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This page intentionally left blank
 MAGNETIC MATERIALS

Fundamentals and Applications

Magnetic Materials is an excellent introduction to the basics of magnetism, mag-

netic materials, and their applications in modern device technologies. Retaining the
concise style of the original, this edition has been thoroughly revised to address sig-
nificant developments in the field, including the improved understanding of basic
magnetic phenomena, new classes of materials, and changes to device paradigms.
With homework problems, solutions to selected problems, and a detailed list of
references, Magnetic Materials continues to be the ideal book for a one-semester
course and as a self-study guide for researchers new to the field.

New to this edition:

r Entirely new chapters on exchange-bias coupling, multiferroic and magnetoelectric mate-
rials, and magnetic insulators
r Revised throughout, with substantial updates to the chapters on magnetic recording and
magnetic semiconductors, incorporating the latest advances in the field
r New example problems with worked solutions

nicola a. spaldin is a Professor in the Materials Department at the Univer-

sity of California, Santa Barbara. She is an enthusiastic and effective teacher, with
experience ranging from developing and managing the UCSB Integrative Gradu-
ate Training Program to answering elementary school students’ questions online.
Particularly renowned for her research in multiferroics and magnetoelectrics, her
current research focuses on using electronic structure methods to design and under-
stand materials that combine magnetism with additional functionalities. She was
recently awarded the American Physical Society’s McGroddy Prize for New Mate-
rials for this work. She is also active in research administration, directing the
UCSB/National Science Foundation International Center for Materials Research.
MAGNETIC MATERIALS
Fundamentals and Applications

Second edition

NICOLA A. SPALDIN
University of California, Santa Barbara
CAMBRIDGE UNIVERSITY PRESS
Cambridge, New York, Melbourne, Madrid, Cape Town, Singapore,
São Paulo, Delhi, Dubai, Tokyo

Cambridge University Press

The Edinburgh Building, Cambridge CB2 8RU, UK

Published in the United States of America by Cambridge University Press, New York

www.cambridge.org
Information on this title: www.cambridge.org/9780521886697
© N. Spaldin 2003, 2011

This publication is in copyright. Subject to statutory exception and to the

provision of relevant collective licensing agreements, no reproduction of any part
may take place without the written permission of Cambridge University Press.
First published in print format 2010

ISBN 13 978 0 511 90071 6 eBook (EBL)

ISBN 13 978 0 521 88669 7 Hardback

Cambridge University Press has no responsibility for the persistence or accuracy

of urls for external or third party internet websites referred to in this publication,
and does not guarantee that any content on such websites is, or will remain,
accurate or appropriate.
Magnus magnes ipse est globus terrestris.
William Gilbert, De Magnete. 1600.
 Contents

Acknowledgments page xiii

I Basics
1 Review of basic magnetostatics 3
1.1 Magnetic field 4
1.1.1 Magnetic poles 4
1.1.2 Magnetic flux 6
1.1.3 Circulating currents 6
1.1.4 Ampère’s circuital law 7
1.1.5 Biot–Savart law 8
1.1.6 Field from a straight wire 8
1.2 Magnetic moment 10
1.2.1 Magnetic dipole 11
1.3 Definitions 11
Homework 12
2 Magnetization and magnetic materials 14
2.1 Magnetic induction and magnetization 14
2.2 Flux density 15
2.3 Susceptibility and permeability 16
2.4 Hysteresis loops 18
2.5 Definitions 19
2.6 Units and conversions 19
Homework 20
3 Atomic origins of magnetism 22
3.1 Solution of the Schrödinger equation for a free atom 22
3.1.1 What do the quantum numbers represent? 25
3.2 The normal Zeeman effect 27

vii
viii Contents

3.3 Electron spin 30

3.4 Extension to many-electron atoms 31
3.4.1 Pauli exclusion principle 32
3.5 Spin–orbit coupling 32
3.5.1 Russell–Saunders coupling 32
3.5.2 Hund’s rules 34
3.5.3 jj coupling 35
3.5.4 The anomalous Zeeman effect 35
Homework 37
4 Diamagnetism 38
4.1 Observing the diamagnetic effect 38
4.2 Diamagnetic susceptibility 39
4.3 Diamagnetic substances 41
4.4 Uses of diamagnetic materials 42
4.5 Superconductivity 42
4.5.1 The Meissner effect 43
4.5.2 Critical field 44
4.5.3 Classification of superconductors 44
4.5.4 Superconducting materials 44
4.5.5 Applications for superconductors 46
Homework 46
5 Paramagnetism 48
5.1 Langevin theory of paramagnetism 49
5.2 The Curie–Weiss law 52
5.3 Quenching of orbital angular momentum 54
5.4 Pauli paramagnetism 55
5.4.1 Energy bands in solids 56
5.4.2 Free-electron theory of metals 58
5.4.3 Susceptibility of Pauli paramagnets 60
5.5 Paramagnetic oxygen 62
5.6 Uses of paramagnets 63
Homework 64
6 Interactions in ferromagnetic materials 65
6.1 Weiss molecular field theory 66
6.1.1 Spontaneous magnetization 66
6.1.2 Effect of temperature on magnetization 67
6.2 Origin of the Weiss molecular field 69
6.2.1 Quantum mechanics of the He atom 70
6.3 Collective-electron theory of ferromagnetism 73
6.3.1 The Slater–Pauling curve 76
 Contents ix

6.4 Summary 76
Homework 78
7 Ferromagnetic domains 79
7.1 Observing domains 79
7.2 Why domains occur 81
7.2.1 Magnetostatic energy 81
7.2.2 Magnetocrystalline energy 82
7.2.3 Magnetostrictive energy 84
7.3 Domain walls 85
7.4 Magnetization and hysteresis 87
Homework 92
8 Antiferromagnetism 96
8.1 Neutron diffraction 97
8.2 Weiss theory of antiferromagnetism 101
8.2.1 Susceptibility above TN 102
8.2.2 Weiss theory at TN 103
8.2.3 Spontaneous magnetization below TN 103
8.2.4 Susceptibility below TN 103
8.3 What causes the negative molecular field? 107
8.4 Uses of antiferromagnets 110
Homework 112
9 Ferrimagnetism 113
9.1 Weiss theory of ferrimagnetism 114
9.1.1 Weiss theory above TC 115
9.1.2 Weiss theory below TC 117
9.2 Ferrites 120
9.2.1 The cubic ferrites 120
9.2.2 The hexagonal ferrites 124
9.3 The garnets 125
9.4 Half-metallic antiferromagnets 126
Homework 127
10 Summary of basics 130
10.1 Review of types of magnetic ordering 130
10.2 Review of physics determining types of magnetic
ordering 131
II Magnetic phenomena
11 Anisotropy 135
11.1 Magnetocrystalline anisotropy 135
11.1.1 Origin of magnetocrystalline anisotropy 136
11.1.2 Symmetry of magnetocrystalline anisotropy 138
x Contents

11.2 Shape anisotropy 139

11.2.1 Demagnetizing field 139
11.3 Induced magnetic anisotropy 141
11.3.1 Magnetic annealing 141
11.3.2 Roll anisotropy 142
11.3.3 Explanation for induced magnetic anisotropy 142
11.3.4 Other ways of inducing magnetic anisotropy 143
Homework 144
12 Nanoparticles and thin films 145
12.1 Magnetic properties of small particles 145
12.1.1 Experimental evidence for single-domain
particles 147
12.1.2 Magnetization mechanism 147
12.1.3 Superparamagnetism 148
12.2 Thin-film magnetism 152
12.2.1 Structure 152
12.2.2 Interfaces 153
12.2.3 Anisotropy 153
12.2.4 How thin is thin? 154
12.2.5 The limit of two-dimensionality 154
13 Magnetoresistance 156
13.1 Magnetoresistance in normal metals 157
13.2 Magnetoresistance in ferromagnetic metals 158
13.2.1 Anisotropic magnetoresistance 158
13.2.2 Magnetoresistance from spontaneous magnetization 159
13.2.3 Giant magnetoresistance 160
13.3 Colossal magnetoresistance 164
13.3.1 Superexchange and double exchange 164
Homework 168
14 Exchange bias 169
14.1 Problems with the simple cartoon mechanism 171
14.1.1 Ongoing research on exchange bias 172
14.2 Exchange anisotropy in technology 173
III Device applications and novel materials
15 Magnetic data storage 177
15.1 Introduction 177
15.2 Magnetic media 181
15.2.1 Materials used in magnetic media 181
15.2.2 The other components of magnetic hard disks 183
15.3 Write heads 183
 Contents xi

15.4 Read heads 185

15.5 Future of magnetic data storage 186
16 Magneto-optics and magneto-optic recording 189
16.1 Magneto-optics basics 189
16.1.1 Kerr effect 189
16.1.2 Faraday effect 191
16.1.3 Physical origin of magneto-optic effects 191
16.2 Magneto-optic recording 193
16.2.1 Other types of optical storage, and the future of
magneto-optic recording 196
17 Magnetic semiconductors and insulators 197
17.1 Exchange interactions in magnetic semiconductors
and insulators 198
17.1.1 Direct exchange and superexchange 199
17.1.2 Carrier-mediated exchange 199
17.1.3 Bound magnetic polarons 200
17.2 II–VI diluted magnetic semiconductors – (Zn,Mn)Se 201
17.2.1 Enhanced Zeeman splitting 201
17.2.2 Persistent spin coherence 202
17.2.3 Spin-polarized transport 203
17.2.4 Other architectures 204
17.3 III–V diluted magnetic semiconductors – (Ga,Mn)As 204
17.3.1 Rare-earth–group-V compounds – ErAs 207
17.4 Oxide-based diluted magnetic semiconductors 208
17.5 Ferromagnetic insulators 210
17.5.1 Crystal-field and Jahn–Teller effects 210
17.5.2 YTiO3 and SeCuO3 211
17.5.3 BiMnO3 213
17.5.4 Europium oxide 214
17.5.5 Double perovskites 215
17.6 Summary 215
18 Multiferroics 216
18.1 Comparison of ferromagnetism and other types of
ferroic ordering 216
18.1.1 Ferroelectrics 216
18.1.2 Ferroelastics 219
18.1.3 Ferrotoroidics 220
18.2 Multiferroics that combine magnetism and ferroelectricity 221
18.2.1 The contra-indication between magnetism and
ferroelectricity 222
xii Contents

18.2.2 Routes to combining magnetism and ferroelectricity 223

18.2.3 The magnetoelectric effect 225
18.3 Summary 228
Epilogue 229
Solutions to selected exercises 230
References 262
Index 270
 Acknowledgments

This book has been tested on human subjects during a course on Magnetic Materials
that I have taught at UC Santa Barbara for the last decade. I am immensely grateful
to each class of students for suggesting improvements, hunting for errors, and letting
me know when I am being boring. I hope that their enthusiasm is contagious.

Nicola Spaldin

xiii
Part I
Basics
 1
Review of basic magnetostatics

Mention magnetics and an image arises of musty physics labs peopled

by old codgers with iron filings under their fingernails.
John Simonds, Magnetoelectronics today and tomorrow,
Physics Today, April 1995

Before we can begin our discussion of magnetic materials we need to understand

some of the basic concepts of magnetism, such as what causes magnetic fields, and
what effects magnetic fields have on their surroundings. These fundamental issues
are the subject of this first chapter. Unfortunately, we are going to immediately run
into a complication. There are two complementary ways of developing the theory
and definitions of magnetism. The “physicist’s way” is in terms of circulating
currents, and the “engineer’s way” is in terms of magnetic poles (such as we find
at the ends of a bar magnet). The two developments lead to different views of
which interactions are more fundamental, to slightly different-looking equations,
and (to really confuse things) to two different sets of units. Most books that you’ll
read choose one convention or the other and stick with it. Instead, throughout this
book we are going to follow what happens in “real life” (or at least at scientific
conferences on magnetism) and use whichever convention is most appropriate to the
particular problem. We’ll see that it makes most sense to use Système International
d’Unités (SI) units when we talk in terms of circulating currents, and centimeter–
gram–second (cgs) units for describing interactions between magnetic poles.
To avoid total confusion later, we will give our definitions in this chapter and the
next from both viewpoints, and provide a conversion chart for units and equations at
the end of Chapter 2. Reference [1] provides an excellent light-hearted discussion
of the unit systems used in describing magnetism.

3
4 Review of basic magnetostatics

1.1 Magnetic field

1.1.1 Magnetic poles
So let’s begin by defining the magnetic field, H, in terms of magnetic poles.
This is the order in which things happened historically – the law of interaction
between magnetic poles was discovered by Michell in England in 1750, and by
Coulomb in France in 1785, a few decades before magnetism was linked to the
flow of electric current. These gentlemen found empirically that the force between
two magnetic poles is proportional to the product of their pole strengths, p, and
inversely proportional to the square of the distance between them,
p1 p2
F ∝ . (1.1)
r2
This is analogous to Coulomb’s law for electric charges, with one important differ-
ence – scientists believe that single magnetic poles (magnetic monopoles) do not
exist. They can, however, be approximated by one end of a very long bar magnet,
which is how the experiments were carried out. By convention, the end of a freely
suspended bar magnet which points towards magnetic north is called the north
pole, and the opposite end is called the south pole.1 In cgs units, the constant of
proportionality is unity, so
p1 p2
F = (cgs), (1.2)
r2
where r is in centimeters and F is in dynes. Turning Eq. (1.2) around gives us the
definition of pole strength:

A pole of unit strength is one which exerts a force of 1 dyne on another unit pole
located at a distance of 1 centimeter.

The unit of pole strength does not have a name in the cgs system.
In SI units, the constant of proportionality in Eq. (1.1) is μ0 /4π , so
μ0 p1 p2
F = (SI), (1.3)
4π r 2
where μ0 is called the permeability of free space, and has the value 4π × 10−7
weber/(ampere meter) (Wb/(Am)). In SI, the pole strength is measured in ampere
meters (A m), the unit of force is of course the newton (N), and 1 newton = 105
dyne (dyn).

1 Note, however, that if we think of the earth’s magnetic field as originating from a bar magnet, then the south
pole of the earth’s “bar magnet” is actually at the magnetic north pole!
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