earth Metals, by J.J. Rhyne and R.W. Erwin
2. Thermal Expansion Anomalies and Spontaneous Magnetostriction in Rare-Earth Intermetallics with Cobalt and Iron, by A.V. Andreev
3. Progress in Spinel Ferrite Research, by V.A.M. Brabers
4. Anisotropy in Iron-Based Soft Magnetic Materials, by M. Soinski and A.J. Moses
5. Magnetic Properties of Rare Earth–Cu2 Compounds, by Nguyen Hoang Luong and J.J.M. Franse
Volume 9
1. Heavy Fermions and Related Compounds, by G.J. Nieuwenhuys
2. Magnetic Materials Studied by Muon Spin Rotation Spectroscopy, by A. Schenck and F.N. Gygax
3. Interstitially Modified Intermetallics of Rare Earth and 3d Elements, by H. Fujii and H. Sun
4. Field Induced Phase Transitions in Ferrimagnets, by A.K. Zvezdin
5. Photon Beam Studies of Magnetic Materials, by S.W. Lovesey
Volume 10
1. Normal-State Magnetic Properties of Single-Layer Cuprate High-Temperature Superconductors and Related Materials, by D.C. Johnston
2. Magnetism of Compounds of Rare Earths with Non-Magnetic Metals, by D. Gignoux and D. Schmitt
3. Nanocrystalline Soft Magnetic Alloys, by G. Herzer
4. Magnetism and Processing of Permanent Magnet Materials, by K.H.J. Buschow
Volume 11
1. Magnetism of Ternary Intermetallic Compounds of Uranium, by V. Sechovský and L. Havela
2. Magnetic Recording Hard Disk Thin Film Media, by J.C. Lodder
3. Magnetism of Permanent Magnet Materials and Related Compounds as Studied by NMR, By Cz. Kapusta, P.C. Riedi and G.J. Tomka
4. Crystal Field Effects in Intermetallic Compounds Studied by Inelastic Neutron Scattering, by O. Moze
Volume 12
1. Giant Magnetoresistance in Magnetic Multilayers, by A. Barthélémy, A. Fert and F. Petroff
2. NMR of Thin Magnetic Films and Superlattices, by P.C. Riedi, T. Thomson and G.J. Tomka
3. Formation of 3d-Moments and Spin Fluctuations in Some Rare-Earth-Cobalt Compounds, by N.H. Duc and P.E. Brommer
4. Magnetocaloric Effect in the Vicinity of Phase Transitions, by A.M. Tishin
Volume 13
1. Interlayer Exchange Coupling in Layered Magnetic Structures, by D.E. Bürgler, P. Grünberg, S.O. Demokritov and M.T. Johnson
2. Density Functional Theory Applied to 4f and 5f Elements and Metallic Compounds, by M. Richter
3. Magneto-Optical Kerr Spectra, by P.M. Oppeneer
4. Geometrical Frustration, by A.P. Ramirez
Volume 14
1. III-V Ferromagnetic Semiconductors, by F. Matsukura, H. Ohno and T. Dietl
2. Magnetoelasticity in Nanoscale Heterogeneous Magnetic Materials, by N.H. Duc and P.E. Brommer
3. Magnetic and Superconducting Properties of Rare Earth Borocarbides of the Type RNi2B2C, by K.-H. Müller, G. Fuchs, S.-L. Drechsler and V.N.Narozhnyi
4. Spontaneous Magnetoelastic Effects in Gadolinium Compounds, by A. Lindbaum and M. Rotter
Volume 15
1. Giant Magnetoresistance and Magnetic Interactions in Exchange-Biased Spin-Valves, by R. Coehoorn
2. Electronic Structure Calculations of Low-dimensional Transition Metals, by A. Vega, J.C. Parlebas and C. Demangeat
3. II–VI and IV–VI Diluted Magnetic Semiconductors – New Bulk Materials and Low-Dimensional Quantum Structures, by W. Dobrowolski, J. Kossut and T. Story
4. Magnetic Ordering Phenomena and Dynamic Fluctuations in Cuprate Superconductors and Insulating Nickelates, by H.B. Brom and J. Zaanen .
5. Giant Magnetoimpedance, by M. Knobel, M. Vázquez and L. Kraus
Volume 16
1. Giant Magnetostrictive Materials, by O. Söderberg, A. Sozinov, Y. Ge, S.-P. Hannula and V.K. Lindroos
2. Micromagnetic Simulation of Magnetic Materials, by D. Suess, J. Fidler and Th. Schrefl
3. Ferrofluids, by S.Odenbach
4. Magnetic and Electrical Properties of Practical AntiferromagneticMn Alloys, by K. Fukamichi and R.Y. Umetsu, A.SakumaandC.Mitsumata
5. Synthesis, Properties and Biomedical Applications of Magnetic Nanoparticles, by P. Tartaj, and M.P. Morales, S. Veintemillas-Verdaguer, T. Gonzalez-Carreño and C.J. Serna
Volume 17
1. Spin-Dependent Tunneling in Magnetic Junctions, by H.J.M. Swagten
2. Magnetic Nanostructures: Currents and Dynamics, by Gerrit E.W. Bauer, Yaroslav Tserkovnyak, Arne Brataas, Paul J. Kelly
3. Theory of Crystal-Field Effects in 3d-4f Intermetallic Compounds, by M.D. Kuz’min, A.M. Tishin
4. Magnetocaloric Refrigeration at Ambient Temperature, by Ekkes Brück
5. Magnetism of Hydrides, by Günter Wiesinger and Gerfried Hilscher
6. Magnetic Microelectromechanical Systems: MagMEMS, by M.R.J. Gibbs, E.W. Hill, P. Wright
Volume 18
1. Magnetic Properties of Filled Skutterudites, by H. Sato, H. Sugawara, Y. Aoki, H. Harima
2. Spin Dynamics in Nanometric Magnetic Systems, by David Schmool
3. Magnetic Sensors: Principles and Applications, by Pavel Ripka and Karel Závěta
Volume 19
1. Magnetic Recording Heads, by J. Heidmann and A.M. Taratorin
2. Spintronic Devices for Memory and Logic Applications, by B. Dieny, R.C. Sousa, J. Hérault, C. Papusoi, G. Prenat, U. Ebels, D. Houssameddine, B. Rodmacq, S. Auffret, L. Prejbeanu-Buda, M.C. Cyrille, B. Delaet, O. Redon, C. Ducruet, J.P. Nozieres and L. Prejbeanu
3. Magnetoelectricity, by L.E. Fuentes-Cobas, J.A. Matutes-Aquino and M.E. Fuentes-Montero
4. Magnetic-Field-Induced Effects in Martensitic Heusler-Based Magnetic Shape Memory Alloys, by M. Acet, Ll. Mañosa and A. Planes
5. Structure and Magnetic Properties of L10-Ordered Fe–Pt Alloys and Nanoparticles, by J. Lyubina, B. Rellinghaus, O. Gutfleisch and M. Albrecht
Volume 20
1. Microwave Magnetic Materials, by Vincent G. Harris
2. Metal Evaporated Media, by Pierre-Olivier Jubert and Seiichi Onodera
3. Magnetoelasticity of bcc Fe-Ga Alloys, by Gabriela Petculescu, Ruqian Wu and Robert McQueeney
4. Rare Earth Moössbauer Spectroscopy Measurements on Lanthanide Intermetallics: Survey, by P.C.M. Gubbens
Contributors
Maria Daniil
Department of Physics, George Washington University, Washington, District of Columbia, USA
Gerhard H. Fecher
Institute for Analytical and Inorganic Chemistry, Johannes Gutenberg-University, Mainz, and Max-Planck-Institute for Chemical Physics of Solids, Dresden, Germany
Claudia Felser
Institute for Analytical and Inorganic Chemistry, Johannes Gutenberg-University, Mainz, and Max-Planck-Institute for Chemical Physics of Solids, Dresden, Germany
Tanja Graf
Institute for Analytical and Inorganic Chemistry, Johannes Gutenberg-University, Mainz, Germany, and IBM Almaden Research Center, San Jose, California, USA
Akihisa Inoue
WPI Advanced Institute for Materials Research, Tohoku University, Aoba-Ku, Sendai, Japan
Dmitri V. Louzguine-Luzgin
WPI Advanced Institute for Materials Research, Tohoku University, Aoba-Ku, Sendai, Japan
Lukas Muüchler
Institute for Analytical and Inorganic Chemistry, Johannes Gutenberg-University, Mainz, and Max-Planck-Institute for Chemical Physics of Solids, Dresden, Germany
Stuart S.P. Parkin
IBM Almaden Research Center, San Jose, California, USA
Zbigniew M. Stadnik
Department of Physics, University of Ottawa, Ottawa, Ontario, Canada
Matthew A. Willard
U.S. Naval Research Laboratory, Magnetic Materials and Nanostructures Section, Washington, District of Columbia, and The Department of Materials Science and Engineering, Case Western Reserve University, Cleveland, Ohio, USA
Juürgen Winterlik
Institute for Analytical and Inorganic Chemistry, Johannes Gutenberg-University, Mainz, Germany
Chapter One
Magnetic Heusler Compounds
Tanja Graf¹, ², Jürgen Winterlik¹, Lukas Müchler¹, ³, Gerhard H. Fecher¹, ³, Claudia Felser¹, ³ and Stuart S.P. Parkin²
¹Institute for Analytical and Inorganic Chemistry, Johannes Gutenberg-University, Mainz, Germany
²IBM Almaden Research Center, San Jose, California, USA
³Max-Planck-Institute for Chemical Physics of Solids, Dresden, Germany
Abstract
Heusler compounds are a remarkable class of intermetallic materials with 1:1:1 (often called Half-Heusler) or 2:1:1 composition comprising more than 1500 members. New properties and potential fields of applications emerge constantly; the prediction of topological insulators is the most recent example. Surprisingly, the properties of many Heusler compounds can easily be predicted by the valence electron count or within a rigid band approach. The wide range of the multifunctional properties of Heusler compounds is reflected in extraordinary magnetooptical, magnetoelectronic, and magnetocaloric properties. Co2-Heusler compounds are predicted and proven half-metallic ferromagnets showing Slater–Pauling type behavior. The recently discovered Mn2-Heusler compounds are another class of half metallic Heusler compounds which even can be designed to be compensated ferrimagnets. Tetragonal Heusler compounds Mn2YZ as potential materials for STT applications can be easily designed by positioning the Fermi energy at the van Hove singularity in one of the spin channels.
Keywords
Heusler; Half metals; Spin polarization; Slater–Pauling
1. Introduction
The history of one of the most exciting material classes can be traced back to the year 1903 when Fritz Heusler discovered that an alloy with the composition Cu2MnAl behaves like a ferromagnet, although non of its constituent elements is magnetic by itself (Heusler, 1903; Heusler et al., 1903). However, it took three decades until the crystal structure was determined to be ordered with a face centered, cubic lattice (Bradley and Rodgers, 1934; Heusler, 1934). Unfortunately, they faded almost in oblivion in the following decades, and only few reports on the synthesis and properties of new Heusler compounds were published in the 1970s and 1980s (Brooks and Williams, 1975; van Engen and Bushow, 1983; van Engen et al., 1983; Webster, 1971). In recent years, Heusler compounds were rediscovered and their enormous potential in many diverse fields, ranging from spintronics, over shape memory alloys and semiconductors (SCs) with tunable band gaps to topological insulators, generated a tremendous research effort. For further insights into Heusler materials from the viewpoint of a chemist, the interested reader is referred to our recent review article (Graf et al., 2011a).
Generally, Heusler compounds belong to a group of ternary intermetallics with the stoichiometric composition XYZ (often called Half-Heusler
) or X2YZ and crystallize in an ordered fcc-based structure. Mostly, X and Y are transition or rare earth (RE) metals and Z is usually a main group element.
The quite new research area of spintronics is a multidisciplinary field. New materials must be found for satisfying the different types of demands. The search for stable half-metallic ferromagnets (HMFs) and ferromagnetic SCs with Curie temperatures (TC) higher than room temperature (RT) is still a challenge for solid state scientists. In principle, a HMF behaves like a metal for one spin direction and like an insulator for the other spin direction. A general understanding of how structures are related to properties is a necessary prerequisite for designing new materials showing desired functionalities. In this context, computational simulations are an important tool.
The development of magnetic Heusler compounds specifically designed for spintronic applications made tremendous progress in the very recent past. The boom about Heusler compounds for spintronic applications and the huge number of both, theoretical and experimental investigations (over 700 publications concerning X2YZ Heusler compounds in the past 8–9 years) began in 2002/2003 with the observation of—at that time—large negative magnetoresistance (MR) in powder compacts of Co2Cr0.6Fe0.4Al (Block et al., 2003). A magnetoresistive effect of 30% in a small magnetic field of 0.1 T at RT was found. This demonstrated for the first time the feasibility of a cheap and simple magnetic sensor based on polycrystalline, intermetallic materials. This value was later optimized by using powder compacts of Co2Cr0.6Fe0.4Al, mixed with insulating Al2O3, to a maximum MR ratio of 88% in an induction field of 0.125 T at 295 K (Block et al., 2006). The discovery of Co2FeSi, the Heusler compound with the highest magnetic moment of 5.97 μB at 5 K and the highest Curie temperature of 1100 K caught further attention by chemists as well as physicists. (Wurmehl et al., 2006a,c).
Indeed, the properties of many Heusler compounds can be predicted by simply counting the number of valence electrons (Felser et al., 2007; Graf et al., 2011a,b), which allows for instance the design of SCs with tunable band gaps (Gruhn, 2010), superconductors (Winterlik et al., 2009), HMF (Barth et al., 2010; Felser et al., 2007; Wurmehl et al., 2006a), compensated ferrimagnets (Balke et al., 2007a; Winterlik et al., 2008), and topological insulators (Chadov et al., 2010; Lin et al., 2010) simply by changing the constituent elements. Despite all these interesting properties of Heusler compounds, in this chapter we will focus on magnetic materials and their applications in the field of spintronics.
Discussing the properties of magnetic Heusler compounds, one major difference between Half-Heusler and Heusler compounds has to be considered: Half-Heusler materials exhibit one magnetic sublattice since only the atoms on the octahedral sites carry localized magnetic moments of considerable sizes, while in X2YZ Heusler compounds two magnetic sublattices are present which are coupled to each other, as shown in Fig. 1.1.
Figure 1.1 Half-Heusler compounds exhibit only one magnetic sublattice since only the atoms on the octahedral sites carry a localized magnetic moment. X 2 YZ Heusler compounds, however, have two magnetic sublattices which can couple ferromagnetically or antiferromagnetically (shown here).
Reprinted from Graf et al. (2011a) with kind permission of Elsevier.
Since the magnetic moment is carried by the X atom occupying an octahedral lattice position, magnetic Half-Heusler materials exist mainly for X = Mn, and RE which is a result of the localized nature of the four 3d electrons of Mn³ +and the 4f electrons, respectively. Among the RE-containing Heusler compounds known in literature, most compounds are semiconducting or semimetallic systems and antiferromagnets with low Néel temperatures (Casper and Felser, 2008; Gofryk et al., 2005). Since the magnetic ions occupy an NaCl-type sublattice, their distance is large which hints at a magnetic interaction based on a super-exchange mechanism. Despite the Mn-containing Half-Heusler compounds, which are HMF with high TC (Casper et al., 2006; de Groot et al., 1983; Kübler, 1984), only very few ferromagnetic Half-Heusler compounds are described in literature, for instance NdNiSb and VCoSb (Hartjes and Jeitschko, 1995; Heyne et al., 2005).
For the X2YZ Heusler compounds the situation is completely different because the two X atoms occupy tetrahedral lattice sites allowing for magnetic interaction between the X atoms. Thus a second, more delocalized magnetic sublattice is formed in addition to the one originating from the Y atoms (compare Fig. 1.1). Due to the two different magnetic sublattices, the X2YZ Heusler compounds can show all kinds of magnetic phenomena, and in fact, today ferromagnetism, ferrimagnetism, antiferromagnetism, and half-metallic ferromagnetism are known.
Tetragonally distortions corresponding to a type of band Jahn–Teller effect have been reported in the 1970s (Suits, 1976). Recently, these tetragonally distorted Heusler compounds have attracted considerable attention (Balke et al., 2007a; Winterlik et al., 2008; Wu et al., 2009, 2010). The tetragonal distortion is observed for Mn2YZ compounds crystallizing in the inverse Heusler structure. In this structure, the Mn atoms occupy two different lattice sites, one with tetragonal and one with octahedral coordination. Theoretical investigations by Kübler showed that the Mn atom on the octahedral site formally possesses an oxidation state of + 3 (Mn³ +, d⁴) (Kübler et al., 1983). According to crystal field theory d⁴ high spin ions in an octahedral coordination sphere undergo a tetragonal distortion, which leads to a rearrangement of the molecular orbitals and an overall energy gain. This phenomenon is commonly known as the Jahn–Teller effect. Alternatively, a double degenerate van Hove singularity, that is, saddle point in the band structure, can lead to a tetragonal distortion since this singularity maximizes the band energy, leading to an unfavorable condition, which is avoided by a tetragonal lattice distortion. In the case of Mn2YZ compounds, the cubic unit cell can undergo an elongation or a compression along the c
. Up two now, only few tetragonally distorted Heusler materials have been studied thoroughly, Mn3 − xGa being the most prominent example (Balke et al., 2007a; Winterlik et al., 2008). These materials are particularly interesting due to the perpendicular magnetic anisotropy (PMA), which can be achieved in thin films (Wu et al., 2009) opening the door to spin-transfer torque (STT) devices. Many potential compounds Mn2YZ and their alloys Mn3 − xYxZ for a STT application are still undiscovered. However, these materials still exhibit certain challenges, which have to be overcome for technological application. It is therefore essential to design new materials that fulfill all the required criteria as we will discuss later.
2. Crystal Structure and Atomic Ordering
, C1b) which is a ternary ordered variant of the CaF2 structure and can be derived from the tetrahedral ZnS-type structure by filling the octahedral lattice sites (Fig. 1.2). A characteristic feature of this Half-Heusler structure type are three interpenetrating fcc sublattices, each of which are occupied by the X, Y and Z atoms (Webster and Ziebeck, 1988). The corresponding occupied Wyckoff positions are 4a (0, 0, 0), 4b (1/2, 1/2, 1/2), and 4c (1/4, 1/4, 1/4). In principle, three inequivalent atomic arrangements are possible, which have to be carefully differentiated, especially if electronic structure calculations are performed, since the correct site assignment is crucial for the obtained electronic structure.
Figure 1.2 (a) Rock salt structure, (b) Zinc blende structure and their relations to the Half-Heusler structure (c), and to the Heusler structure (d).
Reprinted from Graf et al. (2011a) with kind permission of Elsevier.
Viewing the Half-Heusler structure as a ZnS-sublattice (Wyckoff positions 4a and 4c), in which the octahedral sites are occupied (4b), emphasizes the covalent bonding interaction between two of the contained elements which plays a major role for the electronic properties of the material. In contrast, it is worth to mention that the atoms on position 4a and 4b built a NaCl-type sublattice, that is, their interaction has a strong ionic character. The specific ordering of the atoms depends strongly on the chemical nature of the elements. In MgAgAs, for instance, Ag and anionic As form the covalent ZnS-sublattice, while Mg and Ag built the NaCl-type lattice (Nowotny and Sibert, 1941). Consequently, As is eightfold coordinated by monovalent and divalent cations. Even though MgAgAs is the assigned prototype of all Half-Heusler compounds, it has to be clarified that MgAgAs actually crystallizes with a different atomic order compared to most other Half-Heusler compounds (Villars and Calvert, 1991). So in this case a peculiar situation is present: The assigned prototype itself is an exception! MgCuSb is an example which represents the atomic arrangement in most Half-Heusler materials correctly (Nowotny and Sibert, 1941; Nuss and Jansen, 2002); here, Cu and anionic Sb form the ZnS sublattice, and cationic Mg and anionic Sb occupy the ionic NaCl-type sublattice. Thus, Cu is coordinated by four Mg and four Sb atoms in form of an ideal cube.
Which of these two described atomic arrangements is preferred, depends on the one hand on the difference in radii of the involved atoms, and on the other hand on the nature of interatomic interaction. If the difference in radii of the involved cations is rather small (Mg, Ag), the anion has eight cations in its coordination sphere and every cation is surrounded by four anions. From metal–organic chemistry it is well known that some metals exhibit a strong tendency to form covalent bonds, for instance Mg, Ag or Li. This property supports the formation of the covalent ZnS-type lattice, if such elements are contained in the compounds. Examples are LiAlSi, LiMgSb and the above discussed MgAgAs. However, if the cations show distinct differences in size and metal–metal interaction is dominant, as it is the case in MgCuSb, the anion (Sb) is coordinated by four cations (Cu), Cu for his part by four anions and four cations, and Mg by four cations. Further examples for this kind of order are all Half-Heusler compounds containing two transition metals and the REYZ materials. In some cases, both variants are labeled with the same prototype, LiAlSi type (Villars and Calvert, 1991). However, most Half-Heusler compounds containing two transition metals are designated with MgAgAs-type structure (Villars and Calvert, 1991), which is actually wrong. We would like to emphasize that the correct assignment of the lattice positions is essential to understand the structure-to-property relations of these materials and special care has to be taken when performing theoretical studies to obtain correct results.
(space group no. 225) with Cu2MnAl (L21) as prototype (Bradley and Rodgers, 1934; Heusler, 1903; Heusler et al., 1903; Heusler, 1934). The X atoms occupy the Wyckoff position 8c (1/4, 1/4, 1/4), the Y and the Z atoms are located at 4a (0, 0, 0) and 4b (1/2, 1/2, 1/2), respectively. Similar to Half-Heusler materials, this structure consists of four interpenetrating fcc 
cell. The combination of both X-site fcc lattices leads to a simple cubic lattice. The Y and the Z atoms occupy the centers of the simple cubic lattice, which results in the CsCl-like superstructure. This kind of disorder between the Y and Z site is often observed in half-metallic Heusler systems but fortunately does not affect the properties significantly. The shifted Heusler cell, as well as the CsCl structure, are displayed in Fig. 1.3. This description provides an intuitive understanding for one design rule: The combination of two binary alloys crystallizing in the CsCl-type structure leads to the formation of Heusler compounds (Butler et al., 2011).
Figure 1.3 (a) CsCl structure and (b) the Heusler structure which is shifted by (1/4, 1/4, 1/4) with respect to the standard cell to make the CsCl superstructure visible.
Reprinted from Graf et al. (2011a) with kind permission of Elsevier.
In addition to the structure described above, an inverse Heusler structure is observed, if the atomic number of Y is higher than the one of X from the same period (Z(Y) > Z(X)), however, it may also appear in compounds with transition metals from different periods (Puselj and Ban, 1969). In all cases, the element X is more electropositive than Y. Consequently, Y and Z form a zinc blende lattice to achieve an octahedral coordination for X. The remaining X atoms fill the tetrahedral holes with fourfold symmetry. The structure is still described by four interpenetrating fcc 
(space group no. 216). The difference to normal Heusler compounds can be emphasized by expressing the formula as (XY) X′Z. This inverse Heusler structure is frequently observed for Mn2-based materials. A well-studied example is the compound Mn2CoSn or (MnCo)MnSn (Lakshmi et al., 2002; Surikov et al., 1990). These mangenese-based materials are currently attracting considerable research activities and will be discussed in detail later. In case of quaternary Heusler compounds there are two different elements X and X′. They are located at the 4a and 4d position, respectively, Y is placed on 4b and Z on 4c. This structure has the prototype LiMgPdSn. An illustration of the inverse Heusler structure and the quaternary variant is given in Fig. 1.4.
Figure 1.4 (a) The inverse Heusler structure CuHg 2 Ti and (b) the quaternary version LiMgPdSn.
Reprinted from Graf et al. (2011a) with kind permission of Elsevier.
The properties of Heusler materials are strongly dependent on the atomic arrangement of the atoms. Already a partial intermixture can alter the electronic structure distinctly (Kandpal et al., 2007c; Miura et al., 2004a; Picozzi et al., 2004). As described above, Half-Heusler compounds are tetrahedrally filled structures, which are closely related to binary SCs. Covalent bonding interaction plays a significant role and their crystalline order is retained up to the composition temperature (Skovsen et al., 2010). Thus, structural disorder leading to an occupation of the vacant lattice site occurs only rarely in Half-Heusler compounds, whereas the X2YZ phases often display considerable amounts of atomic disorder. Therefore, a careful analysis of their crystal structure is essential to understand the structure-to-property relation and to design new materials with predictable properties. Here, we will focus on disorder effects occurring in the X2YZ materials. The interested reader is referred to Graf et al. (2011a) for further discussion of the Half-Heusler structure.
Figure 1.5 shows the transition from the ordered to the
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