COMPREHENSIVE

SEMICONDUCTOR
SCIENCE AND
TECHNOLOGY
This page intentionally left blank
 COMPREHENSIVE
SEMICONDUCTOR
SCIENCE AND
TECHNOLOGY
Editors-in-Chief
Pallab Bhattacharya
Department of Electrical Engineering and Computer Science,
University of Michigan, Ann Arbor, MI, USA

Roberto Fornari
Leibniz Institute for Crystal Growth, Berlin, Germany
and
Institute of Physics, Humboldt University, Berlin, Germany

Hiroshi Kamimura
Research Institute for Science and Technology,
Tokyo University of Science, Tokyo, Japan

Volume 1
PHYSICS AND FUNDAMENTAL THEORY

Volume Editor
Hiroshi Kamimura
Research Institute for Science and Technology,
Tokyo University of Science, Tokyo, Japan

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CHAPTER 4.09 ATOMIC RESOLUTION CHARACTERIZATION OF SEMICONDUCTOR MATERIALS
BY ABERRATION-CORRECTED TRANSMISSION ELECTRON MICROSCOPY

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Contents of Volume 1
Contributors to Volume 1 vii
Preface ix
Editors in Chief xiii
Contents of All Volumes xv

Physics and Fundamental Theory

1.01 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 1
J. R. Chelikowsky, University of Texas, Austin, TX, USA
1.02 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors:
Bulk Crystals to Nanostructures 42
J. Deslippe and S. G. Louie, University of California at Berkeley and Lawrence Berkeley National
Laboratory, Berkeley, CA, USA
1.03 Impurity Bands in Group-IV Semiconductors 77
M. Eto, Keio University, Yokohama, Japan
H. Kamimura, Tokyo University of Science, Tokyo, Japan
1.04 Atomic Structures and Electronic Properties of Semiconductor Interfaces 113
T. Nakayama, Chiba University, Chiba, Japan
Y. Kangawa, Kyushu University, Fukuoka, Japan
K. Shiraishi, University of Tsukuba, Ibaraki, Japan
1.05 Integer Quantum Hall Effect 175
H. Aoki, University of Tokyo, Tokyo, Japan
1.06 Fractional Quantum Hall Effect and Composite Fermions 210
J. K. Jain, The Pennsylvania State University, University Park, PA, USA
1.07 Spin Hall Effect 222
S. Murakami, Tokyo Institute of Technology, Tokyo, Japan
N. Nagaosa, University of Tokyo, Tokyo, Japan
1.08 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures 279
W. R. Clarke and M. Y. Simmons, University of New South Wales, Sydney, NSW, Australia
C.-T. Liang, National Taiwan University, Taipei, China
1.09 Thermal Conductivity and Thermoelectric Power of Semiconductors 326
I. Terasaki, Nagoya University, Nagoya, Japan

v
vi Contents of Volume 1

1.10 Electronic States and Transport Properties of Carbon Crystalline: Graphene, Nanotube,
and Graphite 359
Y. Iye, University of Tokyo, Kashiwa, Chiba, Japan
1.11 Angle-Resolved Photoemission Spectroscopy of Graphene, Graphite, and Related Compounds 383
T. Sato and T. Takahashi, Tohoku University, Sendai, Japan
1.12 Theory of Superconductivity in Graphite Intercalation Compounds 410
Y. Takada, University of Tokyo, Kashiwa, Chiba, Japan
Contributors to Volume 1
H. Aoki Chapter 1.05 p. 175
University of Tokyo, Tokyo, Japan
J. R. Chelikowsky Chapter 1.01 p. 1
University of Texas, Austin, TX, USA
W. R. Clarke Chapter 1.08 p. 279
University of New South Wales, Sydney, NSW, Australia
J. Deslippe Chapter 1.02 p. 42
University of California at Berkeley and Lawrence Berkeley National Laboratory,
Berkeley, CA, USA
M. Eto Chapter 1.03 p. 77
Keio University, Yokohama, Japan
Y. Iye Chapter 1.10 p. 359
University of Tokyo, Kashiwa, Chiba, Japan
J. K. Jain Chapter 1.06 p. 210
The Pennsylvania State University, University Park, PA, USA
H. Kamimura Chapter 1.03 p. 77
Tokyo University of Science, Tokyo, Japan
Y. Kangawa Chapter 1.04 p. 113
Kyushu University, Fukuoka, Japan
C.-T. Liang Chapter 1.08 p. 279
National Taiwan University, Taipei, China
S. G. Louie Chapter 1.02 p. 42
University of California at Berkeley and Lawrence Berkeley National Laboratory,
Berkeley, CA, USA
S. Murakami Chapter 1.07 p. 222
Tokyo Institute of Technology, Tokyo, Japan
N. Nagaosa Chapter 1.07 p. 222
University of Tokyo, Tokyo, Japan
T. Nakayama Chapter 1.04 p. 113
Chiba University, Chiba, Japan
T. Sato Chapter 1.11 p. 383
Tohoku University, Sendai, Japan
K. Shiraishi Chapter 1.04 p. 113
University of Tsukuba, Ibaraki, Japan

vii
viii Contributors to Volume 1

M. Y. Simmons Chapter 1.08 p. 279

University of New South Wales, Sydney, NSW, Australia
Y. Takada Chapter 1.12 p. 410
University of Tokyo, Kashiwa, Chiba, Japan
T. Takahashi Chapter 1.11 p. 383
Tohoku University, Sendai, Japan
I. Terasaki Chapter 1.09 p. 326
Nagoya University, Nagoya, Japan
Preface
Semiconductors are at the heart of modern living. Almost everything we do, be it work, travel, communication,
or entertainment, all depend on some feature of semiconductor technology. Though this domination has its
roots in developments dating back 60 years, the progress has not been diminished by achievement, and the
demands for improvements in performance continue to push manufacturing limits. As we enhance the
performance of devices, we also extend the range of applications, exploiting what we have learned about
older semiconductors to grow and process newer ones. Whereas once we were content to explore silicon chips
for advanced electronics, and then gallium arsenide and other compound semiconductors for optoelectronics,
we are now addressing critical issues in growth and processing of group III nitrides and silicon carbide for high-
power, high-frequency, and high-temperature electronics and optoelectronics, with the objective of replacing
fluorescent tubes and tungsten filaments in our homes and offices.
While the numerous applications of semiconductors are evident to most, less is known about the seren-
dipitous evolution of basic semiconductor physics, which often paved the way to new device concepts. For
example, in 2000 the Nobel prize for physics was awarded to Zhores Alferov and Herbert Kroemer for the
development of the technology used today in satellite communication and cellular phones, and to Jack Kilby for
the invention and development of the integrated circuit, the forerunner of the microchip and the pocket
calculator. Further in 2009 Willard Boyle and George Smith shared the Nobel prize in physics for the invention
of an imaging semiconductor circuit – ‘the CCD sensor’ – with Charles Kao for his groundbreaking research on
the transmission of light in fibers for optical communication.
From the standpoint of chemistry and materials science, the prediction of semiconductor superlattices by
Leo Esaki and Raphael Tsu in 1969 opened the tailor-made materials age, together with the development of the
molecular beam epitaxy (MBE) and metal organic vapor phase epitaxy (MOVPE) techniques. These tech-
niques paved the way for the realization of tailor-made semiconductor materials, in particular low-dimensional
(two-, one-, and zero-dimensional) heterostructures which immediately became front runners in materials
science. This frontier spirit of semiconductor research has led to the recent splendid realization of a one-atom
thick layer of graphite, the so-called graphene, for which Andre Geim and Konstantin Novoselov received the
2010 Nobel prize in physics.
The discoveries of integer and fractional quantum Hall effects which were awarded the physics Nobel prize
in 1985 (Klaus von Klitzing) and 1998 (Robert Laughlin, Horst Störmer and Daniel Tsui), respectively, are also
undoubtedly among the most fascinating phenomena, not only in semiconductor physics, but also in the entire
subject of condensed matter physics. The integer quantum Hall effect was originally discovered in Si-
MOSFET (MOSFET, metal–oxide–semiconductor field-effect transistor), while the fractional quantum Hall
effect was observed in very pure and atomically abrupt GaAs–AlGaAs heterostructures. As regards the theory
of semiconductors from bulk to nanostructures, the advances in theoretical methodology and computer
technology have been tremendous in the last few decades. In particular, predictions of new stable materials
and device-worthy materials have contributed to remarkable progress in tailor-made materials and devices.
The uniquely strong interplay between theory, experiment, chemistry, materials science, and technology has
greatly contributed to the success of semiconductor-related fields.
The revolution in semiconductor science and technology did not happen by accident. It is based on a
thorough understanding of the diverse science and technology of these fascinating materials, coupled with

ix
x Preface

astonishing facilities for controlling the crystallographic structure and purity. Progress has called for research
by scientists and engineers from many disciplines, and the results of their efforts are documented in thousands
of archival articles, patents, and licensed technologies. Those new to the subject blanch at the thought of
assimilating even a small fraction of this immense knowledge base, and turn to the many specialist books that
attempt to summarize specific aspects of the field. To date, there is no comprehensive work that covers the
complete spectrum from fundamental semiconductor physics to design and manufacture devices which the
physics predicted to be possible, and which are now actually fabricated by materials scientists. In this sense, a
comprehensive work is different from an encyclopedia and a handbook. Comprehensive Semiconductor Science and
Technology consists of much longer chapters, which contain extensive cross-references to other relevant
information within the work and references to the vast available literature beyond the work. Each chapter
may be partly tutorial so that graduate students can greatly benefit from its reading.
This comprehensive comprises six volumes, and has been broadly divided into three main sections:
Section 1: Physics/Fundamental Theory – Edited by Hiroshi Kamimura
Section 2: Chemistry/Preparation – Edited by Roberto Fornari
Section 3: Devices/Application – Edited by Pallab Bhattacharya
Each of these complementary sections will provide a complete description of one aspect of the whole, and
will fuse together to give a comprehensive picture of the semiconductor world. The first section, which covers
Volumes 1 and 2, is concerned with the fundamental physics of semiconductors, showing how the electronic
properties and lattice dynamics change drastically when systems vary from bulk to a low-dimensional structure
and further to an interface and to a nanometer size such as quantum dots. The section describes all the
important characteristics of transport and optical properties. Further, this section includes many new topics
such as spin effects, carbon crystalline systems such as graphene and nanotubes, ultrafast coherent optical
phenomena, quantum information processing, etc., since the field of semiconductors continues to expand.
Throughout Volumes 1 and 2, there is an emphasis on the full understanding of the underlying physics.
Section 2, which covers Volumes 3 and 4, generally deals with technology of semiconductors. This includes
a description of the main methods employed for the preparation of bulk single crystals and thin layers. It is
shown that large single crystals may be conveniently grown from their melt, from solutions, or from the vapor
phase, and that the thermodynamical properties of the semiconductors to be grown actually decide about the
most appropriate method. The reader will also find some specific examples in the chapters devoted to bulk
growth of silicon, wide-bandgap compounds, II–VI and III–V semiconducting compounds. In addition, Section
2 also contains reviews on thin film technology, in particular MBE and MOVPE. In particular, how a basic
technology can be suited to preparation of semiconducting layers with tailored properties is discussed.
Examples of advanced low-dimensional heterostructures and nanostructures are provided along with a specific
chapter on integration of dissimilar materials. Additional chapters highlight the development of technologies
for deposition of high-quality ferroelectric and high-K materials to be applied as memories and gate isolators,
respectively. In addition to growth technology, Volumes 3 and 4 also include contributions regarding proces-
sing and characterization of semiconductors. The reader will find valuable information about the formation of
shallow junctions in semiconductors, the fabrication of ohmic and Schottky contacts as well as several chapters
describing the sophisticated methods used nowadays for investigating the physical and structural characteristics
of substrates, films, and quantum structures.
Volumes 5 and 6, which correspond to Section 3, contain chapters on the physics, technology and
application of devices, and circuits realized with diverse materials and heterostructure systems. The materials
include Si/SiGe, GaAs-, and InP-based heterostructures, antimonides, GaN-, ZnO-, and SiC-based materials,
graphene, HgCdTe, and materials for molecular electronics. Also included are carbon nanotubes and nano-
structured materials for flexible and stretchable electronics. The chapters describe in detail the properties of
high-speed, high-frequency, and high-power bipolar and field-effect transistors made with a variety of
heterostructure systems, negative differential resistance devices, single electron transistors, and microelectro-
mechanical system (MEMS)-based sensors. Several chapters describe the principles and properties of a wide
variety of optoelectronic devices including photodetectors, solar cells, light emitting diodes, and lasers. Passive
 Preface xi

photonic devices such as waveguides and filters are also included. The operating wavelength of these devices
ranges from very short (ultraviolet) to very long (terahertz). The active region of some of these devices includes
low-dimensional quantum-confined heterostructures such as quantum wells and quantum dots. Concepts such
as the manipulation of slow and fast light and disordering of quantum structures for optoelectronic device
integration are described in detail in a couple of chapters. The use of photonic crystals and microcavities in
optical devices is elucidated. Electronics with molecules is included with a good description of the underlying
physics. Finally, the physics, fabrication, and characteristics of spin-based electronic and optoelectronic devices,
more commonly known as semiconductor spintronic devices, are described in a few chapters. Each chapter and
topic is uniquely distinct, complete with the appropriate background material and references.

Pallab Bhattacharya, Roberto Fornari, and Hiroshi Kamimura

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Editors in Chief

Pallab Bhattacharya is the Charles M. Vest Distinguished University Professor

of Electrical Engineering and Computer Science and the James R. Mellor
Professor of Engineering in the Department of Electrical Engineering and
Computer Science at the University of Michigan, Ann Arbor. He received
the M. Eng. and Ph.D. degrees from the University of Sheffield, UK, in 1976
and 1978, respectively. Professor Bhattacharya was an Editor of the IEEE
Transactions on Electron Devices and is Editor-in-Chief of Journal of Physics
D. He has edited Properties of Lattice-Matched and Strained InGaAs
(UK: INSPEC, 1993) and Properties of III-V Quantum Wells and Superlattices
(UK: INSPEC, 1996). He has also authored the textbook Semiconductor
Optoelectronic Devices (Prentice Hall, 2nd edition). His teaching and research
interests are in the areas of compound semiconductors, low-dimensional quan-
tum confined systems, nanophotonics and optoelectronic integrated circuits.
He is currently working on highspeed quantum dot lasers, quantum dot infrared
photodetectors, photonic crystal quantum dot devices, and spin-based hetero-
structure devices. From 1978 to 1983, he was on the faculty of Oregon State
University, Corvallis, and since 1984 he has been with the University of
Michigan. He was an Invited Professor at the Ecole Polytechnic Federale de
Lausanne, Switzerland, from 1981 to 1982.
Professor Bhattacharya is a member of the National Academy of Engineering.
He has received the John Simon Guggenheim Fellowship, the IEEE (EDS) Paul
Rappaport Award, the Heinrich Welker Prize, the IEEE (LEOS) Engineering
Achievement Award, the Optical Society of America (OSA) Nick Holonyak
Award, the SPIE Technical Achievement Award, the Quantum Devices Award
of the International Symposium on Compound Semiconductors, and the IEEE
(Nanotechnology Council) Nanotechnology Pioneer Award. He has also
received the S.S. Attwood Award, the Kennedy Family Research Excellence
Award, and the Distinguished Faculty Achievement Award from the
University of Michigan. He is a Fellow of the IEEE, the American Physical
Society, the Institute of Physics (UK), and the Optical Society of America.

xiii
xiv Editors in Chief

Roberto Fornari studied Solid State Physics at the University of Parma, Italy.
He is presently director of the Leibniz Institute for Crystal Growth (IKZ) in
Berlin and holds the Chair of Crystal Growth at the Physics Dept. of the
Humboldt University Berlin (joint appointment). Before moving to Germany
in 2003, he worked over twenty years as a research scientist at the Institute for
Electronic and Magnetic Materials (MASPEC, later IMEM) of the Italian CNR
where he led different research projects on growth and thermal processing of
bulk III-V semiconductors, HVPE and MOVPE of Nitrides, characterization of
semiconductors by electrical and optical techniques. He has authored/co-
authored about 180 scientific papers, eight patents and different book chapters.
He has edited books and proceedings on crystal growth and semiconductors
physics and was subject editor of the Encyclopedia of Materials published by
Pergamon Press in 2001. He is presently a member of the editorial board of
the Journal of Crystal Growth, the Crystal Research and Technology, and the Journal of
Optoelectronics and Advanced Materials.
He has been Chairman of the IUCr Commission for Crystal Growth and
Characterization of Materials from 1999 to 2005 and then member till 2008.
From 2001 to 2007 he served on the Executive Committee of the International
Organization for Crystal Growth and is currently President of this organization.

Hiroshi Kamimura is currently a Senior Advisor to the Tokyo University of

Science (TUS), and a guest professor of the Research Institute for Science and
Technology at the TUS. He was awarded a Doctor of Science in Physics from the
University of Tokyo in 1959. He worked at Bell-Telephone laboratories at Murray
Hill, USA as a Member of Technical Staff from 1961 to 1964. In 1965 he became a
lecturer, then an associate professor and a professor at the Department of Physics,
Faculty of Science in the University of Tokyo. Between 1974 and 1975 he worked
with Sir Nevill Mott as a guest scholar at Cavendish Laboratory in Cambridge, UK.
In 1991 he retired from the University of Tokyo, and became a professor at the
Department of Applied Physics, Faculty of Science at the TUS. His interests are in
the theory of condensed matter physics and of materials science, in particular
semiconductor physics, high temperature superconductivity and superionic
conduction. He was President of the Physical Society of Japan between 1984 and
1985, and Chairman of IUPAP Semiconductor Commission between 1985 and
1990. He is an honorary fellow of the Institute of Physics, UK, a life-fellow of the
American Physical Society, an emeritus professor of the University of the Tokyo
and an emeritus professor of the Tokyo University of Science.
Contents of All Volumes
Volume 1

Physics and Fundamental Theory

Edited by Professor Hiroshi Kamimura, Research Institute for Science and Technology, Tokyo University of Science,
Tokyo, Japan
1.01 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories
1.02 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors:
Bulk Crystals to Nanostructures
1.03 Impurity Bands in Group-IV Semiconductors
1.04 Atomic Structures and Electronic Properties of Semiconductor Interfaces
1.05 Integer Quantum Hall Effect
1.06 Fractional Quantum Hall Effect and Composite Fermions
1.07 Spin Hall Effect
1.08 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
1.09 Thermal Conductivity and Thermoelectric Power of Semiconductors
1.10 Electronic States and Transport Properties of Carbon Crystalline: Graphene, Nanotube,
and Graphite
1.11 Angle-Resolved Photoemission Spectroscopy of Graphene, Graphite, and Related Compounds
1.12 Theory of Superconductivity in Graphite Intercalation Compounds

Volume 2

Physics and Fundamental Theory

Edited by Professor Hiroshi Kamimura, Research Institute for Science and Technology, Tokyo University of Science,
Tokyo, Japan
2.01 Electronic States and Transport in Quantum-Dots
2.02 Control Over Single Electron Spins in Quantum-Dots
2.03 Contact Hyperfine Interactions in Semiconductor Heterostructures
2.04 Semimagnetic Semiconductors
2.05 Optical Properties of Semiconductors
2.06 Light Emission from Silicon Nanoparticles and Related Materials
2.07 High-Density Excitons in Semiconductors
2.08 Magneto-Spectroscopy of Semiconductors
2.09 Bloch Oscillations and Ultrafast Coherent Optical Phenomena
2.10 Optically Controlled Semiconductor Spin Qubits and Indistinguishable Single Photons for Quantum
Information Processing

xv
xvi Contents of All Volumes

Volume 3

Materials, Preparation, and Properties

Edited by Dr Roberto Fornari, Leibniz Institute for Crystal Growth, Berlin, Germany and Institute of Physics,
Humboldt University, Berlin, Germany
3.01 Bulk Crystal Growth of Semiconductors: An Overview
3.02 Bulk Growth of Crystals of III–V Compound Semiconductors
3.03 Fundamentals and Engineering of the Czochralski Growth of Semiconductor
Silicon Crystals
3.04 Growth of Cd0.9Zn0.1Te Bulk Crystals
3.05 Sublimation Epitaxial Growth of Hexagonal and Cubic SiC
3.06 Growth of Bulk GaN Crystals
3.07 Growth of Bulk AlN Crystals
3.08 Growth of Bulk ZnO
3.09 Organometallic Vapor Phase Epitaxial Growth of Group III Nitrides
3.10 ZnO Epitaxial Growth
3.11 Nanostructures of Metal Oxides
3.12 Molecular Beam Epitaxy: An Overview
3.13 Growth of Low-Dimensional Semiconductors Structures

Volume 4

Materials, Preparation, and Properties

Edited by Dr Roberto Fornari, Leibniz Institute for Crystal Growth, Berlin, Germany and Institute of Physics,
Humboldt University, Berlin, Germany
4.01 Integration of Dissimilar Materials
4.02 Ion Implantation in Group III Nitrides
4.03 Contacts to Wide-Band-Gap Semiconductors
4.04 Formation of Ultra-Shallow Junctions
4.05 New High-K Materials for CMOS Applications
4.06 Ferroelectric Thin Layers
4.07 Amorphous and Glassy Semiconducting Chalcogenides
4.08 Scanning Tunneling Microscopy and Spectroscopy of Semiconductor Materials
4.09 Atomic Resolution Characterization of Semiconductor Materials by Aberration-Corrected
Transmission Electron Microscopy
4.10 Assessment of Semiconductors by Scanning Electron Microscopy Techniques
4.11 Characterization of Semiconductors by X-Ray Diffraction and Topography
4.12 Electronic Energy Levels in Group-III Nitrides
4.13 Organic Semiconductors

Volume 5

Devices and Applications

Edited by Professor Pallab Bhattacharya, Department of Electrical Engineering and Computer Science, University of
Michigan, Ann Arbor, MI, USA
5.01 SiGe/Si Heterojunction Bipolar Transistors and Circuits
5.02 Silicon MOSFETs for ULSI: Scaling CMOS to Nanoscale
5.03 GaAs- and InP-Based High-Electron-Mobility Transistors
5.04 High-Speed InP-Based Heterojunction Bipolar Transistors
5.05 Negative Differential Resistance Devices and Circuits
5.06 GaN-Based Transistors for High-Frequency Applications
5.07 GaN- and SiC-Based Power Devices
 Contents of All Volumes xvii

5.08 Silicon Single Electron Transistors Operating at Room Temperature and Their Applications
5.09 Electronics with Molecules
5.10 Electronic and Optoelectronic Properties and Applications of Carbon Nanotubes
5.11 Micro- and Nanostructured Semiconductor Materials for Flexible and Stretchable Electronics
5.12 MEMS-Based Sensors
5.13 III–V Compound Avalanche Photodiodes
5.14 Disordering of Quantum Structures for Optoelectronic Device Integration
5.15 Quantum-Well Lasers and Their Applications
5.16 Quantum Cascade Lasers
5.17 Slow and Fast Light in Quantum-Well and Quantum-Dot Semiconductor
Optical Amplifiers

Volume 6

Devices and Applications

Edited by Professor Pallab Bhattacharya, Department of Electrical Engineering and Computer Science,
University of Michigan, Ann Arbor, MI, USA
6.01 III-Nitride-Based Short-Wavelength Ultraviolet Light Sources
6.02 Nitride-Based LEDs and Superluminescent LEDs
6.03 Electronic and Optoelectronic Devices Based on Semiconducting Zinc Oxide
6.04 Molecular Beam Epitaxy of HgCdTe Materials and Detectors
6.05 Quantum-Well Infrared Photodetectors and Arrays
6.06 InAs/(In)GaSb Type II Strained Layer Superlattice Detectors
6.07 Terahertz Detection Devices
6.08 Amorphous and Nanocrystalline Silicon Solar Cells and Modules
6.09 Quantum-Dot Lasers: Physics and Applications
6.10 High-Performance Quantum-Dot Lasers
6.11 Quantum-Dot Infrared Photodetectors
6.12 Photonic Crystal Microcavity Light Sources
6.13 Photonic Crystal Waveguides and Filters
6.14 Spintronic Devices Based on Semiconductors
6.15 Spin-Based Semiconductor Heterostructure Devices
6.16 Spin-Polarized Transport and Spintronic Devices
Index
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 1.01 Electrons in Semiconductors: Empirical and ab initio
Pseudopotential Theories
J R Chelikowsky, University of Texas, Austin, TX, USA
ª 2011 Elsevier B.V. All rights reserved.

1.01.1 Introduction 1
1.01.1.1 Early History 1
1.01.1.2 The Phillips–Kleinman Cancellation Theorem 3
1.01.2 Defining Pseudopotentials 4
1.01.2.1 Model Potentials 4
1.01.3 Solving the Electronic Structure Problem 6
1.01.4 The Empirical Pseudopotential Method 6
1.01.4.1 Optical Properties of Semiconductors 6
1.01.4.2 The Structure and Form Factors of Semiconductors 8
1.01.4.3 The Role of Nonlocality in Pseudopotentials 10
1.01.4.4 The EPM Applied to Diamond Structure Semiconductors 11
1.01.4.4.1 The electronic structure of silicon 11
1.01.4.4.2 The electronic structure of germanium, gallium arsenide, and zinc selenide 15
1.01.5 The Ab Initio Pseudopotential Method 26
1.01.5.1 Constructing Pseudopotentials from Density Functional Theory 28
1.01.5.2 Structural Properties of Semiconductor Crystals 31
1.01.5.2.1 Total electronic energy from pseudopotential–density functional theory 31
1.01.5.2.2 Phase stability of crystals 32
1.01.5.2.3 Vibrational properties 34
1.01.6 Summary and Conclusions 37
References 39

1.01.1 Introduction system of interest did not seem so outlandish. One

1.01.1.1 Early History
A long-sought goal of materials physics is to predict
the properties of materials solely from a knowledge
of the atomic constituents. Before the turn of the
twentieth century, such a goal was not in the realm
of possibility. Quantum mechanics had not been
invented, much less applied to materials. Moreover,
as the rudimentary quantum theory evolved, for
example, the Bohr theory of the hydrogen atom, the
arguments of the time were often focused on the
structure of an individual atom and did not dream
of addressing problems of materials. However, as
quantum mechanics became accepted for atoms,
interest in applying quantum theory to materials
grew.
Indeed, once the predictive power of quantum
mechanics for atoms and simple molecules became
clear, the notion of predicting materials properties by
solving the quantum mechanical behavior of the
of the first visionaries was Dirac (1929). In a very
famous quote circa 1930 he stated:
The underlying physical laws necessary for the
mathematical theory of a large part of physics and
the whole of chemistry are thus completely known,
and the difficulty is only that the exact application of
these laws leads to equations much too complicated
to be soluble. It therefore becomes desirable that
approximate practical methods of applying quantum
mechanics should be developed, which can lead to
an explanation of the main features of complex
atomic systems without too much computation.
The implication of this statement was clear. A
solution of the quantum mechanical problem would
yield the ‘whole of chemistry.’ One could predict
properties of the chemical bond and the correspond-
ing materials properties of matter without resort to
laboratory work. Chemistry and materials properties
could be predicted by calculations. Of course,

1
2 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories
‘knowing’ and ‘doing’ are two different issues. The
equations in question were much too complicated to
be solved when Dirac made this statement. In fact,
they are much too complicated to be solved today,
even with state-of-the-art computational platforms.
As Dirac anticipated, the key to progress in this
area is to develop ‘approximate practical methods’.
Today, we have a number of such practical meth-
ods that allow us to access some properties in a
manner Dirac suggested. The first successes
appeared some 30 or 40 years after Dirac’s state-
ment and were led by the development of the
pseudopotential concept. The pseudopotential
model of a solid provided a practical model to
address the quantum mechanical problem and
advances in computers provided the means to over-
come the numerical hurdles.
A key attribute of a pseudopotential is that it
allows us to address directly the electronically or
chemically active valence states of an atom and
remove from consideration the electronically inert
core states. This decomposition between active and
inactive states is readily done for most atoms, for
example, in a silicon atom the 1s22s22p6 core states
are tightly bound compared to the 3s23p2 valence
states. In Figure 1, we illustrate the pseudopotential
model for a crystalline solid. In this case, the core
Nucleus
Core electrons
Valence electrons
Figure 1 Pseudopotential concept of a solid. The ion
cores consisting of the core electrons and valence electrons
are inert. The chemically active valence electrons move
within this array of ion cores.
electrons and nucleus of an atom are treated as an
inert ion core; the valence electrons are treated as an
electron sea moving against the periodic background
of the ion cores. This pseudopotential picture sets a
length and energy scale to the problem that is deter-
mined by only the valence states. A profound
consequence of this length and energy scale is that
all atoms of the periodic table can be treated on an
equal footing. Consider the situation without the
pseudopotential approximation; in this case, an
atom of hydrogen and an atom of cesium would
require all the electronic states to be placed on an
equal footing. The energy and length scales between
the core and valance states would be different by
orders of magnitude and would enormously compli-
cate the problem.
The pseudopotential idea is not new. Several key
elements were recognized after the advent of quan-
tum mechanics. Both Enrico Fermi and Hans
Hellmann contributed seminal papers in the mid-
1930s (Fermi, 1934; Hellman, 1935). Interestingly,
they recognized somewhat different, but important
elements of pseudopotential theory. Fermi’s focus
was on determining the phase shift in wave functions
of high-lying alkali atoms subject to perturbations
from foreign atoms. He correctly recognized that if
one were interested in the long-range behavior of the
wave function, it was not necessary to get the details
correct near the nucleus. It should be possible to
replace the true potential near the nucleus with a
simple potential, or pseudopotential, that yields a
similar value for the long-range part. Fermi also
established the importance of a scattering length
within this paper.
Hellmann’s work is probably closer to our con-
temporary picture (Schwarz et al., 1999a, 1999b).
Hellmann recognized that the valence orbitals for
many-electron atoms contained pronounced oscilla-
tions in the region where the atomic core electrons
remain. Determining an accurate description of the
oscillatory behavior near the core and the long-range
behavior in the chemically relevant region would
render the problem computationally complex.
Hellmann also recognized these core electrons did
not play an important role in determining the che-
mical bond; after all this was clear from the periodic
table. Elements such as Si and Ge have different ion-
core configurations, but the valence electron config-
uration is the same, and their chemical properties are
similar.
In today’s language, we would argue that the
valence electrons experience an additional kinetic
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 3
V (r )
~½ Bond length
r 2m
Core region
Ion potential
Figure 2 Schematic of an ion-core pseudopotential. The
all-electron potential and the pseudopotential ion-core
potential are similar outside of the core region.
energy contribution in the core region because of the
orthogonality requirement, that is, the valence state
of an atom is orthogonal to a core state by nodal
structure in the core region. In this 1935 paper,
Hellmann proposed that this kinetic energy term
could be quantified using the Thomas–Fermi expres-
sion for the kinetic energy of a free electron gas,
which depends only on the electron density. When
this term was added to the attractive Coulomb part of
the valence electron interacting with the ion core, he
argued that the resulting potential was ‘weak and
constant’. An example of a pseudopotential similar
to those Hellmann suggested is schematically illu-
strated in Figure 2.
1.01.1.2 The Phillips–Kleinman
Cancellation Theorem
While the work of Hellmann and Fermi established
the elementary ideas associated with pseudopoten-
tials, a rigorous transformation of an all-electron
potential to a pseudopotential was lacking. One of
the earliest such transformation is based on the ideas
of Phillips and Kleinman (Kleinman and Phillips,
1960a, 1960b; Phillips and Kleinman, 1959; Phillips
and Kleinman, 1962). Although their conclusions are
more far reaching, we will focus on solving the elec-
tronic structure problem for an isolated atom. We
will make the one-electron approximation, that is,
the Schrödinger equation for the atomic orbitals can
be written as
 
– h2 r2
H n ðrÞ ¼ þ V ðrÞ n ðrÞ ¼ En n ðrÞ ð1Þ
where m is the electron mass, h is Planck’s constant
divided by 2, V is all-electron potential, and (En,
n) are the eigen pairs: the energy levels and corre-
sponding wave function. Here, we assume both core
and valence states exist, that is, at this point we do
not consider an element such as H that has no core
states. We express the wave function for the valence
state, v, as
X
v ðrÞ ¼ pv ðrÞ þ av;c c ðrÞ ð2Þ
c
The sum is over the core states, c, and pv represents
the pseudopotential wave function. This form of the
wave function recognizes that near the nucleus the
valence wave function should appear atomic like and
contain elements similar to the core states. Away
from the nucleus, the core states will have little
amplitude and we expect: v ðrÞ  pv ðrÞ:
Moreover, we expect pv(r) to be smoothly varying
over all space. Outside of the core, the potential will
vary slowly. Within the core, we expect its contribu-
tions will be small compared to the core-like
functions. To determine the admixture of the core
with the pseudo-wave-function, we demand the fol-
lowing condition:
Z
c ðrÞv ðrÞd3 r ¼ hc j v i ¼ 0 ð3Þ
where we use the ‘bra–ket’ notation. The valence
state must be orthogonal to the core state, owing to
the nature of the eigenvalue problem. The orthogon-
ality requirement yields
 
av;c ¼ – c j pv ð4Þ
This form of the wave function was first proposed by
Conyers Herring (Herring, 1940) in a different con-
text. He proposed describing electronic states in
crystals using orthogonalized plane waves. In this
model, the valence states in a solid were replicated
using plane waves that were orthgonalized to the
core levels.
If we apply the Hamiltonian in Equation (1) to the
valence wave function, we obtain
X 
H pv þ c j pv ðEv – Ec Þc ¼ Ev pv ð5Þ
c
4 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories

We have recognized that Hc ¼ Ecc. We can define where G are reciprocal lattice vectors. S(G) is a
a pseudopotential Hamiltonian, Hp, as structure factor given by
Hp ¼ H þ V R ð6Þ 1 X
SðGÞ ¼ expðiG ? tÞ ð11Þ
Na t
where we define a potential operator, V R, as
X where Na is the number of atoms in the basis. Va(G) is
VR¼ hc j . . .iðEv – Ec Þc ð7Þ
c
an atomic form factor given by
Z
The empty ‘ket’ given by j. . . > requires an operation 1
Va ðGÞ ¼ Va ðr ÞexpðiG?rÞd3 r ð12Þ
wherein the wave function is projected on c and the a
functional dependence now corresponds to c. If we Here a is the volume per atom and Va is the atomic
define a pseudopotential as Vp ¼ V þ V R , we have potential that we take to be spherically symmetric.
now transformed the one-electron Schrödinger equa- The structure factor contains information on the
tion to crystal structure and the form factors contain infor-
  mation on the electronic interactions. The reciprocal
– h2 r2
Hp pv ¼ þ Vp pv ¼ Ev pv ð8Þ lattice vectors are designed to have the property:
2m
exp(iG?R) ¼ 1 (Kittel, 2005). This insures that the
This description of the atom has a number of advan- potential is periodic:
tages. The repulsive part of the potential, V R, largely P
V ðr þ RÞ ¼ Va ðGÞSðGÞexpðiG?ðr þ RÞÞ
cancels the attractive part of the all-electron poten- G
tial in the core region. The pseudo-wave-function is P ð13Þ
¼ Va ðGÞSðGÞexpðiG?rÞ ¼ VðrÞ
smooth as the core oscillations have been removed G
and the eigen-value, Ev, is identical to the all-electron
While this plane-wave expansion of the potential
potential. While the wave function is now amenable to
reflects the translational symmetry, the expansion is
a simple basis, the pseudopotential within this
only helpful if the number of waves (or reciprocal
construction is more complex than the all-electron
lattice vectors) is manageable. This will not be the
potential. Although the potential is weak and only
case for the all-electron potential owing to the sin-
binds the valence state, this potential is energy depen-
gularity of the Coulomb potential at the nucleus. The
dent, state dependent and involves a nonlocal,
pseudopotential avoids this issue by removing this
non-Hermitian operator. As such, the Phillips–
singularity. What remains is to define a procedure to
Kleinman potential is rarely, if ever, used for calculat-
construct the potential.
ing pseudopotentials. However, the cancellation
theorem is useful in demonstrating the essential
features of a pseudopotential.
1.01.2.1 Model Potentials
A realistic and powerful approach to find the required
form factors is based on experiment. For example, sup-
1.01.2 Defining Pseudopotentials pose we consider a potential similar to what Hellmann
proposed. Let us consider the following model, which
One could attempt to form a potential for an ele- only involves one parameter; the core radius, rc:
mental crystal by writing (
X 0 r  rc
V ðrÞ ¼ Va ðr – R – tÞ ð9Þ Vcp ðr Þ ¼ 2
ð14Þ
R;t – Zv e =r r > rc

where R is a lattice vector, t a basis vector, and Va a

potential that we associate with the atom. For a This defines a potential where the cancellation
crystal, we can explicitly incorporate the periodicity occurs within the ion core (r < rc). Zv is the valence
of the crystal by expressing the potential in a Fourier charge of the ion core. This is an ion-core pseudo-
series in three dimensions. We write potential. It represents the interaction of the valence
electron with the ion core (the nucleus plus core
X
V ðrÞ ¼ Va ðGÞSðGÞexpðiG?rÞ ð10Þ electrons) sans the role of any valence–valence
G electron interactions.
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 5
The next step in defining the atomic form factor is
to employ Equation (12):
– 4Zv e 2
Vcp ðGÞ ¼ cosðGrc Þ
a G 2
The long-range nature of the coulomb tail requires
special handling in executing this integral (Kittel,
2005). The form factor ‘rings’, that is, the form factor
oscillates as a cosine function owing to the disconti-
nuity in the potential at rc. What remains is to screen
the ion-core pseudopotential by including a dielec-
tric screening function that replicates the role of the
valence electron–electron interactions. Often
Thomas–Fermi screening is used for this purpose
(Kittel, 2005):
Vcp ðGÞ
Vcp ðGÞ ¼
TF ðGÞ
Thomas–Fermi screening is given by
Ks2
TF ðqÞ ¼ 1 þ
q2
where 1/Ks is the Thomas–Fermi screening length:
Ks2 ¼ 6ne 2 =EF , where n is the valence electron den-
sity (n ¼ Zv/a) and EF is the Fermi energy. The
atomic form factor is now given by
– 4e 2 n
Vap ðGÞ ¼ cosðGrc Þ
G 2 þ Ks2
A common practice is to set the potential to zero
outside of the second node to remove the oscillatory
or ringing behavior of the cos(Grc) term. An
V(q)
V(r) ~ ∫V(q) eiqr dq
~ (½ BOND LENGTH)–1
– 2/3 EF
Screened ion limit
for metals
Figure 3 Model of an atomic pseudopotential. The required form factors can be extracted from this model. Note the limiting
case of G ¼ 0 for a metallic system.
interesting consequence of Thomas–Fermi screening
is that the potential now has a well-defined value
when G ¼ 0:
– 4e 2 n 2
ð15Þ Vap ð0Þ ¼ ¼ – EF ð19Þ
Ks2 3
The G ¼ 0 term corresponds to setting a reference
energy for the solid as it corresponds to the average
of the potential. This limiting case from Thomas–
Fermi screening is not a very good approximation
for a semiconductor such as silicon and is more
appropriate for a metal. We illustrate a schematic
pseudopotential in Figure 3.
The Phillips–Kleinman cancellation theorem
yields a state-dependent pseudopotential; the poten-
tial depends on the nature of the core states. For
example, in carbon there is no 1p core state and the
valence 2p is not required to be orthogonal to the
ð16Þ
core. This is not true for silicon, in which both s and p
states exist in the core; both the s and p valence states
see a repulsive term. Historically, this difference has
been used to explain why silicon and carbon chem-
ð17Þ
istry are different. The previous model potential can
be modified to reflect the state dependence:
(
Al r  rc;l
p
Vc;l ðr Þ ¼ ð20Þ
2
– Zv e =r r > rc;l
This potential is not a simple function of position, but
ð18Þ rather acts on the l-component present in the wave
function (Cohen and Chelikowsky, 1982, 1989;
Chelikowsky and Cohen, 1992). This can be accom-
plished by using a projection operator as will be
discussed later. Setting this technical issue aside,
q
V(q = G) for typical G’s
6 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories

(
there are now additional parameters to be deter- X  h2 2

mined as the well depth and size must be ðk þ GÞ – En ðkÞ GG9
2m
established for each l-component.
G9 )
ð23Þ
A common procedure in the early days of pseu- þVap ðG9 – GÞS ðG9 – GÞ n ðk; G9Þ ¼ 0
dopotential involved fitting the well depths and sizes
(Al, rc,l) to replicate optical data of ionized atoms. For This corresponds to a set of linear equations, one for
example, to construct an ion-core pseudopotential each G vector in the set. For a nontrivial solution, we
for an Al atom, one needs to consider the optical require the following:
excitations for an Alþ2 ion. In some cases, this is 
relatively easy, for example, treating the Na atom  h2 
  2
does not involve an ionized atom. However, an O det ðk þ GÞ – En ðkÞ GG9
 2m
atom would require examining a C5+ ion. 

ð24Þ
Experimentally, it is a difficult task to multiply ionize p 
þ Va ðG9 – GÞS ðG9 – GÞ ¼ 0
such an atom and measure the atomic levels. Often 
the potentials were estimated by extrapolation from
lighter atoms to heavier ones. Another issue concerns The diagonal elements of this determinant contain
improved dielectric functions for screening the the kinetic energy contribution; the off-diagonal
potentials. Both issues were the subject of a number elements contain the form factors for the pseudopo-
of studies, but without a definitive resolution. By the tential and the structure factor. In this example, we
mid-1960s, an inventory of such model potentials consider only elemental crystals so that the form
existed (Animalu and Heine, 1965; Cohen and factors can be separated out from the structure factor.
Heine, 1970) with some success, especially for metals. This eigenvalue problem is a standard mathematical
problem, and is easily handled, save for highly complex
systems. Typically, for common semiconductors a few
hundred plane waves are required to obtain a con-
1.01.3 Solving the Electronic verged result. This operation can often be performed
Structure Problem on a laptop computer for crystalline semiconductors.

If we are given the crystalline potential, we can solve,

the corresponding eigenvalue problem (Equation (1))
1.01.4 The Empirical
using a variety of approaches. Since the pseudopo-
Pseudopotential Method
tential is weak compared to the all-electron potential,
we can write the wave function in terms of a plane
One of the most significant scientific advances of the
wave basis:
twentieth century was the development of the empiri-
X
n;k ðrÞ ¼ n ðk; GÞexpðiðk þ GÞ?r Þ ð21Þ cal pseudopotential method (EPM). The intuitive
G picture of Fermi and Hellmann was greatly advanced
by Phillips and Kleinman; however, a practical
where n is a band index and k is the wavevector. The
method of predicting accurate energy band structures
sum is over all reciprocal lattice vectors, {G}, but, in
was not achieved until the EPM. This method, devel-
principle, the sum is truncated for jk þ Gj > Gmax .
oped in the late 1960s, was based on fixing an energy
This form of the wave function is consistent with the
band so that an accurate response function, as mea-
Bloch form of the wave function for a periodic poten-
sured, was reproduced. To accomplish this feat, one
tial. The Bloch form of the wave function allows one
had to develop a framework of translating an energy
to express the corresponding periodicity of the wave
band solution to a response function.
function, save a phase factor determined by the
wavevector:
1.01.4.1 Optical Properties of
n;k ðr þ RÞ ¼ expðiðk?RÞexp n;k ðrÞ ð22Þ
Semiconductors
Inserting the crystalline potential (Equation (10)) The optical properties of a semiconductor can be
and the plane wave basis (Equation (21)) in the characterized by an understanding of response func-
one-electron Schrödinger equation yields the tions such as the complex index of refraction,
following: N(!) ¼ n(!) þ ik(!), or the complex dielectric
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 7

function, "(!) ¼ "1(!) þ i"2(!) (Cohen and jMvc ðkÞj2 ¼ jhuv ðkÞjrjuc ðkÞij2 ð31Þ
Chelikowsky, 1989). They are related to each other as
The functions, un(k), are the periodic part of the
follows:
Bloch wave functions:
N 2 ¼ "1 þ i"2
X
"1 ¼ n2 – k2 ð25Þ un ðkÞ ¼ n ðk; GÞexpðiG?rÞ ð32Þ
G
"2 ¼ 2nk
where n is the band index. The periodic part obeys
The normal incident reflectivity of a semiconductor un ðk; r þ RÞ ¼ un ðk; rÞ. Implicit in this expression is
is given by the response functions: the existence of a bandgap that delineates the
  valence and conduction bands. This form also
 N – 1 2 ðn – 1Þ2 þ k2

R¼ ¼ ð26Þ assumes cubic symmetry. The physical content of
N þ 1 ðn þ 1Þ2 þ k2
the dielectric function is clear. The delta function
Hence, a knowledge of the dielectric function, "(!), insures energy conservation and the dipole matrix
is sufficient to yield the complex index of refraction element accounts for symmetry, that is, we assume
and the reflectivity. In fact, only the real (or imagin- dipole transitions. Another implicit factor is that the
ary) part of the dielectric function is required owing transitions from filled bands to empty bands are
to the Kramers–Kronig relation: direct; the wavevector of the initial and final states
Z 1
are equal. This is appropriate for optical transitions
2 !9"2 ð!9Þ where the wavelength of light is orders of magni-
"1 ð!Þ ¼ 1 þ P d!9 ð27Þ
 0 !92 – !2 tude larger than the atomic length scale. Also, the
The principal part of the integral is required as is a Ehrenreich–Cohen form does not include excitonic-
knowledge of "2 over all frequencies, although, in (electron–hole) interactions, local field corrections, or
practice, this is not a stringent requirement. self-energy effects, which can be included (Rohlfing
There are useful sum rules that can be applied to and Louie, 2000) albeit at some considerable compu-
test the accuracy of response functions. One obvious tational cost. Moreover, the qualitative features of the
example is to use the ! ! 0 of the Kramers–Kronig optical spectra are correctly obtained from the
relationship: Ehenreich–Cohen expression.
Z 1
Once the imaginary part of the dielectric function
2 "2 ð!Þ
"1 ð0Þ ¼ 1 þ d! ð28Þ is known, it is straightforward using the Kramers–
 0 !
Kronig transform to find the real part of the dielectric
Another sum rule is function and the reflectivity, which can be directly
Z 1 compared to experiment. To implement the
 p
! ¼ !"2 ð!Þd! ð29Þ Ehenreich–Cohen expression, we need to know the
2 2 0
energy bands, En(k) and the corresponding wave
where !p is the plasma frequency given by functions n,k. This can be obtained once the pseu-
!p 2 ¼ 4ne 2 =m. dopotential is defined.
The connection between the macroscopic response Usually, the dipole matrix elements in Equation
function and the atomistic world can be made by a (31) are smoothly varying with k and can be assumed
computation of the imaginary part of the dielectric constant, except at high symmetry points. In this
function. A realistic, but somewhat simplified, expres- situation, it is useful to remove the matrix elements
sion comes from Ehrenreich and Cohen (EC59). The and isolate that part of "2(!) that produces the major
dielectric function involves transitions between the structure. The resulting function is called the ‘joint
valence band (v) to the conduction band (c): density of states’:
Z
4e 2 h X 2 2
"2 ð!Þ ¼ Jvc ð!Þ ¼ ½!vc ðkÞ – !d3 k ð33Þ
3m2 !2 v;c ð2Þ3 ð2Þ3 BZ
Z ð30Þ
 ð!vc ðkÞ – !ÞjMvc ðkÞj2 d3 k This integral can be recast as
BZ
Z
The integral is over all states in the Brillouin zone 2 ds
Jvc ð!Þ ¼ ð34Þ
where the dipole matrix element is given by ð2Þ3 !¼!vc jrk !vc ðkÞj
8 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories
where ds is a surface element in wavevector space
defined by ! ¼ !vc(k). This is similar to the density of
states, save here we replace the band energy by the
transition frequency between the valence and con-
duction bands. The structure in this joint density of
states occurs at critical points, just as in the density of
states (Cohen and Chelikowsky, 1989). These critical
points occur when
  
rk !vc kcp  ¼ 0
Physically, this occurs when the group velocity of the
hole in the valence band equals that of the electron in
the conduction band. Four topologically distinct cri-
tical points occur: M0, M1, M2, and M3, which
represent a local minimum, two saddle points, and a
local maximum. The structure associated with these
critical points is presented in Figure 4. Structure in
either the imaginary part of the dielectric function or
the density states can be identified with these critical
points (Cohen and Chelikowsky, 1989).
1.01.4.2 The Structure and Form Factors
of Semiconductors
This section focuses on cubic semiconductors that
occur in either the zinc–blende or diamond struc-
tures. These two structures are isostructural; they
have the same atomic arrangement, but the con-
stituent atoms can be different. Semiconductors
such as Si, Ge, GaAs, InSb, ZnSe, and CdTe
occur in these structures. Figure 5 illustrates the
diamond structure. The diamond structure has
cubic symmetry and can be conceptualized by
considering two interpenetrating face-centered
cubic crystals.
The lattice vectors for diamond are given by
Rn1 ;n2 ;n3 ¼ n1 â1 þ n2 â2 þ n3 â3
M1
J(ω)
M0
ω0 ω1
Figure 4 Structure associated with the four types of critical points.
where the lattice basis vectors are given by
â1 ¼ aðŷ þ ẑÞ=2; â2 ¼ aðx̂ þ ẑÞ=2; â3 ¼ aðx̂ þ ŷÞ=2
The diamond and zinc–blende crystals possess a pri-
mitive cell given by these vectors, with the cell
volume given by
c ¼ ja1 ?a2  a3 j ¼ a 3 =4 ð37Þ
There are two atoms in the basis located at
ð35Þ
t ¼ ð1;1;1Þa=8, so the atomic volume, a is given
by a3/8.
The reciprocal lattice vectors are given by
Gm1 ;m2 ;m3 ¼ m1 bˆ1 þ m2 bˆ2 þ m3 bˆ3 ð38Þ
where the reciprocal lattice basis vectors are given by
bˆ1 ¼ ð2=aÞð – x̂ þ ŷ þ ẑÞ=2; bˆ2 ¼ ð2=aÞðx̂ – ŷ þ ẑÞ=2
bˆ3 ¼ ð2=aÞðx̂ þ ŷ – ẑÞ=2
This set of vectors has the desired property that
G ? R is an integral multiple of 2. In some disci-
plines such as crystallography, the factor of 2 is
omitted from the definition of reciprocal lattice
vectors and G ? R is an integer.
For diamond, the structure factor is given by
SðGÞ ¼ cosðG ? tÞ ð39Þ
The structure factor for the zinc–blende crystal can-
not be separated from the potential terms. For a zinc–
blende crystal, A B , where A is the cation and B is the
anion, it is easy to show that the product of the form
factors and structure factor in Equations (23) and (24)
can be replaced by
ð36Þ VA ðGÞexpðiG?tÞ þ VB ðGÞexpð – iG?tÞ=2 ð40Þ
M2
M3
ω2 ω3
ω
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 9
a 3
Figure 5 Ball and stick model for the diamond crystal
structure. The inset shows the tetrahedral coordination. The
zinc–blende structure is isostructural, save the atomic
species alternate.
It is often convenient to introduce a symmetric form
factor, VS, and an antisymmetric form factor, VA, in
which case this term can be regrouped as
VS ðGÞcosðG?tÞ þ iVA ðGÞsinðG?tÞ ð41Þ
where
VS ðGÞ ¼ ðVA ðGÞ þ VB ðGÞÞ=2
VA ðGÞ ¼ ðVA ðGÞ – VB ðGÞÞ=2
In the case of the diamond structure the antisymmetric
form factor vanishes and the symmetric one corre-
sponds to the constituent element of the diamond
crystal. The form factor for the zinc–blende crystal is
complex because the zinc–blende structure lacks
inversion. The plane wave expansion is also complex,
but this does not complicate the calculations signifi-
cantly. The Hamiltonian remains hermitian.
There are two important consequences of this
formalism. First, owing to the crystal symmetry, the
structure factor can vanish for some reciprocal lattice
vectors, meaning that the form factor for this vector is
irrelevant. Second, the number of form factors
required can be quite small if the pseudopotential is
weak and converges quickly in reciprocal space. In
the case of the diamond crystal, this can be as few as
three distinct form factors. In Table 1, we summarize
the needed form factors and structure factors. The
form factors depend only on the magnitude of the
reciprocal vector and are often tabulated by the value
of G2  (a/2)2, that is, the form factors are listed for
G2  (a/2)2 ¼ 0, 3, 4, 8, . . . and are denoted by V(0),
V(3), V(4), V(8), . . . . The structure factors are
Table 1 Structure factors for diamond and zinc–blende
crystals
G2 cos(G?t) sin(G?t) Form factor
0 1 0 VS serves as a reference
energy
pffiffiffi pffiffiffi
1= 2 1= 2 VS, VA both required
4 0 1 VA required
8 1 0 VS required
pffiffiffi pffiffiffi
11 1= 2 1= 2 VS, VA both required
given by cos(G ? t) ¼ cos((n1m1 þ n2m2 þ n3m3)/4);
sin(G ? t) ¼ sin((n1m1 þ n2m2 þ n3m3)/4).
If we focus on the diamond structure only the
symmetric form factors (V(0), V(3), V(8), V(11), . . .)
are meaningful. V(0) represents the average potential
and appears only on the diagonal of the Hamiltonian
matrix. It will displace the energy bands uniformly and
is not important for spectroscopy. In the remainder of
this section, we will omit this term and focus on
spectroscopic issues. If the form factors rapidly con-
verge, it is possible to define the potential by only
three parameters corresponding to V(G2  11). Since
the form factors are not linearly independent, the
number of parameters are less than three. Moreover,
we can get a rough estimate for these form factors from
model potentials (Cohen and Heine, 1970). At a first
pass, it might appear that a total of six parameters are
needed for zinc–blende structures: VS(3), VA(3), VA(4),
VS(8), VS(11), and VA(11). However, we can constrain
the symmetric form factors in the following fashion.
Suppose we are given the form factors for Ge and wish
to find the form factor of GaAs. We can make the
following approximation:
VS ðGaAsÞ ¼ ðV ðGaÞ þ V ðAsÞÞ=2  V ðGeÞ
We express the symmetric form factors, the average
of the Ga and As form factors to be the same as the
Ge form factors. With this constraint, we need to fix
only three parameters (VA(3), VA(4), and VA(11)) to
obtain the GaAs potential.
The EPM method was highly successful in estab-
lishing realistic form factors and energy band
structures for a wide variety of materials. In
Figure 6, we illustrate a block diagram for the EPM.
Initially a set of form factors are chosen. The pseudo-
potential for the crystal and the Hamiltonian is
constructed from this set of form factors and the struc-
ture factor. The one-electron Schrödinger is then
solved and the band structure (En(k)) and wave func-
tions ( n,k(r)) are obtained. From the band structure
10 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories

EPM resulting form factors and the energy band structure

are deemed correct, at least within this framework.
v(G)
One of the first successful implementations of the
EPM was performed by Cohen and Bergstresser
(1965). They examined 14 semi-conductors in the
v(r) = Σ v(G) S(G) exp(i G . r)
G diamond and zinc–blende structures. The Cohen–
Bergstresser form factors were fit to band structure
features such as the fundamental gap. The resulting
H = P2 + V
form factors and lattice constants are given in
Hψ = Eψ Table 2. The overall agreement is quite good; the
Get E(k), and ψ k bandgaps were replicated to within 0.1–0.2 eV.
Other features agreed to within 0.5 eV over a
10 eV range.
Calculate R or R′/R and N(E)

Compare with experiment 1.01.4.3 The Role of Nonlocality in

Alter v (G)
Figure 6 Flow diagram for the empirical pseudopotential
method (EPM).
the imaginary part of the dielectric function can be
obtained and the corresponding reflectivity, which is
then compared to experiment. (It is also possible to
obtain the density of states and compare to the photo-
emission spectrum.) If the agreement between the
calculated and measured properties is not good, the
form factors can be altered and the calculations
repeated. When the agreement is satisfactory, the
Pseudopotentials
The Cohen–Bergstresser approach treats the
pseudopotential as a simple function and neglects
the role of the state dependence expected from
the Phillips–Kleinman cancellation theorem. This
is often the case for tetrahedral semiconductors,
AB, where the constituent elements are not tran-
sition metals (or rare earths) or from the first row
of the periodic table. However, important semi-
conductors such as GaN do contain elements
from the first row, and the state dependence or
angular momentum components need to be expli-
citly considered.
The nonlocal character of the ion-core pseudopo-
tential for an atom can be expressed as

Table 2 Pseudopotential form factors (Ry) and lattice constants for selected diamond and zinc–blende semiconductors

a(Å) VS(3) VS(8) VS(11) VA(3) VA(4) VA(11)

Si 5.43 0.21 0.04 0.08

Ge 5.66 0.23 0.01 0.06
Sn 6.49 0.20 0.0 0.05
GaP 5.44 0.22 0.03 0.07 0.12 0.07 0.02
GaAs 5.66 0.23 0.01 0.06 0.07 0.05 0.01
AlSb 6.13 0.21 0.02 0.06 0.06 0.04 0.02
lnP 5.86 0.23 0.02 0.06 0.07 0.05 0.01
GaSb 6.12 0.22 0.00 0.05 0.06 0.05 0.01
InAs 6.04 0.22 0.00 0.05 0.08 0.05 0.03
InSb 6.48 0.20 0.00 0.04 0.06 0.05 0.01
ZnS 5.41 0.22 0.03 0.07 0.24 0.14 0.04
ZnSe 5.65 0.23 0.01 0.06 0.18 0.12 0.03
ZnTe 6.07 0.22 0.00 0.05 0.13 0.10 0.01
CdTe 6.41 0.20 0.00 0.04 0.15 0.09 0.04

From Cohen ML and Bergstresser TK (1965) Band structures and pseudopotential form factors for fourteen semiconductors of the
diamond and zinc-blende structures. Physical Review 141: 789.
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 11

P
1
1989). Nonlocal components for tetrahedral semi-
P yl Vl;c ðr ÞP l ¼ P ys Vs;c
p
Vcp ðrÞ ¼ p
ðr ÞP s
l¼0 ð42Þ conductors are available in the literature
þP yp Vp;c ðr ÞP p þ P yd Vd ;c ðr ÞP d þ

p p (Chelikowsky and Cohen, 1976). The agreement

between experiment and nonlocal pseudopotential
P l is an operator that projects out the lth component. can be considerably better than for local pseudopo-
The ion core pseudopotential is semilocal. The poten- tentials, albeit more parameters are utilized, typically
tial is radially symmetric, but angular dependent. two per element.
For many semiconductors only the s, p and d
components of the wave functions are significant.
1.01.4.4 The EPM Applied to Diamond
This allows us to write
Structure Semiconductors
P s þP p þP d 1 ð43Þ Group IV elements, save Pb, can form in the
If two of the components are similar, it is often diamond structure (Figure 5). All elements of this
possible to select one component and subsume the group have a valence electron configuration of
other terms into a ‘local potential’. As a specific s2p2. When bonds are formed, we view this process
example, consider the case of GaAs. The energy as the promotion of an electron in the s-state to
band structure can be dramatically improved by con- the p-state to form sp3 hybrids. This explanation
sidering a local potential and altering it with a accounts for the nature of the diamond structure
potential that acts on only d waves: as sp3 hybrid orbitals form tetrahedral bonding
h i patterns. Moreover, the hybridization energy
p y p y
Vcp ðrÞ ¼ Vc;local ðr Þ þ P d Vd ðr Þ – Vc;local ðr Þ P d ð44Þ increases as one descends down the group IV col-
umn (Phillips, 1973). As such, we expect the
A plane wave expedites the use of angular projec- diamond structure to be less stable versus metallic
tions. It can be decomposed as follows: structures such as the face-centered cubic structure
X
1 of Pb, or the gray on structure for Sn. The general
expðiK?rÞ ¼ ð2l þ 1Þi l Pl ðcosðÞÞjl ðjK jr Þ ð45Þ increase in metallicity down the column is also
i¼0 rationalized by the lack of formation of sp3 hybrid
where Pl(x) are Legendre polynomials: P0 ¼ 1, P1 ¼ x, orbitals for the heavy elements.
P2 ¼ (3x2 1)/2,  is the angle between k and r and
j(x) are spherical Bessel functions: 1.01.4.4.1 The electronic structure
of silicon
sinðxÞ The band structure of silicon serves as the hydrogen
j0 ðxÞ ¼
x atom of solid-state physics. Virtually any new band
sinðxÞ cosðxÞ structure method is tested on crystalline silicon.
j1 ðxÞ ¼ –
x2 x There is general accord on the basic energy band


3 sinðxÞ 3cosðxÞ features of silicon, but this was not the case until the
j2 ðxÞ ¼ –1 –
x2 x x2 end of the 1970s. In Figure 7, we present the band
structure of silicon as calculated using two different
Using this decomposition allows one to write the pseudopotentials. One of the potentials contains non-
required matrix element for a nonlocal potential as local corrections and yields a slightly wider valence
D   E 4 band. The energy bands are plotted along directions
 p
k þ GVc;l k þ G9 ¼ ð2l þ 1ÞPl ðcoskþG;kþG9 Þ between high symmetry points in the Brillouin zone
a
Z 1 as indicated in Figure 8.
p
 dr r 2 Vc;l ðr Þjl ðjk þ Gjr Þjl ðjk þ G9jr Þ Silicon is different in a fundamental way from
0
other diamond or zinc–blende semiconductors. The
ð46Þ
ordering of the conduction bands of silicon is differ-
The off-diagonal matrix elements now depend on the ent from that of germanium or tin. In Si, the 15 band
wavevector, k. Typically, a model potential is used is lower than the 29 band. This difference was the
for the nonlocal component. For example, one might source of some controversy in the early days of
p
consider a Gaussian potential: Vc;l ¼ Al expð – ðr =rl Þ. energy band calculations. For example, some workers
In this case the matrix elements in Equation (46) can claimed that the first pseudopotential calculations
be evaluated analytically (Cohen and Chelikowsky, were in strong disagreement with less empirical
12 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories

6
L3 Γ2´
Γ2´
4
Γ15
Γ15
2
L1
X1 Γ25´
Γ25´
0
L3´

–2
Energy (eV)

X4
–4

–6
Si X1
L1
–8
L2´
–10

Γ Γ1
–12

L Λ Γ Δ X U,K Σ Γ
Wavevector, k
Figure 7 Band structure for silicon.

Another feature of the silicon band structure,

related to the lowest conduction band configuration,
L is the nearly parallel dispersion of the lowest con-
U duction band and the uppermost valence band.
Specifically, consider the dispersion along the A
X
direction. Grover and Handler (1974) proposed on
Γ the basis of their electroreflectance data that the
critical point at L is essentially two dimensional,
that is, the experimentally measured transverse
K band mass virtually vanishes. The value they
W obtained for m1 was approximately 0.02 m. The cor-
responding mass calculated by pseudopotential
methods is closer to 0. 1 m, but even this value results
Figure 8 Brillouin zone labeling high symmetry points.
in a nearly two-dimensional M0 critical point at the L
point (Cohen and Chelikowsky, 1989). Moreover, the
methods for determining energy bands and with the dispersion for the valence and conduction bands is
available experimental data (Kunz, 1971). However, such that the energy difference between these bands
optical measurements of silicon–germanium alloys is less than 0.01 eV over half the distance from L to .
strongly suggested that silicon and germanium were This valence–conduction band configuration
different (Kline et al., 1968). The issue was decided by favors excitonic behavior. It has been traditionally
the work of Aspnes and Studna (1972). They used suggested that the rather large discrepancies between
low-field electroreflectance to resolve transitions the theoretical and experimental optical constants in
from 25 to 29, and showed unequivocally that the this energy range arise from such an effect. To illus-
conduction band ordering is in complete agreement trate the point, we have displayed the measured and
with the pseudopotential predictions. calculated imaginary part of the dielectric constant in
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 13

Figure 9. The measured dielectric function is nearly
a factor of 2 larger near 3.4 eV than the calculated
value for the energy region in question. This discre-
pancy is also observed in the real part of the
dielectric function, which is displayed in Figure 10.
While the Ehrenreich–Cohen formalism
(Ehrenreich and Cohen, 1959) replicates the essential
features of the optical constants, it omits local fields
and electron–hole interactions. Local-field correc-
tions were addressed by Adler (1962) and Wiser
(1963). Local fields allow for the microscopic
Si
40
Experiment
With local-field corrections
Without local-field
30 corrections
ε2 (ω)
variation of the field within the unit cell.
Unfortunately, the corrections for local fields do little
to improve the dielectric function in this region as
indicated in Figure 9. The role of the electron–hole
interactions in semiconductors was addressed by a
number of groups. One of the first realistic attempts is
from Hanke and Sham (1974). They examined the
optical properties of diamond, including both local
fields and exchange interactions. More recent work
by Louie and collaborators (Hybertsen and Louie,
1986; Rohlfing and Louie, 1998, 2000) has unequi-
vocally demonstrated the role of excitonic
contributions to the optical response functions.
In Figure 11, we exhibit the calculated and mea-
sured reflectivity spectrum for silicon. As for most
solid-state spectra, the spectrum is not highly struc-
tured, and on first inspection appears to contain little
information. Such an assessment would be incorrect.
Details of the spectrum can be enhanced by numeri-
cally differentiating the spectrum. In Figure 12, we

present the calculated and measured logarithmic

20
derivative of the reflectivity spectrum. The deriva-
×3 tive spectrum does not exhibit the three broad peaks
of the undifferentiated spectrum but numerous sharp
spectral features. These features are classified
10
according to a standard nomenclature. The lowest
energy structural feature is denoted by E0 and corre-
sponds to structure from the smallest direct
0
0 2 4 6 8 10 12 transition. The next higher energy structural feature
Energy (eV)
is denoted by E1. This feature denotes structure asso-
Figure 9 Imaginary part of the dielectric function for Si ciated with the  direction. In the unique case of
with and without local fields. silicon, the E0 and the E1 structural features occur in

50
0.8
Si
40 Theory 0.7 Si
Experiment Theory
0.6 Experiment
30
0.5
20
R (E )
ε1 (E )

0.4

10 0.3

0 0.2

0.1
–10
0
0 1 2 3 4 5 6 7
–20 Energy (eV)
0 1 2 3 4 5 6 7
Energy (eV)
Figure 11 Measure and calculated normal incident
Figure 10 Real part of the dielectric function for Si. reflectivity for Si.
14 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories
+1.0
(a) E1 + E′0
+0.5
Si
–0.5
(eV–1)
–1.0
1 dR
R dE
(b)
+0.5
–0.5
–1.0
2 3
Energy (eV)
Figure 12 Measured and calculated normal incident modulated reflectivity for Si.
the same energy region, that is, the lowest energy
direct transitions at L and at  have nearly the same
energy. In fact, a good deal of work has been
peformed to determine precisely where in the
Brillouin zone this transition takes place.
Piezoelectric experiments (Gobeli and Kane, 1965),
chemical shifts in Ge–Si alloys (Tauc and Abraham,
1961), electroreflectance (Pollak and Cardona, 1968),
and some wavelength-modulation techniques (Koo
et al., 1971) have suggested that the first reflectivity
peak arises near the zone center, perhaps along the 
direction. However, other work (Grover and
Handler, 1974) suggested that this transition occurs
along the  direction. Unfortunately, the pseudopo-
tential work has not resolved this issue since the
reflectivity structure in question arises from contri-
butions near  and along both the  and 
directions. The dominant transition in the calcula-
tions appears to be along the  direction, but no firm
conclusion can be drawn. What is clear is that the
complexity of this structure does suggest a
E2 E1′
Experiment
Theory
4 5 6
multiplicity of critical points within this energy
region. This conclusion has been drawn by several
authors (Welkowsky and Braunstein, 1972). The E2
structure dominates the reflectivity spectrum and
occurs at about 4.5 eV. This structure arises from
large regions of the Brillouin zone.
While optical properties served as a centerpiece
for the first EPM calculations, photoemission mea-
surements provide information inaccessible to
interband transitions. In particular, photoemission
can provide the absolute position of bands relative
to the vacuum. The valence band density of states for
silicon calculated using pseudopotentials is com-
pared with experiment in Figure 13.
Under certain conditions, it is possible to compare
directly the theoretical density of states with photo-
emission measurements. The density of states, D(E),
for crystalline matter, can be defined as
Z
2 X
DðEÞ ¼ d3 kðE – En ðkÞÞ ð47Þ
ð2Þ3 n
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories
(a)
Experiment
XPS spectra (a.u)
Si
(b)
Theory
1.0
(states / eV-atom)
Density of states
0.5
0 The triad of semiconductors Ge, GaAs and ZnSe are
–14 –12 –10 –8 –6 –4 –2 0 2
Energy (eV)
Figure 13 Density of states for crystalline silicon. The top
panel is from X-ray photoemission spectroscopy (Ley et al.,
1972; Cavell et al., 1973).
where  is the cell volume. Typically, the density of
states, which is an extensive property, is normalized
in terms of states per atom. If matrix element effects
are ignored, the density of states can be extracted
from X-ray photoemission spectroscopy or ultraviolet
photoemission measurements. For the testing of
empirical pseudopotential band structures, the photo-
emission spectra have proven invaluable for the
determination of accurate potentials. Photoemission
measurements have indicated that the local pseudo-
potentials cannot provide band pictures where
both the valence and conduction bands are simulta-
neously reproduced accurately when compared to
experimental band pictures.
For diamond-structure semiconductors, the
valence band density of states may be divided into
three general regions as in Figure 13. Using the top
of the valence band as our zero of energy, the region
of 13 to 8 eV is predominantly of s-like character
stemming from the atomic 3s-states of Si. The region
from 8 to 4 eV is a transition region with con-
tributions from both s- and p-states. The region from
5 to 0 eV is predominantly p-like. The feature
which delineates these spectral regions is a sharp
reduction or ‘dip’ in the density of states compared
to the average density. The nonuniformity of the
density of states in contrast to simple metals arises
from hybridization among the atomic orbitals. Any
15
disruption of the crystalline bonding environment
will introduce states into the regions of reduced
state density. For example, in amorphous materials,
where there presumably exist bond angle and bond
length deviations from the ideal crystalline state,
these regions are strongly affected. The dip around
8 eV fills in, and the upper region of the density of
states tends to narrow and shift to higher energies.
For surface states or vacancy states where broken
bonds are clearly involved, the defect localized states
tend to fill in these regions, including the fundamen-
tal gap.
1.01.4.4.2 The electronic structure of
germanium, gallium arsenide, and zinc
selenide
4 6 special. They are isostructural with a bond length
that hardly changes among the three. As such, the
difference between the three can be attributed to
potential differences. In pseudopotential theory, the
symmetric form factors do not significantly change;
the antisymmetric form factors (the difference
between the cation and anion pseudopotentials) con-
trol the band structure, and the optical and
photoemission spectra.
1.01.4.4.2(i) Germanium The valence electron
configurations of germanium and silicon are both s2
p2; however, significant differences exist for the band
structures. The chief differences arise from the core-
charge configuration. While the nuclear charge
increase is exactly balanced by an increase in core
electron number, the larger number of core electrons
is more effective in screening the nuclear charge. The
valence levels in germanium are less tightly bound
compared to silicon, and this is reflected in the more
metallic character of the germanium band structure.
Another significant feature that distinguishes germa-
nium from silicon is the presence of 3d states within
the core. While it is clear that these d-states do not
significantly participate in the cohesive process, they
can still influence the conduction band configuration.
Specifically, the unoccupied bands, which may have
4d character, are influenced by an orthogonality
requirement not present for the 3d states in silicon.
This reasoning is reinforced by empirical evidence
that suggests that the presence of d-electrons, that
is, nonlocal pseudopotentials, which incorporate
d-orbital corrections, appear crucial in describing
the germanium conduction bands (Chelikowsky and
Cohen, 1973; Phillips and Pandey, 1973).
16 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories
L4 + L5
4 Γ8
L6
Γ6
2 Γ7
L6
Γ7 X5
0 Γ8
L4 + L5
–2 L6 Γ7
Energy (eV)
–4 X5
–6
–8 L6
X5
–10 L
6 crystalline germanium. The experimental data is from
–12 Γ6
L Λ Γ Δ x U, K
Wavevector, k
Figure 14 Band structure for crystalline germanium. The
top of the valence band is considered as the energy zero.
In Figure 14, we present the band structure of
germanium as determined from empirical pseudopo-
tentials. This calculation includes spin–orbit
interactions, which are most significant for heavier
elements (Cohen and Chelikowsky, 1989). Unlike
the case of silicon, most band structures for germa-
nium are in reasonably good agreement. The band
structure of germanium differs from silicon most sig-
nificantly in the conduction band arrangement. The
15 and 29 bands, using the notation in Figure 7,
reverse their ordering. Moreover, while germanium
and silicon are both indirect semiconductors, the con-
duction band minimum in germanium occurs at the
L-point as opposed to a point near X in silicon. As
noted earlier, the valence band configuration for dia-
mond semiconductors is insensitivie to the
constituents: silicon, germanium, and tin have almost
identical valence band configurations, but they have
quite different conduction band configurations.
In Figure 15, we present the reflectivity spectrum
of germanium as calculated from pseudopotential
band theory and as determined by experiment
(Grover and Handler, 1974). Compared to silicon,
germanium exhibits a richer spectrum. The addi-
tional structure arises from the larger spin–orbit
coupling occurring in germanium. For example, in
the E1 region near 2.2 eV, a distinct doublet structure
occurs. This doublet arises from the spin–orbit split-
ting in the L39 level.
Γ8
0.6
Γ6
Ge Γ8 0.4
R (E )
Ge
Γ7
Theory
0.2 Experiment
0
0 1 2 3 4 5 6 7
Energy (eV)
Figure 15 Theoretical and experimental reflectivity for
Philipp and Ehrenreich, (1963).
Γ6
Σ
In Figure 16, the logarithmic derivative reflectiv-
ity spectrum is displayed. The derivative spectrum
vividly illustrates the rich reflectivity structure avail-
able using modulated techniques. Perhaps the most
interesting feature of the germanium reflectivity
spectrum is the E2 peak at 4.5 eV. Initially, the origin
of this spectral feature appeared to be located at the
X-point and to involve transitions between the high-
est valence band and the lowest conduction band.
The energy of this transition is near the observed
E2 peak and the dipole matrix elements for these
transitions are large. However, the phase space asso-
ciated with this critical point is too small to yield
such a prominent structure. The observation of a
well-defined interband reduced mass for the E2
structure from electroreflectance (Aspnes, 1973) sug-
gests a relatively well-localized critical-point origin
for this spectral feature. Ruling out transitions near X,
the critical point must reside elsewhere within the
Brillouin zone. Empirical pseudopotential calcula-
tions reinforce this interpretation; these calculations
(Chelikowsky and Cohen, 1973) yield a well-defined
critical point near the special k point (Chadi and
Cohen, 1973).
The density of states for germanium is illustrated
in Figure 17 and compared to photoemission and
inverse photoemission. Photoemission methods such
as X-ray photoelectron spectroscopy (XPS) and
ultraviolet photoemission spectroscopy (UPS) mea-
sure only properties of occupied states. Inverse
photoemission spectroscopy allows one to detect
the properties of empty states. Electrons with a
well-defined energy are directed at a sample. These
electrons decay to the lowest unoccupied states,
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories
2
1 Experiment
1 ΔR (eV–1)
0
R ΔE
–1
–2
0 1 2 3
Energy (eV)
Figure 16 Theoretical and experimental modulated reflectivity for crystalline germanium. The experimental data is from
Zucca and Shen (1970).
with some of the decay transitions being radiative.
Photons emitted in this process are detected and a
photon counts versus incident electron energy spec-
trum is measured. Like photoemission, the inverse
photoemission can be related to the empty state
density of states, ignoring any matrix element effects.
One can obtain a direct measure of the ‘quasi-parti-
cle’ gap, that is, the energy required to obtain a
noninteracting electron–hole pair, by a combination
of photoemission and inverse photoemission spectra.
1.01.4.4.2(ii) Gallium arsenide We can approach
the electronic structure of gallium aresenide from the
perspective of perturbing the germanium potential.
Intuitively, we expect
VS ðGÞ ¼ ½VGa ðGÞ þ VAs ðGÞ=2  VGe ðGÞ ð48Þ
That is, the symmetric part of the potential should
resemble the form factors of germanium. The anti-
symmetric form factor,
VA ðGÞ ¼ ½VGa ðGÞ – VAs ðGÞ=2 ð49Þ
which is a measure of the difference between the
gallium and arsenic potentials, should contain the
essential information which distinguishes germanium
from gallium arsenide. Formally, it is the deviation of
VA(G) from zero that distinguishes zinc–blende from
diamond semiconductors. In this sense, we expect a
smooth transition from a purely covalent semicon-
ductor VA(G) ¼ 0, to a highly ionic semiconductor
where VA(G) deviates notably from zero.
17
Ge
Theory
4 5 6 7
We expect that many properties of semiconduc-
tors, for example, optical gaps, cohesive energies
dielectric constants, bond charges, etc., might be
determined simply with an ionicity factor based on
VA(G) or a similar measure. Actually, this is the case,
and although VA(G) is not explicitly used, a more
sophisticated measure, based on similar concepts, of
ionic versus covalent contributions to crystal binding
in diamond and zinc–blende semiconductors has
been devised by Phillips (1973).
In Figure 18, we illustrate the calculated band
structure for gallium arsenide using the EPM. The
nonlocal pseudopotential EPM approach has yielded
one of the most accurate band structures for GaAs to
date. In fact, as a result of the extensive experimental
studies in this compound, this band structure may be
the most accurate band structure over a large energy
range available for any material. By compiling the
most recent experimental data, we estimate an error
of about 0.1 eV over an energy span of nearly 20 eV.
Thus, we have an accuracy of roughly 1% or better;
this is almost an order of magnitude better than other
band structures.
As we introduce antisymmetric form factors for
the gallium arsenide crystal potential, several signifi-
cant alterations from a germanium-like band
structure may be observed. First, the bottom valence
band, which now has atomic s-like character and is
localized on the anion, splits off from the the rest of
the valence band to form the antisymmetric gap. This
gap grows with increasing ionicity of the crystal or
charge transfer between the cation and anion.
18 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories

In general, as a semiconductor becomes more

ionic, the valence bandwidths narrow and the optical
XPS BIS
gap grows in size. Part of this effect arises from
dehybridization accompanying the change from
covalent to ionic bonding.
Perhaps the most important conclusion from our
n-Ge(111) 2 × 1 experience with GaAs is not simply that the pseudo-
potential approach can yield accurate results.
Consider the parametrized nature of the potential.
One might naively expect that the band structure
L(6,7) could be adjusted at will with parametric nature of
L(10,11)
the form factors. This is not the case for two reasons.
L(2)
L(3,4) First, the form factors are not linearly independent, for
L(1)
example, the form factors V(8) and V(11) characterize
X(13,14)
X(1,2) Γ(12–14) the size of the ion core and tend to move the bands in
X(5,6)
L(8) similar fashion. In a fitting sense, we have only two or
Γ(1)
X(3,4) L(5) Γ(6–8) three parameters to fix all the energy bands. Second,
the form factors are chosen to be close to those
expected from model potentials and are not arbitrary.
L
In GaAs, this issue is important. The band order-
Λ ing of the conduction band minima was first believed
to be an issue with the EPM. In order to explain the
Γ Gunn effect (Gunn, 1964), it was thought that the
correct ordering is c6 Xc6 Lc6. (The Gunn effect
Δ
occurs in III–V and results in negative differential
resistance.) If it were possible to obtain this ordering
X
by a simple adjustments of the form factors, the bands
would have been fit to give ordering suggested by the
W
Gunn effect. In fact, pseudopotential band calcula-
K tions place the Lc6 band below Xc6, resulting in a
c6 Lc6 Xc6. Since experiment is the arbiter of
Σ such issues, the pseudopotential method was deemed
to be in error.
Γ However, in the late 1970s careful experiments
–10 –5 0 5 10 15 20
Energy relative to EV (eV) showed the ordering employed to explain that the
Gunn effect was not correct. In Figure 19, we illus-
Figure 17 Experimental X-ray photoemission
trate the interpretation by Aspnes (1976). Using
spectroscopy (XPS) and Bremsstrahlung isochromat
spectroscopy (BIS) or inverse photoemission spectra for electroreflectance for core to conduction band tran-
crystalline germanium (Chelikowsky et al., 1989). The critical sitions, he was able to show the ordering from the
point features of the theoretical density of states are also EPM was correct.
identified with band structure features. In Figures 20 and 21, we illustrate the computed
optical response functions, that is, real and imaginary
parts of the dielectric function, for GaAs. We also
Another smaller gap arises from the antisymmetric compare these functions to experiment (Philipp and
part of the potential and is located between the first Ehrenreich, 1963). The information content of the
and second conduction bands along the -direction. response functions is considerable. It is for this reason
This smaller gap is important for transport properties that Phillips (1973) based his bonding theories of
of zinc–blende semiconductors and has been semiconductors on spectroscopic data rather than
observed to have subtle effects on the reflectivity following the approach of Pauling (1960), who used
spectrum of the zinc–blendes. We also note that the thermochemical data to analyze molecular bonding
band gaps in gallium arsenide tend to be larger than trends. The general shape of the real part of the
in germanium. dielectric function is that expected for a harmonic
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 19

6 L4, 5
Γ8
L6 Γ8

4 Γ7 Γ7

X7

2 X6
L6 Γ6
Γ6 GaAs
Γ8 Γ8
0
L4, 5 Γ7 Γ7
L6
Energy (eV)

–2
X7
X6
–4

–6

L6 X6
–8

–10 X6
L6

–12 Γ6 Γ6

L Λ Γ Δ X K Σ Γ
Wavevector, k

Figure 18 Energy bands for crystalline gallium arsenide. The top of the valence band is taken to be the zero energy
reference.

oscillator with a resonant frequency at about 5 eV.
We can think of this resonant frequency as a funda-
mental property of GaAs that represents the average
bonding–antibonding energy level separation.
Phillips divides up this average bonding–antibonding
gap into a part that is ionic and a part that is covalent.
One can extract from the dielectric function relevant
parameters for formulating ionicity scales (Phillips,
1973). Such scales are useful for making predictions
of a variety of semiconductor properties. With a
knowledge of the real and imaginary parts of the
dielectric function, we can derive the reflectivity
spectrum and reflectivity derivative spectrum.
While the structure of the calculated imaginary
part of the dielectric function is similar, the magni-
tude in the 2–4 eV region is lower by almost a
factor of 2. This discrepancy was initially attributed
to a failure of the Ehrenreich–Cohen dielectric func-
tion (Ehrenreich and Cohen, 1959) to include
electron–hole ‘excitonic’ interactions. Recent work
based on a many-body formulation of the Bethe–
Salpeter equation confirms this interpretation as
indicted in Figure 22. The Bethe–Salpeter equation
strongly enhances the magnitude of the imaginary
part of the dielectric function, but does not shift the
critical points.
The EPM-calculated reflectivity is shown in
Figure 23. As for the silicon and germanium semi-
conductors, we may divide up the zinc–blende
reflectivity structure into five distinct regions. For
GaAs, the E0 region extends from 1 to 2 eV, the E1
region 2-4 eV, the E90 region 4-5 eV, the E2 region 5-
6 eV, and the E92 region 6-7 eV. The lowest energy
region E0 is dominated by structure originating from
the fundamental gap at . Spin–orbit interactions
split the upper valence bands of gallium arsenide by
about 0.3 eV; for heavier metal constituents, the split-
tings can be quite large, for example, 1 eV or more.
20 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories

L
Lc6
E vs. k
Λ (Lowest C.B.)

Γ
Γc6
k
Δ

X
Xc6
ER spectrum
(Ga 3d Core)
2

–2
104 ΔR/R

–4

L X L X
–6
20 21 22
Energy (eV)
Figure 19 Fine structure in the electroreflectance spectrum for GaAs (Aspnes, 1976). Assignment to the conduction band
minima is indicated.

30
Ga As
25 Theory
Experiment 30
20 GaAs
25 Theory
15
Experiment
10 20
ε1 (E )

ε2 (E )

5 15
0
10
–5
5
–10

–15 0
0 1 2 3 4 5 6 7 8 0 1 2 3 4 5 6 7 8
Energy (eV) Energy (eV)

Figure 20 Real part of the dielectric function for Figure 21 Imaginary part of the dielectric function for
gallium arsenide compared to experiment (Philipp and gallium arsenide compared to experiment (Philipp and
Ehrenreich, 1963). Ehrenreich, 1963).
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 21

30 zone center or along the  direction. If it were to

occur at the zone center, we would expect spin–orbit
GaAs splitting to be important in both the valence and
20 conduction bands. On this basis, recent work by
Aspnes and Studna (1973) has given support to the
⑀2

zone-center assignment. The traditional argument

against this assignment has been the small phase
10
space associated with the  point; however, excitonic
effects may very well enhance its importance.
The E2 peak, which dominates the absorption
0 spectrum, represents the average bonding–antibond-
0 2 4 6 8 10
ing transitions. This peak arises from transitions from
Energy (eV)
the uppermost valence bands to the lowest conduc-
Figure 22 Calculated optical absorption spectrum of tion bands near the points (2/a)(3/4, 1/4, 1/4) in
GaAs with (solid lines) and without (dashed lines) electron–
the Brillouin zone. This assignment is similarly found
hole interaction from Rohlfing and Louie (1998).
in the diamond structure semiconductors. The E2
peak dominates the spectrum because of the large
phase space which contributes to interband transi-
0.7
tions in this region and because of large interband
GaAs dipole matrix elements. At energies above the E2
0.6 Theory
Experiment
peak, reflectivity structure from transitions along
0.5 the  direction.
The E91 structure arises from transitions from the
0.4 top valence band to the second lowest conduction
R (E )

band at or near the zone boundary at L.

0.3
0.2
0.1
0
0 1 2 3 4 5
Energy (eV)
Figure 23 Reflectivity spectrum for gallium arsenide. The
experiment is from Philipp and Ehrenreich (1963).
Thus, the E0 structure actually has a doublet char-
acter. The E1 reflectivity peak originates from
transitions near the zone boundary at L. Again,
spin–orbit interactions can become important in this
region by splitting the upper valence bands. We note
that older, local pseudopotential calculations gave a
different critical point symmetry for this region. The
local potential results put an M0 critical point at L
and an M1 critical point along the  direction. The
nonlocal results move the M1 critical point to the
zone boundary and eliminate the M0 point alto-
gether. This latter configuration is in better accord
with experiment.
The E90 structure has been somewhat controver-
sial. It can arise from either of two regions: near the
By examining the energy gradients and dipole
matrix elements throughout the Brillouin zone, it is
possible to determine the origin of structure of the
imaginary part of the dielectric function. In such a
manner, we analyzed the contribution to the E90
reflectivity structure. This structure is complex and
6 7 8 has been somewhat controversial. In Figure 24, we
label this structure as A, B, and C.
Rehn and Kyser (1972), using electroreflectance,
observed only a  symmetry for this structure and
attributed the structure to the pseudocrossing of the
5 conduction bands. However, Aspnes and Studna
(1973) have pointed out that this interpretation con-
flicts with band structure calculations where some 
symmetry structure is predicted. They further pro-
posed that the  symmetry structure arises from a
pair of M1 critical points approximately one-tenth
way from  to X. EPM calculations agree with their
interpretation (Cohen and Chelikowsky, 1989). The
relevant transitions are indicated in Figure 25.
Aspnes and Studna also noted the possibility of the
pseudocrossing producing some very weak structure
at 4.4 eV. The 4.4 eV (A) transition corresponds to
this type of transition. It should be noted, however,
that there also exists a companion M0 critical point
owing to the spin–orbit splitting of the 5 valence
band. Since this companion critical point occurs
22 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories

GaAs
Theoretical
Experimental

1 dR (eV–1)

A
0
C
R dE

–2
0 1 2 3 4 5 6
Energy (eV)
Figure 24 Reflectivity derivative spectrum of gallium arsenide. See the text for a discussion of the structures: A, B, and C.
Experiment is from Zucca and Shen (1970).

about 0.1 eV higher in energy, it is nearly degenerate
with the E90 structure from  and  at 4.5 eV. In the
calculated derivative spectrum, this structure is masked
by the stronger M1 critical points, and this may be the
case in the electroreflectance measurements.
In Figure 26, we illustrate the calculated valence
band density of states for GaAs, and the results of
XPS measurements and inverse photoemission
(Chelikowsky et al., 1989). As for the diamond struc-
ture semiconductors, we may divide the density of
states into three general regions. The first region is
the most tightly bound energy band. Electron states
corresponding to this band are strongly localized on
the anion and are descendants of the atomic As 4s
states. The next region of note is a peak arising from
the onset of the second valence band. This band
shows almost no energy variation along the X–U
symmetry direction; in fact, it is very flat over the
entire square face of the Brillouin zone. This energy
band configuration results in a sharp onset of states
above the antisymmetric gap. The character of states
associated with the second valence band changes
from predominantly cation s-like states at the band
edge to predominantly anion p-like states at the
band maximum. The third region of interest in the
density of states extends from the onset of the third
valence band (at about 4 eV below the valence band
maximum) to the valence band maximum. This
region encompasses the top two valence bands and
is predominantly p-like and is associated with anion
states.
1.01.4.4.2(iii) Zinc selenide The prototypical II–
VI semiconductor is zinc selenide. However, unlike
the prototypical III–V semiconductor (GaAs) or our
prototypical diamond semiconductor (Si or Ge), we
do not have as detailed a picture for this class of
semiconductors. There are several reasons for this
situation. First, extensive experimental information
is lacking for ZnSe as compared to GaAs. The larger
bandgap in ZnSe requires higher photon energies
than GaAs for reflectivity measurements. Photon
sources at these higher energies have not been rou-
tinely available. Also, some of the powerful optical
techniques such as Schottky barrier electroreflec-
tance cannot be easily applied to ZnSe owing to
fabrication problems. Second, the Zn 3d-level resides
close to the valence band. Traditionally, empirical
pseudopotential band calculations do not explicitly
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 23

Λ6
Δ5
Δ5
Λ4,5
Γ8
GaAs
Λ6 Γ7

4
Δ5

E0′ (Γ) E0′ (Δ)

Δ5
Energy (eV)

Λ6

Γ6

Γ8
0
Λ4,5
Δ5
Λ6 Γ7 Δ5
Λ6 Δ5

(0.3,0.3,0.3) Γ (0.5,0.0,0.0)
Λ Δ
Figure 25 Band structure of gallium arsenide near  showing the critical point locations for the E90 structure. The indicated
transitions give rise to the structure labeled A, B, and C in Figure 24.

include this level in ZnSe. The 3d cation level in
gallium arsenide is significantly below the valence
band and in Ge the 3d level is more than 30 eV
below the top of the valence band.
In Figure 27, we illustrate the band structure of
ZnSe. Most features of this band structure can be
accounted for by extrapolating from Ge to GaAs.
Compared to Ge and GaAs, the bandgaps in ZnSe,
that is, the optical gap and the antisymmetric gap,
have increased considerably in size. Moreover, the
valence bands have narrowed and show less
dispersion.
In Figure 28, we display the calculated and
measured reflectivity spectrum for ZnSe
(Freeouf, 1973; Walter et al., 1970). Some work
using derivative spectroscopy is available (Theis,
1977). Owing to the increased ionic component of
the bonding in ZnSe, the reflectivity spectrum is
shifted to higher energy as compared to Ge or
GaAs. It also exhibits much more structure than
Ge or GaAs because of the larger separation
between bands.
For the most part, the reflectivity spectrum can be
analyzed by analogy with GaAs. The E0 reflectivity
24 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories

XPS BIS

p-GaAs(110) 1 × 1

X(2) X(11,12)
L(9)

L(3,4) L(8)
X(1)
X(15)

Γ(10,11)
X(7,8)

Γ(1) L(6,7)
X(3,4)
Γ(5) Γ(6–8)
L(1)

X(6)

Γ
–10 –5 0 5 10 15 20
Energy relative to Ev (eV)

Figure 26 Experimental X-ray photoemission spectroscopy (XPS) and Bremsstrahlung isochromat spectroscopy (BIS) or
inverse photoemission spectra for crystalline gallium arsenide (Chelikowsky et al., 1989). The critical point features of the
theoretical density of states are also identified with band structure features.
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 25

L4, 5 Γ8
8 Γ8
L6
Γ7 Γ7
6
X7

4 X6
L6

Γ6 Zn Se Γ6
2

Γ8 Γ8
0
L4, 5
Γ7 Γ7
Energy (eV)

L6
X7
–2
X6

–4

L6 X6
–6

–8

–10
L6
X6
Γ6 Γ6
–12

L Γ X k Γ
Wavevector, k

Figure 27 Energy bands for crystalline zinc selenide. The top of the valence band is taken to be the zero energy reference.

structure lies between 2 and 4 eV and corresponds to
the minimum energy gap at . The E1 structure at
4–5 eV arises from transitions near to or at the
L point. The structure corresponding to the E2 peak
arises from a localized region near the special point
(2/a)(3/4, 1/4, 1/4). The E90 structure at 7–8 eV
may be an exception having no analogy in GaAs. It
lies above the E2 structure; thus, the origin of struc-
ture is reversed in ZnSe as compared to GaAs.
However, the origin of the E90 structure appears to
be the same, that from near  and along the 
direction. The highest energy reflectivity structure,
E91, occurs at 8–9 eV and corresponds to transitions
near the L point.
With the exception of the line shape near the E2
peak, the pseudopotential results are consistent with
experiment. It is possible that the line-shape discre-
pancy is an artifact of the sampling scheme used. We
note that at energies above 10 eV or so, the structure
in the reflectivity might arise from transitions invol-
ving the Zn 3d-states.
It should not be surprising that the density of
states of ZnSe may also be interpreted in terms of
an extrapolation from the Ge and GaAs band struc-
tures. In Figure 29, we compare the calculated
density of states for ZnSe with photoemission mea-
surements and inverse photoemission (Chelikowsky
et al., 1989). Some of the early pseudopotential band
structures, which had potentials based on optical data
alone, were in mediocre agreement with the photo-
emission results. Specifically, local pseudopotentials
chosen to reproduce optical gaps tend to overesti-
mate the ionicity of the II–VI semiconductors. As a
consequence, the valence bands become quite narrow
compared to experiment. Nonlocal pseudopotentials
do not suffer from this malady; they can be used to fit
optical gaps with no corresponding increase in
ionicity.
26 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories
0.6
Experiment 1
0.5 Experiment 2
Theory
0.4
R 0.3
0.2
0.1
0
0 1 2 3 4 5
Energy (eV)
Figure 28 Reflectivity spectrum for zinc selenide. Two experimental spectra are presented: the dashed line is from Walter
et al. (1970) and the dotted line from Freeouf (1973).
1.01.5 The Ab Initio Pseudopotential
Method
A deficiency of the empirical pseudopotential
method is that the potential is ‘biased’ by the experi-
mental data to which it was fit. For example, suppose
we fit the optical properties of GaSb and extract a Ga
potential, we must be careful in trying to use this fit
Ga potential in another crystal. This potential might
work fine in GaAs, which has a similar bonding
configuration when compared to GaSb, but the
potential may fail to describe GaN, which is consid-
erably more ionic than GaSb. A related problem is
that the form factors are fit only to a subset of reci-
procal lattice vectors. If the crystal volume or
structure changes, one must extrapolate to a new
subset. Another problem can occur at a surface. In
crystalline GaAs, each Ga atom is surrounded by four
As atoms. For the cleavage plane the (110) surface,
the Ga atom is bonded to three As atoms. Given the
coordination change, the surface Ga atom cannot be
expected to retain a ‘bulk-like’ screening potential.
There is no reason to be confident that the Ga
pseudopotential extracted from the crystalline envir-
onment will be very accurate at the surface. Of
course, this problem is made worse if one wants to
examine a liquid containing Ga atoms where the
coordination may continuously change.
We can consider the form factors to be composed
of two interactions: the ion core–valence electron
ZnSe
6 7 8 9 10
interaction and the valence electron–valence elec-
tron interaction. A fundamental postulate of the
pseudopotential method is that the ion-core pseudo-
potential is not dependent on the chemical
environment. We assume that this part of the poten-
tial can be transferred with no loss in accuracy. The
key problem is to determine the total pseudopoten-
tial by determining the potentials from the valence
electrons interacting among themselves.
A common procedure is to construct a self-
consistent potential. The wave functions obtained
in an electronic structure calculation can be used
to construct a new screening potential, which in
turn can be used with the ion-core potential to
compute a new total potential and new wave func-
tions. When no changes occur in a feedback loop
of this kind, the solution is considered to be self-
consistent.
Let us assume a one-electron Hamiltonian, which
can be based on density functional theory
(Hohenberg and Kohn, 1964; Kohn and Sham, 1965):
 
– h2 r2 p
þ Vion ðrÞ þ VH ðrÞ þ Vxc ðrÞ n ðrÞ ¼ En n ðrÞ
2m
ð50Þ
The ion-core pseudopotential, Vpion, can be taken
as a linear superposition of ion-core atomic poten-
tials. Determining the ionic potential can be
accomplished by resorting to atomic structure
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 27

Assume initial density: ρ

Zn 3d XPS BIS

÷8
= –4 πeρ
Δ 2V
Solve: H

p
Form: VT = Vion +VH +Vxc
n-Zn Se (100) c 2 × 2

2
Δ 2
– p
X(1) L (3,4) Solve: Vion +VH +Vxc Ψn = EnΨn
2m
X(3,4)
Γ(6–8) Γ(15)
X(10)
X(2) L (8)
X(6) 2
Form: ρ = e Ψn
n, occup

Γ(1) Figure 30 Self-consistent field loop. The loop is repeated

Γ(10,11)
L(2)
L(5) until the input and output charge densities are equal to
Γ(9) L (13,14)
within some specified tolerance.
Γ(5)

Λ where  is the valence electron charge density.

The second part of the screening potential, the
Γ exchange-correlation part of the potential, Vxc, is
quantum mechanical in nature. A common approx-
Δ
imation for this part of the potential arises from
the local density approximation, that is, the potential
X
depends only on the charge density at the point of
W
interest, Vxc(r) ¼ Vxc[(r)]. In principle, density func-
tional theory is exact, provided one can obtain an
K exact functional for Vxc. This is an outstanding
problem. It is commonly assumed that the func-
Σ tional extracted for a homogeneous electron gas
(Ceperley and Alder, 1980) is universal and can be
Γ applied to the inhomogeneous gas problem. The
–10 –5 0 5 10 15 20
Energy relative to EV (eV)
procedure for generating a self-consistent field
(SCF) potential is given in Figure 30. The SCF
Figure 29 Experimental X-ray photoemission cycle is initiated with a potential constructed by a
spectroscopy (XPS) and Bremsstrahlung isochromat
super-position of atomic densities. These densities
spectroscopy (BIS) or inverse photoemission spectra for
crystalline zinc selenide (Chelikowsky et al., 1989). The are then used to solve a Poisson equation for the
critical point features of the theoretical density of states are Hartree potential, and a density functional is used to
also identified with band structure features. obtain the exchange-correlation potential. A screen-
ing potential composed of the Hartree and
exchange-correlation potentials is then added to
calculations, as discussed in the following section. the fixed ion-core pseudopotential, after which the
The potential arising from the valence-electron one-electron Schrödinger equation, or Kohn–Sham
interactions can be divided into two parts. One part equation, is solved. The resulting wave functions
represents the classical electrostatic terms, the from this solution are then employed to construct
Hartree or Coulomb potential: a new potential and the cycle is repeated. In prac-
tice, the output and input potentials are mixed using
r2 VH ðrÞ ¼ – 4eðrÞ a scheme that accounts for the history of the pre-
P ð51Þ vious iterations (Broyden, 1965; Chelikowsky and
ðrÞ ¼ e jn ðrÞj2
n;occup Cohen, 1992).
28 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories
1.01.5.1 Constructing Pseudopotentials
from Density Functional Theory
The construction of ion-core pseudopotentials has
become an active area of electronic structure theory.
Methods for constructing such potentials have cen-
tered, on ab initio or first-principles pseudopotentials;
that is, the informational base on which these poten-
tials are based does not involve any experimental
input.
The first step in the construction process is to
consider an electronic structure calculation for a
free atom. For example, in the case of a silicon
atom, the Kohn–Sham equation (Kohn and Sham,
1965) can be solved for the eigenvalues and wave
functions. Knowing the valence wave functions, that
is, 3s2 and 3p2, and corresponding eigenvalues, the
pseudowave functions can be constructed. This is an
easy numerical calculation as the atomic densities are
assumed to possess spherical symmetry and the pro-
blem reduces to a one-dimensional radial integration.
Once we know the solution for an all-electron
potential, we can invert the Kohn–Sham equation
and find the total pseudopotential. We can unscreen
the total potential and extract the ion-core pseudo-
potential. This ion-core potential, which arises from
tightly bound core electrons and the nuclear charge,
is not expected to change from one environment to
another. It should be transferable from the atom to a
molecular state or to a solid state or liquid state. The
issue of this transferability is one which must be
addressed according to the system of interest. The
immediate issue here is how to define pseudo-wave-
functions which can be used to define the corre-
sponding pseudopotential.
Suppose we insist that the pseudo-wave-function
be identical to the all-electron wave function outside
of the core region. For example, let us consider the 3s
state for a silicon atom. We want the pseudo-wave-
function to be identical to the all-electron state out-
side the core region:
p tion at rc. (4) The pseudopotential has zero
3s ðr Þ ¼ 3s ðr Þ r > rc ð52Þ
where p3s is a pseudo-wave-function and rc defines
the core size.
This assignment will guarantee that the pseudo-
wave-function will possess properties identical to the
all-electron wave function, 3s in the region away
from the ion core.
For r < rc, we alter the all-electron wave function.
We are free to do this as we do not expect the valence
wave function within the core region to affect the
chemical properties of the system. We choose to
make the pseudo-wave-function smooth and node-
less in the core region. This will provide rapid
convergence with simple basis functions. One other
criterion is mandated. Namely, the integral of the
pseudocharge density within the core should be
equal to the integral of the all-electron charge den-
sity. Without this condition, the pseudo-wave-
function differs by a scaling factor from the
all-electron wave function. Pseudopotentials
constructed with this constraint are called norm con-
serving (Hamann et al., 1979). Since we expect the
bonding in a solid to be highly dependent on the tails
of the valence wave functions, it is imperative that
the normalized pseudo-wave-function be identical to
the all-electron wave functions.
There are many ways of constructing norm con-
serving pseudopotentials as within the core the
pseudo-wave-function is not unique. One of the
most straight-forward construction procedures is
from Kerker (1980) and later extended by Troullier
and Martins (1991):
(
p r l expðpðr ÞÞ r  rc
l ðr Þ ¼ ð53Þ
l ðr Þ r > rc
p(r) is taken to be a polynomial of the form:
X
6
pðr Þ ¼ c0 þ c2n r 2n ð54Þ
n¼1
This form assures us that the pseudo-wave-function
is nodeless and by taking even powers there is no
cusp associated with the pseudo-wave-function.
The parameters, c2n, are fixed by the following
criteria: (1) The all-electron and pseudo-wave-
functions have the same valence eigenvalue. (2)
The pseudo-wave-function is nodeless and is iden-
tical to the all-electron wave function for r > rc. (3)
The pseudo-wave-function must be continuous as
well as the first four derivatives of the wave func-
curvature at the origin. This construction is easy
to implement and extend to include other con-
straints. An example of an atomic pseudo-wave-
function for Si is given in Figure 31 where it is
compared to an all-electron wave function. Unlike
the 3s all-electron wave function, the pseudo-wave-
function has no nodes. The pseudo-wave-function
is much easier to express as a Fourier transform or
a combination of Gaussian orbitals than the all-
electron wave function.
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories
1.0
 ZR
3s Radial wavefunction of Si
0.5
Pseudoatom
All-electron
0 the scattering phase shift at R ¼ rc and at the eigen-
–0.5
0 1 2 3
Radial distance (a.u.)
Figure 31 An all-electron and a pseudo-wave function for
the silicon 3s radial wave function.
Once the pseudo-wave-function is constructed,
then the Kohn–Sham equation can be inverted to
arrive at the ion-core pseudopotential:
p
p h2 r2 l
Vion;l ðr Þ ¼ p – En;l – VH ðr Þ – Vxc ½ðr Þ
2m l
The ion-core pseudopotential is well behaved as
p, has no nodes and does not vanish. The ion-core
potential appears to be both state dependent and
energy dependent. The energy dependence is
usually weak. For example, the 4s state in silicon
computed by the pseudopotential constructed from
the 3s state is usually accurate. Physically, this
happens because the 4s state is extended and
experiences the potential in a region where the
ion-core, potential has assumed a simple Zve2/r
behavior. However, the state dependence through l
is an issue; the difference between a potential gen-
erated via a 3s state and a 3p can be an issue. In
particular, for first row elements such as C or O,
the nonlocality is quite large as there are no p
states within the core region. For the first row
transition elements for such as Fe or Cu, this is
also an issue as again there are no d-states within
the core. This state dependence can be addressed
in similar fashion as for a nonlocal empirical
pseudopotential.
An additional advantage of the norm conserving
potential concerns the logarithmic derivative of the
pseudo-wave-function (Bachelet et al., 1982). An
identity exists:
29
d 2 ln
– 2 ðr Þ2 ¼ 4 2 r 2 dr ¼ QðRÞ ð56Þ
dE dr R
0
The energy derivative of the logarithmic deriva-
tive of the pseudo-wave-function is fixed by the
amount of charge within a radius, R. The radial
derivative of the wave function is related to the
scattering phase shift from elementary quantum
mechanics. For a norm-conserving pseudopotential,
value of interest is identical to the all-electron case as
Qall elect(rc) ¼ Qpseudo(rc). The scattering properties of
the pseudopotential and the all-electron potential
have the same energy variation to first order when
transferred to other systems.
4 5
There is some flexibility in constructing pseu-
dopotentials. The nonuniqueness of the pseudo-
wave-function was recognized early in its inception.
For example, within the Phillips–Kleinman formu-
lation, one can always add a function, f, to the
pseudo-wave-functions without altering the
pseudopotential provided f is orthogonal to the
core states. Consider the matrix element in
Equation (7). If one  changes
 pv to pv þf,
then c jv þ f ¼ c jv þ hc jf i ¼ c jpv .
p p
ð55Þ
Nothing is changed in the Phillips–Kleinman
pseudopotential by this addition.
The nonuniqueness of the pseudopotential can be
exploited to optimize the convergence of the pseu-
dopotentials for the basis of interest. Much effort has
been made to construct soft pseudopotentials. By soft,
one means a rapidly convergent calculation using
plane waves as a basis. Typically, soft potentials are
characterized by a large core size, that is, a larger
value for rc. However, as the core becomes larger, the
goodness of the pseudo-wave-function can be com-
promised as the transferability of the pseudopotential
becomes more limited. In Figure 32, the ion-core
pseudopotential for carbon is plotted in real space
and in reciprocal space. Although the potentials look
quite different in the core region, they all give reli-
able electronic structure properties for carbon.
As for the nonlocal terms that occur in empirical
potentials (Section 1.01.4.3), we can handle nonlocal-
ity using a plane wave basis in a straightforward
fashion. If we consider a reference potential such
that Vl ¼ Vlocal Vl, then we need to determine
matrix elements as in Equation (46) where Vpc,l is
replaced by Vl. The reference potential can be
chosen to be a local potential. In general, the nonlocal
elements are very short ranged in real space as the
30 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories

(a) 5 (b) 5 (c) 5 (d) 5

1 2 1 2 1 2 1 2
–5 –5 –5 –5
r (a0 ) r (a0 ) r (a0 ) r (a0 )
Vl (r) (Ry)

–15 –15 –15 –15

–25 –25 –25 –25

–35 –35 –35 –35

8 8 8 8
q 2Vl (q) (Ry/a02)

0 0 0 0
6 12 6 12 6 12 6 12

q(a0–1) q(a0–1) q(a0–1) q(a0–1)

–8 –8 –8 –8

Figure 32 Ion-core pseudopotentials for carbon generated by four different methods in real and reciprocal space; (a)
Troullier and Martins (1991), (b) Kerker (1980), (c) Hamann et al. (1979), and (d) Vanderbilt (1985). The dotted and solid lines
correspond to the s and p pseudopotentials, respectively.

size of the core is determined by rc. As such, the
upper limit of the real space integral is slightly
more than rc in practice.
A major strength of ab initio pseudopotentials is
that they can be employed for systems with many
atoms of low symmetry, for example, clusters, liquids,
and surfaces, without having to fit any form factors.
However, a plane wave basis will require a large
cutoff for such systems. In this case, the matrix ele-
ments in Equation (46) can be difficult to evaluate as
elements depend on both k + G and k + G9.
Kleinman and Bylander (1982) suggested an alternate
form for the required nonlocal matrix elements:
P ulm Vl ulm dxdydz
þ GÞYlm ðkd
Ylm ðkd þ G9Þ
m
VlKB ðk þ G; k þ G9Þ ¼ Z where uplm are the reference atomic pseudo-wave-
p p
4a l ðr ÞVl ðr Þl ðr Þdr
Z
p 
 l ðr ÞVl ðr Þjl jk þ G9jr Þr 2 dr
Z these coefficients are dependent on the pseudo-

p
 l ðr ÞVl ðr Þjl jk þ Gjr Þr 2 dr
where pl is the atomic reference pseudo-wave-func-
tion and Ylm is a spherical harmonic with the angles
determined by the unit vector: k d þ G. This matrix
element form has a great advantage as the integrals
are separable in that they are solely a function of
k + G or a function of k + G9. The individual inte-
grals can be stored and retrieved as required in
setting up the matrix.
It is also possible to solve the Kohn–Sham problem
directly in real space (Chelikowsky et al., 1994). In this
case, the Kleinman–Bylander form can be cast as
P p
VlkB ðx;y;zÞ p ðx;y;zÞ¼ Glm ulm ðx;y;zÞVl ðx;y;zÞ
lm
Z
p
ulm Vl p dxdydz ð58Þ
Glm ¼Z
p p
functions. The nonlocal nature of the pseudopoten-
tial is apparent from the definition of Glm; the value of
ð57Þ wave-function, p, acted on by the operator Vl.
This is very similar in spirit to the pseudopotential
defined by Phillips and Kleinman (1959). While we
have focused on a simple plane wave basis, there are
other bases that can be employed, for example, one
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 31

can combine pseudopotentials with Gaussians (Chan Chelikowsky, 1989); however, to understand struc-
et al., 1986) or a uniform grid (Chelikowsky et al., tural properties, we need to employ a different
1994). These real space methods can be easily imple- approach. Since the form factors in the empirical
mented with real space ab initio pseudopotentials pseudopotential have been fit to optical transitions,
(Kronik et al., 2006). there is no reason to believe that they will be very
While our focus has been on norm conserving pseu- accurate for structural properties such as the phase
dopotentials, it is possible to generalize the stability, the equilibrium bond length, the bulk mod-
pseudopotential method to include systems that are ulus, and the phonon spectrum of a crystal. Ab initio
not based on such potentials. It is possible to make the pseudopotentials can be used for this purpose and, in
pseudopotentials even weaker by relaxing this condi- this section, we illustrate their application to the phase
tion. Vanderbilt (1990) proposed such a method for stability of tetrahedral semiconductors such as silicon.
constructing ultrasoft pseudopotentials, which are con- To evaluate the total energy of a crystal can be a
structed as a generalized eigenvalue problem. The difficult task. The total energy of the system contains
norm conservation constraint is relaxed, and the charge terms that individually diverge, for example, the
density within the ion core is not explicitly considered repulsive Coulomb terms between the ion cores and
as part of the pseudo-wave-function. The relaxation of the electron–electron interactions. These terms can
the norm conservation constraint allows one to consider be handled in Fourier or momentum space using a
a much larger core radius and a much softer potential. plane wave basis (Ihm et al., 1979). The total energy
One issue which is relevant for pseudopotential of the system can be written as
constructions, regardless of whether the potential is
intended for use with a plane wave basis or not, ET ¼ Ekin þ Eec þ EH þ Exc þ Ecc ð59Þ
concerns the issue of unbound, or weakly bound,
atomic states. If an atom does not bind a state of ET is the total electronic energy, Ekin represents the
interest, then the atomic wave function correspond- electronic kinetic energy, the electron–ion-core
ing to this state is clearly not normalizable. interaction energy is given by Eec, the electrostatic
Nonetheless, the pseudopotential corresponding to Coulomb energy is given by the Hartree energy, EH,
this state might be of some interest, for example, in the nonclassical exchange-correlation energy is given
a crystal such diverging wave functions are captured by Exc, and the ion core–ion-core classical term is
by the potentials of neighboring atoms. For example, given by Ecc. The momentum-space expressions for
Ba has a strong f-component resonance. However, the electronic energy terms are as follows:
these f-states are not bound for neutral Ba atom. In 1 X  p  2 h 2 j k þ Gj 2
 
order to bind such states, one must consider highly Ekin ¼  n ðk þ GÞ ð60Þ
N n;k;G 2m
ionized atomic states, which result in very strong
pseudopotentials. Sometimes these potentials are so 1 X p
Eec ¼ ðk þ GÞ pn ðk þ G9Þ
strong as to be useless for a plane wave basis, or so far N n;k;G n
removed from the chemical environment of interest
Z  ð61Þ
that their transferability may be suspect. Hamann p 1 Ze 2 3
 Vc ðk þ G; k þ G9Þ þ G;G9 d r
(1989) has suggested a method for handling such c r
cases by integrating out the Kohn–Sham equation c X 4e 2  2

to a large distance and at that point terminating the EH ¼ 2
ðGÞ ð62Þ
2 G;G6¼0 G
pseudo-wave-function. The corresponding termi-
nated wave function is then used to generate a c X 
Exc ¼  ðGÞ"xc ðGÞ ð63Þ
pseudopotential for the component of interest. 2 G
( "
e2 X 4 X 1
1.01.5.2 Structural Properties of Ecc ¼ Zv;s Zv;s9 cosðG?ðtS – tS9 ÞÞ
2 S;S9 c G;G6¼0 G 2
Semiconductor Crystals

2 #
1.01.5.2.1 Total electronic energy from –G 
 exp –
pseudopotential–density functional theory 4
2 c
2
) ð64Þ
Empirical pseudopotentials have been one of the most X erfcð
jR – tS þ tS9 jÞ 2

effective tools in understanding the optical and dielec- þ – pffiffiffi S;S9

jR – tS þ tS9 j 
tric properties of semiconductor crystals (Cohen and R;R6¼0
32 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories
Each term yields the energy per cell; N is the total
number of cells, c is the cell volume, R is a lattice
vector, G is a reciprocal lattice vector, Z is the total
core charge, which is a sum of the individual core
charges Zv, t is the basis vector, k is the crystal
momentum, and pn is the wave function for state n.
ðGÞVcp ðk þ G; k þ G9Þ, and pn ðk þ GÞ represent
the Fourier components of the charge, ion-core
potential and the pseudo-wave-function. The sums
involving the pseudo-wave-functions run only over
the occupied states,
is a parameter that controls the sidered a volume of one-half the ambient volume of
convergence of the Ewald summation in real space
versus momentum space (Ihm et al., 1979).
In practice, it is easier to make use of the eigen-
value explicitly and subtract off the double counting
terms, that is, one can write the total energy as
1X
ET ¼ En ðkÞ – EH þ Exc þ Ecc ð65Þ
N n;k
The sum is over all occupied states. The eigen-
value term contains the exchange-correlation term,
whereas the total energy should contain the
exchange-correlation energy. This term can be
written as
X
Exc ¼ c  ðGÞ½"xc ðGÞ – Vxc ðGÞ ð66Þ
G B0 V
where "xc is related to the exchange correlation via a
functional derivative:
ð "xc ½Þ
Vxc ¼ ð67Þ

where, in the local density approximation,
Z vative at equilibrium. Representative calculated and
Exc ½ ¼ ðrÞ"xc ½ðrÞd 3 r ð68Þ
In the simplest formalism, "xc is extracted from a
homogeneous electron gas (Kohn and Sham, 1965).
1.01.5.2.2 Phase stability of crystals
The total energy, ET, of a crystal structure can be
calculated using Equation (65) as a function of the
lattice constant and any internal structural para-
meters. One of the first applications of this work
was carried out by Ihm and Cohen (1980), and Yin
and Cohen (1980, 1982c, 1982b). This work repre-
sents a seminal point in condensed matter physics
(Chelikowsky, 2000). It demonstrated a workable
scheme for examining the structural properties of
solids and its extension led to molecular dynamics
using quantum forces (Car and Parrinello, 1985).
The first application involved the silicon crystal
with a number of different phases: face-centered
cubic, body-centered cubic, hexagonal close-packed,
hexagonal diamond, cubic diamond, white tin and
simple cubic. For each structure, the energy was
minimized for a given volume by optimizing the
internal coordinates, for example, for a hexagonal
structure the c/a ratio was optimized. Depending on
the system studied the range of volumes considered
is varied. In the case of silicon. Cohen, et al. con-
the known diamond phase of silicon to an upper
limit of about 20% larger than the ambient volume.
For such a diverse set of crystal structures, it is
important to make certain the convergence is similar
to all phases. For structures which yield metallic
systems, the k-point sampling is sometimes critical
because the variations in the Fermi surface make it
difficult to assure that occupied states are being
sampled. Once the total energy is computed for a
finite number of volumes, the energy versus volume
points are fit to an equation of state such as the
Birch (1952) equation or the Murnaghan (1944)
equation.
!
ðV0 =V ÞB90 B0 V 0
ET ðV Þ ¼ ET ðV0 Þ þ þ1 – ð69Þ
B90 B90 – 1 B90 – 1
where B0 and B90 are the bulk modulus and its pres-
sure derivative at the equilibrium volume V0. Using
Equation (69), the fit of the calculated points yields
the equilibrium energy ET(V0), the equilibrium
volume, and the bulk modulus and its pressure deri-
measured values for the lattice constant and bulk
modulus results are given for Si in Table 1. The
results are impressive when one considers that this
is an ab initio calculation requiring only the atomic
number and crystal structure as input. Generally, the
pseudpotential–density functional method yields lat-
tice constants and bulk moduli to an accuracy of
about 1% and 5%, respectively. The cohesive energy
can be calculated by comparing the total energy at
the equilibrium lattice constant with the energy of
the isolated atoms. Spin polarization effects (von
Barth and Hedin 1972; Gunnarsson et al., 1974) and
zero point vibrational energy need to be considered.
Early results computed within the local density
approximation gave reasonable estimates of the
cohesive energies; however, in general the general-
ized gradient approximation yields more accurate
cohesive energies (Becke, 1992).
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 33

1.01.5.2.2(i) Silicon and germanium phases The Car, 1995), most phase stability studies are done at
total energy versus volume curves for seven crystal zero temperature. In this cases, G ¼ U þ PV, where
phases of silicon are shown in Figures 33 and 34. It is the internal energy is given by the total electronic
encouraging that the lowest energy state corresponds energy and the pressure is given by P ¼ dET/dV.
to the diamond structure, as this structure is observed
experimentally under ambient conditions. (As with
–7.82
any such calculation, there is no guarantee that there
is an untried structure with a lower energy state.)
Ge
Experimental data for the structural properties of
silicon and germanium are listed in Table 3.
For small volumes other structural phases are
–7.84
lower in energy than the diamond phase; hence,
pressure-induced solid–solid structural phase transi-
tions are predicted. Structural transitions occur

Estructure (Ry/atom)
fcc
between phases when the Gibbs free energy hcp
bcc
G ¼ U þ PV – TS ð70Þ –7.86 4
sc
for the phases in question are equal. U is the internal β-Tin
energy, P is the pressure, and S is the entropy. 3
Although some attempts have been made to consider
phase transitions at finite temperature (Sugino and
–7.88
Hexagonal
2 diamond

–7.83 Diamond 1

Si
–7.90
0.6 0.7 0.8 0.9 1.0 1.1
Volume
–7.85
Figure 34 Total electronic energy for seven phases of
crystalline silicon as function of the atomic volume. The
Energy (Ry/atom)

volume has been normalized to the measured value of

fcc diamond. The dashed line is a common tangent of the
bcc energy curves for the diamond and -tin phases. The
–7.87
hcp calculations are from Yin and Cohen (1982c). The total
energy reference is the energy per pseudo-Ge atom. fcc,
sh sc face-centered cubic; bcc, body-centered cubic; hcp,
hexagonal close packing.
β-Sn
–7.89
Table 3 Comparison of calculated and measured static
Hexagonal properties of silicon and germanium
diamond
Diamond Lattice Cohesive Bulk
–7.91 constant energy (eV/ modulus
0.5 0.7 0.9 1.1 Semiconductor (Å) atom) (Mbar)
Volume
Si
Figure 33 Total electronic energy for seven phases of Calculated 5.45 4.84 0.98
crystalline silicon as a function of the atomic volume. The Measured 5.43 4.63 0.99
volume has been normalized to the measured value of
Ge
diamond. The dashed line is a common tangent of the
Calculated 5.66 4.26 0.73
energy curves for the diamond and -tin phases. The
Measured 5.65 3.85 0.77
calculations are from Yin and Cohen (1982c). The total
energy reference is the energy per pseudo-Si atom. fcc, The calculated values are from Yin and Cohen (1982c). Measured
face-centered cubic; bcc, body-centered cubic; hcp, values are from Donohue (1974), Brewer (1977) and McSkimin
hexagonal close packing. and Andreatch Jr. (1963).
34 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories
For T ¼ 0, the pressure-induced phase transforma-
tion can be found by a common tangent line between
the ET(V) curves of the two phases considered. The
negative of the slope of the tangent line is the transi-
tion pressure. Examples of common tangent
constructions are given in Figures 33 and 34 for
the transitions from the diamond structure to the -
tin phase for Si and Ge. As hydrostatic pressure is
applied the path indicated in the figures, 1 ! 2 ! 3
! 4, illustrates the change from diamond at 1 to
-tin at 4, with the transformation occurring along
the 2 ! 3 segment of the path where both structures
can coexist. The predicted phase transition pressure
for the diamond ! -tin phase is 99 kbar for Si and
96 kbar for Ge; the measured values are 125 and 100
kbar, respectively (Yin and Cohen, 1982c).
The successful prediction of high-pressure
structural phases such as hexagonal forms of Si and
Ge and face-centered cubic Si are one of the impress-
ive results of the pseudopotential-density functional
theory calculations (Chang and Cohen, 1984; Liu
et al., 1988; Vohra et al., 1986). Moreover, these
high-pressure phases are metallic and predicted to
be superconductors (Chang et al., 1985). Two of the
predictions of superconductivity have been verified
while the others remain untested.
The calculations for the group IV semiconductors
serve as prototypes for the application of the total-
energy pseudopotential method to study structural
properties of solids.
1.01.5.2.2(ii) III–V phases The first extensions to
other solids were made for the III–V semiconductors:
GaAs, AlAs, GaP, AlP, AlSb, GaSb, InP, InAs, and
InSb (Froyen and Cohen, 1983a, 1983b; Zhang and
Cohen, 1987). Total electronic energy calculations
for these III–V semiconductors are displayed in
Figures 35 and 36.
Although these studies for III–V semiconductors
generally give good results for the lattice constants
and bulk moduli, the agreement between the calcu-
lated and measured properties of the high-pressure
phases and for phase transition pressures and
volumes is not always satisfactory. As an example of
the latter, the calculated transition pressures for
the Al compounds are consistently lower by
around 50% than the measured values (Zhang and
Cohen; 1987). In contrast, the calculated lattice
constants are within 0.4, 0.3, and 0.3% of the
measured values for AlP, AlAs, and AlSb, respec-
tively (Zhang and Cohen, 1987). It is unclear why
the transition pressures of the Al compounds are
underestimated.
1.01.5.2.3 Vibrational properties
An important application of the ab initio pseudopo-
tential approach is calculating the vibrational
properties of solids. These calculations are based on
the change in the energy of atom as it moves from an
equilibrium position. Once we have established that
the energy of atom can be accurately calculated as a
function of position, phonon and lattice vibrational
modes can be calculated. The input needed for such
calculations is minimal. In contrast to phenomenolo-
gic force constant models, which often require as
many as 15 parameters to achieve reasonable fits to
phonon dispersion curves, the total energy approach
uses only the masses and atomic numbers of the
constituent atoms. To calculate the phonon disper-
sion curve, !(q), along a specific direction, the
frozen-phonon approach is easy to implement
(Chadi and Martin, 1976; Heine and Weaire, 1970;
Wendel and Martin, 1979; Yin and Cohen, 1980). In
this approach, a supercell is chosen, and the atomic
cores are displaced to simulate a particular phonon
mode. The change in the total energy arising from
the distortion depends on the type of distortion
assumed and the amplitude. Since a specific phonon
wavevector, q, is chosen, this method is limited to
calculating !(q) at specific points in the Brillouin
zone. The phonon frequencies can also be evaluated
by computing the Hellman–Feynman forces on the
displaced atoms. Another approach that allows the
full phonon dispersion to be computed is based on
linear response theory (Baroni et al., 2001). However,
the frozen-phonon approach is the simplest method
for computing !(q) at symmetry points. Calculations
at nonsymmetry points are possible but require larger
unit cells. Standard calculations usually limit the
computations to three or four q-points along a
symmetry direction.
As an example of a frozen phonon supercell
calculation, we briefly examine the calculations of
the phonon properties for the  and X points of the
Brillouin zone for Si and Ge. The phonon polariza-
tions for these points can be easily determined using
group theory as illustrated in Figure 37, and the
primitive cell for the distorted lattice contains two
atoms for the LTO() mode and four atoms for the
phonon modes at X. The phonon-distorted lattice
has inversion symmetry, which simplifies the
calculation.
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 35

150

AIAs AIP

CsCI
100 +
Rocksalt
β-Sn
Energy - mRy

Rocksalt

β-Sn
50

NiAs
Zinc–blende Zinc–blende

150

GaAs GaP

CsCI
100
Rocksalt
NiAs β-Sn
Energy - mRy

β-Sn Rocksalt
50

Zinc–blende Zinc–blende
0

0.6 0.7 0.8 0.9 1.0 1.1 0.6 0.7 0.8 0.9 1.0 1.1
V/V0 V/V0
Figure 35 Total electronic energy for some representative III–V structures as function of the atomic volume. The
calculations are from Froyen and Cohen (1983a, 1983b).

For a given amplitude u, the change in the total where M is the atomic mass. The calculation of the
energy arising from the distortion is ET(u). The total energies or forces is done typically for five
force constant k can be obtained from a second deri- different amplitudes ranging from 0.01 to 0.1 Å.
vative of the ET(u) or a first derivative of the force The total energies can fit by a quadratic function
F(u): to about 1%. For some phonon mode calculations

 such as the LTO() modes in Si and Ge, higher-
@ 2 ET 2ET ðuÞ order fits such as the third-order term are needed.
k¼ ffi ð71Þ
@u2 u¼0 u2 These fits allow the evaluation of anharmonic terms.
or Table 4 illustrates some typical results. An impress-
ive achievement of these calculations is the good


@F F ðuÞ agreement with experiment obtained for the TA(X)
k¼ ffi – ð72Þ
@u u¼0 u modes in Si and Ge. For empirical force constant
model calculations, many-neighbor parameters are
The phonon frequency is given by needed to obtain the correct values for these modes
pffiffiffiffiffiffiffiffiffi because of the important role played by long-ranged
! ¼ 2f ¼ k=M ð73Þ forces.
36 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories

(a) 120 (b) 180 (c) 120

AISb GaSb InP

150
90 90

Rocksalt 120 A5

Energy (mRy/molecule)

Energy (mRy/molecule)
Energy (mRy/molecule)

Rocksalt
60 60 Rocksalt
90
A5

60
30 30
A5
SH
Zinc–blende 30 Zinc–blende

0 Zinc–blende 0
0

–30 –30 –30

0.5 0.6 0.7 0.8 0.9 1.0 1.1 0.5 0.6 0.7 0.8 0.9 1.0 1.1 0.5 0.6 0.7 0.8 0.9 1.0 1.1
Normalized volume Normalized volume Normalized volume

(d) 120 (e) 150

InAs InSb
120
90
Rocksalt
Energy (mRy/molecule)

Energy (mRy/molecule)

90
A5
60

60 A5
Rocksalt
30
30
Zinc–blende
Zinc–blende
0
0

–30 –30
0.5 0.6 0.7 0.8 0.9 1.0 1.1 0.5 0.6 0.7 0.8 0.9 1.0 1.1
Normalized volume Normalized volume

Figure 36 Total electronic energy for some representative III–V structures as function of the atomic volume. The
calculations are from Froyen and Cohen (1983a, 1983b).

The use of the total electronic energy or the earlier. This gives the value of the sound velocity.
forces via the Hellmann–Feynman theorem For example, the q ! 0 TA velocity vTA [110]
involves different approaches to calculate the propagating along the [110] direction with [110]
phonon frequencies, but the results are essentially polarization is associated with the shear modulus
the same as indicated in Table 4. Additional C11 C12:
information can be obtained from the force

calculation. For example, for the LOA(X) mode, C11 – C12 1=2
vTA ½110 ¼ ð74Þ
the forces on atoms 2 and 3 differ for finite 2M
amplitude (see Figure 37). This arises from the where M is the mass density. The calculated
effects of anharmonicity and illustrates that it is results for the velocity and shear modulus are in
more difficult to compress a bond than to stretch good agreement with experiment as shown in
it. For the phonon calculation, the average of Table 5.
the two force constants is used, and this quantity When interlayer force constants are calculated,
does not vary by more than 0.5% with the the resulting phonon spectrum is in good agreement
amplitude. with experiment. For example, for Si the  to X
If the interlayer force constants are computed, phonon dispersion curve was computed by Yin
then the full dispersion can be calculated as discussed and Cohen (1982a) using the calculated interlayer
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 37

force constants. The results are close to the

(110) Plane experimentally determined points as indicated in
Figure 38.
LTO (Γ)
The frozen-phonon total-energy approach can
TA(X) also be used to extract nonharmonic contributions
to the phonon couplings. By examining the ET(u)
TO(X) curves terms beyond the quadratic validity, higher
1 order terms can be obtained. For example,
LOA(X)
Vanderbilt et al. (1986) performed a detailed study
on third- and fourth-order anharmonic coupling
constants for optical, phonons in C, Si, and Ge.
These calculations determined bare phonon–
phonon scattering amplitudes. By including virtual
processes, renormalized multiphonon vertices and
phonon self-energies were calculated. One specific
2 application was the study of the renormalized four-
phonon vertices. These were found to be negative,
which is the wrong sign for allowing the formation
of a proposed two-phonon bound state (Cohen and
Ruvalds, 1969).
3

1.01.6 Summary and Conclusions

The pseudopotential concept has had a profound

4 empirical and ab initio pseudopotential concepts
Figure 37 Phonon polarization at  and X for the diamond
structure. Atoms are numbered and denoted by black dots.
The solid lines denote an atomic chain in a (110) plane, and
the dashed lines denote the projection of an atomic chain a
pffiffiffiffiffiffiffiffi
distance a=2 away from that plane where a is the lattice
constant (Yin and Cohen, 1982b).
impact on our understanding of the electronic struc-
ture of semiconductors. In this chapter, both
were outlined and some central applications
discussed.
Empirical pseudopotentials provided a means
for understanding the optical and dielectric proper-
ties of semiconductors and the underlying energy
band structures. It is sometimes stated that the

Table 4 Comparison of the calculated phonon frequencies, f (in THz), of

Si and Ge (Yin and Cohen, 1982b) at  and X with experiment (Dolling,
1963; Nilsson and Nelin, 1971, 1972)

LTO() LOA(X) TO(X) TA(X)

Si
f (energy) 15.16 ( 2%) 12.16 ( 1%) 13.48 ( 3%) 4.45 ( 1%)
f (force) 15.14 ( 3%) 11.98 ( 3%) 13.51 ( 3%) 4.37 ( 3%)
f (expt) 15.33 12.32 13.90 4.49
Ge
f (energy) 8.90 ( 2%) 7.01 ( 3%) 7.75 ( 6%) 2.44 (2%)
f (force) 8.89 ( 3%) 6.96 ( 3%) 7.78 ( 6%) 2.45 (2%)
f (expt) 9.12 7.21 8.26 2.40

The values of the frequencies were determined by energy and by force

calculations. The deviation from experimental values are given in parentheses.
38 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories

Table 5 Comparison of calculated values (Yin and and whether it could be applied to solid and spe-
Cohen, 1982b) of C11–C12 and the TA velocity along the cifically semiconductors such as silicon. Some
 polarization) for Si and Ge with experiment
[110] (with [110]
(McSkimin and Andreatch Jr., 1963).
workers thought that the electron–hole interactions
for a optical excitation would be so strong as to
C11 C12 (Mbar) vTA [110] (105 cm s 1) obscure any attempt at understanding such excita-
Si
tions using energy band theory. Given that the
Theory 1.07 4.79 EPM allowed adjustments to the one-electron
Expt. 1.03 4.69 potential, if the EPM had failed to work with the
Ge flexibility of choosing a potential, one would have
Theory 0.74 2.64 questioned whether it was possible to construct a
Expt. 0.82 2.77 meaningful one-electron potential and correspond-
ing energy band structure. The consequences of
this failure would have been very damaging to
prospects for using energy bands to interpret opti-
cal, dielectric, photoemission, and transport
16
properties of semiconductors.
LO Fortunately, this was not the case; the EPM pro-
vided a simple and effective way to couple band
structure theory to experimental work and its impact
TO
was immediate. While much of this effort took place
12 in the 1960s and 1970s, the EPM still serves as an
Phonon frequency (THz)

effective means to interpret optical data for semicon-

8 The coupling of density functional theory with
4
0 stabilities showed conclusively the applicability of
0 0.2 0.4
Γ Δ
Figure 38 Phonon branches from  to X along the 
direction from Yin and Cohen (1982a). The dashed lines
are calculated from the computed force constants. The
solid lines are calculated using the computed third-
nearest layer force constants and the frozen-phonon
results at  and X. Experimental points are from Dolling
(1963), Nilsson and Nelin (1972), and Sinha (1973) and
denoted by dots for the transverse modes and triangles
for the longitudinal modes.
empirical pseudopotential method (EPM) estab-
lished the validity of the energy band concept for
solids in general. There is much truth to this
statement. In the 1950s, there was extended discus-
sions about the validity of the one-electron picture
ductors. While more sophisticated methods now exist
LA to examine optical properties, few of the conclusions
of the EPM have been overturned by these methods.
pseudopotentials in the early 1980s resulted in
another impressive advance for understanding the
TA electronic structure of materials. The accuracy of
density functional theory for predicting electronic
and structural energies was problematic at that
time. However, the direct numerical application of
structural energies to problems involving bond
lengths, compressibilities, phonon modes, and phase
0.6 0.8 1.0 pseudopotential methods to these problems. Over
X the last 10 years, more than 10 000 papers have
appeared with pseudopotentials in the title or
abstract and these papers have been cited over
100 000 times.
The vitality and future of the pseudopotential
method is without question. The method is now
used to examine new and exciting materials systems.
These systems include nanoscale systems, amor-
phous solids, glasses, and liquids. Moreover, owing
to strong advances in both hardware and software
(algorithms), it is now possible to address systems
with thousands of atoms on an almost routine basis.
It is for this reason that the pseudopotential concept
is said to be the standard model for condensed
matter. (See Chapter 1.02).
 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories
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 Electrons in Semiconductors: Empirical and ab initio Pseudopotential Theories 41

Further Reading
Cohen ML and Chelikowsky JR (1989) Electronic Structure and
Optical Properties of Semiconductors, 2nd edn. Berlin:
Springer.
Karixas E (2003) Atomic and Electronic Structure of Solids.
Cambridge: Cambridge University Press.
Kittel C (2004) Introduction to Solid State Physics, 8th edn. New
York: Wiley.
Marder MP (2000) Condensed Matter Physics. New York:
Wiley.
Martin RM (2004) Electronic Structure: Basic Theory and
Practical Method. Cambridge: Cambridge University
Press.
 1.02 Ab initio Theories of the Structural, Electronic, and
Optical Properties of Semiconductors: Bulk Crystals to
Nanostructures
J Deslippe and S G Louie, University of California at Berkeley and Lawrence Berkeley National Laboratory,
Berkeley, CA, USA
ª 2011 Elsevier B.V. All rights reserved.

1.02.1 Introduction 42
1.02.2 Ground-State Properties and DFT 44
1.02.3 Ab Initio pseudopotentials 47
1.02.4 Selected Applications of DFT to Ground-State Properties 49
1.02.5 Excited States and Spectroscopic Properties 54
1.02.6 Quasiparticle Properties and the Single-Particle Green’s Function 55
1.02.7 The GW Approximation 57
1.02.8 The GW Formalism and Applications 59
1.02.9 Two-Particle Excitations and the Bethe–Salpeter Equation 63
1.02.10 The GW-BSE Formalism and Optical Response 65
1.02.11 Interactions in Nanostructured Semiconducting Materials 71
1.02.12 Summary 73
References 74

1.02.1 Introduction systems. A laptop today has the same computing

power as the fastest supercomputer in the world
The last few decades have seen dramatic advances in only 15 years ago.
both theoretical methodology and computer technol- In principle, determining the properties of a mate-
ogy that have allowed researchers to investigate rial from first principles involves the solution of a
materials properties in a great variety of systems in quantum many-body interacting problem (over both
a quantitative way from first principles (i.e., without the atomic nuclei and electron coordinates) with the
any input parameters other than the constituent following Hamiltonian (omitting spin and relativistic
atoms making up the material). The advances in effects for simplicity):
theory have been tremendous. Theory has succeeded
X P2j X p2 X Zj Zj 9 e 2 X e2
in reducing a seemingly intractable quantum many- Htot ¼ þ i
þ þ
body problem into one that is computationally feasible j
2Mj i
2m j <j 9
jRj – Rj 9 j i<i9 jri – ri9 j
while retaining the important physics. Today, it is X – Zj e 2
þ :
possible to predict the ground- and excited-state prop- i;j
jRj – ri j
erties for a wide range of important materials, in ð1Þ
particular semiconductor systems, using first princi-
ples (or ab initio) techniques. Such studies have been This Hamiltonian dictates the quantum states via
particularly useful in reduced-dimensional (nano) the many-body time-independent Schrödinger
semiconducting systems characterized by enhanced equation
many-electron interaction effects. The advances in
H ðr1 ; r2 ; . . . ; rN Þ ¼ Eðr1 ; r2 ; . . . ; rN Þ: ð2Þ
computer technology have been equally tremen-
dous, coming in the form of faster central The exact numerical solution of this problem is, in all
processing units (CPUs) with larger cache, larger but the simplest cases, impractical, due to the expo-
capacity, better performing memory, and greater nential increase in size of the Hilbert space for an
space. The same period has seen the advent of N-body problem. The exact solution for a typical sys-
the massively parallel high-performance computer tem of interest would yield an unwieldy many-body

42
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
wave function, which, in general, would give little
or no physical insight. The evaluation of physical
quantities of interest with appropriate approxima-
tions is then required and desirable. Moreover, the
majority of the properties of a condensed matter
system can be determined by investigating just the
interactions of the valence (outer) electrons with the
relatively slower-moving atomic ionic cores (nuclei
plus core electrons) and the interactions of
the valence electrons among themselves. In the
Born–Oppenheimer, or adiabatic, approximation for
electronic properties, the atomic positions are
assumed to be a set of parameters due to the fact
that they are slowly varying compared to motion of
the electrons. This approximation allows the elim-
ination of two of the terms in Htot, leaving just a
Hamiltonian for the electron wave function:
X p2 X e2 X – Zj e 2
i
Hel ¼ þ þ
i
2m jr – ri9 j
i<i9 i i;j
jRj – ri j
Mechanical, structural, and dynamic quantities asso-
ciated with the motion of the atoms (such as phonon
frequencies) can be calculated by evaluating ground-
state total energies at different atomic positions. As
we will discuss later in this chapter, the explicit
dependences of the core electrons can also be
removed through the pseudopotential approach,
leaving an equation for the valence electrons alone.
These interactions determine the electronic struc-
ture of the material which, in turn, determines the
behavior of the material in the ground state and
under external perturbations. We therefore focus
the discussion in this chapter on the state-of-the-art
theoretical and computational methods for calculat-
ing these properties from first principles to further
our understanding of the structural, electronic, and
optical properties of semiconducting materials from
bulk crystals to nanostructures.
It is useful to distinguish the ground-state proper-
ties of a semiconductor from its electronic excited-
state or spectroscopic properties. Properties such as
structure, cohesive energies, charge densities, phase
stability, and vibrational properties are ground-state
properties because they are given collectively by all
the electrons in the many-body ground state. In gen-
eral, these properties may be determined from
knowing the ground-state total energy and related
quantities of the system as a function of the atomic
positions. Practically, for semiconductors, this is done
by applying methods such as those based on the den-
sity functional theory (DFT) (Hohenberg and Kohn,
43
1964; Kohn and Sham, 1965). Such approaches have
been very successful in the ab initio calculation of many
ground-state properties for a wide variety of materials.
Spectroscopic properties, such as those probed in
photoemission, tunneling or transport experiments,
however, involve creating a specific excited particle
(electron or hole) above the ground state. Owing to
many-particle interactions, the excited particle (or
quasiparticle) acquires a self-energy, resulting in a
modified dispersion and finite lifetime. Calculating
such quasiparticle properties is an N þ 1 particle pro-
blem in many-body theory, where N is the number of
particles in the ground-state problem, that, in princi-
ple, requires a different theoretical treatment from
those (such as the standard DFT-based approaches)
used for the ground-state problem (Hedin, 1965;
Hedin and Lundqvist, 1969; Hybertsen and Louie,
1985, 1986). Understanding the optical properties
from first principles is an N þ 2 particle (photo-excita-
: ð3Þ
tion of an electron and hole pair) problem (Rohlfing
and Louie, 1998a, 1998b; Albretch et al., 1998; Benedict
et al., 1998). To study optical properties, therefore, it is
necessary to include the electron–hole interaction,
which can have significant effects on the optical
response in many systems from bulk crystals to nanos-
tructures where such effects often qualitatively change
the calculated spectra. Spectroscopic properties are
best discussed and computed in terms of a Green’s
functions approach (Kadanoff and Baym, 1999),
where the Green’s functions describe the evolution of
the amplitude of a many-body system with the addi-
tion of one or more particles at certain time and
positions.
Because of the reduced dimensionality of nano-
systems, many-electron interaction effects have been
shown to be extraordinarily important in the spectro-
scopic properties of these systems including band-
gap renormalization, quasiparticle spectral functions
such as those measured in photoemission, and optical
properties such as those probed in absorption
and resonant photon scattering. For example, dom-
inantly strong excitonic effects (resulting from
correlations between the photoexcited quasi-electron
and the quasi-hole) in the optical response of semi-
conducting and metallic nanotubes have been
predicted by first-principles theory (Spataru et al.,
2004a; Deslippe et al., 2007) and have subsequently
been confirmed by experiment (Wang et al., 2005,
2007). Experimental advances have also allowed the
measurement and characterization of excitation fea-
tures in the optical response of other nanostructures.
In this chapter, we present some of the fundamental
44 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
concepts and theoretical methods for investigating
the ground- and excited-state properties of semicon-
ductor systems. We illustrate the use of methods first
developed for bulk systems to a wider variety of
structures through their application to nanomaterial
systems. In particular, we discuss several novel theo-
retical results that have been obtained from first-
principles calculations on one-dimensional (1D) and
2D nanostructures.
The organization of the remainder of the chapter
is as follows. In Sections 1.02.2 and 1.02.3, we discuss
the calculation of ground-state properties within
the ab initio pseudopotential density functional
formalism. Sections 1.02.5–1.02.8 introduce the quasi-
particle concept, the electron self-energy, and the
GW approximation and method for calculating the
quasiparticle properties of interacting electron sys-
tems. In Sections 1.02.9 and 1.02.10, we discuss the
extension of this formalism to the calculation of opti-
cal properties of materials with electron–hole
interaction effects included through the Bethe–
Salpeter equation (BSE). The formalism for calculat-
ing accurate quasiparticle and excitonic properties
within the GW–BSE formalism is thus outlined. In
Sections 1.02.11 and 1.02.12, we discuss interesting
features that arise from the application of this form-
alism to nanosystems, and provide some future goals
and avenues of research in this area.
1.02.2 Ground-State Properties
and DFT
The major obstacle in solving the quantum many-
body problem described by the Hamiltonian in
Equation (1), even within the Born–Oppenheimer
approximation, is the interaction between the elec-
trons, which are identical Fermionic particles. For
the purpose of calculating ground-state properties,
this complex many-body problem can be reduced to
solving the simpler problem of a single noninteract-
ing electron moving in an effective field. This field is,
itself, determined from the single-particle orbitals,
and thus the problem must be solved self-consistently
using an iterative procedure. Early attempts at such a
formalism were devised by Hartree and Fock, where
the self-consistent potential (or mean-field potential)
takes the form
Z X 2
e jjn ðr0 Þj2 0
VH ðrÞ ¼ dr ð4Þ
n
jr – r0 j
or
VHF ¼ VH ðrÞ þ Vex ð5Þ
where, jn are the independent electron orbitals, and
Vex is the nonlocal exchange operator. The first term
on the right side in Equation (5), the Hartree poten-
tial, describes the electrostatic interaction of a single
electron with the average charge density produced
by all the electrons in the system. The second term is
the exchange term, resulting from the enforcement of
the Pauli exclusion principle. The Hartree and
Hartree–Fock (HF) potentials can be derived from
minimizing the total ground-state energy if the
many-body wave function is assumed to be a simple
product (the Hartree approximation) or a single
Slater determinant (the HF approprimation) of
single-particle orbitals:
H ðr1 ; . . . ; rn Þ ¼  ji ðri Þ: ð6Þ
i
 
 j1 ðr1 Þ . . . jn ðr1 Þ 
 
 
HF ðr1 ; . . . ; rn Þ ¼  . . . . . . . . . : ð7Þ
 
 j ðrn Þ . . . j ðrn Þ 
1 n
This leads directly to the HF mean-field, self-
consistent field equation (atomic units are used):
 
r2
– þ Vion þ VH þ Vx jn ¼ "n jn : ð8Þ
2
The approximation in the HF approach for the
ground-state energy comes from the fact that the
true many-body wave function cannot, in general,
be described by a single-Slater determinant; rather,
it is a superposition of all Slater determinants that can
be formed by a complete set of single-particle orbi-
tals. Going beyond the HF formalism leads to
corrections that lower the total energy of a many-
electron system. These corrections are collectively
referred to as the correlation energy. Techniques
that systematically improve the many-body wave
function by including increasingly larger number
of higher-energy Slater determinants, called multi-
configuration interaction (CI) techniques, generally
scale exponentially with the number of single-
particle orbitals included; the formalism becomes
quickly intractable for all but the smallest systems
such as atoms and small molecules typically studied
in quantum chemistry.
Unlike mean-field theories such as the Hartree
or HF approximations described above, DFT is in
principle exact in giving the total energy, electron
charge-density distribution, and other related
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
ground-state properties (such as the structural and
vibrational properties) of an interacting many-
electron system. DFT does not approximate the
ground-state energy by putting restrictions on a trial
many-body wave function; instead, DFT rigorously
reformulates the total energy in terms of a functional
of the charge density of the system. Within the
Kohn–Sham scheme, the charge density can be
expressed exactly in terms of sums over single-
particle orbitals. As we will see, in practical calcula-
tions, the basic approximation lies in the construction
of the energy functional itself – no explicit many-
body wave function enters the theory. Today, static
DFT within the Kohn–Sham formulation is arguably
the most popular approach for first-principles inves-
tigations of the ground-state properties of condensed
matter systems from bulk semiconductors and metals
to nanostructures to complex biological molecules.
For an interacting many-electron system in an
external static potential V(r), Hohenberg and Kohn
(1964) demonstrated that, instead of the electronic
ground-state energy being a functional of the com-
plicated ground-state many-body wave function
(r2,r2,. . .,rN), it can be reformulated as a functional
of the electronic ground-state charge density, ,
alone. This functional obeys a variational principle,
that is, it is a minimal value at the physical electron
density. Moreover, Kohn and Sham introduced an
explicit, practical formulation for the total energy
(atomic units are used):
Z R
1 ðrÞðr9Þ
Ev ½ ¼ V ðrÞðrÞdr þ Ts ½ þ dr dr9
2 jr – r0 j
þ Exc ½
ð9Þ
Here, V(r) is the ionic potential, Ts is the kinetic
energy of a noninteracting electron system with the
equivalent ground-state density (r), the third term is
Kohn–sham DFT formulation
Real interacting system:
External potential V(r)
uij = e 2/rij
Ψ(r1, r2, ...), Ev[ρ]
Minimize E V[ρ] with ρeff(r) by varying Veff(r)
Figure 1 Schematic of Kohn–Sham DFT. The real interacting system density is obtained in terms of single-particle
amplitudes of a fictitious non-interacting system. The energy functional is minimized by varying the effective potential.
45
the Hartree energy described above, and Exc is a uni-
versal functional, termed the exchange–correlation
functional, of the density encapsulating everything
not included by the first three terms on the right side
of Equation (9). The exchange–correlation functional,
Exc[], includes all the effects of many-electron
exchange and correlations and the corrections to the
kinetic energy of the interacting system not captured
by that of the noninteracting system. This formalism is
a tremendous conceptual and technical simplification
since the unwieldy 3N-dimensional many-electron
wave function is, in principle, eliminated from the
problem entirely without any approximation to the
many-body total energy or charge density. The major
drawback of this approach is that although the exis-
tence of the universal functional (Exc[]) was shown, its
exact form is not known. A number of highly successful
approximations to Exc[] have been developed over the
years (Dreizler and Gross, 1995; Parr and Yang, 1989),
including the local density approximation (LDA) in
which the exchange–correlation energy density is
taken as that of the homogeneous electron gas at the
local density or the generalized gradient approxima-
tions (GGAs) in which the effects of both the local
density and its gradients are included. These useful
approximations to Exc[] have allowed practical and
quantitatively accurate calculations for ground-state
properties to be made using the DFT approach.
Kohn and Sham (1965) showed that the electron
charge density, and hence the total energy, may be
obtained by solving an associated system of noninter-
acting electrons with the same charge density as the
interacting system. In the Kohn–Sham approach,
properties of the original many-body material system
of interest with interacting electrons are associated
with a fictitious system of noninteracting electrons
under the influence of an effective single-particle
potential Veff (see Figure 1). The equations for
Non interacting system:
Effective potential Veff(r)
uij = 0
{ϕ j(r)} → ρeff(r)
46 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
solving for the physical electron density take on the
form of those of a self-consistent field problem. The
mapping makes use of the fact that the electron
density of the noninteracting system is given by the
single-particle orbitals. The electron density of the
noninteracting system (corresponding to a particular
Veff) is then used as an input to evaluate the total
energy functional of the real system, making use of
the variational principle that the physical density
minimizes the total energy functional given by
Equation (9). By varying the noninteracting system
until the functional is minimized, we arrive at the
physical density and energy of the real fully inter-
acting electron system. This variational approach
gives rise to a set of Euler–Lagrange equations
(the Kohn–Sham equations) that govern the single-
particle orbitals, ji(r), with Lagrange multipliers "i to
ensure orthogonal normality, for the fictitious non-
interacting system:
 
r2
– þ Vion þ VH þ Vxc jnk ¼ "nk jnk ð10Þ
2 properties over the past several decades, in particu-
with
X
occ
ðrÞ ¼ jji ðrÞj ð11Þ
i
and
Exc
Vxc ðrÞ ¼ : ð12Þ
ðrÞ
The effective, self-consistent potential Veff for the
noninteracting system has two terms in addition to
the external potential: a Hartree term, VH, which is
the same as described above in relation to HF the-
ory, and an exchange–correlation term, Vxc, which is
given by the functional derivative of Exc with
respect to the electron charge density. In principle,
if the exact form of Exc were known, a self-consistent
solution to the Kohn–Sham equations would give
the exact electron density and, therefore, the exact
ground-state energy of the fully interacting system
as a function of the atomic coordinates. Here, it is to
be noted that unlike the HF approximation, Vxc is
simply an energy- or state-independent local opera-
tor within the Kohn–Sham framework. However,
one should remember that it can have a highly
nontrivial dependence as a functional of the whole
density, and that it contains the many-electron
interaction contributions to the kinetic energy that
are not captured by Ts[].
The ground-state total energy as a function of
atomic coordinates yields a large number of other
properties such as structural and vibrational para-
meters. However, as mentioned above, Exc is
unknown, and approximations must be made. A com-
mon approach is to assume that the functional can be
written in terms of expectation value of a local
operator
Z
Exc ¼ ðrÞ"xc ðrÞdr ð13Þ
where "xc, an exchange–correlation energy density, is
assumed to be a function of the density (r) alone in
the local density functional approximation (LDA) or
a function of (r) and its derivativesr(r) in GGA.
These approximations use data from the interacting
homogeneous electron gas problem, for which accu-
rate numerical results have been obtained and
approximate analytic expressions derived. Such
approximations have allowed the very accurate
ab initio computation of many ground-state material
lar, those of semiconductors. However, there are
well-known cases, such as systems where van der
Waals interactions or strong electron correlations
are important, that remain outside the scope of such
approximate functionals – though, in principle, not
outside of an exact DFT ground-state formalism.
It is important to note, however, the eigenvalues "i
and eigenfunctions, ji(r), of the Kohn–Sham equa-
tions (Equations (10)–(12)) do not correspond
rigorously to the excitation (or quasiparticle) energies
and amplitudes of the electrons/holes. Formally, only
the electron charge density and total energy are mean-
ingful quantities within the Kohn–Sham formalism.
The Kohn–Sham eigenvalues are only Lagrange mul-
tipliers in the Kohn–Sham variational construct, and
in general, they are not equal to the electron excitation
(or quasiparticle) energies of a system, even if we
knew the exact exchange–correlation functional. As
an example, let us consider the case of the interacting
homogeneous electron gas. Because the density is
homogenous, both the Hartree potential plus the
external potential and the exact exchange–correlation
potential in the Kohn–Sham equation do not
depend on the coordinates of the electron, regard-
less of the exact form of Vxc. Equation (10) then
reduces to
 
p2
þ const: ji ¼ "i ji ð14Þ
2m
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
The solutions to Equation (14) are always plane
waves or free-electron-like states. The dispersion
relation of the Kohn–Sham eigenvalues is then iden-
tical to that of the free (noninteracting) electron
gas system. Therefore, if we were to interpret the
Kohn–Sham eigenvalues as electron quasiparticle
excitation energies, then, the band structure and
therefore the effective mass, m, and occupied band-
width would be identical to those of free electrons,
completely independent of the magnitude of the
interaction. In addition, the lifetime of a quasi-
electron or quasi-hole produced in such a system
would be infinite. This is clearly incorrect. It was
a similar misuse and misinterpretation of the
Kohn–Sham eigenvalues (i.e., using the Kohn–Sham
eigenvalue gap as the quasiparticle excitation
gap) that led to the famous band-gap problem in
semiconductors. Despite this caveat, however, the
Kohn–Sham band structure nevertheless does often
provide a reasonable starting point for the qualitative
understanding of the electronic structure of semicon-
ductor materials.
1.02.3 Ab Initio pseudopotentials
Since the valence electrons of the constituent atoms
determine most of the properties of a material and
the core electrons are often inert from their envir-
onment, it is possible to greatly simplify Equation
(3) by describing the interaction between these
outer electrons with the combined nucleus and
core electrons near an atom in terms of pseudo-
potentials. The concept of pseudopotentials
explains the apparent weak interaction between
the active electrons and the ionic cores in solids,
explaining the many successes of the nearly-free-
electron model in describing simple metals.
Further, the use of pseudopotentials greatly
improves the efficiency in electronic structure
calculations of the properties of real materials.
The use of pseudopotentials removes the core
electrons from the calculations, reducing the com-
plexity of the problem. A weaker pseudopotential and
nodeless pseudo-wave-functions result in smooth
eigenfunctions, greatly reducing the size of the basis
set required to study the valence electrons. The latter
simplification results from the ability to remove the
part of the all-electron valence electron wave function
that oscillates rapidly in order to remain orthogonal to
the core states (Phillips and Kleinman, 1959).
47
The use of pseudopotentials dates back to Fermi’s
work in the 1930s (Fermi, 1934). However, they
are now best viewed conceptually in terms of the
Phillips–Kleinman cancellation theorem (Phillips
and Kleinman, 1959). In this view, the valence orbi-
tals (e.g., the Kohn–Sham orbitals in Equation (8))
being orthogonal to the core orbitals may be written
in the form of
X
jji ðrÞi ¼ ji ðrÞi þ jfc ihfc ji i ð15Þ
c
where ji ðr Þi is a smooth function (pseudo-
wavefunction) and jfc i are core electronic states
or properly normalized sums of these states. The
single-particle Schrodinger equation for the valence
electrons can then be constructed within one of the
theories described in the previous section as
 
p2
– þ V ji ¼ "i ji ð16Þ
2m
where V is the standard independent-particle poten-
tial from the Kohn–Sham formalism, for example.
Solving this equation is then equivalent to solving
the following equation for the pseudo-wave-function
ji ðrÞi:
 
p2
– þ V þ VR i ¼ "i i : ð17Þ
2m
The additional term, VR, given by
X
VR ¼ ð" – "c Þjfc ðrÞihfc ðr9Þj ð18Þ
c
is, in principle, a nonlocal, energy-dependent opera-
tor. However, since the core state energies are, in
general, significantly lower than those of the states
of interest, VR is effectively a repulsive potential
with negligible energy dependence. Thus, VR effec-
tively cancels the strong electron-ion interaction
potential, V, near the core region, resulting in a
net potential seen by the valence electrons
that is weaker than the original potential. This
weak net potential is what is termed the
pseudopotential:
Vp ¼ V þ VR : ð19Þ
The solutions to Equation (17) have the same
eigenvalues as the original Equation (16), and have
wave functions that are similar to those of the all-
electron wave functions outside of the core region
but significantly smoother near the core. The
pseudopotential concept and methodology justify
48 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
why the interaction between the valence electrons
and the crystal potential appears to very weak in
many systems, and provides a number of computa-
tional advantages such as the removal of the core
electronic degrees of freedom in the calculation and
a great reduction in the size and complexity of
the necessary basis sets to expand the pseudo-
wave-function, since these are smooth functions.
The pseudopotentials described above are not
unique since a different choice for the second term
on the right-hand side of Equation (15) would lead to
equally valid but significantly different-looking
pseudopotentials. This ambiguity has led to many
different construction methods in order to optimize
the accuracy and computational efficiency of
pseudopotentials (Pickett, 1989). In general, modern
practical construction of ab initio pseudopotentials is
done by first solving the interacting all-electron pro-
blem for a given atom of interest within one of the
self-consistent theories described in the previous sec-
tion, such as DFT in the LDA. The resulting
all-electron valence orbitals ji are used to form a
set of pseudo-wave-functions, i, using Equation (15)
implicitly, by joining j to a properly chosen smooth,
nodeless function for small distances from the
nucleus (called the cutoff radius), as illustrated in
Figure 2 for the case of the 3s and 3p states of
sodium. One then inverts the Schrödinger equation
(for the constructed i and the true "i),
Na
3s
0.4
Wave functions
3p
0.2
0
–0.2
0 1 2 3
r (a.u.)
Figure 2 (Left) Constuction of ab initio pseudopotentials. The all-electron wave functions for the 3s and 3p states (dashed
lines) oscillate rapidly near the origin because of the orthogonality requirement to the core states. The pseudo-wave-functions
are constructed by replacing this oscillatory part of the wave function with a smooth, nodeless function. By inverting
Equation 20, one finds the corresponding pseudopotentials shown in the (right) panel. Figure courtesy of J.R. Chelikowsky.
 
p2
– þ Vpi i ¼ "i i ð20Þ
2m
to arrive at the corresponding pseudopotential Vp
for the ith state of this particular element. The
procedure is usually done for a neutral atom in a
configuration that is appropriate in the condensed
state. An ab initio ionic pseudopotential describing
the intrinsic interaction of an electron with an
atom stripped of the other outer valence
electrons is obtained by unscreening the neutral
pseudopotential, that is, removing the screening
Hartree and exchange–correlation potential
resulting from the valence electrons themselves.
(The interactions with the other valence electrons will
be treated explicitly in subsequent calculations on
real materials since these effects are environment
dependent.) Various other constraints (such as
norm conservation; Hamann et al. (1979)) to ensure
accuracy and transferability can be implemented in
this procedure for the construction of pseudo-
potentials (Pickett, 1989). The resulting ab initio
ionic pseudopotentials are, in general, highly accu-
rate and transferable to different environments
where the atoms are not isolated (i.e., where the
valence electron distribution differs greatly from
the isolated atoms) and have been successfully
used in first-principles calculations on materials
systems for many different properties in different
environments.
1
s-Potential
0
Potential (Ry)
p-Potential
–1
–2
d-Potential
–3
–4 All electron
–5
4 5 0 1 2 3 4
r (a.u.)
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
1.02.4 Selected Applications of DFT
to Ground-State Properties
The use of the ab initio pseudopotential approach
within the Kohn–Sham formalism of DFT has
proven to be a powerful approach for calculating
the ground-state properties of many materials
(Cohen, 1982) from bulk semiconductors and metals
to nanosystems such as molecules, wires, and sheets.
There are now a number of DFT computational
packages available that vary in the types of
exchange–correlation functionals, basis sets, pseudo-
potentials, and numerical algorithms used. These
packages share the general computational flow struc-
ture of a typical Kohn–Sham calculation laid out in
Figure 3. The input parameters of such a calculation
are typically the atom types, initial structural
arrangement, and methods for construction of
pseudopotentials. Convergence parameters for the
basis set such as the plane-wave energy cutoff
(maximum energy plane wave to use in the bases) or
basis set components in the case of localized basis orbi-
tals are specified from which an initial set of Kohn–
Sham orbitals and charge density are constructed using
Procedure for ab initio DFT calculations
Generate pseudopotentials, atomic positions
Atomic wavefunctions {ϕ(r)}
Create Veff (r)
p2
Construct Heff = + Veff (r)
2m
Diagonalize Heff
no
Is Veff (r) converged?
yes
Compute total energy and forces
Figure 3 Components in performing DFT calculations.
Initial wave functions are constructed from atomic
pseudopotentials. From these wave functions, an initial
effective potential (ionic plus Hartree and exchange–
correlation) is constructed. The Kohn–Sham Hamiltonian is
diagonalized to yield a new set of wave functions and
eigenvalues. The process is repeated until the changes in
wave functions or energies between cycles are below
specified convergence criteria.
49
the atomic wave functions. From the charge density, the
Hartree and exchange–correlation potentials are con-
structed, and the Kohn–Sham eigenvector/eigenvalue
problem is then solved (typically through an iterative
diagonalization method) to get a set of new Kohn–Sham
eigenvalues and orbitals. The process is repeated
until the change in orbitals or eigenvalues between
iterations is lower than a predefined convergence
criteria (i.e., when self-consistency is reached). The
final products are the self-consistent Kohn–Sham
eigenstates of the associated noninteracting system
from which the final electron density is obtained so
that the electron ground-state energy of the physical
system may be evaluated using Equation (7) within a
given approximation to the exchange–correlation
functional used (e.g., the LDA).
In this section, we give several selected examples
of DFT calculations of ground-state properties.
Figure 4 is taken from the classic work of Yin
and Cohen (1980), who first showed that structural
energies (as a function atomic positions) may be
accurately determined using the ab initio pseudopo-
tential density functional approach. The total energy
of the system is given by
Etotal ¼ Eel þ Eionion ð21Þ
for different structural arrangements, where Eel is
the DFT electronic ground-state energy from
Equation (10) and Eion–ion is the classical electrostatic
interaction energy among the ions. By comparing this
quantity over several assumed structures (i.e., con-
sidering the atomic degrees of freedom or
configurations), Yin and Cohen were able to deter-
mine with high accuracy the stable atomic
configuration and other structural parameters such
as the cohesive energies, lattice constants, and bulk
and other elastic moduli. With the approximate
exchange–correlation functionals described above
(i.e., the LDA and GGA), one can now calculate
cohesive energies to within a few percent of the
experimental values. To achieve a higher level of
accuracy, however, further improvement in the treat-
ment of the many-electron interaction effects (such
as the use of hybrid or other functionals) is required.
Relative energies are more accurate, yielding lattice
constants and elastic moduli that are typically within
1% and few percent of experimental values, respec-
tively. In particular, for semiconductor systems, an
accurate determination of energy landscapes and
phase stability is achievable within implementations
of the Kohn–Sham formalism.
50 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors

–7.84 –7.82

Si Ge

–7.86 –7.84
tcc
hcp
Estructure (Ry/atom)

Estructure (Ry/atom)
bcc
tcc
hcp
4 bcc
–7.88 4 sc –7.86
β-TIN sc
β-TIN
3 3

–7.90 Hexagonal –7.88 Hexagonal

diamond diamond
2 2
Diamond 1 Diamond 1

–7.92 –7.90
0.6 0.7 0.8 0.9 1.0 1.1 0.6 0.7 0.8 0.9 1.0 1.1
Volume Volume
Figure 4 Phases of Si and Ge under pressure. The common tangent line between the E vs. V curves show the point where
the Gibb’s free energy at zero temperature (EþPV) of the two phases is the same, since P ¼ -dE/dV. The slope of the line gives
the transition pressure and the change in volume across the phase transition can be determined from the volume of the two
phases at the transition pressure. Modified from Yin MT and Cohen ML (1980) Microscopic theory of the phase-transformation
and lattice-dynamics of Si. Physical Review Letters 45: 1004.

Atomic forces can be calculated by derivatives of calculation at thousands of atomic configurations

the total energy with respect to the atomic positions
(using, for example, the Feynman–Hellman formula):
@Etotal
Fi ¼
@Ri
These forces can be used to evolve a nonequilibrium
atomic distribution in space and time, in molecular
dynamics simulations (Frenkel and Smit, 2002). New
atomic positions and velocities are calculated and
evolved in time using
_ Þ
Rðt þ t Þ ¼ Rðt Þ þ t ? Rðt
and
_ þ t Þ ¼ Rðt
Rðt _ Þ þ t ? Fðt Þ
where t is an appropriately small time step. In
common applications, it is necessary to use thousands
and tens of thousands of time steps to evolve the
system for even short durations of the order of pico-
seconds. The ab initio forces can be taken from a
standard DFT calculation at a given set of coordi-
nates, but the cost of doing a complete DFT
becomes prohibitive. An alternative approach devel-
oped by Car and Parrinello (1985) to overcome this
limitation is to simultaneously evolve both the
ð22Þ atomic positions and electron wave functions. In
this approach, a full solution to the Kohn–Sham
equations is not obtained at every atomic configura-
tion. Instead, both the atomic positions and the
electronic wave functions are evolved in the mole-
cular dynamics simulation, with the latter done
through a fictitious dynamics introduced for the
degrees of freedom associated with the Kohn–Sham
ð23Þ eigenstates (Car, 1984, 2006).
The Car–Parrinello and related approaches have
extended DFT to the realms of ab initio investigation
ð24Þ
of the dynamics and thermodynamic properties of
solids and liquids, including phase transitions, impur-
ity dynamics, etc. For example, this methodology has
been used to examine the dipole moment and pair-
correlation function of water under various condi-
tions (Tassaing, 1998; Silvestrelli and Parrinello,
1999; Boero et al., 2000). In addition, computations
of phase diagrams at high temperatures and pressures
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
including liquid phases have been done using the
ab initio MD approach. Below, we shall consider the
simpler case of pressure-induced phase transition
obtainable through the application of the standard
DFT approach.
It is straightforward, utilizing the equation of state
for the various structures, to determine the behavior
of structural phase transitions under pressure by
evaluating the Gibbs’ free energy (Kittel and
Kroemer, 1980):
G ¼ E þ PV – TS ð25Þ
In particular, at low temperature, the critical transi-
tion pressure between two adjacent structures (as
depicted in Figure 4) is given by the negative of
the slope of the common tangent (pressure) of the
two equations of state, yielding the point where
the Gibb’s free energy of the two phases is the
same. This leads to the determination of the critical
pressure and the volume discontinuity at the phase
transition and provides an ab initio understanding
and prediction of the high-pressure phases of matter
such as those of Si and Ge as shown in Figure 4
(Cohen, 1982).
The preferred structure of a material system such
as that at a surface or near a defect can be found by
minimizing the total energy or the forces on the
atoms. This approach has been used with success in
determining the structural parameters of complex
materials, surfaces, defects, clusters, molecules, and
nanostructured systems of interest under imposed
boundary conditions. For nonperiodic systems, the
standard technique is to carry out the electronic
structure calculations employing a supercell scheme
(Cohen et al., 1975) in which the surface, defect, or
molecule is repeated periodically with sufficient
separation between them in order to mimic the iso-
lated structure. As we will discuss more below, for
studying isolated nanostructures, a way to minimize
the vacuum size needed is to replace the Coulomb
interaction by a new interaction that is the same as
the Coulomb interaction within a cutoff radius but
zero outside of the radius.
In addition, from information on the total energy
of the system as a function of the atomic positions as
well as the forces, we can study the lattice dyna-
mics within the Born–Oppenheimer approximation.
There are two common schemes in determining
the phonon eigenmodes and dispersions from
first principles: (1) the frozen phonon method or (2)
the linear response method. Conceptually, in the
51
frozen phonon approach (Yin and Cohen, 1980),
one calculates the energy difference in the presence
of a finite atomic distortion of the form
ui ðkÞ ¼ u0 cosðk?i þ k Þ frozen into the lowest
energy structure. k here is an overall phase shift of
the distortion. By computing the change in the total
energy of the system, E(uo), as a function of the
distortion amplitude uo, one obtains the phonon
properties via a power series expansion
E ¼ K2 uo2 þ K3 uo3 þ K4 uo4 þ    ð26Þ
where the harmonic contribution to the phonon
frequency is given by the coefficient K2 and the
higher-order coefficients give rise to anharmonic
contributions to the phonon frequency and to pro-
cesses such as phonon lifetime and phonon–phonon
interactions. This ability to easily compute the
anharmonic contributions is a major advantage of
the frozen phonon methodology. However, the size
of the supercell required to contain the distortion
depends on the wavelength of the distortion; only a
finite set of discrete phonons (those of relatively
small wavelength, which are commensurate with
the lattice) can be calculated. Points away from
symmetry points or high symmetry directions,
which lead to a very large supercell, may not be
studied in practice.
Another approach to calculating phonons involves
the use of the density functional perturbation theory
formalism to create the dynamical matrix. In this
scheme, the atomic force constants,
@2E
Cij ¼ ð27Þ
@Ri @Rj
are evaluated using linear response theory (Baroni
et al., 2001; Yin and Cohen, 1982). The resulting
dynamical matrix can be diagonalized to obtain the
phonon frequencies and eigenmodes. This approach
allows the direct computation of phonon properties
at arbitrary wave vector, k, in the Brillouin zone, but
is limited to the harmonic approximation due to the
use of linear response theory. Figure 5 shows
the results of such a linear-response calculation for
the phonon dispersions and density of states for
silicon and germanium. In practice, both frozen pho-
non and linear response approaches have given very
accurate phonon results for a variety of materials
ranging from metals to semiconductors to nanosys-
tems and molecules. This shows again the power of
the ab initio pseudopotential DFT Kohn–Sham
formalism for calculating ground-state properties.
52 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
600
Frequency (cm–1)
400 Si
200
0
Γ K X Γ
400
300
Frequency (cm–1)
Ge
200
100
0
Γ K X Γ
Figure 5 Phonons dispersion relations and density of states (DOS) in Si and Ge calculated within the linear response theory.
After Giannozzi P, Degironcoli S, Pavone P, and Baroni S (1991) Ab-initio calculations of phonon dispersions in semiconductors.
Physical Review B 43: 7231.
In the study of nanostructures, the predictive
power of the ab initio pseudopotential density func-
tional method has led to many important predictions.
We give one illustrative example here – the graphene
nanoribbons. Graphene, a single atomic layer of gra-
phite with a honeycomb structure, has generated
considerable excitement since its isolation and study
in 2005 (Novoselov et al., 2005; Zhang et al., 2005).
This 2D system exhibits many highly unusual proper-
ties and is a promising material for future electronics
and other applications (Geim and Novoselov, 2007;
Castro Neto et al., 2009). If cut into strips of nanometer
widths with the dangling -bonds passivated with
adatoms, the resulting homogeneous edge graphene
nanoribbons (e.g., with either zigzag shaped or
armchair-shaped edges) are predicted to be all semi-
conductors (Son et al., 2006a), unlike the case of
carbon nanotubes (Saito et al., 1998). The semicon-
ducting nature of the graphene nanoribbons has been
confirmed by recent experiments (Li et al., 2008).
Figure 6 shows the calculated gaps as a function of
ribbon width for the armchair nanoribbons. The
L X W L DOS
L X W L DOS
importance of DFT over lower-level theories such
as a simple -orbital-only tight-binding model is
illustrated in the structural dependence of the band
gap. The qualitative differences between the two sets
of results arise from changes at the boundaries of
the structure that are not captured in tight-binding
models based on pristine graphene. In carbon nano-
tubes (i.e., graphene nanoribbons rolled into tubes),
somewhat similar corrections to the tight-binding
results from relaxing the coordinates with respect
to the total energy are found and termed cur-
vature effects (Blasé et al., 1994; Charlier et al., 1994,
1995; Louie, 1994). As we will see in the following
sections, the DFT band structure, however, still needs
to be corrected to represent the quasiparticle
dispersion.
Another interesting result from DFT calculations
is that the zigzag graphene nanoribbons have a semi-
conducting antiferromagnetic ground state that can
be made into a half metal by an applied external
electric field (Son et al., 2006b). Figure 7 shows the
predicted ground-state spin-charge density for a
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors 53

2.5 Tight binding 2.5 LDA

Na = 3p Na = 3p
2.0 Na = 3p + 1 2.0 Na = 3p + 1
Na = 3p + 2 Na = 3p + 2
Δa(eV)

Δa(eV)
1.5 1.5 Δ3p
Δ3p + 1
1.0 1.0
Δ3p + 2
0.5 0.5

0.0 0.0
0 10 20 30 40 50 0 10 20 30 40 50
Figure 6 The Kohn–Sham electronic gap () of armchair graphene nanoribbons as a function of ribbon width between tight-
binding (left) and DFT LDA (right) calculations. The difference stems from the structural relaxation at the edges and a more
accurate treatment of electron–electron interaction effects. N is the number of rows of C-C dimers forming the width of the
ribbon. Armchair nanoribbons can be broken into three families with N¼3p, 3pþ1, or 3pþ2 for integer p. Note that the LDA
predicts a finite gap for the first family which is qualitatively different from the tight-binding result which predicts zero gap.
Modified from Son Y-W, Cohen ML, and Louie SG (2006a) Energy gaps in graphene nanoribbons. Physical Review Letters 97:
216803.

(a) 2 (b)

1
E–EF (eV)

0
–1
Electric field
–2 1.4

–3 0.0
0 π
–1.4
k(1/a)
(c) 2

1
E–EF (eV)

–1 Eext = Eext = Eext =

0.0 (V/Å) 0.0 (V/Å) 0.0 (V/Å)
–2
0 π0 π0 π
k(1/a) k(1/a) k(1/a)
Figure 7 Electronic properties of zigzag graphene nanoribbons. (a) Band structure of an 16-ZGNR with spin degree of
freedom neglected, showing two very flat edge-state  bands at the Fermi energy. (b) The spatial distribution of the charge
difference between -spin and -spin  ðrÞ –  ðrÞ for the ground state when there is no external field. (c) The spin-resolved
band structures of a 16-ZGNR at different external electric field strengths. The red and blue lines denote bands of -spin and
-spin states, respectively. Inset, the band structure in the range of  50 meV to þ 50 meV from the Fermi level. Modified from
Son Y-W, Cohen ML, and Louie SG (2006b) Half-metallic graphene nanoribbons. Nature 444(7117): 347–349.

16-zigzag nanoribbon (16-ZGNR), which has 16 zig-
zag chains forming the width (Son et al., 2006b;
Yang et al., 2007b). The DFT calculations show
that, for this system, the bands near the gap are
twofold degenerate spin-polarized edge states with
one band localized on one edge and the other band
on the opposite edge. The edge-state electrons are
ferromagnetically coupled along one edge and anti-
ferromagnetically coupled across the ribbon. By
applying a transverse electric field, thus creating a
54 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors

potential drop across the ribbon, edge states with one 15

LIF
spin orientation will be pushed into the band gap and
edge states with spin of opposite orientation will be

Fluorite
pushed away from the gap. In this a way, it is possible
to create a half metal with a 100% spin-polarized

Theoretical band gap (eV)

carrier by either applying an electric field with 10

LiCl
strength that would close the gap or by doping or Quasiparticle theory
gating the system with carriers in the presence of a

c-BN
Diamond
weaker applied transverse field.

w-AIN
w-BN
SiC, Fluorite, GaP, AIP
5
1.02.5 Excited States and

w-GaN
Znlo, ZnSe

InS
CdSe, CdTe, BP

c-GaN
CdS, AlSb
Spectroscopic Properties Many-body
corrections

AlAs
InP GaAs
Go GaSb
While DFT has proven to be an extremely useful and

Si
LDA

accurate method in calculating the ground-state
properties of semiconductors and many other con-
densed matter systems, the Kohn–Sham formalism
within static DFT does not generally give accurate
excited-state properties such as band gaps, quasipar-
ticle energies, and optical spectra. Extensions of DFT
to time-dependent density functional theory
(TDDFT), in principle, would be able to yield cer-
tain spectroscopic properties such as the optical
absorption spectrum (Reining et al., 2002). In practice,
however, approximations to date to the time-
dependent exchange–correlation functional have
restricted these studies to small finite systems such
as atoms or molecules. For bulk semiconductors and
extended semiconducting nanostructures, current
implementations of TDDFT (such as those based
on the adiabatic approximation) yield results, which
converge to those of independent particle transitions
for the optical response and thus do not provide any
improvements. This is due to an inadequacy in the
description of both quasiparticle self-energy and
electron–hole interaction effects within current
approximations, although considerable efforts are
being expended to make further progress (Reining
et al., 2002; Botti et al., 2004).
Figure 8 shows a comparison of the calculated
electronic band gap with experimental quasiparticle
band gaps for a range of semiconductors and
insulators. The LDA Kohn–Sham eigenvalues
underestimate the gaps by as much as 50% or
more. For germanium, even the band topology is
qualitatively incorrect; LDA predicts Ge to be a
metal instead of a semiconductor with a gap of
0.7 eV. HF theory, which often does well for small
molecules and atoms where screening is unimpor-
tant, consistently overestimates the band gaps of
semiconductors and insulators – the addition of
InAs
InSb
0
0 5 10 15
Experimental band gap (eV)
Figure 8 Comparison of calculated energy band gaps
with those measured by experiments. The diagonal line
corresponds to a perfect agreement between experiment
and theory. Kohn–Sham band gaps calculated within LDA
(crosses) consistently underestimate the experimental
bandgap, whereas the GW quasiparticle gaps (diamonds)
consistently give good agreement with experiment.
correlation effects systematically reduces the band
gaps since correlations lower the energy required to
create an excited electron or hole. This band-gap
problem and other similar problems that exist in
comparing calculated Kohn–Sham eigenvalues to
experimental excitation energies do not stem from
the approximation of the exchange–correlation
functional in DFT, but arise from a fundamental
and conceptual difference between the theoretical
and measured quantities. As discussed in previous
sections and illustrated by the example of the homo-
geneous interacting electron gas, the Kohn–Sham
eigenvalues are merely Lagrange multipliers within
a variational derivation of the conditions for mini-
mizing the total energy – that is, they do not
physically correspond to the true quasiparticle ener-
gies in general.
For an interacting system, it is important to dis-
tinguish the different kinds of excitations probed
in various experiments. Measurements employing
photoemission, transport, or tunneling techniques
yield, in general, information on individual particle-
like excitations or quasiparticles (excited electrons
and holes) of a system. For example, photoemission
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
(or inverse photoemission) probes a system with a
single additional hole (or electron) of a certain wave
vector and energy. Due to many-electron interac-
tions, the excited particle acquires a self-energy
which changes its dispersion relation from that of
the independent-particle or mean-field picture, and
the excitation acquires a finite lifetime. In an optical
experiment, on the other hand, one creates neutral
correlated electron–hole pair excitations. The
electron–hole interaction (excitonic) effects become
important and can in fact be dominant in many
systems, particularly nanostructures. A treatment of
excitonic effects requires an effective two-particle
approach on top of the quasiparticle picture. Self-
energy, excitonic, and other many-electron interac-
tion effects exist in all semiconductor systems to
various degrees. They are, however, particularly
relevant in understanding the spectroscopic proper-
ties of many systems of contemporary interest,
including clusters, surfaces, polymers, defects, nano-
tubes, and other lower-dimensional materials since
the Coulomb interaction is enhanced in reduced
dimensions.
The behaviors of the single-particle-like excita-
tions in semiconductor materials are best described
in terms of the quasiparticle concept (Hedin, 1965;
Hybertsen and Louie, 1985; Kadanoff and Baym,
1999). It is mostly transitions between the quasi-
particle states that are probed in spectroscopic
measurements. Because of electron–electron and
other interactions in a solid, an excited particle of
wave vector k is dressed with a screening cloud of
electrons and other excitations (e.g., phonons or spin
waves) resulting in a different energy E, effective
mass m, and a finite lifetime. In this chapter, we
focus on the effects of electron–electron interaction
since they give rise to eV-scale modifications in the
electronic excitations in semiconductors. An accu-
rate treatment of the exchange and dynamical
correlation effects, arising from the Pauli exclusion
principle and Coulomb repulsion, seen by an elec-
tron is essential in calculating the quasiparticle
excitation energies and properties. The understand-
ing of optical properties further involves the
interaction between the excited quasi-electron and
the hole that is left behind, which is mediated
through all the other electrons in the system
(Strinati, 1988; Rohlfing and Louie, 1998a, 1998b;
Albretch et al., 1998; Benedict et al., 1998).
As in the case of ground-state properties, tremen-
dous progress has been made in the past two decades
toward calculating the electronic excited-state
55
properties of condensed matter systems. It is now
possible to accurately calculate the quasiparticle
and optical spectra of many systems from first prin-
ciples, in particular, those with moderately correlated
electrons. The approach involves solving for the
single-particle and two-particle Green’s function of
the interacting-electron system. The advantage of
the approach is that one can obtain the spectroscopic
properties including the relevant self-energy and
electron–hole interaction effects without any empiri-
cal parameters and yet still be applicable to real
materials. Applications of this approach have
explained and predicted the spectroscopic properties
of a number of semiconducting systems from bulk
crystals to nanostructures.
1.02.6 Quasiparticle Properties and
the Single-Particle Green’s Function
To predict the spectroscopic properties of semicon-
ductors and other systems, it is convenient to
formulate the problem in terms of quasiparticles.
A direct way to calculate quasiparticle properties is
through a Green’s function formalism of the many-
body problem. The single-particle Green’s function
describes the propagation of the many-body system
after a single particle is added at time t ¼ 0 and
location r. For an interacting many-electron system,
it is defined as
Gðr; r9;t Þ ¼ – ih0jT fcðr; t Þcy ðr9;0Þgj0i ð28Þ
where the c’s are electron field operators, T the time
order operator, and j0i is the many-electron ground-
state wave function. A useful alternate form is the
diagonal elements of G in an orbital basis
representation
Gðp; t Þ ¼ – ih0jT fCp ðt ÞCpy ð0Þgj0i ð29Þ
where p denotes the quantum numbers of a single-
particle state, for example, the band index n and wave
vector k. Physically, the Green’s function is related to
the probability of finding a particle with quantum
number p at time t if one was injected into the system
at time t ¼ 0. While the many-body ground-state and
excited-state wave functions are extremely complex
and impractical to express explicitly in terms of the
3N coordinates of the N electrons in a system, the
single-particle Green’s function depends on only two
space–time coordinates and is, thus, substantially
56 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors

easier to deal with. With some manipulation, for

system with periodic translation symmetry (such as A(k, ε)
crystals), one can arrive at another representation of
the Green’s function, the Lehmann representation
(described here for the interacting electron gas for
simplicity) (Fetter and Walecka, 1971):
"
X h0 jcð0Þjik ihik jcy ð0Þj0 i
Gðk; !Þ ¼ hV ε
i
h! – – "i ðN þ 1Þ þ i
μ
y  k < kF
h0 jc ð0Þji – k ihi – k jcð0Þj0 i
þ ð30Þ
h! – þ "i ðN – 1Þ – i
Figure 9 Qualitative figure of the spectral weight function
A(k,") of the single-particle Green’s function of an
where,  represents the many-body states (0 denotes interacting electron system.
the N-particle system ground state and ik denotes the
ith many-body excited state with wave vector k of
characteristic frequency given by the real part of Ep,
the N þ 1/N  1 particle system), is the chemical
Re(Ep), and damped by 1/p related to the imaginary
potential, and "n is the energy of the nth excited
of Ep. This leads to the usual interpretation that the
state of the N þ 1/N  1 particle system above the
peak position in A(p, !) is the quasiparticle energy
N þ 1/N  1 ground-state energy, and the second
(real part of Ep) and the width (imaginary part of Ep)
quantized operator is cðrÞ ¼ e – iP:r=hcð0Þe – iP:r=h
gives the lifetime of the quasiparticle (contributing to
(Fetter and Walecka, 1971; Mahan, 1981). For a non-
the linewidth in a photoemission experiment, for
interacting system, this representation illustrates that
example). Finding the quasiparticle properties is then
the poles of the Green’s function occur at the inde-
equivalent to solving for the appropriate single-
pendent electron excitation energies of the N þ 1 and
particle states, which give rise to sharp peaks in
N – 1 particle systems. For such a system, the ik state
A(p,!) and is also equivalent to solving for the position
represents a simple single-particle excitation and
of the poles of G in the complex energy plane.
each ik state contributes to a single isolated pole in
For a many-body system with Hamiltonian given
the Green’s function. For a system with relatively
by Equation (1) or equivalently,
moderate electron correlations, G(k, !) along the
X X
real ! axis consists of a series of well-defined peaks, H¼ H0 ðri Þ þ Vc ðjri – rj jÞ ð33Þ
similar to the case in the noninteracting spectrum, i i<j
but each with a finite width corresponding to a pole
in the analytical continuation of this quantity off the where
real axis. In terms of the measurable spectral weight p2
H0 ðrÞ ¼ þ Vion ðrÞ
function, A(p, !)¼(1/)|ImG(p, !)|, a dominant pole 2m
in the Green’s function at a complex energy Ep cor-
responds to an A(p, !) of the form is a one-particle term and Vc the bare Coulomb
interaction, the equation of motion for the single-
ði=2ÞZp particle Green’s function can be written as (Mahan,
Aðp; !Þ ¼ þ c:c: þ correction ð31Þ
! – ½Ep –  1981; Hedin, 1965; Hybertsen and Louie, 1985)
Z
which is sharply peaked as a function of ! (see ðh! – H0 – VH ÞGðr; r9; !Þ – ðr; r0; !ÞGðr0;r9; !Þdr
Figure 9) and gives rise to a form for G in the time
¼ ðr; r9Þ ð34Þ
domain, for positive t :
Gðp; t Þ ¼ – iZp e – iReðEp Þt e – pt þ correction ð32Þ where VH is the usual Hartree potential and  is
known as the electron self-energy operator, which
where Zp is a renormalization factor describing the itself is a functional of G. A formal solution for G can
relative spectral weight present in the quasiparticle be expressed in terms of single-particle amplitudes as
peak and p is the imaginary part of Ep. The physical (Hedin, 1965; Hybertsen and Louie, 1985)
content of Equation (32) is that G, in this particular
X c ðrÞc nk ðrÞ
single-particle orbital basis denoted by p, describes Gðr; r9; !Þ ¼ nk
ð35Þ
a propagation amplitude, which is oscillatory with nk
! – Enk – ink
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
where Enk and cnk(r) are the complex solutions to the
quasiparticle Dyson equation
Z on the lifetime of the quasiparticles being suffi-
Enk – H0 ðrÞ – VH ðrÞ cnk ðrÞ – ðr; r9; Enk Þcnk ðr9Þ
 dr9 ¼ 0:
ð36Þ
Here, n and k are again the band and wave vector
quantum numbers describing the quasiparticle exci-
tations in a crystal. The positions of the poles of the
Green’s function G(!), hence, may be identified with
the complex solutions of Equation (36) and, as dis-
cussed above, are connected to the excitation energy
and lifetime of the quasiparticles. The quasiparticle
band structure and properties, thus, may be obtained
by solving Equation (36).
The quasiparticle equation, Equation (36), is
similar in form to the Schrödinger equation in one-
electron or self-consistent-field theories (such as the
Kohn–Sham or HF formalism). However, in the
Dyson’s equation, ðr; r9; !Þ is a nonlocal, non-
Hermitian and energy-dependent operator, leading
to complex eigenvalues, Enk. As seen in Equation
(32), the real part of Enk corresponds to the quasipar-
ticle energy and the imaginary part gives the lifetime.
We see that this corresponds to a Green’s function
with poles off the real axis, giving rise to peaks of
finite width in the functions G(k, !) and A(p, !) along
the real ! axis. In practice, since Enk is often com-
puted within perturbation theory, it is useful to write
the complex quasiparticle energy as a sum of an
unperturbed non-interacting energy "nk plus a com-
plex self-energy nk containing the many-electron
(exchange–correlation) effects:
Enk ¼ "nk þ nk ð37Þ
Σ = 2 1 + 2
+ 2 1 + 2
+ 2 1 + 2
Figure 10 Diagramatic expansion of the self-energy in terms of the screened Coulomb interation.
57
This physical description of the single-particle
excitations of an interacting electron system relies
ciently long on the time scale of the relevant
experimental probes that is, the widths of the
peaks in the Green’s function should be sufficiently
small so that there are well-defined peaks in
the measured spectra. Within Fermi liquid theory,
for excitation energies near the Fermi energy of a
metal or the fundamental energy gap region of a
semiconductor or insulator, the excitations are
long-lived and the quasiparticles are well-defined,
allowing us to pursue this description (Mahan, 1981;
Figure 9).
1.02.7 The GW Approximation
As discussed above, the Dyson’s equation, Equation
(36), may be solved to yield the quasiparticle
energies, lifetimes, and amplitudes. To make the
approach practical for real materials, we need an
accurate and computationally tractable method to
construct the nonlocal, non-Hermitian self-energy
operator ðr; r9;!Þ. It was shown by Hedin that
 can be systematically expanded in a series in
terms of the dressed Green’s function G and the
screened Coulomb interaction W (Hedin, 1965;
Hybertsen and Louie, 1985):
Z
W ðr; r9; !Þ ¼ " – 1 ðr; r0; !ÞVc ðr0; r9Þdr0 ð38Þ
where "ðr; r9; !Þ is the full r; r9-dependent time-
ordered dielectric matrix of the system
(see Figure 10). The advantage of this expansion in
terms of the screened Coulomb interaction over an
1
1 + 2 1
1 + 2 1...
58 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
expansion in terms of the bare Coulomb interaction
Vc is that W is, in general, much weaker than Vc due
to the dielectric screening. For example, the static
dielectric constant of a typical semiconductor is of
the order 10. Thus, a series expansion in W should
converge with fewer terms than one in Vc. An alter-
native view is that, since W and the dressed Green’s
function themselves can be expressed as series expan-
sions in the bare quantities, each diagram in
Figure 10 is a partial summation over terms in a
conventional expansion, leading to more accurate
physical results with only low-order terms.
In practice, the Dyson’s equation (Equation (36))
is typically solved within a perturbation theory
approach. In perturbation theory, it is greatly bene-
ficial to start from a mean-field scenario that is as
close as possible to the physical system (Hybertsen
and Louie, 1985). The mean-field Hamiltonian that
is typically used in quasiparticle studies for semi-
conductors is the Kohn–Sham DFT Hamiltonian
HKS within either the LDA or GGA, which already
contains the effects of exchange and correlation in
an averaged way. Perturbation theory calculation is
then performed on H ¼ H – HKS ¼  - Vxc. It is
important to point out, however, that the quasipar-
ticle approach does not depend upon DFT, but
only utilizes it as a convenient starting point for
many systems. For some systems, such as materials
with more correlated electronic states, other start-
ing mean-field Hamiltonians may be used such as
those from LDAþU or the hybrid functionals
(Miyake et al., 2006); or one may use some self-
consistent scheme to determine the best mean-field
(van Schilfgaarde et al., 2006). In the studies of real
materials, it is found that, for most cases, only
the first term of the series in Figure 10 for the
self-energy operator is necessary, yielding what is
called the GW approximation (Hedin, 1965), since
 when expressed to first order in G and W is
given by
Z that these theories approximate the solution of the
d! – i!
ðr; r9; EÞ ¼ i e Gðr; r9; E – !ÞW ðr; r9; !Þ
2
where  ¼ 0þ. Within the GW approximation, one
computes  using Equation (39) and solves the
quasiparticle Dyson’s equation for the complex
energy Enk and wave functions cnk ðrÞ, which yield
the quasiparticle properties of the system. If, instead
of expanding  in terms of G and W, we replace
W with the unscreened (or bare) Coulomb interac-
tion Vc, Equation (39) would reduce to the HF
exchange operator. Therefore, much of the physics
in determining the many-electron effects on the
quasiparticle properties, within the GW approxima-
tion, resides in the dielectric response function or
matrix "ðr;r9; !Þ, which is a two-point function in
the spatial coordinates and depends on frequency.
It has been shown that both the nonlocality and
frequency-dependence of the screening matrix play
central roles in obtaining accurate quasiparticle
properties in semiconductors (Hybertsen and
Louie, 1985).
The construction of the dielectric response func-
tion "ðr; r9; !Þ and the single-particle Green’s
function G require the greatest effort in a typical
GW calculation. Both have to be treated adequately
to obtain quantitative results that may be compared
with experiment. As mentioned above, if W is
replaced by the bare Coulomb interaction in
Equation (39), then Equation (36) reduces to the
HF equations. From this point of view, the HF
eigenvalues may be considered as a lowest-order
approximation to the quasiparticle energies, consis-
tent with Koopman’s theorem. The dielectric
function "ðr; r9; !Þ provides the dynamical and spa-
tial-screening response of the electrons that gives rise
to correlation effects going beyond bare exchange.
Similarly, the eigenvalues from the Kohn–Sham
equations in the density functional formalism may
be viewed as another set of very approximate quasi-
particle energies, with the exchange–correlation
potential Vxc(r) approximating the nonlocal, energy-
dependent self-energy operator in Equation (36).
However, we must emphasize that, as discussed
above, in principle, both the HF and Kohn–Sham
eigenvalues are only Euler–Lagrange parameters in
minimizing the total energy in ground-state theories,
and as illustrated in Figure 8, they are usually
not accurate enough as approximations to the quasi-
particle energies. It is only in the extent that
the exchange–correlation operators within self-
consistent field theories actually do approximate 
ð39Þ Dyson’s equation. In fact, different formulations of
the DFT within the Kohn–Sham schedule can lead to
significantly different Kohn–Sham eigenvalues
(Seidl et al., 1996).
The GW approximation was formulated for the
electron gas in the 1960s by Hedin and others.
However, the first-principles approach to make com-
puting quasiparticle excitations practical in real
materials was not developed until over 20 years
later by Hybertsen and Louie (1985, 1986). This
approach has since been employed with success in
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors 59

ab initio studies of the quasiparticle properties of semi- gaps are even negative. However, the GW quasipar-
conductors, insulators, surfaces, nanostructures, and ticle energies (which provide an appropriate
other material systems. A crucial step in the develop- description of particle-like excitations in an interact-
ment was the realization of the importance of the ing system) result in band gaps that are in excellent
off-diagonal elements of the dielectric matrix (called agreement with experiments for a range of materials –
local-field screening effects) in the self-energy as well from the small gap semiconductors such as InSb, to
as efficient ways to calculate and apply the equally moderate gap materials such as GaN and solid C60
important frequency dependence of the dielectric and to the large gap insulators such as LiF. Similarly
response. The latter is typically done by calculat- accurate results have been obtained for surface-state
ing explicitly the static dielectric matrix within the band gaps and for nanostructures.
random-phase approximation and extending it to
finite frequencies using schemes such as the gen-
eralized plasmon pole (GPP) model (Hybertsen
1.02.8 The GW Formalism and
and Louie, 1985). The frequency dependence of
Applications
the dielectric response has also been computed
from analytic continuation from a few points on
The procedure for an ab initio GW calculation of the
the imaginary frequency axis or explicitly on the
quasiparticle energies and wave functions is depicted
real frequency axis in recent applications (Rojas
in Figure 11. In principle, the GW formalism is not a
et al., 1995).
density-functional-based formalism – nor does it
Hybertsen and Louie (1985) showed that, with the
depend on a particular choice of basis set or input
inclusion of the full dielectric matrix, one can obtain
wave functions so long as the basis is complete and
highly accurate quasiparticle energies. Similar to
the Dyson’s equation is solved in full (i.e., diagona-
first-principles ground-state studies, the only inputs
lized within the basis). However, as discussed above,
to the calculations are the atomic numbers of the
a good mean-field starting solution is desirable. In
constituent elements and the geometric structure of
practice, GW calculations often take as input the
the system, which can be determined separately from
Kohn–Sham wave functions and eigenvalues. For
a total energy calculation. Since the screened
the case of most bulk semiconductors, it is further
Coulomb interaction, W, incorporates the dynamical
found that the Dyson’s equation as a matrix equation
many-body effects of the electrons, the dielectric
is nearly diagonal if it is expressed in terms of the
response function "ðr; r9; !Þ is key in determining
basis of the LDA Kohn–Sham eigenstates. This is not
the electron self-energy. Owing to the spatial distri-
bution of atomic positions and electron density
inhomogeneity, "ðr; r9; !Þ of a solid is a function of r
and r9 separately. In a k-space formulation, the crys- Procedure for ab initio GW calculations
talline dielectric function is a matrix "G; G9 ðq; !Þ in Mean Field Solution {ϕ nk (r ), εnk }
the reciprocal lattice vectors G; the off-diagonal
elements of this matrix describe the local field effects
due to the charge inhomogeneity in real materials Construct ε (q, G, G′, ω )
(Hybertsen and Louie, 1987). Inclusion of both local
field and dynamic effects is essential for an accurate Construct W= ε–1Vc
description of the quasiparticle properties of a real
material system.
Let us return to Figure 8, which compares both Construct Σ=GW
the Kohn–Sham gaps and the GW band gaps of a
number of insulating materials against the experi- p2
Diagonalize H = + VH + Σ{ϕ nk (r), Enk }
mentally measured quasiparticle band gaps. A 2m
perfect agreement between theory and experiment
would place the data points on the diagonal line. As
Figure 11 Procedure for carrying out GW calculations as
we discussed before, the Kohn–Sham gaps in the
developed by Hybertsen and Louie. From Hybertsen MS
LDA (or GGA) significantly underestimate the and Louie SG (1985) First-principles theory of
experimental values, giving rise to the well-known quasiparticles: Calculation of band gaps in semiconductors
band-gap problem. Some of the LDA Kohn–Sham and insulators. Physical Review Letters 55: 1418.
60 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
to say that LDA does an accurate job representing the
quasiparticle dispersion in the system; it only says
that the Schrödinger-like equation with either the
LDA Vxc or ¼iGW often has similar eigenfunctions.
They may have significantly different eigenvalues as
illustrated in the band-gap problem discussed above.
In the case of silicon, the LDA wave functions differ
from the fully diagonalized GW wave functions by
less than 0.1% (Hybertsen and Louie, 1985).
However, there are important cases where expressing
 as a matrix within the LDA orbital basis does not
yield a diagonal representation and a more preferred
basis set can be used. We discuss such cases below.
In standard GW studies, the frequency-dependent
polarizability and dielectric function are calculated
within the random-phase approximation (RPA) using
quantities from the mean-field reference system. W is
constructed from Equation (38) and G is constructed
from Equation (35). In principle, we then diagonalize
Equation (36) for the quasiparticle wave functions and
eigenvalues with the approximation that  ¼ iGW.
However, since in many cases, as discussed above,
only the diagonal elements are sizable within the
mean-field orbital basis, in applications to real mate-
rials, the effects of  can be treated within first-order
perturbation theory. In this approach, the idea is to
consider  in the form  ¼ Vxc þ (  Vxc), where
Vxc is some appropriately chosen independent parti-
cle mean-field approximation to the exchange–
correlation, and then to calculate within perturbation
theory the effect of the additional interaction
(  Vxc) within the GW approximation. For mod-
erately correlated electron systems, the best-
available mean-field Hamiltonian may be taken to
be the Kohn–Sham Hamiltonian. Thus, for most
studies in the literature, the Green’s function is typi-
cally constructed using the Kohn–Sham wave
functions and eigenvalues. In principle, the process
of correcting the eigenfunctions and eigenvalues
(which determine W and G) could be repeated until
self-consistency is reached or diagonalized in full;
however, in practice, it is found that an adequate
solution is often obtained within first-order perturba-
tion theory on the Dyson’s equation for a given .
Comparison of calculated energies with experiment
shows that this level of approximation is very accu-
rate for semiconductors and insulators and for most
conventional metals. Also, there is only very limited
experience on the importance of including the
detailed structures of the spectral function self-
consistently for the quasiparticle energies; and it
seems that the effects of self-consistency tend to
cancel those of vertex corrections to  (Hedin and
Lundqvist, 1969; Holm and von Barth, 1998;
Aryasetiawan and Gunnarsson, 1998; Aulbur et al.,
2000). However, as in the case of the effect of
higher-order terms or vertex corrections to , only
an a posteriori experience truly justifies the approx-
imations used.
A typical GW calculation using the procedure in
Figure 11 has a few technical issues worthy of some
discussion. The key ingredient to the calculation
(that is not found in HF, for example) is the full
two-point dynamic dielectric function within RPA.
The calculation of this function is based on the
polarizability and has been traditionally computed
as a sum over Kohn–Sham empty orbitals. Both the
calculations of the empty orbitals and the matrix
elements are considerably more demanding than
that of a typical ab initio pseudopotential DFT calcu-
lation for the ground state. Even requiring a larger
number of empty orbitals is the expression for 
itself.  can be broken into two terms: COH þ
SEX. SEX, called the screened-exchange term, is
simply the exchange, or Fock, term from Hartee–
Fock with Vc replaced by W. COH is an entirely
new term absent in HF theory describing the inter-
action of an electron with the Coulomb-hole created
around the charge quasiparticle. In the static limit,
COH is a local operator but in the dynamic limit, the
COH term, like the polarizability, involves a sum
over the empty orbitals. This sum converges very
slowly with respect to the number of empty orbitals.
In practice, the dependence of COH on empty orbi-
tals significantly increases the CPU time needed to
generate the large number of initial Kohn–Sham
orbitals. However, although each quasiparticle state’s
COH converges quite slowly, often needing thou-
sands of empty orbitals, differences between
quasiparticle energies converge significantly faster.
In bulk systems, where absolute energies are unim-
portant, it is sufficient to converge the calculation to
this lower number of conduction bands, whereas in
nanosystems such as molecules, it becomes essential
to often use huge number of empty orbitals, up to an
energy cutoff of 10s of Rydbergs. Recent research has
focused on approximating this sum with various
schemes, such as calculating the high-energy state
contribution within the static limit or reformulating
the problem so that no empty orbitals are involved
(Tiago and Chelikowsky, 2006; Giustino et al., 2009;
Wilson et al., 2009; Umari et al., 2009a,b; Kohn
and Sham, 1965; Bruneval and Gonze, 2008;
Reining et al., 1997).
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
10
8 Ge
6
L4,5
Γ8
4
L6
Γ6
2 charge quasiparticle is created are often large for
CBM Γ7 Γ8
0
Energy (eV)
L4,5
Γ7
–2 L6
–4
–6
L6
–8
–10 L
6
–12 Γ6
–14
L Λ Γ Δ
Wave vector k
Figure 12 GW band structure of bulk Ge as compared
to inverse photoemission experiments (open and full
symbols) Modified from Ortega JE and Himpsel FJ (1993)
Inverse-photoemission study of Ge(100), Si(100), and
GaAs(100) – bulk bands and surface-states. Physical
Review B 47: 2130.
The full quasiparticle band structures calculated
within the GW approximation for bulk semiconduc-
tors agree very well with data from photoemission
and inverse photoemission measurements. Figure 12
shows an early calculation of the quasiparticle band
structure of Ge (Hybertsen and Louie, 1985; Ortega
and Himpsel, 1993) as compared to photoemission
data for the occupied states and inverse photoemis-
sion data for the unoccupied states. The DFT LDA
band structure for Ge exhibits no gap at the  point,
that is, the system is predicted to be a metal. This
incorrect metallic behavior is corrected in the GW
calculation. For Ge, the agreement in Figure 12 is
within the error bars of experiments. In fact, the
conduction band energies of Ge were theoretically
predicted (Hybertsen and Louie, 1985) before the
inverse photoemission measurement (Ortega and
Himpsel, 1993). For bulk Si and diamond, in the
original work of Hybertsen and Louie, the indirect
gap is corrected from 0.52 eV to 1.29 eV and 3.9 eV to
5.6 eV respectively as shown in Figure 8. Thus, we
see that quasiparticle calculations within the GW
approximation effectively resolve the so-called
band-gap problem discussed above.
61
For isolated nanosystems (molecules, clusters,
nanotubes, nanowires, etc.) there are a few more
technical issues to consider. Since the calculations
are typically done with periodic boundary conditions
in a supercell geometry (Cohen et al., 1975), the
effects of screening by neighboring systems when a
X5 practical supercell dimensions. An efficient way to
eliminate this spurious interaction is to replace the
X5
Coulomb interaction with a truncated Coulomb
interaction in both the construction of the dielectric
function " ¼ 1  Vtrunc  and in W itself. The trun-
cated Coulomb interaction is equal to the true
Coulomb interaction, which goes as 1/r, within a
X5 region encompassing the entire nanostructure, but
is zero outside of this zone (Spataru et al., 2004b;
Ismail-Beigi, 2006).
Beyond the need for truncating the Coulomb
interaction, nanostructures require other considera-
X
tions when applying the GW formalism. For
molecules, it is often the case that H ¼  – Vxc is
not diagonal within the Kohn–Sham eigenfunction
basis. That is, the Kohn–Sham orbitals are not the
same as the quasiparticle states of the molecule for
some of the states. In particular, quasiparticle states
above or near the vacuum energy can change char-
acter dramatically going from a DFT–LDA to a GW
description. One such example is the silane (SH4)
molecule (Rohlfing and Louie, 1998a). The lowest
unoccupied molecular orbital (LUMO) has a quasi-
particle energy of 1.1 eV above the vacuum level
after applying the GW approximation in the com-
mon perturbation theory approach outlined above,
but has a quasiparticle energy of only 0.27 eV above
the vacuum level if the Dyson’s equation is fully
diagonalized (Rohlfing and Louie, 1998a). It is
important to note that this is not a limitation of the
GW approach but is a limit of treating the self-
energy within perturbation theory starting with
LDA eigenfunctions. For such systems, one must
either find a better mean-field starting point for the
first-order perturbation procedure or fully solve the
Dyson’s equation.
Semiconducting single-walled carbon nanotubes
(SWCNTs) illustrate the importance of self-energy
corrections to the Kohn–Sham eigenvalues in lower-
dimensional systems. Carbon nanotubes, like graphene
nanoribbons, are derived from nanometer wide strips of
graphene. In the case of carbon nanotubes, though, the
strips are rolled up into 1D tubes. Depending on the
rolling (chiral) angle and on the tube diameter, nano-
tubes can be either metallic or semiconducting with
62 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
2 (Saito et al., 1998). GW calculations show that the
(8, 0)
1.5
Enk – EnkLDA (eV)
1 diameter limit (i.e., for graphene). In the case of
0.5
0
–0.5
–1
–3 –2 –1 0 1
EnkLDA – EF (eV)
Figure 13 GW corrections to the LDA eigenvalues in the
(8,0) SWCNT. Modified from Spataru CD, Ismail-Beigi S,
Benedict LX, and Louie SG (2004a) Excitonic effects and
optical spectra of single-walled carbon nanotubes. Physical
Review Letters 92: 077402.
varying energy gaps. Figure 13 shows the self-energy
corrections to the Kohn Sham eigenvalues for an (8,0)
semiconducting single-walled carbon nanotube
(SWCNT). The LDA Kohn–Sham eigenfunctions do
represent a good approximation of the quasiparticle
wave functions for this system, yet the eigenvalues
are dramatically changed between solutions to the
Dyson’s equation and the Kohn–Sham equation. For
the (8,0) SWCNT, the electronic energy gap is opened
up by over one eV, yielding a quasiparticle gap more
than twice the Kohn–Sham gap. Obviously, such a
change dramatically impacts researchers’ ability to
connect with experiments that directly probe the
quasiparticle states, not the fictitious Kohn–Sham
states. It also illustrates the role of reduced dimension-
ality which, in general, enhances electron interaction
effects. In addition, a scaling of the band dispersion of
approximately 10% occurs for the (8,0) tube, increasing
the bandwidths of the carbon nanotube.
Although metallic nanotubes seem to be outside of
the scope of this volume on semiconducting systems,
the quasiparticle properties of metallic nanotubes in
many ways are more similar to semiconducting sys-
tems than typical bulk metals – as we see in the
sections on optical properties. In metallic SWCNT
tubes, there is no quasiparticle energy gap at the
Fermi energy, but a quantity of central experimental
interest is the band velocity, the slope of the quasi-
particle energy dispersion, which regulates the carrier
dynamics. In the usual nomenclatures, the (n,n)
SWCNTs are metallic carbon nanotubes with
increasing diameter as the integer n increases
band velocity of the metallic tubes is renormalized
due to electron–electron interactions, with increases
by up to 30% from the Kohn–Sham value in the large
graphene, where the band structure about the Fermi
energy can be described by the conical dispersion of
2D massless Dirac fermions, this quantity has been
directly measured in transport (Zhang et al., 2005;
Novoselov et al., 2005) and in angle-resolved photo-
emission spectroscopy (ARPES) experiments, which
shows excellent agreement with the GW value
2 3
(Siegel et al., in press).
Similar to those in carbon nanotubes, the quasi-
particle excitations in graphene nanoribbons also
show important self-energy effects (Yang et al.,
2007b). Figure 14 shows the band gap versus ribbon
width for the three families of armchair-edge gra-
phene nanoribbons. In each case, the band gap is
dramatically increased with the inclusion of quasi-
particle self-energy corrections. Similar results were
obtained for the zigzag edge graphene nanoribbons.
We note that, in Figure 14, the quasiparticle band
gap scales roughly as the inverse of the width and has
a value of near 1 eV for graphene nanoribbons with
width about a few nanometers, a very desirable range
for possible electronics applications.
6
LDA GW
3p + 1
5 3p + 2
3p
4
Band gap (eV)
3
2
1
0
4 6 8 10 12 14 16
Width (Å)
Figure 14 GW quasiparticle band gaps (red solid)
compared to the corresponding LDA band gaps (blue
empty) for armchair edge graphene nanoribbons of varying
width for the three families N¼3p, 3pþ1,3pþ2 where p is an
integer, as described in Figure 6. From Yang L, Park C-H,
Son Y-W, Cohen ML, Louie SG (2007) Quasiparticle
energies and band gaps in graphene nanoribbons. Physical
Review Letters 99: 186801.
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
From the above examples, it is clear that the
correct formalism, including many-electron effects,
is extremely important in describing the electronic
properties of semiconductors, particularly nanostruc-
tured systems, in connection with quasiparticle
excitations such as those measured in photoemission,
tunneling, and other transport experiments. In many
cases, neglecting these effects can lead to errors on
the order of magnitude of the quantities being
measured or even give qualitatively incorrect beha-
vior –for example, germanium is predicted to be a
metal within DFT–LDA while the GW approach
correctly captures its semiconducting character and
yields quantitatively the value of the band gap.
1.02.9 Two-Particle Excitations and
the Bethe–Salpeter Equation
We now discuss the formalism for the ab initio calcu-
lation of optical properties. For an interacting
electron system, such as a semiconductor, we must
include the interaction between the quasi-electron
and the quasi-hole created in the optical excitation
process. Thus, the study of the optical response
requires knowledge of the correlated electron–hole
excitations, jN ;0i ! jN ;S i, that do not change the
total number of electrons N in a system. (Here jN ;S i
63
Here avþ and bcþ are the second-quantization crea-
tion operators for holes and electrons, respectively.
For simplicity of notation, we use v and c to represent
both the band index and wave vector of the hole
and electron state, respectively, and we use
jvc i ¼ avþ bcþ jN ;0i to denote a configuration in
which a hole with wave vector k is created in the
valence band v and a quasi-electron is created in
the conduction band c with wave vector k þ q, as
illustrated in Figure 15, where the q  0 limit is
taken.
Electron–electron interactions mix electron–hole
configurations of the same center-of-mass q to
form the excited (excitonic) state jN ;S i. The
electron–hole amplitude or exciton wave function
in real space, which describes the spatial correlation
of the electron and hole, is then given by
X
S ðr; r9Þ ¼ AScv cc ðrÞcv ðr9Þ; ð41Þ
cv
with c(r) being the quasiparticle amplitudes (or
wave functions), for example, those obtained from
a GW calculation. As in the case of the Dyson’s
equation for quasiparticles, we use the two-particle
Green’s function’s equation of motion to arrive at
an effective equation for AS and S. These quanti-
ties can be shown to satisfy a Bethe–Salpeter
equation of the form (Strinati, 1988; Rohlfing and
Louie, 2000)
denotes the Sth neutral excited state). That is, we   X   
consider excitations for which no particles are added EckQP – EvkQP ASvck þ vckK eh v9c9k9 ASv9c9k9
or subtracted from the system. k9v9c9
¼ S ASvck : ð42Þ
Just as the quasiparticle excitations are given by
the one-particle Green’s function G, the electron-
Here the EQPs are the quasiparticle energies and Keh
hole excitations may be obtained by investigating
is the electron–hole kernel describing the interaction
the interacting two-particle Green’s function G2
between the excited electron and hole. Solving this
(which is a two-particle generalization of Equation
Bethe–Salpeter equation yields the excitation ener-
(24)) and solving its equation of motion. In the
gies and the excited-state wave functions from which
above discussion on quasiparticles, we assume the
one can compute the optical absorption spectrum,
single-particle excitations are long-lived; the theory
exciton binding energies and wave functions, and
on optical excitations here also assumes that the
other related optical quantities.
electron–hole excitations are long-lived and that
the Tamm–Dancoff approximation (Kadanoff and (a) c c (b)
Baym, 1999) is valid. The excited state jN ;S i with c
energy S (referenced to the ground-state energy)
can then be expressed as a linear combination of
noninteracting electron–hole configurations plus
υ υ υ
correction terms that are not important in the eva-
luation of the optical oscillator strength: Figure 15 (a) Schematic of a photo-excited exciton state
as a superposition of independent electron–hole vertical
hole X
X elec transitions. (b) Feynman diagrams for the BSE consisting of
j N ; Si ¼ ASvc avþ bcþ j N ; 0i þ    ð40Þ a repulsive exchange term and an attractive direct
v c interaction.
64 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
The interaction kernel, Keh, is an operator that
describes the scattering of an electron–hole pair going
from one configuration to another ðjvc i ! jv9c9iÞ
due to the Coulomb interaction among the electrons.
Using the notation 1¼(r1, 1, t1), K is given by the func-
tional derivative (Rohlfing and Louie, 1998a; Strinati,
1988)
½VH ð1Þð1; 3Þ þ ð1; 3Þ
K ð12; 34Þ ¼ : ð43Þ
Gð4; 2Þ
where the self-energy operator, , is typically treated
within the GW theory in practical implementations.
With the additional assumption that the functional
derivative of W with respect to G can be neglected
(Rohlfing and Louie, 2000), K is simplified to
K ð12; 34Þ ¼ – ið1; 3Þð2 – ; 4ÞV ð1; 4Þ
þ ið1; 4Þð3; 2ÞW ð1þ ; 3Þ
¼ Kx þ Kd :
Equation (44) has two terms, as illustrated in
Figure 15: a bare repulsive exchange interaction Kx
and a screened attractive interaction Kd. The meth-
ods for the evaluation of the matrix elements of the
kernel K and the solution to the Bethe–Salpeter
equation have been discussed in detail in the litera-
ture (e.g., Rohlfing and Louie, 2000). When spin is
considered, the exchange term only affects the singlet
excitons. Dynamical (i.e., the frequency dependent)
screening can further be neglected in Kd if the excita-
tion energies S are close to the energy of the
noninteracting pairs – in other words, the exciton-
binding energy is small compared to the optical
excitation energy itself. From the solution of the
Bethe–Salpeter equation (Equation (42)), the optical
absorption spectrum and other optical properties are
obtained from the imaginary part of the macroscopic
dielectric function,
162 e 2 X
"2 ð!Þ ¼ jhN ; 0 j e?v j N ; S ij2 ðs – h!Þ ð45Þ
!2 s
where e is the normalized polarization vector of light,
and v ¼ ð1=hÞ½H ; r is the single-particle velocity
operator. The importance of inclusion of the
electron–hole interaction comes from the nontrivial
correlations of different electron–hole configurations
jvc i in the excited state, jN ; S i, leading to coherence
effects in the optical transition matrix elements:
X Optical functions of chemical vapor deposited thin-film
hN ; 0 j e?v j N ; Si ¼ AScn hc j e?v j vi:
cv
Equation (46) is a coherent sum of the interband
transition matrix elements of the individual contri-
buting electron–hole pair transitions where the
amplitudes and phases of the AS often lead to inter-
esting interference effects. It is absolutely crucial
therefore to keep the relative phases of A intact dur-
ing the calculation and to consider a sufficiently
complete basis sets of single-particle transitions.
The Bethe–Salpeter formalism for two-particle
excitations is therefore a natural extension of the
GW formalism for quasiparticle excitations. In first-
principles implementations, calculations within both
formalisms use the same approximations for the self-
energy  and Green’s Function G. Figure 16 illus-
trates the importance of the BSE framework in
calculating the imaginary part of the dielectric func-
tion in silicon (Rohlfing and Louie, 1998a; Albretch
et al., 1998; Benedict et al., 1998). Only after including
ð44Þ
excitonic effects is quantitative agreement with
experiment in the first peak height and also the
position of the second peak reached, resolving a
long-standing puzzle in the field. This redistribution
of oscillator strength does not derive from the exis-
tence of bound excitons at the peak position but of
the mixing interband excitations from a large k and
energy range giving a large enhancement in the first
absorption peak. Such rearrangements of optical
strength also give rise to an apparent shift of nearly
50 Expt
Interacting
Nonint.
40
30
ε2
20
10
00 2 4 6 8 10
Energy (eV)
Figure 16 The imaginary part of the macroscopic
dielectric function, "2(!), as a function of incident photon
energy. Dashed line: without electron–hole interaction
effects. Solid red line: with electron-hole interaction effects.
Circles are data from ellipsometry experiment. Modified
from Jellison GE, Chisholm MF, and Gorbatkin SM (1993)
ð46Þ silicon determined by spectroscopic ellipsometry. Applied
Physics Letters 62: 3348.
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
0.5 eV for the second peak in Figure 16 (Rohlfing
and Louie, 1998a). Beyond the oscillator strength
redistribution, as in a simple hydrogenic model for
excitons in semiconductors, a series of bound exciton
states is found below the onset of absorption edge,
though their oscillator strength is weak and binding
energy is only of the order of 10 meV for Si. As seen
below, the GW–BSE approach is capable of obtain-
ing highly accurate optical spectra from first
principles and has helped elucidate the optical
response of a wide range of systems ranging from
nanostructures to bulk semiconductors to surfaces
and defects to 1D systems such as polymers and
nanotubes.
1.02.10 The GW-BSE Formalism and
Optical Response
Figure 17 illustrates the procedure for carrying out
an ab initio GW–BSE calculation to obtain quasipar-
ticle and optical properties. The BSE calculations
take as input the quasiparticle energies and wave
functions from a GW calculation. In addition, the
BSE calculation takes the full dielectric matrix cal-
culated in the GW step, which is used to screen the
attractive direct electron–hole interaction. The
direct and exchange part of the electron–hole kernel
are calculated, and the electron–hole kernel plus the
kinetic energy term as a matrix in the quasiparticle
electron–hole pair basis is then diagonalized yielding
the exciton wave functions and excitation energies.
Exciton binding energies can be inferred from the
Procedure for GW-BSE calculations
Mean Field Solution {ϕnk (r ), εnk }
GW solution {ϕQPnk (r ), εQP nk }
Construct Bethe−Salpeter K (k,c,v,k′,c′,v ′)
Diagonalize BSE Hamiltonian A S c,v,k,E S
Figure 17 Procedure for a GW-BSE calculation. The end
result of such a procedure is the ab initio calculation of the
quasiparticle and exciton states of a material system as well
as a description of the optical properties through the
expression of the oscillator strength, Equation (45).
65
energy of the correlated exciton states relative to the
interband transition continuum edge. With the exci-
tation energies and amplitudes of the electron–hole
pairs, A, one can then calculate the macroscopic
dielectric function for various light polarizations
using Equation (45), and also obtain quantities such
as electron–hole correlation functions in real space
and higher-order optical effects such as multi-photon
absorption and phonon-assisted absorption spectra.
When applying this method to isolated nanosystems
in supercell calculations, it is important, as it is in the
GW calculation, to replace W with the appropriate
screened truncated interaction. As will be illustrated
in the final section, even with well-separated systems
that are considered reasonable in DFT calculations,
the nature of the interaction between the electron
and hole in an untruncated interaction calculation
can be very different from the isolated case owing
to the unwanted influence of neighboring replicas.
Because of the generally reduced screening and con-
finement effects, one expects stronger excitonic
effects in reduced dimensional systems, which as
seen below, is indeed the case.
Figure 18 depicts the optical spectrum of bulk
GaAs. As seen from this figure and the results for Si
in Figure 16, only after the inclusion of electron–
hole interaction, there is good agreement between
theory and experiment. As already discussed above
for Si, there is a redistribution of optical oscillator
strength to the lower energy peak, enhancing it by
nearly a factor of 2. In addition, the electron–hole
interaction shifts and heightens the second main
peak, yielding agreement with experiment. This
30
25
GaAs
20
ε2
15
10
5
0
0 2 4 6 8 10
Energy (eV)
Figure 18 Calculated optical absorption of GaAs with
(solid line) and without (dashed line) electron–hole
interaction, compared to experimental data [Aspnes,
Lautenschlager]. Modified from Rohlfing M and Louie SG
(1998a) Excitonic effects and the optical absorption
spectrum of hydrogenated Si clusters. Physical Review
Letters 80: 3320.
66 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
shift of nearly 0.5 eV in the second peak (with posi-
tion near 5 eV) is not due to a negative shift of the
transition energies since the density of photo-excited
states remains nearly unchanged by the electron–
hole interaction from that of the non-interacting
case. The changes in the position and height of the
second peak in the optical spectrum in Figure 18
originate from the coupling of states over a large
energy range, effectively leading to a constructive
coherent superposition of oscillator strengths for
states on the lower-energy side of the peak and a
destructive superposition for states on the high-
energy side. Spin–orbit interaction was not included
in the calculated results in Figure 18, and, hence,
some of the fine structures associated with the two
peaks in the experimental spectrum of GaAs are not
reproduced in the theory. Within the GW–BSE
approach, in addition to oscillator strength redistri-
bution in the continuum part of the spectrum,
discrete bound exciton states below the absorption
edge are also obtained. These states come out
directly from the BSE calculation without the use
of any effective mass or other approximations. The
calculated binding energy of the lowest energy exci-
ton states in GaAs (Rohlfing and Louie, 1998a) is
4.0 meV as compared to experimental value of
4.2 meV (Michaelis et al., 1996; Sell, 1972). The the-
ory has reproduced essentially all the observed
bound excitonic structures to a good level of accu-
racy in GaAs. Thus, it is possible to obtain the
binding energy of bound excitons very accurately
from Equation (42), even if the binding energy is
only of the order of few meVs. To achieve such a
good description of the optical response of GaAs, a
very fine sampling of the Brillouin zone and the
inclusion of spin–orbit interaction are required, so
that the quasiparticle energy bands are calculated
with high accuracy.
Electron–hole effects are even more important
when applied to silicon nanowires (Yang et al.,
2007c). Silicon nanowires are quasi-1D solid wires
of silicon terminated by passivating adsorbates on the
wire surface. Such nanowires represent a potential
building block for nanoscale devices and have
recently been synthesized (Cui and Lieber, 2001;
Duan et al., 2001; Morales and Lieber, 1998; Holmes
et al., 2000). Si nanowires with diameter as small as
1.3 nm have been fabricated (Ma et al., 2003).
Figure 19 depicts a model of a Si nanowire passi-
vated with hydrogen of a diameter of 1.2 nm, with the
wire axis along the [110] direction.
y
x z
Figure 19 Ball and stick model of a silicon nanowire
terminated with hydrogen (small atoms). The wire is periodic
in the z-direction but finite in the x and y directions. Modified
from Yang L, Spataru CD, Louie SG, and Chou MY (2007c)
Enhanced electron–hole interaction and optical absorption
in a silicon nanowire. Physical Review B 75: 201304(R).
No e–h interaction
4
(// polarization)
2
A
0
α2(ω) (nm2)
With e–h interaction
4 (// polarization)
2 A1
0
2 With e–h interaction
(⊥ polarization)
0
2 4 6 8
Energy (eV)
Figure 20 Absorption vs. photon energy for the silicon
nanowire shown in Figure 19 for light polarized (top two
panels) parallel to the wire axis and (bottom panel)
perpendicular to the wire axis. The arrows marked by A and
A1 indicate the fundamental gap and the lowest-energy
exciton locations, respectively. The top panel shows the
spectrum without electron–hole interaction effects
included, whereas the middle panel contains the full
solution to the BSE. The bottom panel illustrates that light
polarized perpendicular to the wire axis is absorbed very
weakly due to depolarization effects. Modified from Yang L,
Spataru CD, Louie SG, and Chou MY (2007c) Enhanced
electron–hole interaction and optical absorption in a silicon
nanowire. Physical Review B 75: 201304(R).
In Figure 20, we show the calculated optical
spectra of the Si nanowire shown in Figure 19
employing the GW-BSE approach, with and without
electron–hole interaction effects included. The
absorption for light polarized parallel to the wire
axis exhibits two new peaks with inclusion of
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors 67

electron–hole interaction, giving rise to an appear-
ance of a shift of the spectrum by nearly 2 eV
(comparison of top and middle panel in Figure 20).
The dominant peaks in the spectrum (middle panel)
are due to resonant excitons. In addition, there is a
bound exciton state although with very weak optical
strength, labeled A1, deep inside the quasiparticle
band gap at 2.1 eV with a binding energy of 1 eV.
This binding energy is two orders of magnitude
larger than the exciton-binding energies in bulk Si.
This enhanced binding energy is a result of the
reduced dimensionality of the system, and of the
unique nature of screening in lower dimensions as
discussed in the next section.
When the GW-BSE method is applied to semi-
conducting SWCNTs, the results are extraordinarily.
Because of the 1D nature of the nanotubes, excitonic
(and quasiparticle self-energy) effects (Spataru et al.,
2004a, 2004b; Ando, 1997) are shown to be domi-
nantly important in these systems even at room
temperature. Figure 21 compares the calculated
absorption spectrum of a (8,0) semiconducting
SWCNT between the cases with and without
electron–hole interactions. As for the Si nanowires,
because of depolarization effects (Ajiki and Ando,
1994), the optical response of a tube-like object is
the strongest when the polarization of the light is
along the tube axis – the polarization used in the
calculations. The two resulting spectra are radically
different. When electron–hole interaction effects are
included, the spectrum is dominated by bound and
resonant exciton states. Each of the structures
derived from a van Hove singularity in the noninter-
acting joint density of states gives rise to a series of

(a) 250
A′1 (8,0)

200
With e−h interaction (b)
Without e−h interaction
150
ε2 (a.u.)

B′1
100 C′1

Exciton A’1
A′2
50 A
B′2 B C
A′2
C′2
0
1 1.5 2 2.5 3 3.5 4
Photon energy (eV)

(c) 300 (d) 100

Exciton A′1 Exciton C′1

75
200
|φ|2

|φ|2

50

100
25

0 0
−50 −25 0 25 50 −100 −50 0 50 100
Z (Å) Z (Å)

Figure 21 Excitons in semiconducting (8,0) SWCNTs. (a) Absorption spectra plotted with and without the electron–hole
interaction included. The oscillator strength from the continuum is almost entirely moved to the sharp bound exciton
transitions. (b) Exciton amplitude square plotted with the hole position fixed (dot in the center). (c,d) Exciton amplitude square
plotted along the tube axis with hole position fixed at z¼0.
68 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
exciton states, and these states rob all the optical
transition strength from the continuum transitions.
Panels (b), (c) and (d) in Figure 21 give the spatial
correlation between the excited electron and hole for
two of the exciton states, one bound (A’1) and one
resonant state (C’1). The extent of the exciton wave
function is about 2 nm for both of these states. For the
(8,0) nanotube, the lowest-energy bound exciton has a
binding energy of nearly 1 eV. Note that the exciton-
binding energy for bulk semiconductors of similar size
band gap is in general only of the order of tens of meVs,
illustrating again the dominance of many-electron
Coulomb effects in reduced dimensional systems.
Similar results have been obtained for other semicon-
ducting carbon nanotubes (Spataru et al., 2004a, 2004b).
These results predicted extraordinarily large exciton
binding energies, although first met with skepticism,
have been verified by recent experiments (Wang et al.,
2005; Ma et al., 2005). Owing to the unique electronic
structure of the carbon nanotubes, in addition to the
optically active (or bright) excitons shown in
Figure 21, there exist also a number of optically inac-
tive (or dark) excitons associated with each of the bright
ones. These dark excitons can be observed experimen-
tally with an applied magnetic field or light with
different polarization. These dark excitons also play
an important role in the optical properties of the nano-
tubes; for example, they strongly affect the radiative
lifetime of the optically created excitons in semicon-
ducting carbon nanotubes (Spataru et al., 2005).
For the boron nitride (BN) nanotubes, which are
wide band-gap materials, it is found that excitonic
effects are even stronger than in SWCNTs. Figure 22
shows the calculated optical spectra of an (8, 0) BN
(a) 32 With e−h interaction
28 Without e−h interaction
24 I1
α2 (ω) (nm2)
20
16
12
8 K I′1
I2 I3
4 II1
5 6 7 8
Photon energy (eV)
Figure 22 Absorption spectra and band structure of a (8,0) boron-nitride nanotube. (a) The spectrum is plotted with (solid)
and without (dashed) electron–hole interaction included. (b) Schematic of the four pairs of bands from which mixing of these
interband transitions forms the lowest bound exciton. Modified from Park CH, Spataru CD and Louie SG (2006) Excitons and
many-electron effects in the optical response of single-walled boron nitride nanotubes. Physical Review Letters 96: 126105.
nanotube. Again, the electron–hole interaction leads
to a series of sharp lines in the absorption spectrum
due to strongly bound excitonic states, and the optical
strength as in the case of carbon nanotubes is virtually
completely transferred to these states. For the (8, 0) BN
nanotube, which has the same diameter as the (8, 0)
SWCNT, the exciton binding energy of the lowest
energy exciton is over 2 eV (Park et al., 2006). This is
consistent with the fact that BN nanotubes are wide-
gap insulators. Unlike the carbon case, however, the
lowest-energy exciton is composed of almost equal
weight from four sets of nearby interband transitions,
which lead to a considerably more localized electron–
hole correlation in real space along the circumference
direction.
A surprising prediction was further made when
GW-BSE calculations were carried out for the metal-
lic SWCNTs – bound/resonant exciton states exist
despite metallic screening from the carriers (Spataru
et al., 2004a; Deslippe et al., 2007). To our knowledge,
these are the first bound excitons known to exist in
metallic systems, and they have subsequently been
observed by measurements (Wang et al., 2007). The
existence of excitons in metallic SWCNTs is a result
of the increased efficiency of an attractive interaction
in forming bound states in one dimension. This can
be seen as a result of the fact that, in one dimension,
(1) electronic screening is greatly reduced and(2) any
Rpotential (other than V ¼ 0) satisfying the constraint
V ðx Þdx  0 (i.e., is negative on average) is guaran-
teed to have at least one bound state (Kocher, 1977;
Simon, 1976).
Figure 23 shows the LDA band structure for a
(10, 10) and a (12, 0) metallic SWCNTs. For incident
(b)
6
4
E QP (eV)
2
0
(x4) –2
I4
9 Γ X
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors 69

2
2 1

Energy (eV)
0 (12,0)
0 (10,10)
−1

−2
−2
−3
0 0.2 0.4 0 0.2 0.4
k(2π/a)

Figure 23 Band structure of metallic nanotubes showing allowed optical transitions (solid arrow) and forbidden optical
transitions (dashed arrow).

light polarized along the tube axis, the optical

perturbation operator, A ? p, belongs to the identity
Without e−h interaction
representation in the group of the k-vector (Deslippe With e−h interaction
et al., 2007; Barros et al., 2006a). Therefore, the optical
transitions obey well-defined selection rules deter-
mined by the representations of this group (Barros
et al., 2006a, 2006b). This is a result of the quasi-1D
nature of nanotubes where every k-point lies along
α (ω) (a.u.)

the same high-symmetry direction causing optical

transitions to obey well-defined selection rules across
entire subbands instead of just at points of high sym-
metry. The first optically allowed transitions in the
(10,10) tube occur between the second and third
valence subbands (the bands are degenerate) and
the second and third conduction subbands (shown
by the solid red transition line drawn in Figure 23.
The facts that (1) there exists a symmetry gap pre-
venting optical transitions between the linear
dispersing bands that cross at the Fermi energy, and
2), in achiral tubes, electron–hole pairs formed from
these bands are of a different representation of
the group of the k-vector (Barros et al., 2006a,
2006b) than those of the first optically active
electron–hole pair (preventing mixing between
these two types of electron–hole states) are both
factors that also contribute to the prominence of the
excitons in the metallic carbon nanotubes. Mixing
does occur between the continuum of electron–hole
states associated with the first active interband tran-
sition (denoted by E11) and excitons associated with
the second interband transitions (E22); however,
owing to the dominance of the joint density of states
(JDOS) at the E22 van Hove singularity, resonant
excitons are formed with a contribution of over
90% from E22 transitions.
Figure 24 presents the optical absorption spectra
for the (12,0) and (10,10) carbon nanotubes over the
energy range of the first three optically allowed
Without e−h interaction
With e−h interaction
1.5 2 2.5 3 3.5 4 4.5
Energy (eV)
Figure 24 Absorption spectra of the (10,10) SWCNT (top)
and (12,0) metallic nanotubes (bottom). Although these
tubes are metallic, they behave optically as if they were
semiconductors. The binding energy for exciton states in
each tube is 50 meV, greater than the exciton binding
energy in bulk Si.
inter-subband transitions. Each feature in the fully
interacting spectrum is dominated by a single sym-
metric peak followed by a smaller tail derived from
the 1D van Hove singularity located at the position of
the peak in the noninteracting spectrum (Deslippe
et al., 2007).
In both metallic tubes, excitonic effects qualita-
tively change the spectrum due to the existence of
the exciton states. In the (10,10) tube, the bound
exciton associated with the first interband transition
has a binding energy of 50 meV. Figure 25 provides a
more detailed view of the lowest exciton in the
70 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors

100 Without e−h Int. 25 Without e−h Int. (scaled)

With e−h Int. With e−h Int.
80 20
α 2 (ω)

60 15

40
10
20
5
0
0
1.5 2 2.5 1.5 2 2.5
Energy (eV)
Figure 25 Spectral shape of absorption spectra in the (10,10) metallic nanotube plotted with (solid) and without (dashed)
the electron–hole interaction and with Lorentzian broadening of 20 meV (left panel) and 80 meV (right panel). The right panel
plot has the noninteracting spectra shifted and scaled to match the position and height of the interacting spectra for
comparison.

(10,10) SWCNT. In the left panel of Figure 25, we
see that the optical peak arises almost entirely from
the single exciton state, showing a profile that is
significantly different from the interband transition
case. As a comparison, the right panel in Figure 25
shows the noninteracting spectrum scaled and shifted
to match the peak height in the interacting case. We
see that the two lineshapes are distinctly different.
This predicted change in lineshape was recently
confirmed by experiment using optical absorption
techniques on isolated metallic SWCNTs (Wang
et al., 2007). The measured exciton-binding energy
for the (21,21) metallic SWCNT was 50 meV (Wang
et al., 2007), in good agreement with values derived
from the ab initio calculations (Deslippe et al., 2009).
The large excitonic effects described here are not
unique to the systems studied but are characteristic of
1D (as well as 0D and 2D) systems in general.
Graphene nanoribbons (see Figure 26), 2D graphene
and bilayer graphene all show similar large excitonic
effects (Yang et al., 2007a, 2008, 2009). This is largely
because of the unique nature of screening in reduced
dimensional systems that will be discussed in the next
section.

(a) (b)

E11
1 E11
1
W/o e−h interaction W/o e−h interaction
With e−h interaction With e−h interaction
Optical absorption (a.u.)

11-AGNR 12-AGNR

E11
E11

0 2 4 0 2 4
Energy (eV)
Figure 26 Absorption spectra of armchair graphene nanoribbons with 11 carbon dimer rows (left panel) and 12 carbon
dimer rows (right panel) forming the width of the ribbon. Oscillator strength from the continuum is moved almost entirely into
the sharp bound exciton peaks. Modified from Yang L, Cohen ML, and Louie SG (2007a) Excitonic effects in the optical
spectra of graphene nanoribbons. Nano Letters 7(10): 3112–3115.
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
1.02.11 Interactions in
Nanostructured Semiconducting
Materials
The application of the GW-BSE method to semicon-
ducting nanostructured materials has illuminated and
predicted several exciting new physical behaviors of
these systems. As discussed above, many-body effects
are crucial for even a qualitative understanding of
their excited state properties. This can be seen as
consequence of two general principles: first, the
Coulomb interaction is more effective in lower
dimensions, and, second, screening has a unique nat-
ure in two- or less-dimensional systems.
The first point is illustrated in Figure 27. In
the case of three (or two) dimensions, a particle
under the influence of a Coulomb potential can
avoid the singularity by traveling around the ori-
gin of the potential. The expectation value of the
3D potential can be approximately expressed as
R 3 ðrÞ
d r jr j . If  is reasonably well behaved, as it is
for the hydrogen model, than the 3D integral
about the origin integrates to a finite value with
R Vbare ðqÞ
no divergence. However, in the 1D case, dz jðzzjÞ
logarithmically diverges if the origin is included in
the integral. In the 1D Coulomb interaction, the
singularity is unavoidable for an oscillating parti-
cle, leading to large binding energies. In real
quasi-1D nanosystems, it is the finite extent of
the physical system in the other directions that
prevents the interaction between charge particles
in the system from diverging. For example, one
can define an effective screened electron–electron
or electron–hole interaction in a quasi-1D system
using an averaging in the nonperiodic directions as
(Deslippe et al., 2009)
3D/2D 1D
e
e added charge particle is zero with regions where
h
h density of the same sign is induced. A qualitative
Figure 27 3D/2D vs. 1D electron–hole interaction. In 1D,
the singularity is unavoidable, leading to greatly enhanced
exciton binding energies and other electron–electron
interaction effects. For example, the 1D bare attractive
Coulomb interaction has a bound state of infinite binding
energy compared to the value of 13.6 eV of the 3D case.
71
Z
V ðzÞ ¼ dx9dy9dr2 W ðr9 þ r2 ; r2 Þjcc ðr9 þ r2 Þj2 jcv ðr2 Þj2 :
ð47Þ
The divergence at the origin is removed due to
the spatial extent to which the particles can still be
separated when the z separation is zero. In an
SWNT, this spatial extent is the tube diameter.
While not containing a singularity, the potential
still leads to exciton binding energies much greater
than those found in higher-dimensional systems due
to the fact that the phase space over which the inter-
action is large does not vanish.
In order to truly appreciate all the physics con-
tained in the electron–hole kernel, Equation (43), it is
useful to model the dielectric function, which deter-
mines the screened interaction W. We can express an
effective 1D dielectric function in the case of a nano-
tube as "(q)¼1 – (q)Vbare (q) and the total screened
potential generated by a single ring of charge on a
tube is then (Deslippe et al., 2009; Leonard and
Tersoff, 2002)
V ðqÞ ¼
1 – ðqÞVbare ðqÞ
: ð48Þ
For the case of a semiconducting tube with band
gap, Eg, and diameter, d, the susceptibility, , can be
obtained from a 1D generalization of the Penn model
(Penn, 1962).
The interesting behavior is that the dielectric
function in momentum space approaches unity at
both large and small q (Leonard and Tersoff, 2002;
van den Brink and Sawatzky, 2000). In a typical bulk
semiconductor on the other hand, the dielectric func-
tion approaches the bulk dielectric constant at small
q. This behavior is a direct result of the fact that,
unlike in 3D semiconductors where the induced
charge is of the opposite sign as the added charge
and is a finite fraction (1 – 1/"0) of the added charge,
in 1D the total induced charge seen far away from the
charge density of the opposite sign as the external
charge is induced, as well as regions where charge
explanation for the phenomenon is shown in
Figure 28 where the polarizable charge distribution
of a semiconducting system is modeled by a simple
ball-and-spring dielectric medium (Deslippe et al.,
2009). In three dimensions, because the surface area
of a spherical shell is proportional to the radius
squared and the force generated by a charge at the
72 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors

V(z) (eV)
–0.5 (8,0)
(8,0) Vbare
h
h
–1

0 5 10 15 20
z (nm)
Figure 29 Screened (solid) and bare (dashed) Coulomb
interaction in semiconducting (8,0) SWCNTs. Modified from
Figure 28 Screening in a polarizable medium in three
Deslippe J, Dipoppa M, Prendergast D, Moutinho MVO,
dimensions (left) and one dimension (right). In three
Capaz RB, and Louie SG (2009) Electron–hole interaction in
dimensions, the amount of charge induced inside a sphere
carbon nanotubes: Novel screening and exciton excitation
of radius r is constant as a function of increasing radius,
spectra. Nano Letters 9(4): 1330–1334.
whereas in one dimension the amount of charge induced
inside a box of length z goes to zero for large z.

origin on a spring at distance r is proportional to 1/r2,
the total induced charge in a shell of radius r is
constant with respect to r. So, at large distances
from the external charge, there is a net induced
charge of the opposite sign observed surrounding
the external charge. In quasi-one-dimension, how-
ever, the surface area perpendicular to the tube axis
of a box does not change as the box length changes in
the z-direction. The total induced charge in larger
and larger size boxes drops to zero; so at large length
scales, there is effectively no screening (Deslippe
et al., 2009).
What is even more unusual is that at some inter-
mediate distance, the effect of screening in 1D
systems, such in SWCNTs, is to actually enhance
rather than weaken the Coulomb interaction. That is,
there are ranges of separations over which two par-
ticles see an anti-screening effect. This is
demonstrated for the case of a (8, 0) SWNCT using
Equation (48) in Figure 29. Because the screened
Coulomb interaction is very different in 1D, a very
distinct excitation spectrum is created for the higher-
energy exciton states form from a given pair of inter-
As discussed above, because essentially every
k-point in a quasi-1D system is on a high symmetry
direction, the optical absorption to exciton states
obey strict symmetry selection rules across entire
bands. In the semiconducting SWCNTs, the first
allowed optical excitation is just one of many (four
in the case of the zigzag tubes mentioned below)
nearly degenerate exciton states due to the band or
valley degeneracy of the quasiparticle states. These
exciton states, and their relative oscillator strengths,
come out directly from the GW-BSE calculation and
are shown in Figure 30 for the (10, 0) SWCNT.
These states can be investigated through symmetry
breaking probes such as by applying a magnetic field
or through careful analysis of photoluminescence
spectra (Shaver et al., 2007).
1.02
(10,0)
Dark –
0E6
1 Bright –
0A0
δ2
δ1
hΩ(0) (ev)

0.98
band transitions. The actual spectra are qualitatively - Dark 0B0
-
0B0
and quantitatively different from those of excitons in 0.96 -
0E6
3D or in 1D models that neglect the anti-screening
A -
0 0
effect. The higher states in the excitonic series are 0.94
considerably more bound due to the presence of the Triplet Singlet
anti-screening region; evidences consistent with 0.92
this prediction have been observed in recent mea- Figure 30 The first optical transition oA
0 in zigzag (10,0)
surements on semiconducting SWCNT (Lefebvre SWCNT is accompanied by several dark states due to the
and Finnie, 2007, 2008). well-defined symmetry in SWCNTs.
 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
1.02.12 Summary
In this chapter, we have presented the basic concepts
and methodologies in understanding and calculating
both ground- and excited-state properties of semi-
conductors and semiconductor nanostructures.
The development of ab initio pseudopotential and
DFT has led to the ability to calculate accurate
ground-state properties for many systems from first
principles. Through the advent of the GW-BSE
methodology, it is now also possible to explain and
compute the excited-state and spectroscopic proper-
ties from first principles employing the interacting
Green’s function formalism. Together these methods
form a very versatile set of theoretical techniques
that can be used on a wide range of material systems
with predictive power. We demonstrate their useful-
ness in understanding and predicting the structural,
electronic, and optical properties through some
selected examples, with a particular emphasis on
the rapidly developing field of nanoscience.
The challenges for first-principles theories are
evident on several fronts. One is on investigating
complex materials with large numbers of different
type of atoms in complex arrangements or on pro-
cesses/phenomena that span very long timescales.
The challenges here are mainly due to the greatly
increased Hilbert space needed to study large sys-
tems, and that time steps in ab initio molecular
dynamics simulations are dictated by electronic
frequencies. In general, standard DFT, GW, and
BSE calculations all tend to have bottlenecks that
scale roughly as N3 where N is the number of atoms
in the system. Even with this scaling (which is in
general superior to quantum chemistry techniques),
current methodologies and algorithms have allowed
the study of systems containing thousands of atoms at
the DFT level and hundreds of atoms at the GW-
BSE level. Another frontier is the first-principles
study of correlated electron systems such as the tran-
sition metal oxides, multiferroics, and high Tc
superconducting cuprates and pnictides. At the
DFT level, standard approximations such as the
local spin density approximations (LSDAs) can
sometimes give an incorrect ground state for the
highly correlated materials. The construction of bet-
ter exchange–correlation functionals is needed, and
is currently an active and important endeavor in the
field. Since the GW-BSE formalism is based on
many-body perturbation theory, having a good
mean-field starting point is essential for more
73
correlated systems. There have been considerable
efforts along this direction to improve upon the
methodology (Miyake et al., 2006; Bruneval et al.,
2006). Also, attempts are being made to practically
rid of the empty orbitals in the GW formalism and to
include vertex corrections or higher-order terms
(Giustino et al., 2009; Wilson et al., 2009; Umari
et al., 2009; Bruneval and Gonze, 2008; Reining
et al., 1997).
For many semiconducting/insulating systems,
upon promotion to an excited state, the system may
undergo major changes that would give rise to inter-
esting and technologically important phenomena
such as Stokes shifts, self-trapped excitons, molecular
or defect confirmational changes, etc. Some recent
work has been done to include forces within the
GW-BSE framework to study the structural effects
through the many-body Green’s function formula-
tion (Ismail-Beigi and Louie, 2003). Finally, for the
case of nanostructured materials where symmetry
plays a larger role, nonlinear optical spectroscopies
(Wang et al., 2005; Maultzsch et al., 2005) have proven
particularly efficient in characterizing the excited
states of the system. Work toward extending the
GW-BSE methodology to calculate nonlinear optical
properties such as multi-photon absorption, ultrafast
spectroscopy, and phonon-assisted absorption is
another avenue attracting considerable attention.
Progress in these and other areas are anticipated
to greatly expand our ability to study from
first-principles increasingly complex materials and
novel phenomena. (See Chapters 1.01, 1.04, 1.10 and
2.05).
Acknowledgments
This work was supported by National Science
Foundation Grant No. DMR07-05941 and by
the Director, Office of Science, Office of Basic
Energy Sciences, Division of Materials Sciences
and Engineering Division, US Department of
Energy under Contract No. DE-AC02-05CH11231.
Computational resources have been provided by
NSF at the San Diego Supercomputing Center
(SDSC) and DOE at the National Energy Research
Scientific Computing Center (NERSC). J. Deslippe
acknowledges funding from the DOE Computational
Science Graduate Fellowship (CSGF) under grant
number DE-FG02-97ER25308
74 Ab initio Theories of the Structural, Electronic, and Optical Properties of Semiconductors
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Academic Press.
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Martin R (2004) Electronic Structure Basic Theory and Practical
Methods. New York: Cambridge University Press.
Rohlfng M and Louie SG (1998) Electron–hole excitations in
semiconductors and insulators. Physical Review Letters
81: 2312.
Saito R, Dresselhaus G, and Dresselhaus MS (1998) Physical
Properties of Carbon Nanotubes. London: Imperial College
Press.
Yu PY and Cardona M (1996) Fundamentals of Semiconductors.
New York: Springer.
Relevant Website
http://www.top500.org – TOP500 Supercomputing.
 1.03 Impurity Bands in Group-IV Semiconductors
M Eto, Keio University, Yokohama, Japan
H Kamimura, Tokyo University of Science, Tokyo, Japan
ª 2011 Elsevier B.V. All rights reserved.

1.03.1 Introduction 78
1.03.1.1 Isolated Donor Atom in Semiconductors 79
1.03.1.2 Quantum Computer Using Si:P 80
1.03.2 Localization Theories in Impurity Bands 81
1.03.2.1 Impurity Conduction 81
1.03.2.2 Mott Transition 82
1.03.2.3 Effects of Localization and Anderson Transition 82
1.03.2.4 Computer Studies of Anderson Model 84
1.03.2.5 Scaling Theory of Localization 84
1.03.3 Electron–Electron Interactions in Impurity Bands 86
1.03.3.1 Theoretical Formulation 87
1.03.3.1.1 Transfer diagonal representation 87
1.03.3.1.2 Anderson-localized states 87
1.03.3.1.3 Interaction terms 88
1.03.3.2 Theory of Intrastate Interaction 88
1.03.3.2.1 Spin susceptibility and specific heat 89
1.03.3.2.2 Comparison with experiment on Si:P 90
1.03.3.3 Interstate Interactions 91
1.03.3.3.1 Direct and kinetic-type exchanges 91
1.03.3.3.2 Spin-pair model 92
1.03.3.3.3 Specific heat anomaly and spin susceptibility 93
1.03.3.4 Numerical Simulation for Interacting Donor Electrons in Si:P System 94
1.03.3.4.1 Gaussian model 95
1.03.3.4.2 Electron configurations and many-electron states 96
1.03.3.4.3 Specific heat and spin susceptibility 98
1.03.3.4.4 Comparison with experiment 99
1.03.4 Hopping Conduction and Related Phenomena 101
1.03.4.1 VRH and Mott’s Law 101
1.03.4.1.1 Formulation of hopping conduction 101
1.03.4.1.2 Mott’s law 102
1.03.4.2 Coulomb Gap 102
1.03.4.3 Formula for Magnetoresistance in the Variable-Range Regime 104
1.03.4.3.1 Appearance of spin-dependent mechanisms 104
1.03.4.3.2 Calculated results 105
1.03.4.3.3 Comparison with experiments 106
1.03.4.4 Magnetocapacitance in Intermediate-Concentration Regime 107
1.03.4.5 Spin-Dependent Behavior of Magnetoresistance in Other Systems 109
1.03.5 Conclusions 109
References 110

77
78 Impurity Bands in Group-IV Semiconductors
1.03.1 Introduction
Research on the electronic structures and physical
properties of lightly doped semiconductors is very
important, because it forms the basis of present-day
semiconductor technology. In this context, research on
impurity bands in group-IV semiconductors such as Si
and Ge has played an important role not only in the
semiconductor physics but also in the device physics.
When group-V elements such as P, Sb, and As are
doped into Si or Ge, a hydrogen 1s-like shallow
impurity state appears just below the conduction
band. This impurity state is called a donor state,
because it can contribute a free electron to the host
crystal. With an increase in impurity concentration,
various energy levels are formed by random impurity
distributions. The term ‘impurity band’ means the
continuous distribution of one-electron energies
with a certain probability distribution. In this sense,
the impurity band is quite different from an ordinary
energy band in periodic systems in which the wave-
vector is a good quantum number. Similarly, group-
III elements such as B, Al, Ga, and In doped into Si or
Ge form an acceptor state, which can contribute a
free hole to the host semiconductor.
When the impurity concentration is sufficiently
low, electronic states are localized in an impurity
atom (low-concentration regime). In the intermedi-
ate concentration regime, electronic states in the
impurity band are still localized in space, but spread
over a number of impurity atoms (Anderson localiza-
tion). The hopping conduction takes place from a
localized state to another, which shows an activa-
tion-type temperature dependence. When the
impurity concentration is larger than a critical
value, the electronic states are extended over the
whole samples, which give rise to a metallic conduc-
tivity. This metal–insulator (MI) transition, the so-
called Mott–Anderson transition, in which both the
randomness of donor position and electron–electron
interaction are important, has been one of the main
topics in solid-state physics (Mott, 1990).
Although diamond is also the same group-IV ele-
ment as Si and Ge, pure diamond is an insulator with
a wide bandgap of 5.5 eV, so that one has not con-
sidered the existence of an impurity band in
diamond. Recently, however, Ekimov et al. (2004)
reported the discovery of superconductivity in the
boron-doped diamond synthesized at high pressure
and high temperature. Their measurements showed
that boron-doped diamond with a hole-carrier
density of 5  1021 cm3 is a type II superconductor
below the superconducting transition temperature
Tc  4 K. The doped boron acts as an acceptor with
a hole-binding energy of about 0.37 eV. Baskaran
(2006) suggested an important role of the electron
correlation-driven superconductivity in an impurity
band in p-type diamond, so that a topic of the impurity
band in diamond suddenly attracted keen interests.
Although the observation of superconductivity in
boron-doped diamond is interesting, recent experi-
mental results suggested that superconductivity
occurs in heavily boron-doped samples (Yokoya
et al., 2005). This means that the holes in valence
bands in diamond may be responsible for supercon-
ductivity. Thus, the topic of superconductivity in
boron-doped diamond is not a main theme of the
this chapter. In this context, for readers who have
interests in the boron-doped superconductivity, we
would like to suggest to read a review article on
superconductivity in diamond by Takano (2008).
In this chapter, we describe various physics of an
impurity band, mainly focusing on the localized
states and hopping conduction on the insulating
side of the MI transition. The MI transition from
the metallic side was studied by many theoretical
groups, using the scaling theory and perturbation
calculations with respect to the random potential
(e.g., refer to a review article by Lee and
Ramakrishnan (1985)). On the other hand, localized
states of electrons on the insulating side were exam-
ined by a limited number of researchers. We would
like to stress the importance of strong electron cor-
relation as well as the disorder effect in the insulating
regimes, which results in very rich physics: unique
properties of electronic states and their influence on
physical properties, for example, specific heat, spin
susceptibility, and hopping conductivity.
Recently, the impurity state in semiconductors is
attracting a new interest in the field of quantum
information processing. In the quantum computation
the fundamental unit is a quantum bit (qubit), which
is a quantum-mechanical superposition of ‘0’ and ‘1’
(Nielsen and Chuang, 2000). An electron spin S ¼ 1/2,
or a nuclear spin I ¼ 1/2, can be used as a qubit.
Indeed, if spin states j "i and j #i represent ‘0’ and
‘1’, respectively, a spin state is given by their coherent
superpositition
j i ¼ C0 j "i þ C1 j #i
(jC0j2 þ jC1j2 ¼ 1). Kane proposed a silicon-based
nuclear spin quantum computer utilizing a

nanofabrication technique on phosphorus-doped sili-
con (Si:P) (Kane, 1998). The qubits are nuclear spins
I¼1/2 of 31P atoms, which can be controlled by
nuclear magnetic resonance (NMR). The nuclear
spins interact with electron spins in the phosphorus
atoms by the hyperfine interaction. Any qubit opera-
tion is achieved by tuning the resonant frequency of
NMR and electrical control of electronic states using
small metallic gates attached on the silicon surface.
One of the key elements in Kane’s quantum compu-
tation is the control of an antiferromagnetic coupling
between electron spins at adjacent donors (Section
1.03.1.2). This coupling was studied by one of the
authors of this chapter with his collaborators in the
1970s for the impurity band of Si:P with intermediate
concentration regime, to explain experimental
results of the anomalous behavior of specific heat at
low temperatures. The spin coupling can be ferro-
magnetic as well as antiferromagnetic in the case of
impurity band (Section 1.03.3.3). Therefore, our
study of electronic states in the impurity band should
be noteworthy from the modern point of view.
The organization of this chapter is as follows. In
the rest of the present section, we briefly explain the
hydrogen 1s-like electronic state in an isolated
impurity doped in semiconductor (Section 1.03.1.1)
and the basic idea of Kane’s quantum computer using
Si:P (Section 1.03.1.2). In Section 1.03.2, we overview
the transport phenomena in the impurity band and
the localization theories of electronic states. The
historical development of localization theory and
MI transition in doped semiconductors are also
surveyed.
Sections 1.03.3 and 1.03.4 are the main parts in this
chapter. These sections are devoted to a theoretical
investigation of the electronic states and hopping
conduction in the insulating regimes of doped semi-
conductors. Section 1.03.3 begins with the theoretical
formulation to examine the interplay between disor-
der and electron–electron interaction (Section
1.03.3.1). In Section 1.03.3.2 the important role of
the intrastate interaction in localized states, the lar-
gest component of the interaction, is described in
detail. The description clarifies that the intrastate
interaction results in the coexistence of doubly occu-
pied, singly occupied, and unoccupied states. The
experimental result of specific heat is compared
with the theoretical result. In Section 1.03.3.3, we
describe the effects of the interstate interactions,
particularly antiferromagnetic or ferromagnetic cou-
pling between electron spins in the singly occupied
states. The theoretical and experimental results of
Impurity Bands in Group-IV Semiconductors 79
specific heat at low temperatures and of spin suscept-
ibility are reviewed, and it is shown how the observed
strange behaviors of specific heat and spin suscept-
ibility can be explained by the theory described in
this subsection. In Section 1.03.3.4, numerical simula-
tion based on a cluster model is reviewed. Then, it is
shown how the physics of the localized states with
interstate as well as intrastate interactions is verified
by the numerical study for real Si:P systems.
The hopping conduction is described in Section
1.03.4. In the impurity band the variable-range
hopping plays an important role, as was proposed
by Mott (1968). The Mott’s law, resistivity
(T) _ exp[(T0/T)1/4] as a function of temperature
T, is described in Section 1.03.4.1. Then it is
shown how the Mott’s law is modified in the low-
concentration regime of compensated samples. In
connection with this topic, the so-called Coulomb
gap, which is a gap in the density of states at the
Fermi level caused by the long-range Coulomb
interaction, is discussed in Section 1.03.4.2. In
Section 1.03.4.3, we describe the hopping conductiv-
ity in the intermediate concentration regime using
the theoretical formalism given in Section 1.03.3. In
particular, theoretical work on the magnetoresistance
developed by Kurobe and Kamimura (1982) is
reviewed in Section 1.03.4.3, and that on magnetoca-
pacitance in Section 1.03.4.4. It should be mentioned
that their spin-dependent theory has been applied
not only to impurity bands in doped semiconductors
but also to a wide variety of materials and of systems
such as sandwiched semiconductors, amorphous
semiconductors, doped polymers, carbon fibers, etc.,
as briefly mentioned in Section 1.03.4.5.
In reviewing theories for impurity bands in
doped semiconductors, we should first mention
that we are greatly indebted to the textbooks by
Mott (1990), Kamimura (1986, 1985), Kamimura
and Aoki (1989), and Shklovskii and Efros (1984).
1.03.1.1 Isolated Donor Atom in
Semiconductors
We briefly explain the electronic state in an isolated
donor atom doped in silicon (Si) or germanium (Ge).
These elements possess a diamond crystal structure
in which (ns)2(np)2 valence electrons form sp3 cova-
lent bonds. When an atom of group-V element is
doped into the materials, four valence electrons in
the atom participate in forming the sp3 covalent
bonds, whereas a remaining electron is bound to the
nucleus of the atom by the Coulomb potential:
80 Impurity Bands in Group-IV Semiconductors
e2
U ðrÞ ¼ – ð1Þ
r
where  is the static dielectric constant of the host
crystal. A large value of  (  12 for Si and 16 for
Ge) reduces the binding energy of the impurity state
and enlarges the spatial extension compared with the
lattice constant. This enables us to employ the effec-
tive mass approximation for the impurity state (Kohn
and Luttingel, 1955).
If the bottom of the conduction band is nonde-
generate in the host crystal, the wave function of the
impurity state is expressed as
ðrÞ ¼ F ðrÞuðrÞ ð2Þ
where u(r) is the Bloch state at the bottom of con-
duction band. The smooth envelope function F(r)
follows the effective mass equation
 
h2 e2
–  – F ðrÞ ¼ EF ðrÞ ð3Þ
2m r
The isotropy of the effective mass m is assumed.
Equation (3) yields a hydrogen 1s-like ground state
F ðrÞ ¼ ðaB3 Þ– 1=2 expð – r =aB Þ ð4Þ
with the effective Bohr radius aB ¼ h =ðm e 2 Þ. Here
2
aB  30 Å for the case of Si:P, which is indeed much
larger than the lattice constant. The binding energy
is given by E1s
¼ m e 4 =ð22 h2 Þ X Ry , where Ry is
called an effective Rydberg energy and
Ry  45 meV in Si:P.
The shallow impurity state appears at Ry below
the bottom of conduction band. At finite tempera-
tures, electrons are excited from the impurity state to
the conduction band. Hence, the impurity atoms of
group-V element work as donors.
In a real case of Si (Ge), the conduction band has
six (eight) equivalent minima, the so-called valleys.
The wave function of impurity state is given by
X tional NMR technique. To rotate one of the qubits
ðrÞ ¼ i Fi ðrÞui ðrÞ ð5Þ
i
where ui(r) is the Bloch state at the bottom of valley i,
and the coefficients i are determined from the crys-
tal symmetry. In the effective mass equation, we have
to take account of anisotropy of m, since an effective
mass in the longitudinal direction ml is different from
that in the transverse direction mt , where ml ¼ 0:98
and mt ¼ 0:19 (ml ¼ 1:6 and mt ¼ 0:08) for Si (Ge)
in units of the electron mass in the vacuum. For the
calculations considering the multivalley and aniso-
tropic effective mass, the reader is referred to
Kamimura and Aoki, (1989) and Kohn and
Luttinger (1955).
In a usual case, the wave function in Equation (4)
is a good approximation to describe the impurity
state in the length scale much larger than lattice
constant. The valley degeneracy at the bottom of
conduction band is irrelevant except for quantitative
discussion of excited states (Section 1.03.3.4).
1.03.1.2 Quantum Computer Using Si:P
As an example of recent application of the above-
mentioned impurity state in Si:P, we briefly explain
a silicon-based nuclear spin quantum computer
proposed by Kane (1998). A phosphorus atom pos-
sesses a nuclear spin I¼1/2, which is used for a qubit
in the proposed quantum computer. As shown in
Figure 1(a), phosphorus atoms are aligned in a
one-dimensional array. Two kinds of metallic gates
are attached on the surface of the host silicon sepa-
rated by a barrier of silicon oxide layer: A-gates are
located just above phosphorus atoms while J-gates
are between neighboring phosphorus atoms. For the
NMR, static and alternating magnetic fields are
applied on the whole system.
A nuclear spin I interacts with an electron spin S
trapped by a phosphorus atom through the contact
hyperfine interaction
Hhyperfine ¼ A I ? S ð6Þ
with A ¼ (32/3)Bgnnj (0)j2, where B is the Bohr
magneton, and gn and n are nuclear g-factor and
nuclear magneton, respectively. The (0) is the
value of the electron wave function at the position
of nucleus. The electronic states can be controlled
electrically using metallic gates.
An idea of quantum computation is as follows.
Single-qubit operation. Nuclear spins I ¼ 1/2 in
phosphorus atoms can be controlled by the conven-
selectively, we change the resonant frequency of the
qubit using the A-gate. An electric field applied on
the A-gate pulls the electron wave function away
from the donor and thus the value of (0) is reduced
(Figure 1(b)). As a result, the effective magnetic field
by the hyperfine interaction is decreased and hence
the resonant frequency of the nucleus decreases.
Two-qubit operation. Two nuclear spins in adjacent
donors interact with each other through electrons
trapped at the donors:
H ¼ A1 I1 ? S1 þ A2 I2 ? S2 þ J S1 ? S2 ð7Þ

(a) A-gate J-gate
Barrier
31P 31P 31P Si
(b) (c) J-gate
A-gate (V = 0) A-gate (V > 0) (V > 0)
e− e− e−
Figure 1 Schematic drawing of silicon-based nuclear spin
quantum computer proposed by Kane. (a) Phosphorus atoms
are aligned in a one-dimensional array in the host silicon. Each
phosphorus atom has a nuclear spin I ¼ 1/2, which is used as
a qubit, and weakly binds an electron. Two kinds of metallic
gates, A-gates and J-gates, are attached on the surface of
silicon. (b) Using A-gates, electron wave functions of the
impurity state are modified, which changes the effective
magnetic field on the nuclear spin through the hyperfine
interaction. (c) Using J-gates, the antiferromagnetic coupling
J is tuned between electrons in adjacent phosphorus atoms.
Modified from Kane BE (1998) Nature 393: 133.
where Ii and Si are nuclear and electron spins at donor
i. An antiferromagnetic interaction J works between
the electron spins, the strength of which can be con-
trolled by changing the electron population between
the donor atoms using a J-gate. Through the control
of electronic states using the J-gate, the energy differ-
ence between two states of the nuclear spins I1 and I2,
þ and , can be tuned, where
1
 ¼ pffiffiffi ðj "i1 j #i2  j #i1 j "i2 Þ
2
Here j"ii, j#ii indicate the states of Ii. In , nuclear
spins I1 and I2 are entangled with each other: when
spin 1 is j "i, spin 2 is j #i, while when spin 1 is j #i,
spin 2 is j "i. The creation and control of the entan-
glement is one of the key ingredients of the two-qubit
operations.
The combination of single- and two-qubit opera-
tions enables any quantum computation in principle
(Nielsen and Chuang, 2000). The fundamental
researches for this quantum computer are in progress.
1.03.2 Localization Theories in
Impurity Bands
When impurities of group-V element (P) are doped
in Si or Ge, the shallow impurity states appear just
below the conduction band, as described in Section
Impurity Bands in Group-IV Semiconductors 81
1.03.1.1. By the random distribution of the impurities,
they form an impurity band in which the energy
levels are continuously distributed.
When the impurity concentration is low, the elec-
tronic states are still localized in space. Then, the
hopping transport is observed between the localized
states. By increasing the concentration above the
critical value, the insulating phase is changed to
metallic phase. In this section, we review the locali-
zation theories and the scaling theory of the MI
transition from a historical point of view.
1.03.2.1 Impurity Conduction
Various transport phenomena observed in the impur-
ity band are called impurity conduction. The
phenomenon of the impurity conduction was intro-
duced by Hung and Gliessman (1950) as a new
conduction mechanism at low temperatures in
doped silicon and germanium. Then, Fritzsche
(1958) reported that in n-type-doped semiconductors
there are three regimes of donor concentration
according to the features of electronic conduction at
low temperatures. In the low-concentration regime,
each electron is trapped in the hydrogenic 1s state
around each donor impurity. The conduction takes
place at low temperatures only in compensated sam-
ples, where, besides donors, the smaller number of
acceptors are doped. In the compensated samples, the
empty donor states coexist with the occupied ones
since the acceptors capture an extra electron. Then
ð8Þ an electron in an occupied state can hop to a vacant
state, giving rise to an activation-type conductivity:
 ¼ 3 expð – "3 =kB T Þ ð9Þ
(see Section 1.03.4.1.1). As the impurity concentra-
tion is increased, there appears another insulating
regime called intermediate concentration regime. In
this regime, the conduction is of activation type:
 ¼ 2 expð – "2 =kB T Þ ð10Þ
The activation energy "2 decreases with increasing
donor concentration and finally vanishes at the cri-
tical impurity concentration nc, where the MI
transition takes place. Above nc, the conduction
becomes metallic.
Summarizing the above results, the conductivity
is expressed in the form
 ¼ 1 expð – "1 =kB T Þ þ 2 expð – "2 =kB T Þ
þ 3 expð – "3 =kB T Þ ð11Þ
82 Impurity Bands in Group-IV Semiconductors
Here, "1 is the energy required to eject an electron
into the conduction band.
As regards the origin of the concentration-
dependent activation energy, "2, it was first ascribed
to the energy required to remove an electron from
one donor and transfer it on another donor that
already has an electron. The final state is called
D ion, that is, a negative donor ion. Figure 2
shows that, with increasing donor concentration,
both the donor ground (1s) state and D state
broaden to form a band of energy levels. They are
called D band and D band, respectively. In the
uncompensated case, the D band is completely filled
by electrons and the conduction occurs only by
exciting electrons from the D band to the D band.
Thus, the activation energy, "2, corresponds to the
energy gap between these bands. It is seen in
Figure 2 that this gap energy, "2, decreases as the
donor concentration, nD, increases and finally it
vanishes at a certain concentration, nc, at which
the MI transition takes place. Since the appearance
of the D band is due to the electron-correlation
effect in a donor atom, this MI transition was first
considered as the Mott transition, which was
induced by electron–electron interaction.
1.03.2.2 Mott Transition
Mott pointed out an important role of electron–
electron interaction in the electronic states, originally
to explain the insulating character of NiO (Mott,
1990). If the disorder effect is irrelevant in the
impurity band, the simplest model to consider the
electron–electron interaction is the Hubbard model
D − state D − band
ε2
D state D band
nD
nc
Figure 2 Schematic illustration of D and D bands as a
function of donor concentration (nD). When each donor
impurity has one electron, the D band is completely filled by
the electrons when nD is smaller than the critical value (nc).
Thus, an extra electron is accommodated in the D band,
while a hole exists in the D band when an electron is taken
out from a donor impurity. In this sense, the D and D bands
are the bands for quasi-particles.
in a regular lattice (Hubbard, 1963, 1964a, 1964b;
Mott, 1976):
X y
X
H¼ tij ci cj  þ U ni" ni# ð12Þ
ij  i
y
where ci and ci are creation and annihilation opera-
tors of an electron at site i with spin , respectively.
The transfer integral tij is a constant V for the nearest
neighbors and zero otherwise. Further, U is the
Coulomb energy when two electrons occupy the
same site, or it corresponds to the energy of D
state. Let us consider the half-filling case where the
number of electrons is the same as the number of
lattice sites (donors), corresponding to the uncom-
pensated case in doped semiconductors. When the
distance between the donors is so large that the
transfer integral V is much smaller than interaction
energy U, it is favorable that each electron stays at
one donor owing to the repulsive interaction energy
between two electrons. This is the case of insulating
phase (Mott insulator). With increasing donor con-
centration, nD, the donor–donor distance decreases
and in consequence the transfer integral, V, increases:
the D and D bands in Figure 2, which are called
lower and upper Hubbard bands, respectively, in
terms of the Hubbard model, are broadened with V.
When V  U, the electrons move around to gain the
kinetic energy, which corresponds to the metallic
phase. At a critical value of the concentration, nc,
the MI transition takes place. This MI transition
due to the electron–electron interaction is called
Mott transition.
Nowadays, it is known that the disorder effect
is relevant to the MI transition in the impurity
band (Anderson transition) rather than the elec-
tron–electron interaction (Mott transition). On the
other hand, the Hubbard model has been intensively
studied in the context to investigate the strongly
correlated systems, including copper-oxide materi-
als of high-Tc superconductivity (see a review
article by Imada et al. (1998)).
1.03.2.3 Effects of Localization and
Anderson Transition
Anderson (1958) showed that in a random potential
one-electron wave functions are localized if the ran-
dom potential is strong enough. Following
Anderson’s theory, Mott (1967) and Cohen et al.
(1969) introduced the concept of the mobility edge
in such a way that the electronic states caused by the

disorder are localized in one energy range and
extended in another, both ranges being separated
from each other by a critical energy Ec:
ðEÞ ¼ 0 for E < Ec
ðEÞ 6¼ 0 for E > Ec
where (E) represents the mobility at energy E. This
is why Ec is called as the mobility edge.
In the late 1960s, Mott developed an idea of
localization by disorder and suggested that the effect
of disorder plays an important role in the impurity
band (Mott, 1990; Mott and Davis, 1979). According
to his idea, at low donor concentration all states in
the D band are localized in the Anderson sense,
which he called Anderson-localized states. As the
donor concentration nD increases, D and D bands
broaden and eventually overlap with each other. In
this case the states at the upper part of the D band
become extended, as in Figure 3, and a mobility edge
Ec separates extended states from localized states.
This is the situation in the intermediate concentra-
tion regime, where the current is carried by electrons
excited above the mobility edge Ec. The activation
energy, "2, in Equation (10) is thus given by
" 2 ¼ Ec – EF
where EF is the Fermi energy.
As nD further increases, Ec  EF diminishes and even-
tually disappears at nD ¼ nc. For nD > nc, the system
shows a metallic behavior. In this case, the mechan-
ism of the MI transition is of one-electron nature,
namely, at nc the wave function at EF changes from a
localized nature illustrated in Figure 4(b) to an
extended one in Figure 4(a). This MI transition is
called where Ef is the Fermi energy Anderson transi-
tion. It was suggested that the MI transition at nc in
doped semiconductors is of Anderson type rather
than Mott type.
D(E)
E
EF Ec
Figure 3 Schematic drawing of the electronic density of
states in the intermediate concentration regime. Electronic
states are localized at E < Ec (hatched region).
Impurity Bands in Group-IV Semiconductors 83
(a)
ψ(r)
r
ð13Þ
(b)
exp(−|r − r0| /ξ)
ψ(r)
r
r0
Figure 4 Wave function of an electron in (a) extended
states and (b) Anderson-localized states.
The existence of localized states around EF for
nD < nc was supported by experimental results of
variable-range hopping conduction in Ge:Sb at very
low temperatures in the intermediate concentration
regime by Allien and Adkins (1972). Prior to their
experiment, the conduction was predicted by Mott
ð14Þ (1968), in which the conductivity varies with tem-
perature T as
hop ¼ 4 expð – A=T 1=4 Þ ð15Þ
This hopping conduction is treated in detail in
Section 1.03.4.
In addition to the concept of the variable-range
hopping conduction, Mott (1970, 1972) also pro-
posed another important concept, minimum
metallic conductivity. According to his idea, the
zero-temperature conductivity  (T ¼ 0) jumps at
nc from zero in the insulating phase to a minimum
metallic value given by
min ¼ const  e 2 =ðhnc– 1=3 Þ ð16Þ
where the constant is 1/20 within a factor of 2. An
intuitive derivation of min is as follows. In the metal-
lic regime, the conductivity can be expressed by the
Drude formula,  ¼ e 2 kF2 l=ð32 hÞ, where kF is the
wavevector at the Fermi level and l is the mean free
path. With increasing disorder, the mean free path
decreases but it cannot go below the wavelength 1/kF
where the Drude formula becomes meaningless.
Therefore,  should be larger than the value
which is estimated by  at kFl  1. Mott called
min as the minimum metallic conductivity, and
84 Impurity Bands in Group-IV Semiconductors
using the Kubo–Greenwood relationship he showed
that 2 in Equation (10) is equal to min.
Although the scaling theory does not favor the
presence of min, as we see later, the concepts of
minimum metallic conductivity and variable-range
hopping stimulated many researchers in the field of
disordered systems.
1.03.2.4 Computer Studies of Anderson
Model
Through a number of attempts to check the validity
of Mott’s concepts theoretically and experimentally,
much progress was made in the research of disor-
dered systems in the 1970s. As one such attempt,
various theoretical groups tried to calculate the elec-
tronic structures and metallic conductivity of
disordered systems by computer simulation. The
computer simulation is based on the Hamiltonian
proposed by Anderson (1958), called the Anderson
model. The Anderson model is essentially a tight-
binding model in a regular lattice, with on-site ener-
gies distributed randomly. In the notation of second
quantization, the Anderson model is expressed by the
Hamiltonian
X y
X y
H¼ "i ci ci þ tij ci cj 
i ij 
where i, j represent the sites in a regular lattice. The
one-electron energy, "i, which takes a random value,
is uniformly distributed over the range from W/2
to W/2. The transfer integral is tij ¼ V for the nearest
neighbors and zero otherwise. The computer simula-
tion can be carried out more easily for two-
dimensional systems than three-dimensional systems.
Edwards and Thouless (1972) were probably the
pioneers for such a calculation. Yoshino and
Okazaki (1976, 1977) performed elaborate calcula-
tions on a square lattice of size 100  100 and
obtained the eigenstates in this system. They found
that for W/V ¼ 8 the wave functions at the center of
the band are strongly localized and decay exponen-
tially with a localization length of about 5 atomic
spacings. Further, they inferred that the MI transition
might take place at W/V  6.5.
Although the existence of exponentially localized
states in two dimensions was established from their
results, there remained a problem concerning the
existence of extended states. Licciardello and
Thouless (1978) extended their earlier calculations
(Licciardello and Thouless, 1975a,b) based on the
scaling idea of Thouless (1974) to the systems of
larger size. In the scaling arguments, Thouless
related the degree of localization to the sensitivity
of the energy levels to the boundary condition. For
samples of size L, a dimensionless conductance is
defined by
gðLÞ ¼ "ðLÞ="ðLÞ ð18Þ
where "(L) is the mean shift of the energy levels by
changing the boundary condition from periodic to
antiperiodic and "(L) is the mean spacing of energy
levels. If the wave functions at energy E are localized
with an exponential envelop, like
j ðrÞj  exp½ – ðEÞjr – r0 j ð19Þ
with (E) being the inverse localization length, then
"(L) and hence g(L) will behave as
gðLÞ ¼ exp½ – 2ðEÞL ð20Þ
If the wave functions are extended, on the other
hand, "(L) should be basically independent of L.
Then, g(L) yields the conductance in units of e2/h.
The quantity g is often called the Thouless number.
Licciardello and Thouless found that, with suffi-
ciently large sample sizes, the states identified as
extended previously exhibit the Thouless number
that decreases with increasing sample size. They
ð17Þ
suggested, therefore, that these states are actually
localized states with long localization lengths. This
also meant that their earlier results, which were con-
sistent with the existence of minimum metallic
conductivity, might not be conclusive.
This conclusion affected the research on disor-
dered systems since most researchers had assumed
the existence of the minimum metallic conductivity.
Since the computer simulation was limited to sys-
tems of finite size, it was necessary to derive real
conductance in a system of infinite size. For this
purpose, the scaling theory was most appropriate.
This was the dawn of the scaling theory of
localization.
1.03.2.5 Scaling Theory of Localization
Abrahams et al. (1979) developed a scaling theory
based on the arguments of Thouless (1974). The
problem concerns the behavior of the conductance g
in Equation (18) when the linear-dimension L of the
system is changed. To change the system size, cubes
of size L in d dimensions are put together to make a
larger cube of size bL. Abrahams et al. (1979, 1980)

asserted that g(L) is the relevant dimensionless ratio
that determines the change of energy levels when the
hypercubes are fitted together. Thus, when a new g
for larger blocks is computed, the only relevant quan-
tity determining the new g(bL) is the old one, namely
g(L). Hence,
gðbLÞ ¼ f ½b; gðLÞ ð21Þ
where f is a universal function depending only on the
dimensionality of the system. Taking an infinitesimal
increase in the scale size, b ¼ 1 þ ", Abrahams et al.
obtained the following scaling equation for g(L):
 
d ln gðLÞ 1 qf ðb; gÞ
¼ X ðgÞ
d ln L gðLÞ qb b¼1
where (g) is called scaling function.
The asymptotic forms of (g) are given for g ! 0
and g ! 1 in the following: (1) in the strongly loca-
lized regime (g ! 0), we have g(L) _ exp(2L/
) et al. (1982) tried to confirm the above-mentioned
with
being the localization length, so that (g) !
ln g þ constant; and (2) in the opposite limit of g !1,
the conductance is given in terms of the conductivity
, as g(L) _ Ld  2 in d space dimensions, which
yields (g) ! d  2. Assuming that (g) is monotonic
in g, Abrahams et al. obtained the behavior of the
scaling function as a function of g for one (d ¼ 1),
two (d ¼ 2), and three (d ¼ 3) dimensions, as illu-
strated in Figure 5. Important conclusions deduced
from the figure are:
1. For dimensionality d > 2, there exists a mobility
edge at which conductivity continuously tends to
zero. This implied that, first, there is no minimum
metallic conductivity, and, second, d ¼ 2 is the
lower critical dimensionality, above which both
extended and localized states can exist.
1
gc d=3
β(g)
0 g
d=2
−1
d=1
Figure 5 Schematic drawing of scaling function (g) in
one, two, and three dimensions. Arrows indicate the flow
toward larger scales.
Impurity Bands in Group-IV Semiconductors 85
2. For d ¼ 2, there is no true metallic conduction. All
the states are localized in the limit of infinite
system size. The conductance as a function of L
always decreases with increasing L in two dimen-
sions, with a logarithmic dependence for small g
and an exponential dependence for larger g.
The scaling theory gave great impetus to the
problem of the impurity conduction. In order to
check experimentally whether or not the minimum
metallic conductivity exists at the MI transition in
doped semiconductors, Rosenbaum et al. (1980) mea-
sured the conductivity of uncompensated Si:P
ð22Þ samples with donor concentration very close to the
MI transition. Their result indicates that the transi-
tion is very sharp but the conductivity extrapolated
to T ¼ 0 goes below the value of the minimum metal-
lic conductivity, min, predicted by Mott. Paalanen
experimental results by making a high-resolution,
zero-temperature study of the MI transition, apply-
ing uniaxial stress to one sample of slightly insulating
concentration. Figure 6 shows their experimental
results, which can be fitted by the form
ð0Þ ¼ c ½ðn=nc Þ – 1 & ð23Þ
with n being the electron concentration (n ¼ nD in
the uncompensated samples), where c ¼ 260  20
103
Insulator Metal
σ (T = 0) (Ω−1cm−1)
102
σmin
10
1
0 2 4 6
nD (1018 cm−3)
Figure 6 Experimental results for zero-temperature
conductivity (0) shown against the donor concentration nD
for Si:P systems obtained by Paalanen et al. (1982) (open
circles) and by Rosenbaum et al. (1980) (solid circles).
Modified after Rosenbaum TF, Andres K, Thomas GA, and
Bhatt RN (1980) Physical Review Letters 45: 1723.
86 Impurity Bands in Group-IV Semiconductors
( cm)1 and  ¼ 0.55  0.10. This observed criti-
cal behavior is not consistent with the scaling theory
by Abrahams et al. that predicted  ¼ 1. The incon-
sistency between the scaling theory and experimental
result in Figure 6 may suggest an important role of
the electron correlation at the transition in Si:P sys-
tems, which is not taken into account in the scaling
theory.
The experimental result for another
three-dimensional disordered system, Si-doped Alx
Ga1xAs, is shown in Figure 7 (Katsumoto et al.,
1987). In this system, carriers are created when elec-
trons trapped in deep donor states are photoexcited to
conductive states, resulting in the persistent photo-
conductivity. By this method, Katsumoto et al. tuned
the electron concentration, n, to a resolution of 0.2%
around the critical concentration. Figure 7 clearly
shows that the conductivity changes as  _ n/nc  1
in the metallic region (n > nc), indicating  ¼ 1 in
accordance with the scaling theory.
Regarding the puzzle of a critical exponent, that
is, about a question of whether the value of  is
explained by the scaling theory or not, there have
been a significant amount of experimental work to
n (1016 cm−3)
2.4 2.8
0.4
σ (S cm−1)
2 0.2
0
0 0.02
n/nc−1
0 electron picture in the metallic phase and investi-
520 600
Total exposure time (a.u.)
Figure 7 Experimental results for the conductivity as a
function of the concentration of photoexcited electrons in Si-
doped AlxGa1xAs. The carrier concentration n is tuned by
changing the total exposure time of light. The conductivity 
changes as  _ nD/nc  1 in the metallic region (n > nc) in the
vicinity of critical concentration nc (inset). Modified from
Katsumoto S, Komori F, Sano N, and Kobayashi S (1987)
Journal of the Physical Society of Japan 56: 2259.
determine the critical exponent  (Milligan et al.,
1985; Löhneysen, 2003). Recently, Itoh et al. (1996,
2004) performed a detailed study for the critical
behavior of conductivity on the metallic side and
that of dielectric susceptibility on the insulator side
in homogeneously doped p-type Ge samples. To
examine the vicinity of the MI transition, the pre-
paration of homogeneously doped samples is
required. For this purpose, they employed the neu-
tron transmutation doping (NTD) technique to a
chemically pure and isotropically enriched 70Ge
crystal. When the samples are irradiated with ther-
mal neutrons, some of the 70Ge atoms capture a
neutron and change to 71Ga acceptors. This NTD
technique enables homogeneous doping to the
atomic level and fine-tuning of the carrier concen-
tration. They concluded that   1 for compensated
samples and   0.5 for uncompensated samples (Itoh
et al., 1996, 2004). Even in uncompensated samples,
the critical behavior with   1 was observed in the
very vicinity of MI transition. However, this should
be attributable to unexpected compensation effect.
Their experimental result implies that the scaling
theory can describe the MI transition for the com-
pensated samples but cannot for the uncompensated
samples, possibly due to strong correlation effect in
the latter. In this context, the understanding of the
MI transition requires further theoretical studies,
taking into account the electron–electron interaction
(Kawabata, 1985; Altshuler and Aronov, 1985;
Fukuyama, 1985; Kaveh, 1985; Di Castro, 1988;
Belitz and Kirkpatrick, 1994).
1.03.3 Electron–Electron
Interactions in Impurity Bands
There are two main streams of theoretical approach
to investigate the MI transition in doped semicon-
ductors, which are complementary to each other.
The first stream of approach starts from the free-
gates how the localized states begin to be formed by
the scattering of free electrons with impurities. These
studies were prevalent with use of the diagrammatic
expansion and renormalization technique for the
so-called weakly localized regime of doped semicon-
ductors (Lee and Ramakrishnan, 1985). The second
stream of approach covers the insulating phase con-
sisting of the Anderson-localized states and
investigates the Anderson localization itself.
 Impurity Bands in Group-IV Semiconductors 87

In this section, we describe the theoretical work both random variables, while the second part
along the latter stream (Kurobe and Kamimura, 1982, represents the electron–electron Coulomb interac-
1983; Kamimura, 1986, 1985, 1978b, 1978a, 1980, tion U, where hij jU jkl i is its matrix element. If we
1982; Kamimura and Yamaguchi, 1978; Yamaguchi adopt the eigenstates of H0 as a set of basis func-
et al., 1979, 1980; Kamimura et al., 1982, 1983; tions, called transfer-diagonal representation, the
Takemori and Kamimura, 1982, 1983a, 1983b; Hamiltonian can be rewritten as
Kurobe et al., 1984). In the preceding section, we X 1X
have already seen that both the electron correlation H¼ " n̂ þ U n̂ n̂ – 

2 
and disorder play important roles in the MI transi- 1 X9 X y y
tions in doped semiconductors. Here, we would like þ U  c c 9 c9 c ð25Þ
2   9
to point out remarkable effects of electron–electron 

interaction in the intermediate concentration regime where ji represents an eigenstate of H0 with eigen-
of doped semiconductors. In this regime, T-linear energy ". It is expressed as
specific heat was observed by Kobayashi et al. X
(1977). This fact means that the density of states at ji ¼ vi jii ð26Þ
i
the Fermi level D(EF) is finite in spite of the insulat-
ing phase. Nevertheless, the spin susceptibility does with a unitary matrix vi. Here, the one-electron
not obey the Pauli law. Ue and Maekawa (1971) and energy " is also a random variable. We have also
Quirt and Marko (1972a,b) observed Curie-type sus- introduced the notation of
ceptibility in the intermediate concentration regime
y
in electron spin resonance (ESR) experiments. The
occurrence of the Curie-type susceptibility should be
ascribable to the effect of electron correlation, as
pointed out by various authors (Kamimura, 1978a,
1978b; Kapian et al., 1971; Kobayashi et al., 1978).
n̂ X c c ; U  X h jU ji; U X U
In Equation (25) we have separated the electron–
electron interactions into those within a state ji
and the remaining off-diagonal interactions,
denoted by the summation 9 excluding the case
Therefore, we have to investigate the electronic of  ¼ ¼  ¼ . The former are called intrastate
states in the intermediate concentration regime, tak- interactions and the latter interstate interactions.
ing into account both effect of the electron–electron The interstate interactions are further classified
interaction and disorder on an equal footing. into direct Coulomb U  , direct exchange
U , and the remaining interactions as we shall
see later.
1.03.3.1 Theoretical Formulation
1.03.3.1.1 Transfer diagonal
representation 1.03.3.1.2 Anderson-localized states
Following Kamimura (1985, 1982), the Hamiltonian in If there is stronger disorder, the transfer-diagonal
the presence of both disorder and electron–electron representation bases ji are localized in the
interaction is written generally in the tight-binding Anderson sense although there exist also extended
scheme as states above the mobility edge. In the strongly loca-
lized regime the amplitude of the wave functions
H ¼ H0 þ H1 decreases with the distance apart from the localiza-
P y P y tion center, on the average, in an exponential
H0 ¼ "i ci ci þ tij ci cj 
i ij  ð24Þ envelope function (Figure 3(b)). Thus, the coeffi-
1XX y y cients in the linear combination of impurity wave
H1 ¼ hij jU jklici cj 9 cl9 ck
2 ijkl 9
functions in Equation (26) can be written as


where y
ci and ci are the creation and annihilation vi ¼ v~i expð – jri – r j=
 Þ ð27Þ
operators of an electron at the ith site with spin , where v~i represents a random phase factor,
 the
respectively, ji i is a Wannier function at the ith localization length, and r the center of the localized
site with one-electron energy "i, and tij is the state ji. From the normalization condition, hji ¼ 1,
transfer integral between ith and jth sites. In this we obtain
Hamiltonian, the first part represents the single-
particle Hamiltonian with "i and tij, which are jvei j2 ¼ 4ðR0 =
 Þ3 =3 ð28Þ
88 Impurity Bands in Group-IV Semiconductors

where R0 is half the average distance between For

¼ R0, the most probable values of the spin-
impurities defined by dependent nearest-neighbor interactions are esti-
mated to be
4R30 =3 ¼ 1=nD ð29Þ  
U < 0:47U ð35Þ
In deriving Equation (28), the summation over the 
impurity sites has been replaced by the integral over and
the whole space divided by the average volume  
U  < 0:31U ð36Þ
occupied by each impurity. The quantity
 is a 
function of one-electron energy " and considered These values are, however, still overestimates,
to have the following critical behavior in the vicinity because if we are to consider only the localized states
of the mobility edge Ec: with state energies close to each other, the average

 =aB _ j1 – " =Ec j – ð30Þ distance between their localization centers r must
be larger than the average impurity distance R0, and
where is the critical exponent and aB is the effective the interactions between them should be much smal-
Bohr radius. ler than the values estimated above.
It must be noted that the above estimates of inter-
action terms are made for the case where
is of an
1.03.3.1.3 Interaction terms order of R0. If the impurity concentration is increased
Bearing the form of Equation (27) in mind, we can to approach nc, U becomes smaller as localization
estimate the magnitudes of interaction terms U and becomes weaker and all the interaction terms U 
U . If we neglect the overlaps between different will be of the same order of magnitude.
Wannier states, we obtain
X
 
U  ¼ vi vj vi vj  hij jU jij i ð31Þ
ij
1.03.3.2 Theory of Intrastate Interaction

If we further assume that an intra-Wannier-state As shown in the previous subsection, in the

correlation energy hiijU jiii is a constant U0 and a Anderson-localized regime the interstate interactions
Coulomb potential between different Wannier states are small compared with the intrastate interaction
has a functional form of hij jU jiji ¼ e2/ jri  rj j, the except in the vicinity of the MI transition. Thus, in
largest is the intrastate interaction energy U and is this regime it is reasonable to consider only the
estimated to be intrastate interaction as the first approximation, and
  we consider the following Hamiltonian:
1 4U0 R30 5e 2 X
U  þ ð32Þ 1X
8 3
3 8
  H¼ " n̂ þ U n̂ n̂ –  ð37Þ

2 
The first term dominates in the Anderson-localized
regime where the localization length is comparable On the basis of this Hamiltonian, Yamaguchi et al.
to the average impurity distance. In such a case, the (1979, 1980) investigated the interplay of disorder
intrastate interaction energy depends on the state and intrastate interaction in the Anderson-localized
energy in the following way: regime. The effects of interstate interactions, which
are neglected in this subsection, are discussed in the
U =U0 _ ð1 – " =Ec Þ3 ð33Þ following subsection.
Since there is no electron transfer in Hamiltonian
if we adopt the form of Equation (30) as the state-
(37), the eigenstates are given by single configura-
energy dependence of localization length
.
tions for electron occupation of one-electron states.
Similarly, we can estimate the magnitudes of the
For each state , there are four possible values of
other interactions U  (Kamimura, 1985; Takemori
energy E, corresponding to the four different electron
and Kamimura, 1983). Assuming the random distri-
occupancies of the state: (i) E ¼ 0 when state ji is
bution of localization centers, the distribution of
empty; (ii) E ¼ " þ BH when occupied by a spin-up
nearest-neighbor distance is given by the Poisson
electron; (iii) E ¼ "BH when occupied by a spin-
distribution:
down electron; and (iv) E ¼ 2" þ U when occupied
d by spin-up and -down electrons, where we have
PðRÞ ¼ exp½ – ðR=R0 Þ3 ð34Þ
dR included the Zeeman energy in an external magnetic
 Impurity Bands in Group-IV Semiconductors 89

field H. Denoting the chemical potential by , the E E

partition function  is then given by
W
Y 
" –  þ B H

¼ 1 þ exp –
 
kB T
  
"  –  – B H 2" – 2 þ U
þ exp – þ exp –
kB T kB T
EF
ð38Þ
so that the free energy is expressed as an independent
sum over states 
F ¼ – kB T ln    
X "  –  þ B H
¼ – kB T ln 1 þ exp –

kB T
    0
"  –  – B H 2" – 2 þ U D1(E) N/W N/W D2(E)
þ exp – þ exp –
kB T kB T Figure 8 Density of states for the first electrons, D1(E),
ð39Þ  6, where U
and that for the second electrons, D2(E). W=U¼ 
is defined by Equation (46). Regions corresponding to singly
The average occupation number of state  with spin and doubly occupied states are shown by hatched and
 ¼  is calculated from this free energy as cross-hatched areas, respectively.
 
q F
hn i ¼ kB T
q" kB T constant density of states is assumed for the state
ð40Þ

e þe U energy distribution for 0
"
W. Then
¼ 8
1 þ eþ þ e – þ eU
< 1=W for 0
E
W
where " ¼ " þ BH with  ¼ . We have abbre- D1 ðEÞ ¼ ð42Þ
: 0 otherwise
viated as e ¼ exp[("  þ BH)/kBT] and
eU ¼ exp[(2" þ U  2)/kBT]. The chemical
potential  is determined by the condition
The density of second-electron states D2(E) is related
X
hn i ¼ ne ð41Þ to D1(E) by
  
dU – 1
where ne is the concentration of electrons. D2 ð" þ U Þ ¼ D1 ð" Þ 1 þ ð43Þ
d"
According to Hamiltonian (37), an energy " is
required for the first electron to occupy state  while This is enhanced over D1(E) because the intrastate
an energy " þ U is necessary for the second elec- correlation energy, U, is a decreasing function of
tron to occupy the state which is already occupied by state energy ("), as seen in Equation (33).
another electron of opposite spin. If the energy for
the second electron " þ U is below the Fermi level, 1.03.3.2.1 Spin susceptibility and
the state is occupied by two electrons. If " þ U is specific heat
above the Fermi level, on the other hand, this state The expression for a magnetic moment M(H) is
cannot accommodate two electrons even if the one- obtained from the free energy (39):
electron state energy " is below the Fermi level. In qF X eþ – e –
consequence, at and below the Fermi level there are MðH Þ ¼ ¼ B þ þ e – þ eU
ð44Þ
qH 
1 þ e
the states that are occupied by only one electron
(singly occupied (SO) states) as well as those that The spin susceptibility is given by  ¼ (qM/ qH)H !0.
are doubly occupied (DO states). The states with Similarly, the specific heat C(H) is obtained from
energy higher than the Fermi level are unoccupied  
q2 F ðq2 F =qT qÞ2
(UO states). The density of states for the first electron CðH Þ ¼ – T – ð45Þ
qT 2 q2 F =q2
and that for the second electron to occupy a state are
denoted by D1(E) and D2(E), respectively, and these Yamaguchi et al. (1979, 1980) calculated the tempera-
are shown schematically in Figure 8, where a ture dependence of susceptibility and specific heat
90 Impurity Bands in Group-IV Semiconductors

for the case of half-filled band. They took into (a)

account the explicit dependence of U on the state
energy " in Equation (33), where the mobility edge 10
was assumed to be located at the top of the band
(Ec ¼ W). The only parameters in the theory are the
bandwidth W and the averaged magnitude of the

χ (μ 2B n/W )
intrastate interaction energy:
10 20 40 80
Z W 1
1
U ¼ U ðEÞ dE ð46Þ
W 0
W/U = 5
The numerical results of spin susceptibility and spe-
cific heat are presented in Figure 9 for several values
of W=U . 0.1
As seen in Figure 9(a), the spin susceptibility 0.1 1 10
shows Curie-type behavior at low temperatures so kB T/U
that kB T  U . This is due to the localized spins of (b) 0.6
SO states and is expressed as
  2B nS =kB T ð47Þ
20
where ns is the number of SO states per unit volume. It
should be noted that the appearance of this Curie-type 10
0.4
susceptibility is the result of the intrastate interaction,
because in the absence of this interaction the Pauli-
C/kB n

type susceptibility is expected from the finite density 6

of states at the Fermi level. As an increase in tempera-
ture T, the susceptibility gradually becomes less
dependent on T and tends to show a Pauli-type beha-
vior in the temperature range of U  kB T  W
when W is much larger than U . When the temperature
is further increased beyond the state-energy distribu-
tion width W, electrons are no longer degenerate and
the susceptibility becomes again of Curie type:
  2B ne =kB T ð48Þ
In this case, the total number of electrons ne
contributes to .
The calculated results of electronic specific heat
are shown in Figure 9(b), in the absence of magnetic
field (H ¼ 0). At low temperatures, the specific heat is
a superposition of Schottky-type specific heat corre-
sponding to the fluctuation of occupation number at
each state . The superposition of the specific heat
with various excitation energies results in the
T-linear behavior, which reflects the density of states
at the Fermi level:
C ¼ 2kB2 T ½D1 ðEF Þ þ D2 ðEF Þ I ð49Þ
W/U = 5
0.2
0 0.05 0.10 0.15
kBT/W
Figure 9 (a) Calculated results of spin susceptibility  as a
function of temperature T in logarithmic scales, using a model
with an energy-dependent intrastate interaction U. The value
of W=U  is indicated in the panel. (b) Calculated results of
electronic specific heat C as a function of temperature T,
using the same model as in (a). The dotted line represents the
specific heat in the absence of electron–electron interaction.
Modified from Yamaguchi E, Aoki H, and Kamimura H (1979)
Journal of Physics C: Solid State Physics 12: 4801.
We stress that the T-linear behavior of the electronic
specific heat is a result of the continuous distribution
of the random energy ".

where 1.03.3.2.2 Comparison with experiment

Z on Si:P
1
x2e x Let us now compare the calculated results with the
I ¼ dx  1:885 ð50Þ
x 2
– 1 ð1 þ 2e Þ experimental data on phosphorus-doped silicon
 Impurity Bands in Group-IV Semiconductors 91

(Si:P) in the intermediate concentration regime, 1.03.3.3 Interstate Interactions

where the phosphorus concentration, nD, is between
1.0  1018 and 3.2  1018 cm3 (see, e.g., a review
article by Kamimura (1980)). The spin susceptibility
was first measured by Sasaki and Kinoshita (1968)
using a static method and then by Ue and Maekawa
(1971) and by Quirt and Marko (1972a, 1972b) using
the ESR method. The overall behavior of spin sus-
ceptibility is of Curie type at low temperatures (see
Figure 11 in the next subsection), consistent with the
present theory with intrastate interaction.
The specific heat of Si:P was measured by Marko
et al. (1974) and by Kobayashi et al. (1977, 1979).
Figure 10 shows the experimental data of the elec-
tronic specific heat taken by Kobayashi et al. (1977).
The specific heat is almost T-linear, as is also
expected from the present theory, except at very
low temperatures below 2 K. The anomaly at low
temperatures is discussed in the next subsection.
We can determine the values of parameters in the
theory by fitting the calculated results to the experi-
mental data. Yamaguchi et al. (1979) found that
W ¼ 19 meV and U ¼ 3.4 meV by fitting to the sus-
ceptibility and the specific heat observed for
nD ¼ 1.7  1018 cm3. The solid line in Figure 10
shows the results calculated for these values of the
parameters.
1.03.3.3.1 Direct and kinetic-type
exchanges
The SO states carry a localized spin of S ¼ 1/2. If
there are interactions among these spins, they are
expected to affect the spin susceptibility and to give
an excess specific heat which is dependent on an
external magnetic field.
It was seen in Figure 10 that there appears an
excess specific heat over the T-linear behavior at
temperatures below 2 K. This anomaly in the specific
heat of Si:P was first observed by Marko et al. (1974)
and was investigated in detail by Kobayashi et al.
(1979) for various samples of different donor concen-
trations in the presence of magnetic field. Kobayashi
et al. observed that the hump in the specific heat
grows and shifts to higher temperatures with increas-
ing magnetic field. These results suggest that the
excess specific heat is due to the freezing of the
spin degrees of freedom in the SO states. The spin
susceptibility of Si:P at low temperatures, on the
other hand, was investigated in detail by Andres
et al. (1981) for samples of donor concentration
between 1.1  1017 and 4.0  1018 cm3, at tempera-
tures down to 2 mK. Figure 11 shows the Curie–
Weiss plot of the molar donor susceptibility for

20 18 −3
n =1.2 × 10
18 −3
cm 0.7 × 10 cm
100 D
C (μJK −1 mol−1)

10
χ−1 (mole/e.m.u.)

18 −3
0.1 × 10 cm

50
0
150
18 −3
n =3.7 × 10 cm
100 D

0 2 4 50
T (K)
Figure 10 Electronic specific heat of Si:P for 0 2 4
nD ¼ 1.7  1018 cm3 as a function of temperature. The full
T (K)
curve represents the theoretical result by Yamaguchi et al.
(1979) with W ¼ 19 and U ¼ 3.4 meV, whereas the circles Figure 11 Curie–Weiss plots of the molar donor
represent the experimental result reported by Kobayashi susceptibility for several concentrations of phosphorus
et al. (1977). The enhanced region of the specific heat above reported by Andres et al. (1981). The solid line shows
the T-linear line is shown as the hatched area. free-spin behavior.
92 Impurity Bands in Group-IV Semiconductors

several samples. The solid straight line in the figure with

indicates the free-spin behavior. It is seen from the kin jU j2
figure that the susceptibility increases monotonically J ¼ ð52Þ
U þ " – "
as if it were to diverge with decreasing temperature,
in the same temperature range as the excess specific Since J kin
is always positive, the energy of the singlet
heat is observed. state is lowered. In this view, the interstate interac-
In this subsection, the microscopic origin of these tion resulting from U is called the kinetic-type
features is discussed by taking into account the inter- exchange interaction although in this case the mixing
state interactions U  in the last term of
Hamiltonian (25). As estimated in Section 1.03.3.1.3,
the dominant spin-dependent interstate interactions
are U  and U . The first type is the direct
exchange, which favors the parallel-spin configura-
tion of two SO states  and , just like the Hund’s
rule in atoms, because the Anderson-localized states
ji are orthogonal to each other.
Now, we discuss the effect of the second type of
interaction, U , which also acts between SO
states (Kamimura, 1982; Yamaguchi et al., 1979;
Takemori and Kamimura, 1982). Suppose we con-
sider two-electron configurations shown in
Figure 12, one in which there are two SO states
 and with their spins being antiparallel to each
other, and the other in which two electrons occupy
the same state . We denote the former and latter
configurations by 1 ¼ j", #i and 2 ¼ j", #i,
Þ ð54Þ
respectively. Then, the interstate interaction
represents the localization length, which is
y y
U c" c# c # c" mixes states 2 and 1. This
type of configuration interaction always favors
energetically the spin-singlet state for a pair of
electrons by transferring an electron virtually
from state j #i to state j#i. By the second-
order perturbation calculation with respect to
U , the change of the energy of state 1,
Ekin, can be expressed in the following spin
Hamiltonian:
 
kin kin 1
E ¼ J S ?S – ð51Þ
4
α β α β
from a localization center,
Mixed by Uαααβ
¼ R0 and 30% of electrons are in the
Figure 12 Two-electron configurations mixed by kinetic-
type exchange process.
matrix elements arise from the electron–electron
interaction, but not from the transfer terms.
The direct-exchange interaction J dir
ðX U  Þ
which favors the spin-triplet configuration also exists
between SO states  and , as already mentioned.
Thus, the spin Hamiltonian for the SO states  and
can be written as
H ¼ – J ðr Þ S ? S ð53Þ
where S ¼ S ¼ 1/2 and J ¼ J dir kin
– J . The
dependence of J dir
on the distance between
the localization centers in states  and , r , is the
same as J kin
in Equation (52) and both decay expo-
nentially with the distance r . We reasonably
assume the following form for the exchange interac-
tion J (r ):
J ðr Þ ¼ J0 expð – 2r =
where
assumed here to be independent of states  and .
The sign of J may be positive or negative, depend-
ing on the relative magnitude of the direct and
kinetic-type exchanges.
1.03.3.3.2 Spin-pair model
As we have a spin system with a network of effective
exchange interactions J which take randomly posi-
tive or negative values, we are faced with an
intractable problem of the random spin glass. In
order to calculate the specific heat and magnetization
of the spin system of SO states, a simple model of spin
pairs was proposed by Takemori and Kamimura
(1982) as a first approximation of treating such a
system. As we consider the concentration region
where the localization length is close to half the
average impurity distance R0, there are a few SO
states within the distance
and we expect that the behavior of each localized
spin is most strongly influenced by the spin nearest to
it. In fact, if localization centers are randomly dis-
tributed with
SO states, which is actually the case for Si:P of
nD ¼ 1.7  1018 cm3 as seen later, the probability of
 Impurity Bands in Group-IV Semiconductors 93

finding more than two SO states within the distance

where h¼2BH/kBT and j¼J/kBT. These values are
from a localization center of SO state is less than evaluated numerically as functions of temperature T
3.7%. Moreover, when the nearest spin is located and magnetic field H for various values of the
within
/2, the probability that the interaction with parameters. Let us first consider the cases of spin-
the next-nearest spin exceeds 1/e of the interaction triplet (S¼1) pairs or spin-singlet (S¼0) pairs only.
with the nearest spin is less than 16%. Therefore, one The calculated results are shown in Figure 13.
can assume that each localized spin of SO state forms The spin susceptibility is small for the spin-singlet
a pair with its nearest neighbor, so that the whole case, while it is approximately of Curie type for
spin system can be regarded as an ensemble of non- the spin-triplet case but with slight deviation from
interacting spin pairs. the Curie law due to the existence of excited states
Let us now proceed with the spin-pair model. By of spin singlet. The specific heat is quite small at
the interaction (53), each pair splits into a spin-triplet H¼0 for the spin-triplet pairs because the ground
state (S ¼ 1) and a spin-singlet state (S ¼ 0) with the state is triply degenerate, so that there is residual
energy difference J . The partition function of the entropy at T¼0. It then rises sharply with an
spin pair with exchange interaction J is given by external magnetic field and the peak shifts to
higher temperatures as the field is increased. For
ZðJ Þ ¼ 1 þ 2coshð2B H =kB T Þ þ expð – J =kB T Þ ð55Þ the spin-singlet pairs, the specific heat is insensi-
and the free energy of the spin system is expressed as tive to the magnetic field.
X Although the calculated susceptibility for the spin-
F ¼ – kB T lnZðJ Þ ð56Þ triplet pairs can explain the Curie-type susceptibility
pairs observed in Si:P, the calculated results of specific heat
If the probability distribution function of the random give too sharp rise with increasing magnetic field and
values of J is denoted by P(J), Equation (56) can be are not consistent with the observation. A good fit to
written in the form the experimental results for both C and  is obtained
Z by mixing an equal number of spin-triplet and singlet
nS pairs. The calculated results of specific heat in this
F¼ – kB T dJPðJ ÞlnZðJ Þ ð57Þ
2 case are shown in Figure 14 together with the
where ns is the number of SO states per unit volume. experimental data taken by Kobayashi et al. (1979).
Function P(J) is determined, for example, from The best fit values are jJ0 j ¼ 5.1 K, nþ/n ¼ 1.0,
Equation (54) with Poisson distribution for the dis- ns ¼ 0.3nD ¼ 5.6  1017 cm3, and
¼ 81 Å.
tance between localization centers. For simplicity, we Although the spin-pair model is simple, the best-
assume an equal magnitude of jJ0 j for both positive fit values of the parameters seem reasonable. The mag-
and negative J . Then, the parameters we have are nitude jJ0 j is of the order of the intrastate interaction.
jJ0 j, the ratio of the number of spin-triplet pairs to The localization length and the number of SO states do
that of spin-singlet pairs, nþ/n, the number of SO not contradict the estimates made by the intrastate-
states ns ( ¼ nþþ n), and the localization length
. interaction theory. The number of SO states,
ns/nD ¼ 33%, yields the residual entropy, Sres ¼
kBnsln 2 ¼ 96 J (K?mol)1 for nD ¼ 1.7  1018 cm3.
1.03.3.3.3 Specific heat anomaly and spin This agrees with the experimental value of
susceptibility 90 J (K?mol)1 obtained from the formula for the
From free energy in Equation (57), the specific heat residual entropy:
and spin susceptibility are calculated as follows: Z
C
2 j Sres ¼ dT ð60Þ
2h ½2 þ coshðhÞ þ e coshðhÞ T
Z
1 –4jhe j sinhðhÞþj 2 e j ½1þ2coshðhÞ
C¼ PðjkB T Þdj where C is the observed excess specific heat over
kB T 2 ½1 þ 2coshðhÞ þ e j 2
the T-linear term (Kobayashi et al., 1979).
ð58Þ It is concluded that the coexistence of the direct
and and the kinetic-type exchange interactions is impor-
Z tant in an Anderson-localized electronic system. Both
1 the specific-heat anomaly and spin susceptibility of
 ¼ 22B PðjkB T Þdj ð59Þ
3 þ ej Si:P in the intermediate concentration regime can be
94 Impurity Bands in Group-IV Semiconductors

(a)
9.7
(a)
6

10 4.9
4

5 2
H = 0 kG
χ (μ 2B /K)

ΔC/kB
0 0
(b) (b)
10
6 H = 0 kG
9.7

4.9
5 4

2
0 0.2 0.4 0.6 0.8
T (K)
0 0.2 0.4 0.6 0.8
T (K)
Figure 13 Spin susceptibility  and anomaly in electronic specific heat, C per pair of singly occupied states, as functions
of temperature T, calculated in the spin-pair model for (a) spin-triplet pairs and (b) spin-singlet pairs. Modified from Takemori T
and Kamimura H (1982) Solid State Communications 41: 885.

explained by the spin-dependent interstate interac-

tions between SO states.
40

H = 9.7 kOe 1.03.3.4 Numerical Simulation for

Interacting Donor Electrons in Si:P System
ΔC (μ J K–1 mol–1)

In order to investigate how the Anderson-localized

4.9
20 2.9
0
0 0.4
T (K)
Figure 14 Calculated results of magnetic-field-
dependent anomaly in the electronic specific heat for donor
concentration of nD ¼ 1.7  1018 cm3 in Si:P (solid curves).
The experimental data taken by Kobayashi et al. (1979) are
also shown for various values of magnetic field.
states are constructed from the impurity states on
each donor site, Takemori and Kamimura (1983a,b)
performed numerical simulation using a finite cluster
model for donors. The cluster model contains six
donors located randomly in a space, corresponding
to several donor concentrations between 1.0  1018
and 2.4  1018 cm3 of Si:P. The calculation is carried
out for an ensemble of 80 samples with different
geometrical configurations of donors, for each
donor concentration. The electron–electron interac-
0.8
tion is fully taken into account in the simulation.
Although the cluster size is quite small, this should
not cause serious limitations because the localization
length is of an order of average donor distance, for
the concentration considered here, and does not
exceed the cluster diameter. By examining the
ground and low-lying excited states, the validity of

the physical picture described in the preceding sub-
sections is confirmed. Furthermore, the direct
calculations of the specific heat and spin susceptibil-
ity reproduce the characteristic features observed in
Si:P.
1.03.3.4.1 Gaussian model
The Hamiltonian is composed of the kinetic energy
of electrons K, Coulomb potential due to donor
impurities V, and electron–electron interaction U:
H ¼K þV þU ð61Þ
where
XNe
1 2
K ¼ p ð62Þ
i¼1
2m i
X
Ne
V ¼ Vi ð63Þ
i¼1
X e2
U¼ ð64Þ
i<j
jri – rj j
Here, ri and pi are the space coordinate and momen-
tum of the ith electron, m is the effective mass, and
Vi the Coulomb potential of the i th donor. The
number of electrons, Ne, is identical to that of donor
impurities in uncompensated samples considered
here. No valley degeneracy of the conduction band
in Si is assumed.
The donor centers are distributed randomly in a
sphere of volume Ne/nD, where nD is the donor
concentration. A Gaussian wave function
i ðr Þ ¼ expð – jr – Ri j2 =2 Þ ð65Þ
is attached to each donor center Ri and the electronic
wave functions are represented by their superposi-
tions. The spatial extent  in Equation (65) is
determined to be 1.88 times the effective Bohr radius
so as to give the largest binding energy (0.82 Ry) for
an isolated donor. The Gaussian function is
employed instead of the usual exponential 1s func-
tion, which enables us to obtain the analytical
expression for all the matrix elements for the elec-
tron–electron interaction (Boys, 1950).
First, the one-electron Hamiltonian is diagona-
lized to obtain the orthonormal base for the
transfer-diagonal representation. On doing so, an
appropriate choice of the one-electron Hamiltonian
is required in order to facilitate the interpretation
of the results although the final calculated results
of physical quantities such as energy levels,
Impurity Bands in Group-IV Semiconductors 95
specific heat, and spin susceptibility do not depend
on the special choice of the one-electron
Hamiltonian.
As one choice, the one-electron Hamiltonian H0 is
taken in such a way as
hijH0 jii ¼ h j jH0 jj i ¼ hijK jii þ hijVi jii ð66Þ
for the diagonal elements and
hijH0 jj i ¼ hijK j j i þ hijVi j j i þ hijVj j j i ð67Þ
for the transfer energy. Note that the Coulomb
potentials due to impurities other than i (i and j) do
not contribute to the ith diagonal element (transfer
energy between i and j). This choice of one-electron
Hamiltonian effectively introduces the long-range
screening effect into the one-electron Hamiltonian.
The one-electron Hamiltonian H0 is diagonalized,
and the eigenstates and eigenenergies are adopted
as the orthonormal basis functions and corresponding
state energies for the transfer-diagonal representa-
tion. Using this basis set, all the matrix elements of
the Hamiltonian are calculated.
Next, we calculate the matrix elements of the
Hamiltonian in the multielectron configuration
space. The total number of the configurations in
which six electrons occupy the six transfer-diagonal
!
12
states is ¼ 924 if the spin degrees of freedom
6
are considered. Although the Hamiltonian has no
symmetry in the coordinate space, it is invariant
against the rotation in the spin space. Each many-
body eigenstate of the Hamiltonian is always an eigen-
state of total spin S and its z-component Sz and thus
either a spin-degenerate multiplet or a nondegenerate
singlet. It is, therefore, convenient to confine ourselves
to the subspace with Sz ¼ 0. This reduces the number
of configurations to 400, while we still retain the
whole energy spectrum. The energy levels and
many-electron wave functions in a cluster are then
obtained by diagonalizing the obtained 400  400
Hamiltonian matrix in the configuration space.
Since the Hamiltonian is diagonalized exactly, the
calculated results do not depend on the choice of
basis set for one-electron states. Advanced methods
developed in quantum chemistry yield a more suita-
ble basis set to elucidate many-body states. We
adopted the multi-configuration self-consistent field
(MCSCF) method to discuss the Anderson-localized
states in the uncompensated samples of Si:P (Eto and
Kamimura, 1988, 1989) and in the compensated
samples (Eto and Kamimura, 1989).
96 Impurity Bands in Group-IV Semiconductors

1.03.3.4.2 Electron configurations and z

many-electron states
We now present numerical results for the ground 2, 5
state and low-lying excited states of the clusters.
For the comparison with the preceding subsections,
y
we concentrate on the results for the donor concen-
tration of nD ¼ 1.7  1018 cm3 for Si:P.
One-electron states. The distribution of the eigen-
energies of transfer-diagonal states is shown in
Figure 15. It has a peak near the isolated donor
level ("0 ¼ – 0:82Ry ) and extends to both higher x
and lower energies with a broad width. The distribu-
tion width of state energies is found to increase with
donor concentration nD. The transfer-diagonal wave 4
1, 6
functions in one of the clusters are shown in
Figure 16 schematically, where the states are num-
bered in increasing order of the energy. The wave
functions extend typically over two donor sites for 3
the donor concentration considered here.
Spin-dependent interactions. We can determine the
spin degeneracy of the ground state in a cluster by
examining mixing coefficients of electron configura- Figure 16 Schematic drawing of the transfer-diagonal
tions. About one-fourth of the clusters are found to states for one sample. The states are numbered in
have a spin-triplet ground state. Here, we describe in increasing order of state energy. Solid circles (*)
represent donor sites.
detail the ground state of the cluster in Figure 16,
which actually turns out to be one of the spin-triplet
clusters. electrons in each transfer-diagonal state with its
The ground state of this cluster has an energy state energy. It is found that the transfer-diagonal
12.4329 Ry, whereas the first excited state has an states 1 and 2 are doubly occupied, states 3 and 4
energy higher by 0.0044 Ry. These many-electron are singly occupied, and states 5 and 6 are unoccu-
states are shown in Figure 17, in which many con- pied, in consistent with the physical picture given in
figurations appear since the electron–electron the preceding subsections.
interaction is taken into account exactly. Table 1 As seen in Figure 17(a), the largest contributions
presents the average occupation numbers by six (75%) to the ground state jgrdi come from two con-
figurations where states 1 and 2 are doubly occupied
and states 3 and 4 are singly occupied:
Density of one-electron states (1/Ry*)

jgrdij1"2"3";1#2#4#i – j1"2"4";1#2#3#i
1.0
The mixing coefficients have the opposite signs for
the two configurations, indicating that spins are par-
allel in states 3 and 4 in the present notation so that
the ground state is triply degenerate with total spin
0.5 S ¼ 1.
As regards the first excited state, the average
occupation numbers of transfer-diagonal states are
εo almost the same as in the ground state, as seen in
Table 1. The largest contributions come also
0
–1.6 –0.8 0.0 0.8 1.6 from the same two configurations as those in the
E (Ry*) ground state, but with the mixing coefficients of
Figure 15 Distribution of transfer-diagonal state energies the same sign. This means that electron spins are
of the six-donor clusters corresponding to the donor antiparallel in states 3 and 4 and hence the first
concentration nD ¼ 1.7  1018 cm3 of Si:P. excited state is a spin singlet (nondegenerate) with
 Impurity Bands in Group-IV Semiconductors 97

(a)

C: 0.61 –0.24 –0.14 0.13 –0.07 –0.06

C: –0.61 0.24 0.14 –0.13 0.07 0.06

Weight: 74.8% 11.4% 3.7% 3.2% 0.9% 0.8%

(b)

C: 0.46 0.42 –0.36 –0.18 –0.16 0.15 0.14 –0.12

C: 0.46 –0.18 0.14 –0.12

Weight: 42.0% 17.5% 13.1% 6.3% 2.6% 2.1% 3.8% 2.8%
Figure 17 The electron configurations in terms of transfer-diagonal states for (a) the ground state and (b) the first excited
state in a cluster shown in Figure 16. The mixing coefficient C is shown at the bottom of each configuration together with the
weight of the spin conjugate configurations C2. The horizontal lines representing the one-electron states merely represent
the order of the state energy and the line spacing does not represent the actual difference in energy.

Table 1 The state energies of transfer-diagonal states in a total spin S ¼ 0. The next largest components are
cluster shown in Figure 16
the configurations in which the transfer-diagonal
Average occupation state 3 or 4 is doubly occupied. This is due to the
number kinetic-exchange interaction between the two
Ground First excited
transfer-diagonal states, discussed in Section
State  State energy " (Ry) state state 1.03.3.3.1. The effective exchange interaction J is
given by the energy difference E between the
1 1.474 1.947 1.958
ground and the first excited states, that is,
2 1.104 1.742 1.755
3 0.834 1.000 1.096 J ¼ E ¼ 0.0044 Ry.
4 0.582 1.001 0.916 Besides the spin-triplet clusters, there are a
5 0.424 0.289 0.276 large number of clusters in which the transfer-
6 1.202 0.018 0.001 diagonal states 3 and 4 are singly occupied with
The average occupation numbers are also tabulated in the ground antiparallel spins in the spin-singlet ground state
and first excited states. (S ¼ 0) and parallel spins in the first excited states
98 Impurity Bands in Group-IV Semiconductors
(S ¼ 1). In such cases, the energy difference can be
regarded as the antiferromagnetic coupling J
between the spins in states 3 and 4. This result
indicates the coexistence of ferromagnetic and
antiferromagnetic interactions between the spins
in SO states.
1.03.3.4.3 Specific heat and spin
susceptibility
Since all the eigenstates and eigenenergies for each clus-
ter are obtained by the numerical study, we can readily
calculate the spin susceptibility and specific heat. In the
presence of magnetic field H, the energy level En of each
spin multiplet splits into the Zeeman terms:
Eðn; Sz Þ ¼ En þ 2B Sz H
if we neglect the higher-order effects.
The specific heat C and spin susceptibility  are
then calculated by the following equations:
  
E 2 E 2
C=kB ¼ – kBT > 6  103 Ry, the curves for H ¼ 0 are almost
kB T kB T
 2
P Eðn; Sz Þ exp½ – Eðn; Sz Þ=ðkB T Þ
¼ contrast to the experimental results. As discussed in
n;Sz kB T Z
" #2
X Eðn; Sz Þ exp½ – Eðn; Sz Þ=ðkB T Þ
– ð69Þ
kB T Z
n;Sz
and
 X S 2 exp½ – Eðn; Sz Þ=ðkB T Þ 
 Sz2 z
¼ ¼
42B kB T H ¼0 k T
n;Sz B
Z 
where the partition function Z is given by
X exchange interaction between the spins of SO states.
Z¼ exp½ – Eðn; Sz Þ=ðkB T Þ ð71Þ
n;Sz
and the summation over Sz is taken from S to S
when the energy level n has the total spin S.
Figure 18(a) shows the calculated results of the
specific heat and spin susceptibility of a spin-triplet
cluster. The spin susceptibility is of Curie type with a
slight deviation from the Curie law owing to the
presence of spin-singlet excited states. The
Schottky-type hump in the specific heat, which is
located at kBT  103 Ry in the absence of magnetic
field, is caused by the ferromagnetic exchange inter-
action J between the SO states. The lowest state is a
spin triplet and this state splits into three components
of Sz ¼ 1, 0, 1 in magnetic fields. The hump of C
shifts to higher temperatures with increasing
magnetic field, reflecting the excitation among the
Zeeman-split states. The specific heat increases again
at higher temperatures, due to the excitations that
change the occupation numbers of transfer-diagonal
states.
For a spin-singlet cluster (Figure 18(b)), a
Schottky-type hump appears in the specific heat,
but it is insensitive to the magnetic field. The peak
of C is situated at kBT  102Ry, which reflects the
excitation energy to the spin-triplet state, E ¼ J.
The spin susceptibility  is quite small compared
with the spin-triplet clusters. The  tends to zero at
low temperatures, whereas  increases with tempera-
tures up to kBT  E because the excited state is a
spin triplet.
ð68Þ In order to simulate the experimental observation;
the specific heat and spin susceptibility are averaged
over all the clusters for the same donor concentra-
tion. The calculated results of specific heat for
various magnetic fields are plotted against tempera-
ture in Figure 19. At high temperatures, such as
T-linear but do not extrapolate to zero at T ¼ 0, in
Section 1.03.3.3.3, the T-linear specific heat is caused
by continuous distribution of state energy ". For the
clusters of a finite size, the state energies " are
discrete and the calculated specific heat retains the
structure of the discrete excitations. Therefore, the
 weak downward bending of the calculated curves of
C should be attributable to the limited size of the
 cluster. On the other hand, there appears a hump in
H ¼0
the specific heat for H ¼ 0 that grows and shifts to
ð70Þ
higher temperatures with increasing magnetic field.
As seen above, this is due to the ferromagnetic
The hump is smaller relative to the T-linear part for
higher donor concentration. This indicates that
the ratio of the number of SO states to that of donors,
ns/nD, decreases with increasing nD, in agreement
with the experimental data on Si:P (Kobayashi, 1979).
Figure 20 shows the Curie–Weiss plot of the
ensemble-averaged spin susceptibility for several
values of donor concentration in Si:P. The curves
are almost T-linear (Curie type) with a downward
bending at low temperatures. This characteristic
behavior is in good agreement with the experiment
on Si:P by Andres et al. (1981). The Curie–Weiss plot
for six free spins is also plotted in the figure for
comparison. The ratio of the number of SO states is
estimated from the susceptibility at
kBT ¼ 1.4  102 Ry,
 Impurity Bands in Group-IV Semiconductors 99

(a) (b)
C/kB 0.8 2.0

C/kB
0.4 H = 3 × 10−3 (Ry*/μ B) 1.0
H=0
2 1 × 10−3 (Ry*/μ B)
1 2
3
0
0 0
12
6
χ/μ 2B (103 Ry*–1)

χ/μ 2B (10 Ry*–1)

8
4

4 2

0 0
0.8 1.6 8 16
kBT (10−2 Ry*) kBT (10−2 Ry*)

Figure 18 Electronic specific heat C for various values of magnetic field and spin susceptibility , as functions of
temperature T, of (a) a spin-triplet cluster and (b) a spin-singlet cluster consisting of six donors.

nS =nD ¼ cluster =free spins ¼ 28:3%
18 3
for nD ¼ 1.7  10 cm . The molar donor suscept-
ibility decreases with increasing donor concentration
nD, which is also in accordance with the observation
in Si:P. This also indicates a decrease in the number
of SO states with increasing nD.
1.03.3.4.4 Comparison with experiment
In order to compare the calculated results with
experimental data on Si:P, it is necessary to take
into account multivalley effects in the conduction
band of Si, because no valley degeneracy is assumed
for the numerical calculations. There are six valleys
in the conduction band of Si (see Section 1.03.1.1).
The crystal field of tetrahedral symmetry around an
impurity atom splits the one-electron energy levels
of sixfold degeneracy into a nondegenerate state of
A1 symmetry, doubly degenerate state of E symme-
try, and triply degenerate state of T2 symmetry.
This is called valley–orbit splitting. The effect is
large for the first electron to occupy the state, but
small for the second electron because the crystal
field is screened by the first electron. The optical
ð72Þ experiment on Si:P shows that the binding energy of
the orbitally nondegenerate one-electron state with
A1 symmetry is larger than that for the other states
by 12 meV (Aggarwal and Ramdas, 1965). This
implies that, for T < 100 K, the electronic state for
the first electron is expressed as a superposition only
of A1 states of donors with no appreciable valley
effects.
When two electrons occupy a donor, the electro-
nic configuration is specified by assigning the first
electron to the orbital of A1 symmetry and the second
electron to that of A1, E, or T2 symmetry with appro-
priate spin configuration. Thus, the two-electron
energy levels are split due to the valley–orbit inter-
actions and by the Coulomb interaction between the
two electrons. The energy splitting can be estimated
from the binding energy of the D state, which was
evaluated to be 1.01 meV (11.7 K) for Si:P (Natori and
Kamimura, 1977; Kamimura 1979). The splitting is
expected to be smaller for Anderson-localized states,
which are more extended than the isolated-donor
state, and we can consider that all the six valleys
are available for the second electrons in the tempera-
ture range larger than 1 K.
100 Impurity Bands in Group-IV Semiconductors

(a) The multivalley effect on the specific heat is,

μ BH = 3 × 10−3 Ry* therefore, included in the following way. The
2 T-linear specific heat, which reflects the density
0.4 of states at the Fermi level, is enhanced by a
1 factor of 6. The hump in the specific heat, how-
C/kB

ever, comes from the spin-dependent interactions

0 for the SO states. Since the SO states are con-
0.2
structed by linear combinations of the A1 state of
each donor, no effect of valley degeneracy is
expected. Thus, the observed specific heat is
(b) 0 given by
μ BH = 3 × 10−3 Ry*
0.4 2 C ¼ 6CL T þ CR ð73Þ

1 where CLT and CR represent the T-linear part and

the remainder of the calculated specific heat, respec-
C/kB

0 tively. The result is in fair agreement with the

0.2
0 0.8
kBT (10−2 Ry*)
Figure 19 Ensemble-averaged electronic specific heat
against temperature with various values of magnetic field for
the cluster model of six donors. The donor concentration
corresponds to (a) 1.7  1018 cm3 and (b) 2.4  1018 cm3
in Si:P, respectively. Modified from Takemori T and
Kamimura H (1983a) Journal of Physics C: Solid State
Physics 16: 5167; Takemori T and Kamimura H (1983b)
Advances in Physics 32: 715.
experimental results for Si:P of nD ¼ 1.7  1018 cm3
(Kobayashi et al., 1979), as shown in Figure 21.
As for the spin susceptibility at T < 1 K, it is
determined by the number of SO states and inter-
actions among them. Since the valley–orbit
1.6 splitting is large for SO states, we expect few
valley-degeneracy effects on . The overall beha-
vior of calculated spin susceptibility shown in
Figure 21 is in good agreement with the experi-
mental observation on Si:P in Figure 11. For the
case of nD ¼ 1.7  1018 cm3, the estimated
number of SO states (ns/nD ¼ 28.3%) also agrees
with the experimental result of ns/nD ¼ 29%
(Kobayashi et al., 1979).

1.2 60
nD = 2.4 × 1018 cm–3
1/χ (10–2 Ry*/μ 2B )

C (μJ K–1 mol–1)

0.8 1.7
40
1.0

0.4
20
Free spins

0 0.8
kBT (10−2 Ry*)
Figure 20 Curie–Weiss plot of the ensemble-averaged spin
susceptibility for the cluster model of six donors corresponding
to various donor concentrations in Si:P. The susceptibility for
six free spins is also shown (broken line) for comparison.
Modified from Takemori T and Kamimura H (1983a) Journal
of Physics C: Solid State Physics 16: 5167; Takemori T and
Kamimura H (1983b) Advances in Physics 32: 715.
1.6
0 1.0 2.0
T (K)
Figure 21 Specific heat calculated for Si:P with impurity
concentration nD ¼ 1.7  1018 cm3, as a function of
temperature, for H = 0 (full line) and 20 kOe (broken line). The
multivalley effect has been taken into account. Experimental
data taken by Kobayashi et al. (1976) are also shown for
H = 0 (triangles) and H = 19.1 kOe (circles).

1.03.4 Hopping Conduction and
Related Phenomena
In this section, the hopping conductivity in doped
semiconductors at low temperatures T is discussed.
When kBT is much smaller than the width of the
impurity band, the variable-range hopping (VRH)
ðT Þ ¼ 0 exp½ðT0 =T Þ1=4 ð74Þ
, is assumed
is observed, instead of activation-type conductivity,
Equation (11), as predicted by Mott (1968).
The Mott’s theory of VRH is briefly reviewed
. The pre-exponential factor,
ph, is related to
in Section 1.03.4.1. In the low-concentration regime
of compensated samples, the VRH shows a different
T dependence because of the disappearance of the
ph depends on r , its dependence is
density of states at the Fermi level caused by the
long-range Coulomb interaction. The theory of
ph is treated as a constant.) The electron
the so-called Coulomb gap is described in Section
1.03.4.2. In Sections 1.03.4.3 and 1.03.4.4, VRH and
related phenomena are studied for the intermediate
concentration regime, based on the transfer-diagonal
representation formalism presented in the preced-
ph exp½ – 2r =
–  =kB T ð77Þ
ing section. The theory successfully explains
experimental results of magnetoresistance and
magnetocapacitance.
1.03.4.1 VRH and Mott’s Law
Let us begin with the hopping conduction between
Anderson-localized states, neglecting the electron–
electron interaction. The hopping conductivity is
usually evaluated using a model of random resis-
þ " =kB T Þ ð79Þ
tance network proposed by Miller and Abrahams
ph
(1960) (Section 1.03.4.1.1). Based on the model, the
Mott’s law of the VRH is derived in Section
1.03.4.1.2.
1.03.4.1.1 Formulation of hopping
conduction
Consider an elementary hopping process from ji to
j i when the state energies " and " are different.
The hopping of an electron is accompanied by the
phonon absorption or emission for the energy con-
servation. The number of electrons making the
transition per unit time is given by
 ¼
ph e – 2r =
Nph ðEÞf ð" Þ½1 – f ð" Þ ð75Þ state with smallest r , as illustrated by process (i)
in the case of phonon absorption with E ¼ " Equation (79) results in an activation-type
" > 0, and
 ¼
ph e – 2r =
½Nph ð – EÞ þ 1 f ð" Þ½1 – f ð" Þ ð76Þ
Impurity Bands in Group-IV Semiconductors 101
in the case of phonon emission with E < 0. Here,
r is the distance between the localization centers
and
1 1
Nph ðEÞ ¼ ; and f ð"Þ ¼ "=ðk T Þ
e E=ðkB T Þ – 1 e B þ1
are boson and fermion distribution functions, respec-
tively. The state energies are measured from the
Fermi level. The localization length,
to be independent of state energy, so that the transfer
integral between the two states gives the factor of
e – 2r =
the product of the square of electron–phonon matrix
element and the density of states of phonons.
(Although
much weaker than that of the exponential part.
Hence,
spins are disregarded in Sections 1.03.4.1 and 1.03.4.2.
At sufficiently low temperatures, it is usually
expected that kBT  j"  " j, j"j, and j" j. Then,
the hopping rate can be written in a unified form of
 ¼
where
1
" ¼ ½j" – " j þ j" j þ j" j ð78Þ
2
Here  is equal to j" " j when the state energies
lie on opposite sides of the Fermi energy and max (j"j,
j" j) otherwise. The resistance of the hopping is
given by
kB T kB T
R ¼ 2
¼ 2 expð2r =
e  e
(Shklovskii and Efros, 1984). Miller and Abrahams
(1960) proposed a random resistance network in
which resistance R connects a pair of vertices, as
shown in Figure 22(a). The conductivity of the
whole system is determined by a set of {R }. An
important feature of the network is its extremely
wide spectrum of resistance, R , due to the expo-
nential dependence on r and  .
When the temperature is not too low, the r -
dependent part in Equation (79) dominantly deter-
mines the conductivity in the system. Then electrons
hop from a localized state to its nearest-neighbor
in Figure 22(b). The temperature dependence in
conductivity:
 ¼ 3 expð – "3 =kB T Þ
102 Impurity Bands in Group-IV Semiconductors
(a)
α
Rαβ β kB
(b) (ii)
(i)
EF
ph exp½ – ðT0 =T Þ1=4 ð82Þ
Optimized r (T )
].
Figure 22 (a) Random resistance network proposed by
Miller and Abrahams (1960) to evaluate the hopping
conductivity in the Anderson-localized regime. The
resistance R between sites  and is given by Equation
(79). (b) Schematic drawing for (i) the nearest-neighbor
hopping and (ii) variable-range hopping conduction. In the
latter, the hopping length increases with decreasing
ph, where r is given by Equation
temperature.
for the nearest-neighbor hopping. The activation
energy, "3, is evaluated using the percolation method.
The calculation is explained in detail in Section 8 in
the textbook by Shklovskii and Efros (1984).
3 ð85Þ
1.03.4.1.2 Mott’s law
At low temperatures, the energy term in Equation
(79) leads to a strong resistance dispersion as well as
the distance term. Then, there are two competing
factors in the hopping rate: a larger hopping distance,
r , enables us to find a state with smaller " , but a
larger r results in a smaller transfer integral at the
same time. The average of hopping distance, r, which
optimizes the product of the two factors, turns out to
be r _ T – 1=4 , which leads to the hopping conductiv-
ity in Equation (74). Since the optimized hopping
distance varies with T, as illustrated by process (ii)
in Figure 22(b), this mechanism of hopping conduc-
tion is known as the VRH.
Following Mott, we present an intuitive deriva-
tion of Equation (74). The problem is to find the
optimized hopping distance r which maximizes  in the VRH conduction. The interaction results in
in Equation (77). Since there are (4/3)r3D(0) states
available in a spherical region of radius r, where
D(0) is the density of states at the Fermi level per
unit volume, the average of " is estimated to be
[(4/3)r3D(0)]1. The minimization of the average
hopping rate
 
2r 1 3
 ¼
ph exp – –
kB T 4r 3 Dð0Þ III elements are occupied by an extra electron and
yields the optimized hopping distance
 1=4
9
r¼ ð80Þ
8Dð0ÞkB T
and average hopping energy
¼ ðT0 T 3 Þ1=4 ð81Þ
4
This gives the optimized hopping rate
 ¼
3
with kBT0 ¼ 18.1/[D(0)
The conductivity is expressed as  ¼ e 2 DDð0Þ
from the Einstein relation, where the diffusion con-
stant D is written as D ¼ r 2 . Thus, we arrive at
 ¼ 0 exp½ – ðT0 =T Þ1=4 ð83Þ
2 2
with 0 ¼ e D(0)r
(80). Generally, in d-dimensional systems, we have
 _ exp½ – ðT0 =T Þ1=ðdþ1Þ ð84Þ
with
kB T0 ¼ =½Dð0Þ
where the numerical coefficient depends on d.
After the qualitative derivation by Mott, Equation
(84) was confirmed numerically by the percolation
method (Ambegaokar et al., 1971; Pollak, 1972) and
Monte Carlo method (Skal and Shklovskii, 1971).
The numerical coefficient in Equation (85) was
determined by these numerical calculations. Those
are  21.1 for d ¼ 3 and 13.8 for d ¼ 2.
As regards the VRH, it should be mentioned that
Kamimura and Mott (1976) pointed out a possibility
that the VRH is induced by the ESR.
1.03.4.2 Coulomb Gap
In the low-concentration regime of compensated
samples, the long-range Coulomb interaction
between charged impurities plays an important role
the reduction in density of states around the Fermi
level. This is called the Coulomb gap. The Coulomb
gap affects remarkably the T dependence of the
hopping conductivity. In this subsection, we briefly
explain the theory of Coulomb gap following
Shklovskii and Efros (1984) (also see (Efros and
Shklovskii, 1985)).
At low temperatures, all the impurities of group-
 Impurity Bands in Group-IV Semiconductors 103

thus negatively charged, resulting in acceptors. Some whereas the Coulomb energy from donor i is counted
of the donor levels are occupied by an electron and in "j because donor i is occupied in the ground state.
the others are empty. Here, the former are neutral The condition (88) must hold for any pair of donors
while the latter are positively charged. The electro- with "i < 0 and "j > 0.
nic states in the system are identified by the number Consider donors whose energies fall in a narrow
of electrons ni (¼1 or 0) at donor site i if the electron band [ – "~=2; "~=2] around the Fermi level. From
spins are neglected. This situation is described by the Equation (88), any two donors in this band must be
Hamiltonian separated from each other by a distance rij larger
" than e2/"~ when the energies are on the opposite
P
d on e2 1 X don X
don
ð1 – ni Þð1 – nj Þ sides of the Fermi level, "i"j < 0. As a result,
H ¼ "D n i þ
i  2 i j 6¼i
ri j the donor concentration in this band n("~) cannot
#
don X
X acc
1 – ni 1 Xacc Xacc
1 exceed ð3=4Þð"~=e 2 Þ3 . Thus, the density of states
– þ ð86Þ Dð"~Þ ¼ dnð "~Þ=d "~ tends to zero when "~! 0, at least
i k
rik 2 k l6¼k rkl
as fast as "~2 . (D("~) cannot tend to zero faster than "2
where "D is the energy level of the isolated donors, because the decrease in the density of states stems
don and acc mean the summations over all donor from the strong interaction between the low-energy
and acceptor sites, respectively. The second term in states. Otherwise, the separation between the donors is
the Hamiltonian represents the long-range Coulomb too large and hence the interaction is too weak to be
interaction between ionized donors, the third term responsible for lowering the density of states so much.)
the Coulomb interaction between ionized donors and We conclude that
acceptors, and the last term the Coulomb interaction
3 "~2
between acceptors. The set of occupation numbers Dð"~Þ ¼ 3 ð89Þ
{ni} in the ground state is determined by minimizing e6
H with a fixed total number of electrons, or by where 3 is a numerical coefficient. The reduction in
minimizing the density of states in the vicinity of the Fermi level
X
don is called Coulomb gap by Efros and Shklovskii
H~ ¼ H –  ni (1975). The width of the Coulomb gap  is estimated
i
from D()  D0(0), where D0(0) is the density of
The chemical potential  is chosen to be zero. states at the Fermi level in the absence of Coulomb
As a result, the energy level at donor site i is given interaction. Thus,   e3D0(0)1/2/3/2.
by Similar arguments in the two-dimensional case
" # lead to the law
qH e2 X
don
1 – nj Xacc
1
"i ¼ ¼ "D þ – þ ð87Þ 2 j"~j
qni  rij rik Dð"~Þ ¼ 2 ð90Þ
j 6¼i k e4
The numerical coefficients were estimated to be
The determined values of "i’s become random due to
3 ¼ 3/ and 2 ¼ 2/ (Baranovskii et al., 1978).
the long-range Coulomb interaction from the other
The width of the Coulomb gap is   e4D0(0)/2 in
impurities. Hence, the width of the impurity band is
the two-dimensional case.
r Þ, where r¼ ð4nD =3Þ – 1=3 is the
of an order of e 2 =ð
The Coulomb gap in the density of states signifi-
average distance between donors.
cantly affects the T dependence of the VRH
For an electron transfer from a filled donor i to an
conduction at temperature T  . The hopping
empty donor j in the ground state, the total energy
conductivity is derived in the same way as that in
must be increased:
the preceding subsection. Let us find the optimized
e2 hopping distance r which maximizes  in Equation
ij ¼ "j – "i – >0 ð88Þ
rij (77). From the above-mentioned argument, the hop-
The increment ij in energy is derived by the fol- ping energy is evaluated to be " ¼ 9e2/r for a given
lowing argument. First, an electron is transferred hopping distance r, with 9 being a numerical factor.
from donor i to infinity, which requires the energy Hence, we minimize the hopping rate of
"i. Second, the electron is placed on donor j, which is " 0
#
2r  e2
empty in the ground state. The energy cost in the  ¼ ph exp – –

kB T r
second stage is "j  e2/rij since donor j is empty,
104 Impurity Bands in Group-IV Semiconductors

and obtain the optimized hopping distance 1.03.4.3.1 Appearance of spin-dependent

 1=2 mechanisms

e2 It was mentioned in Section 1.03.3.2 that there exist
r¼ ð91Þ
kB T  three types of electronic states in the presence of
apart from a numerical prefactor, and average intrastate interaction: unoccupied (UO), singly occu-
hopping energy pied (SO), and doubly occupied (DO) states.
Corresponding to these three electronic states, there
kB are four kinds of elementary hopping processes, as
¼ ðT1 T Þ1=2 ð92Þ
2 shown in Figure 23:
The optimized hopping rate is 1. from an SO state to an UO state;
 ¼ ph exp½ – ðT1 =T Þ 1=2
ð93Þ 2. from an SO to another SO state;
3. from a DO to an UO state; and
with 4. from a DO to an SO state.
e2
kB T1 ¼ 1 ð94Þ The total hopping rate  from a localization


state ji to state j i is given by the sum of the

The numerical coefficient 1 depends on the dimen- hopping rates of the four elementary processes:
sionality d, whereas the exponent of T dependence of
X
4
 is identical for both dimensions of d ¼ 3 and 2.  ¼
ðlÞ
 ð96Þ
Finally, the hopping rate  in Equation (93) yields l¼1
the hopping conductivity of
If we assume that each state is statistically indepen-
ðlÞ
 _ exp½ – ðT1 =T Þ 1=2
ð95Þ dent of each other, each hopping rate  ðl ¼ 1 – 4Þ
ðlÞ
is the product of an intrinsic hopping rate  and
This VRH conduction is observed in many samples. appropriate occupation probabilities, as follows:
Here, we have considered only the single-electron
ð1Þ P ð1Þ
transfer from a donor to another. In some cases, a  ¼ hn ð1 – n –  Þihð1 – n  Þð1 – n –  Þi
¼
simultaneous transfer of many electrons plays an
ð2Þ P ð2Þ
important role in the hopping conduction. Then, a  ¼ hn ð1 – n –  Þihð1 – n  Þn –  i
hopping process of an electron is accompanied by the ¼
ð3Þ P ð3Þ
transfer of many electrons surrounding the initial and  ¼ hn n –  ihð1 – n  Þð1 – n –  Þi
final donors of the electron hopping, that is, a polaron ¼

cloud is formed around the hopping electron. For a ð4Þ P ð4Þ

 ¼ hn n –  ihð1 – n  Þn –  i
detailed discussion, the reader is refered to section 10 ¼

in Shklovskii and Efros (1984). where n is the number operator in state ji and
spin .
Regarding functional forms of the intrinsic hop-
1.03.4.3 Formula for Magnetoresistance in ðlÞ
ping rates  , we assume that they are similar to
the Variable-Range Regime
those given in Equation (75) and (76):
As discussed in Section 1.03.3, intrastate and inter- ðlÞ
ðlÞ
state interactions play important roles in the  ¼ ph e – 2r =
Nph ðE ðlÞ Þ
Anderson-localized states. In this subsection, we  0 exp½ – 2r =
ðlÞ – E ðlÞ =kB T ð97Þ
show that these interactions are important for the
magnetoresistance in the VRH conduction in the
intermediate concentration regime of uncompen- εβ εβ
EF
sated samples. We assume that the long-range part εα εα
U U
of the Coulomb interaction is screened out by U
εβ
extended states over several impurity sites. Kurobe εα εβ
εα
and Kamimura (1982) calculated the resistivity due
to the VRH between the Anderson-localized states (1) S U (2) S S (3) D U (4) D S
by the percolation method (Pollak, 1972) taking into Figure 23 Four kinds of hopping processes in the
account the intrastate interaction. presence of intrastate interaction U.
 Impurity Bands in Group-IV Semiconductors 105

for E(l) > 0, where as Now, we discuss the magnetic-field dependence

ðlÞ
of VRH conduction following Kurobe and
 ¼ ph e – 2r =
ðlÞ ½1 – N ð – E ðlÞ Þ  0 exp½ – 2r =
ðlÞ Kamimura (Kurobe and Kamimura, 1982;
ð98Þ Kamimura et al., 1982, 1983; Kurobe, 1986). By
(l) neglecting the change of localization length due to
for E < 0, where r is the distance between the
a magnetic field, the total transition rate  (H) from
localization centers of states ji and j i. The pre-
localized state  to state can be expressed as
exponential factor,  0, is assumed to be independent
of l. The E(l) is the difference in the total energies  ðH Þ ¼ ½Z ðH ÞZ ðH Þ – 1
before and after the hopping process of type l: Xn
 exp½ – ð" þ B H Þ=kB T  ð1Þ
E ðlÞ ¼ " – " ðl ¼ 1; 4Þ ¼
þ exp½ – ð" þ " Þ=kB T  ð2Þ
¼ " – " þ U ðl ¼ 2Þ
þ exp½ – ð2" þ U Þ=kB T  ð3Þ
¼ " – " – U ðl ¼ 3Þ o
þ exp½ – ð2" þ " þ U – B H Þ=kB T  ð4Þ
In the presence of intrastate interaction, the localiza-
tion length of DO state
2(") is different from that ð102Þ
of SO states
1(") by an analogy with the case of a where Z(H) is the partition function in magnetic
D state (Natori and Kamimura, 1977; Kammimura, field H:
1979). We take the larger of the two as the localiza-
tion length
(l) in the hopping processes l ¼ 2 and 3 in Z ðH Þ ¼ 1 þ 2coshðB H =kB T Þexpð – " =kB T Þ
which the localization length is different before and þ expð – ð2" þ U Þ=kB T Þ ð103Þ
after the hopping, following the treatment by When a magnetic field is applied, the spins of SO
Kirkpatrick (1973). Therefore, the relevant localiza- states tend to become parallel to the field. Therefore,
tion lengths in Equation (97) and (98) are
(1) ¼
1 the probability to find a pair of SO states whose spins
and
(l) ¼
2 (l ¼ 2, 3, 4). are antiparallel to each other becomes smaller with
increasing magnetic field. As a result, the hopping
1.03.4.3.2 Calculated results processes from SO to SO states, which take place
For the random resistance network in the present only when the spins are antiparallel to each other,
problem, the percolation calculation gives the fol- are suppressed by the magnetic field as long as spin-
lowing results for the temperature dependence of flip processes are neglected. The processes from DO
resistivity in d dimensions (Kurobe and Kamimura, to UO states are connected with those from SO to SO
1982, Kurobe 1986): states by the relation of a detailed balance. Therefore,
the processes from DO to UO states are also sup-
 ¼ 0 expðT0 =T Þ1=ðd þ1Þ ð99Þ
pressed. This suppression of hopping processes by
where the magnetic field gives rise to a positive magnetore-
c ð3Þ
13 þ 3
23 sistance. When the hopping processes of type 2 and 3
kB T0 ¼ ð100Þ
D1 ðEF Þ ð
1 þ
23 Þ2 þ 4
26
3 are completely suppressed, only the processes of
types 1 and 4 contribute to the hopping conduction.
for d =3 and
Thus, the magnetoresistance saturates for a magnetic
c ð2Þ
12 þ 3
22
kB T0 ¼ ð101Þ field stronger than a certain value.
D1 ðEF Þ ð
12 þ
22 Þ2 þ 4
24
Figure 24 presents numerical results for the
for d ¼ 2. The coefficients are c(3) ¼ 2268 (3)/(115) magnetic-field dependence of the resistivity for various
and c(2) ¼ 105 (2)/(11) with (d) ¼ 201/(d þ 1). Here, temperatures in three dimensions (Kamimura et al.,
D1(EF) is the density of states for the first electron at 1982, 1983). The state-energy dependence is neglected
the Fermi level defined in Section 1.03.3.2. The for the localization length,
, and for the intrastate
energy dependence of localization lengths
1 and
2 interaction energy (U). The values of the parameters,
is neglected here, and
2 is taken to be larger than
1.
1,
2, D1(EF) and U (X U), correspond to those in Si:P
This result shows that Mott’s law still holds even in with a donor concentration of nD ¼ 1.7  1018 cm3.
the presence of intrastate interaction, but with a pre- The result clearly indicates that the magnetoresistance
factor T0 which now depends on both the localization grows and then saturates with an increase in magnetic
lengths of SO and DO states,
1 and
2. field. The saturation value increases when the
106 Impurity Bands in Group-IV Semiconductors

E
T = 0.2 K
Ec
3
Ec
0.5 K
Δρ /ρ

2 EF
1.0 K EF

1
3.0 K

2μ BH
0 10 20 30 40
D–(E ) D+(E )
H (kOe)
Figure 25 Schematic illustration of the negative
Figure 24 Calculated result for the positive component of
contribution to the magnetoresistance due to the state-
the magnetoresistance in the variable-hopping conduction
energy dependence of the localization length.
regime, as a function of magnetic field for various
temperatures, in three dimensions. The parameters used
are U ¼ 3.4 meV, D1(EF) ¼ 9.5  1019/cm3 eV,
1 ¼ 49 Å, and

2 ¼ 98 Å. Modified from Kurobe A and Kamimura H (1982) parallel to the magnetic field, this effect gives rise
Journal of the Physical Society of Japan 51: 1904. to a negative magnetoresistance. Combining this
effect with the opposite effect discussed above, the
total magnetoresistance is written conventionally in
temperature T decreases. The saturation value also the form
increases when the density of states D1(EF) decreases,
or when the localization lengths decrease with the ratio ðH Þ ðH Þ – ð0Þ
¼ ¼ P ðH Þ þ N ðH Þ ð105Þ
of
1/
2 being fixed. The analytical expression for the ð0Þ ð0Þ
saturated value is given by where P(H) and N(H) represent positive and
8  d d 1=ðdþ1Þ negative parts of the magnetoresistance, respectively.
< c ðdÞ
1=ðd þ1Þ
1 þ
2
ðH Þ
ð0Þ sat
j
¼exp
: D1 ðEF ÞkB T

2d
1 þ
2
2d For comparison with experimental results, we
discuss the magnetoresistance in a transition metal
#) ð104Þ dichalcogenide system, 1T-TaS2, which has a layer-
!
d d 1=ðd þ1Þ type sandwich structure with a commensurate

1 þ3
2 –1
–
ð
1d þ
2d Þ2 þ4
22d charge density wave (CDW) phase below
T ¼ 200 K (Williams et al., 1974, 1975; Wilson et al.,
in d dimensions (Kurobe and Kamimura, 1982; 1974, 1975). In this phase, the material is an insula-
Kurobe, 1986). tor with an energy gap which is interpreted as
arising from the CDW modulation. DiSalvo and
1.03.4.3.3 Comparison with experiments Graebner (1977) found a T1/3 law of conduction in
As an effect of the magnetic field on the transition this phase, which should be ascribed to the VRH
rate, we have so far considered the change in occupa- conduction among the Anderson-localized states in
tion probabilities of UO, SO with spin  ¼ , and the energy gap in the quasi-two dimensional system.
DO states. In addition, we have to take into account The magnetoresistance was later measured in this
an effect of the magnetic field on the localization system by Kobayashi and Muto (1979), Onuki et al.
length. Since the localization length is a function of (1980), and also by Tanuma (1983). Figure 26 shows
state energy, it is changed through the Zeeman shift, their experimental results of the magnetoresistance
as schematically shown in Figure 25. This mechan- as a function of magnetic field for various
ism was first proposed by Fukuyama and Yosida temperatures.
(1979). The localization length increases to Let us apply the present theory to the above-

(" þ BH) for spin-up electrons while it decreases mentioned experimental results. We assume that
to
("  BH) for spin-down electrons if
(") is an
1(") ¼
2(")/2 and that the localization lengths
increasing function of state energy " (we assume depend on the state energy, ", in the following way:
that EF is located below the mobility edge Ec). Since
the majority carriers have the magnetic moments
1 ð" Þ ¼
2 ð" Þ=2 _ ðEc – " Þ – 1 ð106Þ

0.2
T = 1.42 K
0
0.39 K
–0.2
Δρ /ρ
–0.4
0.1 K
–0.6
0.05 K
–0.8
0 20 40 60 80
H (kOe)
1(EF) ¼ 100 Å. Modified from Kamimura H (1982)
Figure 26 Experimental data on magnetoresistance of
1T-TaS2 in the temperature range from 1.42 to 0.05 K.
Modified from Kobayashi N and Muto Y (1979) Solid State
Communications 30: 337.
where Ec is the mobility edge although there is
no mobility edge in two-dimensional systems of
infinite size (Abrahams et al., 1979, 1980). Choosing
the values of the parameters to be Ec  " ¼ 1.0 meV,
U ¼ 1.7 meV, D1(EF) ¼ 5.3  1014 cm2eV, and
1(EF) ¼ 100 Å, the magnetoresistance was calcu-
lated. The calculated result is shown in Figure 27.
The result shows that the magnetoresistance is posi-
tive in low magnetic fields and then changes to
negative in high magnetic fields. The magnitude of
the positive part decreases with increasing tempera-
ture. These features are consistent with the
experimental results. However, experimental data
show only negative magnetoresistance below about
0.1 K (see Figure 26). This behavior does not agree
with the theoretical result. This discrepancy between
the theoretical result and experiments can be
explained by the spin-dependent interstate interac-
tions between Anderson-localized states, which is
given by Equation (53).
When the interstate interaction is antiferromag-
netic, the spins in the SO states retain spin-singlet
states and hardly become parallel to the magnetic
field if the magnetic field is weak. Thus, the suppres-
sion of hopping processes of types 2 and 3 in
Figure 23 may not occur, and in consequence
Impurity Bands in Group-IV Semiconductors 107
T = 0.4 K
2
1 0.6 K
Δρ /ρ
1.0 K
0
–1
0 50 100
H (kG)
Figure 27 Calculated result for the magnetoresistance of a
two-dimensional 1T-TaS2 system, in the presence of
intrastate interactions. Both positive and negative
components are taken into account. The parameters are
(EcEF) ¼ 1.0 meV, U ¼ 1.7 meV, D1 (EF) ¼ 5.3  1014 cm2eV
and
Progress of Theoretical Physics Supplement 72: 206.
P(H) disappears in Equation (105). When the tem-
perature is lower than a certain temperature
corresponding to the order of average interstate inter-
action, the magnetoresistance becomes negative even
in low fields. The observation of an anomaly in the
specific heat of this material (Nishio et al., 1978) sug-
gests the existence of spin-dependent interstate
interactions, as discussed in Section 1.03.3.3, where
the magnitude of the interaction is estimated to be
about 1 K. If the average interstate interaction is taken
as 0.5 K, the calculated result of magnetoresistance is
in good agreement with the experimental results
(Kamimura et al., 1982, 1983).
1.03.4.4 Magnetocapacitance in
Intermediate-Concentration Regime
In this subsection, we consider the magnetic-field
dependence of the electrical polarizability  for
Si:P in the intermediate-concentration regime. The
magnetocapacitance reflects elementary processes of
the hopping between the Anderson-localized states
although it is not a transport property.
New et al. (1982) reported an experimental result
that the electrical polarizability depends drastically
on the magnetic field. Figure 28(a) shows their
experimental result of the magnetocapacitance
(MC) of Si:P, where the MC is plotted as a function
of magnetic field H. The MC is defined as
108 Impurity Bands in Group-IV Semiconductors

(a) (b)
10–1

10–1

T=1K
10–2

ln Reff (H)
ln Reff (H)

10–2

T = 1.3 K
2
10–3 3
10–3 4
1.9
5
2.9
4.2

1 10 0.1 1 10
B (T) B (T)
Figure 28 (a) Experimental result for logarithmic of magnetocapacitance, Reff(H), plotted against magnetic field for Si:P at
various temperatures. The donor concentration is nD ¼ 1.0  1018 cm3. (b) Calculated result for Reff(H) for Si:P with donor
concentration nD ¼ 1.7  1018 cm3 with U ¼ 3.4 meV and W ¼ 19 meV. (a) Modified from New D, Lee NK, Tan HS, and Castner
TG (1982) Physical Review Letters 48: 1208. (b) Modified from Kurobe A, Takemori T, and Kamimura H (1984) Physical Review
Letters 52: 1457.

D ð0Þ Anderson-localized states in the intermediate-

Reff ðH Þ ¼ ð107Þ
D ðH Þ concentration regime. The electrical polarizability,
, is calculated by the Kubo formula, taking account
where the effective polarizability of donors, D, is
related to the dielectric constant  by of four kinds of excitations in Figure 23:

4nD D  ¼ 1 þ 2 þ 3 þ 4 ð109Þ
 – 0 ¼ ð108Þ
1 – 4nD D =ð30 Þ 2e 2 X hn ð1 – n –  Þihð1 – n  Þð1 – n –  ÞijhjX j ij2
1 ¼
V   " – "
Here 0 is the dielectric constant of the host material. ð110Þ
The electrical polarizability  is obtained from the
relation of  ¼ 0 þ 4 . This experimental result 2e 2 X hn ð1 – n –  Þihð1 – n  Þn –  ijhjX j ij2
2 ¼
shows that ln Reff(H) _ H2 for low fields and the V   ð" þ U Þ – "
dependence becomes weaker for higher fields, imply- ð111Þ
ing the behavior of spin-dependent electrical
polarizability. 2e 2 X hn n –  ihð1 – n  Þð1 – n –  ÞijhjX j ij2
3 ¼
New et al. (1982) ascribed their experimental result V   " – ð" þ U Þ
to the Zeeman splitting of excited spin-triplet states in
ð112Þ
spin-singlet paris of donors. Their model may be
suitable for the low-concentration regime of the 2e 2 X hn n –  ihð1 – n  Þn –  ijhjX j ij2
donors. For the present case, however, we have to 4 ¼ ð113Þ
consider the Anderson-localized states in the inter-
mediate-concentration regime. Kurobe et al. (1984)
adopted the theory in the preceding subsection to
calculate  in the intermediate-concentration regime.
Although there are various excitations, the domi-
nant contribution to electrical polarizability comes
from the one-electron excitations among the
V   ð" þ U Þ – ð" þ U Þ
where h i represents the thermal average and h jX j i
is the matrix element of the x-coordinate which is
proportional to the electric dipole moment. In general,
there is also contribution to  from excitations into
states of antibonding characters, which reduces  in
the low-concentration regime, as discussed by New
 Impurity Bands in Group-IV Semiconductors
et al. (1982). In the intermediate concentration, however,
the antibonding states have much higher energies.
Besides, the states are more extended and hence the
matrix elements in Equations (110–113) are small.
Hence, the above-mentioned excitations among the
Anderson-localized states dominantly contribute to .
The calculated result is shown in Figure 28(b) on
simplifying assumptions that the matrix element
h jX j i does not depend on the kind of process
and that the localization length,
, and intrastate
interaction, U, are independent of the state energies.
For low magnetic fields, we have
ln½Reff ðH Þ _ ðB H =kB T Þ2 ð114Þ
Physically, spins of SO states tend to be aligned with
increasing H. Since an electron cannot be excited to a
state which is already occupied by another electron
of the same spin, the contribution from an SO state to
another SO state in Equation (111) (2) decreases
with increasing magnetic field. Therefore, at high
fields (H > 5 T), where this type of excitation is
almost suppressed, MC becomes less dependent on
magnetic field. All these characteristics of MC are in
good agreement with experimental results.
1.03.4.5 Spin-Dependent Behavior of
Magnetoresistance in Other Systems
As we have described in the previous subsections, the
theory of magnetoresistance and MC developed by
Kurobe and Kamimura (Kurobe and Kamimura, 1982;
Kamimura et al., 1982, 1983; Kurobe, 1986) has played
an important role in clarifying the spin-dependent
effects on the transport properties due to the elec-
tron–electron interactions in doped semiconductors
(New et al., 1982; Agrinskaya and Kozub, 1998;
Agrinskaya et al., 2000; Kozub, 2002; Meir, 2001).
Recently, their theory has been widely applied to
other systems. For example, two-dimensional hole
system in the GaAs/AlGaAs heterostructure in mag-
netic fields (Yoon et al., 2000; Noh et al., 2004), silicon
MOSFETs in magnetic fields (Mertes et al., 2001),
amorphous indium oxide films (Frydman and
Ovadyahu, 1995; Lee et al., 2002; Orlyanchik and
Ovadyahu, 2005), amorphous Bi films (Hernandez
et al., 2003), Mn–Fe–Ge antiferromagnets (Du et al.,
2007), and icosahedral Al-Pd-Re materials (Srinivas
et al., 2001). In particular, it is interesting to see that
the theory of Kurobe and Kamimura has been used
for elucidating magnetoresistance phenomena in
one-dimensional and quasi-one-dimensional systems
109
such as metallic or doped polyacetylene (Kaneko
et al., 1994; Ishiguro et al., 1995; Choi et al., 1999),
metallic polypyrrole (Singh et al., 2008), entangled
carbon-nanotube network (Kim et al., 1998), carbon
nanomaterials (Demishev et al., 2008), disordered
nanographite network (Takahara et al. 2007), etc.
1.03.5 Conclusions
In this chapter, we have described how the impurity
band in group-IV semiconductors manifests a rich
diversified physics. In Section 1.03.2, we have surveyed
the transport phenomena in the impurity band, MI
transition, and the historical development of localiza-
tion theory. In Section 1.03.3, we have described the
theoretical formulation to treat the interplay of disor-
der and electron–electron interactions in the strongly
Anderson-localized regime just in the insulating side
of the MI transition, developed by Kamimura and
co-workers. Their theory successfully explains the
anomaly of specific heat and spin susceptibility at low
temperatures. The theoretical formulation has been
confirmed by numerical simulation for the electronic
states in the Anderson-localized regime. Section 1.03.4
has been devoted to the description of the hopping
conduction in the Anderson-localized regime. We
have reviewed the Mott’s law for the VRH and
Coulomb gap theory for the compensated samples.
Then, we have described the theory by Kurobe and
Kamimura on the magnetoresistance and MC in the
VRH regime, considering spin-dependent effects due
to electron–electron interactions. Their theory has
now been applied to magnetoresistance phenomena
observed in a wide variety of systems such as polymers,
carbon-nanotubes, and other exotic materials.
Recent development of the nanofabrication tech-
nology on semiconductors is opening new research
fields in solid-state physics. As we have mentioned in
Section 1.03.1.2, for example, it is an interesting sub-
ject to control single impurity states in doped
semiconductors for the quantum information proces-
sing. It is very impressive that Kamimura and
co-workers predicated the spin-dependent effects
on various physical phenomena in the strongly
Anderson-localized regime two decades ago before
extensive researches on solid-state quantum compu-
ters have begun. We believe that the present chapter
will be useful for graduate students and young
researchers who will work on the physics and
technology of semiconductors. (See Chapters 1.05,
1.06, 2.02 and 2.04).
110 Impurity Bands in Group-IV Semiconductors
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 1.04 Atomic Structures and Electronic Properties of
Semiconductor Interfaces
T Nakayama, Chiba University, Chiba, Japan
Y Kangawa, Kyushu University, Fukuoka, Japan
K Shiraishi, University of Tsukuba, Ibaraki, Japan
ª 2011 Elsevier B.V. All rights reserved.

1.04.1 Introduction 114

1.04.2 Interface Formation and Stability 115
1.04.2.1 Semiconductor Epitaxy 115
1.04.2.1.1 Epitaxial growth diagram 115
1.04.2.1.2 Competition of growth direction 117
1.04.2.2 Growth Modes in Heteroepitaxy 121
1.04.2.2.1 Growth modes 121
1.04.2.2.2 Theory based on macroscopic energetics 122
1.04.2.2.3 Mode transition during epitaxy 123
1.04.2.2.4 Theory based on atomistic energetics 124
1.04.2.3 Defect Formation in Heteroepitaxy 126
1.04.2.3.1 Heterovalency-induced defects 126
1.04.2.3.2 Impurity-induced defects 128
1.04.2.4 Interface Formed by Oxidation 130
1.04.2.4.1 Phenomenological theory 130
1.04.2.4.2 Mechanism of oxidation 131
1.04.2.4.3 Optical control of oxidation 137
1.04.2.5 Stability of Interfaces 141
1.04.2.5.1 Metal induced inter-diffusion 141
1.04.2.5.2 Silicidation 143
1.04.3 Electronic Structures of Interfaces 145
1.04.3.1 General Features 145
1.04.3.1.1 Origins of interface states 145
1.04.3.1.2 Semiconductor/semiconductor interface states 146
1.04.3.1.3 Metal/semiconductor interface states 149
1.04.3.2 Band Alignment 150
1.04.3.2.1 Schottky barrier 150
1.04.3.2.2 Charge neutrality level 151
1.04.3.2.3 Band bending 153
1.04.3.2.4 Band offset 154
1.04.3.3 New Features of Schottky Barrier 157
1.04.3.3.1 Breakdown of Schottky–Mott limit 157
1.04.3.3.2 Generalized charge neutrality level 158
1.04.3.3.3 Interface reaction and Fermi-level pinning 161
1.04.3.3.4 Correlation between interfaces 163
1.04.4 Future Prospects 167
References 170

113
114 Atomic Structures and Electronic Properties of Semiconductor Interfaces
1.04.1 Introduction
An interface is a boundary between two different
materials A and B (denoted henceforth as A/B).
Because the vacuum, a gas, or a liquid system is a
material form, the surface of any material is also
considered as an interface. Since the number of
material combinations, A/B, are infinite, we can
expect a variety of physical phenomena to be
observed at the interfaces. Moreover, in the last
decade, the subject of interfaces has increasingly
extended from representative solid/solid interfaces
made of inorganic materials to a wide area that
includes organic and liquid/solid interfaces. A
complete review of the overall features of these
interfaces and of the important progress in relation
to ordinary solid/solid interfaces is beyond the
scope of the present chapter. Thus, we restrict
ourselves to the limited subject of atomic and elec-
tronic structures of semiconductor interfaces, with
which the authors have been closely concerned,
and explain fundamental physical concepts
revealed by recent researches.
To understand the atomic structures of inter-
faces, it is essential to clarify the formation of an
interface and its stability. This is because the inter-
face is sometimes produced in nonequilibrium
environments and often becomes a metastable
structure. In Section 1.04.2, we consider the forma-
tion and stability of interfaces. Two representative
phenomena are discussed with respect to the inter-
face formation. One is the epitaxial growth.
Semiconductor interfaces are often produced by
stacking other materials on the substrate. In this
case, we naturally ask what conditions are neces-
sary to realize the epitaxial growth, which interface
direction is selected in the epitaxy, what kinds of
crystal shapes are produced in the epitaxy, and
why the defects are generated at the interface.
The answers to these questions are discussed in
Sections 1.04.2.1, 1.04.2.2, and 1.04.2.3.
The other topic concerning the interface forma-
tion is the oxidation. Si/SiO2 interfaces, which are
the most important interfaces of present semicon-
ductor technology, are produced by oxidizing the Si
surfaces. Recent progress in surface/interface mea-
surements has uncovered a surprising oxidation
process; Si/SiO2 interfaces are produced by layer-
by-layer oxidation. We wonder how the oxidation
proceeds, why the layer-by-layer chemical reaction
is realized, and how we observe and control such
oxidation. Section 1.04.2.4 is devoted to a discussion
of the answers to these questions. On the other
hand, the produced interfaces are not stable forever.
They sometimes change the shape by the interface
reaction of interface atoms. For an example of these
reactions, the random atom intermixing and the
compound formation like silicidation at metal/
semiconductor interfaces are discussed in Section
1.04.2.5.
The most important physical quantity to char-
acterize the electronic structures of an interface
A/B is the Schottky barrier in case of metal/
semiconductor interfaces and the band offset in
case of semiconductor/semiconductor interfaces.
These quantities represent the energy difference
of the electronic states between A and B materials.
The Schottky barrier height becomes a key quan-
tity to inject the electron and hole carriers from
metal electrodes into semiconductors, thus govern-
ing the electronic transport properties in
semiconductors. Meanwhile, in quantum super-
structures made of semiconductors, such as a
quantum-well and a superlattice, the band offset
values determine the electron and hole confinement
into the well-material layers and control band
structures, thus becoming the key quantities to
control optical properties. In Section 1.04.3, we
concentrate on these quantities and explain what
produces such energy difference of electronic
states. Interfaces have unique electronic states not
present in bulk systems having a periodicity. The
general features of interface electronic structures
and their examples are illustrated in Section
1.04.3.1. Based on these features, in Section
1.04.3.2, we explain the conventional views on
the origins of Schottky-barrier and band-offset
formation. On the other hand, unusual behaviors
of Schottky barriers, such as the breakdown of the
Schottky limit and the reaction-induced Fermi-
level pinning, which have never been explained
by conventional views, have been found very
recently in the development of some of the leading
Si nanoscale devices. These new features are
explained in detail in Section 1.04.3.3. Section 1.04.4
is devoted to some of the prospects for future
interface physics, by illustrating a new Fermi-level
stabilization by multivalent materials and cross-
dimensional phenomena at nanocontact interfaces,
such as quantum frictions in current and vibrational
motion and electron transport between an electrode
and the quantum-dot.
 Atomic Structures and Electronic Properties of Semiconductor Interfaces
1.04.2 Interface Formation and
Stability
1.04.2.1 Semiconductor Epitaxy
1.04.2.1.1 Epitaxial growth diagram
Fabrication of semiconductor devices such as high-
electron-mobility transistors (HEMTs) and light-
emitting diodes (LEDs) are carried out using vapor
phase epitaxy (VPE) techniques, for example,
molecular beam epitaxy (MBE) and metal organic
vapor phase epitaxy (MOVPE). The adsorption–
desorption behavior of the constituent atoms on
semiconductor surfaces is of fundamental impor-
tance in these growth techniques. In particular, the
behavior of constituent atoms must be known to
understand surface and thin film growth-related
phenomena such as the change in surface recon-
structions and growth processes. In the present
section, we discuss the relationships between
adsorption–desorption behavior and growth condi-
tions such as beam equivalent pressure (BEP),
p, and temperature, T.
We can consider adsorption–desorption behavior
from a viewpoint of vapor–solid phase equilibrium.
If the free energy of an atom/molecule in the
vapor phase is smaller than that on the surface, an
impinging atom/molecule is easily desorbed from
the surface and stabilized in vapor phase. On the
other hand, an atom/molecule is absorbed if the
free energy of the atom/molecule in vapor phase is
larger than that on the surface. Here, the free energy
of the atom/molecule, which is called the chemical
potential (), can be computed by using quantum
statistical mechanics. The energy gain of an adsorbed
atom/molecule on the surface (i.e., the adsorption
energy (Ead)) is estimated, for example, by ab initio
calculations. By comparing  with Ead, we can discuss
the adsorption–desorption behavior as shown in
Figure 1.
Adsorption E Desorption
μ of the symmetry number  in (3) is 2 for As2. The
Ead Ead
μ The values of  and r for As2 estimated by the
Figure 1 Schematics of the magnitude correlation
between chemical potential  and adsorption energy Ead and
its relationship with the adsorption–desorption behavior.
115
The chemical potential  for the ideal gas is
given by (Fowler, 1936; Tolman, 1938; Fowler and
Guggenheim, 1939; Mayer and Mayer, 1940;
Rodebush, 1931; Fowler and Sterne, 1932; Kassel,
1936):
 ¼ – kB T lnðgkB T =p  trans rot vibr Þ ð1Þ
 3=2
 trans ¼ 2mkB T =h 2 ð2Þ
n on=2
rot ¼ ð1=Þ 83 ðIA IB :::Þ1=n kB T =h 2 ð3Þ
 vibr ¼ Pi3N – 3 – n f1 – expð – hvi =kB T Þg – 1 ð4Þ
where  trans,  rot, and  vibr are the partition functions
for the translational motion, the rotational motion,
and the vibrational motion, respectively. Here, kB is
Boltzmann’s constant, T the temperature, g the
degree of degeneracy of the electron energy level, p
the BEP of the particle, m the mass of one particle, h
the Planck’s constant,  the symmetric factor, II the
moment of inertia, n the degree of freedom of the
rotation, N the number of atoms in the particle, i the
degree of freedom for the vibration, and  the fre-
quency. II is written as
II ¼ mI r 2 ð5Þ
where mI is the reduced mass and r the radius of
gyration.
Practical applications of this theory are as follows.
During the typical GaAs MBE process, monatomic
Ga and As2 molecule are supplied on the substrate
surface under an ultrahigh vacuum (UHV) condition.
In the UHV condition, the ideal-gas assumption is
applicable because impingement of each atom/mole-
cule is negligible. In the case of monatomic Ga, the
value of N and I are 1 and 0, respectively. Therefore,
all that is required to compute the chemical potential
 of monatomic molecule is considering the partition
function of translational motion. The value of para-
meter g for monatomic Ga in Equation (1) is 2. The
values of g for typical elements are summarized in
Table 1 (Glasstone et al., 1964). In the case of As2
molecule, we should consider the partition functions
for rotational and vibrational motions. Here, the value
values of  and r for As2 in Equations (4) and (5) can
be estimated by ab initio molecular orbital calculations.
Gaussian 98 program (Frisch et al., 1998) are
446 cm1 and 1.0621 Å (Kangawa et al., 2002), respec-
tively. By using these values, we can compute the
chemical potentials of monatomic Ga and As2
116 Atomic Structures and Electronic Properties of Semiconductor Interfaces
Table 1 Degeneracy of the electron energy level of the
various elements
Element
I H, Li, NA, K, Rb, Cs, Cu, Ag, Au
II Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg
III B, Al, Ga, In, Tl
IV C, Si, Ge, Sn, Pb
V N, P, As, Sb, Bi
VI O, S, Se, Te, Po
VII F, Cl, Br, I
0 He, Ne, Ar, Kr, Xe, Rn
Reproduced with permission from Kangawa Y, Ito T, Taguchi A,
Shiraishi K, and Ohachi T (2001) A new theoretical approach to
adsorption–desorption behavior of Ga on GaAs surfaces. Surface
Science 493: 178.
molecule as a function of growth parameters p and T.
On the other hand, the adsorption energy Ead of Ga or
As2 on reconstructed surfaces can be obtained by ab
initio calculations. For the results in this section, the
first-principles pseudopotential method based on the
local-density functional formalism (Hamman et al.,
1979) is used, adopting the Kleinman–Bylanders
separable pseudopotentials, careful treatment of the
cut-off value of local potential (Ohno, 1993), the con-
ventional repeated-slab geometry, and termination of
bottom-layer Si by fictitious H atoms. Here, we show
the results of the calculated adsorption energy of Ga
on GaAs(001)-(4  2)2 surface and desorption
energy (Ead) of As2 from c(4  4) surface.
First, we discuss about adsorption–desorption
behavior of Ga on GaAs(001)-(4  2)2 surface.
Figure 2 illustrates the GaAs(001)-(4  2)2 surface.
The calculated results show that the Ga adatom is
most stable at the site ‘E’ on the surface where two
Ga–Ga bonds (E-1 and E-2 bonds) and a Ga–As bond
(E-3 bond) are formed around the adatom. The most
favorable site for adatom on the semiconductor sur-
face is frequently discussed using an electron
counting model (Farrel et al., 1987; Pashley, 1989).
This is a model for discussing the structural stability
of reconstructed surface structure of compound
semiconductors. The lowest-energy structure is
obtained by filling all dangling bonds on the anion
atom and keeping empty those on the cation atom.
This is because energy levels of dangling bonds on
anion atom are generally located around the valence
bands and those on cation atom are around the con-
duction bands. The stability of reconstructed
structure and the adsorption site of constituent
atoms on GaAs surface is well discussed by Ito
(1995). The adsorption energies of Ead can be
Ga
g
2 As B A
1
2 C 3
3
D E
4
[110]
3 1 2
2 [110]
1
[001]
[110]
Figure 2 Schematic of GaAs(001)-(4  2)2 surface.
Adsorption sites are indicated by the letters A–E.
Reproduced with permission from Kangawa Y, Ito T,
Taguchi A, Shiraishi K, and Ohachi T (2001) A new
theoretical approach to adsorption–desorption behavior of
Ga on GaAs surfaces. Surface Science 493: 178.
calculated as the difference between the total energy
when the Ga adatom is located at the most stable site
(E-site) and when the Ga atom is in the vacuum
region. In the calculation, we gradually pulled the
Ga apart from the E site to the vacuum region and
confirmed the convergence of the total energy
difference when the distance between the position
of Ga atom and the E site is larger than 4 Å.
Consequently, the calculated adsorption energy Ead
for Ga at the E site on the Ga-rich surface is esti-
mated to be 3.3 eV. This implies that the Ga
adsorbed structure is formed when the chemical
potential for Ga atom is larger than the calculated
adsorption energy (3.3 eV). On the other hand, it is
thought that the GaAs(001)-(4  2)2 surface with-
out Ga adatom is stable when the chemical potential
for Ga is less than the adsorption energy (3.3 eV).
Figure 3 shows the chemical potential for Ga atom as
a function of temperature. Considering the typical
BEP value (pGa ¼ 1.0  105 torr), the calculated line
crosses the line of Ga ¼ 3.3 eV at 700  C; there-
fore, the critical temperature for Ga adsorption is
700  C at this BEP value. By similar calculations
to obtain crossing points at other BEPs, a p–T dia-
gram for the adsorption–desorption transition was
obtained as Figure 4. This result agrees well with
experiments, that is, GaAs(001)-(4  2) surface
becomes unstable and Ga droplets are formed at
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 117

–2.0
700 Desorption
1.0 ×10–4 torr

Temperature (°C)
c(4 × 4) unstable
650
–2.5
1.0 ×10–5 torr
Chemical potential (eV)

600

–3.0 1.0 ×10–6 torr 550

500 Adsorption
c(4 × 4) stable
–3.5 450
10–8 10–7 10–6 10–5 10–4
–4.0 μ Ga = –3.3 eV
As2 BEP (torr)

Figure 5 p–T dependence of adsorption–desorption

–4.5 transition curve for As2. Reproduced with permission from
Kangawa Y, Ito T, Hiraoka YS, Taguchi A, Shiraishi A, and
600 700 800 900 Ohachi T (2002) Theoretical approach to influence of As2
Temperature (°C) pressure on GaAs growth kinetics. Surface Science 507–
Figure 3 Chemical potential as a function of temperature. 510: 285.
Reproduced with permission from Kangawa Y, Ito T,
Taguchi A, Shiraishi K, and Ohachi T (2001) A new
theoretical approach to adsorption–desorption behavior of Ead-dimer (¼3.6 eV per dimer at Ga coverage
Ga on GaAs surfaces. Surface Science 493: 178.
Ga ¼ 0.0 (Shiraishi and Ito, 1998)) with the chemical
potential of As2 molecule As2 . That is, desorption of
As-dimer proceeds and the c(4  4) reconstructed
850
structure may be decomposed when As2 is less than
800 Desorption Ead-dimer, whereas adsorption of As2occurs and As-
Temperature (°C)

dimer on c(4 4 ) is stabilized when As2 is larger

750 than Ead-dimer. Figure 5 shows the p–T dependence of
adsorption–desorption transition curve of As2 (As-
700
dimer) on GaAs(001)-c(4  4). In Figure 5, we find
650 Adsorption
that c(4  4) surface is stable at higher pressures and
lower temperatures. This agrees well with experi-
600 ments, that is, the c(4  4)-like structure appears at
10–7 10–6 10–5 10–4 10–3
T < 500  C for pAs2  1  107 torr (Bell et al., 1999),
while the (2  4)-like structure is observed at
Ga BEP (torr)
T ¼ 580  C for pAs2  1  106 torr (Itoh et al., 1998).
Figure 4 p–T dependence of adsorption–desorption The result suggests that the theoretical approach is
transition curve for Ga. Reproduced with permission from
applicable for predicting the adsorption–desorption
Kangawa Y, Ito T, Taguchi A, Shiraishi K, and Ohachi T
(2001) A new theoretical approach to adsorption– behavior of As2 molecule. More detailed discussions
desorption behavior of Ga on GaAs surfaces. Surface are described elsewhere (Ito et al., 2004).
Science 493: 178.

600  C during the conventional MBE growth under 1.04.2.1.2 Competition of growth direction
Ga-rich condition (Yamada et al., 1989), whereas Ga Control of the interface/surface shape is a crucial factor
desorption proceeds and reconstructed surface for fabricating semiconductor devices with better-
appears at 700  C after turning off the Ga flux defined epi-layers. In this section, we discuss, for exam-
(Kojima et al., 1985; Gibson et al., 1990). This suggests ple, how to control the surface shape of cubic GaN
that the theoretical approach is feasible for predicting (c-GaN) during growth. If we can control the surface
the dependence of the temperature and BEP on shape, we can also control the interface shape between
adsorption–desorption behavior. the layer and the post-growth layer. In case of c-GaN
Next, we discuss the stability conditions of growth, control of surface shape is indispensable to
GaAs(001)-c(4  4) surface. The conditions where fabricate a better-defined epi-layer as well as to control
the -c(4  4) appears are predicted by comparing the the grown phase.The following information has been
adsorption energy of As-dimer on the surface obtained about c-GaN growth: {111} facet formation
118 Atomic Structures and Electronic Properties of Semiconductor Interfaces

during growth causes hexagonal GaN (h-GaN) mixing, (a) Top view
that is, in the regions grown toward the <111> direc- 2nd layer N
1st layer Ga
tions, the stacking sequence of . . .ABCABC. . . easily
collapses and changes to . . .ABABAB. . . (Kuwano et al.,
A B C
1994). This implies that two-dimensional (2D) growth
D E
without facet formation is important to grow single-
phase c-GaN. Here, we apply the theoretical approach Side view
described in Section 1.04.2.1.1 on the adsorption process A B C
D E
of monatomic Ga and N on GaN(001) and (111) facet
planes in order to investigate the 2D growth condition
range. The shape of a growing surface can be investi- 1st layer Ga
gated by comparing the adsorption energy of the 2nd layer N
constituent atoms on each surface; top surface and (b) Ga N
facet plane.
0

Adsorption energy (eV)

It is known that GaN(001)-(4  1) reconstructed
–1
structure based on a linear Ga tetramer is stable under
typical MBE growth conditions for c-GaN –2

–2.1 eV

(Neugebauer et al., 1998; Al-Brithen et al., 2005).
Therefore, we assumed the (4  1) reconstructed
surface as the initial substrate and investigated the
relationship between adsorption–desorption behavior
of monatomic Ga and N on the surface and growth
conditions such as BEP and temperature. Here, we
consider monatomic N, because the source gas is
supplied on the substrate surface in case of radiofre-
quency (rf) MBE. Figure 6 shows a schematic drawing
of the GaN(001)-(4  1) surface and the adsorption
energy on the sites denoted by the capital letters
(A–E), respectively. In Figure 6, one can see that the
most favorable sites for adsorption are ‘E’ site for Ga
and ‘A’ site for N. In the case of Ga adsorption, the
adsorption energy is 2.1 eV. This value is larger than
the formation energy of a Ga droplet (2.8 eV;
Honing and Karmer, 1969). Therefore, the formation
of a Ga droplet is easier than that of a Ga-adsorbed
structure in this case. In the case of N adsorption, the
adsorption energy is 6.4 eV. Using these values of
adsorption energy, we can obtain phase diagrams
related to the surface structures (Figure 7). In
Figure 7 shows that no Ga-adsorbed structure
would be formed, though Ga droplets seem to
be formed on the surface at high Ga BEP and in the
low-temperature region. Here, the boundary line
satisfies the conditions of Ga ¼ EGadroplet where
Ga is the chemical potential of monatomic Ga and
EGa-droplet the formation energy of a Ga droplet
(2.8 eV). On the other hand, the N-adsorbed
structure is stable at typical growth conditions as
shown in the phase diagram. These results suggest
that a N-adsorbed structure appears instead of a
Ga-adsorbed structure in the case of adsorption of
the first atom.
–6.4 eV
–3
–4
–5
–6
A B C D E A B C D E
Site (–) Site (–)
Figure 6 (a) Schematic drawing of GaN(001)-(41)
surface. (b) Adsorption energies of Ga and N on sites A–E
shown in (a). Reproduced with permission from Kangawa Y,
Matsuo Y, Akiyama T, Ito T, Shiraishi K, and Kakimoto K
(2007) Theoretical approach to initial growth kinetics of GaN
on GaN(001). Journal of Crystal Growth 300: 62.(Kangawa
et al. 2007)
In the same way, we can discuss the adsorption of
a second atom on the N-adsorbed GaN(001)-(4  1)
surface. Figures 8(a) and 8(b) show a schematic
drawing of the N-adsorbed GaN(001)-(4  1) surface
and the adsorption energy on each site, respectively.
In Figure 8(a), it can be seen that the most favorable
sites are ‘D’ for Ga adsorption and ‘B’ for N adsorp-
tion. However, if a N atom is adsorbed near the N
atoms on the surface, that is, the case of adsorption on
‘A’ and ‘D’ sites, N atoms would desorb as a N2
molecule instead of N-dimer formation because a
N-dimer is unstable on the surface. Phase diagrams
were made using the calculated adsorption energies,
that is, 3.7 eV for Ga and 6.0 eV for N, as shown in
Figure 9. The results imply that the stable region of
the Ga-adsorbed structure appears in the phase
diagram after the first N adsorption. That is, a
Ga-adsorbing site appears after adsorption of the
first N adatom. On the other hand, it is found that
N adsorption might occur under the condition shown
in the diagram; however, N adatoms seem to desorb
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 119

(a) (b)

Temperature (°C)
800 Ga desorption
Ead-Ga > μGa
700 N adsorption
Ead-N > μN
600 Ga droplet

10–6 10–5 10–4 10–3 10–2 10–6 10–5 10–4 10–3 10–2
Ga BEP (torr) N BEP (torr)
Figure 7 p–T dependence of adsorption–desorption behavior of (a) Ga and (b) N on the initial surface. Reproduced with
permission from Kangawa Y, Matsuo Y, Akiyama T, Ito T, Shiraishi K, and Kakimoto K (2007) Theoretical approach to initial
growth kinetics of GaN on GaN(001). Journal of Crystal Growth 300: 62.

(a) Top view (a) (b)

Temperature (°C)
800
A B C Ga adsorption
D E Ead-Ga < μGa
700 N adsorption
Side view Ead-N> μN
D A 600
Ga droplet
B C
E 10–6 10–5
10–4 10–3 10–2 10–6 10–5 10–4 10–3 10–2
Ga BEP (torr) N BEP (torr)

Figure 9 p–T dependence of adsorption–desorption

1st layer Ga
2nd layer N behavior of (a) Ga and (b) N on a N-adsorbed surface.
Reproduced with permission from Kangawa Y, Matsuo Y,
(b) Ga N Akiyama T, Ito T, Shiraishi K, and Kakimoto K (2007)
0 Theoretical approach to initial growth kinetics of GaN on
Adsorption energy (eV)

GaN(001). Journal of Crystal Growth 300: 62.

–1
–2
–6.0 eV
–3.7 eV

–3
–4
–5
–6
A B C D E
Site (–)
Figure 8 (a) Schematic drawing of N-adsorbed GaN(0 0
1)-(41) surface. (b) Adsorption energies of Ga and N on
sites A–E shown in (a). Reproduced with permission from
Kangawa Y, Matsuo Y, Akiyama T, Ito T, Shiraishi K, and
Kakimoto K (2007) Theoretical approach to initial growth
kinetics of GaN on GaN(001). Journal of Crystal Growth
300: 62.
as a N2 molecule if a N adatom migrates to the sites
on another N adatom. These results suggest that
c-GaN growth on the GaN(001)-(4  1) surface pro-
ceeds via the following process during the initial
growth stage. First, a N-adsorbed structure is formed
instead of a Ga-adsorbed structure.
Subsequently, Ga adsorption on the N adatom
occurs. Here, the N adatom is stabilized by being
covered with a Ga adatom. This is different than
the GaAs case, that is, group-III atoms are incorpo-
N2 N2
rated in the crystal by being covered with group-V
A B C D E
atoms in the case of GaAs. Though more detailed
Site (–)
examinations are required, Ga adsorption might be
the rate-limiting process during c-GaN growth and
the adsorption energy is 3.7 eV in this case.
We have already noted that the vapor–solid equi-
librium condition changes during the growth process.
That is, change in coverage of adatom/molecule
leads to a change in adsorption site for the subsequent
adatom/molecule and adsorption energy. Therefore,
the adsorption–desorption behavior changes regu-
larly during the growth process. In a similar
manner, we have to consider the influence of the
spatial dependence of the adsorption–desorption
behavior if there are more than one plane on the
surface. In the following paragraph, we discuss the
120 Atomic Structures and Electronic Properties of Semiconductor Interfaces
(a) Top view (b) Top view
1st layer Ga
1st layer Ga
2nd layer Ga 2nd layer Ga
B
B T1
T1
Side view Side view
B T1
B T1
Figure 10 Schematic of (a) Ga monolayer and (b) Ga
bilayer structure on (111) surface. Reproduced with
permission from Kangawa Y, Akiyama T, Ito T, Shiraishi K,
and Kakimoto K (2009) Theoretical approach to structural
stability of GaN: How to grow cubic GaN. Journal of Crystal
Growth 311: 3106.
adsorption–desorption behavior on the faceted
surface and the change in growth form.
To compare the adsorption energies of constitu-
ent atoms on GaN(001)-(4  1) surface with those
on {111} facet plane, we studied the adsorption–
desorption behavior of monatomic Ga and N on
{111} facet plane. Figures 10(a) and 10(b) show
schematics of Ga monolayer and bilayer surfaces,
respectively, which were observed on GaN(0001)
(Adeimann et al., 2002; Northrup et al., 2000). These
structure also appear on GaN(111) because the
atomic arrangement of the topmost and second
monolayers of (111) is the same as that of (0001).
Therefore, we discuss the adsorption–desorption
behavior on these surfaces henceforth. In Figures
10(a) and 10(b), one can see that there are two
kinds of atomic sites, that is, T1 site which is on the
Ga in underling layer and B site which is on the
bridging site between Ga atoms in the underling
layer. Table 2 shows the desorption energies of
Ga occupying the T1 and B sites on Ga mono-
layer and bilayer surfaces. In Table 2, it is found
that Ga atoms at the B sites are unstable com-
pared with that at T1 sites. This implies that
decomposition of each layer starts by desorption
of Ga at B sites. Moreover, the results suggest that
Table 2 Desorption energies of Ga at T1 and B
sites shown in Figure 10 on Ga-monolayer and
bilayer surfaces
Monolayer Bilayer
Site T1 B T1 B
Desorption energy (eV) 4.1 3.8 3.7 3.4
Reproduced with permission from Kangawa Y,
Akiyama T, Ito T, Shiraishi K, and Kakimoto K (2009)
Theoretical approach to structural stability of GaN:
How to grow cubic GaN. Journal of Crystal Growth
311: 3106.
Ga monolayer is stable compared with Ga bilayer
surface because desorption energy of Ga on the
monolayer surface (3.8 eV) is larger than that on
the bilayer surface (3.4 eV).
Here, the adsorption energy is equal to the nega-
tive of the desorption energy if there is no activation
energy during the desorption process. That is, the
adsorption energy of Ga at B site on the monolayer
and bilayer surface is 3.8 eV and 3.4 eV, respec-
tively. Using these values and the adsorption energy
of Ga on (001)-(4  1) surface (3.7 eV), we can
classify the growth conditions into three regions:
region (I)–(III), as shown in Figure 11. In regions
(I) and (II), the chemical potential, Ga , is less than
3.4 eV, which is the adsorption energy of Ga on
(111) Ga bilayer surface. Therefore, Ga monolayer
surface appears on the faceted surface and the
adsorption energy on the surface is 3.8 eV. In case
of region (I), Ga is less than 3.7 eV, which is the
adsorption energy of Ga on GaN(001)-(4  1). In this
region, impinging Ga adsorbs only on the (111) facet
plane. In the case of region (II), impinging Ga adsorbs
on the facet plane, and then adsorbs on the (001)
surface because Ead-Ga(111) < Ead-Ga(001) < Ga , where
Ead-Ga(hkl) is the Ga adsorption energy on (hkl) plane.
In the case of region (III), Ga is larger than 3.4 eV,
which is the Ga adsorption energy on Ga bilayer
surface, and, therefore, the bilayer surface appears
on the facet plane under the growth conditions. In
the region, impinging Ga atoms adsorb on the (001),
and then adsorb on the facetted surface because Ead-
Ga(001) < Ead-Ga(111) < Ga . These results imply that
2D growth occurs when the growth condition is
suitable in regions (I) and (II), whereas facet forma-
tion occurs when the growth condition is in region
(III). That is, we can control the surface shape and
suppress h-GaN mixing by choosing proper growth
conditions.
 Atomic Structures and Electronic Properties of Semiconductor Interfaces
(a)
(I)
Temperature (°C) 800
700
600
10–6 10–5 10–4
Ga partial pressure (torr)
Figure 11 (a) Phase diagram of growth form and (b) schematic of growth mode in regions (I)–(III). Reproduced with
permission from Kangawa Y, Akiyama T, Ito T, Shiraishi K, and Kakimoto K (2009) Theoretical approach to structural stability
of GaN: How to grow cubic GaN. Journal of Crystal Growth 311: 3106.
1.04.2.2 Growth Modes in Heteroepitaxy
1.04.2.2.1 Growth modes
Heteroepitaxial growth is one of the most important
techniques for the fabrication of semiconductor
heterostructures which is the basic building block
of semiconductor optical and electronic devices.
Therefore, an understanding of heteroepitaxial
growth mechanism is crucial for both scientific and
technological viewpoints (Venables et al., 1984).
Among them, it is well known that several growth
modes appear in a heteroepitaxial growth with lat-
tice-mismatched systems. In Figure 12, three typical
examples of Frank–van der Merwe (FM) mode,
Stranski–Krastanov (SK) mode, and Volmer–Weber
(VW) mode are schematically illustrated. As shown, a
two-dimensional flat epitaxial layer is observed
during growth in the FM mode. In the SK mode,
however, three-dimensional islands (called SK
islands) appear after two-dimensional wetting-layer
(a) (b) (c)
Figure 12 Schematic illustration of three typical growth
modes: (a) Frank–van der Merwe (FM) mode; (b) Stranski–
Krastanov (SK) mode; and the (c) Volmer–Weber (VM) mode.
121
(b) (I) –3.8 < μ Ga < –3.7 (eV)
–3.7 –3.8
(II) (III)
Monolayer
(II) –3.7 < μ Ga < –3.4 (eV)
–3.7
–3.8
Monolayer
Ga droplet
(III) –3.4 < μ Ga < –2.8 (eV)
10–3 10–2
–3.7 –3.8
Bilayer
formation. In the case of the VW mode, three-dimen-
sional growth proceeds without forming a two-
dimensional wetting layer. It is noted that the FM
mode originally means the growth mode in which a
two-dimensional growth layer appears after the for-
mation of misfit dislocations at the interface between
a substrate and a growth layer, as described in the
original paper of van der Merwe (1991). Nowadays,
all two-dimensional growths are often categorized
into the FM mode, contrary to the original definition.
It is well known that growth modes of a semicon-
ductor are quite complex and the physical
mechanisms of various growth modes have intensively
studied so far (van der Merwe, 1963a,b, 1991;
Matthews and Blakeslee, 1975, 1976; Tersoff, 1988,
1998; Nakajima, 1999). However, it is difficult to sys-
tematically explain the various and complex behaviors
of the growth modes observed experimentally. This is
because semiconductor crystal growth involves
various and complex phenomena: for example, the
formation of misfit dislocations at growth interfaces
and of three-dimensional growth islands, as well as the
inter-diffusion of atoms at the growth interfaces.
In the case of lattice-mismatched epitaxial
growths, the most crucial question is about how the
strain relaxation occurs. There have been a lot of
reports that discuss the relationship between growth
processes and each individual strain relaxation
mechanism. For example, van der Merwe (1963a,b,
1991) and Matthews and Blakeslee (1975, 1976)
122 Atomic Structures and Electronic Properties of Semiconductor Interfaces
investigated the relationship between the generation
of misfit dislocations and growth processes from the
viewpoint of the energy competition between the
strain in growth layers and the generation of misfit
dislocations. However, their approaches focused on
the misfit dislocations and three-dimensional island
formations were not taken into account. On the other
hand, Tersoff (1988, 1998) intensively studied the
relationship between the three-dimensional SK
island formation and growth mode, although he did
not discuss the generation of misfit dislocations.
Nakajima (1999) systematically studied the competi-
tion between strain energies, surface energies, and
interfaced energies, and discussed the growth
modes. However, he did not include the effect of
misfit dislocations.
In this subsection, we show the simple but sys-
tematic theoretical studies that discuss the
competition between several strain relaxation
mechanisms, such as the generation of misfit dislo-
cations and three-dimensional island formations
(Okajima et al., 2000). This theory is not only easy
to understand but also can naturally include various
mechanisms such as misfit dislocation and
three-dimensional island formations. Moreover, we
comment on the importance of atomistic level infor-
mation for systematic understanding of various
macroscopic growth processes.
1.04.2.2.2 Theory based on macroscopic
energetics
In this subsection, we discuss the growth mode of
lattice-mismatched epitaxy when two kinds of strain
relaxation mechanisms of misfit dislocation and
three-dimensional island formations are taken into
account (Okajima et al., 2000). First, we discuss a
theory that includes misfit dislocation and SK island
formations. This theory includes several macroscopic
parameters, for example, the elastic constants. In the
following, we will discuss a procedure that deter-
mines these macroscopic parameters based on the
atomistic simulations (e.g., first-principles calcula-
tions) showing an example that initial
heteroepitaxial growth process of InAs/GaAs(110)
can quantitatively be reproduced by the discussion
using first-principles calculations.
It should be noted that dynamics as well as the
energetics play a crucial role in crystal growth. In the
present discussion, however, we only take into
account energetics in order to simplify the discus-
sions. In the following discussion, we will show that
various and complex behaviors of lattice-mismatched
heteroepitaxial growth can be qualitatively described
on the basis of energetics.
First, we define the ‘optimal growth mode’, which
is key to the discussion in lattice-mismatched hetero-
epitaxy. The optimal growth mode has the minimum
free energy at a given film layer thickness h. Here, we
determine the optimal growth mode by considering
the energetics, instead of the system free energies, for
simplicity. To determine the growth mode, we
should consider the possible growth modes. If two
mechanisms of misfit dislocation and SK island for-
mations are considered, possible growth modes can
be categorized as follows:
1. mode with neither SK islands nor misfit disloca-
tions (two-dimensional coherent growth),
2. mode with only SK island formation (SK coherent
growth),
3. mode with only misfit dislocation formation (two-
dimensional growth with misfit dislocation), and
4. mode with both misfit dislocations and SK islands
(SK growth with misfit dislocation).
These growth modes are schematically illustrated in
Figures 13(a)–13(d). Accordingly, the optimal growth
mode is one with the lowest energy among the above
four growth modes at a given film thickness h.
Therefore, by considering the change in the optimal
growth mode with the increase of h, we can system-
atically investigate the epitaxial growth process.
Next, we describe the system energies of four
types of growth modes. Here, we define the physical
parameters that will commonly be used in this sub-
section as follows:
(a) (b)
(c) (d)
Figure 13 Schematic illustrations of four growth modes
that appear when misfit dislocation and SK island formation
are competed: (a) two-dimensional coherent growth, (b) SK
coherent growth, (c) two-dimensional growth with misfit
dislocation formation, and (d) SK growth with misfit
dislocation formation.
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 123

 –1
: surface energy of a growth layer, i: Increase in the opt h 2D – MD
l2D – MD ðh Þ ¼ l0 1 – c ð10Þ
surface area by SK island formation, h

: decrease in strain energy by SK island formation,

M: effective elastic constant, where hc 2D-MDs is the critical thickness of two-
": lattice mismatch at the hetero-interface, dimensional growth with misfit dislocations, and
l: average distance of misfit dislocations at the hetero- hc 2D-MD can be written as
interface, Ed
l0: average distance of misfit dislocations at which hc2D – MD ¼ ð11Þ
M"02 l0
lattice-mismatched strain at the hetero-interface
can perfectly be relaxed, In the case of SK growth with misfit dislocations,
Ed: formation energy of a misfit dislocation, and lopt(h) can be given as follows:
h: thickness of a growth layer.  –1
opt h SK – MD
lSK – MD ðh Þ ¼ l0 1 – c ð12Þ
It is noted that the reason why lattice-mismatch h
induced strain can effectively be relaxed by the where hc SK-MDs is the critical thickness of SK growth
three-dimensional island is the increase in surface with misfit dislocations, and it is given as follows:
regions in which constituent atoms can freely move.
This situation is included in the parameter
, which Ed
hcSK – MD ¼ ð13Þ
gives the energy gain by the above effective strain M ð1 –
Þ"02 l0
relaxation. By using Euations (10) and (12), the system energies
First, we discuss the energy of two-dimensional of two-dimensional and SK growth with misfit dis-
coherent growth. The system energy can be locations can be given as follows:
described as the sum of the surface energy and the
strain energy of a growth film, and it given as a 2D Ed Ed2
Eopt MD ðh Þ ¼ þ – ð14Þ
function of a film thickness h: l0 2M"02 l02 h

SK Ed Ed2
2D 1 Eopt MD ðh Þ ¼ þ – ð15Þ
Ecoh ðh Þ ¼ þ M"02 h ð6Þ l0 2M ð1 –
Þ"02 l02 h
2
In the case of SK coherent growth, an increase in By comparing the system energies of four possible
surface area and strain relaxation by the formation of growth modes given in Equations (6), (7), (14), and
SK islands should be added and given as follows: (15) at a given film thickness of h, we can determine
the optimal growth mode as a function of h. Further
1 more, we can discuss the various growth processes by
SK
Ecoh ðh Þ ¼ ð1 þ Þ þ M ð1 –
Þ"02 h ð7Þ
2 considering the h dependence of the optimal growth
In the case of two-dimensional growth with misfit mode.
dislocations, the system energy is a function of an Here, we briefly mention the treatment of VW
average distance in misfit dislocations l as well as a growth in which a wetting layer does not appear. To
film thickness h as follows: describe VW growth, we should set the parameter
(surface energy of a growth layer) as negative. By this
  treatment, we can describe various and complex
2D 1 l0 2 Ed
EMD ðh; l Þ ¼ þ M"02 1 – hþ ð8Þ growth processes, such as the three-dimensional
2 l l
island formation, without wetting layer formation,
Similarly, the system energy of SK growth with subsequent formation of misfit dislocations, and
misfit dislocations can also be described as h and l: coalescence of three-dimensional islands.
 
SK 1 2 l0 Ed
EMD ðh; l Þ ¼ ð1 þ Þ þ M ð1 –
Þ"0 1 – hþ ð9Þ 1.04.2.2.3 Mode transition during epitaxy
2 l l
Tracing the trajectory of the optimal growth mode,
In real epitaxial growth, an average distance of misfit while varying the layer thickness h, should reveal the
dislocations l should be the value lopt(h) at which the change in growth mode during heteroepitaxy. By
system energy becomes minimum. In addition, lopt(h) varying Ed, two types of typical growth behavior are
can be described as follows in two-dimensional demonstrated when other parameters are appropri-
growth with misfit dislocations: ately chosen, as shown in Figure 14. In the case of
124 Atomic Structures and Electronic Properties of Semiconductor Interfaces

2D-coh SK-coh
SK-MD
Ed = 2.0 2D-MD
P

Free energy per unit area

SK
C1
2D
C1

T
2D-MD
Ed = 1.0
2D
C1

2D SK
hC1 hT hC1 hP
Layer thickness
2D
2D C1 : FM-mode
hC1 < hT
2D-coh 2D-MD
SK
2D T C1
hC1 > hT
2D-coh SK-coh
P : SK-mode
SK-MD 2D-MD
Figure 14 Change in the free energy with layer thickness h. By tracing the trajectory of the optimal growth mode, the
change in the growth mode can be described. Two typical growth behaviors (FM and SK) are illustrated. Typical FM and SK
modes can well be reproduced by changing the formation energy of misfit dislocation (Ed ¼ 1 and 2 eV Å1 for FM and SK
modes). Reproduced with permission from Shiraishi K, Oyama N, Okajima L, et al. (2002) First principles and macroscopic
theories of semiconductor epitaxial growth. Journal of Crystal Growth, 237–239: 206–211.

the small formation energy of a misfit dislocation
(Ed ¼ 1.0 eV Å1), the initial two-dimensional coher-
ent growth mode changes into the two-dimensional
growth mode with misfit dislocations, when the layer
thickness h exceeds hc 2D-MD . However, no change
occurs after h ¼ hc 2D-MD . This growth process corre-
sponds to the typical FM growth that is observed in
InAs/GaAs(110) and InAs/GaAs(111) heteroepitax-
ial systems (Belk et al., 1997; Yamaguchi et al., 1997).
On the other hand, the two-dimensional coherent
growth mode first changes into the SK-coherent
one at h ¼ hT, when Ed is comparatively large
(Ed ¼ 2.0 eV Å1). By increasing the growth layer
thickness, this SK-coherent growth mode changes
to the SK growth mode with misfit dislocations
when h exceeds hc SK-MD . Further increase in the
growth layer thickness, however, induces the change
of SK growth mode with misfit dislocations into two-
dimensional growth mode with misfit dislocations.
This is a typical SK growth process that is observed
in many lattice-mismatched systems.
It is well known that dynamics and energetics play
an essential role in determining the growth processes
in actual systems. Now, we briefly mention the effect
of dynamics. For example, it becomes difficult to
generate misfit dislocations at the interface when
the epi-layer thickness is quite large. In this case,
even though the free energy of the growth mode
with misfit dislocation is at its lowest, misfit disloca-
tions are rarely generatd. This is related to the fact
that the experimental critical thicknesses of many
lattice-mismatched systems are much larger than
the theoretical values.
1.04.2.2.4 Theory based on atomistic
energetics
We have noted in the above that the formation ener-
gies of misfit dislocations play a crucial role in
determining epitaxial growth processes. These ener-
gies of misfit dislocations are often discussed based
on the elastic theory. However, the above approach
cannot include the individual and atomistic charac-
teristics of materials. To investigate the formation
energies of misfit dislocations, quantum mechanical
and atomistic approaches are desirable, although
these involve generally need large-scale calculations.
 Atomic Structures and Electronic Properties of Semiconductor Interfaces
Here, we show an example of a first-principles inves-
tigation of misfit dislocations formed at the
heteroepitaxial interface of InAs/GaAs(110) systems
(Oyama et al., 1999). Moreover, we discuss the growth
processes based on the first-principles results.
It has been reported by scanning tunneling micro-
scopy (STM) experiments that misfit dislocations
with average distance of 60 Å appear at the very
initial stage of InAs heteroepitaxial growth on a
GaAs(110) surface after 2.8 ML (‘monolayer units’)
InAs growth (Belk et al., 1997). In addition, it is also
observed that two-dimensional growth continues
without forming SK islands. The existence of misfit
dislocations can be observed based on STM experi-
ments by estimating the vertical displacement of
surface atoms with 0.5–0.7 Å.
The first-principles calculations with norm-conser-
ving pseudopotentials (Hamman et al., 1979; Ihm et al.,
1979) were carried out for model systems in which two
and four InAs monolayers are coherently grown on
GaAs(110) substrates, and are grown with misfit dis-
locations, respectively. One InAs epi-layer unit was
forcibly removed for every 15 (GaAs) units to generate
misfit dislocations. After the optimization, we obtained
the final structures. The so-obtained structures of four
InAs epi-layers are shown in Figure 15. The 90 
perfect-misfit dislocations were generated in the
[001] direction. The most noticeable points in this
structure are the fivefold coordinated In atoms that
have covalent bonds with the nearest five As atoms
along the dislocation line. Although this fivefold coor-
dinated structure was not confirmed experimentally, it
is expected that further experimental developments
will observe such brand-new dislocation core struc-
tures. Due to the dislocation formation, the epi-layer
2.52 2.52
2.57 2.57
2.64 2.63
3.12 2.86
2.70 2.60
2.39
2.28 2.30
2.34 2.34
2.40 2.40
Figure 15 The dislocation core structure obtained for InAs/GaAs(110) heterointerface with an InAs layer is 4 ML. Light, dark,
and black circles indicate In, Ga, and As atoms, respectively. The numbers in the figure represent bond lengths (Å).
Reproduced with permission from Shiraishi K, Oyama N, Okajima L, et al. (2002) First principles and macroscopic theories of
semiconductor epitaxial growth. Journal of Crystal Growth, 237–239: 206–211.
125
surface was depressed just above the misfit dislocation
line due to the strain field caused by the misfit disloca-
tions. The vertical displacement of the top surface As
atoms is about 0.54 Å when the InAs epi-layer thickness
is 4 ML. This vertical displacement is in good agree-
ment with the reported value (Oyama et al., 1999).
The above first-principles results also gave the
total energy difference between coherent and dis-
located growth modes. The calculated energy
difference are DE(2 ML) ¼ 3.15 eV per cell and
DE(4 ML) ¼ 0.85 eV per cell, respectively. From
these values, we can estimate the critical thickness
as well as the phenomenological parameters. The
calculated phenomenological parameters (Ed and
M) and the critical thickness hc 2DMD are
0.96 eV A1, 1.22  1011 N m2, and 2.35 ML,
respectively, for the InAs/GaAs(110) system. The
value of elastic constant M is of the same order
as the reported bulk modulus of InAs
(0.58  1011 N m2). On the other hand, the value
of the formation energy of a misfit dislocation is
much smaller than the typical value of misfit dis-
locations in crystals (1.86.9 eV Å1). This is
because this dislocation core structure only con-
tains stable In–As bonds without relatively unstable
In–In or As–As bonds (Kobayashi and Nakayama,
2008). Moreover, the critical thickness is obtained
as 2.35 ML. Thus, the first isolated misfit disloca-
tion is expected to appear when the epi-layer
thickness exceeds 3 ML, in fairly good agreement
with the experiments (Yamaguchi et al., 1997). The
above consideration indicates that the atomistic
information of misfit dislocations is crucial for
understanding the macroscopic growth modes
appearing in the heteroepitaxial growth.
Vertical surface displacement
= 0.542 Å
:Ga
:In
:As
2.36
[110]
[001] [110]
126 Atomic Structures and Electronic Properties of Semiconductor Interfaces
1.04.2.3 Defect Formation in Heteroepitaxy
1.04.2.3.1 Heterovalency-induced defects
In the previous section, we explained how the
elastic strain originating from lattice mismatch pro-
duces nanostructures such as quantum-dots in
heteroepitaxy. In both hetero- and homoepitaxy
of semiconductor films, another kind of nanostruc-
ture is often generated near the interface
originating from other origins. In this section, we
concentrate on the stacking-fault tetrahedron
defects (SFTs) (Finch et al., 1963; Mendelson,
1964; Kanisawa et al., 2001; Nakayama and
Kobayashi, 2005) and show that they are generated
by (i) the heterovalency, that is, the valency mis-
match of two semiconductors, and (ii) the existence
of impurity atoms on the growth surface, by
demonstrating the cases of ZnSe/GaAs interface
formation and Si homoepitaxy.
ZnSe and GaAs have the same zinc-blende crystal
structure and similar lattice constants of 5.65 and
5.64 Å, respectively. Therefore, there is no elastic
strain at ZnSe/GaAs interfaces. However, the het-
eroepitaxy of ZnSe on a (001) GaAs substrate often
produces various defects such as vacancies and inter-
stitials at the interface, followed by macroscopic
defects like dislocations, partials, and SFTs (Kuo
et al., 1996a, 1996b; Yasuda et al., 1996). What is the
origin of such extensive defect formation at ZnSe/
GaAs interfaces?
As shown in Section 1.04.2.1.1, most semicon-
ductor surface structures satisfy the electron
counting condition, where the surfaces stabilize
to become semiconducting by decreasing the dan-
gling-bond electrons, that is, by producing cation/
anion dimer bonds on the surface and transferring
the excess electrons of surface-cation dangling
bonds into the partially occupied dangling bonds
of surface anion atoms. In the case of ZnSe/GaAs
heteroepitaxy, however, the electron-deficit
Zn–As acceptor and electron-excess Ga–Se
donor bonds inevitably appear at the interface
and the electron transfer occurs among these
bonds in addition to the surface dangling bonds
(Nakayama, 1992a; Oda and Nakayama, 1992;
Murayama et al., 1998; Nakayama and
Murayama, 2000a).
The simplest atomistic model that includes these
charge-transfer effects has the total energy form as
(Nakayama and Sano, 2001)
X
H¼ VAB
A;BX
þ k0 minðjQAþ j; jQA – jÞ
A
3 X
X
þ kn minðjQA j; jQB jÞ ð16Þ
n¼1 A;B
In this model, all atoms are assumed to be located at
zinc-blende tetrahedral site. The first term represents
the bonding energies between the first-nearest neigh-
boring atoms, A and B, and between the second-
nearest neighboring surface dimer-bond atoms in
the same epitaxy layer. The values of VAB are eval-
uated from the first-principles calculations of
cohesive energy for zinc-blende AB crystal and sur-
face energies of various configurations. The second
term in the equation represents the energy gains due
to the electron transfer between four tetrahedral
bonds around an atom, A, where electrons are trans-
ferred from the donor bonds such as As–Se to the
acceptor bonds like As–Zn. Since this transfer
changes the electron occupancy from the antibond-
ing states to the bonding states, the gain energy is
proportional to the sum of excess or deficit electron
number, QAþ or QA around the A atom. After this
intra-site electron transfer, there still exist excess or
deficit electrons, QA ¼ QAþ þ QA, around the atom
A. We can assume that such electrons are transferred
within the first (n ¼ 1) to third-nearest (n ¼ 3) neigh-
boring sites, hence the third term being introduced.
The parameters, k0, k1, k2, and k3, are taken to be 2.00,
0.32, 0.08, and 0.02 eV, respectively, which are again
obtained by fitting the GaAs and ZnSe surface
energies in the first-principles calculations.
The growth simulation is performed using the
conventional stochastic Monte Carlo method (Ito
and Shiraishi, 1998a, 1998b), where the absorption,
evaporation, surface-atom diffusion, dimerization,
and atom exchange between the surface and substrate
are considered as fundamental processes. The occur-
rence probability of these processes is described by
the Boltzman factor, exp(E), where E is the surface
energy change between before and after the process
and  ¼ 1/kBT. The growth simulation starts on
GaAs (001) (2  4)2 surfaces with an area of
(12  12) and (20  20).
Three typical cases are shown here for the initial
growth of ZnSe on GaAs: (i) the case when Zn and Se
are simultaneously supplied from the beginning, and
the case when Zn and Se are simultaneously supplied
after some amount of (ii) Zn or (iii) Se exposure.
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 127

(a) (b) (a)

z=4 As As As As

(001)
Zn
3
Se Ga Ga Ga Ga
Ga
(–110)
As 2
(b)
(001)

Vacancy
1 z = –1 Zn Sc
V As As
z = –2 As As
0
A z = –3
Ga Ga Ga Ga
–1
(c)
Se
–2 As As As
As

–3 )
(11 10
0) (–1
Figure 16 Calculated ZnSe atom configurations (a) at
the initial stage of growth and (b) after 4 ML ZnSe
adsorption on GaAs (001) (2  4)2 substrate. Zn and Se
atoms are simultaneously supplied. Reproduced with
permission Nakayama T and Sano K (2001) Monte Carlo
simulation of defect formation in ZnSe/GaAs heterovalent
epitaxy. Journal of Crystal Growth 227/228: 665.
Ga Ga Ga Ga
Figure 17 Atom structures of trench sites of GaAs (001)
(2  4) 2 surfaces viewed from the (110) direction: (a)
before ZnSe adsorption, (b) after Zn adsorption, and (c) after
Se adsorption. In (b), the second adsorption occurs at the
cation site by Se atom, while, in (c), As evaporation occurs
after the Se adsorption. Reproduced with permission
Nakayama T and Sano K (2001) Monte Carlo simulation of
defect formation in ZnSe/GaAs heterovalent epitaxy.
Journal of Crystal Growth 227/228: 665.

First, we consider case (i). Figures 16(a) and

16(b) show the grown atom configurations at the
initial stage and after ZnSe adsorption in the four
topmost monolayers, respectively, where the top As-
dimer layer of GaAs corresponds to the z ¼ 0 layer.
At initial growth in Figure 16(a), Zn and Se atoms
are adsorbed at trench (missing Ga) sites in the
z ¼ 1 layer, which was also observed in STM
experiments (Ohtake et al., 1999). When the growth
proceeds further, as seen in Figure 16(b), most of
these Se atoms move to other sites by diffusion and
exchange processes and most trench sites become
occupied by Zn atoms; thus, the cation–anion order
is realized in most upper grown layers. However, it is
noticed that a few Se antisites, denoted by A, are
observed at trench sites (z ¼ 1), and these antisites
are accompanied by vacant sites, V, in the upper
layers (z > 1). Even if the growth proceeds further,
these vacant defect structures remain stationary and
never disappear.
The appearance of such defect structure is closely
related to both the electron transfer between
heterovalent bonds and the growth process. When
the GaAs (2  4)2 surface is exposed to a ZnSe
beam, as shown in Figure 17(b), the cation site
between the As dimers in the z ¼ 1 layer is first
occupied by a Zn atom and the next adsorption
occurs at the nearest cation site by breaking the As
dimer. The adsorption energies of Zn and Se to this
cation site are, respectively, 3.03 and 2.70 eV in the
absence of electron transfer, kn ¼ 0, while 3.61 and
3.84 eV in the presence of electron transfer, kn 6¼ 0.
The energy gain of Se adsorption occurs in the latter
case because the Se adsorption produces As–Se
donor bonds, which compensate the electron defi-
ciency in nearest Zn–As acceptor bonds caused by
the first Zn adsorption. In this way, the electron
transfer prefers to locate a Se atom at this cation
site, that is, induces the co-adsorption of Zn and Se,
and produces the Se antisite as shown in
Figure 17(b). Of course, when the growth proceeds
further, most such Se atoms change the position into
anion layers by diffusion and atom-exchange
128 Atomic Structures and Electronic Properties of Semiconductor Interfaces
processes. However, once a certain number of anti-
sites are produced nearby, they do not disappear
through the diffusion and atom-exchange processes
between different layers, and, as seen in
Figure 17(b), the vacant sites appear over these anti-
sites. Moreover, it should be noticed here that, as seen
in Figure 16(b), the boundary between adsorbed and
vacant regions is occupied by antisite atoms of Zn and
Se. This indicates the displacement tendency of
adsorbed atoms and might induce large defects such
as dislocations and SFTs observed in experiments.
We now consider the effects of initial treatment of
the substrate. Figure 18(a) shows the grown atom
configuration after 4 ML of ZnSe are adsorbed in
case (ii), while Figure 18(b) shows the surface struc-
ture after Se atoms are supplied on GaAs substrate in
case (iii). In Figure 18(a), all trench sites in the
z ¼ 1 layer are occupied by Zn atoms, and there is
no antisite and vacancy, hence no sign of defect
production even when further growth proceeds. On
the other hand, in Figure 18(b), Se atoms are
adsorbed not only on the GaAs surface but also at
(a) (b)
z=4
(001)
Zn
3
Se
Ga
2 As
1 0
0 semiconductors, crystallographic defects such as
–1
–1
–2
–2
–3
–3 )
10
(11
0) (–1
Figure 18 Calculated ZnSe atom configurations after
4 ML ZnSe adsorption on GaAs (001) (2  4) 2 surfaces.
Zn and Se are simultaneously supplied after some amount
of (a) Zn and (b) Se exposure. The symbol notations are the
same as in Figure 16. Reproduced with permission from
Nakayama T and Sano K (2001) Monte Carlo simulation of
defect formation in ZnSe/GaAs heterovalent epitaxy.
Journal of Crystal Growth 227/228: 665.
the anion sites which had ever been occupied by As
atoms. Moreover, one can see that a number of sub-
strate As atoms evaporate and disappear on the
surface and even in the inner z ¼ 2 layer. This As
evaporation is induced by the Se adsorption as fol-
lows: in case (iii), the supplied Se atom first occupies
the cation trench site as shown Figure 17(c).
Although the Se desorption from this configuration
is a major process in the next step, the second-nearest
neighboring As atom sometimes evaporates. This is
because there are many electrons around the
adsorbed Se due to the Se–As donor bonds, and
when the neighboring As atom evaporates the large
energy gain is obtained by transferring excess
electrons into the dangling bond of the nearest As
generated by As evaporation.
Moreover, since there is no As supply, vacant sites
are never occupied by As atoms once As atoms eva-
porate. Since the resulting surface is so bumpy, there
appear more number of defects than those shown in
Figure 16(b) when ZnSe is grown on this surface.
All the above-mentioned results are qualitatively
in agreement with experiments; the defect starts just
at the interface and the Zn/Se exposure before ZnSe
supply decreases/increases the defect density in
grown layers. These results clearly demonstrate that
both the heterovalency and the initial treatment of
heteroepitaxy are key factors to control the interface
crystalline shape. The cases of other interfaces are
also shown in the literature (Nakayama et al., 2002a).
1.04.2.3.2 Impurity-induced defects
Next, we consider the defect formation in the Si
homoepitaxy. During the thin-film growth of most
point defects and dislocations are often generated,
originating from impurity atoms on the substrate
surface. Among various defects, SFTs have unique
features; as shown in Figure 19, SFTs have a
Si(111)
Face film
wn
Ridge G ro t e
Apex tra
bs
Su
Figure 19 Schematic picture of stacking-fault
tetrahedron (SFT) in Si(111) grown film.
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 129

diamond structure in their tetrahedron body and are (a)

surrounded by (111) and three equivalent faces with
stacking-fault layers. Most SFTs are nucleated at the
interface between the substrate and the grown film
such that one of the four apexes of a tetrahedron is
located at the interface, and they become larger,
reaching the size of a few tens of micrometers, as (b)
the film grows thicker (Mendelson, 1964). However,
these are phenomenological characterizations, and it
has not been clarified from a microscopic viewpoint
how and why the SFTs are nucleated at the interface
and what crystal structures are realized around the
apex, that is, the starting point of the SFT generation.
The standard classical molecular dynamics (MD)
simulations were used to simulate the SFT genera- (c)
tion (Kobayashi and Nakayama, 2004), by adopting
the Nose ´–Hoover thermostat algorithm and the
empirical interatomic potentials. Since the Si growth
proceeds with the supply of chlorinated Si gases, such
as SiH2Cl2, a certain number of Cl atoms always exist
on the Si substrate, mainly as SiCl with a single Si–Cl
bond (Sakurai and Nakayama, 2002). Thus, the simu-
lations begin with such a Cl-adsorbed Si(111)
substrate, with the supply of Si and adoption of the
atom diffusing as an equilibrium process at a typical
Figure 20 Side views of surface structures during Si
temperature of 900  C. growth. Gray and open circles denote, respectively, Si and
When the Si atoms are supplied on Si substrate, Cl atoms. (a) Initial Si substrate for the simulations, where
the Si bilayer is first produced, as shown in two Cl atoms are adsorbed; (b) surface after initial bilayer
Figure 20(b), except at the region around the Cl growth; and (c) surface after three-bilayer growth.
atoms. As the growth proceeds further, however, Reproduced with permission from Kobayashi R and
Nakayama T (2004) Theoretical study on generation and
most Cl atoms leave the substrate by diffusing onto atomic structures of stacking-fault tetrahedra in Si film
the Si surface, as shown in Figure 20(c), and the growth. Thin Solid Films 464/465: 90.
grown Si layers produce an ordered diamond struc-
ture without any defects. This is because the Cl atom
has only a single bond with the nearest neighboring which is the reason for the stability of this structure.
Si due to the monovalency of Cl, thus being pushed In fact, once this dome structure is produced, it
out from the substrate onto the grown surface to remains intact during the subsequent Si growth
avoid the energy loss due to promoting Si dangling even when the Cl atoms are removed.
bonds around Cl atom. When the Si layers are formed on this dome
With a very small but finite possibility, however, structure, their crystal structures strongly depend
the Cl atoms remain at the initial adsorption sites on on the number of adsorbed Cl atoms on the substrate.
the substrate and are buried in the Si film after the When only one Cl atom is left on the substrate, a
Si growth. In this case, after the production of two small region of Si overlayers shows a disordered
Si bilayers shown in Figure 21(a), the deposited Si structure. As seen in Figure 21(c), however, most
atoms can find stable positions above the Cl atoms by Si layers are deposited with the diamond structure
producing covalent bonds with Si atoms in the wall and the Cl atom is buried in Si films as a point-like
around the Cl atoms, as shown by the arrow in defect, thus no SFT structure appears. On the other
Figure 21(a). Then, as shown in Figure 21(b), the hand, when more than one Cl atoms are present in
deposited Si atoms can be located at positions about the nearest neighbouring sites on the substrate, as
one bilayer above the Cl atoms such that they form a shown in Figure 21(d), the Si layers in a region
dome over the Cl atoms. Most of these Si atoms in above the Cl atoms are located at positions slightly
the ceiling of the dome are tetrahedrally coordinated, higher than the corresponding layers in the other
130 Atomic Structures and Electronic Properties of Semiconductor Interfaces

(a) (b)

(c) (d)
Ridge SF

Figure 21 Side views of surface structures during Si growth. (a) Surface after the growth of two Si bilayers in the case when
two Cl atoms are left on the substrate; (b) surface after a few Si atoms are supplied on the surface shown in (a). The dome
structure is produced over the Cl atoms. (c) Surface after the growth of three bilayers with one Cl atom left on the substrate. (d)
Surface after the growth of three bilayers with two Cl atoms left on the substrate. Dotted lines, labeled SF and Ridge,
respectively, show the stacking fault face and the ridge line of SFT. Reproduced with permission from Kobayashi R and
Nakayama T (2004) Theoretical study on generation and atomic structures of stacking- fault tetrahedra in Si film growth. Thin
Solid Films 464/465: 90.

region and have a diamond structure. Moreover, we
can see the stacking-fault faces and the ridge line
around this region, indicating the growth of the
SFT-like structure. From these results, we can con-
clude that the SFTs can be produced when more
than one Cl atoms are present nearby on the sub-
strate, and the dome structure shown here is one of
the candidates for the apex structure of SFTs. This
conclusion is consistent with the observation that the
SFT density is proportional to the square of the Cl
coverage on the Si substrate (Mazumdar et al., 1995;
Takakuwa et al., 1997). In fact, after producing such
an apex, there appear three partial dislocations as
ridge lines (Kobayashi and Nakayama, 2008).
1.04.2.4 Interface Formed by Oxidation
The Si/SiO2 interface is a building block of Si metal-
oxide field-effect transistor (MOSFET) in large-
scale integration (LSI) circuits. The realization of
MOSFET in modern LSI circuits stems from the
high-quality Si/SiO2 interfaces (Kahng, 1960). In
fact, a Si/SiO2 interface can provide us a nearly
ideal two-dimensional electron gas (2DEG) that
leads to the discovery of quantum Hall effects, etc.
(von Klitzing et al., 1980). This is due to the sharp and
nearly defect-free characteristics of the Si/SiO2
interface. The typical interface defect density is of
the order of 1010 cm2, and the TEM observation
really indicates the sharp interface structure. Such
sharp interface comes from the layer-by-layer oxida-
tion of Si surfaces and interfaces, which has been
observed on Si(111) (Ohishi and Hattori, 1994) and
Si(100) surfaces (Watanabe et al., 1998).
1.04.2.4.1 Phenomenological theory
The Deal and Grove model of Si oxidationhas been
widely accepted for a long time. First, we introduce
the conventional understanding of Si thermal oxida-
tion by Deal and Grove (1965). The suggested steps
consist of an oxidant diffusion process followed by an
interfacial reaction process. When a Si substrate is
exposed to an oxygen (O2) atmosphere at around
700–1100  C, the substrate surface changes into Si
 Atomic Structures and Electronic Properties of Semiconductor Interfaces
oxide. This is the thermal oxidation process. While
this process can be described by a simple chemical
reaction formula, Si þ O2  > SiO2, its microscopic
picture is much complicated. During the oxidation,
O2 molecules from the atmosphere must meet the
substrate Si to react, but the surface of the substrate is
covered by Si oxide. Therefore, O2 molecules must
move through the Si oxide covering the surface. So,
Deal and Grove assumed that the O2 molecules move
(the diffusion process) and arrive at the interface
between the Si oxide and substrate Si and react
with the latter (the reaction process). By combining
these two processes, they successfully explained the
kinetics of oxide thickness growth. Experiments with
O isotopes basically supported this scheme (Han and
Helms, 1988; Lu et al., 1995): isotope-labeled O atoms
are located at Si/SiO2 interfaces, which indicates that
O2 molecules diffuse through SiO2 layer and react at
the Si/SiO2 interface. Moreover, their model could
reproduce the experimental oxidation rate as follows.
The time evolution of oxide thickness can be written
as X 2 þ AX ¼ B ðt þ  Þ, where X and t are oxide
thickness and oxide time, respectively, and A and B
are, respectively, the constants related to oxidation
reaction and O2 diffusion through SiO2. The charac-
teristic nature of their model is that there exist two
regions called the reaction- and diffusion-limited
oxidation regions that correspond to thin and thick
oxide thickness, respectively. In the case of reaction-
limited oxidation, oxide thickness X is proportional
to the oxidation time, t. On the other hand, pffiffi in the
diffusion limited case, X is proportional to t .
However, as Deal and Grove also pointed out in
their original paper, this picture cannot explain sev-
eral issues related to the thermal oxidation process
(Deal and Grove, 1965; Deal, 1988). In particular, it
cannot explain the so-called initial enhanced oxida-
tion, the rapid oxide growth when the oxide
thickness is thinner than a few tens of nanometers.
One important factor, which is not taken into account
in the Deal–Grove scheme, is that the volume of the
newly formed oxide is more than 2 times larger than
that of the reacted substrate Si. Since the reaction
occurs at the interface surrounded by the substrate
and the surface oxide, the excess volume should
cause a large compressive strain on the newly formed
oxide. Such accumulated strain could be released by
viscoelastic deformation of the Si oxide. The Si den-
sity drastically decreases after Si thermal oxidation
due to the volume expansion, indicating that Si spe-
cies should move from interface region to release
accumulated strain. Therefore, it is natural to think
131
that the transport of Si is also important during the
thermal oxidation, though the Deal–Grove scheme
considers only the transport of O. Thus, the move-
ment of both O and Si should be clarified
microscopically in detail to obtain a precise scheme
of the thermal oxidation process.
1.04.2.4.2 Mechanism of oxidation
Although the Deal and Grove model can describe the
important characteristics of thermal oxidation, it is
agreed that it fails to explain the oxidation process,
especially in the thin-oxide case. Here, we introduce
a more realistic scheme for the mechanism of the Si
thermal oxidation process based on the knowledge
obtained by the computational sciences and related
experiments (Kageshima and Shiraishi, 1998;
Kageshima et al., 1999; Uematsu et al., 2000, 2001,
2004; Fukatsu et al., 2003; Watanabe et al., 2006;
Ming et al., 2006).
• Oxidation direction Kageshima and Shiraishi
clearly show by the first-principles calculations
that the preferential growth direction of the oxide
nucleus on the surfaces is vertical to the substrate,
whereas, at the interfaces, it is lateral. Moreover,
they have shown that Si atoms are inevitably
emitted from the interface to release the stress
induced during Si oxide growth (Kageshima and
Shiraishi, 1998)
First, the growth directions of an oxide nucleus on
Si surfaces and at Si-oxide/Si interfaces are dis-
cussed. The surface growth direction is investigated
by using the Si(100) surface with buckled dimmers as
the initial surface. For such a surface, the most stable
adsorption site of the initial O atom is the back-bond
of the lower dimer atom (Kato et al., 1998). The first
O atom is placed at that site and another is added
between the SiSi bonds neighboring the first
SiOSi bond. Second, the most stable adsorption
site for the second O atom is determined by the first-
principles results. The possible sites are shown in
Figure 22(a). The calculated total energies are 0.10,
0.02, 0.33, and 0.61 eV per unit cell, for the sites B,
C, D, and E, respectively, relative to the total energy
of the site A. Using the dihydride Si(100) surface
model (Northrup, 1991) as the initial surface,
Kageshima and Shiraishi also investigated the growth
direction for a H-terminated surface. The most stable
adsorption site for the initial O atom is the outermost
SiSi bond. The first O atom is placed at that site
and another one is added between the SiSi bonds
neighboring the first SiOSi bond. Then, the most
132 Atomic Structures and Electronic Properties of Semiconductor Interfaces

(a) (b) (c)

C D
C
E C
B
A B
D A
B A

Figure 22 Atomic structures for studying the oxide nucleus growth. (a) Top view for the clean surface, (b) top view for the
dihydride surface, and (c) side view for the oxide/Si interface with the less-stressed quartz-like oxide. The filled circles are O
atoms, the empty circles are Si atoms, and the small hatched circles are H atoms. Reproduced with permission from
Kageshima H and Shiraishi K (1998) First-principles study of oxide growth on Si(100) surfaces and at SiO2/Si(100) interfaces.
Physical Review Letters 81: 5936.

stable adsorption site of the second O atom can be
determined. The calculated total energies are 0.12,
0.22, and 0.59 eV per unit cell, for the sites B, C,
and D, respectively, relative to the total energy of the
site A (Figure 22(b)). These calculations indicate
that the oxide nucleus on the (100) surface preferen-
tially grows vertically into the substrate, being
independent of the surface reconstruction.
Next, we discuss the oxide growth direction at Si/
SiO2 interfaces. For the investigation of the growth
direction for interfaces, the quartz/Si(100) interface
model is used as the initial interface (Figure 22(c))
(Kageshima and Shiraishi, 1998). While the real
oxide layer formed by oxidation is amorphous, for
simplicity, the oxide is modeled by a crystal of SiO2.
However, this crystal model certainly has a perfect
bond network without large stress, which is an
important feature of the real amorphous oxide inter-
face. The first O atom is added to the interface and
the stable structure is determined. Next, the second
and third O atoms are introduced to the interface,
assuming that all of the SiOSi bonds formed are
connected. The calculations show that the structure
in which the second O atom is inserted into the site A
is energetically more stable (by 0.29 eV per unit cell)
than the structure in which the second one is inserted
into the site B. Moreover, the structure in which the
second and third O atoms are inserted into the sites A
and C is more stable (by 0.05 eV per unit cell) than
the structure in which the second and third ones are
inserted into the sites A and B. These results indicate
that the oxide nucleus at the Si-oxide/Si(100) inter-
face preferentially grows laterally, parallel to the
interface.
The preferential growth direction of the oxide
nucleus for the (100) substrate is thus governed
by the difference between ‘on the surface’ and ‘at
the interface.’ Since the vertical oxide growth on
the surfaces is independent of the surface reconstruc-
tion, the stress (rather than the bonding nature or
the charge transfer) seems to control the growth
direction. Actually, it is easy for SiOSi bonds on
the surfaces to expand vertically because the surface
atoms in the Si region can move upwards with almost
total freedom, while it is not easy for the bonds to
expand laterally. Thus, the initial oxide nucleus on
the surface should grow vertically in order to mini-
mize the stress. In the case of the interface, the
vertical expansion of SiOSi bonds is not easy
because their movement is restricted by the covered
oxide layer. Therefore, the energy gain due to the
stress release by vertical growth is quite restricted.
On the other hand, to minimize the interface energy,
the initial oxide nucleus at the interface should grow
laterally. These results have been confirmed by
examining the stress distribution of the calculated
atomic structures estimated from the shortening of
the Si–Si bond lengths. These findings show the
importance of the stress in determining the growth
direction. A simple phenomenological model that
includes oxidation induced compressive strain also
reproduces the lateral oxide growth (Shiraishi et al.,
2000). Recently, it has been pointed out that a simple
Monte Carlo simulation that includes the diffusion of
O species through SiO2 region can reproduce layer-
by-layer growth qualitatively (Watanabe et al., 2004).
The above considerations agree with the experi-
mental results fairly well. A previous STM-based
measurement of the oxide growth on a clean
Si(111) surface (Ono et al., 1993) showed that oxide
islands are formed in the initial stage at 600  C. The
depth of the islands reaches several atomic layers at
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 133

the very initial stage. Furthermore, many experi-
ments have clearly shown that the oxide grows
atomically layer by layer at the Si-oxide/Si(100)
and (111) interfaces (Gibson and Lanzerotti, 1989;
Komeda et al., 1998; Ohishi and Hattori, 1994;
Watanabe et al., 1998). These are consistent with the
findings based on the computational results.
The results discussed above indicate that a uni-
form oxide layer can be obtained with any thickness
by thermal oxidation, once a uniform surface oxide
layer is formed. Therefore, the preparation of the
initial surface oxide is crucial for obtaining a uniform
oxide layer with atomically controlled thickness,
which gives an important guiding principle for mod-
ern Si nanotechnologies. Although first-principles
results also indicate that the initial growth direction
of the oxide nucleus on the surfaces is vertical into
the substrate, this is true only when the thermody-
namics govern the oxidation process. Actually, the
STM measurement has shown that oxidation does
not form islands, but instead forms an atomically thin
surface oxide layer from the very first stage at room
temperature, where the oxidant cannot diffuse into
the substrate easily (Ono et al., 1993). It has been
reported that the O2 adsorption in the second layer
of the clean Si(100) surface has a nonzero barrier of
about 0.3 eV, while the adsorption in the outermost
layer is barrierless (Watanabe et al., 1998). Therefore,
thermal oxidation at a lower oxidant pressure and
lower temperature could result in the formation of a
well-controlled atomically thin uniform oxide layer.
The efficiency of these oxidation processes is sup-
ported by the experiments (Ohishi et al., 1994;
Watanabe et al., 1998).
• Stress release We now turn to the mechanism for
the release of the accumulated stress during oxida-
tion. Stress release was first investigated using a
dihydrided Si(100) surface as the initial surface. We
sequentially insert O atoms between SiSi bonds of
the surface, assuming atomical layer-by-layer oxide
growth. This assumption simplifies the analysis of the
accumulated stress, as will be shown below. When
eight O atoms per unit cell are introduced
(Figure 23(a)), the formed oxide has a SiOSi
network similar to that of the cristobalite of crystal
SiO2 (Wyckoff, 1963). However, the structure is
highly compressed compared to that of the cristoba-
lite. The a and b axes of the obtained oxidized region,
which are parallel to the interface, are 23% shorter
than the corresponding axes of the a-cristobalite.
Despite the elastic theory, the c axis, which is per-
pendicular to the interface, is only 20% longer than
the corresponding axis of the a-cristobalite. Thus, the
structure is largely compressed to about three-
fourths of the volume of the a-cristobalite. This sug-
gests the existence of strain release mechanism
during the oxide growth. One possibility is the

(a) (b) (c)

(d) (e) (f)

Figure 23 Side views of the atomic structures for studying the accumulation and the release of the stress. (a) The structure
after sequential oxidation by two Si atomic layers; (b, c) the structures before and after the Si emission on the dihydride
surface; (d) the structure with the Si emission after oxidation by two Si atomic layers; (e, f ) the structures before and after the
emission at the oxide/Si interface with the less-stressed quartz-like oxide. The broken circles indicate the position where the
Si atom is emitted. Reproduced with permission from Kageshima H and Shiraishi K (1998) First-principles study of oxide
growth on Si(100) surfaces and at SiO2/Si(100) interfaces. Physical Review Letters 81: 5936.
134 Atomic Structures and Electronic Properties of Semiconductor Interfaces
breaking, deformation, and rebonding of the formed
SiOSi network, which would correspond to a
viscous flow of oxide. However, bond breaking and
deformation after oxide formation require a lot of
energy. Therefore, there must be some other
mechanisms that work to release the stress before
the compressed oxide is formed.
It is found that the atomic structure, when three O
atoms per unit cell are introduced, is the key to the
stress release (Figure 23(b)) (Kageshima and
Shiraishi, 1998). In this structure, an O atom is quite
close to a surface Si atom, which has only one SiO
bond. Thus, these two atoms can form a bond by
breaking the bonds with the second-layer Si atom.
Moreover, the second-layer Si atom, whose two
bonds were broken, could be emitted from the sur-
face because of laterally compressed stress on it
(Figure 23(c)). The calculated total energy of such
a Si-emitting structure indicates it to be only 0.04 eV
per unit cell higher than that of the nonemitting
structure, though there remain two dangling bonds.
This structure resembles the well-known A center (or
the VO center) in bulk Si crystal (Pajot, 1994; Chadi,
1996). In addition, when we sequentially insert O
atoms, the total energies for all of the emitting struc-
tures are more stable than those for the
corresponding nonemitting structures (Figure 24).
The energy advantage is up to 2 eV per unit cell.
This is because the two remaining dangling bonds
first form a weak bond by laterally compressed stress,
and are finally terminated by forming a SiOSi
bond. This also indicates that the Si emission scarcely
results in the creation of the interfacial gap states.
3 Si emission (up to 2 eV) is smaller than the
Energy advantage
2 Emission preferential
(eV \ unit cell)
1
0
–1
–2 No-emission preferential
–3
0 1 2 3 4 5 6 7
Number of O atoms
Figure 24 Energy advantage of Si-emitting structures
compared with the nonemitting structures as a
function of the number of inserted O atoms per unit
cell. The most stable structures for each case are
compared, assuming the atomical layer-bilayer oxide
growth. Reproduced with permission from Kageshima H
and Shiraishi K (1998) First-principles study of oxide
growth on Si(100) surfaces and at SiO2/Si(100)
interfaces. Physical Review Letters 81: 5936.
Moreover, when six O atoms per unit cell are intro-
duced to the emitting structure (Figure 23(d)), the
resulting bond network resembles the quartz struc-
ture of SiO2. The a axis of the obtained oxidized
region is only 8% longer than the corresponding
axis of the b-quartz. The b and c axes are only 1%
and 0.2% shorter, respectively, than the correspond-
ing axes of the b-quartz. Thus, the accumulated strain
is successfully released by removing Si atoms during
Si oxidation. In the real experimental situation, it is
expected that the remaining stress in the formed
oxide would be completely released after the Si
emission during oxide growth.
Silicon emission also occurs at the Si-oxide/Si
interfaces. Si emission from the interfaces has been
considered using the quartz/Si(100) interface
model (Kageshima and Shiraishi, 1998). The total
energy of the emitting structure (Figure 23(f)) is
more stable (by 0.41 eV per unit cell) than that of
the nonemitting structure (Figure 23(e)), although
two Si dangling bonds are formed after Si emission.
This means that, even at the oxide/Si interfaces, Si
atoms are preferentially emitted during oxide
growth. Moreover, although layer-by-layer oxida-
tion is assumed as mentioned above, further
calculations show that the Si emission is indepen-
dent of the oxide growth mode. Even after the
initial vertical oxide growth on the surfaces, the
emission can occur again when the oxide islands
connect with each other. Since stress accumulation
is inevitable in the Si oxidation process, the release
of this stress by Si emission should be essential and
universal.
• Si emission As discussed above, the emitted Si
atoms should play an important role in the oxidation
process. Since the energy advantage of the
formation energy of the Si interstitials (4.9 eV)
(Car et al., 1984), which is thought to induce the
oxidation-induced stacking faults (OSF) (Thomas,
1963; Ravi and Varker, 1974; Hu, 1975), oxidation-
enhanced diffusion (OED), and oxidation-reduced
8 diffusion (ORD) (Mizuo and Higuchi, 1982; Tan
and Gösele, 1985). However, the energetically
most stable way for emitted Si is that emitted Si
atoms flow back toward the SiO2 region and react
with O species as (Si þ O2 ! SiO2). This is because
the energy gain of this reaction amounts to 11.0 eV.
Accordingly, the microscopic oxidation mechanism
given by Deal and Grove (1965), which only con-
siders the O diffusion, should be modified by taking
into the backflow diffusion of emitted Si species
 Atomic Structures and Electronic Properties of Semiconductor Interfaces
O species SiO2 Si species
Si
Si species
Figure 25 Schematic illustration of Si oxidation
processes. Oxygen molecules should diffuse through a SiO2
layer before reacting with Si at Si/SiO2 interfaces.
from the Si/SiO2 interface. As a result, the oxidation
process contains diffusion of both O and Si species,
as illustrated in Figure 25.
Next, we show the experimental findings of Si
species backflow from Si/SiO2 interface to SiO2
region during oxidation. First experimental example
is that the B and Si self-diffusion near the Si/SiO2
interface is remarkably enhanced (Uematsu et al.
2004; Fukatsu et al., 2003). This is thought to be the
effect of emitted Si species from the Si/SiO2 inter-
faces. To investigate the B diffusion in SiO2 by
secondary-ion mass spectroscopy (SIMS) analysis,
the samples are prepared as follows. The isotopically
enriched 28Si epi-layer was thermally oxidized in dry
O2 to form 28SiO2 with thickness 200, 300, and
650 nm. The samples were implanted with 30Si at
50 keV to a dose of 2  1015 cm2 and capped with
a 30-nm-thick silicon nitride layer. Subsequently,
the samples were implanted with 11B at 25 keV to a
dose of 3  1015 cm2. The final structure is shown in
Figure 26. The samples were pre-annealed at
1000  C for 30 min to eliminate implantation
damages, and were annealed in the resistively heated
annealing furnace at various temperatures in the
range of 1100–1250  C. The diffusion profiles of 11B
and 30Si were measured by SIMS.
Si3N4 30 nm
200–650 nm
28SiO
2 activation barrier (Otani et al., 2003). Considering
28Si
Implanted
30Si
Implanted 11B
Figure 26 The sample structure employed for
considering the enhanced B diffusion near Si/SiO2
interfaces.
135
1019
B concentration (cm–3)
B 5 ×1013 cm–2
1018
1200 °C 24 h
28SiO
2 thickness
200 nm
1017
300 nm
650 nm
As-impla
1016
0 50 100 150 200
Depth (nm)
Figure 27 Diffusion profiles of B in SiO2 with various
thicknesses. Samples were implanted with B to a dose of
5  1013 cm2 and annealed at 1200  C for 24 h. The nearer
the Si/SiO2 interface, the broader the B profiles becomes.
Reproduced with permission from Uematsu M, Kageshima
H, Takahashi Y, Fukatsu S, Itoh KM, and Shiraishi K (2004)
Correlated diffusion of silicon and boron in thermally grown
SiO2. Applied Physics Letters 85: 221.
Figure 27 shows the depth profiles of 11B before
and after annealing at 1250  C for 6 h. As shown in
Figure 27, the profiles of 11B become broader with
decreasing thickness of the 28SiO2 layer, that is, B
diffusivity increases with decreasing distance from
the Si/SiO2 interface. If B diffusion is governed by a
single process, the B diffusivity should depend on
the distance. However, it is physically unnatural.
The distance dependence of diffusivity is also
observed in the Si self-diffusion in SiO2 (Fukatsu
et al., 2003). In the case of Si self-diffusion, SiO
molecules generated at the interface and diffusing
into the oxide enhance Si self-diffusion (Fukatsu
et al., 2003). These results indicate that SiO mole-
cules also enhance B diffusion, because B diffusivity
is higher near the interface, where the SiO
concentration is high. Moreover, first-principles
calculations show that interstitial BO complexes
can diffuse through SiO2 layers with relatively low
that this interstitial BO complex is stoichiometri-
cally equivalent to the BSiSiO complex, these
first-principles results may indicate that the
existence of SiO species also enhances B diffusion
(Uematsu et al., 2006).
Taking into account the effect of SiO, coupled
diffusion equations that include normal thermal B
136 Atomic Structures and Electronic Properties of Semiconductor Interfaces
diffusion and SiO-assisted B diffusion can readily be
constructed (Uematsu et al., 2004). As shown in
Figure 27, a numerical simulation that includes
the mechanism that SiO species generated from
Si/SiO2 interface enhance B diffusion well repro-
duces the distance dependence of B diffusivity,
although constant diffusivities are assumed.
Moreover, the time dependence of B diffusivities
has also been reported. It is expected that SiO con-
centration generated from Si/SiO2 interface
increases with longer annealing time. Considering
the above discussions that SiO species enhance the
B diffusion, B diffusivity is expected to be increased
with longer annealing time. Actually, the clear
enhancement in B diffusivity has been confirmed;
1.5  1016 and 3.0  1016 cm2 s1 B diffusivities
are obtained after 8 and 24 h 1200  C anneals,
respectively. This time dependence also supports
the fact that B diffusion is assisted by SiO
(Uematsu et al., 2006).
Next, we show much direct proof of Si species
emission during Si oxidation (Ming et al., 2006).
Experiments use the characteristic material proper-
ties of SiO2 in thin HfO2. It is known that SiO2 and
HfO2 reveal phase separation when HfO2 is thin
enough. Thus, when the HfO2/SiO2/Si stacked sam-
ple is oxidized and Si substrate oxidation occurs, it is
expected that emitted Si species diffuse through
HfO2 and segregate at the surface. Thus, surface-
sensitive observations can detect the emitted Si
15
400 keV He+ HfO2 /SiO2 /Si [111] channeling
As-grown
900 °C × 2 min
10
Counts (a.u.)
5 Si
0
320 340
Energy (keV)
Figure 28 High-resolution Rutherford backscattering spectra of as-grown and annealed HfO2/SiO2/Si. Reproduced with
permission from Ming Z, Nakajima K, Suzuki M, et al. (2006) Si emission from the SiO2/Si interface during the growth of SiO2 in
the HfO2/SiO2/Si structure. Applied Physics Letters 88: 153516.
species which segregate at the surface. Ming et al.
(2006) performed the high-resolution Rutherford
backscattering (HRBS) measurement and confirm
the existence of surface Si component around
361 keV in addition to the Si peak at the Si/SiO2
interface near 350 keV, only when interfacial SiO2
growth occurs, as clearly shown in Figure 28. This
experiment clearly confirmed that Si emission during
Si oxidation, which was predicted by the first-prin-
ciples calculations (Kageshima and Shiraishi, 1998) is
surely observed.
Here, we introduce the physical origin of initial
enhanced oxidation, which has been a mystery of Si
oxidation for a long time. First, we introduce the Si
emission model (Kageshima et al., 1999). If the effect
of such SiO interstitials as discussed previously under
the so-called Si emission model is considered, the
initial enhanced oxidation can systematically be
reproduced (Kageshima et al., 1999; Uematsu et al.,
2000). As per Deal and Grove, the oxide growth rate
equation can be derived from the reaction–diffusion
equation, while newly considered SiO flow from the
interface to the surface should be included besides
the O2 flow from the surface to the interface
(Figure 29).
Due to the SiO flow, the interfacial reaction rate
of O2 must be modified. SiO should be much easily
oxidized on the surface than in the oxide because the
oxidation of SiO should be incorporated with the
volume expansion. Then, in the thin-oxide limit,
×5 Hf
360 380 400
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 137

Gas Oxydant

Point (2) k′
S
k: rapid reaction C Si C SO

x Point (1)
k : slow reaction
DSi Interfacial reaction rate
k C Si(x) DO k = k0 (1–C ISi /C 0Si)
Oxide

x
C ISi C IO

k
Silicon
V

Emitted Si
Figure 29 Schematic view of the reaction-diffusion kinetics in the Si emission model. From Kageshima H, Uematsu M,
Akiyama T, and Ito T (2007) Microscopic mechanism of silicon thermal oxidation process. ECS Transactions 6: 449.

the combined reaction–diffusion equations are ana- 100

lytically solved as Our theory
dX =dt ¼ B=ðA þ 2X Þ þ K expð – X =LÞ ð17Þ Experiment 1000°C

where X is the oxide thickness and t the oxidation

Oxide thickness (μm)

time. This is quite similar to the empirical equation 10–1

for the initial enhanced oxidation proposed by
Massoud et al. (1985). The Si emission model also 1 atm O2
indicates the physical meaning of the parameters A, (100) substrate
B, K, and L. For example, L is related to the diffu- 900°C
10–2
sion length of SiO. By solving numerically the 800°C

combined equations of Si emission model, the

experimental results can well be reproduced
including the initial enhanced oxidation as well as
the growth rate for thicker oxide, as shown in
Figure 30.
Recently, it has been reported that the initial
enhanced oxidation can be reproduced by taking into
account the increase in the diffusion barrier by the
accumulated stress near the Si/SiO2 interfaces
(Watanabe et al., 2006; Watanabe and Ohdomari, 2007).
They suppose a compressively strained oxide layer with
thickness L localized in the proximity of the SiO2/Si
interface. By considering the diffusion barrier modifica-
tion, initial enhanced oxidation can also be reproduced
(Watanabe et al., 2006; Watanabe and Ohdomari, 2007).
1.04.2.4.3 Optical control of oxidation
In the downsizing trends of Si-related nanoscale
devices, the in situ monitoring and thickness control
of Si oxidation received an increasing demand as one
10–3 0
10 101 102 103 104 105
Oxidation time (s)
Figure 30 Comparison of our theory of the oxide growth
kinetics with experimental data. From Uematsu M,
Kageshima H, and Shiraishi K (2000) Unified simulation of
silicon oxidation based on the interfacial silicon emission
model. Japanese Journal of Applied Physics 39: L699.
of the key process technologies. As explained in the
above, Watanabe et al. (1998) clearly demonstrated
visually by employing the scanning reflection elec-
tron spectroscopy (SREM) that the thermal
oxidation of Si(001) surface proceeds in a layer-by-
layer manner. Since the SREM uses electrons as a
probe, however, the observation is limited to the
oxidation of ultrathin layers under the ultrahigh
138 Atomic Structures and Electronic Properties of Semiconductor Interfaces
vacuum environment. On the other hand, the reflec-
tance difference spectroscopy (RDS) is a powerful
in situ optical measurement to observe the electronic
structures of semiconductor surfaces/interfaces and
their time evolution (Aspnes and Studna, 1985;
Hingerl et al., 1993; Uwai and Kobayashi, 1994;
Nakayama, 1997; Murayama et al., 1998). Since the
electromagnetic light penetrates deep into the Si
substrate, that is, an order of 1000 Å, the RDS can
detect, in principle, the layer-by-layer thermal oxi-
dation. Nakayama and Murayama proposed the use
layers are isotropic, while the surface/interface layers
(ILs) are anisotropic. Thus, since the polarization ani-
sotropy originates from the anisotropy of surface/
interface electronic states, the RDS can teach us the
nature of surface/interface electronic structures. In
particular, the spectral shape reflects the localized nat-
ure of the interface states. The simplest picture of
polarization around the semiconductor interface is
obtained by the bond polarization model (Nakayama
and Murayama, 1999). The bond polarization in
the nth semiconductor layer is represented by
of RDS to control the layer-by-layer thermal oxida-
tion, by theoretically investigating the variation of
RDS spectra of buried SiO2/Si interfaces (Nakayama
and Murayama, 2000).
At first, we briefly explain the RDS. The RDS
measures the difference in reflectance of surface/inter-
face between two perpendicular light-polarization
directions as shown in Figure 31(a). The inner bulk
n ¼ ð – 1Þn b ð!Þ þ sn ð!Þ, where b ð!Þ is the bulk
polarization corresponding to the light with h! energy,
while sn ð!Þis the deviation of polarization from the
bulk values. The (-1) prefactor denotes that the RDS
measures the reflectance difference because the odd
and even layers contribute to the spectra with alter-
native signs. By summing up the contributions from all
layers, the spectra become
X X
ð!Þ ¼ n ?e – 2na ¼ b ð!Þ=2 þ sn ð!Þ ð18Þ
(a)
where – 1 is the decay length of the light in semi-
(001) RDS spectra ∝ conductor. Figure 31(b) shows the typical spectral
ε2,(−110)− ε2,(110) shapes of the RDS. When there exist interface states
(−110) strongly localized at the interface, the sn ð!Þ term
becomes extremely large because the optical transi-
(010)
tions between localized states are large. Thus, the
RDS shows the peak-like shape at the transition
energy, as shown by A in Figure 31(b). When there
are no interface states but the electrons in bulk have
localized nature, the first term, b ð!Þ=2, produces
spectra having the shape of bulk dielectric function,
as shown by B in Figure 31(b). When the electronic
Bulk is isotropic Surface is anisotropic
states are extended from the interface, we can rewrite
the sn ð!Þ term as qb ð!Þ=q!?" because the bond
(b) polarization gradually changes the excitation energy
from the surface for extended electronic states. As a
result, the RDS spectra have the energy-derivative
shape for the dielectric function, as shown by C in
RDS spectra

Figure 31(b). In this way, using the optical proper-

C ties of surface/interface electronic states, from the
A B
Photon energy
Figure 31 (a) Schematic picture of RDS experiment.
(b) Typical spectral shapes observed in RDS. Reproduced
with permission from Nakayama T and Murayama M (1999)
Tight-binding-calculation method and physical origin of
refrectance difference spectra. Japanese Journal of Applied
Physics 38: 3497.
RDS spectral shape, one can know the localization
nature of the surface/interface electronic states.
Then, we explain why the RDS can detect the
layer-by-layer oxidation. Figure 32(d) shows the
schematic picture of SiO2/Si interfaces viewed from
the (001) direction. As explained in the previous sec-
tion, roughly speaking, the oxidation corresponds to
the insertion of the oxygen atoms into SiSi bonds.
Whenever the monolayer oxidation is completed in
the layer-by-layer process, as seen in this figure, the
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 139

(a) (b)

[001]
O O
Si Si

SiO2
Si

(c) (d)
O
Si

Si O Si
[–110]

0 O

2 1) [110]
(00
3

Figure 32 Schematic diagrams of SiO2/Si (001) interfaces. (a) Flat interface A with the desorption of interface Si atoms;
(b) flat interface B after 1 ML oxidation of A interface; and (c) flat interface with crystalline SiO2 layers around the interface.
(d) Bird’s eyeview of layer-by-layer oxidation of Si(001) surface as noted from the surface along [001]. Reproduced with
permission from Nakayama T and Murayama M (2000b) Atom-scale optical determination of Si-oxide layer thickness during
layer-by-layer oxidation: Theoretical study. Applied Physics Letters 77: 4286.

edge SiSi bonds terminated at SiO2/Si interface
alternatively change the direction between [110]
and [110]. Therefore, since the RDS measures the
reflectance difference between two perpendicular
directions, that is, the anisotropy of interface polar-
ization originating from the interface electronic
structure, one can optically detect the change of
interface-bond direction and know the advance of
monolayer oxidation.
Figures 33(a) and 33(b) show the calculated RDS
spectra of two SiO2/Si interfaces, A and B, which are
displayed in Figures 32(a) and 32(b), respectively
(Nakayama and Murayama, 2000). It is noted that the
interface B corresponds to the interface when the
monolayer oxidation is completed starting from the
interface A, and vice versa. Namely, these two inter-
faces alternatively appear during the layer-by-layer
oxidation. The detailed atomic positions at these
interfaces are taken from the first-principles calcula-
tions (Kageshima and Shiraishi, 1998). Here, we
concentrate on two features in Figures 33: (i) we
first notice that the spectra of the interfaces, A and
B, have similar shapes and opposite signs. This result
indicates that when the A and B interfaces appear
alternatively during oxidation, the RDS signals
oscillate between positive and negative values,
which is similar to the reflectance high-energy elec-
tron diffraction (RHEED) oscillation in the epitaxial
layer-by-layer growth. Especially, such an observa-
tion is apparently effective around 3.5/4.5 eV, where
140 Atomic Structures and Electronic Properties of Semiconductor Interfaces
the RDS signal is large. In this case, the period of
oscillation corresponds to the bilayer oxidation and
one can know the number of oxidized layers by
counting the oscillation; (ii) the other feature
observed in Figure 33 is the spectral shape of the
large peaks around 3.5 and 4.5 eV, which, res-
pectively, correspond to the E1 and E2 van Hove
singularity energies of bulk Si shown in
Figure 33(d). These peaks have shapes similar to
those of the energy derivatives of "2, which indicates,
based on the general theory of spectral shapes
(a)
20 Å
(b)
RD spectra: Δ ε2 •d
(d)
E1
E2
6 again in good agreement with the theoretical pre-
8 4
2 differences in the magnitude. Figure 29(c) shows
(c)
5 around the interface. The existence of this kind of
7 3
9 and Tersoff (2002). The agreement of spectral
1 2 3 4 5 6
Photon energy (eV)
Figure 33 Calculated RDS spectra of SiO2/Si (001)
interfaces as a function of photon energy. (a) Interface A
shown in Figure 32(a); (b) interface B shown in Figure 32(b);
and (c) the crystalline interface shown in Figure 32(c).
Observed RDS spectra after 2 ML oxidation are shown in (d),
together with the imaginary parts of the dielectric function of
bulk Si (dashed line). In (c), the bold line corresponds to the
RDS spectra, while the thin lines with numbers n, respectively,
correspond to layer contributions to the RDS spectra of the
nth layer bonds shown in Figure 32(c). Reproduced with
permission from Nakayama T and Murayama M (2000b)
Atom-scale optical determination of Si-oxide layer thickness
during layer-by-layer oxidation: Theoretical study. Applied
Physics Letters 77: 4286.
discussed above, that the anisotropic RDS signals
appear due to the modulation of bulk electronic
structures that are extended around the interface
(Nakayama and Murayama, 1999). In fact, such a
modulation can be examined by analyzing the layer
contributions to the RDS, which are also shown in
Figure 33(c).
This theoretical prediction was confirmed by
the RDS experiments by Yasuda et al. (2001).
Figure 34(a) shows the spectral oscillation mea-
sured at around 3.5 eV, while the observed spectra
after 2 ML oxidation are shown in Figure 33(d).
The spectral oscillation is clearly seen as a func-
tion of oxidization time, being in good agreement
with the theoretical prediction. We note that the
oscillation amplitude decreases as the oxidation
proceeds. This is because both interfaces A and
B grow to coexist within the spot size of the
reflectance light, indicating some disordering of
the layer-by-layer process. By analyzing the tem-
perature and pressure dependence of the
oxidation time as shown in Figure 34(b), we can
ε2 know the microscopic mechanism of oxidation,
such as the oxidation speed and the activation
2ML-Exp.
energy of oxidation (Matsudo et al., 2002; Yasuda
E3 et al., 2003). With respect to the spectral shapes,
the experiments showed shapes similar to those of
the energy derivatives of "2 around 3.5/4.5 eV,
diction in Figure 33(a). However, we note some
0 the calculated spectra of the interface shown in
Figure 33(c), which has crystalline SiO2 structure
1
ILs was suggested by Ikarashi et al. (2000) and Tu
shapes and magnitude is fairly good, indicating
7 the appropriation of SiO2 crystalline structures
around the oxidation front interfaces.
In this way, the RDS measurement can observe
not only the dynamical change of the interfaces
but also the detailed electronic/atomic structures
of interfaces. Moreover, from these studies, we
obtained the in situ method of Si oxidation con-
trol. Similarly, the dot formation on the surface
was also observed by the optical measurement
(Kita et al., 2002). These studies have demon-
strated a new direction in semiconductor
nanotechnology that the microscopic theoretical
investigation is indispensable to the development
of new technologies.
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 141

(a) gate electrodes and wirings. It has long been known

Heating on
that the intermixing of metal and semiconductor
atoms occurs at a number of metal/semiconductor
interfaces, even around room temperature (Hiraki,
2 × 10–4

1980). For example, Au shows intermixing with

several semiconductor substrates, such as Si, Ge, InP,
GaAs, etc., while the Si substrate exhibits intermixing
Δr/r at 2.90 eV

with many kinds of metals, such as Au, Ag, Cu, Ni, Al,
etc. Such intermixing typically ranges from nano- to
micrometers and provides serious damages to nanos-
t2 t3 cale devices such as circuit shortening. Thus, it is
O2 in
important to understand what the motive force of
intermixing is and how the intermixing proceeds.
On the other hand, in the case of metalSi
101 102 103 combinations that show the intermixing at inter-
Elapsed time (s) faces, it is well known that most transition metals
and rare-earth metals, typically Ni metal, produce
(b) metal silicides by intermixing, while sp-orbital
The 3rd layer
(one-step ox.) metals like Al and a few transition metals such as
Au and Ag have no silicide phases. In addition, in
103 spite of various bulk silicide phases of NixSiy, only
the silicides with specific stoichiometry of
(x,y) ¼ (1,2), (1,1), (2,1) are allowed to grow on Si
t3 (S)

substrate (Hiraki, 1980). What origins distinguish

102
101
0.8 0.9
1000/T (K1)
Figure 34 (a) Observed RDS oscillation during the
layer-by-layer oxidation of Si(001) surfaces, as a function of
oxidation time. The peaks around 80 and 500 s, respectively,
correspond to the completion of 1 and 3 ML oxidation, while
the dip around 150 s to that of 2 ML oxidation. Reproduced
with permission from Yasuda T, Yamasaki S, Nishizawa M,
et al. (2001) Optical anisotropy of oxidized Si(001) surfaces
and its oscillation in the layer-by-layer oxidation process.
Physical Review Letters 87: 037403. (b) Arrhenius plot of
activation energy for the third Si-layer oxidation as a function
of inverse temperature. Reproduced with permission from
Yasuda T, Kumagai N, Nishizawa M, Yamasaki S, Oheda H,
and Yamabe K (2003) Layer-resolved kinetics of Si oxidation
investigated using the reflectance difference oscillation
method. Physical Review B 67: 195338.
1.04.2.5 Stability of Interfaces
Metal/semiconductor interfaces are essential struc-
tures to semiconductor physics and technology
because metal layers are often used as source/drain/
between such differences in silicide formation? In
pO2 (Pa) this section, we show one of the answers to these
0.060 questions, based on the first-principles theoretical
0.20
calculations.
0.60
2.0
20 1.04.2.5.1 Metal induced inter-diffusion
First, we consider how intermixing proceeds and dis-
1 1.1 cuss the motive force of intermixing. Figure 35(a)
shows the calculated adiabatic potentials of interface
Au and Al atom diffusion movements at Au/Si and
Al/Si (111) interfaces, respectively, from the stable
initial-interface positions, z ¼ 0, into Si substrate,
z < 0 (Nakayama et al., 2002b, 2006a; Murayama et al.,
2001). It is clearly seen that both potentials have
stable minimum positions at around z ¼ 1.8 Å.
Since the barriers are at most 0.4 eV, the thermal
diffusion of metal atoms becomes possible into Si
layers at both interfaces. To analyze the origin of
such diffusion, we show in Figure 36(a) and 36(b)
the valence charge densities of Au/Si and Al/Si
systems, respectively, in cases when metal atoms are
moved to locate around z ¼ 1.8 Å.
In the case of Au/Si system, it is clearly recog-
nized that the diffused innermost Au atom produces
AuSi bonds with the second-top-layer Si as well as
the top-layer Si. Note that the charge density of
SiSi bond between top and second-top layers is
smaller that that of AuSi bonds. Namely, the
142 Atomic Structures and Electronic Properties of Semiconductor Interfaces

(a) 2 (b) 3 SiSi one. Since such bond rearrangement appar-

Si surface ently stabilizes the system and produces the potential
Adiabatic potential (eV)

Adiabatic potential (eV)

1 Al/Si
−0
0
Au/Si
−1
−3 −2 −1 0 0
Metal-atom position z (Å)
Figure 35 Calculated adiabatic potentials for interface-
atom diffusion. (a) Metal-atom diffusion into Si substrate
around Au/Si and Al/Si interfaces; and (b) Si-atom diffusion
into metal layers around Au/Si interfaces. z ¼ 0 corresponds
to the initial interface, while z < 0 and z > 0 to spaces within
Si and within metal layers, respectively. From Murayama
et al. (2001); Nakayama et al. (2002b, 2008). Reproduced
with permission from Nakayama T, Itaya S, and Murayama
D (2006) Nano-scale view of atom intermixing at metal/
semiconductor interfaces. Journal of Physics: Conference
Series 38: 216.
charge on Au-Si bonds is mainly supplied from the
nearest SiSi bonds. This charge transfer occurs
because the electronegativity of Au, 2.5 (Pauling’s
value), is much larger than that of Si, 1.9, and the
AuSi bonding state has lower energy than the
w/o Au minima, one can say that the rebonding is the motive
2
force of the Au diffusion and thus the intermixing.
On the other hand, Figure 35(b) shows the calcu-
1
lated adiabatic diffusion potential of top-layer Si
atom into metal layers when Au atom is located
around z ¼ 1.8 Å. For comparison, we also show
the diffusion potential (broken line) when Au atom
Au/Si interface
does not diffuse and is located at z ¼ 0. It is clearly
1 2
Si-atom position z (Å)
seen that, once such rebonding weakens the interface
SiSi bonds, the interface Si atoms can easily diffuse
into Au layers (z > 0) with a small potential barrier
around 0.2 eV.
On the other hand, in the case of Al/Si system, we
cannot clearly see the creation of AlSi bonds in
Figure 36(b). In fact, the charge density between the
innermost Al and Si atoms is smaller than that of the
SiSi bond between top and second-top layers.
However, the charge density of the SiSi bond
between top and second-top layers is much smaller
than that of the SiSi bonds in inner layers. We note
that the charge density has almost constant values in
the region surrounded by Al and Si atoms. This is
because the electronegativity of Al atom, 1.6, is small
compared to that of Si, 1.9, and the interface Al atoms
partially present their valence electrons toward Si

(a) (b)
Au/Si(111) Al/Si(111)

Au Al
Al
Au
Si(1) Si(1) Si(1)
Au Si(1)
Al
Si(2) Si(2) Si(2)
Si(2)
Si(3) Si(3)

Si Si(1)

Si Si

Figure 36 Calculated electron-density contour map around (a) Au/Si and (b) Al/Si interfaces. Three ML Au and Al are
deposited on Si(111) surface and innermost metal atoms are moved into Si layers by about 1.8 Å (z ¼ 1.8 Å in Figure 35(a)).
From Murayama et al. (2001); Nakayama et al. (2002b, 2008). Reproduced with permission from Nakayama T, Itaya S, and
Murayama D (2006) Nano-scale view of atom intermixing at metal/semiconductor interfaces. Journal of Physics: Conference
Series 38: 216.
 Atomic Structures and Electronic Properties of Semiconductor Interfaces
atoms and spread their valence-electron density
widely over the Si substrate. As a result, the electron
density increases around Si atoms, and such an
increase screens up and decreases the charge density
of Si–Si bond (Hiraki, 1980). Once such screening
weakens the interface SiSi bonds, the interface Si
atoms can diffuse again into Al layers similar to the
case of Au/Si interface. In fact, the calculated barrier
of Si diffusion in the case of Al/Si is also small,
around 0.2 eV. Therefore, one can roughly say that
the screening due to the charge extension is the
motive force of intermixing for Al/Si interfaces.
In this way, the charge redistribution during the
diffusion and the motive force of intermixing
are somewhat different between Au/Si and Al/Si
interfaces. From this result, we can expect the
difference of diffusion and intermixing patterns of
metal atoms between Au/Si and Al/Si interfaces.
Since the production of AuSi bonds is the origin
of Au atom diffusion, the Au diffusion has direc-
tional tendency and the penetration of Au into Si is
expected to proceed in a needle-like line pattern.
On the other hand, since the charge extension of Al
toward Si atoms in various directions is the origin
of Al-Si intermixing, the Al diffusion has no direc-
tivity and the intermixing of Al and Si is expected
to proceed with a two-dimensional face-like front
interface.
It should be noted here that, in contrast to the
cases shown above, no mixing is observed at most
of the metal/(wide-gap-semiconductor) interfaces,
such as Au/GaN, although Au shows intermixing
at interfaces with several semiconductors. There
are two factors to prevent intermixing. One is the
elastic energy loss; since the atomic radius of Au,
1.44 Å, is much larger than the average atomic radii
of Ga and N, 1.0 Å, the diffusion of Au pushes the
GaN substrate to induce a simple compression
strain of GaN layers and produces the elastic
energy loss. For example, Pb metal layers were
observed showing no intermixing on Si substrate,
because the atomic radius of Pb, 1.8 Å, is much
larger than that of Si, 1.1 Å. The other factor to
prevent the mixing is the chemical-bonding energy
loss; since the electronegativities of Ga, Au, and N
atoms are 1.6, 2.4, and 3.0, respectively, the Ga
atoms prefer locating among N atoms to Au
atoms. When the Au atom is located on GaN sur-
face, the top-layer Ga is surrounded by Au and N.
On the other hand, when the Au atom moves
between Ga and N, the top-layer Ga is surrounded
only by Au atoms, thus losing the Ga-N high ionic
143
bonding energy gain. In this way, one can know
that the small atomic radius and the larger/smaller
electronegativity of metal atoms are relevant fac-
tors to realize intermixing.
1.04.2.5.2 Silicidation
Next, we consider what factors distinguish the
silicide formation between various metals. When
MSi2 silicide (M ¼ metal atom) is selected as a
representative phase among a variety of stoichio-
metric phases, the calculated formation energies
of TiSi2, NiSi2, AuSi2, and AlSi2 become 0.4,
0.1, þ0.3, and þ0.4 eV, respectively (Nakayama
et al., 2008, 2009). This result indicates that Ti
and Ni silicides are stable, while Au and Al sili-
cides are unstable, being in good agreement with
the observed bulk phase diagrams (Madelung,
1997). The reason for such difference in formation
energies is clearly understand by noting the band
structures. Figures 37(a) and 37(b) show the cal-
culated band structures of Ni and Au bulks
(Nakayama et al., 2008, 2009). In the case of Ni,
one can see five flat bands between 4 and
þ0.5 eV, which are made of Ni d orbitals. The
band that ranges from 9 to 7 eV and crosses
these d bands is made of Ni s orbitals. Similar d
and s bands are seen for bulk Au between 7.5
and 2 eV and from 11 to 4 eV, respectively.
The most important difference between Ni and
Au is the electron occupation in d bands; all d
bands are occupied by electrons for Au, while
about half of the electrons are unoccupied in the
top d band of Ni.
On the other hand, Figures 37(c) and 37(d)
show the band structures of NiSi2 and AuSi2 sili-
cides. One can see the deformation of metal-
originated bands, which is caused by the produc-
tion of covalent-like bonds between metal and Si
atoms due to the hybridization of s þ d orbitals of
metal atom and s þ p orbitals of Si, as seen in the
case of Au/Si interface shown in Figure 36(a).
However, we can roughly identify that the rela-
tively flat d-like bands, from 9 to 3 eV for
NiSi2 and from 9 to 6 eV for AuSi2, are located
far below the Fermi energy in the case of silicides,
compared to the case of bulks. This result indicates
that the d bands of Ni, which are partially unoc-
cupied in bulk, become fully occupied in NiSi2.,
thus indicating the electron charge transfer from Si
sp orbitals to Ni d orbitals. However, in the case of
AuSi2, the d bands are already fully occupied by
144 Atomic Structures and Electronic Properties of Semiconductor Interfaces

(a) (b)
25 Ni Au
15
20
10
15

Energy (eV)

Energy (eV)
10 5

5
EF0
EF0
–5
–5
–10
–10
G XK G L KW X G XK G L KW X
(c) (d)
NiSi2 AuSi2
5
5

EF0
Energy (eV)

EF0 Energy (eV)

–5 –5

–10 –10

–15
G XK G L KW X G XK G L KW X
Figure 37 Calculated band structures of (a) Ni, (b) Au, (c) NiSi2, and (d) AuSi2. Reproduced with permission from Nakayama
T, Shinji S, and Sotome S (2008) Why and how atom intermixing proceeds at metal/Si interfaces: Silicide formation vs. random
mixing. ECS Transactions 16(10): 787–795 and Nakayama T, Sotome S, and Shinji S (2009) Stability and Schottky barrier of
silicides: First-principles study. Microelectronic Engineering 86: 1718.

electrons in bulk Au, and such a transfer never
occurs. From these results, one can conclude that
the stability of metal silicides is realized by the
electron transfer from Si to unoccupied d-orbital
states of transition-metal atoms. This stabilization
scenario of metal silicides well explains why tran-
sition metals, except Au and Ag, produce stable
silicides at metal/Si interfaces and why Al does
not produce silicides.
Next, we consider why only the NixSiy silicides
with specific stoichiometry, (x,y) ¼ (1,2), (1,1), (2,1),
are allowed to grow on Si substrate among various
silicide phases. Figures 38(a) and 38(b) show the
calculated phase diagrams of NixSiy as a function of
chemical potentials of Ni and Si, in the case of
the bulk growth and the growth on the Si substrate,
respectively (Nakayama et al., 2008, 2009). Chemical
potentials represent the supply ratios of Ni and Si
and the gray regions correspond to the allowed
regions to grow in thermal equilibrium. It is clearly
seen that all NiSi2, NiSi, Ni2Si, and Ni3Si phases are
realized in the bulk growth, depending on the growth
condition, while the Ni3Si phase becomes difficult to
grow on the Si substrate. Such changes in stability are
caused by two factors. One is the elastic strain in
NixSiy on the Si substrate. As the proportion of Ni
increases, the lattice constant of NixSiy increases and
the compressed strain in it increases. The other factor
is the energy loss of the interface bonding. With
increasing Ni, the number of stable Si–Si covalent
bonds decreases, which also promotes the instability
of Ni3Si.
Finally, we point out that the above stabilization
mechanism is closely related to the work function at
silicide/Si interfaces (Nakayama et al., 2009). Since
the p-orbital valence energy states of Si are located
above those of Ni, the charge transfer occurs from Si
to Ni in NixSiy and lowers the positions of Fermi
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 145

(a) 1.04.3 Electronic Structures of

–3.8 Interfaces
NiSi2 1.04.3.1 General Features
Ni3Si
μ of si [Ht]

1.04.3.1.1 Origins of interface states

Electronic states at the interface, A/B, are generally
categorized into two types: (i) states originated from
NiSi
A and/or B bulks and (ii) those intrinsic to the A/B

Ni2Si
interface. Figure 40 schematically shows the relation
–4.3 of the complex band structures of A and B bulks to
–41.6 –41.4 –41.2
electronic states at the interface. In A and B bulks,
(b) μ of Ni [Ht] because of the crystal periodicity, the electronic
–3.8 states are characterized by the extended Bloch wave
functions, n;k ðrÞ, where n is the band index and k
NiSi2 the Bloch wave-number real vectors. Reflecting the
periodicity, the energy spectra, "n,k, show the band
–4
structure having band gaps. However, since the
Ni3Si

interface breaks this translational symmetry along

Ni2Si

NiSi
–4.2
–41.6 –41.4
μ of Ni [Ht]
Figure 38 Calculated phase diagrams of NixSiy as functions
of Ni and Si chemical potentials, in cases of (a) bulk growth and
(b) growth on the Si substrate. Gray regions are regions where
NixSiy is allowed to grow in thermal equilibrium. Reproduced
with permission from Nakayama T, Shinji S, and Sotome S
(2008) Why and how atom intermixing proceeds at metal/Si
interfaces: Silicide formation vs. random mixing. ECS
Transactions 16(10): 787–795 and Nakayama T, Sotome S,
and Shinji S (2009) Stability and Schottky barrier of silicides:
First-principles study. Microelectronic Engineering 86: 1718.
the z-direction, that is, perpendicular to the interface,
the electronic states with the energy within the band
gaps of bulks and complex wave-number kz are
allowed to exist. Because Im kz 6¼ 0, such states
–41.2
show amplitude decay along the z-direction and are
sometimes called as the evanescent wave states. For
example, the electronic state having energy "1 in
Figure 40 is constructed by the connection of two
propagating Bloch states in A and four evanescent-
wave states in B, which all are described by the
intersection points of the band structures and the
energy plane. Since this state propagates along the
z-direction to z ¼ 1in A (z < 0) but decays sharply
in B (z > 0), we can call it the state originating from

E E
(a) (b)
ψε1 (r)
Si conduction band Si conduction band

ε1
NiSi2 0.55eV TiSi2 0.69 eV
0.42
0.27 TiSi Complex band
Ni2Si NiSi 0.48 Ti2Si 0.64 ψε2 (r)
Ti3Si
Ni3Si 0.21 0.40
ε2
Valence band Si Valence band

Real band
Figure 39 Calculated Fermi-energy positions of NixSiy
and TixSiy. Reproduced with permission from Nakayama T,
Sotome S, and Shinji S (2009) Stability and Schottky barrier
of silicides: First-principles study. Microelectronic Re kz
Re kz
Engineering 86: 1718.
Im kz Im kz

Material A Material B
energy originating from Si electronic states for Ni-
rich silicides. Thus, as seen in Figure 39, the work Figure 40 Schematic diagram of complex band
function of silicides increases as the proportion of Si structures of A and B materials and connection of wave
decreases in NixSiy. function at A/B interface.
146 Atomic Structures and Electronic Properties of Semiconductor Interfaces
material A. On the other hand, the electronic state
having energy "2 is made of evanescent-wave states
of both A and B materials, and is localized near the
interface, thus called the interface state. It is apparent
that the state that has energy within the band gaps of
both A and B bulks becomes the type-(ii) interface
state, while the state that has energy within the band
spectrum of either A or B becomes the type-(i) state
that propagates deep into either A or B. These are
necessary conditions of energy for judging the types
of interface states. It should be noted here that the
number of complex bands that produce the interface
states is in general infinite, though the finite ones are
displayed in Figure 40. However, their contribution
becomes considerably small when they are located
far from the real band structures.
For the type-(i) bulk-like interface states, the
existence of interface is sometimes renormalized to
be described as some potential, combined with the
effective-mass approximation. This treatment is
often called the quantum-well-picture representa-
tion. For example, as shown in Figure 41 for the
case of GaAs/AlAs superlattice, AlAs layers are trea-
ted as potential barriers and GaAs ones as quantum-
wells. By adopting this picture, many interesting
electronic phenomena are analyzed. In such cases,
the key quantity that governs the electronic states is
the band offset, which is the energy difference of
bands between the two semiconductors (represented
by Ec and EV in Figure 41). The details of this
band offset are discussed in the next subsection.
The physical origins of the existence of type-(ii)
interface states are also categorized into two groups:
(a) extrinsic origins such as dislocations and impurity
atoms at interfaces, which are sometimes produced
and incorporated in the case of interface formation, as
shown in the previous section; and (b) intrinsic
E E
Ve (z)
Ec (AlAs)
Band gap
Ev (AlAs)
Vh(z)
kz
AlAs
AlA GaAs
Figure 41 Quantum-well diagram and band offset, in the case of GaAs/GaAs superlattice.
origins for interfaces owing to the breakdown of
translational symmetry at the interface and the pro-
duction of new types of atomic bonds between A and
B at the interface. Since, at present, there are no
definitive experimental tools, such as STM, for the
surface to observe the interface atomic structures, it
is sometimes difficult to separate these origins.
The details of the intrinsic origins are considered
in the next two subsections. Here, we briefly illus-
trate examples of the extrinsic origins in Figure 42.
New atomic environment shown in the number
region ‘2’ and the existence of impurity atoms
shown in regions ‘6’ and ‘7’ often produce the inter-
face states in the band gap. The step structures of the
substrate shown in ‘3’ and ‘4’, which are left in the
heteroepitaxy, and the appearance of misfit disloca-
tions shown in ‘5’, which are produced by the lattice
mismatch between A and B, also become the struc-
tural origins of interface states.
1.04.3.1.2 Semiconductor/semiconductor
interface states
We first consider the Ge/GaAs (110) nonpolar
interface as an example. Figure 43 shows the
atomic structure near the interface (Pickett and
Cohen, 1978). Because Ge and GaAs have similar
lattice constants, the interface has few dislocations
and becomes remarkably sharp. The atomic bonds
represented by broken lines, GeGa and GeAs,
are not present in tetrahedral bulk semiconductors.
GeGa and GeAs bonds have 1.75 and 2.25
electrons, as opposed to the ordinary semiconduc-
tors, which have 2.0. Thus, these bonds are often
called acceptor and donor bonds, respectively.
To judge the existence of interface states, it is
convenient to compare the two-dimensional band
structure of an interface with the projected spectra
LB Lw
Conduction
ΔEc
z band
Ec (GaAs)
Ev (GaAs)
z ΔEv
Valence
band
kz
GaAs
AlAs GaAs AlAs
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 147

(a)

6
5
4 7
1
2 3
(b)

Figure 42 Schematic examples of interface structures that produce extrinsic interface states.

Ga Ge As Ge-GaAs interface states

GaAs Ge Projected band structure

1st GaAs layer 2

0 B2 P2

Interface layer
–2
Energy (eV)

P1
–4
1st Ge layer S2 B1
–6

z –8

x
y
Figure 43 Atomic structure of Ge/GaAs (110) interface.
Reproduced with permission from Pickett WE, Louie SG, and
Cohen ML (1978) Self-consistent calculations of interface
states and electronic structure of the (110) interfaces of
Ge–GaAs and AlAs–GaAs. Physical Review B 17: 815.
of bulk band structures into two-dimensional
Brillouin zone. Figure 44 shows such a comparison
for Ge/GaAs interface, where band structures are
calculated using super unit cells and self-consistent
pseudopotential method (Pickett et al., 1978).
Shaded regions correspond to bulk bands, thus
pointing to the existence of only the bulk-like
interface states even at the interface. The electro-
nic states, S1B2, appearing outside the shaded
regions (gap, pockets), are states intrinsic to inter-
face and are localized at the interface as shown in
Figures 45(a)–45(d). S1 and B1 states ((d) and (b))
are made of s and p orbitals and localized at the
–10
–12 S1
Γ X M X′ Γ
k
Figure 44 Band structure of Ge/GaAs (110) interface.
Reproduced with permission from Pickett WE, Louie SG, and
Cohen ML (1978) Self-consistent calculations of interface
states and electronic structure of the (110) interfaces of
Ge–GaAs and AlAs–GaAs. Physical Review B 17: 815.
GeAs bond, while S2 and B2 ((c) and (a)) are
similar states localized at the GeGa bond. In this
way, the interface states at nonpolar sharp inter-
faces appear to originate from new interface bonds.
However, there appear no interface states within
the fundamental band-gap region, 0.01.0 eV in
Figure 44. This is because all dangling bonds
that exist on the Ge and GaAs surfaces are termi-
nated at the interface. As a result, the physical
148 Atomic Structures and Electronic Properties of Semiconductor Interfaces

(a) 6 chemical tendency of interface states (Pickett and

Ge 8 Ge As Cohen, 1978). There exist only the bulk-like states
32
when the ionicity of materials is small, while the
Ge Ga
4
Ga
intrinsic interface states appear and their energy
4 positions leave the bulk band spectra as the material
B2 Ge-Ga interface state ionicity increases. Since the charge transfer occurs
from donor bonds to acceptor ones, the atomic posi-
tions at the interface are relaxed. However, even in
(b) B1 Ge-As interface state
such cases, there is little change for the energy-level
positions of interface states.
8 Ge As
18
As
24
Next, we consider the polar interfaces. The
14
(001) and (111) interfaces become polar interfaces
Ge Ge Ga 4 because either anion or cation atoms are located on
these crystal planes. When we consider a Ge/GaAs
(001) sharp interface as an example, there exist two
(c) S2 Ga s-like
interface state
kinds of interfaces: the interface with only acceptor
6 bonds, GeGa, and the interface with only donor
Ge Ge As
bonds, GeAs, as shown in Figures 46(a) and
4
46(b). However, these interfaces are sometimes
Ge Ga Ga unstable due to large deficiency or excess of elec-
24
trons around the interface. Instead, to compensate
such unfavorable charge in a short range, the atom
(d) S1 As s-like interface state
intermixing often occurs at these interfaces as
shown in Figures 46(c) and 46(d) This kind of
Ge As As
interface instability becomes notable for heterovalent
42 8
interfaces, as discussed in Section 1.04.2.3.1. Even at
Ge Ge Ga these interfaces, however, electronic states are pro-
duced based on the tetrahedral bonds, thus often
Figure 45 Charge distribution of interface states at Ge/ appearing around the bulk band edges but not deep
GaAs (110) interface. Reproduced with permission from in fundamental band gaps (Pollmann and Pantelides,
Pickett WE, Louie SG, and Cohen ML (1978) Self-consistent 1980; Konc and Martin, 1981; Oda and Nakayama,
calculations of interface states and electronic structure of 1992). In spite of this, the electron transfer from
the (110) interfaces of Ge–GaAs and AlAs–GaAs. Physical
Review B 17: 815.
donor bonds to acceptor ones largely changes the
band offset between two semiconductors, as shown
in the following subsections. To take advantage of
properties such as electron transport are not influ- such controllability of band offset, the acceptor and
enced by these interface states. donor bonds are sometimes produced artificially by
The above-mentioned features apply to other the insertion of ultrathin layer between A and B
combinations of semiconductors. Table 3 shows the semiconductors during the crystal growth.

Table 3 Ionicity and character of inferface state at (110) semiconductor/

semiconductor interfaces

Bond charge

A/B Ionicity Bulk state Interface state Acceptor Donor

GaAs/AlAs Small Yes No 2.00 2.00

GaAs/Ge Middle Yes Yes 1.77 2.23
ZnSe/Ge Large Yes Yes 1.54 2.46

Reproduced with permission from Pickett WE and Cohen ML (1978) Theoretical trends in
the abrupt (110) AlAs–GaAs, Ge–GaAs, and Ge–ZnSe interfaces. Journal of Vacuum
Science and Technology 15: 1437.
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 149

(a) (c) from region III to region IV, which is discussed in

the next subsection.
(001)

Figure 48 shows the local density of states (LDOS)

in regions I–VI. The positions of these regions are
denoted in Figure 47. In inner layers of Al, that is, in
(b) (d) region I, the LDOS shows the square-root energy
dependence, indicating a free-electron-like electronic
structure of bulk Al. On the other hand, in inner layers
of Si, that is, in region VI, the band gap appears around
Ge, Ga, As the Fermi energy and the LDOS is similar to that of
Figure 46 Schematic atomic structures of Ge/GaAs (001) bulk Si. In the LDOS in region IV, one can see the
interfaces. (a) Ge–Ga interface, (b) Ge–As interface, and interface state, Sk, around 8.5 eV. The most important
(c,d) charge-compensated interfaces.

1.0 Al-Si Interface

1.04.3.1.3 Metal/semiconductor Region I
0.5 EF
interface states
Metal/semiconductor structures are essential in
0
almost all electronic devices to inject carriers
from metal electrodes into semiconductors and 1.0
Region II
activate the device operation. Here, we adopt the 0.5 EF
Al/Si interface as an example and consider the
features of metal/semiconductor interfaces. 0
Figure 47 shows the valence electron distribution 1.0
Region III
around the interface, which was calculated by the 0.5 EF
Local density of states (a.u.)

pseudopotential method using a super unit cell and

employing a jellium model for Al layers (Louie 0
and Cohen, 1976). The electron density is almost 1.5 Region IV
constant and the small Friedel oscillation is seen in EF
SK
1.0
Al sides, while the electrons are accumulated on
the covalent bonds between Si atoms in Si side. 0.5
We can see a small amount of electron transfer
0
1.5
Region V
1.0 EF

0.5

0
1.5
Region VI
EF
1.0

0.5

0
−14 −12 −10 −8 −6 −4 −2 0 2 4
Energy (eV)
Figure 47 Valence charge distribution around the Al/Si Figure 48 Local DOS around the Al/Si (111) interface.
(111) interface: (a) contour map display and (b) distribution Regions I–VI are displayed in Figure 47. Reproduced with
averaged along the interface. Reproduced with permission permission from Louie SG and Cohen ML (1976) Electronic
from Louie SG and Cohen ML (1976) Electronic structure of a structure of a metal–semiconductor interface. Physical
metal–semiconductor interface. Physical Review B 13: 2461. Review B 13: 2461.
150 Atomic Structures and Electronic Properties of Semiconductor Interfaces
(a) Al-Si interface
states with E = 0 to 1.2 eV
1.8 1.5 1.8 1.5
1.7
1.5 1.8 1.5
1.8
(b)
2.0
Al-Si interface
1.0
0
Figure 49 Charge distribution of metal-induced gap
states (MIGSs) at the Al/Si (111) interface: (a) contour map
display and (b) display average along the interface.
Reproduced with permission from Louie SG and Cohen ML
(1976) Electronic structure of a metal–semiconductor
interface. Physical Review B 13: 2461.
feature is the appearance of electronic states within the
band gap of Si in regions IV and V, which contributes to
the formation of Schottky barrier height. The charge
density of one of these states is displayed in Figure 49.
Though this state has relatively large density on the
dangling bond of interface Si, it is apparently different
from the dangling-bond state on Si surface that is
strongly localized around Si. Instead, this state looks
like the free-electron-like state of Al that penetrates
into Si layers or connects with the Si localized state.
This electronic state, which is also present in semicon-
ductors and has energy within the band gap, is called
the metal-induced gap state (MIGS) (Heine, 1965;
Louie and Cohen, 1976). The density of states (DOS)
is shown in Figure 50 for MIGSs in some
12 (a) Si
DOS (1014 states/eV cm2)
10
8 the breakdown of translational symmetry of
EF
6
4 MIGSs. In fact, as shown in Section 1.04.3.1.3, ab initio
2 exist in Si at Al/Si interfaces. On the other hand, in
0
0 0.4 0.8 0 0.4 0.8 1.2 0 1.0 2.0 3.0 4.0
Figure 50 DOS for MIGSs within the band gap of the
semiconductor. Reproduced with permission from Louie
SG, Chelikowsky JR, and Cohen ML (1977) Ionicity and the
theory of Schottky barriers. Physical Review B 15: 2154.
semiconductors. One can see that the number of
MIGSs becomes small as the ionicity of semiconductor
2.1
increases. This is because a semiconductor of large
1.8
0.6 1.0 0.0
ionicity has larger band gap and thus the DOS is largely
0.3
0.3 decreased because the complex band leaves the real
1.8
band, has a large imaginary part of wave number, ImKz,
0.9 2.7
and the MIGS is strongly localized at the interface.
P (z)
States with E = 0 to 1.2 eV
1.04.3.2 Band Alignment
The Schottky barrier is the energy difference between
the valence (or conduction) band edge of the semicon-
ductor and the Fermi energy of the metal, while the
band offset is the energy difference of valence (or
conduction) bands of two materials that construct the
interface. In this subsection, we review the representa-
tive theories and consider how these quantities are
determined, that is, how the bands of two materials
align at the interface. We start from the Schottky
barrier at metal/semiconductor interfaces.
1.04.3.2.1 Schottky barrier
We first consider the metal/metal interface. At this
interface, the statistical mechanics teaches us that the
movable carriers such as free electrons easily move
across the interface to produce a dipole potential at
the interface and equalize the Fermi energies of both
metals with each other. Since there are no electric
fields in metals in an equilibrium, the transferred
carriers are often localized within a few atomic layers
around the interface (Kajita et al., 2007). In the case of
a metal/semiconductor interface, if one can define
Fermi energies for semiconductors, the same
scenario as that of metal/metal interfaces applies.
At the metal/semiconductor interface, the semi-
conductor generally possesses electronic eigenstates
(b) GaAs (c) ZnS that have eigenenergies within the band gap of bulk
semiconductor, as shown in Section 1.04.3.1.1. For
intrinsic interface states, these states appear due to
EF semiconductor bulk crystals at the interface perpen-
EF dicular to the interface direction and are called
calculations demonstrated that these MIGSs really
the case of extrinsic origins, these states appear due
to structural disorders such as defects. In any case,
Energy (eV) these states are made of eigenstates in complex band
structures of bulk materials and have complex wave
numbers, and are thus localized around the interface.
Such states are schematically shown by short bars in
the energy diagram of Figure 51(a).
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 151

(a) interface to equalize their Fermi energies, CNL ,

Conduction band
and EF. In the case of Figure 51(a), electrons
EF
CB-like transfer from the metal to the semiconductor. The
MIGS excess positive carriers in the metal are accumulated
φCNL at the interface because the dielectric constant of a
VB-like
MIGS metal is infinitely large, while the excess electrons in
the semiconductor enter the interface MIGSs and
Valence band penetrate into the semiconductor at most a few Å.
Metal Semiconductor In this way, the electron transfer between metal and
semiconductor produces the dipole at the interface
and results in the final band alignment between the
(b) Conduction band two. The energy difference between EF and the
Schottky ECB lowest conduction-band state of the semiconductor,
barrier
ECB, or between EF and the highest valence-band
EF φCNL one, EVB, acts as a potential barrier for electrons or
holes, respectively, and is called the Schottky barrier
E VB or ‘contact potential’. In addition, the energy position
Valence band
of EF relative to vacuum is sometimes called as an
effective work function (WF) of a metal.
Metal Semiconductor The change of the metal Fermi energy (effective
WF) with varying metals is simply regulated using the
(c) DCB slope parameter (S parameter) (Cowley and Sze,
S
ECB 1965). The S parameter is defined by the derivative as
EF
S ¼ ðeffective WFÞ=ðvacuum WFÞ ð19Þ
(Low-WF metal) B EG
where  means the variation by the change of metals
B φCNL at the interface (see also Figure 58(a)). The theory of
EF CNL predicts that the metal Fermi energy moves
S EVB
(High-WF metal) toward a single position of CNL , as shown in
DVB
Figure 51(c), thus decreasing the energy differences
Metals Semiconductor
of effective WF among metals. This indicates that
Figure 51 Schematic band alignment at metal/ 0 < S < 1. When the densities of MIGSs is small and
semiconductor interface (a) before and (b) after the there is little charge transfer across the interface,
connection. (c) Normal movement of the metal Fermi energy
effective WF has the same values as vacuum WF, as
relative to the electronic structure of semiconductor. In (c),
the bold-arrow lines denote that the Fermi energy of the shown by the S-arrows in Figure 51(c), which rea-
metal tends to move toward the charge neutrality level, lizes the S ¼ 1 limit. On the other hand, when the
CNL , by transferring electrons around the interface. density of MIGSs is large and the CNL position
Dashed-arrow lines S and B, respectively, correspond to hardly changes by the interface charge transfer, all
the Schottky (S ¼ 1) and Bardeen (S ¼ 0) limits.
effective WFs have the same value (Fermi-level pin-
ning) for all metals, as shown by the B-arrows, which
As shown in Figure 51(a), some of the MIGSs indicates that S ¼ 0. These two limits are called the
are occupied from the bottom, corresponding to Schottky–Mott and Bardeen limits, respectively
the number of electrons around the interface and (Schottky, 1938; Mott, 1938; Bardeen, 1947). As long
the highest occupied MIGS determines the effec- as the Schottky barrier height (SBH) is considered to
tive Fermi energy of the semiconductor around the be produced based on this conventional CNL con-
interface. Since this Fermi energy is determined by cept, the S parameter never goes out of the 0 < S < 1
the electron number to keep the original semicon- region.
ductor as neutral, it is often called the charge
neutrality level (CNL). Hereafter, we denote
CNL as CNL . When the semiconductor is in con- 1.04.3.2.2 Charge neutrality level
tact with a metal, as in Figure 51(b), electrons in We now consider the location of CNL . Tersoff
the semiconductor and metal move across the (1984a,b) noted that the key is the nature of MIGS
152 Atomic Structures and Electronic Properties of Semiconductor Interfaces

and proposed that
CNL is determined only by the
electronic structure of the bulk semiconductor. As
explained above, the MIGS is the eigenstate in com-
plex band structures having energies within the band
CNL . Based on their systematic XPS
gap of the bulk system. Since the complex bands
connect with real bands at the band edge of real
bands, the MIGSs with lower energies possess a
valence-band character, while those having higher
energies carry a conduction-band character (see
Figure 51(a)). The effective Fermi energy,
CNL , is types such as vacancies and antisite atoms.
defined as the boundary between these valence-band-
and conduction-band-like states, and are thus
approximately given by the sign-changed boundary
energy of the cell-averaged propagating Green
function:
Z XZ jnk ðr Þjnk ðr þ RÞ
G ðR;
CNL Þ ¼ dr d3 k
n
CNL – "nk DOS value of DIGS; thus, such energy state acts as a
unitcell
where jnk ðrÞ and "nk are eigen wave function and
CNL for
energy of the electronic states of bulk semiconductor,
respectively, with the band index n, and the Bloch
wave number k. Here, R is the real lattice vector
perpendicular to the interface. In a one-dimensional
system,
CNL coincides with the branching point of
the complex band. Using
CNL calculated by this average of sp3-orbital energies of semiconductors.
formula, Tersoff succeeded in reproducing SBHs of
various metal/semiconductor interfaces. Table 4
CNL theories. At first, due
shows the calculated SBH values, together with the
observed values in experiments. The agreement is
quite good, especially for semiconductors with
small band-gap energies. This is because the MIGS
CNL . For example, using a Penn-like model,
picture, which assumes the metallic electronic states
in semiconductor layers near the interface, is well
CNL . However,
applicable to such systems because of the large den-
sity of MIGSs.
CNL for many semiconductors. This occurs because
When the interface states appear due to the
extrinsic origins such as structural disorders, we
have to consider other methods for calculating
experiments,Spicer et al. (1980, 1989) were the first
to point out the importance of defect-induced inter-
face electronic states to determine the Schottky
barrier. Drummond (1999) extended this concept
and categorized observations into various defect
It is often observed that the DOS of interface
states shows a U-like shape in the band gap for a
variety of disordered metal/semiconductor inter-
faces, as shown in Figure 52(a). Hasegawa and
Ohno called these states as disorder-induced gap
states (DIGS). They found that the Fermi energies
of metals match the energy position of the lowest
¼0
CNL-like Fermi energy of semiconductors
ð20Þ
(Hasegawa and Ohno, 1986). Figure 52(b) shows
the basic concept they used for calculating
disordered interfaces. They considered that the
DIGS appears due to the disorder of semiconductor
bonds at the metal/semiconductor interfaces and
proposed that the CNL-like energy that separates
the bonding and antibonding states is obtained as an
Here, we would like to point out two important
features in these kinds of
to some ambiguity in determining the boundary
between valance- and conduction-band-like MIGS
or DIGS, there exist several versions of the definition
of
Cardona and Christensen (1987) proposed to adopt
the dielectric mid-gap energy as
most of these theories present similar values of

Table 4 Calculated Schottky barrier height, , and localization length, , for

various combination of metal and semiconductor

f e (eV)

Au Al Other metals Theory (eV)  (Å) Band gap (eV)

Si 0.83 0.70 0.70–0.82 0.76 3.0 1.12

Ge 0.59 0.48 0.38–0.64 0.48 4.0 0.66
GaAs 0.94 0.78 0.71–0.94 0.74 3.0 1.42
ZnS 2.00 0.80 0.80–2.00 1.40 1.5 3.60

From Tersoff J (1984a) Schottky barrier heights and the continuum of gap states.
Physical Review Letters 52: 465, Tersoff J (1984b) Theory of semiconductor
heterojunctions: The role of quantum dipoles. Physical Review B 30: 4874 and Tersoff J
and Harrison WA (1987) Transition-metal impurities in semiconductors – their connection
with band lineups and Schottky barriers. Physical Review Letters 58: 2367.
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 153

(a) 0 Ec assuming that the interface DOS is considerably large

GaAs PCVD - SiO2 because CNL does not change even if the charge
(annealed at 800 °C)
Energy (eV)

–04 transfer occurs. For example, assuming a simple

PCVD - SiO2
Ei band structure for semiconductor, where valence
–08 and conduction bands have constant DOS, we can
–12 Anodic native derive that CNL ¼ EVB þ EG  DVB =ðDVB þ DCB ),
oxide where EVB and EG are the valence-band edge and
Ev
0 Ec band-gap energies, respectively, while DVB and DCB
InP are DOS of valence and conduction bands, respec-
Energy (eV)

–04 As-grown tively. This formula is derived from the theories of

Tersoff and Cardona and Christensen, and indicates
–08 Annealed for 16 h Ei
that both theories estimate similar values. It should
Electrolytic Optimized be noted that this formula is described by the physi-
–12 Plasma Al2O3 /native oxide
Ev cal quantities intrinsic to bulk semiconductors. In
0 Ec case of DIGS interface states, since the interface is
Inx Gax As x = 0.65 randomly disordered, Hasegawa and Ohno assumed
Energy (eV)

–04
x = 0.53 x = 0.25 the simple average of orbital energies of semiconduc-
–08
tors, thus again depending on only the bulk
x=0
properties.
–12 Al O /native oxide
2 3
Ev 1.04.3.2.3 Band bending
1011 1012 1013 1014
(cm–2 eV–1) Most semiconductors contain impurity atoms that
are introduced unintentionally in the growth process
Disordered
(b) semiconductor E
or intentionally by doping. Here, we consider an n-
layer type semiconductor having movable electron carriers
Ec
as an example. Figures 53(a) and 53(b) show the
Anti-bonding band alignments before and after the contact. Before
Semi- III II I contact, in a semiconductor, some of electrons origi-
conductor EHO nating from donor atoms transfer into interface states
Bonding and the positive-impurity sites appear around the
interface. Due to this positive charge distribution,
Er
Insulator or metal Nss the potential (therefore, the conduction and valence
Figure 52 (a) DOS of interface states at disordered
bands) bends as shown in Figure 53(a), which is
interfaces. (b) Schematic diagram explaining the appearance called the band bending. When metal and semicon-
of disorder-induced gap states (DIGSs). Reproduced with ductor are in contact with each other, electron
permission from Hasegawa H and Ohno H (1986) Unified transfer occurs from the interface states of semicon-
disorder induced gap state model for insulator– ductor and inner donor states to the electronic states
semiconductor and metal–semiconductor interfaces. Journal
of Vacuum Science and Technology B 4: 1130.
in metal in case of the alignment in Figure 53(a), to
equalize the Fermi energies of metal and semicon-
ductor, M and S. The alignment after the contact is
they commonly assume the existence of interfaces
states and the charge transfer between metal states (a) (b)
Depletion layer
and interface states. Since such charge transfer is
conceptually similar to that between metallic materi- μS φC
μM μM μS
als, we can say that the full contact of electronic states
is assumed between metals and semiconductors in
these conventional CNL theories, details of which
will be discussed in the following section. Metal n-Type
The second important feature is that CNL is semiconductor
defined as intrinsic to not the interface but the bulk Figure 53 Schematic view of band bending at metal/
properties of semiconductors, which is equivalent to semiconductor interface: (a) before and (b) after contact.
154 Atomic Structures and Electronic Properties of Semiconductor Interfaces

shown in Figure 53(b). A more precise band-bending
feature is obtained by solving the Poisson equation in
the electromagnetism, considering the charge trans-
fer self-consistently. The region around the interface
with no electrons is often called the depletion layer,
with typical width around 100 Å.
Here, we briefly comment on the experimental
methods to measure SBHs. Figure 54 shows schema-
tically the principal views of three methods. In the
current–voltage (I–V) method, one applies a voltage
perpendicular to the interface and measures the ther-
mal electrons that pass the Schottky barrier potential
from semiconductor to metal. Because the current is
proportional to expð –
B =kB T Þ, one can determine structures of material surfaces and the atomic and
B from the temperature dependence. In the capaci-
tance–voltage (C–V) method, one applies the
alternating voltage V and measures the capacitance C
of inversion layer.pSince the width of inversion layer is
ffiffiffiffiffiffiffiffiffiffiffiffiffi
proportional to
B – V , the capacitance becomes
proportional to 1=
B – V , from which
B is deter-
mined. Because the capacitance also includes effects
of tunneling currents, resistance in semiconductors,
and distribution of impurity atoms, the analysis is
sometimes complicated. In the method using internal
photoelectric effect, one produces hot electrons by
photoelectric excitation and measures the inverse
current flowing over the barrier. These methods
have an advantage in observing the deeply buried
interface. We can also measure the barriers by using
XPS and STM when metal layers are thin enough.
CNL theory at metal/semiconductor
1.04.3.2.4 Band offset
Next, we consider how the band offset appears at a
semiconductor/semiconductor interface. Anderson
(1962) proposed that the conduction band offset at
A/B interface is given by the electron affinity differ-
ence between A and B materials as Ec ¼ B – A .
Using the observed band-gap energies, one can
also derive the valence-band offset as
EV ¼ EC þ EGB þ EGA . On the other hand, since
the valence-band structures of zinc-blende semicon-
ductors are well described by the nearest-neighbor
tight-binding approximation using sp3 orbital sets,
Harrison and Tersoff (1986) and Monch (1996) pro-
posed that the valence-band offset, EV, is obtained
as the energy difference of the valence-band top
between A and B; they calculated various EV values
by adopting empirical parameters. These results are
shown in Table 5 for various combinations of semi-
conductors. It is seen that the agreement with
experiments is largely improved by the latter theory.
This is because the affinity is sensitive to the atomic
electronic structures are generally different for sur-
faces and interfaces. On the other hand, though we do
not consider the charge transfer at the interface in
these theories, the agreement is not so poor, indicat-
ing the quantity intrinsic to bulk semiconductor is an
important factor to determine the offset.
In these theories, we use the vacuum level as the
reference energy for comparison. Recently, Van der
Walle and Neugenbauer (2003) proposed the band
alignment assuming that the hydrogen impurity level
has the same energy position in most of the semi-
conductors. This proposal can be conceptually
similar to the above-mentioned two theories.
To advance a more reliable calculation of the band
offset, one has to consider the charge transfer at the
interface (Nakayama, 1993). In this case, the scenario
based on the
interfaces applies straightforwardly to semiconductor/
semiconductor interfaces. Figure 55 illustrates how the
band offset is determined at the semiconductor/semi-
conductor interface. At the semiconductor interfaces
Table 5 Calculated valence-band offset at various
semiconductor/semiconductor (110) nonpolar interfaces,
in eV

Thermal electron emission A/B Exp. EAR HAO TER LDA

I
GaAs/AlAs 0.50 0.15 0.04 0.35 0.37
GaSb/InSb 0.51 1.12 1.12 0.43
φB
GaAs/InAs 0.17 0.24 0.32 0.20
EF Conduction band Si/Ge 0.20 0.33 0.38 0.18
GaAs/ZnSe 0.96 1.26 1.05 1.59
Inpurity levels Ge/ZnSe 1.52 1.97 1.46 2.17
Depletion layer
Ge/GaAs 0.53 0.35 0.41 1.12 0.63
Capacitance C = dQ/dV InP/CdS 1.63 1.27 1.48

Exp: experiments; ERA: electron affinity theory; HAO: tight-binding

Figure 54 Schematic principles to measure the Schottky theory; TER: charge neutrality level theory; LDA: local density
barrier height (SBH). functional calculations.
 Atomic Structures and Electronic Properties of Semiconductor Interfaces
A B
εBF
εAF
εAF
Figure 55 Schematic view to explain the formation of
band offset.
A and B, there exist MIGS-like interface states and
these states are occupied by interface electrons from
the bottom to the effective Fermi energies (left figure).
When the interface is realized, the charge transfer
occurs between these states to equalize such Fermi
energies (middle figure). As a result, one obtained the
band alignment shown in the right.
Harrison and Tersoff (1988) were the first to
adopt this picture and calculate the band offsets for
various combinations of semiconductors; their results
are shown in Table 5. It is seen that the
155
Semiconductors The results in Table 5 demonstrate that not only
A B
the electronic structures of bulk semiconductors but
also the charge transfer at the interface are important
εBF
to determine the band offset at the interface. It should
be noted here that the charge transfer across the inter-
face is often realized by the orbital hybridization
between the constituent interface atoms of semicon-
ductors, thus producing the dipole at the interface. To
examine whether such a dipole is really produced at the
interface by charge transfer, we had better introduce
another freedom at the interface and study the variation
of charge transfer. Figure 56 shows the calculated
valence-band offset at ZnSe/ZnTe (001) interface as a
function of the strain (Nakayama, 1992). The strain can
be varied by changing the lattice constant, that is, the
composition, of the substrate for ZnSe/ZnTe system.
Because by increasing the Te composition, the differ-
ence of bulk energy, ", decreases, it reflects the
deformation potentials of the bulk system. On the
other hand, there is an increase in the charge transfer
CNL theory from ZnTe to ZnSe, , and this increases the dipole
also succeeded in predicting valence- and conduc- potential, V. As a result of compensation between "
tion-band offsets of a number of semiconductor/ and V, the valence-band offset gradually decreases. It
semiconductor interfaces. should be noted that such a correlation between "

(a) ZnSe/ZnTe (b)

3.2 0
C
: IV family
Δρ (10–2e)

: III–V compounds
ΔV (eV)

ΔV Si
: III–VI compounds
Δ & ΔEv,hh (eV)

Offset of hh state (eV)

Level-shift difference & offset

0.2
1.6 –1 Δρ

SiC

Δ
Charge transfer

Dipole potential

0.1 GaSb AIAs

AlSb AIP, GaP
GaAs
0 –2 ΔEv 1 InSb AIN
, hh InP ZnTe CdSe
ZnSe ZnS
InAs GaN
CdTe Cds
HgTe HgSe HgS
0

0 2 4 6
0 Ionicity, ε cp – ε ap (eV)
0 0.5 1
LznTe
X=
LZnSe + LZnTe

Figure 56 (a) Strain dependence of valence-band offset at ZnSe/ZnTe (001) interface. Strain changes corresponding
to the composition of the substrate. (b) Band offset at wurtzite/zinc-blende interface for the heavy-hole states of
various semiconductors as a function of ionicity. (a) Reproduced with permission from Nakayama T (1992b) Valence
band offset and electronic structures of zinc-compound strained superlattices. Journal of the Physical Society of Japan
61: 2434. (b) Reproduced with permission from Murayama M and Nakayama T (1994) Chemical trend of band offsets
at wurtzite/zinc-blende heterocrystalline semiconductor interfaces. Physical Review B 49: 4710.
156 Atomic Structures and Electronic Properties of Semiconductor Interfaces

and V indicates the charge transfer expected by the
CNL theory really occurs.
At the heterovalent interfaces such as ZnSe/GaAs
(001), the charge transfer governs the band offset
itself. Figure 57(a) shows the measured valence-
band offset as a function of R ¼ Zn/Se ratio at the
interface, which is realized by changing the growth
treatment (Nicolini et al., 1994). Zn–As acceptor and
Se–Ga donor bonds exist at this interface. The charge
transfer of about 101e occurs between these bonds,
which produces a dipole potential V. Depending on
the growth treatment, the configuration of these
bonds changes as shown in Figures 57(b) and 57(c)
and the direction of charge transfer is opposite in
these two cases. As a result, as seen in Figure 57(a),
the offset varies by about 0.7 eV.
The above result for ZnSe/GaAs interface
demonstrated that the atomic structures at the inter-
face are also important to determine the band offset
in some of the interfaces. In fact, by producing the
heterovalent bonds by intentionally inserting
foreign-family atoms at the interface, one can some-
times control the modulation of the band offset.
Lambrecht and Segall (1990) developed the simple
tight-binding model to include such effects in the
case of covalent bonding systems.
More precise values of band offsets are evaluated
using the first-principles calculations. The results
using the local density-functional calculations are
also shown in Table 5. When the quasiparticle GW
calculation is applied, one can obtain the most pre-
cise values, for example, 0.5 eV for GaAs/AlAs
interface (Zhang et al., 1989). These first-principles
calculations can consider the effects of any atomic
structures of interface and apply to new systems that
have not ever been produced in experiments. For
example, the heterocrystalline interfaces, which is
the interface between the same semiconductors
with different crystal structures, are proposed and
produced in experiments (Murayama and
Nakayama, 1993, 1994; Hibino and Ogino, 2000).
The calculated band offsets at hexagonal/cubic

(a)
1.6
ZnSe/GaAs(001)
band offset

1.2
R = Zn/Se

0.8

Substrate types
0.4 p+ n+
p n
pc (4 × 4) nc (4 × 4)
p 3×1 n 3×1
0 No doping R
0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3
ΔE (eV)

(b) (c)
Charge transfer

Se
Zn
direction

Ga

As

Small R Large R
Figure 57 (a) Valence band offset, E, at heterovalent ZnSe/GaAs (001) interface, as a function of the composition ratio of
R ¼ Zn/Se. (b,c) Charge transfer at anion and cation mixed interfaces. Reproduced with permission from Nicolini R, Vanzetti L,
Mula G, et al. (1994) Local interface composition and band discontinuities in heterovalent heterostructures. Physical Review
Letters 72: 294.

(wurtzite/zinc-blende) homomaterial twin interfaces
are shown in Figure 56(b). This result indicates that
not only the heteroatoms but also the topology of
bond connection are the origins of offsets.
1.04.3.3 New Features of Schottky Barrier
1.04.3.3.1 Breakdown of Schottky–Mott
limit
Koyama et al. (2004) deposited Au, Pt, and Al metals
on HfSiO substrate and measured their effective
WFs, which results are displayed in Figure 58(a).
They found that effective WFs of Au and Pt become
large compared to WFs in vacuum, opposite to what
happens with Al This result indicates that the S
parameter becomes larger than 1, that is, beyond
the conventional limit. A similar anomaly was
observed in the XPS experiment by the Miyazaki
CNL the-
group (Shiraishi et al., 2005). They deposited Au
nanoscale dots on HfO2 substrate, measured the
CNL level in the band gap of a high-k dielectric
CNL ,
(a) 6
Effective WF on HisiD (eV)
5.5
5 electronic structures using the first-principles cal-
4.5
Al
4
4 4.5
(b)
Au4f
3 nm
Intens. (a.u.)
4 nm
88 86 84 82
Binding energy (eV)
Figure 58 (a) Effective work functions of Al, Au, and Pt on
HfSiON as a function of vacuum work function, reported by
Koyama et al. (2004). (b) Observed binding energies of Au
nanodots on HfO2 by XPS measurement (Shiraishi et al.,
2005). The sizes of dots are described in the figure. (c)
Schematic diagram of the observed Fermi-energy
movement of metals on Hf-related high-k materials.
Atomic Structures and Electronic Properties of Semiconductor Interfaces 157
biding energies of Au, and found that the binding
energy increases as the size of dots and thus the
interface area increases, as shown in Figure 58(b).
This result clearly indicates that at Au/HfO2 inter-
face the electrons transfer from Au to HfO2, which
promotes the increase of Au effective WF. Similarly,
by using the CV techniques, WF shifts were observed
on HfAlOx substrate for Al metal with a decrease of
0.36 eV, and for Ni and Au metals with increases of
0.20 and 0.22 eV, respectively.
The change of WFs from in-vacuum to on-high-k-
dielectrics is schematically summarized by arrows in
Figure 58(c), for various metals. The Fermi energies
of p-metals such as Ni and Au, which have larger
WFs, are shifted toward the valence band of high-k
dielectrics, whereas those of n-metals, such as Al,
having smaller WFs move toward the conduction
band. These WF changes are quite different from
expectations deduced by the conventional
ories. The conventional theories state that there is a
single
and the metal Fermi energies are aligned to this
as shown in Figure 51(c). Thus, the variation in
Figure 58(c) was beyond our ordinary understanding.
Ps
Au
In order to clarify what happens at metal/high-k
interfaces, Shiraishi et al. (2005) investigated the
culations, and found that two important
preconditions implicitly assumed in conventional
S > 1 !! theories are broken at these interfaces. The first is
concerned with the penetration length of MIGSs
5 5.5 6 from the interface into insulating materials.
Vacuum WF (eV) Figures 59(a) and 59(b) show the charge densities
(c)
CB Interface
2 nm (a)
Al
W
Ni
Ru
Metal Si
Au
EF
HfO2 VB Metal (jellium) HfO2
(b)
O
Hf
Interface
Figure 59 Contour plots of MIGS wave functions at (a)
metal/Si and (b) metal/HfO2 interfaces (Shiraishi et al., 2005).
158 Atomic Structures and Electronic Properties of Semiconductor Interfaces

of typical MIGSs around metal/Si(111) and metal/ (a) AI

HfO2(110) interfaces, respectively. Here, the metal 25
is represented by the jellium model. In the case of 20
DOS

Energy (eV)
metal/Si, the MIGS penetrates deep into Si, about 15 EF
five atomic layers. Thus, the Si side of the interface 10
has movable electrons and looks like a metal. The 5
band alignment is realized by moving electrons in 0
these states. Note here that, since the MIGS pene- Γ XK Γ L KWX
trates deep and touches a number of Si atoms
around the interface, the detailed interface atomic (b) Au
structure does not govern the electronic structure of 40
the interface. In other words, one can say that the 35

full contact of electronic states is realized at this
metal/Si interface. On the other hand, in case of
metal/HfO2, the penetration of MIGS into HfO2 is
seen to be at most one to two atomic layers, thus the
full contact of electronic states not being realized at
metal/HfO2. This occurs because of the high ioni-
city and large band gap of HfO2. The present result
indicates that the electronic structure at metal/
high-k interface is very sensitive to the interface
atomic structures, that is, to which atom contact is
realized, and we had better start with the bonding
picture of atoms to understand the electronic
structure at this interface.
The other precondition is related to the indivi-
duality of metals. Figures 60(a) and 60(b) show
band structures of Al and Au metals around the
respective Fermi energies, EF. The schematic pic-
tures of DOS are also shown on the right. As the
extended s- and p-orbital electrons are valence elec-
trons, Al has featureless DOS around EF. On the
other hand, due to the localized d-orbital electrons,
Au has small-dispersion bands below EF. Thus, DOS
is extremely large below the Fermi energy, whereas
it is comparable to the Al case above the Fermi
energy. As shown in the following, this kind of
metal character is not considered in the conven-
tional theory.
The full contact of electronic states at the inter-
face and the featureless metal DOS are essential
conditions in conventional theories. This is apparent
because
CNL is defined using quantities intrinsic to The high-k dielectric such as HfO2 is represented by
bulk materials, such as EVB, EG, DVB, and DCB, and
does not include the interface information, such as
atomic structures and characteristics of metals. The
same conditions are also assumed in the case of the
theory of DIGSs (Hasegawa and Ohno, 1986); for
example, the interface is assumed to have random
amorphous-like structures, and some sort of averages
that realize the full contact of electronic states are
implicitly taken to deduce
CNL . However, as shown duction-band states of HfO2, while tM-O is that
Energy (eV)
30
25
20 DOS
EF
15
10
5
Γ XK Γ L KWX
Figure 60 Band structures of (a) Al and (b) Au bulk metals,
calculated by the first-principles method. Schematic
diagrams of DOS are displayed on the right. From Shiraishi
K, Akasaka Y, Miyazaki S, et al. (2005) Universal theory of
work functions at metal Hf-based high-k dielectrics
interfaces – guiding principles for gate metal selection. In:
Technical Digest of IEEE International Electron Devices
Meeting, p. 29. Washington, DC, USA, December.
in the above, it is clear that these conditions are not
satisfied at metal/high-k interfaces.
1.04.3.3.2 Generalized charge neutrality
level
In order to simulate the electronic structures of
metal/high-k dielectrics interfaces, we have to take
into account the interface atomic structures and char-
acteristics of metals. To realize such interfaces,
Shiraishi et al. (2005) adopted the effective-four-
level tight-binding model of an interface. The sche-
matic diagram of this model is described in
Figure 61(a). They characterize a metal with the
Fermi energy, EF, and the effective local DOS at
the interface below and above EF, Docc and Dunocc.
the energies of valence-band top and conduction-
band bottom (EVB and ECB, respectively) and the
effective local DOS of valence and conduction
bands at the interface (respectively, DVB and DCB).
Since HfO2 is an ionic material, the conduction bands
are mainly made of Hf d-orbitals, while the valence
bands are made of O p-orbitals. tM-Hf is a transfer
energy between the occupied metal states and con-
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 159

(a) Hf 5d jtM-Hf j2 Docc DCB jtM-O j2 Dunocc DVB

s. p Dunocc tM–Hf DCB – ¼0 ð22Þ
EF ECB ECB þ V – EF EF – EVB – V

φGCNL
EVB By solving this equation, the generalized charge neu-
s. p. d Docc trality level of HfO2 that should match the Fermi
tM–O DVB
O 2p energy of metal is obtained by GCNL ¼ EF – V as

Metal HfO2 (nonmetal)

jtM-O j2 Dunocc DVB
G CNL ¼ EVB þ EG
(b) (c) jtM-O j Dunocc DVB þ jtM-Hf j2 Docc DCB
2

ð23Þ
s. p Hf 5d Hf 5d
s. p where EG ¼ ECB  EVB is the band-gap energy of
φGCNL φGCNL HfO2.
EF
d EF In the case of ordinary metal/semiconductor inter-
s. p O 2p O 2p faces, we can expect the full contact of electronic
states, tM-Hf ¼ tM-O, and the DOS of the metal is fea-
Al HfO2 Au, Ni HfO2 tureless, Docc ¼ Dunocc. Thus, we can reproduce the
conventional CNL as EVB þ EG  DVB =ðDVB þ DCB )
Figure 61 (a) Schematic diagrams of interface
hybridization models to derive the generalized neutrality (Cardona and Christensen, 1987), which is the
levels at metal/nonmetal interfaces. EF, Doccu., and quantity intrinsic to a bulk semiconductor. This is
Dunoccu are Fermi energy and DOS variables for the metal why we call the present G CNL
the generalized charge
below and above EF, while ECB, EVB, DCB, and DVB are neutrality level.
the conduction- and valence-band edges and their DOS
Next, we explain how the new G theory
for the nonmetal. tM-Hf and tM-O are orbital hybridization CNL

energies between electron occupied and unoccupied
states, which promote charge transfer across the
interface. (b,c) Hybridization-induced charge transfer at
Au/HfO2 and Al/HfO2 interfaces. Bold arrows denote
major charge transfer.
between the unoccupied metal states and valence-
band states of HfO2. It should be noted here that the
charge transfer between a metal and HfO2 is gener-
ally realized only by such orbital hybridization
between unoccupied and occupied states. Transfer
energies between occupied states and those between
unoccupied states never induce the charge transfer
between the metal and HfO2, thus being not relevant
to determine the band alignment and being excluded
in the present model.
By applying the second-order perturbation theory
of quantum mechanics, the charge transfer from a
metal to HfO2 is written as (Nakayama, 1993;
G approaches the bottom
Nakayama et al., 2006b)
jtM-Hf j2 Docc DCB jtM-O j2 Dunocc DVB
explains the unusual behavior of work functions at
metal/high-k interfaces. As representative interfaces
made of n and p metals, the Al/HfO2(110) and Ni/
HfO2(110) interfaces were investigated by the first-
principles calculations. Figures 62(a) and 62(b),
respectively, display the most stable adsorption posi-
tions of Al and Ni atoms on the HfO2 substrate, while
Figure 62(c) shows the adsorption energies of Al and
Au on HfO2 as a function of the adsorption position
(Nakayama et al., 2006b). Adsorption positions, 1–7,
are denoted on the right. It is clearly seen that Al
atoms prefer to locate on oxygen atoms and produce
the connection only with oxygen atoms. This occurs
because the reactivity of Al with oxygen is high. As a
result, one can reasonably approximate tM-Hf << tM-O.
Meanwhile, the variation of Al DOS is monotonously
continuous and featureless as shown in Figure 61(b),
indicating that Docc ¼ Dunocc. Therefore, the charge
transfer occurs from O to Al, as shown in
Figure 61(b). As a result,
CNL
of HfO2 conduction bands, ECB, and the effective WF
of Al decreases as shown in Figure 58(c). With
 _ – ð21Þ
ECB – EF EF – EVB
This charge transfer produces the dipole potential at
the interface and increases the energies of EVB and
ECB in HfO2. Since the charge transfer should be
completed by inducing a final dipole potential of
V, the self-consistent equation of V becomes as
respect to Au/HfO2, the Au atom appears to have
no preference for the adsorption position and is
expected to locate between Hf and O atoms on aver-
age on the HfO2 surface, thus indicating tM-Hf ¼ tM-O.
However, as seen in Figure 60(b), the Au DOS
below the Fermi energy is much larger than that
above the Fermi energy. Thus, we can approximate
160 Atomic Structures and Electronic Properties of Semiconductor Interfaces
(a) (b)
3.56Å 1.89Å 1.95Å
2.64Å
Al-adsorbed structure Ni-adsorbed structure
(c)
Adsorption energy [eV]
0 top view
Au
–0.5
–1
Al
–1.5
–2
1 2 3 4 5 6 7
Atom position
Figure 62 Stable adsorption positions of metal atoms on
HfO2 (110) substrate: (a) Al and (b) Ni atoms. (c) Calculated
adsorption energies of Al (solid line) and Au (broken line)
atoms on HfO2 (110) substrate, as a function of adsorption
position. Adsorption positions are displayed on the right.
Reproduced with permission from Nakayama T, Shiraishi K,
Miyazaki S, et al. (2006) Physics of metal/high-k interfaces.
ECS Transactions 3: 129–140.
Docc >> Dunocc. Therefore, the charge transfer occurs
mainly from Au to HfO2 as shown in Figure 61(c),
GCNL
approaches the top of HfO2 valence bands, EVB,
and the effective WF of Au increases as shown in
Figure 58(c).
It might seem quite strange that the new
G CNL (position 3). This common variation to both Al and
theory predicts the charge transfer from O to Al at
G theory. By
Al/HaO2 interface and from Au to Hf at Au/HfO2
interface because electronegativities of O and Au
atoms are, respectively, much larger compared to Al
and Hf. However, this really does occur! The most
important point is the fact that O and Hf are not
G CNL
atoms but elements in bulk HfO2, thus the O and
Hf atoms are fully ionized in HfO2 as O2 and Hf4þ.
Thus, there is no space to receive additional elec-
trons around O and holes around Hf. Instead, once
the Al/HfO2 and Au/HfO2 interfaces are grown and
the Al-O and Au-Hf connections are produced, O
and Au atoms partially present electrons to Al and Hf
atoms, respectively.
The strictest examination of the generality of new
G
CNL theory is to consider the extreme artificial cases;
what happens when the Al atoms contact with not O
but Hf atoms at Al/HfO2 interface. This is because
the new theory argues the importance of interface
atom coupling, thus the theory is justified by
38
1.97Å
36
CB
Energy (eV)
2.84Å
34
Al
32 Au
VB
30
HfO2
1 2 3 4 5 6 7 ∞
Metal-atom position
0 Figure 63 Calculated Fermi-energy positions of Al and Au
4 2 3
monolayer metals relative to the conduction- and valence-
7 6
1 5 band edges of HfO2, as a function of interface atomic
Hf position on the HfO2 (110) substrate. Atomic positions are
displayed in Figure 62(c). 1 shows the Fermi-energy
position realized at real metal/HfO2 interfaces, which are
obtained for thicker metals and as an average of stable
interface configurations in Figure 62(c).
studying the relation between the atom coupling
and the WF value at the interface. Figure 63 shows
the Fermi-energy positions of Al and Au calculated
by the first-principles method when monolayer metal
atoms are located at various positions of HfO2 inter-
faces (Nakayama et al., 2006b). It is clearly recognized
that the Fermi-energy position depends on not only
the metal kinds but also the metal-atom positions
Especially, Fermi energies of both Al and Au are
low when the metal atoms are located on Hf (position
1), while they become high when located over O
Au clearly justifies the generalized
CNL
analyzing the charge distribution, one can also check
that such a variation of Fermi energy occurs, reflect-
ing the charge transfer caused by the orbital
hybridization at the interface.
Other aspects of the universality of the new
theory are observed by considering the band offsets,
that is, band-edge discontinuity, at semiconductor/
semiconductor (S/S9) interfaces (Nakayama et al.,
2006b). In the case of (S/S9) interface, the band
alignment is determined by equalizing the following
equation:
B A
V þ EVB þ EG ¼ E9VB þ E9G ð24Þ
AþB AþB
where A ¼ |t9CB-VB|2DCBD9VB and B ¼ |t9VB-
2
CB| DVBD9CB are effective couplings at the interface,
while V is the interface dipole. Various D’s are DOS
of S and S9, while various E’s and t’s are, respectively,
band-edge energies and electron transfer energies at
 Atomic Structures and Electronic Properties of Semiconductor Interfaces
the interface, which all are defined as in Figure 61(a).
This equation represents the balance of two charge
neutrality levels (Nakayama, 1993).
Finally, we remark on the universality of the new
GCNL
concept.
GCNL
is constructed by using the repre-
sentative physical quantities of the interface. The
energies EF, EVB, and ECB and DOS values Docc,
Dunocc, DVB, and DCB represent properties intrinsic
to bulk materials originating from bulk band struc-
tures, while the transfer energies, tM-Hf and tM-O, are
introduced to describe the microscopic atomic struc-
tures of interfaces, that is, the interface bonds. This
fact indicates that both band and bond pictures,
which, respectively, correspond to itinerant and loca-
lized characters of electrons, are necessary to
describe electronic structures at the interface. In
this way, the first-principles theoretical approaches
have played key roles in creating the new science
concepts such as
G in recent Si nanotechnology, formation enthalpy of HfO2 is larger than that of
CNL
and they are further leading not only the Si nano-
technology but also the frontier fields of nanoscience
such as organic semiconductors and nano-bio devices
(Oda and Nakayama, 2008).
1.04.3.3.3 Interface reaction and
Fermi-level pinning
We first introduce an example where the thermody-
namics of interface reaction determine the SBH. An
unexpected SBH behavior at the interface between
heavily B doped Si (pþpoly-Si) and HfO2. has been
reported. Hobbs et al. (2003) reported that the differ-
ence in SBH between nþpoly-Si and pþpoly-Si
becomes only 0.2 eV, although their intrinsic Fermi-
level difference amount to 1 eV reflecting the Si band
gap (Figure 64). This is called ‘Fermi level pinning’
(FLP) in LSI jargon. Since HfO2 is a typical wide-gap
Si conduction
band
0.2 eV
Ferml level 0.2 eV
of n + poly Si
Ferml level
0.6 eV
of p + poly Si
Si valence
band
On SiO2 On HfO2
Figure 64 Schematic illustration of the unusual behaviors
of the relative Schottky barrier heights (SBHs) at the pþpoly-
Si/HfO2 interface compared with that at the nþpoly-Si/HfO2
interface. For comparison, the well-known SBH behavior at
the poly-Si/SiO2 interfaces is also shown on the left.
161
insulator (band gap is about 5.6 eV), SBH behavior is
expected to be similar to the Schottky limit according
to the conventional CNL concepts. However, the
observed behavior rather resembles the Bardeen limit.
The physical origin of this unusual behavior is in the
mechanism of the SBH formation being much different
from the conventional mechanism. This is governed by
the thermodynamics of the interface reaction.
The physical mechanism is as follows. The rela-
tively higher energy level of oxygen vacancy (Vo) in
HfO2 causes a notable thermodynamic behavior of
interfaces, when HfO2 is in contact with Si. Recent
experiments indicate that the Vo level is located
about 0.4 eV above the bottom of Si conduction
band (about 1.2 eV below the bottom of HfO2 con-
duction band) (Takeuchi et al., 2004).
It is well known that Hf atoms can bind much
more strongly than Si atoms to O atoms. Actually, the
SiO2 by about 2.2 eV. Further more, recent first-
principles calculations show that the Vo formation
energy in bulk HfO2 is larger than that in bulk SiO2
by about 1.2 eV (Scopel et al., 2004). At first glance,
the fact that Hf–O bonds are stronger than SiO
bonds indicates that the partial oxidation of poly-Si
gates by pulling an O atom out of the HfO2 dielec-
trics is an endothermic reaction with 1.2 eV energy
loss, and this reaction occurs with difficulty.
However, the situation changes completely if we
take into account the electron behavior.
FLP in Hf-related high-k gate stacks with pþpoly Si
gates can naturally be explained by taking into account
the electron behavior as follows. In Figures 65(a)–
65(c), the mechanism of Vo formation in HfO2 and
subsequent electron transfer across the poly-Si/HfO2
interface is schematically illustrated. First, let us assume
that the poly-Si is partially oxidized by the formation of
SiOSi bonds by O atoms being pulled out of HfO2.
As a result, SiOSi bonds in the poly-Si and Vos in
HfO2 are formed (Figure 65(a)). An O atom in HfO2
takes an O2 ion form, but an O atom in a SiOSi
bond is neutral. Accordingly, two additional electrons
are generated after one O atom is pulled out, and if
these electrons remain inside HfO2, they occupy the Vo
level in HfO2 (Figure 65(b)). The assumption that two
additional electrons remain in HfO2 corresponds to the
same situation as the bulk calculations that give a
1.2 eV energy loss. However, since HfO2 is in contact
with the poly-Si gate, electrons have to transfer into the
gate. This is because the Vo level is located above the
poly-Si Fermi level (Figure 65(c)). Now, we estimate
roughly the two ultimate cases of energy loss (gain)
162 Atomic Structures and Electronic Properties of Semiconductor Interfaces

(a) (b) (c)

E(Vo) E(Vo) E(Vo)
0.4 eV 0.4 eV 0.4 eV
Ec Ec Ec
1.1 eV 1.1 eV 1.1 eV
Ev HfO2 Ev HfO2 Ev HfO2
Poly-Si- Vo Poly-Si- Vo Poly-Si- Vo
gate gate gate
SiO2 SiO2 SiO2
+1.2 eV +0.4 eV = (1.2–2×0.4) –1.8 eV = (1.2–2×1.5)
Figure 65 Schematic illustrations of Vo formation in HfO2 with partial oxidation of poly-Si gate and subsequent electron
transfer into the gate electrodes. (a) Partial poly-Si oxidation by pulling out an O atom from HfO2. (b) Energy loss in an nþpoly-
Si gate. (c) Large energy gain in a pþpoly-Si gate. Reproduced with permission from Shiraishi K, Yamada K, Torii K, et al.
(2006) Oxygen-vacancy-induced threshold voltage shifts in Hf-related high-k gate stacks. Thin Solid Films 508: 305.

when HfO2 is in contact with the poly-Si gate: one is
with an nþpoly-Si gate and the other is with a pþpoly-
Si gate. For an nþpoly-Si gate, the two-electron trans-
fer results in an energy gain of 0.8 eV (2  0.4 eV), and
the total energy loss is reduced from 1.2 eV (bulk value)
to 0.4 eV. Despite the energy reduction due to the
electron transfer, the reaction for an nþpoly-Si gate is
still endothermic. For a pþpoly-Si gate, on the other
hand, the situation is quite different. The Fermi level
position of a pþpoly-Si gate is located about 1.5 eV
below the Vo level in HfO2. As a result, the two-
electron transfer results in a total energy gain of
1.8 eV (2  1.5 eV  1.2 eV). Surprisingly, the interface
reaction, accompanied by Vo formation and subsequent
electron transfer, becomes exothermic with an energy
gain of 1.8 eV, when the HfO2 is in contact with a
pþpoly-Si gate. Actually, TEM observations show
that some interfacial reaction layers are observed in a
pþpoly-Si gate HfAlOx MISFET, as shown in
Figure 66, and such reaction layers have not been
observed in nþpoly-Si gate MISFETs. These results
p + poly -Si HfAIOx
IL
Si substrate
20 nm
Figure 66 Cross section of replacemnt pþgate HfAlOx
MISFET observed by TEM. Reproduced with permission
from Shiraishi K, Yamada K, Torii K, et al. (2006) Oxygen-
vacancy-induced threshold voltage shifts in Hf-related high-
k gate stacks. Thin Solid Films 508: 305.
completely corroborate the above discussion based on
the ‘oxygen vacancy model’.
Now, we move on the Vfb shift originating from
the formation of Vo in HfO2. For an nþpoly-Si gate,
the interface reaction that induces the electron trans-
fer occurs with difficulty, since it is endothermic. For
a pþpoly-Si gate, however, the interface reaction
accompanied by the formation of Vo in HfO2 occurs
easily, since this reaction has a large energy gain of
1.8 eV. At the same time, electrons transfer from
HfO2 into the poly Si occurs. As a result, an interface
dipole is formed as illustrated in Figure 67. This
dipole formation raises the position of the Fermi
level of the pþpoly-Si gate and flat band voltage
(Vfb) decreases. It is noticeable that the energy gain
of the interface reaction decreases when the Fermi
level is elevated. A simple consideration indicates
that the position at which the Fermi level is pinned
corresponds to the energy level that makes the
energy gain of the interfacial reaction zero. The
final Fermi level position satisfies the equation 1.2
(0.4 þ x) ¼ 0, where x is the final pinning position
measured from the nþpoly-Si Fermi level. The
Fermi level position of a pþpoly-Si gate obtained
from this is about 0.2 eV below the nþpoly-Si gate
Fermi level, which is in fairly good agreement with
the experimental results (Hobbs et al., 2003). As
discussed above, ‘oxygen vacancy model’ can quanti-
tatively reproduce the Fermi level pining position of
pþpoly-Si gate/HfO2 interfaces.
Next, we comment on the effect of inserting cap
insulator between pþpoly-Si and HfO2 gate dielec-
trics. Recent experiments show that the FLP of
pþpoly-Si gates cannot essentially be improved by
inserting SiO2 or SiN cap layers between pþpoly-Si
gates and high-k Hf-related dielectrics (Cartier et al.,
 Atomic Structures and Electronic Properties of Semiconductor Interfaces
(a)
Si CB
1.1 eV Vo
0.4 eV
Si VB
(EF)
0.2 eV
Interface Pinning level
dipole
Poly-Si
gate Vo HfO2
SiO2
Figure 67 (a) Schematic illustration of interface dipole formation and subsequent Fermi-level elevation toward the pinning level.
(b) Schematic illustration of the cap layer effect for Fermi-level pinning (FLP). Reproduced with permission from Shiraishi K, Yamada
K, Torii K, et al. (2006) Oxygen-vacancy-induced threshold voltage shifts in Hf-related high-k gate stacks. Thin Solid Films 508: 305.
2004). The oxygen vacancy model naturally explains
the results of these experiments. The schematic illus-
trations are shown in Figure 67. As shown in this
figure, the pinning position is governed only by the
energy position that balances the Vo formation
energy loss and the electron transfer energy gain.
The final pinning position measured from the
nþpoly-Si Fermi level (x) satisfies the equation 1.2̃
(0.4 þ x) ¼ 0, which is the same equation without a
cap layer. Accordingly, if O atoms can penetrate
through the cap layer until the system reaches ther-
mal equilibrium, the final pinning position remains
the same, regardless of the existence of a cap layer.
Systematic experiments have been reported by
Kamimuta et al. (2005). They examined three geo-
metries of poly-Si/HfO2 gate stacks. The schematic
illustrations are shown in Figure 68. The usual gate
stack structures in which FLP is observed in pþpoly-
Si gates are structures with no barrier layer and thin
IL as shown in Figure 68(a). At first, the effect of
boron segregated near the Si/HfO2 interfaces
(Takayanagi et al., 2003) or interfacial Hf–Si bonds
(Hobbs et al., 2003) were thought to be the cause of
FLP of p-poly-Si gates. However, FLP cannot be
avoided even if a barrier layer is inserted between a
pþpoly-Si gate and HfO2, as described in
Figure 68(b), indicating that neither B effect nor
Hf–Si bonds can be the cause of FLP at pþpoly-Si/
HfO2 interfaces. They have found that FLP relaxa-
tion can be achieved only when the gate stack
structure contains both thick barrier layer and thick
163
(b)
EC
0.4 eV
x eV
– –
EV
1.1–x eV
Poly-Si gate HfO2
Cap Vo
layer
+
SiO2
+
IL, as illustrated in Figure 68(c). Their experimental
finding indicates that interaction between HfO2 and a
Si substrate is very important for FLP as well as that
between poly-Si gate and HfO2. In other words, FLP
disappears only when the interaction between Si and
HfO2 is weak enough. Further, it is expected that
indirect interaction between Si and HfO2 can induce
FLP. In short, the thermal equilibrium between Vo
formation and annihilation reaction at the Si/HfO2
interface given by the following equation determines
the SBH (FLP position) at pþpoly-Si/HfO2 inter-
face, as shown in Figure 69:
 
ðHfO2 Þ þ Si ! SiO2 þ HfO2 þ Vo 2þ þ 2e ð25Þ
1.04.3.3.4 Correlation between interfaces
It has been reported that SBHs of p-metals decrease
remarkably, revealing FLP behavior when IL is thin,
after high-temperature annealing. However, FLP does
not appear when IL is thick enough (Lee et al., 2006).
This is called ‘Vfb roll-off’. The noticeable fact is that
the energy position of FLP is similar to the pinning
position of pþpoly-Si gates (Hobbs et al., 2003), as
mentioned in previous section. This experimental
fact indicates that FLP of p-metal is also governed
by a mechanism similar to FLP of pþpoly-Si gates
mentioned above (Akasaka et al., 2006).
Now, we consider the mechanism of FLP of
p-metal gates subjected to a high-temperature
treatment. Since usual p-metals are nonreactive
164 Atomic Structures and Electronic Properties of Semiconductor Interfaces

e– transfer O transfer

(a)
Occur Occur
FLP 2+ Poly-Si
Vo
Occur
Very small
p+ poly-Si2 HfO Si sub.

(b)
Not Occur
occur Poly-Si
FLP Vo2+ with
barrier layer
Occur
Very small
p+ poly Barrier HfO2 Si sub.

(c)
Not Not Poly-Si
occur occur with barrier
FLP
relaxation Vo2+ layer and
thick IL
Occur
Very small
p+ poly Barrier HfO2 Si sub.

Figure 68 Schematic illustration of three poly-Si/high-k gate stack structures examined by Kamimuta et al. (2005). (a) Usual
pþpoly-Si gate stack structure. (b) Gate stack structure with barrier layer between a pþpoly-Si gate and a high-k dielectric. (c)
Gate stack structure in which barrier layers are inserted both between a pþpoly-Si gate and a high-k dielectric and between a Si
substrate and a high-k dielectric. Reproduced with permission from Akasaka Y, Nakamura G, Shiraishi K, et al. (2006) Modified
oxygen vacancy induced fermi level pinning model extendable to P-metal pinning. Japanese Journal of Applied Physics 45: L1289.

(a) (b)
Electron Interface
transfer dipole
EC EC
E(Vo) E(Vo)

EV + + E(p+) EV E(p+)
p+poly- HfO2 p+poly- HfO2
Si-gate Si-gate
Interface
dipole Thermal Electron
SiO2 equilibrium SiO2 transfer
Vo Vo annihilation
O transfer – – Vo
EV(HfO2) – –

Pinned (EF = EV = E(p+)) Pinned (another aspect)

Figure 69 Schematic illustration of another understanding of Fermi level pinning (FLP). (a) Vo generation and (b) Vo
annihilation are balanced, and the system reaches thermal equilibrium.

materials, the situation of p-metal/high-k gate
stack can be schematically illustrated as in
Figure 70. O transfer hardly occurs from high-k
dielectrics to p-metals due to low reactivity of
p-metals. However, O transfer is still possible if IL
is thin (Figure 70(a)). Transfer of O from high-k
dielectrics is inhibited when IL is thick enough
(Figure 70(b)). As discussed in Figure 68, the
interface reaction between high-k dielectric and
Si substrate still occurs when IL is thin. Further-
more, reaction with the Si substrate induces
electron transfer from Vos to p-metal gates. A
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 165

(a) e– transfer O transfer

Not
Occur p-Metal
occur
FLP Vo 2+ with thin
IL
Occur
Very small
p-metal HfO2 Si sub.

(b)
Not Occur
FLP occur p-Metal
relaxation Vo2+ with thick
Occur IL
Very small
p-metal HfO2 Si sub.

Figure 70 Schematic illustration of two typical p-metal/high-k gate stack structures. (a) A p-metal/high-k gate stack
structure with thin IL. (b) A p-metal/high-k gate stack structure with thick IL. Reproduced with permission from Akasaka Y,
Nakamura G, Shiraishi K, et al. (2006) Modified oxygen vacancy induced fermi level pinning model extendable to P-metal
pinning. Japanese Journal of Applied Physics 45: L1289.

schematic illustration of this situation is given in
Figure 71. It is noticeable that the net reaction
between high-k dielectrics and the Si substrates is
the same as that between poly-Si gates and high-k
dielectrics, although electron transfer and O trans-
fer directions are opposite to each other. In fact,
the reaction equation with the Si substrate can be
described as
 
ðHfO2 Þ þ Si ! SiO2 þ HfO2 þ Vo 2þ þ 2e
which is the same as in the case of pþpoly-Si gates
described in the previous subsection. According to
Figure 71, the pinning position corresponds to the
energy at which the energy loss (G1) and energy
gain (G2) by electron transfer from Vo in high-k to a
gate metal are canceled by each other (i.e., G1 
G2 ¼ 0). This means that the FLP positions of
p-metal gates are the same as that of the pþpoly-
Si gate, irrespective of the metal species. In fact,
our observed EWFs of p-metals are almost inde-
pendent of metal species, as shown by the C–V
ð26Þ
curves in Figure 72.
It is better to note that the Vo-related mechanism
is not the only cause of Vfb shift. The Vo-related

(a)
Vo
EF Semiconductor
HfO2 (Si)
Metal
Reaction with Si sub. – G1

O SiO2

(b)
Vo
EF elevation Energy gain by Semiconductor
EF
electron transfer G2 (Si)
Metal
Reaction with Si sub. – G1
HfO2
SiO2

Figure 71 Schematic illustration of interface reaction with the Si substrate and subsequent electron transfer from Vo to gate
metals in p-metal/high-k gate stacks. (a) O transfer into the Si substrate through thin IL. (b) Subsequent electron transfer from
a Vo level to a p-metal gate which induces gate Fermi-level elevation.
166 Atomic Structures and Electronic Properties of Semiconductor Interfaces

WF(Ru) = 4.7 eV
FLP can be avoided if the reaction between high-k
WF(TiN) = 4.72 eV
WF(Ir) = 4.63 eV dielectrics and the Si substrate is suppressed. In order
2×10–6 to suppress the corresponding reaction, there are two
possibilities. One is insertion of thick IL, and the other
C (F cm–2)

is the low temperature process. The former one leads

1×10–6
Ru
Ir
TiN 1000 °C spike
0 dielectrics.
–3 –2 –1 0 1
Vg (V)
Figure 72 Observed C–V curves of Ru, Ir, and TiN. The
estimated effective work functions are similar to those of
Fermi-level pinning (FLP) position of the pþpoly-Si gate.
Reproduced with permission from Akasaka Y, Nakamura G,
Shiraishi K, et al. (2006) Modified oxygen vacancy induced
fermi level pinning model extendable to P-metal pinning.
Japanese Journal of Applied Physics 45: L1289.
mechanism determines the final position of FLP. For
example, if other factors such as surface strain (Ikeda
et al., 2006) or MIGSs lower the EWFs of gate metals,
relatively less Vo generation is sufficient to reach the
FLP position. The thermodynamics of the interfacial
reaction between high-k dielectrics and the Si sub-
strates that generates the Vo and Vo-induced interface
dipole determines the final position of FLP, when the
system can reach thermal equilibrium. Accordingly,
the pinning position is independent of the process
condition and the film quality. This is the main con-
cept of ‘oxygen vacancy model’.
As discussed above, FLP of p-metals naturally
occurs if IL is thin, since the reaction between high-k
dielectrics and the Si substrate is inevitable. However,
to a remarkable increase in the effective oxide thick-
ness (EOT). Thus, it is not suitable for use in future
LSI technologies. It is naturally expected that the
latter (a low-temperature process) is a promising
solution to avoid FLP if we use Hf-based high-k gate
2 3 It is also noted that the interface dipole modula-
tion between high-k dielectrics and Si substrates is
also effective, since this modulation does not
change the thermodynamics of interface reactions
that generate O vacancies. In other words, the
relative energy difference between the neutral Vo
level and the FLP position of a gate metal does not
change as a result of this dipole modulation. F
incorporation (Inoue et al., 2005) or counter-doping
effects are categorized in this recipe which modu-
lates the dipole at IL/Si interfaces. It has also been
proposed that Al and La incorporation into Hf-
related oxides can modulate the dipole at high-k/
IL interfaces; this is also included in this recipe
(Iwamoto et al., 2007).
Now, we discuss the experiments that confirm
the validity of the oxygen-vacancy model. After the
high-temperature treatment, which causes FLP of
p-metals, the Si substrate is removed. Next, oxygen
atoms are injected from the substrate side into Hf-
based high-k dielectrics at room-temperature ozone
treatment (Ohta et al., 2006). The schematic illustra-
tion of the experiments is given in Figure 73. The
results obtained are shown in Figure 74. As clearly
shown in this figure, EWF of TiN increases with the

(a) Vo
Semiconductor
EF elevation Energy gain by
EF (Si)
electron transfer G2
Metal
Reaction with Si sub. – G1
HfSiON

(b)
Vo
EF elevation O injection
EF HfSiON by ozone at RT
Metal

Figure 73 Schematic illustration of the experimental procedure that confirms our Vo model. (a) FLP occurs after a high-
temperature treatment. (b) After the removal of Si substrates, ozone is injected into Hf-based high-k dielectrics at room temperature.
 Atomic Structures and Electronic Properties of Semiconductor Interfaces
4.5
4.6
TiN work function (eV)
Ralative
Hf4f position
4.7
On SiO2
4.8
On HfSiON
4.9
0 200 400
UV-O3 oxidation time (s)
Figure 74 Observed TiN effective work function and
relative Hf4f position as functions of UV-ozone oxidation
times. Experiments are based on XPS measurements. From
Ohta A, Miyazaki S, Akasaka Y, et al. (2006) Extended
Abstracts of 2006 International Workshop on Dielectric Thin
Films for Future ULSI Devices – Science and Technology,
p. 61. Kawasaki, Japan, November.
ozone injection time, and it reaches the original
position releasing FLP. Thus, these experimental
results clearly indicate that O deficiency is the
main cause of FLP of TiN. It is also noticeable
that the quantity of the Hf core level shift does not
match the total increase in EWF of TiN. This
means that Vo generation in Hf-related high-k
dielectrics is not the only cause of Fermi level
shift of TiN gates. Other factors also contribute to
the shift of EWF. It is consistent with the oxygen-
vacancy model that the thermodynamics of Vo gen-
eration determines the final position of FLP,
although other factors also contribute to the Vfb
shift (Ohta et al., 2006). As discussed above, the
oxygen-vacancy model can naturally explain the
FLP of p-metals observed when IL is very thin,
and our model is experimentally confirmed.
Finally, we mention a new finding of physics of
Schottky barriers. In the above mechanism of
Schottky barrier formation, SBH at a metal/HfO2
interface is determined by the thermodynamics of
the reaction at the other interface at HfO2/Si, instead
of the corresponding metal/HfO2 interfaces. This is
completely different from the conventional under-
standing of SBH that it is determined by the dipole at
the corresponding interfaces.
167
1.04.4 Future Prospects
0 To conclude this chapter, we mention some of our
self-opinionated prospects for future studies of inter-
Relative Hf 4f position (eV)
faces. Owing to the rapid progress in controlling the
fabrication of organic systems and our keen interest
0.1
in biosystems such as proteins (Oda et al., 2008),
understanding organic interfaces acquires intensive
investigations. The cohesion mechanisms in organic
0.2 semiconductors are quite different from those in
inorganic semiconductors. They mainly consist of
P-conjugated highly covalent bonds, fluctuating
hydrogen bonding, and very weak van der Waals
0.3 interactions. Therefore, when we study the forma-
tion, stability, and electronic properties of organic
600 interfaces, we can expect the need to apply quite
different new physical concepts. For example, it has
been well known that the Schottky barriers at metal/
organic semiconductor interfaces often show time
evolution due to the quasi-equilibrium nature of
interfaces (Ishii et al., 1999). It rapidly becomes
indispensable to investigate what really happens.
Other advances are expected in the field of elec-
tric chemistry, where the liquid/solid interfaces are
the main stages for chemical reactions such as mate-
rial synthesis and decomposition, and catalyst
phenomena. Wetting under the nonequilibrium con-
ditions is also included (Kajita et al., 2007). The
effects of electric field in liquids and the behavior of
water molecules are also keys to understand the
interface (Otani and Sugino, 2006; Akagi, et al.,
2004). Not only the microscopic elucidation of
these interfaces but also the development of universal
pictures of interface reactions are greatly expected.
Next, we discuss a new technique to improve the
Schottky-barrier stability at oxide interfaces. The
key is to use multivalent materials such as Ce. As
discussed previously, excess or deficiency of oxygen
atoms results in an unexpected interface behavior,
such as the instability of SBHs, which can sensitively
depend on the ambient O chemical potential.
Therefore, stabilizing the chemical potential of oxy-
gen throughout the process is the key technology for
obtaining reliable interface properties. It is known
that Ce can take multivalent states of 3þ and 4þ,
with The corresponding Ce oxides Ce2O3 and CeO2,
respectively. If Ce2O3 and CeO2 coexist in a capping
Ce-oxide layer, as shown in Figure 75, the chemical
potential of O can be fixed to the intrinsic value
determined by the following equation, irrespective
of process conditions (Kouda et al., 2009):
168 Atomic Structures and Electronic Properties of Semiconductor Interfaces

Oxygen
chemical Reducing process Oxidizing process
potential
CeO2 Ce2O3 CeO2 Ce2O3
CeO2 Ce2O3 CeO2 Ce2O3
Release Absorb
Vo2+ Vo2+ O
O O 2– O 2–
High-k i High-k i

μo
Stable flat and voltage μo is kept constant
with Ce-oxide capping

CeO2 → Ce2O3 + O Ce2O3 + O → CeO2

o –2e → O
I2– –
V2–
o +O

Figure 75 Schematic illustrations of the recipe for fixing the chemical potential of oxygen during reduction and oxidation
processes by using a capping layer of multivalent oxides. In the reduction process, CeO2 supplies O atoms into the oxide
layer. On the other hand, Ce2O3 absorbs O atoms from the oxide layer in oxidizing ambient. From Kouda M, Umezawa N,
Kakushima K, et al. (2009) Charged defects reduction in gate insulator with multivalent materials. In: Digest of Technical, 2009
Symposium of VLSI Technology, p. 200. Kyoto, Japan, 18 June 2009.

ðOÞ ¼ 2ðCeO2 Þ – ðCe2 O3 Þ ð27Þ schematically illustrated in Figure 76(a) (Sakurai

Actually, by using the multivalent oxide capping
layer technique, we can experimentally succeed in
reducing the O-related charged defects, such as the O
vacancy and interstitials. Multivalent materials have
been studied only as strongly correlated electron
systems in pure physics for a long time. However,
these materials are now expected as key materials to
synthesize stable and reliable oxide interfaces in the
technological world.
Finally, we discuss other examples of our interest:
the interfaces made of two different-dimensional sys-
tems. Electron tunneling through such interfaces, for
example, would provide new interface physics.
Although electron tunneling between different-
dimensional systems commonly occurs in real situa-
tions, there are few reports on this subject. Tunneling
from two-dimensional to zero-dimensional systems is
a typical phenomenon. For example, tunneling cur-
rents through a dielectric barrier via zero-dimensional
quantum-dots (QDs) or defects have been studied
extensively from both scientific and technological
viewpoints (Torii et al., 2004; Meirav et al., 1990;
Takahashi et al., 1996; Austing et al., 1996; Sasaki
et al., 2000). However, the geometrical matching of
wave functions between initial and final states has
not been considered so far, although it should be a
very important factor in tunneling phenomena
between different-dimensional systems, as
et al., 2010). As shown in the figure, electron tunneling
occurs only when the electron wave functions are
sufficiently wave-packet-like just below the zero-
dimensional sites caused by the thermal fluctuation.
Thus, unexpected temperature dependence might
occur in the tunneling phenomena between differ-
ent-dimensional systems, although conventional
direct-tunneling phenomena should lack temperature
dependence.
Sakurai et al. prepared a sample in which sub-10-
nm-diameter Si QDs were weakly coupled to a two-
dimensional electron gas through a 3.5-nm-thick
SiO2 barrier layer. The electron injection currents
from the 2DEG to Si QDs were measured as func-
tions of the gate voltage (VG). Figure 76(b) shows the
observed displacement electron currents as functions
of VG and temperature (T). Surprisingly, the gate
voltages necessary for the electron injection from
the 2DEG to Si QDs had a clear temperature depen-
dence, although the electron injection currents
through a sufficiently thin 3.5-nm SiO2 barrier layer
have conventionally been described using a tempera-
ture-independent direct-tunneling scheme. The
observed gate voltages necessary for the electron
injection markedly changed from 3.7 to 2.2 V as the
temperature increased from 120 to 240 K. This unex-
pected temperature dependence can be qualitatively
reproduced on the basis of the phenomenological
 Atomic Structures and Electronic Properties of Semiconductor Interfaces 169

(a) quantum-point contacts (QPCs), and QDs, has

recently attracted intensive investigations. From
Electron density

z these studies, interesting physics, such as the quanti-

y
zation of conductance, the Coulomb blockade, and
Kondo effects, has been revealed. However, most of
x
these are concerned with steady-state properties and
physical properties of nanoscale systems themselves.
(b) 100 On the other hand, these nanoscale systems are also
interesting from the viewpoint of the interface. In the
80
case of molecular bridges, for example, the molecule
A)

60 is sandwiched and connected to metal electrodes by a

Current (p

40
limited number of atomic bonds. The molecule is
sometimes a zero- or one-dimensional system and
20
has a small number of freedoms, while the electrode
0 is a two- or three-dimensional system and has a
120
larger number of freedoms. Therefore, the contact
e (K)

140
160
between molecule and electrodes is also a typical
eratur

interface between two systems with different

180
dimensions.
Temp

200 Figure 77 shows the transient current behavior of

220 a molecular bridge (or QPC or QD) system. Such an
experiment has become possible recently (Naser
240
et al., 2006). One can see the relaxation of current,
1 2 3 4
which reflects the dissipation of energy and entropy
Gate voltage (V)
(information entropy) from low- to high-dimensional
Figure 76 (a) Schematic illustration of electron tunneling
from a two-dimensional system to a zero-dimensional
system. If the geometrical matching of the electron wave
functions is not satisfied, electron tunneling from a two- Molecular
dimensional to a zero-dimensional system does not occur Step-pulse
bridge
(left). Electron tunneling can occur only when geometrical voltage
matching of the wave functions is achieved (right). (b) 20
Obtained displacement currents (I) measured at different
Left-contact current (a.u.)

temperatures and the temperature dependence of the gate 1

voltage necessary for electron injection obtained by

Electron number
experiments. At each temperature, the gate voltage was
swept with a 10 mV step between 4 and 4 V, 10 v = 0.2
corresponding to the effective gate voltage between 2 and Electrodes
6 V, at a sweep rate of 63 mV s1. Reproduced with 0.1
permission from Sakurai Y, Iwata J, Muraguchi M, et al.
(2010) Temperature dependence of electron tunneling 0
between two dimensional electron gas and Si quantum
dots. Japanese Journal of Applied Physics 49(1): 014001.
v = 0.2
assumption that sufficiently wave-packet-like wave 0.1
functions, which satisfy ‘geometrical matching’ 0
between different-dimensional systems, can contri- 0 20 40 60
bute to electron tunneling of these systems. Time, t (a.u.)
Other interest is concerned with the dynamics at Figure 77 Transient current behavior at nanocontact
the interface made of two different-dimensional sys- molecular bridge (quantum point contact) system.
tems because these systems have different degree of Reproduced with permission from Tomita Y, Ishii H, and
Nakayama T (2009) Transient current behavior through
freedom. As discussed in other chapters in this pub-
molecular bridge systems: Effects of intra-molecule current
lication, electronic transport through nanoscale on quantum relaxation and oscillation. e-Journal of Surface
systems, such as molecular bridges, semiconductor Science and Nanotechnology 7: 606.
170 Atomic Structures and Electronic Properties of Semiconductor Interfaces
systems. This occurs because the energy and entropy
have the general tendency to move from small-free-
dom system to large-freedom system, which
phenomena are often called the friction and the loss
of information in physics. In this way, such interfaces
provide a new stage for studying quantum friction
(Ishii et al., 2008; Tomita et al., 2009), in addition to
the conventional representative friction systems
(Caldeira and Leggett, 1985). On the other hand, we
can also see the oscillation of current in Figure 77.
This occurs due to the quantum motion of electrons
between the molecule and electrode, the period of
which reflects the difference of Fermi energy in the
electrode and the energy level in the molecule. In
other words, we can observe the electronic properties
of the electrode in the current through the molecule.
In this way, not only the electronic properties of the
molecule (or QPC or QD) but also the interaction
between the molecule and the electrode through the
interface becomes important in the dynamics of
nanoscale objects. Another example of such quantum
friction is seen in the attenuation behavior of micro-
scopic molecular vibration (Shigeno and Nakayama,
2007). (See Chapter 1.01).
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vol. 61, pp. 144–261. New York: Academic Press.
 1.05 Integer Quantum Hall Effect
H Aoki, University of Tokyo, Tokyo, Japan
ª 2011 Elsevier B.V. All rights reserved.

1.05.1 Introduction 175

1.05.1.1 2D Electron Gas 176
1.05.1.2 2DEG in Strong Magnetic
Fields – Classical Mechanics 177
1.05.1.3 2DEG in Strong Magnetic Fields – Quantum Mechanics 178
1.05.2 Integer QHE – Experiments 181
1.05.2.1 Materials and Sample Geometry 181
1.05.2.2 Optical Properties 183
1.05.2.3 Other Properties 183
1.05.3 IQHE – Theories 184
1.05.3.1 Localization in Landau Levels 184
1.05.3.2 Linear-Response Theory 186
1.05.3.3 Středa–Widom Formula 188
1.05.3.4 Gauge Argument 188
1.05.3.5 Topological Arguments 189
1.05.4 Localization problem 189
1.05.4.1 Scaling Theory of Localization in 2D Systems 189
1.05.4.2 Quantum Criticality and xx xy Diagram 190
1.05.4.3 Fractal Wave Functions and Dynamical Scaling 192
1.05.5 QHE Edge States and Edge Transport 193
1.05.6 Real-Space Imaging 195
1.05.7 QHE Resistance Standard and the Fine-Structure Constant 196
1.05.8 Breakdown of QHE 197
1.05.9 Quantum-Dot and Periodically Modulated Systems in Strong Magnetic Fields 197
1.05.9.1 Quantum-Dots in Magnetic Fields 197
1.05.9.2 Hofstadter Spectrum 199
1.05.9.3 QHE in Three Dimensions 199
1.05.10 Integer versus Fractional QHEs 200
1.05.11 Recent Developments and Related Phenomena 202
1.05.11.1 QHE in Oxides 202
1.05.11.2 QHE in Graphene 203
1.05.11.3 Anomalous Hall Effect and Spin Hall Effect 206
References 208

1.05.1 Introduction To start with, QHE comes from quantum mechan-

Quantum Hall effect (QHE) is undoubtedly one of
the most fascinating and important phenomena not
only in the semiconductor physics, but, more gen-
erally, in the condensed matter physics. This can be
immediately realized if one notes that the quantum
Hall physics encompasses fundamental physics –
topological phenomenon in terms of the quantum
field theory – down to applicational physics – as
exemplified by the QHE as the resistance standard.
ical physics in two spatial dimensions (2D) as
opposed to the 3D space in which electrons usually
dwell. Surprisingly, 2D is a special dimension in
which there exist phenomena specific to 2D, as
known in field theories, and QHE is the most
remarkable one. In this sense 2D is definitely not
just a reduced dimensionality. This accounts for the
remarkable width and depth of the physics of QHE,
which has now become as large a field as those for
superconductivity/superfluidity.

175
176 Integer Quantum Hall Effect

QHE consists basically of the integer QHE (a)

p - Si
discovered in 1980, which is essentially a one-body Metal SiO2
problem (but see Section 1.05.10), and the fractional
QHE discovered in 1983, which is a many-body
D
effect. Here, we concentrate on the integer QHE.
Even so, the field is so vast that here we shall describe M O S A
the bare essentials.
S
If we just summarize the peculiar properties of the
QHE system,
VG
1. Energy spectrum. A completely discrete, line spec-
trum (i.e., Landau levels) arises in the clean limit, c.b.
which is most unusual, since the system is a bulk.
This gives a starting point for the integer QHE. EF
When an integer number of Landau levels are

Energy
fully filled, then we can regard the system as a
v.b.
giant closed shell.
2. Transport properties. The closed shell is not an
ordinary one, since the quantized Hall conductiv-
ity (integer times e2/h) is given entirely in terms Distance from interface(z)
of physical constants (e : elementary charge,
h : Planck’s constant). (b)

In all these, noncommutative x and y coordinates are

relevant. Namely, in magnetic fields, the position Alx Ga1–x As GaAs
coordinate in real space and the wave number k for
a charged particle are mixed. On top of this, there is a
fortuitous coincidence of the Hall conductivity with Si doped
a topological invariant.

1.05.1.1 2D Electron Gas
As a background we should start with describing
the two-dimensional electron gas (2DEG). The
usual electron gas is a system of electrons that
move more or less freely in a continuous space,
as typically realized in simple metals. In
semiconductor physics, we can realize 2DEG in
metal-oxide-semiconductor field-effect transistors
(MOSFETs; Figure 1(a)) mainly before c. 1970s,
and subsequently QHE is observed primarily in
semiconductor heterostructures (Figure 1(b))
(Ando et al., 1982).
In these structures, electrons are confined to a 2D
plane, due to a Schottky barrier between the metal
and the oxide in an MOSFET, or between different
semiconductors in a heterostructure. There, an elec-
tron moves in the 2D plane, with the electronic
structure of the constituent materials entering only
through the effective mass in the effective-mass
approximation. The wave function has a finite thick-
ness in the direction perpendicular to the plane, but
the motion along this direction is quantized, so that
Electrode
GaAs
AlGaAs c.b.
c.b.
EF
~100Å
Figure 1 Structures of MOSFET (a) and semiconductor
heterostructure (b). In each frame, the upper panel shows
the sample structure, while the lower panel the electronic
band structure around the interface. Typical wave functions
are plotted in black against the direction perpendicular to
the interface.
the band structure comprises 2D electronic bands
associated with the quantized levels in the normal
direction, which are called subbands. When only the
lowest subband is occupied by electrons (or, more
precisely, if the transitions between adjacent subbands
 Integer Quantum Hall Effect 177

can be neglected), we can regard the motion genuinly part. The resulting drift of the center coordinate
2D. The Schrödinger equation reads accounts for the classical Hall effect.
  When the system is disordered, due to, for exam-
1 2
H ¼ p þ U ðzÞ ¼E ð1Þ ple, impurities, then an electron is scattered, and
2m
the drift velocity acquires a component along E
where m is the effective mass of the electron, p is the (Figure 2(b)). If we define the conductivity, the
momentum in the 2D plane (x, y), and U(z) is the quantity is a tensor in the presence of a magnetic
confining (Schottky) potential. If we ignore disorder field, where the current, j, and E are related as
(interface roughness, impurities, etc.), the wave func- 0 1 0 10 1
jx xx xy Ex
tion is expressed as @ A¼@ A@ A
  jy yx yy Ey
¼ exp iðkx x þ ky yÞ fn ðzÞ ð2Þ
0 1 0 10 1 ð3Þ
Ex xx xy jx
up to a normalization constant, where the 2D motion @ A¼@ A@ A
reduces to plane waves and fn is the nth quantized Ey yx yy jy
wave function along z.
In semiconductor heterostructures, typically where m is the conductivity tensor and m the
GaAs/AlGaAs grown with the molecular beam resistivity tensor. They are inverse matrices with
epitaxy (MBE), the Fermi energy is EF  10 meV, each other, so that we have, with xx = yy, yx = -xy,
so that the electron system is a degenerate Fermi 0 1 0 1–1 0 1
xx xy xx xy xx – xy
gas at liquid He temperature (0.4 meV). @ A¼@ A ¼ 1 @ A
yx yy – xy xx 2xx þ 2xy  
xy xx
0 1 0 1
xx xy xx – xy
1.05.1.2 2DEG in Strong Magnetic @ A¼ 1 @ A
Fields – Classical Mechanics 2 þ 2
yx yy xx xy xy xx
If we apply a magnetic field, B, normal to a 2DEG, ð4Þ
classically an electron undergoes a circular motion
If we introduce a phenomenological relaxation
(called Larmor’s motion) due to the Lorentz force,
time,  0, in zero magnetic field to describe the
ev  B (e: elementary charge, v: velocity of the
scattering in a classical transport theory with the
electron). When there is an external electric field, E,
equation of motion given by m(d/dt þ 1/
the classical orbit becomes a trochoid (Figure 2(a)),
 0)v ¼ e(E þ v  B), then we have
where the center of the circular motion drifts in a
direction perpendicular to E with a drift velocity 0
xx ¼
cE  B/B 2 (c: speed of light). 1 þ !2c 02
ð5Þ
This is because the electron is accelerated (decel- 0 !c 0 nec xx
xy ¼ ¼ – þ
erated) when it moves along (against) E, while the 1 þ !2c 02 B !c 0
Lorentz force (_ v) is always balanced with the where 0 ¼ ne2 0/m is the conductivity in the
centrifugal force (_ the radius of the circular absence of magnetic fields, and
motion), so that the trajectory is elongated in the
accelerated part while contracted in the decelerated !c ¼ eB=m c

(a) (b)
z y z y

B B

(X, Y )
x x
Ex Ex

Figure 2 Classical orbits for a charged particle in a magnetic field (k z) in an applied electric field (k x) for a clean system (a)
and in a disordered system with scatterers (crosses) (b).
178 Integer Quantum Hall Effect

(a) (b) H′ (c)

Rxy
S D
S
B Rxx H
S

2D
EG D
S
D y
D
x
Figure 3 (a) Sample geometry for measuring the QHE. (b) Top views of a Hall bar and a Corbino sample, with source (S) and
drain (D) electrodes. (c) Equipotential lines in the QHE condition.

the cyclotron frequency. When !c 0 >>» 1 (which is ,2  

ð; Þ ¼ y ; – x ð7Þ
required for an electron to accomplish the Larmor h
motion between scattering events), the leading term, Here,
xy  nec/B, on the right-hand side of Equation (5)
is the main term (the classical Hall conductivity in rffiffiffiffiffi
ch
the clean case) while the second term a small correc- ,X ð8Þ
eB
tion. Thus, we have a voltage (Hall voltage) in the
direction perpendicular to the electric field when the is the length scale of the cyclotron motion, called the
sample has open boundaries in that direction, or magnetic length, which does not depend on material
we can measure the Hall current if electrodes are parameters and has a typical value of 81 A for the
attached. Figure 3 depicts the sample geometry. magnetic field of 10 T.
Thus, the relative coordinate, (, ), is a quantum
mechanical operator, which implies that the center
coordinate, ðX ;Y Þ ¼ ðx – ð,2 =hÞy ;y þ ð,2 =hÞx Þ;
1.05.1.3 2DEG in Strong Magnetic Fields – is a quantum mechanical operator as well.  From the
Quantum Mechanics standard commutation relation, ½x; px  ¼ y; py ¼ ih,
If we go to quantum mechanics, an electron is still we have commutation relations,
subject to a circular motion in the correspondence ½;  ¼ – i,2 ; ½X ; Y  ¼ i,2 ð9Þ
principle, but now with a quantum mechanical
uncertainty. We should start from a Hamiltonian, namely, x coordinate does not commute with y coor-
dinate, which implies an uncertainty , between
1 2
H 0 ¼  ð6Þ the components of the relative coordinate. The
2m same applies to the center coordinate. This is rather
where the momentum p is now replaced with the unusual, since ordinarily it is the momentum with
canonical momentum p ¼ p þ (e/c)A(r) with A being which the real-space coordinate does not commute.
the vector potential representing the magnetic field Quantum mechanical states can be derived algeb-
B ¼ rot A. raically. For this we first note that the commutation
If we now decompose the cyclotron motion into relations for (X, Y) and (, ) enable us to introduce
the center R X (X, Y) of the circular motion (guiding two sets of harmonic-oscillator operators,
center) and the relative coordinate x X (, ), the
latter is related to the velocity as v ¼ !cêz  x ,   1
a ¼ pffiffiffi x – iy ¼ – pffiffiffi ð þ iÞ
where êz stands for a unit vector normal to the 2D 2h 2,
ð10Þ
plane. The presence of a magnetic field renders a 1
b ¼ pffiffiffi ðX þ iY Þ
skew (i.e., vector product) relation between x and v. 2,
We can now apply the correspondence principle,
where we adopt a quantum mechanical expression, which have bosonic commutation relations,
v ¼ ði=hÞ½H 0 ; r ¼ p=m , for the velocity. This  y  y
means we have x ¼ (c/eB)êz  p, that is, a; a ¼ b; b ¼ 1 ð11Þ
 Integer Quantum Hall Effect 179

Then the one-particle Hamiltonian, H 0 for the where 0 X ch/e ¼ 4  107G cm2 is the flux quantum,
clean system, which is quadratic in p, can be so that n amounts to the number of flux quanta pene-
expressed as trating the unit area. Alternatively, we can say that the

total degeneracy, S2/2,2, is of the order of the number
1
H 0 ¼ h!c a y a þ ð12Þ of cyclotron orbits that cover the sample area S.
2
To see this, we can look at the wave functions. We
in terms of the operator a only, which is natural since first note that the operator b is related

with the orbit
b involving (X, Y) should not appear in a translation- 1
center as X 2 þ Y 2 ¼ 2,2 b y b þ . The formula-
ally invariant system. Since the Hamiltonian has the 2
same form as a linear harmonic oscillator, the energy tion so far does not depend on the gauge (i.e., how
eigenvalues are we fix the vector potential A which has an ambiguity

related with the gauge transformation). The wave
1 function does depend on the gauge. Let us adopt
EN ¼ h!c N þ ; N ¼ 0; 1; 2; . . . ð13Þ
2 1
the symmetric gauge, A ¼ B  r. This amounts to
where N is called the Landau index. 2
So we have here a truly abnormal situation where taking, out of the degenerate wave functions, the set
the energy spectrum, despite the system being a bulk, that diagonalizes, simultaneously with the energy, the
is completely discrete (Figure 4(a)). In 3D systems angular momentum, L ¼ r  p, which is along z when
we do have Landau’s quantization, but the extra the motion is within the (x,y) plane. We can show that
motion along B makes the density of states a con- L̂z ¼ ½r  ðp – ðe=cÞAz ¼ a y a – b y b ð16Þ
tinuum (Figure 4(a)). In 2D each level, called the
Landau level as labeled by Landau index, has then a with h = 1. For the N ¼ 0 Landau level we have a
macroscopic degeneracy. The degeneracy can be harmonic-oscillator form for Lˆz ¼ byb, so that the
estimated by noting that the density of states of a eigenfunction having the eigenvalue of Lz ¼ m is
2DEG, which is a constant, DðE Þ ¼ m =2h2 per unit given by
 y m
area, integrated over an interval h!c should corre- b
spond to the degeneracy per unit area: jmi ¼ pffiffiffi j0i; m ¼ 0;1;2; . . .
m!
where j0i is the vacuum of boson b. If we go to the
n ¼ h!c DðEÞ ¼ 1=ð2,2 Þ ð14Þ
first-quantized form the wave function is expressed,
This number can be expressed as in polar coordinates (r,
), as
  jmj
n ¼ B= 0 ð15Þ Nm ðrÞ_ exp – im
– r 2 =4,2 r m LN ðr 2 =2,2 Þ ð17Þ

(a) (b)

3D

2
Density of states

0
0
2D
1
N=0 1 2

hωc
0 N=0
0 1 3 5 7 9
2
hωc 2
hωc 2
hωc 2
hωc 2
hωc
E
Figure 4 (a) Density of states for a clean system in the absence (dashed lines) and in the presence (solid lines) of a magnetic
field in two-dimensional (lower panel) or in three-dimensional (upper) systems. (b) Wave functions for a 2D system for various
values of the Landau index N.
180 Integer Quantum Hall Effect
ðmÞ
where LN ðzÞ is associated Laguerre polynomial.
They are depicted in Figure 4(b). By restricting the
radius R of these wave functions within a radius of a
disk, we recover the degeneracy of a Landau level.
In terms of the degeneracy, we can now define the
Landau level filling factor, that is, the fraction of the
occupied states for a given Landau level. If we denote
the density of electrons by ne, the Landau level filling
factor is
 X ne =n ¼ 2,2 ne ð18Þ
In other words, 1/ is the number of flux quanta
per electron. This is the essence of Landau’s quantiza-
tion, formulated by Landau in 1930, and the discovery
of the QHE in 1980 coincided with its half centenary.
When only the lowest (or lowest few) Landau
level(s) are occupied (i.e.,  . 1) for strong enough
magnetic fields, the situation is called the quantum
limit. For GaAs with a typical density of electrons
n  1011 cm2, we have
4  
¼  n 1011 cm – 2
B ðTÞ
where B is in units of tesla and ne in 1011 cm2, so that
the quantum limit is realized for B & 4 T.
So far we have considered a clean system. In
the presence of disorder, such as a random potential
V(r) arising from impurities and interface roughness,
cyclotron orbits that have different center coordinates
(X, Y) are no longer degenerate, but are subject to
scattering. Then the equation of motion for (X, Y)
may be obtained from its commutator with H as
i ,2 qV
X_ ¼ ½V ;X  ¼
h h qy
ð19Þ
i ,2 qV
Y_ ¼ ½V ;Y  ¼ –
h h qx
The fact that R_ _ êz  rV implies that R X (X,Y)
moves, classically, along equipotential contours
with a velocity proportional to jrVj. Quantum
mechanically, however, the Hamiltonian, with the
Landau wave functions as a basis, reads
X 1
y
H ¼ N þ h!c cNX cNX
NM X
2 h!c ¼ 0:12 B ðTÞðm0 =m ÞmeV
y pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
þ hNX jV jN 9X 9icNX cN 9X 9 ð20Þ
NXN 9X 9
mechanical hopping between cyclotron orbits at dif-
ferent positions. The hopping matrix element
hNXjVjN9X9i becomes large when the random poten-
tial varies rapidly in space (on the magnetic length
scale, Equation (8), since each function jNXi has a
spatial extension ,).
In the presence of the hopping, each Landau level
is broadened from the line spectrum. Electronic
structure and transport properties of the disordered,
Landau-quantized systems in 2D were theoretically
studied with the self-consistent Born approximation
in the 1970s by Uemura, Ando and co-workers
(Ando et al., 1974, 1974b, 1982). In this approxima-
tion, the lifetime of an electronic state due to disorder
is taken into account in a self-consistent way, which
is imperative, since the unperturbed system has
anomalous, delta-function spectra. Let us assume
that the random potential V(r) ¼ i 2,2V0(r  ri)
is expressed as a sum of the contributions from short-
range (delta-function like) impurity potentials at
position ri, with the average number of impurities
per unit area ni. For dense impurities (to be more
precise, for the dimensionless concentration ci X 2
,2ni  1), we can adopt the Born approximation.
There, the self-energy due to the impurity scattering
is ðEÞ ¼ ci V02 GðEÞ, where the self-consistency
demands that Green’s function, G(E), contains the
effect of (E). Then each Landau level is broadened
pffiffiffi
with a width,  ¼ 2 ci V0 :
In other words, the ratio between the Landau-
level broadening  and the cyclotron energy is
=ðh!c Þ  1=ð!c 0 Þ1=2 ð21Þ
where 0 ¼ ðni V02 m =h3 Þ – 1
is the scattering relaxation
time due to the disorder in zero magnetic field.
Intuitively, the quantity !c 0 gives a measure of
how many times an electron can rotate on a cyclotron
orbit between scattering events on average. For
sufficiently larger magnetic field and/or smaller
disorder we have =h!c < 1 ðor !c 0 > 1Þ, for
which Landau levels are separated, while Landau
levels are merged in the opposite condition. To
give an idea about the magnitudes of relevant quan-
tities, we have
  0:15 B ðTÞ=

where cyNXcreates an electron in the Landau’s wave where B is measured in units of tesla, the effective
function jNXi (here in the Landau gauge (A ¼ (0, Bx)) mass m ¼ 0.067m0 (m0: bare mass of an electron) for
rather than in the symmetric gauge), and the second GaAs and  ¼ e 0/m is the carrier mobility here
term on the right-hand side represents the quantum measured in units of 104 cm2 V1 s1.

1.05.2 Integer QHE – Experiments
The Landau quantization in 2DEG described above
is reflected in various properties, especially in trans-
port properties. There are prehistories for the the
QHE physics that are precursors of the discovery.
As early as in the 1960s, Shubnikov de Haas effects
were observed in Si-MOSFETs by Landwehr’s
group, and by groups in US and in Japan.
Shubnikov de Haas effect is an oscillatory (in B)
transport phenomenon that generally occurs in mag-
netic fields, but the effect in 2DEG is peculiar, since
the oscillations in xx and xy reflect the line-like
spectrum Landau levels. In the 1970s more elaborate
experimental studies did exhibit oscillatory beha-
viors indicative of Landau levels in 2D. Figure 5
shows a typical example (Igarashi et al., 1975;
Kawaji and Wakabayashi, 1981; Kawaji, 2008), along
with a theoretical result. It was also recognized that
there are regions of vanishing xx and flat xy
between Landau levels, which were called plateaux.
In 1980, von Klitzing, Dorda, and Pepper found an
astonishing behavior in the Hall conductivity as
shown in Figure 6 (von Klitzing et al., 1980). In a
Si-MOSFET in strong magnetic fields, the heights of
nec
10
H
Experiment
Theory
8
σxx , –σxy (10–4Ω –1)
6 AlGaAs, which include 2D hole (as opposed to
4 and 2D hole gases coexist side by side, and Si/
5
3 band structure and higher effective mass than those
4 σxx
2 in Si MOSFETs.
N=2
1 bar geometry and Corbino geometry (Figure 3(b)).
0 The former is usually adopted with a multiterminal
0
0 20 40
VG(V)
Figure 5 A typical experimental result (solid lines) along
with a theoretical result (dashed lines) for xx and xy against
VG (see Figure 1) which is roughly _ n in a MOSFET sample.
From T. Igarashi, J. Wakabayashi and S. Kawaji, Suppl.
Progr. Theoret. phys. 57, 176 (1975).
Integer Quantum Hall Effect 181
the Hall resistance Rxy are quantized very accurately
into integer multiples of h/e2 ¼ 25 813, or when
translated to the Hall conductivity as
e2
xy ¼ – N ; N ¼ integer ð22Þ
h
Astonishing, because (1) the quantized value only
contains the fundamental physical constants, the
elementary charge e and Planck’s constant h (whereas
ordinarily transport properties are naturally affected
by various material parameters, etc.), and (2) this
occurs in disordered systems. This has become
known as the quantum Hall effect. A few years after
this discovery the fractional QHE was discovered, so
the original effect is sometimes called the integer
quantum Hall effect (IQHE). Remarkably, the accu-
racy of the quantization is experimentally confirmed
to be better than 107. Hall effect was discovered
by Edwin Hall in 1879, so it was almost exactly a
century later when the remarkable Hall effect was
discovered. Subsequently, experimental data were
refined, where the quantum Hall steps are almost a
series of step functions, as typically shown in
Figure 7, which were then interpreted in terms of
the localization, as we shall see in the section on
localization.
–σxy
1.05.2.1 Materials and Sample Geometry
Historically, the IQHE was discovered in Si-
MOSFETs, but subsequently studied for 2DEGs in
semiconductor heterostructures, typically GaAs/
AlGaAs (Figure 1). Integer QHE has also been
observed in heterostructures other than GaAs/
7 electron) gas systems in p-type GaAs, type III het-
6 erostructures such as GaSb–InAs where 2D electron
Si1xGex strained heterostructures with different
There are basically two sample geometries – Hall
60 80 geometry. In the latter, where electrodes are attached
to the inner and outer perimeters of an annular
sample, an advantage is that we do not have to
worry about the sample edges and edge transports,
nor do we need to worry about hot spots
(Figure 3(c)); see the Section 1.05.6. Namely, in the
QHE condition (xy : integer  e2/h, xx ¼ 0 with the
182 Integer Quantum Hall Effect

Rxx /Ω
400

200

0
23.0 23.5 24.0 24.5
UH/mV Uxx/mV VG/V

RH /Ω
6500

25 2.5
6400
B = 13.0 T
T = 1.8 K
6300
20 2.0
6200
23.0 23.5 24.0 24.5
VG/V

15 1.5

Uxx
10 1.0

5 0.5
UH

0
0 5 10 15 20 25
N= 0 N= 1 N= 2
VG/V

Figure 6 The original QHE result. For the Hall (UH) and longitudinal (Uxx) voltages against the gate voltage VG. Inset shows the
detail around the fully occupied N = 0 Landau level. Reprinted figure with permission from K. von Klitzing, G. Dorda and M. Pepper,
Physical Review Letters 45, 494 (1980). Copyright 2010 by the American Physical Society. For information, see: http://link.aps.org/

14 000

12 000 GaAs-AlxGa1–xAs
T = 50 mK
10 000

8000
ρxy (Ω)

6000

4000

2000

300

5
200 6 3
ρxx (Ω)

7 4 2
100
N=1
2 1
0
0 20 40 60 80
B (kG)
Figure 7 A typical result for IQHE in GaAs-AlxGa1  xAs. Reprinted figure with permission from M. A. Paalanen et al., Physical
Review B 25, 5566 (1982). Copyright 2010 by the American Physical Society. For information, see: http://link.aps.org/
 Integer Quantum Hall Effect 183

Hall angle (¼ tan1 xy/xx) of 90 ), the Hall current

flows around the annulus. QHE has also been
observed in Corbino geometry. In fact, some of the
early Shubnikov de Haas experiments were done for
this geometry.
An electron has a spin 1/2, and the associated
Cyclotron absorption
Zeeman energy in a magnetic field. The Zeeman
energy is much smaller than the cyclotron energy
in usual experimental situations (although quan-
EF
titatively the spin splitting is enhanced due to

Energy
exchange interactions), so that every Landau level
is almost twofold spin-degenerated. Later, the
effects of the spin splitting on QHE have been ela-
borated with various experimental techniques. In the
case of Si-MOSFET, a valley degeneracy also exists,
since the bulk Si has multiple valleys in the band Inelastic light
structure. scattering
~ Luminescence

1.05.2.2 Optical Properties

QHE systems exhibit characteristic optical pro-
perties as well. Optical measurements have an
advantage that (1) they are a contactless method
and (2) we can probe both luminescence and absorp-
tion. In the QHE regime luminescence spectra have
been obtained for Si MOSFETs and semiconductor
heterostructures. The luminescence spectra, which
measure the radiative recombination of 2D elec-
trons with photoexcited holes, basically reflect the
Landau-level structure. One feature is that the
Landau-level width as deduced from the width of
the luminescence spectra oscillates with magnetic
field with a maximum every time a Landau level
is filled. This is associated with the screening
which becomes effective when the Landau levels
are partially filled (i.e., an open shell). There
are other properties such as spin-dependent
relaxation.
Cyclotron absorption is another important experi-
mental technique in the QHE regime. The technique
can probe lower carrier density regions than in trans-
port measurements. Landau-level structures have
been obtained, where oscillatory linewidths, spin
splitting, nonparabolicity effects, etc, have been
observed. Inelastic light scattering is another power-
ful optical method that compliments luminescence.
These methods are schematically illustrated in
Figure 8.
Most recently, the optical Hall conductivity
xy(!) is theoretically predicted to have a Hall pla-
teau structure in the THz regime in quantum Hall
systems. Although the plateau height is no longer
~
Density of states
Figure 8 Various optical processes are schematically
shown.
quantized in ac, the structure remains robut against
disorder reflecting the localization in QHE regime.
The effect has subsequently been experimentally
detected with Faraday rotation, with its magnitude
characterized by the fine-structure constant
(Ikebe et al, 2010).
1.05.2.3 Other Properties
There are host of other properties that have been
measured. One is the electronic specific heat, which
probes the Landau quantization through the density
of states (that include both localized and delocalized
states), while transport measurements mainly probe
the delocalized states. Another method to probe
the density of states is the magnetocapacitance
(Figure 9). Magnetization has also been measured,
with torque magnetometers or micromechanical
cantilevers, where jumps are observed as EF traverses
the Landau levels (Figure 10).
Various other properties have been experimen-
tally studied, among which is the thermoelectric
184 Integer Quantum Hall Effect

Filling factor
14 12 10 8

200

Capacitance (pF)

180

1.0 1.4 1.8 2.2

Magnetic field (T)
Figure 9 Experimental (solid line) and theoretical (dashed) results for the capacitance against magnetic field. Landau-level
filling is indicated on the upper axis. Reprinted figure with permission from T. P. Smith et al., Physical Review B 32, 2696
(1985). Copyright 2010 by the American Physical Society. For information, see: http://link.aps.org/

Filling factor flow (or a temperature gradient) that is perpendicular

87 6 5 4 3 2 to both the electric current and the magnetic field,
known as the Nernst–Ettingshausen effect. Namely,
the electric field E and the temperature gradient rT
are related as E ¼ S rT. Here, S is the thermopower
tensor, where Sxx corresponds to the thermopower,
while Sxy to the Nernst–Ettingshausen coefficient
(Figure 11) (Fletcher, 1999). The Ettingshausen
ΔT, Hall resistivity (a.u.)

effect has been studied both theoretically and experi-

mentally in conjunction with the breakdown of QHE
as probed by the temperature change rT, in the
heat-pulse method.
ρxy

1.05.3 IQHE – Theories

0 1 2 3 4 5
Magnetic field (T)
Figure 10 Experimental (thick line) and theoretical (thin)
results for the magnetization, along with xy against
magnetic field. From E. Gornik et al., Physical Review
Letters 54, 1820 (1985).
effect, which probes how the electrons sustain tem-
perature gradients in 2DEGs, where the dominant
mechanism for the thermopower is phonon drag.
Another magneto-thermoelectric effect is a heat
1.05.3.1 Localization in Landau Levels
Let us start with the localization problem in the QHE
system, since this has to do with a first essential
question about the integer QHE – the presence of
6 7 8 plateaux in xy plotted against the density of elec-
trons n (or vs. B _ 1/ for a fixed n). Experimentally,
the plateau in xy goes hand in hand with a region of
vanishing xx. This is an interesting situation, since,
usually xy should be an increasing function of n and
xx as a function of n should not be zero (even when
there is a gap in the density of states).
This has been explained from the Anderson locali-
zation of the wave functions in the Landau levels that
arises from disorder in the system. The Anderson
localization was proposed back in 1958 for general
 Integer Quantum Hall Effect 185

50
40 –Sxx

Thermopower (μVK–1)
30
20
10
0
–10
–Sxy
–20
–30
–40
0.0 1.0 2.0 3.0 4.0
Chemical potential
Figure 11 A typical theoretical result for the diagonal (Sxx) and off-diagonal (Sxy) components of the thermopower tensor
against chemical potential. Reprinted figure with permission from M. Jonson and S. M. Girvin, Physical Review B 29, 1939
(1984). Copyright 2010 by the American Physical Society. For information, see: http://link.aps.org/

electron systems in the presence of disorder, and was
subsequently culminated as the scaling theory of loca-
lization in 1979. In a clean crystal, every wave function
is a Bloch state that extends over the entire sample. In a
disordered system, wave functions can be spatially
localized, whose spatial extension is characterized by
the localization length that depends on energy. In the
presence of magnetic fields, the Anderson localization
was suggested to occur as well for wave functions in
the Landau levels in the 1970s (Figure 12). For ran-
dom potentials slowly varying in space, an electron
follows, semiclassically, an orbit that is an
equipotential contour as we have shown above.
Quantum mechanically, however, an electron tunnel
between these orbits even for a slowly varying poten-
tial, while the quantum mechanical hopping becomes
more frequent for rapidly varying (i.e., short-ranged)
random potentials (see Figure 13). So the localization
is a quantum mechanical effect. Then plateaux in xy
and regions of vanishing xx have been suggested to
come from the localization. A peculiarity in the loca-
lization in the QHE system is that the disorder has a
dual role: disorder causes the localization on the one
hand, but it gives rise to quantum mechanical hopping

(a)
ψ
| |2 y

x
(b)

Localization length
(c)
D(E )

(d)
E

a bc d e
(e)

Figure 12 Typical wave functions in a disordered QHE system obtained in a computer simulation for various eigenenergies
as indicated on the right panel, which shows the density of states and the localization length against energy. From H. Aoki,
Journal of Physics C 10, 2583 (1977).
186 Integer Quantum Hall Effect

(a) (b)

l (c)

Figure 13 A random potential rapidly varying as compared with the magnetic length l (left panel) and a slowly varying one
(rigth) are schematically shown. (c) A typical contour plot with shaded areas indicating negative energies and thick lines E ¼ 0
contour. From H. Aoki, Reports on Progress in Physics 50, 655 (1987).

Z Z 
of cyclotron guiding centers to contribute to transport 1 1
at the same time, as pointed out by Aoki and Here hhAB ii X dt expð – t Þ dhAð – ihÞ
L2 0 0
Kamimura (1989). Bðt Þi; where hi is the canonical ensemble average
plus the average over disorder,  ¼ 1/kBT,  a
positive infinitesimal, and A(t) the Heisenberg repre-
1.05.3.2 Linear-Response Theory sentation of A.
The most standard method to treat conductivities xy is expressed as a combination
microscopically is the linear-response theory, or hhY_ X_ iihhX_ Y_ ii for the following reason. For the
the Kubo formula. Aoki and Ando (1981, 1993) have conductivity tensor in a magnetic field B, Onsager’s
applied this to the QHE problem. While the plateaux reciprocal theorem dictates that
in xy and vanishing regions in xx are explained by  ðBÞ ¼  ð – B Þ
the localization, the puzzle remains as to why the
value of the plateaux in disordered systems is quan- so that we can decompose  into the symmetric part
tized into the universal e2/h, which is originally the s and the antisymmetric part a. Then the current j
value for the clean 2DEG with just an integer is expressed as
X
Landau-level filling. In other words, if a disorder j ¼ s E þ axy ðE  êz Þ ð25Þ
makes xx zero, why does the disorder allow xy to 
stick to the quantized value. where the part of the current (i.e., the Hall current)
In the linear-response theory, the conductivity is that is induced by the magnetic field and is perpen-
given by a current–current correlation function. In dicular to the applied electric field E is related to a
the QHE system, the current has to do with the (Landau et al., 1984).
dynamics of the cyclotron guiding center (X, Y), The linear-response formula may be written in
which is subject to quantum mechanical hopping. terms of Green’s function as
The conductivities, both longitudinal and Hall, are Z 1
e 2 h
given as correlation functions of X_ and Y_ as xy ¼ dEf ðEÞ
iL2 –1
  * " #+
xx ¼ e 2 X_ X_ q  
 Tr X_ ReGðEÞY_ ImGðEÞ – X_ $ Y_
ne ð23Þ qE
xy ¼ – þ xy
B ð26Þ
–1
e  _ _   _ _ 
2
where G ðE Þ ¼ ðE – H þ iÞ is the Green’s
xy ¼ YX – XY ð24Þ
2 function, f(E) ¼ [e(E  m) þ 1]1 is the Fermi’s
 Integer Quantum Hall Effect 187

distribution function, and $ denotes the term with X_ implies that, (ii) at least in the limit of strong magnetic
and Y_ exchanged. In this expression, the Hall con- fields all the states cannot be localized, otherwise xy
ductivity xy is contributed by all the states below EF, would be zero over the whole region. This is impor-
unlike xx that is related to an energy-dissipating tant, since, according to the scaling theory of
process around EF. In terms of the eigenstates of the localization all the states are localized in two dimen-
Hamiltonian, the Hall conductivity is expressed as sions. The only way to go around this universal
! argument is to go to another universality class, either
ihe 2 X f ð" Þ – f ð" Þ jx jy – jy jx
   
to the unitary class (e.g., systems in magnetic fields
xy ð!Þ ¼ 2 ð27Þ
L 6¼ " – " " – " þ i where the time-reversal symmetry is broken) or to the
symplectic class (e.g., systems that have spin–orbit
where " is -th eigenenergy, and j  the current interactions). QHE system belongs to the unitary
matrix elements between the eigenstates. class, which is why delocalized states are allowed to
From this formalism, we can show, in the presence exist, which in turn makes the QHE to be realized.
of localization arising from disorder, that (i) the Hall The theoretical picture explained here for broadend
conductivity xy should be rigorously flat (at T ¼ 0) Landau levels, xx and xy are summarized in
as a function of the density n of electrons in the Figure 15.
region where the states are localized. This accounts As we shall see below, the quantization of xy into
for the flatness of plateaux in the QHE, as depicted in e2/h can be shown for finite magnetic fields, where the
Figure 14. required condition is EF being in a gap in the density
We can also show that the quantized xy ¼ Ne2/h
of states or in a localized regime (mobility gap). Even
in a plateau should hold in the limit of strong magnetic
in the treatment above, however, different Landau
fields where adjacent Landau levels are well separated
levels are not treated as being completely indepen-
and when EF is in the gap between them. This in turn
dent. As seen from the fact that the Landau’s
quantization is formally equivalent to a 1D harmonic
oscillator, the current operator has matrix elements
Density of states

N=0 N=1 N=2

D(E)

Inverse loc
length

0
σxx

σxx

0 0
3
e 2 = ntotalec
–σxy(e 2/h)

h H nec 2
H
–σxy

0
0 1
2πl 2n
Figure 14 Theoretical density of states D(E) (with shaded
areas indicating the localized states), the longitudinal
conductivity xx, and the Hall conductivity xy are
schematically plotted against the Landau-level filling 2,2n.
The horizontal dashed line indicates how the quantized
value is achieved despite the presence of localization.
0
0 1 2 3
E/hωc
Figure 15 Theoretical density of states (with shaded
areas indicating the localized states) along with the inverse
localization length, xx, and xy are schematically plotted
against energy for a series of Landau levels. Each white
region representing the delocalized states actually has zero
width in the thermodynamic limit at T ¼ 0. From H. Aoki and
T. Ando, Solid State Communications 38, 1079 (1981).
188 Integer Quantum Hall Effect

between N and N 1 levels, so the mixing between
them is implicitly included (in fact, the treatment in
terms of the guiding center (X, Y) corresponds to
taking this mixing to the leading order).
It may first seem counterintuitive that xy attains
the quantized value despite the presence of localized
¼ /2r (in cylindrical coordinates), the flux exerts
states. Physically, we can say the following. From the
equation of motion for the guiding center the Hall
current jx in an electric field Ey is given as
) ! exp[i(/ 0)
], on the wave function , where
X 
delocalized
jx ¼ – ð1=B Þ h
9jqV =qy j
9i þ eEy
9
P original periodic boundary condition every time
There is a kind of sum rule, all
9 h
9jV =qy j
9i ¼ 0;  increases by 0 in a time interval t. When
which means that delocalized states move faster to
just compensate the localized states, which has been
confirmed numerically and field theoretically as well.
1.05.3.3 Středa–Widom Formula
As another formalism for the Hall conductivity,
Středa’s formula (Středa, 1982) is also often evoked.
He showed that the Kubo formula for the Hall con-
ductivity can be decomposed into a form,
xy ¼ Ixy þ IIxy ; where Ixy is the Drude-like part
that tends to Ixy ! – !c 0 xx in the relaxation time
picture. The second term is expressed as
 
qN ðEÞ
IIxy ¼ ec
qB E¼EF
where N(E) is the integrated density of states. When
the Fermi energy EF is in an energy gap, Ixy
vanishes, while we can show that IIxy ¼ – ðe 2=hÞN
when EF is in a gap between the Nth and (N þ 1)th
Landau levels. Thermodynamically, we have the
in which a QHE system is wound into a cylinder (but
the magnetic field is still applied perpendicular to
every point on the cylinder), as in Figure 16. To this
we add a magnetic flux  (due to, say, a solenoid) that
pierces the cylinder. Through its vector potential,
A
an Aharonov–Bohm effect on the electrons. We can
eliminate the vector potential with a gauge transforma-
tion at the cost of the boundary condition twisted to
(
 0 ¼ eh/e is the flux quantum.
If we increase  with time, we recover the
the Fermi energy EF is in a gap in the density
of states or in the energy region for localized states
(as described in the previous section), the occupa-
tion of electrons must be the same when we make
 !  þ 0. The only change, then, should be a
transfer of an integer (M) number of electrons from
one electrode to another, which we assume to be
attached to either edge of the cylinder as Hall
probes. From the Maxwell equation, an electric
field LEy ¼ (1/c)q/qt is induced along the cylin-
der of circumference L, which should result in a
Hall current, jx ¼ (e)M/(Lt) ¼ (Me2/h)Ey,
and we have xy ¼ Me2/h. So the derivation
applies arbitrary strength of the magnetic field as
ð28Þ far as the Fermi energy EF is in a gap in the density
of states, or in the energy region for localized
states.
electric field, E ¼ r(m/e) with  being the electro-
chemical potential, so that the Hall current
jH ¼ cr  M with M being the magnetization can
be expressed as jH ¼ ecE  (qM/q). If we use,
following Widom, the thermodynamic Maxwell’s Φ
relation, qM/q ¼ qN/qB, which comes straight B
from M ¼ q/qB with the grand potential , we
Hall
recover the formula for IIxy (Widom, 1982). Note current
that the Středa–Widom formula is applicable to the
situation where the spectrum has an energy gap.

1.05.3.4 Gauge Argument

As a transparent approach to QHE, Laughlin has pro- V
posed an argument based on a gauge transformation
(Laughlin, 1981). Consider a Gedanken-experiment, Figure 16 Geometry considered by Laughlin.
 Integer Quantum Hall Effect 189

1.05.3.5 Topological Arguments Alternatively, we can express the linear-response

Hall conductivity in terms of Green’s function G as
In Laughlin’s argument we have introduced a mag-
netic flux, but subsequently it has been shown that we   Z ZZ 0 =L
can go even further to express the Hall conductivity as xy 1
¼ dz dAx Ay
a topological invariant, which guarantees the quanti- e 2 =h 82 C 0
" # ð30Þ
zation in a mathematically rigorous manner. Namely, qG – 1 qG – 1 qG – 1
Tr G G G – ðx $ yÞ
Thouless et al. (1982) have considered, for a QHE qAx qAy qz
system periodic in both x and y directions, the twisted
boundary condition for both x and y directions, which
When EF is in a localized regime, we can close the
corresponds to introducing a vector potential, A ¼ (Ax,
contour C on the plane of complex energy z, and the
Ay), describing fictitious fluxes. Then the Hall con-
above expression coincides with another topological
ductivity averaged over (Ax, Ay) reads invariant (Pontrjagin number). This expression
reduces, for a fixed number of electrons, to the for-
  occup Z Z  

xy 1 X qu qu qu qu mula by Thouless et al. if we note j ¼ qH =qA.

¼ j – j dAx dAy
2
e =h 2i
qAx qAy qAy qAx For clean systems, the topological expression indi-
Z cates that the Hall conductivity, for arbitrary strength of
e2 dk X B, is quantized topologically when EF is in a gap of the
¼ –i f ð"
k Þ½rk  h
kjrk j
kiz
L2 ð2Þ2
density of states. For disordered systems, the topological
expression indicates that the Hall conductivity is quan-
e2 X (29)
¼ C
tized when EF is in the energy region of localized states,
h

since in that case A-averaged xy is equal to the unaver-
ð29Þ aged one. In reality, xy is a smooth function (rather
In the first line u
is the
th eigenfunction and than a step function) of energy for finite systems or at a
the summation is over the occupied states, while in finite T, and this may seem contradictory to the topo-
the second line L the sample size, f the Fermi distribu- logical argument. However, we can show that, even
tion function, "
k the energy of the Bloch wave though xy for each of disordered samples is individu-
function j
ki in the
th band, and rk is the gradient ally quantized, the quantity becomes a smooth function
with respect to k. The expression coincides with a of energy after the ensemble average over randomness
topological invariant C
(that always takes integer (which corresponds to the observable quantity), and the
values) known as the first Chern character in the differ- latter tends to the xy (not integrated over A) in the
entialgeometry.
 R This is seen if we rewrite the formula thermodynamic limit (Aoki and Ando, 1986).
as xy _ dkrk  A
ðkÞ, where A
ðkÞX – i Field theoretically, we can introduce a topological
h
kjrk j
ki is a fictitious gauge potential. So the term (as in the
term in the Yang–Mills field theory)
Hall conductivity (in units of e2/h) is just the topological in the Lagrangian in the nonlinear  model for
invariant. The reason why a differential geometry is the QHE system (Pruisken, 1990). Topological phe-
relevant is that the wave function in 2DEG in a mag- nomena abound in condensed-matter physics, as
netic field has such a property that different wave exemplified by vortices in superfluids and fluxoids in
functions arise between the cases when we adiabatically superconductors, but QHE thus forms an important
change (Ax, Ay) as ! (Ax þ Ax, Ay) ! (Ax þ Ax, and distinct class in the topological phenomena, which
Ay þ Ay) and as ! (Ax, Ay þ Ay) ! (Ax þ Ax, has spinoffs in the physics of topological insulator, etc.
Ay þ Ay). The difference is related to the phase of the
wave function, which is a kind of Berry’s phase that
generally arises when a quantum system is subject to an
adiabatic change. When a vector (to which a wave 1.05.4 Localization problem
function belongs in a Hilbert space) ends up with
1.05.4.1 Scaling Theory of Localization in
different vectors for different parallel transports, we
2D Systems
say the space in which the vectors reside is curved.
The integrand in the expression for the Hall conduc- As we have seen, the integer QHE is intimately related
tivity happens to represent the curvature (Berry’s with the localization problem. We have also mentioned
curvature here), and Euler’s theorem dictates that the that the system falls upon an interesting universality
curvature integrated over the surface is an integer. class of the unitary class in 2D. Details of the
190 Integer Quantum Hall Effect
localization (which is a nonperturbative problem) have
been extensively studied with numerical methods and
field theoretical methods. Figure 12 shows typical
behaviour, obtained numerically, of the wave function
along with the localization length versus energy, which
shows that the localization is strong toward the edges of
a Landau level and the weakest at the center.
Classically, this corresponds to the fact that contours
of a random potential, along which the cyclotron guid-
ing center drifts in the semiclassical picture, are valleys
(hills) for energies well below (above) the level center,
while the contours tend to percolating paths for ener-
gies close to the center. However, the localization is
quantum mechanical phenomenon related with inter-
ference of wave functions.
If we look at the behavior of the localization length
in a numerical method (finite-size scaling for the
Thouless number), the localization length, although a
smooth function of E, exhibits a rather singular beha-
vior, in which the inverse localization length becomes
zero only at the level center (i.e., extended states only
occur there), as schematically shown in Figure 15.
The delocalized states, marginally allowed to appear
in the presence of magnetic fields in two dimensions,
thus coalesce into a single point E0 (the center of each
Landau level) on the energy axis. The localization
length, denoted here as , behaves around this point as
1=jE – E0 js ð31Þ
where s (numerically shown to be & 2) is the localiza-
tion critical exponent (Aoki and Ando, 1985; Ando
and Aoki, 1985). This value may be compared with
the exponent s ¼ 7/3 for the percolation problem.
The effect of quantum mechanical tunneling has
also been extensively studied in terms of a network
model due to Chalker and Coddington, who have
modeled the quantum mechanical tunneling across
the paths (see Figure 13(c)), (Chalker and
Coddington, 1988; Kramer et al., 2005).
The critical exponent s has also been shown to
depend on the Landau level (e.g., larger for N ¼ 1
than for N ¼ 0). A mapping onto the  nonlinear
 
model gives an estimate , exp 2SCBA , with
SCBA  (N þ 1/2)e2/h being xx in the self-consistent
Born approximation (Ando and Uemura, 1974; Ando
1974a, 1974b; Ando et al., 1975) and , the magnetic
length. So the localization length increases with N, but
so does the critical exponent. The localization length
also depends strongly on whether the randomness is
rapidly varying in real space or slowly varying as
compared with the magnetic length.
1.05.4.2 Quantum Criticality and xx xy
Diagram
One way to display the critical behavior is the xx–xy
diagram. Namely, while at T ¼ 0 xy is a step function
and xx nonzero at discrete points, at finite tempera-
tures not only the Fermi distribution is smeared by
kBT, but we have also a finite inelastic scattering
length L. This can be summarized as the (xx, xy)
flow diagram when T is varied for various values of
EF, as originally evoked in the nonlinear  model
(Figure 17(a)). Namely, we can map the QHE
system onto a field-theoretic model called the non-
linear  model, for which the renormalization into
larger sample sizes can be discussed (Huckestein,
1995).
We can also vary the sample size for numerical
works on the QHE system to look at the renormali-
zation flow. Alternatively, we can change the
temperature, which changes the inelastic scattering
length, hence effectively changes the sample size
(Figure 17(b)). This implies that experimental (xx,
xy) flow lines can be obtained by varying the tem-
perature (Figure 17(c)).
We can also discuss the so-called plateau-
to-plateau transition, which is the energy interval over
which one plateau crosses over to another. In terms of
the localization, the states that satisfy L" < (E) are
effectively delocalized, where L" is the inelastic scatter-
ing length and  the localization length (Figure 18(a)).
If we assume the inelastic scattering time behaves like
 "(Tp) with p ¼ 2 in the diffusive regime, the energy
region whose width is Tp/2s behaves as delocalized,
since the localization length has a critical behavior
  jE  E0js while L" _ 1/Tp/2. If the magnetic
field is varied instead, the plateau transition width
against B has the width B  Tp/2s with the same
exponent. Figure 18(b) displays an experimental result.
One important question is how the QHE plateaux
vanish as the degree of disorder is increased, which
should take place since for a large-enough disorder the
Landau quantization, along with QHE, should go away.
Kivelson et al. (1992) have considered the problem
in terms of what is called the global phase diagram on
a xyxx plane. In this diagram xx is regarded as
a measure of the strength of disorder, while xy
the Landau-level filling. As shown in Figure 19(a),
the midpoints, xy ¼ (N þ 1/2)e2/h, between the pla-
teaux in the Hall conductivity are bifurcation points in
the xxxy flow lines, so that we can take the points,
 
xy ¼ 1= 2xx þ 2xy ¼ ðN þ 1=2Þe 2=h, as boundaries
 Integer Quantum Hall Effect 191

(a) (b) (c)

3
1.5K
T = 0.32K
1.78K
10.0K 0.35K
2 n=1 (1 –)

σxx /σSCBA
2.0
(0 –)
0.35K
n=0
1
T = 1.5K

0 0
0 1 1 3 2 5 0 1 2 3.0 3.5 5.0 5.5 6.0
2 2 2 –σxy / (e 2/h)

Figure 17 Results for the xxxy diagram: (a) Renormalization flow lines obtained in the nonlinear  model [Reprinted
figure with permission from A. M. M. Pruisken, Physical Review Letters 61, 1297 (1988) Copyright 2010 by the American
Physical Society. For information, see: http://link.aps.org/]. (b) A numerical result [From H. Aoki and T. Ando. Surface
Science 170, 249 (1986)]. (c) An experimental result [From M. Yamane et al., Journal of the Physical Society of Japan 58, 1899
(1989)].

(a) (b)
Inverse localization length ∝ E s 10 μm
1 18 μm
32 μm
64 μm
ΔB (T)

T p/2s 0.3
1
~ T p/2
Lε

E0
E
0.1
30 100 300 1000
T (mK)
Figure 18 (a) In a plot for the inverse localization length against energy, the effectively extended states (white region) is
shown for the inelastic scattering length L" at a given temperature T [after H. Aoki and T. Ando, Surface Science 170, 249
(1986)]. (b) An experimental result for the plateau-to-plateau transition width on the B-axis plotted against T for various values
of the sample size. Reprinted figure with permission from S. Koch et al., Physical Review Letters 67, 883 (1991). Copyright
2010 by the American Physical Society. For information, see: http://link.aps.org/

up to which the QHE effect survives when the strength
of disorder is increased (Figure 19(b)). The global
phase diagram has also been experimentally examined
for IQHE systems.
It is also important to consider how the situation
crosses over to the weak magnetic field case, since all
the states should become localized in the limit of
B ! 0, so that the fate of the delocalized states is
quite nontrivial. It has been suggested that the ener-
gies corresponding to the delocalized states go up in
energy, which is called the floating.
Another question of heuristic interest is what is
the classical limit (i.e., Planck’s constant h ! 0). In
this limit, the Landau-level filling 2,2n ¼ (h/eB)n
192 Integer Quantum Hall Effect
(a)
σ 2
σxy
1
σxx
N=0
n 1
(b)
ρxx0
σxy /(e 2/h) = 1
2
4 3
0 1
ρxy 0/(h/e 2)
Figure 19 (a) How a xxxy diagram is obtained from their n-dependence is schematically shown, with the flow lines
bifurcating at xy /(e2/h) ¼ half integer indicated. (b) The global phase diagram.
vanishes for a fixed n. The measure of the Landau-
level mixing, on the other hand, is the Landau-level
broadening divided by the cyclotron energy,
pffiffiffiffiffiffiffiffiffi pffiffiffi
=h!c 1= !c 0 . Since =h!c diverges like 1= h
for h ! 0 with fixed B and  0, the classical limit
amounts to a regime of dilute (_ h) in weak mag-
netic fields.
1.05.4.3 Fractal Wave Functions and
Dynamical Scaling
It is an intriguing question to ask whether a transition
between localized and extended states, in general, is
similar to phase transitions in statistical mechanics. A
suggestion came in 1983 by Aoki to the effect that the
wave function at the Anderson transition, which has
no characteristic length scale with the diverging loca-
lization length, should be self-similar (fractal) (Aoki,
1983), just as the critical point in a phase transition is
characterized by scale-invariant states with a diver-
ging correlation length.
For the QHE system in particular, the transition
point occurs at the center of each Landau level, so
that the delocalized states at the center of a Landau
level are just not the usual extended states, but fractal
(sometimes called critical) wave functions (r) that
have a fractal dimensionality, d < 2. In other words,
the density autocorrelation decays with a power law,

hj (r) (r þ R)j2i  1/R2  d . Typical wave functions
in Figure 20, which are obtained numerically for
σxx
3
2 2
σxy /(e 2/h)
2
larger sample sizes than in Figure 12, show that the
wave function is very scattered both in amplitude and
spatial extent.
To be more precise, the self-similarity in critical
wave functions extends beyond a single scale trans-
formation, so the idea has been subsequently
developed into the multifractal analysis, with which
we can analyze the delocalized states around the
Landau level center (Huckestein, 1995). As described
in the section below, real-space imaging such as
STM begins to visualize the fractal states.
Among the physical quantities that are affected
by the fractality of the wave functions is the
anomalous diffusion in transport. Namely, the
dc conductivity  obeys, in ordinary systems,
Einstein’s relation,  ¼ limq;!!0 ¼ e 2 DðEF ÞD 0 ,
where D 0 is the diffusion constant. At a critical
point, the conductivity becomes q, !-dependent. In
the dynamical scaling ansatz, the ac conductivity
should depend on !, where the relaxation rate
goes to zero like 1/  1/z around the transition.
Here, z is the dynamical critical exponent, which is
usually 2 in noninteracting systems. If we combine
this with the sample size scaling in L/, q, !-depen-
dence should take a form
 
ðq; !Þe 2 DðEF ÞD q=!1=z ð32Þ
At the criticality,
 pffiffiffi the
 fractality
 p offfiffiffithe
 states is shown
to lead to D q= !  D 0 = q= ! with  ¼ 2  d.

(a)
N=0
d=0
(c)
(b)
N=1
d=0
Figure 20 Typical wave functions (represented as their squared amplitude) around the center of each Landau level
obtained in a computer simulation for a disordered QHE system with a system size of 300l  300l for (a) N ¼ 0 and (b) N ¼ 1
Landau levels with short-range scatteres, and for (c) N ¼ 1 with long-range (d 6¼ 0) scatteres. Reprinted figure with permission
from T. Terao et al, Physical Review B 54, 10350 (1996). Copyright 2010 by the American Physical Society. For information,
see: http://link.aps.org/
1.05.5 QHE Edge States and Edge
Transport
The role of sample edges in the QHE transport has
been an issue of interest from an early stage when
the problem was raised by Halperin in the 1980s
(Halperin, 1982). Classically, there are edge currents
that correspond to cyclotron motions skipping
along the edges (Figure 21(b)). Quantum mechani-
cally, edge states also exist (Figure 21(a)). The
energy diagram plotted against the real-space
position across the sample width will look like
Figure 22(a). Edge states are rather ubiquitous in
quantum mechanics, but the peculiarity in the QHE
is that the edge currents flow, with no backscatter-
ing, in a definite direction dictated by the direction
of the applied magnetic field. When one takes the
electron–electron interaction into account, the edge
states may be regarded as special, incompressible
electronic states called the chiral Tomonaga–
Luttinger liquid, usually discussed in the context
of the fractional QHE.
In terms of the topological nature of the QHE, the
appearance of edge states is a prime example of a much
wider concept of the bulk-edge correspondence,
that is, the nature of edge states are dictated by the
nature of bulk states, which corresponds to the problem
Integer Quantum Hall Effect 193
N=1
d = 0.71l
of boundary states in field theories. In a finite QHE
sample, the edge states exist, which appear on the
energy spectrum as the edge modes that cross from
one Landau level to another in a Landau gap. These
modes have to exist, and sometimes called topologi-
cally protected in QHE systems. More importantly, the
topological nature of the QHE edge states manifests
itself, as shown by Hatsugai, in the properties that
(1) the edge Hall conductivity is also expressed as a
topological invariant (Chern number), and (2) this
quantity exactly coincides with the topological Chern
number for the bulk Hall conductivity (Hatsugai,
1997). Alternatively, we can visualize, in
Figure 22(b), that we can continuously change the
situation from the edge-picture limit (where currents
exist only at edges) to the bulk-picture (where a bulk
potential gradient exists) by deforming the current
distribution, but there is always the total current pre-
servation, I bulk ¼ I left edge  I right edge, which implies
bulk edge
xy ¼ xy (Koshino et al., 2001, 2002a, 2002b).
One way to describe the edge transport is
Büttiker’s formula (Büttiker, 1992) which is an exten-
sion of Landauer’s formula for transport processes in
terms of an S matrix for transmission and reflection
channels in ballistic transports. Büttiker’s formula can
explain some of the experimental results, including
the quantization of the Hall conduction. However,
194 Integer Quantum Hall Effect

Edge

(a) (b)

Figure 21 Typical edge states in a QHE system in quantum mechanics (a) and classical mechanics (b) From H. Aoki, in
G. Landwehr (ed.): Application of High Magnetic Fields in Semiconductor Physics (Springer, 1983), p. 11.

(a) (b)
μ0

μ0 eV

Bulk picture
μ2
μ2 Bulk Edge
μ1
E
μ1
Edge picture

Position along sample width

Edge Edge
l2 l1

Figure 22 (a) Energy spectrum against the position along the width is schematically shown for a sample with edges with the
chemical potential at the left edge (1) and at the right (2). (b) How the edge picture (in which all the currents are carried by
edge states) continuously crosses over to the bulk picture (where a bulk contribution exists) is schematically shown. From M.
Koshino et al., Physical Review B 66, 081301(R) (2002).

this does not mean that all the QHE currents are
carried by edges. In general, there exist both bulk
and edge Hall currents. Bulk and edge states can even
be hybridized. The details have been studied both
experimentally and theoretically, which largely indi-
cate that there are contributions from both bulk and
edges, whose proportions depend on the width of the
sample, T-dependent xx, etc. Real-space imaging
results also indicate that there are bulk potential
gradients in QHE samples.
Physically, a macroscopic system may be regarded
as comprising subsystems each having a linear
dimension of the phase coherence length L . The
transport is described by the Kubo formula xx, xy
if the sample size is much greater than L where the
Hall field and Hall current distributed over the sam-
ple, while the edge transport in the manner of
Büttiker starts to dominate when the size is compar-
able with L .
One of the characteristic features in the edge
transport is that highly nonlocal phenomena can
arise that extend over length scales far exceeding
the bulk mean free path. This can be probed in
Hall-bar samples by selectively injecting currents

from the contacts affects the conduction, where the
conduction can strongly depend on which terminals
to employ in multiterminal measurements.
The width of edge states has experimentally been
measured with various methods, including transport
(e.g., QHE breakdown), magnetocapacitance, and
magnetoplasmon measurements. One recent method
utilizes the nuclear spins. Usually, the nuclear spins
are irrelevant to electron systems, since the nuclear
Zeeman energy is as small as 1/2000 of the electronic
counterpart. When there are almost degenerate elec-
tronic states, however, nuclear spins can affect the
electron system via the hyperfine interaction. This
occurs not only in the fractional QHE systems close
to a spin-polarization transition, but also in the inte-
ger QHE where left and right edge states are
degenerate in energy, so that the nuclear spin is
probed via the scattering between the left and right
edge channels.
In semiconductor superlattices, which realize a
stack of 2DEGs, an application of a strong magnetic
field along the growth direction makes the system a
stack of IQHE systems. There, the edge states are also
stacked along the edge surfaces, which is called sheath
currents and have been experimentally observed.
1.05.6 Real-Space Imaging
Experimentally, there have been a body of studies for
real-space imaging of the QHE systems, including the
Hall field. Fontein et al. have studied a potential profile
imaging with the electro-optical effect (which utilizes
the birefringence (Pockels effect) with the phase
Figure 23 A typical real-space image for the potential distribution obtained with the electro-optic imaging for B ¼ 10.8 T
corresponding to the center of a plateau. From R. Knott et al., Semiconductor Science and Technology 10, 117 (1995).
Integer Quantum Hall Effect 195
difference between different polarizations probing
the potential) to show that an electric field exists
over the whole sample, although the field becomes
stronger toward the edges. An example of the imaging
is shown in Figure 23. This is followed by various
other methods, including scanning capacitive, force,
and polarization optical microscopies (Morgenstern,
2007).
One such probing, which is particularly suited to
examine nonequilibrium carriers around the hot spots,
is the imaging of cyclotron emission due to Komiyama
et al. (2004). In a Hall bar sample in the QHE condition
(with xx ¼ 0, xy 6¼ 0), the electric lines of force are
forced to be distorted to make the rectangular sample
geometry compatible with the Hall angle of 90 ,
resulting in singularities which have to appear at two
positions around the electrodes (Figure 24(a)). These
are called the hot spots. In the imaging of cyclotron
emission (Figure 24(b)), the QHE detector, which is
itself an IQHE system having by nature sensitive
photoresponses at the cyclotron resonance frequency,
is used to scan the QHE system. In the result the hot
spots are clearly seen, with edge channel also visible
for the Landau-level filling 6¼ integer. The imaging of
cyclotron emission has also been used to examine the
breakdown of QHE (see section 1.05.8).
Recently, STM and scanning tunneling spectro-
scopy (STS) begin to be performed for a special kind
of 2DEG, that is, the adsorbate-induce 2DEG, where
for example, Cs atoms are deposited on cleaved
n-InSb. The STS imaging is also used to directly
observe the quantum Hall transition from one loca-
lized regime to another via the delocalized states that
have a fractal character as shown in Figure 25
(Hashimoto et al., 2008).
196 Integer Quantum Hall Effect

(a)

S D

(b) 2DEG XY-stage

Hall-bar
– ν = 2.22 B + (mitter)
Si-SIL
1800
Y (μm)

Condenser lens
1400 14.6mm

1000
QHE
1000 2000 3000 4000 etector
X (μm)

Figure 24 (a) The electric lines of force are schematically shown for the QHE condition, with S: source electrode and
D: drain, (b) A real-space imaging obtained with the cyclotron emission detected by the QHE device (inset). Reprinted figure
with permission from K. Ikushima et al., Physical Review Letters 93, 146804 (2004). Copyright 2010 by the American Physical
Society. For information, see: http://link.aps.org/

50 nm (a) (b) (c) (d)

Lowest spin-LLs High

c
dl/dV (a.u.)
dl/dV (a.u.)

b
d
a

Low
–120 –110 –100 –90 –80
Sample voltage (mV)
Figure 25 A real-space image obtained by STS for 0.01 monolayer of Cs on a cleaved n-InSb(110) at T ¼ 0.3 K for various value
of the Landau-level filling, (a)-(d), as indicated in inset. Reprinted figure with permission from K. Hashimoto et al., Physical Review
Letters 101, 256802 (2008). Copyright 2010 by the American Physical Society. For information, see: http://link.aps.org/

1.05.7 QHE Resistance Standard and et Mesures (CIPM), that the QHE be adopted as the
the Fine-Structure Constant electrical resistance standard, with which ohm is
defined via the QHE resistance,
After the recognition that the accuracy of the QHE  
quantization is experimentally better than 106 RK ¼ h=e 2 ¼ 25 812:807  ð33Þ
(nowadays around 107 or even better), it was
decided, in 1990 by Comité International des Poids where RK is called the von Klitzing constant.
 Integer Quantum Hall Effect 197

(a) (b)

H 10–8α 10–6h

RK NPL-88
RK LNE-01
KJ PTB-91
RK NMI-97
KJ NMI-89
RK NIST-97
KJ2RK NPL-90
KJ2RK NIST-98
KJ2RK NIST-07
ae U Washington-87
ae Harvard-06 CODATA-02
CODATA-06
CODATA-02
CODATA-06 5 6 7 8 9 10
597 598 599 600 601 602 603 604 [h/(10–34Js) – 6.6260] × 105

(α–1 – 137.03) × 105

Figure 26 (a) Values of the fine-structure constant obtained with various methods. Those marked with RK are from the QHE
measurements at various institutes, ae from the electron magnetic moment anomaly, (b) A similar plot for the Planck constant h.
CODATA-recommended values are also indicated. From P. J. Mohr et al., Reviews of Modern Physics 80, 633 (2008).

The constant, now adopted as a resistance stan-
dard, has a profound significance related with a
fundamental physical constant. Namely, the
fine-structure constant
e2
¼ .1=137:036 ð34Þ nonequilibrium phenomena. Several factors can be
hc
which is the coupling constant in the quantum elec-
trodynamics (QED) (Kinoshita, 2007), one of the
most basic physical constants, is directly related
with RK via
¼ 2/RKc. Here, c ¼ 2.99 792. . .  108
m s1, the speed of light in vacuum, is, in SI, a
defined value. Figure 26(a) shows the values with
error bars of
obtained by various methods includ-
ing that from RK obtained by various institutes. If we
combine RK with the Josephson constant, KJ ¼ 2e/h,
we can deduce the value of Planck’s constant via
h ¼ 4/K2JRK (Figure 26(b)). For a recent review, see
Mohr et al. (2008).
this phenomenon, known from an early stage of the
QHE studies, is called the breakdown of QHE. The
breakdown is important from both applicational
aspects (since it affects the accuracy of the QHE) and
fundamental aspects since this is an interesting
involved, among which are tunneling between differ-
ent Landau orbits or Landau levels, and/or electron
heating effect. Also relevant is how the breakdown is
related with the current profile in real space in the
Hall bar. Although there are some prevailing experi-
mental and theoretical results, we seem to be some
way from a unified picture (Nachtwei, 1999).
Sometimes metastable or bistable states are observed
around the breakdown regime, which is also of interest.
As for nonequilibrium phenomena, we can men-
tion that the microwave-induced magnetoresistance
oscillation is one remarkable nonequilibrium phe-
nomenon, although this occurs in a weak magnetic
field regime rather than in the QHE regime.

1.05.8 Breakdown of QHE

When we increase the source–drain voltage to
increase the source–drain current in Hall effect mea-
surements in the Hall-bar geometry, the longitudinal
resistance Rxx, which is close to zero in the QHE
plateau region, abruptly increases for sufficiently
large voltages, as typically shown in Figure 27. This
is accompanied by disrupted plateau structures in Rxy.
Thus, the Hall current, which is originally dissipation-
less in the QHE condition, becomes dissipative, and
1.05.9 Quantum-Dot and Periodically
Modulated Systems in Strong
Magnetic Fields
1.05.9.1 Quantum-Dots in Magnetic Fields
Semiconductor quantum-dot is a nanostructure that
confines a few electrons. The physics of quantum-
dots is a very large area of investigation, as reviewed
in the chapter on this. Here, we only mention its
relevance to the QHE system. quantum-dots are
198 Integer Quantum Hall Effect

Ey (Vcm–1)
–80 –40 0 40 80

ρxx
4

Ex (Vcm–1) 2
0 5
B(T)

–2

–4

–6
–0.8 –0.4 0 0.4 0.8
jx (Am–1)

Figure 27 A typical current–voltage characteristics at  ¼ 2 (the arrow in the inset). From Nachtwei, Physica E 4, 79 (1999).

generally fabricated by applying a lateral confining Quantum-dots are also investigated in strong
potential to a 2DEG system. This can be realized by magnetic fields. In a magnetic field, B = rot A,
an electrode that exerts an electrostatic confining applied perpendicular to the dot plane the
potential, or alternatively we can mesa-etch the sys- Hamiltonian, in the one-body problem here, reads
tem to have a finite system (Figure 28(a)). The
confining potential is usually cylindrically parabolic 1  2 1
H ¼ 
pi þ ðe=c ÞAðrÞ þ m !20 r 2 ð35Þ
to a good approximation. 2m 2

(b) 50

40

(a) A
30
E (meV)

Drain
Side
AlGaAs Gate 20
InGaAs
AlGaAs
10
Source

0
0 2 4 6 8 10
B (T)
Figure 28 (a) A typical mesa-etched quantum-dot structure. From P. A. Maksym et al, Physical Review B 79, 115314 (2009).
(b) Energy levels of the Fock–Darwin states against magnetic field for a harmonic confinment. From P. A. Maksym et al,
Journal of Physics: Condensed Matter 12, R299 (2000).

where h!0 is the confinement energy and we have
ignored the Zeeman energy.
The exact eigenstates of this Hamiltonian are
known as the Fock–Darwin states, since they were
first investigated by Fock and Darwin in the 1920s.
They are given, up to the normalization constant, by
 2   2  – im
systems was first considered by Wannier and by
nm ðrÞ ¼ r jmj Ljmj 2 2
n r =2 exp – r =4 e ð36Þ
in 2D polar coordinates with eigenenergies given by
Enm ¼ ð2n þ 1 þ jmjÞh – mh!c =2. Here, m is the
angular momentum, n a radial quantum number, Ljmj n fractal, because each Landau level splits into p levels
the associated Laguerre polynomial, 2 ¼ !20 þ !2c =4
with the cyclotron frequency !C ¼ eB/m. Thus, the
wave function is almost the usual Landau’s wave
function as far as the parabolic confinement is con-
cerned, where pthe difference is in the length
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
parameter,  ¼ h=ð2m Þ. In Figure 28(b) depict-
ing the energy levels we can indeed see that
a crossover from the states of a 2D harmonic oscillator
in the zero field limit to the Landau states of a
free electron in the strong field limit. When we con-
sider the electron–electron interaction, a variety of
states emerge, which include the maximum-density
droplet that corresponds to the Landau-level filling
 ¼ 1, and the electron-molecule states (Maksym
et al., 2000).
So the dots in strong mangetic fields are a kind
of confined QHE systems, or artificial atoms in
magnetic fields. Their properties have been exten-
sively studied with various methods. For instance,
dot wave functions have been probed experimen-
tally with techniques such as magneto-tunneling
spectroscopy. Other properties include magneto-
capacitance, electron addition spectra, and transport
spectra in magnetic fields, from which the ground-
state quantum numbers are deduced. Dot arrays
have also been studied in the QHE regime,
where resonant scattering effects, etc., have been
reported.
1.05.9.2 Hofstadter Spectrum
What happens to QHE when we have periodic sys-
tems rather than a translationally invariant 2DEG?
Condensed-matter physics tells us that in a periodic
system we have Bloch’s theorem, which dictates that
electronic states for periodic systems are dominated
by Bragg’s reflection, which results in band structures
and Bloch states. So here we are talking about
Landau’s quantization in the presence of Bragg’s
reflection. We can realize that Bragg’s reflection
Integer Quantum Hall Effect 199
and Landau’s quantization interfere with each other,
since the application of a magnetic field, B ¼ rot A,
gives rise to, semiclassically, the Peierls phase,
Z
e r
exp – i Aðr9Þ ? dr9 ðrÞ, in the wave function
h
. Landau’s quantization in periodic and lattice
Hofstadter (1976). It has been shown that the energy
spectrum plotted against magnetic field is a curious
fractal (sometimes called Hofstadter’s butterfly);
when the magnetic flux within a unit cell in units of
flux quantum equals to q/p (Figure 29).
When EF is in one of these gaps, we should have
IQHE, for which xy in units of e2/h, the Chern
number, has been calculated with the topological
formula due to Thouless et al.
Recent advances in the electron-beam litho-
graphy has made it possible to fabricate 2DEGs
with 2D periodic modulations, and the butterfly
begins to be observed (Geisler et al., 2004).
1.05.9.3 QHE in Three Dimensions
While usually the QHE is an effect specific to 2D
systems, can we conceive a similar effect in 3D sys-
tems, and, if so, how? If we go back to the topological
argument, we do not use the fact that the system is
2D except for the presence of inter-Landau-level
gaps in the energy spectrum. This implies that, if
there exist, for some reason, energy gaps in 3D
systems in magnetic fields, we should have a quanti-
zation (for the Hall conductance Rxy– 1 in 3D), when EF
is in a gap. Note that in d-dimensional systems of size
L the conductance R-1 and conductivity  are related
as Rxy– 1 ¼ Ld – 2 xy , so that only in 2D do they happen
to coincide with each other.
Usual wisdom, however, is that gaps do not tend
to appear in 3D. One possibility is to use 3D systems
that have periodic structures or potentials. Koshino
et al. have shown that 3D Hofstadter spectra can
appear in periodically modulated structures in the
energy spectrum against the tilting angle in tilted
magnetic fields, where an interference of Landau’s
quantizations due respectively to the components By
and Bz of the magnetic field is responsible (as com-
pared with 2D where Hofstadter’s butterfly comes
from an interference between Bragg’s reflection and
Landau’s quantization). Then each of xy and zx are
quantized when EF is in each gap with the current
200 Integer Quantum Hall Effect

B
1/4
3/8
1/2

–σxy /(e2/h)
3

0
–1

–2

–3
–4 –2 0 2 4
E
Figure 29 Hofstadter butterfly (energy spectrum against magnetic field) for a square lattice (upper panel), and the
corresponding QHE at the value of magnetic field for which the magnetic flux penetrating a unit cell of the periodic system is
3/8 in units of the flux quantum [after H. Aoki, in G. Landwehr (ed.): Application of High Magnetic Fields in Semiconductor
Physics III (Springer, 1991), p.17].

1,
1
E/tx
1,

1
0
3 3 2 –2 –3
0,4
0,3
4,0

1,
1,02,–20,2 2,0 0,1 3,0

2 –1 1 1,–2
–1
–1,3 –2,2
3,–1 ,1 –2,1
–2 2 1,–3 2, –1 –3,1
0
2

–3 3
1 1,–4
0,

–4,1
1,–1
E/tx

2 2 –3,4 4,–3 ,1
–1
0 –2,3 3,–2
2,–1
2 2 0,4
0,3 0,1 –1,2 1,0 2,
0
4,0
–1 3,0
0,2

3 –3
2 1 –1 –2
–2 3,–3 3,–3
–1,2 2,–1
2,–2 –2,2
–3 –3 –2 2 3 0,0 1,–1 –1,1 0,0
0
0 0.2 0.4 0.6 0.8 1 0 30 60 90
φ θ (degree)

Figure 30 (Right) Energy spectrum against the tilting angle,

, of the magnetic filed applied to a 3D, periodic system. The
QHE values (in units of e2/ah with a: lattice constant) for (xy and zx) are indicated by a pair of numbers attached to each gap
in the spectrum. The region indicated by a dashed line has a one-to-one correspondence to the Hofstadter butterfly in 2D (left
panel). [Reprinted figure with permission from M. Koshino et al., Physical Review Letters 86, 1062 (2001) Copyright 2010 by
the American Physical Society. For information, see: http://link.aps.org/].

j ¼ s  E where s = (yz, zx, xy) (Figure 30). 1.05.10 Integer versus Fractional
Experimental realization is yet to come. QHEs
A kind of Landau quantization has been known to
occur in 3D systems, typically in a quasi-2D organic The integer QHE has subsequently been developed
conductor (TMTSF in the Bechgaard salt family). into the fractional QHE (FQHE) as is described in
This is the field-induced spin-density wave (SDW) the present volume (see Chapter 1.06). In FQHE the
in strong magnetic fields with a many-body origin. Hall conductivity is quantized into xy ¼ e2/h for
Namely, the Landau quantization takes place within fractional Landau-level fillings  ¼ 1/3, 2/3, 3/5, . . .
the pockets formed by incompletely-nested Fermi as opposed to the IQHE for  ¼ integer. Let us com-
surfaces, which gives rise to a series of gaps around pare the IQHE with FQEH in this section.
the main SDW gap. Physically, the integer QHE is primarily understood

in terms of a one-body problem as described here,
while FQHE is inherently a many-body effect, and
this is a customary way to distinguish the IQHE and
FQHE. It is then natural that the IQHE was origin-
ally discovered in Si-MOSFET, while the FQHE
effect in GaAs–AlGaAs heterostructures, where the
latter system is atomically much cleaner with typical
mobility exceeding 106cm2 V1 ? s1 against the for-
mer’s 104cm2 V1 ? s1. The FQHE has in fact been
observed in clean-enough Si-MOSFETs.
One clear way to realize that the FQHE, a many-
body effect, emerges as the degree of disorder is
lowered is to look at the historical developments
from IQHE to FQHE in Figure 31, which shows
how the fractional effect appears as the sample qual-
ity (as characterized by the carrier mobility) becomes
higher. In the clean limit, the system is indeed in the
limit of strong electron correlation in that the kinetic
energy is quenched due to Landau’s quantization so
that the ratio of the interaction energy to the kinetic
energy is infinite (although more rigorously we have
to consider the inter-Landau-level matrix elements).
Integer Quantum Hall Effect 201
Although the FQHE as a new class of many-body
states is associated with fractional Landau-level
fillings, the electron–electron interaction exists for
integer fillings as well. In fact, an integer is a kind
of fraction in that Laughlin’s wave function for the
FQHE liquid for clean systems, allowed for odd
fractions ( ¼ 1/m with m an odd integer), also
accommodates m ¼ 1. So the real question is the
nature of the energy gap: in the integer QHE the
excitation gap is primarily the one-body gap
between the adjacent Landau levels (or between
the mobility edges in disordered systems), while
the excitation gap in the FQHE has a many-body
origin.
The relative magnitude of the one-body and
many-body gaps depends on the degree of disorder
(and the g-factor in the case in which the adjacent
Landau levels are Zeeman-split ones). To quantify
this, we can examine various energy scales.
Figure 32 plots
1. h!C (the cyclotron energy),
2. e2/", (typical size of the electron–electron
Coulomb interaction),
where e is the elemental charge, "(¼ 13 for GaAs)
the dielectric constant of the material and , the
magnetic length, and
3. gBB (the Zeeman energy),
2 1
3 3 where g is Landé’s g-factor, B ¼ he=ð2mc Þ the
Bohr magneton. We can see that for B  few tesla
the Zeeman energy is relatively negligible, while the
cyclotron energy and the Coulomb energy are com-
1982 parable. For disordered systems we have to compare
ρxx

0
these with the Landau-level broadening , which is
roughly estimated in the self-consistent Born approx-
imation as =ðh!c Þ1=ð!c 0 Þ1=2 , where  0 is the
1984
scattering relaxation time in zero magnetic field. So
the Landau-level broadening is comparable with the
cyclotron energy for !c 0  1.
0
3 2 While the two-dimensionality in IQHE appears in
2 3 5
3 5
6 4
7 the fact that the Hall conductivity represents a topo-
45 9
79 5 11
11 8
logical quantum number (Chern number) in terms of
7 13
13
the Berry’s curvature, in FQHE the spatial dimension-
1987 ality of two is essential in allowing the composite
4 5 fermion picture (i.e., a Chern–Simons gauge field the-
5 7
0 oretic treatment) of the many-body quantum liquid.
1 1/2 1/3
Landau level filling This is the reason why the FQHE accommodates such
novel concepts as anyon quasi-particles.
Figure 31 The developments of the fractional structure in
samples of progressively higher quality From D. C. Tsui et al.,
The relevant chapter should be referred to for the
Physical Review Letters 48, 1559 (1982), A. M. Chang et al., FQHE, so suffice it to mention that FQHE is
ibid 53, 997 (1984), R. Willett et al., ibid 59, 1776 (1987). regarded as an IQHE of composite fermions in the
202 Integer Quantum Hall Effect

35

30 N=1
hωc hωc
25 N=0 Zeeman splitting

Energy (meV)
20

15
e2/εl
10

5
gμBB
0
0 5 10 15 20
B (T)
Figure 32 Various energy scales (cyclotron, Coulomb, and Zeeman) against magnetic field, here plotted for GaAs. Inset
schematically shows the Landau levels with Zeeman splitting.

composite fermion picture. As explained in that When heterostructures such as ZnO/MgxZn1  xO

chapter, the Landau-level filling is expressed as
 ¼ Ne/N , for Ne electrons in N flux quanta, so
that an odd fraction, say,  ¼ 1/3 implies that there
are three flux quanta per each electron on average. In
the composite fermion picture we attach two flux
quanta to each electron (in a kind of gauge transfor-
mation), and we are left with one flux quantum. So
the  ¼ 1/3 state can be mapped to a  ¼ 1 state of
composite fermions in a mean-field sense. One appli-
cation of this correspondence is the global phase
diagram: we have explained the xx  xy diagram
above for the IQHE. If we combine this with the
composite particle transformation, we can, again in
a mean-field sense, a phase diagram for the integer
and fractional QHE phases against the Landau-level
filling and the degree of disorder.
are grown with MBE, MgZnO layer acts as a poten-
tial barrier for the 2DEG in ZnO layer in realizing a
2DEG. The carrier density (typically  1012cm2)
systematically depends on x and the growth temp-
erature, where spontaneous and piezoelectric
polarization effects work to accumulate carriers at
the heterointerface. The condition necessary to
have QHE (i.e., !c 0 > 1) is met, and a typical result
(Figure 33) exhibits a clear IQHE. Since oxides have
various possibilities, broad applications are expected
(Tsukazaki et al., 2008).
1.0 10
T = 0.3 K
ν=3
n = 8.7 × 1011 cm–2
0.8 μ = 20 000 cm2 V–1s–1 8

4
0.6 6
1.05.11 Recent Developments and
ρxx (kΩ/ )

ρxy (kΩ)

5
Related Phenomena
6
0.4 4
There are a multitude of recent developments in the
integer QHE and closely related physics. Extensions
are being made both for various classes of materials, 0.2 2
and various novel phenomena. Let us here briefly
mention them.
0.0 0
0 5 10 15
1.05.11.1 QHE in Oxides B (T)
Figure 33 QHE in an oxide heterostructure ZnO/
A notable breakthrough in the attempts to widen the
MgxZn1  xO. Reprinted figure with permission from A.
classes of materials is the realization of QHE in oxide Tsukazaki et al., Physical Review B 78, 233308 (2008).
heterostructures. The system is zinc oxide (ZnO), Copyright 2010 by the American Physical Society. For
which is an insulator, or a wide-gap semiconductor. information, see: http://link.aps.org/

1.05.11.2 QHE in Graphene
One fascinating aspect of the condensed-matter phy-
sics is that we can have various field theories
effectively realized on low-energy scales. Recent
emergence of the physics of massless Dirac particles
(or Weyl particles in the language of field theoretic
texbooks) in graphene is a good example. While the
3D graphite has long been studied extensively,
experimental fabrication of graphene had to wait for
the accomplishment by Geim’s group around 2004.
IQHE then received a strong impetus when seminal
series of works on graphene, in particular the IQHE,
were launched for graphene after around 2005
(Novoselov et al., 2005; Geim and Novoselof, 2007;
Castro Neto et al., 2009).
Graphene is a monolayer graphite with a honey-
comb array of carbon atoms (Figure 34(a)), while
graphite is a stack of graphene sheets (in a staggered
manner called Bernal stacking). Electrons on a single
layer of honeycomb lattice, despite its simplicity,
provide interesting problems in condensed matter
physics. Specifically, it has long been known that its
band dispersion (for  orbitals) is composed of a pair
of k-linear conical electron and hole dispersions that
touch with each other at E ¼ 0 (Figure 34(b)), so that
the graphene is a condensed-matter realization of
massless Dirac fermions around E ¼ 0 (at which EF
usually resides). This was noted by Wallece as early
as in 1947. Subsequently, the reason why honeycomb
symmetry implies the massless Dirac dispersion was
revealed group-theoretically by Lomer and by
Coulson in the 1950s. Band analysis in terms of the
k ? p perturbation was also done by Slonczewski and
Weiss. Graphene is to be contrasted with graphite,
whose band structure is a semimetal with Fermi sur-
face comprising small electron and hole pockets.
(a)
Figure 34 Crystal structure (a) and the band dispersion (b) of graphene.
Integer Quantum Hall Effect 203
To be more precise, graphene has two, inequiva-
lent Dirac cones at K and K9 in the first Brillouin
zone (Figure 34(b)). To see this, we should go back
to the honeycomb lattice, which is a non-Bravais
lattice that contains two (A and B) sublattice sites in
a unit cell. The lattice is bipartite, so that the energy
spectrum is electron–hole symmetric about E ¼ 0 if
we only consider nearest-neighbour hopping. The
tight-binding model (for  electrons) on a honey-
comb lattice reads, in k-space,
0 1
P 0 ðkÞ
H ¼t @ A;
k  ð k Þ 0 ð37Þ
ðkÞ ¼ 1 þ e – ik1 þ e – ik2 ;
where the 2  2 matrix represents the AB sublattices,
k1, k2 are the wave vectors along the primitive vectors
in k-space. Around K and K9 points in the Brillouin
zone, the k?p perturbation shows that the
Hamiltonian linearized in p reduces to
 
H ¼ vF x z px þ y py ð38Þ
where vF . 108 cm s1 is the Fermi velocity, and m
Pauli matrix in the 2  2 matrix representation, while
 z is another Pauli matrix with  z ¼ 1(1) for K (K9)
point. So the equation (for each value of  z) is just the
Dirac equation for a massless particle in two spatial
dimensions. The Hamiltonian anticommutes with z
(which plays the role of  5 in (3 þ 1) dimensions), and
this symmetry is called the chiral symmetry.
In the presence of a magnetic field, we can
replace p in the above equation with p ¼ p þ (e/c)A
as far as the effective, k ? p band structure is
concerned. Then the Landau levelspbecome, ffiffiffiffi as
shown by McClure in 1956, E N ¼ N h! c with
pffiffiffi  pffiffiffi
!c ¼ 2=, vF ¼ ð2evF =chÞ B , the magnetic
(b)
E
K K′
ky
kx
204 Integer Quantum Hall Effect
length as usually defined (Equation (8)), and N ¼ 1,
2,. . . (N ¼ 1, 2,. . .) correspond to pelectron
ffiffiffiffi (hole)
Landau levels. The Landau levels _ N is not uni-
formly spaced in sharp contrast to the usual,
uniformly spaced Landau levels, and, in particular,
there is the N ¼ 0 Landau level right pffiffiffiat the Dirac
point E ¼ 0. The cyclotron energy _ B is also unu-
sual. The N ¼ 0 Landau level is quite peculiar, which
is brought home by noting that the level is comple-
tely outside the Onsager’s semiclassical quantization
scheme in magnetic fields (because the Landau tube,
which is the set of cylinders of varying radii for the
semiclassical quantization, cannot be defined around
the Dirac point). In fact, this level is an outcome of
a topological property of the massless Dirac cone,
so that its presence is topologically protected. If we
go back to the original honeycomb lattice in mag-
netic fields, the problem becomes a Hofstadter
butterfly for the honeycomb lattice (Figure 35),
which was obtained by Rammal in 1985.
Incidentally, it is heuristic to look at the Landau’s
quantization in the (massive) relativistic particles.
From the Dirac equation for a Dirac particle
in a magnetic field, the energy levels are
EN ¼ [m2c4 þ mc2(h!c(2N þ 1 1))]1/2 (MacDonald,
1983), (which contains the nonrelativistic limit,
EN ¼ mc2 þ h!c(N þ 1 1/2)), as the leading term in
h!c/mc2 expansion). In the massless limit, m ! 0, we
have to note that !c ¼ eH/mc also contains the mass
to recover the graphene Landau levels.
E is the topological number identified in the graphene
0 indeed algebraically calculate the Chern number in
B an interesting issue in its own right). We have men-
Figure 35 Energy spectrum against magnetic field for a
honeycomb lattice.
Soon after the fabrication of graphene samples, an
anomalous IQHE was observed by Geim’s group, and
by Kim’s group (Novoselov et al., 2005; Geim and
Novoselof, 2007; Castro Neto et al., 2009). As
Figure 36 shows, the IQHE in graphene has
e2
xy ¼ – 2 ð2N þ 1Þ ð39Þ
h
2
e
as contrasted with the usual xy ¼ – 2 N when the
h
carriers are filled up to the Nth Landau level. The
prefactor of 2 in these equations is for the spin
degeneracy. The peculiarity of the Dirac cone
appears as the factor (2N þ 1) replacing the ordinary
N as shown by Zheng and Ando, 2002; Gusynin and
Sharapov, 2005. There are K and K9 points that
contribute equally to the Hall conduction, so that if
we take out the factor of 2 along with the spin
e2
degeneracy, we can write xy ¼ – 4 ðN þ 1=2Þ,
h
where, remarkably, a fraction (1/2) appears.
The situation around the N ¼ 0 Landau level is
indeed unusual. Let us compare the situation with the
ordinary one where we have a (massive) conduction
band and a (massive) valence band in Figure 37. In
the latter case, we have an ordinary IQHE sequence,
0 ! 1 ! 2 ! . . ., for electrons (in the conduction band)
and another, 0 ! 1 ! 2 ! . . ., for holes (in the
valence band). For a Dirac cone, the IQHE step
across N ¼ 0 at the Dirac point (i.e., an electron–
hole symmetric point) cannot be 0 ! þ 1 nor
1 ! 0, which would be incompatible with the elec-
tron–hole symmetry. Instead, the step changes from
1/2 to þ1/2 at N ¼ 0. Another peculiarity is that
the quantum Hall step remains robust even at room
temperature (Figure 38), which is quite unusual.
We have mentioned that the quantum Hall num-
ber in usual systems is identified as a topological
quantum number according to Thouless et al. How
QHE? Hatsugai et al. (2006) have shown that we can
the manner of Thouless et al. extended to the QHE
on the honeycomb lattice, which precisely gives
e2
xy ¼ – 2 ð2N þ 1Þ. The topological analysis also
h
leads to another topological character, namely edge
states (Figure 39) for a finite graphene in storng
mangetic fields appear (which should not be confused
with the graphene edge states in zero magnetic field,
tioned above that the bulk and edge QHE topological
numbers are equal, that is, edge bulk
xy ¼ xy , which can
 Integer Quantum Hall Effect 205

B = 14 T and T = 4K 7/2

5/2

10
3/2
σxy = (2N + 1) (e 2/h)

σxy (4e2/h)
ρxx (kΩ) 1/2
0
–1/2
5 ρxx
–3/2

–5/2

–7/2
0
–4 –2 0 2 4
n (1012 cm–2)
Figure 36 QHE observed in graphene. From K. S. Novoselov et al., Nature 438, 197 (2005).
σxy /(–e2/h)

2
σxy /(–e2/h)

3/2
(a) 1 (b)
1/2
0
–1
–1/2
–2
–3/2
vb cb
k k

E
E
–1 N = 0 1

Figure 37 Band dispersion and Landau levels (lower panels) and the QHE steps (upper) are compared between the
ordinary 2D system with valence and conduction bands (a) and graphene with k-linear, zero-gap dispersion (b).

be identified by connecting the topological integers σxy B = 29 T 4

for the bulk and for the edge states. The same applies 30 T = 300 K
to the graphene IQHE. Energy spectrum against
real-space position also differs in graphene from the 2

usual QHE system as depicted in Figure 40. Edge

σxy (e2/h)

20
ρxx (kΩ)

states in graphene in magnetic fields are beginning to 0

be observed with STM.
As for the effect of disorder and its effect on –2
localization, graphene samples themselves are atom- 10
ρxx –4
ically clean (although there are extrinsic source of
disorder such as charged impurities), so that graphene
can have a very high mobility. One intrinsic disorder 0
–6
is corrugations of the graphene sheet, called ripples. –60 –30 0 30 60
As for the Landau quantization in magnetic fields, Vg (V)
ripples, when their effect is represented as random Figure 38 An experimental result for the QHE in graphene
hopping energies or random compontents in the at room temperature. From K. S. Novoselov et al., Science
magnetic field (which respect the chiral symmetry), 315, 1379 (2007).
206 Integer Quantum Hall Effect

the other hand, dominates the scattering between K

and K9 points, where the longer-ranged the disorder
the K–K9 scattering becomes less effective.
Physics of graphene is now extended to various
properties other than transport (such as optical prop-
erties). There is also a proposal for the Landau level
laser that exploits the transitions between the Landau
levels, which was originally proposed for the ordin-
ary 2DEGs (Aoki, 1986; Morimoto et al., 2008).
Extensions are also being made for bilayer graphene,
where the particle becomes massive, and for many-
body physics including FQHE. Another material
with a Dirac cone has also been discovered, which
is an organic metal -(BEDT-TTF)2I3, although the
cone is tilted and does not sit at the corner of the
Brillouin zone in this material.

1.05.11.3 Anomalous Hall Effect and Spin

Figure 39 A typical edge states in graphene in a strong
magnetic field obtained numerically from H. Aoki et al.,
International Journal of Modern Physics B 21, 1133 (2007).
are shown to exert anomalously small effect on the
broadening of the N ¼ 0 Landau level. This is also a
topological effect, related with Atiyah–Singer’s index
theorem in field theory. The range of the disorder, on
Hall Effect
QHE has other Hall effects, the anomalous Hall
effect and the spin Hall effect (Figure 41), as close
relatives, so let us briefly describe them in relation to
the IQHE, while details are described in the chapter
on the spin Hall effect. While the QHE is a topolo-
gical phenomenon intrinsic to the nature of the
generic 2DEG, the anomalous Hall effect (Hall effect
in ferromagnetic materials) and the spin Hall effect
(Hall effect for the spin degrees of freedom in mate-
rials that have strong spin–orbit interactions) arise

(a) (b)

E E
N=1
N=0
N=1
N=0

x x
Figure 40 Energy spectrum against the real-space position along the width for a finite sample is schematically compared
between the ordinary QHE system (a) and graphene QHE system (b).

E
B M

+q –q +q –q

Quantum Hall effect Anomalous Hall effect Spin Hall effect

Figure 41 Quantum Hall effect, anomalous Hall effect, and spin Hall effect are schematically shown.

from system’s magnetic structure, band structure and
interactions, so they occur in 3D systems as well.
The anomalous Hall effect, in which the Hall
resistivity is
RH ¼ Rnormal B þ Ranomalous M ð40Þ
with Rnormal being the normal Hall resistivity,
Ranomalous the anomalous Hall resistivity, and M
the magnetization of the material, was discovered
in metallic ferromagnets in the nineteenth century,
where the Hall current flows even in zero external
magnetic fields. Theoretical analysis was initiated in
the 1950s by Karplus and Luttinger as a (multi-)
band effect in the presence of spin–orbit interaction.
To be more precise, two mechanisms have been
identified, one (called extrinsic) is the impurity
scattering in the presence of spin–orbit interaction
and magnetization (skew scattering þ side jump) and
the other (called intrinsic) is Berry’s curvature con-
tribution to the Hall conductivity as in the QHE,
which is included in the linear-response formula.
Experimentally, the anomalous Hall effect has
been observed in various materials, typically
Nd2Mo2O7 with noncollinear spin configurations
and (Sr, Ca)RuO compounds.
In the spin Hall effect, which also occurs in zero
magnetic field, " spins and # spins flow in the oppo-
site directions in an electric field (as opposed to the
ordinary Hall effect in which opposite charges flow
in the opposite directions in a magnetic field). This
effect, which also comes from the spin–orbit interac-
tion, is another topological effect. The effect,
predicted in the 1970s, is recently being experimen-
tally observed with, for example, Kerr rotation
microscopy in both n- and p-type GaAs-based semi-
conductor heterostructures.
QHE, anomalous Hall effect and spin Hall effect
are related in that they are manifestations of the
phase of the wave functions in magneto-transport
properties. In a wide context, electrical polarization
is also formulated recently in terms of Berry’s
phase.
An intimate relation between QHE and the spin
Hall effect has been brought home by a more recent
quantum spin Hall effect (QSHE) (König et al., 2008;
Murakami, 2008) which was predicted originally for
graphene. The idea starts as follows. Graphene is
described, as mentioned above, by a Dirac equation
for two spatial dimensions, where K and K9 points in
the Brillouin zone are distinguished by a pseudospin
 z. In the presence of a spin–orbit interaction, we
Integer Quantum Hall Effect 207
have an extra term that couples the real spin and
the pseudospin, and this gives rise to an energy gap
(a mass gap in the language of the Dirac theory).
Since the gapped state cannot be reached by an
adiabatic change of the system, the insulator is called
a topological insulator. Associated with the gap in the
bulk are the edge states, which are also dictated to
exist and called topological edge states. In this
respect, the QSHE is distinct from the spin Hall
effect, and the whole situation is rather similar to
the IQHE, where an essential difference is that the
edge states carry charges in IQHE while edge states
carry spins in the QSHE. The energy dispersion
(Figure 42) of the edge states in a QSHE system,
which may be thought of as arising from Kramers’
doublets, is gapless with the two dispersion crossing
at a point in the Brillouin zone. The conductivity
calculated with the linear-response theory for each of
the spin-up and spin-down electrons gives a quan-
tized (Chern number) conductivity, where the
directions of the current are opposite between the
up and down spins, with a quantized spin Hall con-
ductivity shown to be spin
xy ¼ e=2.
While the original proposal, due to Kane and
Mele (2005) was made for graphene, the system has
turned out to have too small a spin–orbit interaction.
Subsequently, the effect was shown to be realized in
quantum-wells with narrow-gap semiconductors,
HgTe/CdTe. While both of HgTe and CdTe have
zincblende crystal structure, their band structures are
affected by the spin–orbit interactions which are sig-
nificant in these materials. Specifically, the bulk
1
E/t
0 I
–1
0 π/a kx 2π/a
Figure 42 Energy spectrum for a system that exhibits
quantum spin Hall effect. Bunch of lines represent bulk
states, while a pair of isolated lines the edge states. Inset
shows how the spin-up and spin-down electrons flow in real
space. Reprinted figure with permission from C. L. Kane and
E. J. Mele, Phys. Rev. Lett. 95, 226801 (2005). Copyright
2010 by the American Physical Society. For information,
see: http://link.aps.org/
208 Integer Quantum Hall Effect
1.0 T = 1.6K
ρxx
ρxy
0.8
ρxx (kΩ)
0.6
ν=5
ν=6
0.4 ν=7
0.2
0.0
0 1 2 3
B (T)
Figure 43 QHE in a HgTe quantum-well [after A. Pfeuffer-Jeschke et al., Physica B 256–258, 486 (1998).]
HgTe has a band structure called inverted, since a
band that usually forms the valence band lies above
another band that usually forms the conduction band,
where the former consists of two (heavy- and light-
mass) bands that touch with each other at a point in
the Brillouin zone with opposite curvatures (i.e., the
bulk system is a semimetal). While IQHE itself
(Figure 43) became observable in HgTe/CdTe
quantum-wells and superlattices grown by MBE, a
recent breakthrough is the observation of the QSHE.
The band structure behind this is, when HgTe is
sandwiched between CdTe to make a quantum-
well, the bands in HgTe well remain inverted for
wide wells, while the bands become normal for thin
enough wells. So the well thickness can act to control
the presence or otherwise of a mass gap, and the
system should be a quantum spin Hall insulator
above a critical thickness. With the spin Hall effect,
we can electronically manipulate the spin degrees of
freedom, so that applications to the spintronics is
anticipated. (See Chapters 1.03, 1.06 and 1.07).
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Ando T, Fowler AB, and Stern F (1982) Reviews of Modern
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0.4
0.35
ν=3
0.3
ν=4 0.25
ρxy (h /e2)
0.2
0.15
0.1
0.05
0.0
4 5 6 7 8
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(reprinted in Aoki H and Ando T (1993) Solid State
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Kane CL and Mele EJ (2005) Physical Review Letters
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Kawaji S (2008) Proceedings of the Japan Academy, Series B
84: 199.

Kawaji S and Wakabayashi J (1981) In: Physics in High Magnetic
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König M, Buhmann H, Molenkamp LW, et al. (2008) Journal of
the Physical Society of Japan 77: 031007.
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417: 211.
Landau LD, Lifshitz EM, and Pitaevskii LP (1984)
Electrodynamics of Continuous Media, 2nd edn., Pergamon.
Laughlin RB (1981) Physical Review B 23: 5632.
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Maksym PA, et al. (2000) Journal of Physics: Condensed Matter
12: R299.
Mohr PJ, Taylor BN, and Newell DB (2008) Reviews of Modern
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Morimoto T, et al. (2008) Physical Review B 78: 073406.
Murakami S (2008) Progress of Theoretical Physics Supplement
176: 279.
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Pruisken AMM (1990) In: Prange RE and Girvin SM (eds.)
The Quantum Hall Effect, 2nd edn., 117. New York:
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Further Reading
Aoki H (1987) Reports on Progress in Physics 50: 655.
Chakraborty T and Pietiläinen P (1988) The Fractional Quantum
Hall Effect. Springer.
Das Sarma S and Pinczuk A (eds.) (1997) Perspective in
Quantum Hall Effects. New York: Wiley.
Landwehr G (1986) Festkörperprobleme 26: 17.
Prange RE and Girvin SM (eds.) (1990) The Quantum Hall Effect,
2nd edn. New York: Springer.
Yoshioka D (2002) The Quantum Hall Effect. Springer.
 1.06 Fractional Quantum Hall Effect and Composite
Fermions
J K Jain, The Pennsylvania State University, University Park, PA, USA
ª 2011 Elsevier B.V. All rights reserved.

1.06.1 Introduction 211

1.06.2 Quantum Hall Effect Phenomenology 211
1.06.2.1 The Hall Effect 211
1.06.2.2 Integral Quantum Hall Effect 211
1.06.2.3 Fractional Quantum Hall Effect 212
1.06.3 Electrons in a Magnetic Field: Landau Levels 212
1.06.3.1 Landau-Level Degeneracy 213
1.06.3.2 Filling Factor 214
1.06.4 Integral Quantum Hall Effect Theory 214
1.06.5 The Fractional Quantum Hall Effect Problem 214
1.06.6 Composite Fermions: Basic Foundations 214
1.06.7 Consequences 216
1.06.7.1 Theory of Fractional Quantum Hall Effect 216
1.06.7.2 Quantitative Tests against Exact Results 217
1.06.7.3 Composite Fermion Fermi Sea 218
1.06.7.4 Effective Magnetic Field 218
1.06.7.5 Spin Physics 218
1.06.7.6 Interacting Composite Fermions: New Fractions 219
1.06.7.6.1 FQHE of composite fermions 219
1.06.7.6.2 Pairing 219
1.06.7.7 Fractional Charge 220
1.06.8 Open Issues 220
References 220

Glossary
Composite fermions Bound states of electrons
and quantized vortices.
Degeneracy Multiplicity of an energy level.
Fermi sea The state in which fermions occupy all
states below certain energy.
Filling factor Number of filled Landau levels.
Fractional quantum Hall effect Observation of
plateaus in the Hall resistance at quantized values
characterized by simple fractions.
Hall effect Observation of a voltage transverse to
the direction of the current flow in the presence of a
magnetic field.
Integral quantum Hall effect Observation of
plateaus in the Hall resistance at quantized values
characterized by integers.
Landau levels Quantized kinetic energy levels of
electrons in a magnetic field.

Nomenclature h Planck’s constant

B magnetic field I current
B magnetic field experienced by composite N number of electrons
fermions Pf Pfaffian
e electron charge R resistance
E electric field RH Hall resistance

210
 Fractional Quantum Hall Effect and Composite Fermions 211

1.06.1 Introduction
B
Collective quantum behavior is of fundamental
interest in condensed matter physics, where a collec- I
tion of interacting particles behaves in a surprising
manner that would be difficult to guess from the I
knowledge of the properties of single particles.
Superconductivity and superfluidity are two such VL
VH
well-known examples. During the last three decades,
a new collective quantum fluid state of matter has
been discovered and studied, which occurs when
electrons are confined to two dimensions, cooled to Figure 1 Schematics of magnetotransport measurements.
near absolute zero temperature, and subjected to a I, VL, and VH are the current, longitudinal voltage, and the Hall
strong magnetic field. The most dramatic, and unex- voltage, respectively. The longitudinal and Hall resistances
pected, manifestation of this phase is the ‘fractional are defined as RL X VL/I and RH X VH/I.
quantum Hall effect’ (Tsui et al., 1982). The fractional
quantum Hall effect (FQHE) and many other
The phenomenon has a classical origin. The
properties of this state result from the formation of
Lorentz equation of electrodynamics
a new class of topological particles, called ‘composite
 
fermions’, which are bound states of electrons 1
F¼q Eþ vB ð3Þ
and quantized microscopic vortices. The composite- c
fermion quantum fluid provides a new paradigm for
gives the force on a particle of charge q, moving with
collective behavior. This chapter describes the essen-
a velocity v, in the presence of electric and magnetic
tial phenomenology of the fractional quantum Hall
fields. A consequence of this equation is that for
effect, how the composite fermion theory resolves it,
crossed electric and magnetic fields, say E ¼ Eŷ and
and other consequences of the existence of composite
B ¼ Bẑ, the charged particle drifts in a direction
fermions.
perpendicular to the plane containing the two fields,
with a velocity v ¼ c(E/B)x̂.
Current density is given by J ¼ qv, where  is
the (three-dimensional) density of particles. That
1.06.2 Quantum Hall Effect produces the Hall resistivity
Phenomenology
Ey B
1.06.2.1 The Hall Effect H ¼ ¼ ð4Þ
Jx qc
The Ohm’s law is given by
The Hall measurement is used routinely to measure
J ¼ E ð1Þ the density  of the mobile charges, as well as the sign
of the charge carriers (i.e., whether they are electrons
where  is the conductivity, and J ¼ qv is the cur- or holes).
rent density for particles of charge q and density 
moving with a velocity v. The more familiar I ¼ V/R
can be obtained from this local relation. In the pre- 1.06.2.2 Integral Quantum Hall Effect
sence of a magnetic field, the electron current flows
When the Hall experiments are performed in a sys-
in a direction perpendicular to the plane containing
tem in which electrons are confined to two
the electric and the magnetic fields. Alternatively,
dimensions (such confinement is achieved, for exam-
passage of a current induces a voltage perpendicular
ple, by constructing AlGaAs–GaAs quantum-wells to
to the direction of the current flow, called the Hall
confined motion in one dimension), the behavior
voltage, VH, as seen in Figure 1. In addition to the
changes in a qualitative manner, as shown in
usual (longitudinal) resistance, R ¼ VL/I, a new resis-
Figure 2, taken from Stormer (1999). Instead of
tance, called the Hall resistance, is defined as
being proportional to B, now Hall resistance shows
VH plateaus. Most prominent are plateaus on which the
RH ¼ ð2Þ
I Hall resistance is precisely quantized at
212 Fractional Quantum Hall Effect and Composite Fermions

3 1/3 more precisely), and therefore the Hall resistance

measurements also provide an accurate estimate of
Hall resistance, RH (h/e2)

2/5 the fine structure constant. Concurrent with the

3/7
4/9 quantized plateaus is a dissipation-less current flow
2 1/2
3/5 4/7
in the limit of zero temperature.
2/3 2/5 1/3
RH 4/5 3/7
1 1
4/3 1.06.2.3 Fractional Quantum Hall Effect
5/3
2 2/3 3/5
3 4/3 4/5 At lower temperatures, higher magnetic fields, and
4 4/7 4/9
5/3
0 with better quality samples, plateaus are observed on
which the Hall resistance is precisely quantized at
Resistance, R

43 2
h
1 RH ¼ ð8Þ
fe 2

1/2 where f is a fraction. This is the ‘fractional quantum

00
10 20
Magnetic field (T)
Figure 2 Hall and the longitudinal resistances for a two-
dimensional electron system. The Hall resistance shows
precisely quantized plateaus whereas the longitudinal
resistance exhibits minima. Stormer HL (1999) Nobel
lecture: The fractional quantum Hall effect. Reviews of
Modern Physics 71: 875–889.
h The theory of FQHE must explain: the origin of
RH ¼
ne 2
where n is an integer, h is the Planck’s constant, and
e is the electron charge. This is referred to as the
integral quantum Hall effect (IQHE), or the ‘von
Klitzing effect’ (von Klitzing et al., 1980). The quan-
tization of the Hall resistance is independent of
materials details, sample type, or geometry; it is also
robust to variation in temperature and disorder, pro-
vided they are sufficiently small. The precision of the
quantization, that is the correctness of the preceding
equation, has been verified to one part in 107 for
absolute accuracy, and to a few parts in 1011 for
relative accuracy. The constant
h
RK ¼ ¼ 25813:807 . . . 
e2
is called the von Klitzing constant, and has been
adopted as the unit of resistance. It should be noted
that the fine structure constant
e2
¼
hc
also involves the same combination of the Planck’s
constant and the electron charge as the von Klitzing
constant (the speed of light c being known much
Hall effect’ (FQHE) also known as the Tsur–
30
Stormer–Gossard effect (Tsui et al., 1982). More
than 75 fractions have been observed to date, and
more are being observed as the experimental condi-
tions and the sample quality are improved. Most of
the observed fractions have odd denominators, and
they occur in certain sequences, with some examples
given later in Equations (50)–(52). One exception to
the ‘odd denominator rule’ is the FQHE state with
f ¼ 5/2.
ð5Þ
gaps in a partially filled Landau level; the dominance
of odd denominator fractions; the origin of sequences;
the order of stability of fractions; the nature of state at
even denominator fractions; the origin of 5/2; the
role of spin; and the nature of neutral and charged
excitations. We shall see below that the composite
fermion theory provides a natural explanation of
these facts, besides giving a microscopic theory that
allows detailed quantitative comparisons with exact
numerical results as well as experiment. At the same
time, the composite fermion theory makes verifiable
predictions (such as the existence of composite fer-
mions; the composite fermion Fermi sea; and
effective magnetic field) and unifies the fractional
ð6Þ and the integral quantum Hall effects.
1.06.3 Electrons in a Magnetic Field:
Landau Levels
ð7Þ
The Hamiltonian for a nonrelativistic electron (rela-
tivistic effects are neglected throughout) moving in
two dimensions in a perpendicular magnetic field is
given by
 Fractional Quantum Hall Effect and Composite Fermions 213

  1
1 eA 2 H ¼ ay a þ ð22Þ
H¼ pþ ð9Þ 2
2mb c
This is the familiar Hamiltonian of a simple harmo-
Here, e is defined to be a positive quantity, the
nic oscillator.
electron’s charge being e, and mb is the band mass
The angular momentum operator is defined as
of the electron. The canonical momentum is defined
as p ¼ ihÑ, and A satisfies

L ¼ – h b y b – ay a ð23Þ
Ñ  A ¼ B ẑ ð10Þ
Exploiting the property [H,L] ¼ 0, the eigenfunctions
The Schrödinger equation are chosen to diagonalize H and L simultaneously.
The analogy to the Harmonic oscillator problem
H ¼ E ð11Þ
immediately gives the solution
can be solved in several gauges, but the most con-
venient for the fractional quantum Hall effect is the H jn; mi ¼ En jn; mi ð24Þ
symmetric gauge:  
1
En ¼ n þ ð25Þ
Br B 2
A¼ ¼ ð – y; x; 0Þ ð12Þ
2 2
ðb y Þmþn ðay Þn
Choosing the unit of length as the magnetic length jn; mi ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffi j0; 0i ð26Þ
ðm þ nÞ! n !
 1=2
hc where n is called the Landau level index, and
,¼ ð13Þ
eB m ¼ n, n þ 1,. . . is the angular momentum quan-
and the unit of energy as the cyclotron energy tum number. The single-particle orbital at the
bottom of the two ladders defined by the two sets of
eB raising and lowering operators is
h!c ¼ h ð14Þ
mb c
1 1
the Hamiltonian can be expressed as hrj0; 0i X 0;0 ðrÞ ¼ pffiffiffiffiffi e – 4zz ð27Þ
2
  which satisfies
1 q2 1 q q
H¼ –4 z – z þ z
þ z ð15Þ
2 qzqz 4 qz q
z aj0; 0i ¼ b j0; 0i ¼ 0 ð28Þ

Here we have defined new variables z and z: The single-particle states are especially simple in
the lowest Landau level (n ¼ 0):
z ¼ x – iy ¼ r e – i ; z ¼ x þ iy ¼ r ei ð16Þ
1
We further define the following sets of ladder ðb y Þm zm e – 4z z
0;m ¼ hrj0; mi ¼ pffiffiffiffiffi 0;0 ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffi ð29Þ
operators: m! 22m m !
 
1 z q where we have used Equations (18) and (27). Aside
b ¼ pffiffiffi þ2 ð17Þ from the ubiquitous Gaussian factor, a general state
2 2 qz
  in the lowest Landau level is simply given by a
1 z q polynomial of z. In other words, apart from the
b y ¼ pffiffiffi –2 ð18Þ
2 2 qz Gaussian factor, the lowest Landau level wave func-
  tions are analytic functions of z.
y 1 z q
a ¼ pffiffiffi –2 ð19Þ
2 2 qz
 
1 z q
a ¼ pffiffiffi þ2 ð20Þ 1.06.3.1 Landau-Level Degeneracy
2 2 q
z
which have the property that States with a given n but different m are degener-
ate. To obtain the degeneracy of a Landau level,
   
a; ay ¼ 1; b; b y ¼ 1 ð21Þ consider a disk of radius R centered at the origin,
and ask how many states lie inside it. The degen-
and all the other commutators are zero. In terms of eracy can be shown to be independent of the
these operators, the Hamiltonian can be written as Landau level. Taking, for simplicity, the lowest
214 Fractional Quantum Hall Effect and Composite Fermions
Landau level, the eigenstate j0, mi has itsffi weight
pffiffiffiffiffi
located at the circle of radius r ¼ 2ml. Thus,
the largest value of m for which the state falls
inside the disk is given by m ¼ R2/2l2, which is
also the total number of eigenstates in the lowest
Landau level that fall inside the disk (ignoring
order one corrections). Thus, the degeneracy per
unit area is
1 eB B
G¼ ¼ ¼ ð30Þ
2l 2 hc 0
Here we have defined the flux quantum as 0 ¼ hc/e;
the degeneracy for each Landau level is equal to the
flux quanta penetrating the sample.
1.06.3.2 Filling Factor
The filling factor is the number of occupied Landau
levels, which depends on the density and the mag-
netic field. It is given by
0
¼ ð31Þ
B Landau-level (LLL) subspace, and the last two terms
where  is the two-dimensional (2D) density of
electrons. The filling factor is inversely propor-
tional to the magnetic field. As the magnetic field
is increased, each Landau level can accommodate
more and more electrons, and, as a result, fewer
and fewer Landau levels are occupied. Only the
lowest Landau levels is occupied at sufficient high
magnetic fields.
1.06.4 Integral Quantum Hall Effect
Theory
The integral quantum Hall effect can be explained
(Laughlin, 1981) in a model that neglects interac-
tions between electrons. It occurs because the state
of electrons at an integral filling factor is very
simple: it contains a unique ground state contain-
ing an integral number of filled Landau levels,
separated from excitations by the cyclotron or
the Zeeman energy gap. (In other words, the
state is incompressible, because to compress the
ground state creates finite energy excitations.)
It should be noted that the detailed explanation
of the existence of the plateaus also requires a
consideration of disorder-induced Anderson loca-
lization of some states.
1.06.5 The Fractional Quantum Hall
Effect Problem
The phenomenon of FQHE indicates that gaps open
not only at integral fillings (where their physics is
straightforward), but also at many fractional filling
factors. The essential goal for the theory of the
FQHE is to explain the origin of these gaps. This
requires a consideration of interelectron interactions,
because gaps occur only at integral fillings for
noninteracting electrons.
At high magnetic fields all electrons occupy the
lowest Landau level. Their kinetic energy is then
constant, hence irrelevant. With proper units for
energy and length scales, interacting electrons in a
high magnetic field are mathematically described by
the Hamiltonian
!
X1
H ¼P LLL P LLL þ Ve – bg þ Vbg – bg ð32Þ
r
j <k jk
Here rjk ¼ jzj  zkj is the distance between the elec-
trons j and k, P LLL denotes projection into the lowest
denote interaction between electrons and a uniform
positive background. There are no parameters in the
Hamiltonian; all energies are to be expressed in units
of the Coulomb energy:
e2
VC ¼ ð33Þ
",
where " is the dielectric constant of the background
material ("  13 for GaAs).
For some condensed matter systems, a nontrivial
collective phenomenon can be understood as an
instability of a normal state, which is the state
obtained when the interaction is switched off. For
the FQHE problem, switching off the interaction
produces a large number of degenerate ground states;
for example, for 109 electrons at ¼ 2/5 the number
of degenerate ground states in the absence of inter-
8
action is 10710 . Further, there is no small parameter
in the theory, which prevents a meaningful perturba-
tion theory.
1.06.6 Composite Fermions: Basic
Foundations
With the observation of many fractions, an analogy
between the FQHE and the IQHE could be identi-
fied, which led to the postulation of composite
 Fractional Quantum Hall Effect and Composite Fermions
fermions, and an explanation of the FQHE as the
IQHE of composite fermions (Jain, 1989). The most
important accomplishment of the composite fermion
(CF) theory is the identification of the particles of the
FQHE which can be considered as weakly interact-
ing to a good approximation. The CF theory can be
motivated by a Chern–Simons mean field theory
(Jain, 1989; Lopez and Fradkin, 1991; Halperin et al.,
1993), but its final outcome can be stated succinctly.
The eigenfunctions and eigenenergies for the ground
and (low-energy) excited states of strongly interact-
ing electrons at an arbitrary lowest Landau level
filling are expressed in terms of the known solu-
tions of the noninteracting electron problem at the
Landau level filling  as follows:
Y
2p BA
 ¼ P LLL zj – zk  
j <k
and
D P  E
  j <k r1 
E ¼
jk
þ Vel – bg þ Vbg – bg
h j i
where
 and equate the entire phase to the AB phase due to an
¼ ð36Þ
2p   1
B  ¼ B – 2p0
Here,   are the eigenfunctions of noninteracting
electrons at , P LLL projects the wave function to its
right into the lowest Landau level, p is an integer, and
B is an effective magnetic field. These equations
define a one-to-one correspondence between the
ground and excited states at filling factor (or mag-
netic field B) and  (magnetic field B). The problem
is often much simpler at , and for  ¼ n (where n is
an integer), we know the exact solution for the
ground and low energy states. The wave function
for the ground state at ¼ 1/(2p þ 1) was known
previously (Laughlin, 1983).
Electrons capture vortices to turn into composite
fermions because this is the most effective way for
them to stay away from one another. A typical wave
function satisfying the Pauli principle vanishes as
r when two particles approach one another, r being
the distance separatingQ them, but the unprojected
wave functions  j < k(zj  zk)2p vanish as r2p þ 1,
with the Jastrow factor contributing 2p to the expo-
nent and  contributing the rest. The Jastrow factor
is very effective in keeping particles apart from one
another, producing favorable correlations. It can be
215
argued that these correlations survive projection into
the lowest Landau level. Q
2p
The Jastrow factor j < k(zj  zk) attaches 2p
quantized vortices to each electron in  . The
bound state of an electron and 2p vortices is inter-
preted as a particle called the composite fermion. As
composite fermions move about, the vortices bound
to them produce Berry phases, which cancel part of
the Aharonov Bohm phases originating from the
external magnetic field. The effective magnetic
field can be determined in a Berry-phase calculation.
When a composite fermion, that is an electron along
with its vortices, is taken in a closed loop enclosing an
area A, it acquires a Berry phase
 ¼ – 2 þ 22pNenc ð38Þ
ð34Þ 0
where Nenc is the number of composite fermions inside
the loop. The first term is the familiar Aharonov Bohm
(AB) phase due to a charge going around in a loop.
ð35Þ The second is the Berry phase due to the 2p vortices
going around Nenc particles, with each particle con-
tributing a phase of 2. For uniform density states, we
replace Nenc in Equation (38) by its average value A
effective magnetic field, B, to obtain Equation (37).
Composite fermions thus sense a magnetic field B
ð37Þ
that is much smaller than the applied magnetic field,
and can even be zero or negative. This property of
composite fermions distinguishes them from electrons,
and lies at the root of most of the phenomenology.
Composite fermions form Landau-like levels in the
reduced magnetic field, which are called  levels, and
occupy  of them.
Composite fermions represent a new class of par-
ticles realized in nature. A vortex is a topological
object, because the quantum mechanical phase asso-
ciated with a closed loop around a vortex is exactly 2,
independent of the shape and the size of the loop.
(The topological character of vortices is implicit in
the fact that we count them.) As a result, composite
fermions are collective, topological particles. All fluids
of composite fermions are thus topological quantum
fluids. The most direct consequence of the topological
quantization of the vorticity of composite fermions is
the effective magnetic field, which is responsible for
the FQHE and several other phenomena.
The Chern–Simons field theoretic formulation of
composite fermions (Jain, 1989; Lopez and Fradkin,
1991; Halperin et al., 1993) proceeds through a sin-
gular gauge transformation defined by
216 Fractional Quantum Hall Effect and Composite Fermions

!2p
Y z –z 1.06.7 Consequences
¼  j k 9 ð39Þ
z j – z k  1.06.7.1 Theory of Fractional Quantum Hall
j <k
Effect
under which the eigenvalue problem transforms
into The FQHE of electrons is a manifestation of the
integral QHE for composite fermions. The latter
H 99 ¼ E9 ð40Þ occurs because a gap opens when composite fermions
" # fill an integral number of  levels, that is, when
1 X e e 2
H9 ¼ pi þ Aðri Þ – aðri Þ þV ð41Þ  ¼ n. These fillings correspond to electron filling
2mb i c c
factors given by the sequences:
2p X 9 n
aðri Þ ¼ 0 Ñi ij ð42Þ ¼ ð47Þ
2 j
2pn  1

zj – zk A gap here results in an FQHE plateau at RH ¼ h/fe2,

where jk ¼ iln   is the relative angle between
with
zj – zk 
the particles j and k. The prime denotes that j ¼ i is to n
f ¼ ð48Þ
be excluded from the sum. The magnetic field cor- 2pn  1
responding to a(ri) is given by
FQHE at f also implies an FQHE at the hole partner:
X
9
n
bi ¼ Ñi  aðri Þ ¼ 2p0
2 ðri – rl Þ ð43Þ f ¼ 1– ð49Þ
l
2pn  1

The above transformation thus amounts to attaching
a point flux of strength 2p0 to each electron, which
is how the composite fermion is modeled in this
approach.
To proceed further, one makes a mean-field
approximation, which amounts to spreading the
point flux on each electron into a uniform magnetic
field. Formally, one writes
A – a X A þ
A ð44Þ because they are all derived from the integer sequence
 
Ñ  A ¼ B ẑ
The transformed Hamiltonian then becomes
These fractions can be obtained by defining the
original problem in terms of holes – rather than
electrons – in the lowest Landau level, and making
composite fermions by binding vortices to holes.
The composite fermion (CF) theory provides
a natural explanation of many experimental facts.
The fractions f given by Equations (48) and (49)
are precisely the prominently observed fractions.
Furthermore, the fractions appear in sequences
of the IQHE. Some of the experimental sequences are:
ð45Þ
f ¼ 1=3; 2=5; 3=7; 4=9; . . . ; 10=21 ð50Þ
f ¼ 2=3; 3=5; 4=7; . . . ; 10=19 ð51Þ
1 X e
2
H9 ¼ pi þ A ðri Þ þV þ V 9 ¼ H0 þ V þ V 9
2mb i c
where V is the Coulomb interaction and V 9 denotes
the terms containing
A. The solution to H0
describes free composite fermions in an effective
magnetic field B , and V þ V 9 is the effective inter-
action between them, which is to be treated
perturbatively. When one transforms this problem
into the field theoretical Langrangian, it is seen to
be equivalent to the familiar Chern–Simons theory.
This approach is believed to capture the topological
properties of composite fermions, but does not lend
itself to a systematic perturbative treatment because
of the lack of a small parameter.
f ¼ 1=5; 2=9; . . . ; 6=25 ð52Þ
The fractions have odd denominators because the
ð46Þ
vortex quantum number 2p is an even integer.
Different flavors of composite fermions (i.e., com-
posite fermions carrying different numbers of
vortices) occur in different filling factor regions.
The filling factor range 1/2   1/3 is described
in terms of composite fermions carrying two vortices;
the range 1/3 >  1/5 in terms of composite fer-
mions carrying four vortices (with B antiparallel to
B for 1/3 > > 1/4); and so on. The region 1 >  1/2
of electrons maps into 0 <  1/2 of holes as a result
of particle–hole symmetry in the lowest Landau level,
and can be understood in terms of composite fermions
made of holes.
 Fractional Quantum Hall Effect and Composite Fermions 217

1.06.7.2 Quantitative Tests against Exact
Results
Exact results can be obtained for the Hamiltonian in
Equation (32) for a small number of particles by a
brute force diagonalization, because the dimension of
the Fock space in the lowest Landau level is finite for
a finite system. Typically, depending on the filling
factor, 10–16 electrons can thus be studied. The exact
solution gives the eigenenergies and eigenfunctions
for all eigenstates. The CF explanation of the FQHE
is fully confirmed by comparison to exact results
(Dev and Jain, 1992; Wu et al., 1993; Jain and
Kamilla, 1998)
A convenient geometry is the spherical geometry,
in which electrons move on the surface of a sphere,
with a radial magnetic field produced by a magnetic
monopole of strength Q at the center, which produces
a total magnetic flux of 2Q0. The eigenstates are
conveniently labeled by the total orbital angular
momentum L. The exact spectra at ¼ 1/3, 2/5,
and 3/7 (the first, second, and third rows, respec-
tively) are shown in Figure 3 (dashes). This figure
also shows the predicted energies from the CF the-
ory, without any adjustable parameters, as dots. The
ground state corresponds to one, two, or three filled
 levels of composite fermions, the the lowest energy
branch of excitations is a particle–hole pair of com-
posite fermions. The predicted energies agree to
within 0.1%, and the overlaps between the exact
and the CF wave functions are greater than 99%
for the numerical systems. Furthermore, the states
in between the special fractions n/(2pn  1) are
well described in terms of composite fermions at a
nonintegral filling factor.
Monte Carlo methods allow determination of the
thermodynamic limits of various experimentally
measurable quantities, such as excitation gaps.
These are often in 20–50% agreement with experi-
ment, with the discrepancy caused primarily by
disorder. An important quantity is collective modes,
101
111
168
175
227
230
277
31
42

–0.41

–0.42
E (e2/εl)

–0.43

–0.44 N = 10, v = 1/3 N = 8 , v = 1/3

–0.45
179
212
304
328
416
52
83

21
22
35
33
8
8

–0.44
–0.45
E (e2/εl)

–0.46

–0.47

–0.48 N = 10, v = 2/5 N = 8 , v = 2/5

–0.49
1182
127
263
493
621
952
744

21
22
35
33
45
8
8

–0.46
–0.47
E (e2/εl)

–0.48

–0.49

–0.50 N = 12, v = 3/7 N = 9 , v = 3/7

–0.51
0 3 6 9 12 0 3 6 9 12
L L
Figure 3 Comparison of spectra obtained from exact diagonalization (dashes) and CF theory (dots). The spectra in the three
rows are for ¼ 1/3, 2/5, and 3/7, respectively. The x-axis label L is the total orbital angular momentum of the state. From Jain
JK and Kamilla RK (1998) Composite fermions: Particles of the lowest Landan level. In: Heinonen O (ed.) Composite Fermions,
ch. 1. New York: World Scientific.
218 Fractional Quantum Hall Effect and Composite Fermions

which are understood as excitons of composite fer- found between the low energy spectra of the exact
mions; the experimental measurements of the solutions of interacting electrons at B (from numer-
energies and the dispersions (Pinczuk et al., 1993; ical diagonalization) and the exact solutions of
Kukushkin et al., 2009) at various fractions such as noninteracting electrons at B. In addition, several
1/3, 2/5, 3/7, and 4/9 are in excellent agreement experiments have measured the radius of the cyclo-
with the predictions of the composite fermion theory tron orbit of the current carrying entities in the
(Scarola et al., 2000). vicinity of ¼ 1/2, and confirmed that it is deter-
mined by B rather than the applied magnetic field
1.06.7.3 Composite Fermion Fermi Sea (Willet et al., 1993; Kang et al., 1993; Goldman et al.,
1994; Smet et al., 1996).
No general principle excludes FQHE at even-
denominator fractions. Such FQHE has been
observed, for example, at f ¼ 5/2. The CF theory
provides a natural explanation for why even denomi- 1.06.7.5 Spin Physics
nator FQHE is rare: the model of noninteracting The spin degree of freedom is frozen when the
composite fermions produces only odd-denominator Zeeman splitting is large compared to the interaction
fractions; any even-denominator fraction must neces- energy. In that limit, all FQHE states in the lowest
sarily owe its existence to weak residual interactions Landau level are fully spin polarized. One might
between composite fermions, and, therefore, can be expect, by application of the Hund’s maximum spin
expected to be much weaker. rule to electrons in the lowest Landau level, that the
The nature of state at ¼ 1/2, the simplest frac- state would be fully polarized at all Zeeman energies.
tion, has been of interest. It is obtained as the n ! 1 That is not the case, however. The actual state is
limit of the sequence f ¼ n/(2n þ 1). If the model of determined by application of the Hund’s rule to
noninteracting composite fermions continues to be composite fermions.
valid in this limit, their effective magnetic field B In a model that assumes that composite fermions
vanishes and they form a Fermi sea, called the CF can be taken as nearly independent particles with an
Fermi sea (Halperin et al., 1993; Kalmeyer and Zhang, effective mass, their physics is straightforward. The
1992). The lack of FQHE follows because the Fermi IQHE of composite fermions occurs at  ¼ n ¼ n" þ
sea has no gap to excitations. Several experiments n#, where n" is the number of occupied spin-up 
have confirmed the formation of composite fermions
levels and n# is the number of occupied spin-down 
in the vicinity of ¼ 1/2 and of the CF Fermi sea at
levels. This fraction corresponds to electron fillings
¼ 1/2. These include. Shubnikov de Haas oscilla-
tions of composite fermions (Du et al., 1994), linear n n" þ n#
opening of the CF gap (Du et al., 1993); measurement ¼ ¼ ð53Þ
2pn  1 2pðn" þ n# Þ  1
of the cyclotron resonance of composite fermions
(Kukushkin et al., 2007); and measurements of the The spin polarization of the state is given by
CF Fermi wave vector through the semiclassical n" – n#
e ¼ ð54Þ
cyclotron orbit of composite fermions (Willet et al., n" þ n#
1993; Kang et al., 1993; Goldman et al., 1994; Smet
and wave function for the FQHE state is
et al., 1996)
Y
2p
2pnþ1
n ¼P LLL n" ;n# zj – zk ð55Þ
j <k
1.06.7.4 Effective Magnetic Field
or
The reduced effective magnetic field, which is a
Y
2p
direct evidence of binding of vortices to electrons 2pnþ1 ¼P 
zj – zk ð56Þ
n LLL n" ;n#
and the formation of composite fermions, has been j <k
confirmed directly by numerous means. The appear-
ance of fractional sequences that correspond to the where
integer sequence of the noninteracting fermions and n" ;n# ¼ n" n# ð57Þ
the formation of a Fermi sea at 1/2 filled Landau
level are experimental proofs of the effective mag- are wave functions of IQHE states with n" spin-up
netic field, as is the one-to-one correspondence and n# spin-down Landau levels occupied.
 Fractional Quantum Hall Effect and Composite Fermions 219

Thus, while inclusion of spin does not give new 1 2

f ¼1þ and f  ¼ 1 þ ð60Þ
fractions, it produces, in general, many states at a 3 3
given fraction, whose spin polarizations are predicted which produce new electron fractions
by the CF theory. Take the example of ¼ 4/9,
which corresponds to n ¼ 4 of composite fermions. 4 5
f ¼ and f ¼ ð61Þ
There are three possibilities: (n", n#) ¼ (2,2), (3,1), 11 13
and (4,0). The unpolarized state (2,2) is obtained at between the familiar fractions 1/3 and 2/5, consistent
the lowest Zeeman energies (as application of Hund’s with experimental observations (Pan et al., 2003).
rule to composite fermions would predict), the par- Here, composite fermions in the partially filled sec-
tially polarized state (3,1) at intermediate Zeeman ond  level capture two more vortices to turn into
energies, and the fully polarized (4,0) at large composite fermions of a different flavor, which con-
Zeeman energies. Upon increasing Ez, the ground- dense into their own  levels, thereby opening a gap
state spin changes discontinuously when the  levels and producing quantum Hall effect. This physics has
of up and down spins cross one another. A quantita- been confirmed by exact diagonalization studies
tive determination of the energies of these states (Chang and Jain, 2004; Wójs et al., 2004), as shown
leads to a theoretical determination of the actual in Table 1. Many more FQHE states can similarly be
phase diagram of the FQHE states as a function constructed.
of the Zeeman energy (Wu et al., 1993; Park and
Jain, 1998) 1.06.7.6.2 Pairing
The Zeeman energy can be varied experimentally As noted above, FQHE has been observed (Willet
by application of a magnetic field parallel to the et al., 1987) at ¼ 5/2. Writing
two-dimensional layer (tilted field experiment), or
by changing the density so the FQHE state occurs 5 1
¼2þ ð62Þ
at different B. The above physics has been fully 2 2
confirmed by extensive experimentation (Du et al., and treating the lowest filled Landau level as inert
1995; Kukushkin et al., 1999). (which, counting the spin degree of freedom,
accounts for the 2 on the right hand side) shows
that 5/2 corresponds to a filling of 1/2 in the second
1.06.7.6 Interacting Composite Fermions: Landau level. Thus, half-filled second Landau level
New Fractions behaves qualitatively differently from the half-filled
lowest Landau level.
1.06.7.6.1 FQHE of composite fermions The currently most promising scenario for the
n
While the fractions ¼ are obtained most explanation of the 5/2 FQHE is that composite fer-
2pn  1 mions form a p-wave paired state, described by a
immediately in the CF theory, other fractions are not Pfaffian wave function (Moore and Read, 1991):
ruled out. To see the physics of the next generation, " #
 Y
fractions consider electrons in the filling factor range 1
2 1X 2
Pf
1=2 ¼ Pf zi – zj exp – jzk j ð63Þ
zi – zj 4 k
1=3 < < 2=5 ð58Þ i<j

which map into composite fermions in the range

1 <  < 2 ð59Þ
The lowest  level is fully occupied and the
second one partially occupied. (We take composite
fermions to be fully spin-polarized.) No FQHE
would result in this region for noninteracting com-
posite fermions, just as non-interacting electrons in
the partially filled second Landau level do not exhi-
bit any FQHE. The weak residual interaction
between composite fermions, however, can possibly
cause a gap to open at certain filling factors. A natural
expectation is that the strongest new CF fractions are
Table 1 Energies of two wave functions for 4/11: the
exact Coulomb state ex 4=11 and the trial wave function
tr4=11 ¼ P LLL 4=3 21
Eex Etr Overlap
0.441214 0.44088(4) 0.99
Results are for N ¼ 12 particles. The overlap is defined as
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
htr jð0Þ i= hð0Þ jð0Þ ihtr jtr i, where (0) is a state that is
very close to the exact ground state (obtained by a method
called CF diagonalization). From Chang C-C and Jain JK
(2004) Microscopic origin of the next-generation fractional
quantum Hall effect. Physical Review Letters 92: 196806.
220 Fractional Quantum Hall Effect and Composite Fermions
where Pf stands for Pfaffian. The Pfaffian of an anti-
symmetric matrix M is defined, apart from an overall
normalization factor, as
Pf Mij ¼ AðM12 M34 MN – 1;N Þ
where A is the antisymmetrization operator. The
usual Bardeen–Cooper–Schrieffer wave function for
fully polarized electrons can be written as
BCS ¼ A½0 ðr1 ; r2 Þ0 ðr3 ; r4 Þ 0 ðrN – 1 ; rN Þ
ð65Þ However, the CF theory in its simplest form is not
which is a Pfaffian. (The fully symmetric spin part is
1 levels is indicated by the observation that while
not shown explicitly.) Analogously, Pf ¼
zi – zj
describes a p-wave pairing of electrons (p-wave
because the system is fully spin-polarized), and
Pf
1=2 is interpreted as the p-wave paired state of
composite fermions carrying two vortices. The
Pfaffian wave function was originally motivated in a
conformal field theory approach, which also suggests
that its quasiparticles obey so-called nonabelian
braiding statistics (Moore and Read, 1991).
1.06.7.7 Fractional Charge
The excitations of an FQHE state are excited com-
posite fermions. A sole composite fermion in an
otherwise empty  level is often called a CF quasi-
particle, and a missing composite fermion from an
otherwise filled  level is called a CF quasihole. This
description has been confirmed extensively in exact
diagonalization studies. In a localized representation,
these represent a localized excess or deficiency of
charge relative to the uniform ground state. The
charge excess associated with a CF quasiparticle is
the sum of the charge of an electron (e) and the
charge of 2p vortices:
– e  ¼ – e þ 2pev
where ev is the charge of a single vortex. The charge
of the vortex can be shown to be
ev ¼ ve
The local charge of a CF-quasiparticle at
¼ n/(2pn þ 1) therefore has the fractional value
e quantum Hall effect. Physical Review Letters 63: 199.
– e ¼ –
2pn þ 1
The topological quantization of the vorticity implies
that this charge is precisely quantized. The fractional
charge was originally predicted theoretically
(Laughlin, 1983), and has been measured in shot
noise experiments (de Picciotto et al., 1997).
ð64Þ
1.06.8 Open Issues
The FQHE and other phenomena in the lowest
Landau level are well described by the CF theory.
fully satisfactory for the second Landau-level
physics. One difference between the two Landau
there is no FQHE at ¼ 1/2, an FQHE occurs at
¼ 5/2. Further, far fewer fractions are observed in
the second Landau level, and they are much more
delicate than those in the lowest Landau level. While
other fractions in the second Landau level also have
odd denominators (such as 2 þ 1/3 and 2 þ 2/5),
their wave functions are rather different than those
of the corresponding fractions in the lowest Landau
level. Several imaginative approaches are currently
being pursued, which have excitations with exotic
character (e.g., nonabelian braiding properties).
(See Chapters 1.03, 1.05 and 1.07).
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Wu XG, Dev G, and Jain JK (1993) Mixed-spin incompressible
states in the fractional quantum Hall effect. Physical Review
Letters 71: 153.
Further Reading
Das Sarma S and Pinczuk A (eds.) (1996) Perspectives in
Quantum Hall Effects. New York: Wiley.
Heinonen O (ed.) (1998) Composite Fermions. New York: World
Scientific.
Jain JK (2007) Composite Fermions. London: Cambridge
University Press.
 1.07 Spin Hall Effect
S Murakami, Tokyo Institute of Technology, Tokyo, Japan
N Nagaosa, University of Tokyo, Tokyo, Japan
ª 2011 Elsevier B.V. All rights reserved.

1.07.1 Introduction – Early History and Background of Spin Hall Effect (SHE) 224
1.07.2 Intrinsic and Extrinsic Mechanism of SHE 227
1.07.2.1 Intrinsic SHE in p-Type Semiconductors 228
1.07.2.2 Rashba Model for n-Type Semiconductors 230
1.07.2.3 Impurity Scattering Effect 231
1.07.2.3.1 Spin-independent impurities 231
1.07.2.3.2 SO coupling modified by impurities 235
1.07.2.3.3 SHE in the hopping regime 236
1.07.2.4 Mesoscopic SHE 237
1.07.2.5 Experimental Observation of SHE in Semiconductors 239
1.07.2.5.1 Measurement of SHE in semiconductors by KR 239
1.07.2.5.2 Measurement of SHE in semiconductors by spin LED 241
1.07.2.6 Various Issues on the SHE 243
1.07.2.6.1 Definition of the spin current 243
1.07.2.6.2 Ab initio calculations 245
1.07.3 SHE in Metals 245
1.07.3.1 Experiments of SHE in Metals 245
1.07.3.2 Theories of SHE in Metals 251
1.07.4 Quantum Spin Hall Effect 253
1.07.4.1 Inverted Band Structure and SHI 253
1.07.4.2 QSHE and Z2 Topological Invariants in 2D and 3D 254
1.07.4.3 Helical Edge Modes in QSH systems 257
1.07.4.4 Models and Candidate Materials for QSHE 258
1.07.4.5 Experimental Observation of QSHE 259
1.07.4.6 Further Developments in the QSHE 261
1.07.4.6.1 Spin-charge separation and charge fractionalization 261
1.07.4.6.2 Effective theory and quantized magneto-electric effect 262
1.07.4.6.3 Superconducting QSHSs 262
1.07.4.6.4 Localization problem related to the QSHS 263
1.07.4.6.5 SHE in strongly correlated systems 264
1.07.5 Summary and Perspectives on SHE 264
1.07.5.1 Comparison between AHE and SHE 264
1.07.5.2 Comparison between Integer QHE and QSHE 265
1.07.5.3 Generalization of SHE and Future Directions 266
1.07.5.3.1 Optical SHE 266
1.07.5.3.2 Multiferroics 267
1.07.5.3.3 Future directions 268
References 269

Glossary
Aharonov–Bohm effect The wave function of a potential along the path, leading to the change in the
charged quantum mechanical particle acquires a interferenceofthedifferencepathsduetothemagnetic
phase given by the contour integral of the vector flux. This effect is called Aharonov–Bohm effect.

222

Aharonov–Casher effect Analogously to the
Aharonov–Bohm effect, the wave function of a
quantum mechanical particle with spin acquires a
phase factor which is given by the contour integral
of the vector product of the electric field and the
spin. This effect is called Aharanov–Casher effect.
Angle-resolved photoemission spectroscopy
(ARPES) The momentum- and energy-resolved
spectroscopy of the emitted electrons from the
sample kicked by the high-energy incident light.
This can detect the spectral function of the Green’s
function for occupied states.
Berry phase In 1984, M.V. Berry formulated the
quantum phase associated with the adiabatic
change of the Hamiltonian. Through the adiabatic
change, the wave function is confined within the
subspace of the Hilbert space, which leads to the
gauge structure and is represented by this Berry
phase.
BW phase One of the p-wave pairing states for
superfluid with the isotropic energy gap. It is now
established that the B-phase of 3He is described by
this state.
Chiral edge channel In quantum Hall system,
there appear edge channels at the edges of the
sample, which have the definite propagation
direction and are called chiral edge channels. The
backward scattering is forbidden in the chiral edge
channels, which explains the quantized Hall
conductance in quantum Hall system.
Coulomb blockade In the tunnel junction with
small capacitance, the Coulomb charging energy
can be larger than the thermal energy, and the
tunneling process is blocked. This Coulomb
blockade depends on the charge q at the junction
periodically, leading to the characteristic oscillation
of the tunneling current as a function of gate
voltage.
Dirac fermion P.A.M. Dirac introduced the
relativistic equation of quantum particles with
four-component spinor wave function starting from
a few fundamental requirements. This is called
Dirac equation, and the fermions obeying Dirac
equation are the Dirac fermions. In condensed
matter systems, it often occurs that the band
structure is described by four- or two-component
Dirac equations locally in momentum space.
eg and t2g orbitals Under the crystal field of Oh
symmetry, the five d-orbitals are split into two
groups, that is, eg-orbitals (x2  y2, 3z2  r2) and
t2g-orbitals (xy,yz,zx).
Spin Hall Effect 223
Hanle effect In 1924, Hanle showed the variation
of the polarization of the resonant fluorescent light
in atoms, which is called the Hanle effect. This
effect is now used to measure the lifetime and
g-factor of atoms and molecules.
Keldysh formalism L. Keldysh developed a
Green’s function method which is applicable even
to states far away from the equilibrium. This
method is called the Keldysh formalism, and is now
applied in various transport problems.
Kondo effect When a magnetic impurity is
inserted into a metallic host, its magnetic moment
is screened by the spins of the conduction
electrons to form a spin singlet. This phenomenon
is called the Kondo effect.
Kramers theorem In the system with the odd
number electrons, it is proved that the electronic
states are energetically (at least doubly) degenerate
when the Hamiltonian has the time-reversal
symmetry. The doublet related by the time-reversal
symmetry operation is called Kramers doublet.
Kubo formula In 1957, R. Kubo formulated the
linear response theory based on the density matrix
formalism. This provides the most fundamental
formula of the response functions, and basis to
study the physical properties of systems.
Light-emitting diode (LED) The light is emitted
through the recombination of the electrons and
holes when the current is applied into the p–n
junction.
Magnetic Kerr rotation The rotation of the
polarization occurs when the light is reflected from
the magnetic system due to the relativistic
spin–orbit interaction.
Magneto-electric effect The phenomenon where
the magnetization is induced by the electric field or
the electric polarization is induced by the magnetic
field.
Majorana fermion In 1937, E. Majorana proposed
the real fermions satisfying the relation f† = f called
the Majorana fermion (f† (f) is the creation
(annihilation) operator of the fermion). Roughly
speaking, Majorana fermion is half of the usual
fermion. Majorana fermion appears in the exact
solution to two-dimensional Ising model, and also
in the theory of pairing state of spinless fermions.
Mott scattering N.F. Mott derived the formula for
the cross section of the Coulomb scattering
between the two identical fermions with spin 1/2.
By using this formula, the Mott detector to measure
the spin state of electrons has been developed.
224 Spin Hall Effect
Multiferroics Materials showing multiple
symmetry breakings. Usually, it means those
showing the magnetic order and the ferroelectricity
simultaneously.
Noether’s theorem The theorem connecting the
invariance with respect to some transformation and
the conservation law in field theory. By using this
theorem, one can define the current from the
invariance of the Lagrangian.
Noncentrosymmetric
superconductor Superconductors without the
inversion symmetry. In the presence of the
spin–orbit interaction, novel properties such as the
mixture of singlet and triplet pairing emerge.
Nonlinear sigma model A model in field theory
describing the field with constraint. This is used to
analyze the localization problem in disordered
systems.
Nomenclature
H Hamiltonian
H(k) Hamiltonian matrix in the Bloch wave
number k
jj charge current flowing along ĵ
direction
jij spin current with +î spin moving to +ĵ
and î spin moving to ĵ
k wave number
k the size of the wave number (=k)
kb unit vector parallel to k, defined as
kb= k/jkj
1.07.1 Introduction – Early History
and Background of Spin Hall Effect
(SHE)
Hall effect, which is one of the most important effects
in condensed matter physics, has been discovered by
Hall in 1893 (Hurd, 1973). When the charge current j
flows with an applied magnetic field perpendicular to
it, a voltage drop occurs in the direction transverse
both to the current and magnetic field. This voltage
drop VH between the two edges of the sample, called
Hall voltage, divided by the current j defines the Hall
resistance. This Hall effect originates from the
Seebeck effect The effect where the voltage drop
is induced by the temperature gradient.
Soliton In field theory, the order parameter field
can have the spatial dependence creating a
localized kink structure. This localized structure is
called soliton.
Umklapp scattering In crystals, the conservation
of the momentum is relaxed by the reciprocal
lattice vectors G’s, and scattering process using
this G’s is called Umklapp scattering.
Virtual bound state The d-orbitals in metals are
almost localized near the atomic nucleus. However,
due to the hybridization with the conduction
electrons, the d-levels have the finite lifetime and
energy broadening, and are called the virtual bound
states.
Z2 group The group whose elements are (1,1)
only.
si (i = x,y,z) spin operators with s = 1/2
V(x) impurity potential at the position x
measured from the impurity
x position
*? (as in x_ ) time derivative
s spin Hall conductivity
i time-reversal invariant momentum
(TRIM). There are four TRIMs in
two-dimensional (2D) Brillouin zone
and eight in 3D.
Lorentz force acting on the orbital motion of the
electrons under the magnetic field; hence, the sign
of Hall coefficient is determined by the sign of the
charge carriers while its magnitude by the carrier
density. A few years after. Hall himself discovered
the anomalous Hall effect (AHE) (Hurd, 1973), in
which the transverse Hall voltage originates from the
spontaneous magnetization even without the exter-
nal magnetic field in metallic ferromagnets. This
effect is driven by the relativistic spin–orbit (SO)
interaction, while there are both intrinsic (Karplus
and Luttinger, 1954) and extrinsic (Smit, 1955, 1958;
Berger, 1970) mechanisms. The intrinsic mechanism

is due to the anomalous velocity of the Bloch wave
function, and is purely the band structure effect.
Recently, this intrinsic contribution is reexamined
from the modern topological viewpoint, that is, the
Berry curvature in the momentum space (Nagaosa,
2006). The extrinsic ones, on the other hand, are due
to the impurity scattering influenced by the SO
interaction and are classified into (1) the skew scat-
tering (SS) mechanism (Smit, 1955, 1958), where the
scattering probability Pk ! k9 from k to k9 is different
from Pk9 ! k, and (2) the side jump SJ mechanism
(Berger, 1970), where the wavepacket experiences
the transverse shift at the scattering.
In nonmagnetic metals, one can imagine that each of
the up- and down-spin electrons show the AHE in the
opposite directions due to the SO interaction. Then,
one expects the spin current flow or the spin voltage
drop in the transverse direction both in the direction of
the charge current and the spin-polarization direction.
This effect, called the spin Hall effect (SHE), is the
subject of this chapter, which constitutes a rapidly
growing field in the spintronics. The SHE was first
proposed by D’yakonov and Perel (1971a,b). They
considered the extrinsic SS as the origin of the SHE
predicting the spin accumulation at the edge of the
sample due to the spin current. Here, one remark is
that the spin current is time-reversal even, in sharp
contrast to the spin accumulation or charge current
which are time-reversal odd. This means that the
conversion of the spin current into the spin accu-
mulation requires the irreversibility due to the spin
relaxation. Later Hirsch (1999) proposed an experi-
mental method to detect the SHE by the
measurement of the voltage. With the charge cur-
rent flowing in the x-direction in the spin Hall
system, the spin Hall voltage is produced along the
y-direction. When the two edges at y = L/2, with L
being the width of the sample, are connected to each
other with a conductor, the spin current circulates
along the y-direction. This circulating spin current
induces the voltage at the conductor along the
x-direction. In Hirsch (1999), the voltage signal
has been estimated to be of the order of 60 mV for
the sample size l ¼ 100 mm for a usual metal. Zhang
(2000) also discussed the SHE with a semiclassical
Boltzmann equation taking into account the spin
diffusion, since SO interaction is the origin for
both the SHE and the spin relaxation through the
spin-flip processes. As mentioned above, this spin
relaxation is also indispensable for the spin accumu-
lation at the edges of the sample.
Spin Hall Effect 225
In these works, the SHE has been considered as an
extrinsic effect, due to impurities in the presence of
SO coupling. Nevertheless, there were no detailed
discussions on the size of the effect, and this extrinsic
effect is not easily controllable because it is caused by
impurities. On the other hand, two groups indepen-
dently proposed an intrinsic SHE in different
systems. Murakami et al. (2003) proposed the SHE
in p-type semiconductors such as p-GaAs. Sinova
et al. (2004) independently proposed the SHE in
n-type semiconductors in two-dimensional (2D) het-
erostructures. These proposals are called the intrinsic
SHE, because they do not rely on impurities but they
stem from the band structure itself, as we discuss in
this review. These two proposals triggered extensive
research, both theoretical and experimental. After
5 years from the theoretical predictions of the intrin-
sic SHE, more than 500 papers have been published.
In p-type semiconductors, for example, the SHE
in the linear response is expressed as
jji ¼ s "ijk Ek ð1Þ
where jij is the current of the ith component of the
spin along the direction j and "ijk is the totally anti-
symmetric tensor in 3D (see Figure 1(a)). The spin
current jijroughly corresponds to a product of velocity
vj and the spin Si. It describes a spin current with
spins along +iˆdirection going to the +jˆdirection, and
spins along iˆ direction going to the jˆ direction. In
Figure 1(a), the electric field is applied along the
z-direction (k = z), and it produces the spin currents
jy x (S xvy) and jx y (S yvx) with jy x = jx y . For
example, the Sx-spin current flows in the y-direction,
and S y-spin current flows in the x-direction. As an
example, we consider a thin semiconductor slab and
apply an electric field as shown in Figure 1(b). The
electrons with opposite spins are deflected toward
opposite directions, resulting in a spin current per-
pendicular to the applied field.
In the context of SHE, we often restrict ourselves to
a situation with time-reversal symmetry, which means
the absence of magnetism and magnetic field. We can
consider the SHE in systems without the time-reversal
symmetry. In such case the charge Hall effect arises (or
in ferromagnet AHE arises), and the Hall current is a
mixture of charge and spin current. Only when the
system respects the time-reversal symmetry, the Hall
current is a pure spin current. The spin current will
induce a spin accumulation near the sample boundary.
The amount of accumulated spins is roughly estimated
as a product of spin current and spin relaxation time Ts
226 Spin Hall Effect
(a) y (b)
x current
z Up-spin
E p-GaAs
Figure 1 Schematic of the spin current induced by an electric field.
(Murakami et al., 2003). The spin accumulation also
affects the spin current itself near the boundaries
(Ma et al., 2004; Hu et al., 2004). Because spin current
is even under time reversal, it can be induced even
when the time-reversal symmetry is preserved. It also
implies that the spin Hall current is dissipationless. In
doped semiconductors, however, the longitudinal
conductivity is finite and the system undergoes
Joule heating. Nevertheless, there exist spin Hall
insulators (SHIs), which are band insulators with
nonzero SHE; in such systems the longitudinal con-
ductivity is zero, and the SHE accompanies no
dissipation (Murakami et al., 2004a).
Because the predicted effect in p-type semiconduc-
tors and in n-type heterostructures is large enough to
be measured, this intrinsic SHE attracted much atten-
tion, and one of the important issues was the disorder
effect. Among many works on disorder effect, Inoue
et al. (2003, 2004) considered dilutely distributed
impurities with short-ranged potentials in the n-type
semiconductor in heterostructure, and calculated the
SHE, incorporating the vertex correction in the ladder
approximation. Remarkably, the resulting spin hall
conductivity (SHC) is exactly zero in the clean limit.
After this work, many people thought the SHE to be
fragile to impurities; namely, only a small amount of
impurities might completely kill the intrinsic SHE.
However, this turned out to be a special case, and is
not true in general. In fact, the SHC is, in general,
nonzero even in the presence of disorder, as we see
later.
In such circumstances, two seminal experiments on
the SHE have been done. Kato et al. (2004) observed
spin accumulation in n-type GaAs by means of Kerr
rotation (KR). The observed spin accumulation at the
two edges was interpreted as that caused by a bulk spin
current. Both unstrained and strained samples, with
various orientations of the sample, are used to measure
the SHE, and the resulting spin accumulation agreed
well with that expected from the extrinsic SHE.
Spin
Current Down-spin
Wunderlich et al. (2005) observed a circularly polar-
ized light emitted from a spin light-emitting diode
(LED) structure, using spin current from the p-type
semiconductor. This circularly polarized light is
attributed to the SHE in the p-type semiconductor.
After those works, there followed a number of experi-
mental papers. In particular, the SHE has been
observed in various metals such as Al, Pt, and Au.
As the Hall effect has a quantized variant, that is,
the quantum Hall (QH) effect, the SHE also has an
analogous effect: quantum spin Hall effect QSHE.
(Note that the spin Hall conductance is not quan-
tized, so it cannot be called quantized SHE.) The
QSH effect is a spin analog of the QH effect, and
they share many fundamental aspects in common.
Yet, the QSH effect is realized in zero magnetic
field, which is in strong contrast with the QH effect.
This effect has been experimentally observed
recently (König et al., 2007).
Although there have been many works concerning
the SHE in these few years, there are many issues to
be resolved. In this review, we also introduce these
remaining issues and open questions. There are
already several articles on the recent developments
of this field (Alderson and Hurd, 1971; Awschalom
and Flatte, 2007; Bratkovsky, 2008; Chazalviel, 1975;
Fabian et al., 2007; Fertig, 2003; Nagaosa, 2008; Wolf
et al., 2001). One may be referred also to other intro-
ductory articles on the recent developments and
perspectives of the SHE (Bauer, 2004; Day, 2005;
Inoue and Ohno, 2005). Readers can also be referred
to earlier short reviews (Murakami, 2005), and more
recent ones (Schliemann, 2006; Engel et al., 2006).
This chapter is organized as follows. In Section
1.07.2, we introduce a basic framework and discuss
the mechanism of the SHE in semiconductors. In
Section 1.07.3, we discuss the SHE in metals.
Section 1.07.4 is devoted to the QSH effect. We
give concluding remarks and discuss miscellaneous
topics in Section 1.07.5.

1.07.2 Intrinsic and Extrinsic
Mechanism of SHE
The intrinsic SHE can be described from various
viewpoints. In this section, we start with the Berry
phase theory of the intrinsic SHE. According to this
theory, the SHE is driven by the ‘‘Berry phase cur-
vature in momentum-space.’’ This occurs because of
the wave nature of the electrons. The Berry phase
(Berry, 1984; Shapere and Wilczek, 1989; Bohm et al.,
2003) is a change of a phase of a quantum state
caused by an adiabatic cyclic change of some para-
meters characterizing the Hamiltonian. As this phase
is determined only by a path in the parameter space,
it is sometimes referred to as a geometric phase.
Various physical phenomena involve this Berry
phase, depending on which parameters are regarded
to change adiabatically, and are studied and
reviewed in Shapere and Wilczek (1989), Bohm
et al. (2003), Bérard and Mohrbach (2004, 2006),
Bliokh (2005), Bliokh and Bliokh (2005), Culcer
et al. (2004), Culcer and Winkler (2007a,b, Culcer
et al. 2005a), Dai and Zhang (2007), Erlingsson et al.
(2005), Hu et al. (2003a), Imura and Shindou (2005),
Raimondi et al. (2007, 2006), Shindou and Imura
(2005), Sinova et al. (2006), Sun et al. (2004), Lu
et al. (2006), and Středa (2006). As for the electronic
states, this Berry phase is known to appear in various
kinds of Hall effects, such as the QH effect (Thouless
et al., 1982; Kohmoto, 1985; Sundaram and Niu,
1999), the AHE, or the SHE. To demonstrate the
effect of the Berry phase in k space, we here consider
a clean system with crystal translational symmetry,
where the Bloch wave number k is a good quantum
number. We regard k as parameters which are adia-
batically changed. Then the notion of the Berry
phase can be expressed in a gauge field in k-space
(Berry, 1984). It plays an important role in AHE
(Matl et al., 1998; Ye et al., 1999; Chun et al., 2000;
Ohgushi et al., 2000; Taguchi et al., 2001; Jungwirth
et al., 2002; Fang et al., 2003) and in magnetic super-
conductors (Murakami and Nagaosa, 2003).
We define the U(1) gauge field An(k) and corre-
sponding field strength Bn(k) as
    Z momentum space has been studied in the recent
q y qunk
Ani ðkÞ ¼ – i nk nk X – i unk dx
qki unit cell qki
Bn ðkÞ ¼ rk  An ðkÞ
where unk(x) is the periodic part of the Bloch wave
function nk(x) = eik ? xunk(x) and n is the band index.
Spin Hall Effect 227
Here An(k) is a gauge field, and is subject to a gauge
transformation accompanied by a change of phase for
the wave function of unk: u9nk = ei(k)unk. The corre-
sponding field strength Bn(k) = rk  An(k) remains
unchanged, that is, gauge invariant. Because a
contour integral of A(k) along a loop in k space is
the Berry phase, An(k) and Bn(k) are called Berry
connection and Berry curvature, respectively.
We consider a wavepacket as a superposition of
the Bloch states. It is localized both in the real space
and in the momentum space. The width x of the
wavepacket in the real space and the width k in
momentum space is restricted by the uncertainty
principle: xk & 2. We consider k is much
smaller than the size of the Brillouin zone
k  2=a; where a is the lattice constant, and
consequently we have x  a. This wavepacket
acquires a phase when the wave number k is changed.
The motion of a wavepacket made of the Bloch states
then undergoes a shift because of the interference of
Bloch states.
By incorporating the effect of Bn(k), the
Boltzmann-type semiclassical equation of motion
(EOM) acquires an additional term due to the
Berry phase (Adams and Blount, 1959; Blount, 1962;
Sundaram and Niu, 1999):
1 qEn ðkÞ _
x_ ¼ þ k  Bn ðkÞ ð4Þ
h qk
hk_ ¼ – e ðE þ x_  BðxÞÞ ð5Þ
The term kB_ n ðxÞ represents the effect of Berry
phase, and is called an anomalous velocity.
When we apply an electric field, the wave number
will change in time. The second term on the
right-hand side of Equation (4) then gives rise to an
additional velocity perpendicular to the electric field,
namely the Hall effect. This theory has already been
proposed in the 1950s in a discussion of AHE (Karplus
and Luttinger, 1954; Nagaosa, 2006), and has renewed
interest from the QHE (Thouless et al., 1982) and the
Berry phase (Berry, 1984). The SHE is among the
phenomena due to this anomalous velocity. This
intrinsic Hall conductivity (7) was first recognized by
Karplus and Luttinger (1954). This Berry phase in
ð2Þ works on AHE (Ye et al. 1999; Ohgushi et al. 2000;
Taguchi et al. 2001; Jungwirth et al., 2002; Fang et al.
ð3Þ 2003; Yao et al. 2004), as well as those on the SHE.
These equations were originally proposed by Adams
and Blount (1959) and Blount (1962). They are re-
derived in Chang and Niu (1995, 1996) and Sundaram
228 Spin Hall Effect
and Niu (1999) using time-dependent variational
principle and investigated in the context of the Berry
phase. We note that when there is a band degeneracy
for every wavevector k, for example, as a result of
symmetry such as Kramers degeneracy, the above
formalism is modified accordingly (Murakami et al.,
2003; Culcer et al., 2005b). The wavepacket consists of
the degenerate wave functions
Z ture T. Meanwhile, apart from such intrinsic terms
X calculated from the first-principles calculation, an
jw i ¼ ddkaðk;t Þ i ðk;t Þji i
i extrinsic term coming from impurities always exists,
where jii (i = 1,. . .,N) denote the degenerate Bloch
wave functions and N is the degeneracy of the con-
sidered states. The Berry connection and curvature
should then be replaced from U(1) to SU(N). The
resulting EOMs for x and k are similar to
Equations (4) and (5), with Bn(k) replaced by the
matrix element of the SU(N) Berry curvature sand-
wiched by the vector i. In the course of propagation,
the components i can change, and this propagation
also involves the Berry connection.
These EOMs, Equations (4) and (5), can be used
for calculating the Hall conductivity. For 2D systems,
for example, the Hall conductivity xy in a clean
system is calculated from Equations (4) and (5) as
Z in its denominator, Bn(k) becomes large, when two
e2 X
xy ¼ – d2 k nF ð"n ðkÞÞBnz ðkÞ
2h n BZ
where nF("n(k)) is the Fermi distribution function for
the nth band, and the integral is over the entire
Brillouin zone. This formula agrees with the result
from the Kubo formula in a bare vertex diagram. In
this sense, this formula represents the intrinsic contri-
bution, which does not rely upon impurity scattering.
In reality, there are also extrinsic contributions coming
from impurity scattering, which should be evaluated
separately. Given the Hamiltonian, the vector field
Bn(k) is calculable, and we can get the intrinsic Hall
conductivity, as in the ab initio calculation of the AHE
(Fang et al., 2003; Yao et al., 2004). This Hall effect
comes not only from the states on the Fermi level but
also from all the occupied states. We note that this
formula can be recast into a sum of a quantized part
and a part which comes from the states on the Fermi
energy (Haldane, 2004). When the Fermi energy lies in
a gap, the extrinsic contribution vanishes and the
intrinsic one (7) can be shown to be quantized in a
unit of e2/h, which explains the integer QHE (Thouless
et al., 1982; Kohmoto, 1985). This formula was also
applied to the AHE in ferromagnetic metals (Matl
et al., 1998; Ye et al., 1999; Chun et al., 2000; Ohgushi
et al., 2000; Taguchi et al., 2001; Jungwirth et al., 2002)
including first-principles calculations for SrRuO3
(Fang et al., 2003), thin film Sr1  xCaxRuO3 (Mathieu
et al., 2004), bcc Fe (Yao et al., 2004), thin film Mn5Ge3
(Zeng et al., 2006), and CuCr2Se4  xBrx (Yao et al.,
2007). In some cases, a quantitative agreement has
been reached as a function of parameters such as
composition x, the magnetization M, or the tempera-
ð6Þ
and it depends on whether the intrinsic terms
dominate.
To see what the field Bn(k) is like and how we can
enhance this field, we rewrite the formula as follows:
       
X nkqH mk  mkqH nk
qk qk
Bn ðkÞ ¼ i ð8Þ
mð6¼nÞ ðEn ðkÞ – Em ðkÞÞ2
where we assumed that the energy spectrum has no
degeneracy. This formula shows that the Berry phase is
a multiband effect, and it vanishes when there is only
one band. We note that it is straightforward to extend
this formula to a spectrum with degeneracy; the gauge
field becomes non-Abelian (Wilczek and Zee, 1984).
Because this formula has a square of energy difference
ð7Þ energy spectra come close. In particular, when two
bands touch (i.e., are degenerate) at a certain wavevec-
tor k, B(k) can diverge. We note that degeneracy does
not necessarily mean divergence of Bn(k). For example,
when the HamiltonianPnear the degeneracy point is
expressed as H ðkÞ ¼ a¼x;y;z a ka , like the massless
Dirac fermions, Bn(k) diverges and has a monopole or
antimonopole, while it does not when P only two com-
ponents are involved as in H ðkÞ ¼ a¼x;y a ka .
1.07.2.1 Intrinsic SHE in p-Type
Semiconductors
In cubic p-type semiconductors with diamond struc-
ture (e.g., Si, Ge) or zincblende structure (e.g., GaAs,
InSb), the valence band consists of two doubly-
degenerate bands called heavy-hole (HH) and
light-hole (LH) bands (Kittel, 1987). These two
bands are degenerate at the -point (k = 0). They
consist of the three p-orbitals, px, py, pz, with spin up
and down. In the presence of the relativistic SO
coupling, these six states are split into fourfold
degenerate S = 3/2 states and twofold degenerate
S = 1/2 states. Here, S denotes the total angular
momentum of the atomic orbital, obtained through
 Spin Hall Effect 229

the coupling of the orbital angular momentum l and 1 qE

ðkÞ
ẋ ¼ þ k̇  B
ðkÞ; hk̇ ¼ eE ð11Þ
the spin angular momentum s. The second-order h qk
perturbation in the k ? p results in the effective Because we are considering holes, the sign of the
Hamiltonian near k = 0: charge has been changed. By straightforward calcula-
X y tion, we get B
ðkÞ ¼
ð2
2 – 7=2Þk=k3 . This has a
Ĥ0 ¼ c;k H ðkÞ c;k
k form of the field radiated isotropically from a mono-
"  # pole at k = 0. The reason why the monopole is at k = 0
h2 5 X is because the HH and the LH bands are degenerate at
2 2 i 2
H ðkÞ ¼ 1 þ 2 k – 2 2 ki ðS Þ ð9Þ
2m 2 i k = 0. When we apply a uniform electric field E(x) = E
X independent of time, we can write down the EOM for
– 2 3 ki kj ðS i S j þ S j S i Þ k and x representing the time evolution. When we
i6¼j
solve the equations analytically, the trajectory in the
where k = (kx, ky, kz), S = (Sx, Sy, Sz), and k = jkj. We x-space is shown as in Figure 3. Due to the anomalous
changed the sign of the energy in order that the energy velocity, the motion of the holes is deflected from an
of the hole be positive. 1, 2, and 3 are called otherwise straight motion along k (dashed line). Here,
Luttinger parameters, for example, GaAs has the values we only show the trajectory in the direction perpen-
1 = 6.98, 2 = 2.06, and 3 = 2.93 (Vurgaftman et al., dicular to E. The shift of the motion is opposite for the
2001). S = (Sx, Sy, Sz) are the spin-3/2 matrices. opposite signs of the helicity
, referring to whether
Strictly speaking, the zincblende structure has also the spin S and the wavevector k are parallel or anti-
odd-order terms in k, due to structural inversion-sym- parallel. This means that the shift is the opposite for
metry breaking (Kittel, 1987). These terms are usually the opposite spin (Figure 3). This shift amounts to the
very small and often neglected. SHE. By summing up this shift over all the occupied
In many semiconductors 2 and 3 are of similar states of holes, one obtains the spin current as
order, and are often considered to be equal ( 2 = 3) (Murakami et al., 2003)
for simplicity. With this approximation, the jji ¼ s "ijl El ð12Þ
Hamiltonian becomes
 

h2 5
H ðkÞ ¼ 1 þ 2 k2 – 2 2 ðk?SÞ2 ð10Þ
2m 2
1.5
CB
This approximation is called spherical approxima- Helicity:
tion, because it restores spherical symmetry, while a 1.4
calculation without it is also possible (Bernevig et al., k FL kH
F λ = ± 3/2
0 HH
2004). This Hamiltonian is theoretically easy to –EF
k?S
Energy, E (eV)

handle, because the helicity defined as

¼ –0.1 λ = ± 1/2
k
becomes a good quantum number. This amounts to LH
taking the spin quantization axis to be kb= k/k. The –0.2
eigenvalues of
are
H ¼ 3=2 and
L ¼ 1=2 for
HH and LH bands, respectively. The corresponding –0.3
1 – 2 2 2 2 SO
eigenenergies are EH ¼ h k (HH band) and
2m –0.4
1 þ 2 2 2 2
EL ¼ h k (LH band). The band structure is –1 –0.5 0 0.5 1
2m
schematically shown in Figure 2. Each eigenvalue is Wave number k(nm–1)
doubly degenerate, due to the Kramers theorem Figure 2 Schematic band structure for GaAs. CB, HH,
based on the time-reversal symmetry. LH, and SO represent the conduction, heavy-hole, light-
We begin with a semiclassical description of the hole, and split-off bands, respectively. This figure is an
approximate one, and in reality the cubic structure induces
SHE, and apply it to the p-type semiconductors
an anisotropy for the band dispersions depending on the
(Murakami et al., 2003). The semiclassical EOM for direction of k. In addition, the absence of the inversion
the position x involves an anomalous velocity. The symmetry in the zincblende structure induces k-linear
semiclassical EOM reads as terms, which are small and neglected here.
230 Spin Hall Effect

λ >0 of the s-orbitals. On the other hand, in high-mobility

2D electron gas (2DEG), structural inversion-
asymmetry (SIA) due to the heterostructure induces
Spin λ <0 the so-called Rashba SO coupling. The Hamiltonian
is approximated as
H ðkÞ ¼ H0 ðkÞ þ HR ðkÞ ð14Þ
k E
h2 k2
Figure 3 Trajectory of holes from the semiclassical
H0 ðkÞ ¼ ð15Þ
2m
equation of motion with Berry-phase terms. This is a
projection on the plane perpendicular to the electric field E. HR ðkÞ ¼
R ð  kÞz ¼
R ðx ky – y kx Þ ð16Þ
The direction of the transverse shift of the trajectory is the i
opposite to each other depending on the sign of the helicity. where  is the Pauli matrix. The second term is called
The transverse shift of the trajectory is to the opposite the Rashba term (Rashba, 1960; Bychkov and Rashba,
direction, depending on the sign of the helicity
= bk?S. The 1984), representing the SO coupling. The coupling
bold gray arrows represent the direction of spin S. constant
can be experimentally determined, and
can be controlled by the gate voltage (Nitta et al.,
with 1997). The Rashba coupling is of the order
e  H L (0.5–1)  1011 eVm for InGaAs/InAlAs heterostruc-
s ¼ 3kF – kF ð13Þ
122 ture (Nitta et al., 1997). Its eigenenergies are given by
which is of the form of (1). Here kH L
F and kF are the h2 k2
Fermi wave numbers for the HH and LH bands, "s ¼ þ s
R k ðs ¼ Þ ð17Þ
2m
respectively. Nominal values of the SHC for
p-GaAs are of the similar order of magnitude as the with eigenstates
conductivity at room temperature (Murakami et al., !
1 ik?x isk – =k
2003). In GaAs, the energy difference of the two ks ðxÞ ¼ pffiffiffiffiffiffi e ð18Þ
2V 0
bands is larger than the room temperature, and the
effect can, in principle, survive even at room tem- where V is the area of the system, and k = kx  iky.
perature. This intrinsic mechanism of the SHE and The dispersion and the spin directions for the two
other related phenomena have been studied bands are shown in Figure 4.
(Bernevig et al., 2004; Dai et al., 2006; Jiang et al., In n-type semiconductors with zincblende struc-
2005; Kleinert and Bryksin, 2006; Luttinger, 1956; ture, there is another type of the SO coupling in 2D.
Ma and Liu, 2006a,b; Zarea and Ulloa, 2006; The bulk inversion asymmetry (BIA) induces
Kravchenko and Tsoi, 2007, 2008; Lou and Xiang, Dresselhaus coupling of the form (Dresselhaus, 1955)
2005; Raichev, 2007; Wang and Zhang, 2005).
We note that this calculation is based on the HD ¼
D ðkx x – ky y Þ ð19Þ
semiclassical theory. In quantum mechanics the velo- The ratio between Rashba and Dresselhaus terms can
city and the spin are not commutable, and thus be experimentally determined through photocurrent
cannot be determined simultaneously. Therefore, measurements of the spin-galvanic effect (Ganichev
the above picture that a hole with definite spin is et al., 2002, 2004). For an InAs quantum-well (QW),
traveling with a definite velocity is not valid. the ratio
R/
D = 2.15 was obtained (Ganichev et al.,
Moreover, in reality, impurities will scatter the 2004). For an InGaAs QW, in a weak antilocalization
holes traveling along the trajectory. These effects experiment, the ratio
R/
D = 1.5–1.7 is obtained
should be taken into account, and will be discussed (Knap et al., 1996), while k ? p calculation suggests
in the subsequent sections.
R/
D = 1.85 (Pfeffer and Zawadzki, 1999). The total
Hamiltonian reads as

1.07.2.2 Rashba Model for n-Type h2 k2  

Semiconductors H0 þ HR þ HD ¼ þ
R x ky – y kx
2m  
þ
D x kx – y ky ð20Þ
In n-type semiconductors with diamond or zincble-
nde structure, the SO coupling is small. This is Sinova et al. (2004) applied the Kubo formula to
because the conduction bands (CBs) consist mainly this Rashba Hamiltonian. For this procedure, they
 Spin Hall Effect 231

E(p)
2006; Li and Shen, 2007; Shen, 2004; Shen et al., 2005,
py
2004; Sinitsyn et al., 2004; Wang et al., 2006a; Wang and
Vasilopoulos, 2007; Winkler, 2003; Zhou et al., 2008; Li
et al., 2005; Lipparini and Barranco, 2007; Lucignano
et al., 2008; Miah, 2006; Rashba, 2004a, 2005; Schulz
px
and Trimper, 2008; Sensharma and Mandal, 2006;
py Shen, 2005; Song et al., 2006b; Wang et al., 2008,
2006d; Zhang and Shen, 2008; Dimitrova, 2005).
px

Figure 4 Dispersion of the Rashba model and the spin 1.07.2.3 Impurity Scattering Effect
directions of the eigenstates Sinova et al. (2004).
In this section, we explain various studies on the
effects of impurity scatterings on SHE. The extrinsic
defined the spin current jzy to be a symmetrized SHE has been studied in several methods, partially in
1 qH order to examine to what extent the experimental
product of the spin sz and the velocity vy ¼ ,
h qky reports can be accounted for by the extrinsic
namely mechanism. Before going into details, we note that
  the impurity scattering effect on the SHE is similar to
1 h h2 ky z that on the AHE (Crépieux and Bruno, 2001). What
jyz ¼ v y ; z ¼  ð21Þ
2 2 2m has been established in the AHE is as follows. The
To calculate the SHC, we calculate the correlation impurity effects are classified into the skew scattering
function between the spin current jzy and the charge (SS) and the side jump (SJ). First, the SO coupling at
current jx defined as the impurity gives rise to a left–right asymmetry at
  the scattering, as is known as Mott scattering. This
e qH hkx
R y mechanism of the AHE is called as the SS
jx ¼ – evx ¼ – ¼ –e –  ð22Þ
h qkx m h (Figure 6(a)). Second, the impurity potential in the
where the electron charge is taken to be e = jej. By Hamiltonian gives rise to an additional anomalous
using the Kubo formula for the bare bubble diagram in term to the velocity. It gives an SJ of the electron
Figure 5 representing the intrinsic SHE, the resulting trajectory at the scattering event, without changing
is zyx = zxy = e/8, which is independent of the the direction of the particle away from the scattering
Rashba coupling
. The Rashba term in Equation center (Berger, 1970; Figure 6(b)). These two con-
(16) can be regarded as a k-dependent effective tributions, SS and SJ, sum up to give an extrinsic
Zeeman field Beff =
(ẑ  k). In equilibrium the spins AHE. In the Kubo formula, the SS and SJ correspond
are pointing either parallel or antiparallel to Beff for to Figures 7(d) and 7(c), respectively, whereas the
the lower and upper bands, respectively. An external self-energy correction (Figure 7(b)) may be
electric field Ejjx̂ changes the wavevectors k of Bloch regarded as the correction to the intrinsic SHE
wave functions, and Beff also changes accordingly. The (Figure 7(a)). The situation for the SHE well resem-
spins will then precess around Beff, and tilt to the z- bles that for the AHE, and we use the same
direction, depending on the sign of ky. This appears as terminology as in the AHE. The readers are also
the SHE, and the SHC is calculated to be e/8, in referred to the papers focusing on some new aspects
agreement with the Kubo formula. We also note that of disorder effects (Hankiewicz and Vignale, 2006;
the same result was obtained by the functional integral Tserkovnyak et al., 2007).
method (Rebei and Heinonen, 2006). In addition, var-
ious aspects of the SHE in Rashba-type models have 1.07.2.3.1 Spin-independent impurities
been studied (Bryksin and Kleinert, 2006; Bernevig, There are many works on the calculation of the SHC
2005; Chang, 2005; Cheche, 2006; Cheche and Barna, in the presence of impurities. The most studied case
is the system with randomly distributed impurities
i
with -function potential:
jj jk
X
V ðxÞ ¼ V ðx – xi Þ ð23Þ
Figure 5 Diagram for calculating the intrinsic SHC. i
232 Spin Hall Effect

(a) Impurity (b) Impurity Spin

Spin

Figure 6 Schematic of (a) side-jump and (b) skew scattering at an impurity.

(a) (b) (c) (d)

jji jk jji jk jji jk jji jk

jji jk jj i jk jji jk

Figure 7 The calculation of the SHC. (a) bare vertex, (b) self-energy corrections, (c) vertex corrections (side-jump), and
(d) skew scattering.

One can include an effect of the self-energy In Krotkov and Das Sarma (2006), the Rashba
broadening 1/ by disorder (Schliemann and Loss, model with an arbitrary form of (spin independent)
2004, 2005) (Figure 7(b)). In both Rashba and kinetic term is considered, and it is found that the
Luttinger models, the intrinsic SHE is gradually cancelation of the SHC is specific to the quadratic
 2 2
reduced as  is decreased from 1. In the clean h k
limit, the SHC reproduces its intrinsic value. In the form of the kinetic term. In Dimitrova
2m
Rashba model, the characteristic energy scales are (2004b) and Chalaev and Loss (2005), in particular,
the Rashba energy "R ¼ m
R =h2 and the Fermi it is argued that because the conventional definition
energy " ; the SHC is reduced when h= exceeds
pffiffiffiffiffiffiffiffiffiffi F of spin current (21) is proportional to S_ y , its expecta-
"R "F . In the Luttinger model, the SHC is reduced tion value is physically expected to vanish in the
when h= exceeds "SO, which is the energy splitting steady state: hjyz i  hS_ y i ¼ 0: In an explicit form,
between the LH and HH bands at the Fermi energy. the spin current in the Rashba model is written as
Subsequently, Inoue et al. (2003, 2004) found an
important result. They assumed dilutely distributed hky z 1 1 y
jyz ¼ ¼ ½H ;y  ¼ – s_ ð24Þ
impurities with a -function potential and took the 2m 4im
R 2m

clean limit. In a clean limit, they obtained a vertex- which is roughly because the SO term is linear in k
correction contribution (Figure 7(c))  e/8 to the (Dimitrova, 2004b; Chalaev and Loss, 2005). The
SHC, exactly canceling the intrinsic value e/8. In vanishing of the SHC can be shown rigorously
addition, subsequent papers found that the SHC using the Keldysh formalism (Sugimoto et al., 2006).
vanishes even for finite  and for long-range impurity
potential (Mishchenko et al., 2004; Dimitrova, 2004b;
Chalaev and Loss, 2005; Khaetskii, 2006; Raimondi and
Schwab, 2005; Rashba, 2004b; Mal’shukov and Chao,
2005; Liu and Lei, 2004, 2005c,a,b; Sugimoto et al., 2006;
Krotkov and Das Sarma, 2006). In Raimondi and
Schwab (2005), the SHC is calculated for weak disorder
Using the Keldysh formalism, one can show that the
time derivative O_ of an arbitrary operator O, which is
independent of k, x, time t, and frequency !, has a
vanishing expectation value in the steady state,
_ = 0 even with a general form of the impurity
hOi
(Sugimoto et al., 2006). We note that a system with
Dresselhaus and Rashba terms also satisfies the simi-
h= 
R pF  "F , with general form of impurity lar relationship
potential. For weak disorder, we can evaluate the SHC
within the Born approximation and ladder summation 1 d
jyz ¼ ð
R s y –
D s x Þ ð25Þ
for vertex corrections. It is found that the SHC is zero. 2mð
2D –
2R Þ dt
 Spin Hall Effect 233

and its SHC vanishes for general impurity potential Long-range impurity potential will give an extrinsic
for finite  (Liu and Lei, 2005c).
In the calculation of linear response such as the
SHC, the Keldysh formalism is equivalent to the
Kobo formula calculation. Nevertheless, the
Keldysh formalism can sometimes give us a clearer
physical picture for transport properties. In addition,
the Keldysh formalism is suitable for calculating
time- and space-dependent properties. For example,
in Mishchenko et al. (2004), the Keldysh formalism is
used to derive diffusion equation for the spin and
term, which has an opposite sign and a bit smaller
compared with the intrinsic one; thus, is the extrinsic
piece due to long-range impurity potential makes the
SHC smaller (Liu and Lei, 2005a,b). The Keldysh
formalism is used for more generalized cases in the
Rashba model and related models (Liu and Lei, 2004,
2005a,b,c; Sugimoto et al., 2006).
One may wonder whether the SHE vanishes in
other systems, and there remain some controversies
in this respect. After debates on the vanishing of
charge in the two-probe geometry. The impurity the SHC for finite , has now been reached consensus
potential is assumed to be of the -function form. that the SHE vanishes in the Rashba model with
The resulting diffusion equation describes the SHE, -function impurities in the clean limit (Inoue et al.,
the spin relaxation, and diffusion in a unified way. It 2003, 2004) and even for finite  (Mishchenko et al.,
is found that the spin Hall current appears only near 2004; Dimitrova, 2004b; Chalaev and Loss, 2005;
the electrodes, whereas the bulk spin Hall current Khaetskii, 2006; Raimondi and Schwab, 2005; Liu
vanishes irrespective of the lifetime  (Mishchenko
et al., 2004), in accordance with the vanishing SHC by
the Kubo formula. In the calculation, some approx-
imation is used based on an assumption that EF is
much larger than the SO coupling  and the self-
and Lei, 2004; Sugimoto et al., 2006; Nomura et al.,
2005a; Sheng et al., 2005a) or for finite-ranged impu-
rities (Inoue et al., 2004; Khaetskii, 2006; Raimondi
and Schwab, 2005; Liu and Lei, 2004). Here, we note
that the Rashba model is exceptional, in that the SHE
energy broadening  1: EF  , EF   1.
To analyze the origin of the vanishing SHC in the
Rashba model, several works have been done without
such approximation. In the Keldysh formalism, the
density matrix is calculated using the quantum
Boltzmann equation in the electric field E. The
resulting density matrix contains several terms linear
in the electric field E. Some of such linear terms are
proportional to the Fermi distribution function nF("),
while the others are proportional to dnF/d". The
former terms stem from interband matrix elements
of the (spin) current operators, and correspond to
intrinsic contributions, while the latter terms repre-
sent intraband matrix elements, leading to extrinsic
contributions. In the study by Liu and Lei (2004), the
range of the impurity potential is finite, and the self-
vanishes rather accidentally, namely because the spin
current operator jzy is proportional to s_ y ¼ i½H ;s y 
(Shekhter et al., 2005; Dimitrova, 2004b; Chalaev
and Loss, 2005; Rashba, 2004b; Liu and Lei, 2005c).
In fact, one can check that the SHE does not vanish
for other models in general (Murakami, 2004;
Bernevig and Zhang, 2004; Liu and Lei, 2005a,b;
Krotkov and Das Sarma, 2006); for example, when
the Rashba model is generalized, to have a higher-
order term in k in the Rashba coupling (Murakami,
2004) or to deviate the band dispersion from para-
bolic to a more general one (Krotkov and Das Sarma,
2006), the SHC no longer vanishes. In addition, there
are some models where the vertex correction does
not cancel the intrinsic value (Liu and Lei, 2005a,b),
energy broadening  is ignored, and the vanishing or even vanishes by symmetry (Murakami, 2004;
SHC has been concluded. Later, this result is gener- Bernevig and Zhang, 2004). Magnetic impurities
alized by considering also the self-energy broadening also make the SHC to be nonvanishing, where the
 (Sugimoto et al., 2006; Liu et al., 2006a). In Liu and
Lei (2005c) the system with Dresselhaus and Rashba
terms is analyzed on the same assumptions, and again
zero SHC is concluded. On the other hand, the cubic
Rashba model is also investigated on the same
assumptions, which gives nonvanishing SHC (Liu
and Lei, 2005a,b). The extrinsic term has the same
sign and its magnitude is somewhat smaller than the
intrinsic value 9e/8. In the case of the Luttinger
model, on the other hand, the -function impurities
will have no effect on the SHC (Murakami, 2004).
exchange coupling between magnetic impurities and
itinerant electrons can be isotropic (Inoue et al., 2006)
or anisotropic (Wang et al., 2007). The SHC depends
on the anisotropy of the magnetic interaction (Wang
et al., 2007) or on the amount of magnetic impurities
when both magnetic and nonmagnetic impurities
coexist (Inoue et al., 2006). We note that in this case
the SHC does not vanish even in the clean limit. In
the 2D hole gas (2DHG) models such as the cubic
Rashba model, the vertex correction vanishes for
-function impurities (Bernevig and Zhang, 2005).
234 Spin Hall Effect
A Boltzmann-type equation can also be used to
study impurity scattering with arbitrary angular
dependence (Shytov et al., 2006). We consider a 2D
system
1
H ¼ "k – bðkÞ? þ V ðxÞ ð26Þ
2
where k = (kx, ky) and b(k) represents the SO
coupling. We note that b(k) = b(k) required by
time-reversal symmetry. It is assumed that
bz ¼ 0; bx þ iby ¼ b0 ðkÞeiN  ð27Þ
i
where kx + iky = ke . Since the result is also affected
by the behavior of b0(k) and the energy dispersion "k
near the Fermi energy, we write
q" 1þ
jb0 j _ kN̂ ; vk ¼ _k ð28Þ
qk
near the Fermi energy. These three exponents, N, Ñ,
and
, characterize the intrinsic SHE. For 2D elec- ical error. On the other hand, for the cubic Rashba
tron system on a (100) surface of a III–V
semiconductor, we have
= 0 and Ñ = 1. bulk is extrapolated to be nonzero. It is also found
Furthermore, N = 1 corresponds to the pure
Rashba term, and N = 1 to the pure (linear-k)
Dresselhaus term. The 2D hole system with the
cubic Rashba term is represented as N = Ñ = 3 and
= 0. Here, the direct SO term
 ? (k  rV) is model is numerically studied (Sheng et al., 2005a).
neglected because the constants
and  are, in The model is represented by a tight-binding
principle, independent. This gives vanishing result
for the pure Rashba system or the pure Dresselhaus
system (N = 1). For 2D hole system, for example,
the SHC is different from that for the isotropic
scattering potential (Shytov et al., 2006). The order
of magnitude for the SHC observed in the spin-
LED experiment by Wunderlich et al. (2005) seems
consistent with the value predicted here.
Numerical studies based on the Kubo formula
have also been carried out. An earlier numerical
calculation for the Rashba model (Nomura et al.,
2005a) suggested that the SHC is finite for weak
disorder for finite systems. Nevertheless, it has been
superseded by a later paper (Nomura et al., 2005b,
2006). In the latter paper (Nomura et al., 2005b)
three models are studied – the (k-linear) Rashba
model, the k-cubic Rashba model, and a modified
Rashba model:
h2 k2
H¼ þ
k2 ðx ky – y kx Þ ð29Þ clude that there is no spin transfer across the sample
2m
The calculation is based on the Kubo  formula with
ji ¼ ðe=hÞqH =qki ; jyz ¼ h– 1 qH =qky ;sz =2, where
sz ¼ ðh=2Þz . The disorder potential is assumed to
P i
be short ranged: V ðrÞ ¼ V Ni¼1 ðx – xi Þ, where Ni
is the number of impurities. For each disorder con-
figuration, they calculate the eigenstates
numerically and put them into the Kubo formula.
The treatment of the small imaginary part of the
frequency  in the Kubo formula requires care. In
the linear response theory of the Kubo formula, the
 controls the speed of adiabatic switching of the
external electric field. In a calculation of longitudi-
nal charge conductivity, in order to absorb energy
from the external electromagnetic field, the level
spacing of the system, , should be much smaller
than  (Imry, 1997):   . We can expect that
similar argument applies to the SHE. In Nomura
et al. (2005b), the SHC is calculated for various
system sizes, where the relationship    is
retained. Bulk quantity is obtained by extrapolating
to  ! + 0. For the k-linear Rashba model, the
extrapolation seems to suggest s  0 within numer-
model and the modified Rashba model, s in the
that the variation of the s by changing disorder
configuration is much larger than the average
value of s.
The tight-binding counterpart of the Rashba
Hamiltonian with Rashba SO coupling on a square
lattice:
X y
H ¼ H TB þ "i ci ci ð30Þ
i;
where HTB represents the nearest-neighbor tight-
binding Hamiltonian with the Rashba coupling
(Ando model (Ando, 1989)), and "i is set to be a
random variable within [W/2, W/2] when disorder
effect is considered. In Sheng et al. (2005a), the
authors apply the Laughlin’s gauge argument
(Laughlin, 1981) to relate the SHC to the carried
spins during insertion of a flux quantum into a hole
of the system, which is periodic only along one direc-
tion (see also Figure 27). This flux insertion
corresponds to the twisting of the phase in the
boundary condition. The energy spectrum, shown
as a function of boundary phases, shows anticrossings
between energy levels, from which the authors con-
during flux insertion, resulting in the vanishing SHC.
Nevertheless, it is not clear whether the gapless
system like the Rashba model can be treated within
the Laughlin’s gauge argument to calculate the SHC.
 Spin Hall Effect 235

Numerical calculation for Luttinger model using where

represents the strength of the SO coupling
Kubo formula has been performed as well (Chen and V represents the impurity potential. In a vacuum,
et al., 2005b). Eigenstates for each disorder config- the free-electron value for
is
= 
2c/4, where
uration are calculated, and the SHC is calculated
c = h/(mec) = 3.8  103Å, the Compton wavelength.
through the Kubo formula with i = 0. The spin The key issue here is a large enhancement (106) of
1
current operator jxy ¼ fvx ; s y g is defined as an j
j in a solid like GaAs (Berger, 1970; Engel et al., 2005;
2
anticommutator between the spin and the velocity, Tse and Das Sarma, 2006), and the sign is changed
as adopted before. Even in the pure system without (Engel et al., 2005). Because the intrinsic SHE is a
disorder, the resultant SHC largely fluctuates as a multiband effect, the SHE of this single-band
function of EF when the system is not sufficiently Hamiltonian is only due to the extrinsic one. This
large, and the fluctuation becomes much larger Hamiltonian is studied using the Boltzmann equation
when the disorder is introduced. Instead of increas- (Engel et al., 2005). The scattering cross section d/d
ing the system size to suppress the fluctuation, in is spin dependent due to the SO coupling. By omitting
Chen et al. (2005b), averaging over the twisted the details of the calculation, the solution of the
boundary condition reduces the fluctuation effec- Boltzmann equation for the 2  2 distribution function
tively, leading to quantitative estimate for the f̂(k) in the spin space is (Engel et al., 2005)
SHC and its width due to disorder. By increasing h i
EF from the band bottom (EF =  3.5), the SHC fˆðkÞ ¼ f0 ðkÞ1̂ þ k? E þ ð  EÞ ð32Þ
2
increases from zero to 4.2e/8. By fixing EF in
2.27 EF 2.07 as an example, the SHC is where X kF is the transport skewness at the Fermi
around 3:5 8e for the pure system, and it is almost level. The spin Hall current due to SS is calculated
unchanged for weak disorder up to W 2t. For from this fˆ(k), and the corresponding SHC is
stronger disorder, the SHC gradually decreases but h
remains nonzero up to around W  Wc, the critical SS
s ¼ – xx ð33Þ
4e
strength of the Anderson localization. This behavior
The SJ term is
is different from that of the Rashba model, where
the SHC vanishes for the disorder strength SJ
s ¼ n
e ð34Þ
much weaker than the Anderson localization. On
the other hand, the width s has a prominent Thus, the SS becomes more dominant over the SJ as
e the system becomes cleaner. For the n-type GaAs in
peak s 15 at around W  t, and it gradually experiments by Kato et al. (2004), the transport skew-
8
decreases when the disorder becomes stronger. ness is evaluated to be  1/900. The calculated SHC
1 1 1 1
System-size dependence becomes much weaker for is SJ
yx = 0.8  m and SJ yx = 1.7  m . Here, we
W
2t, suggesting that there is a characteristic take the unit of SHC as that of the charge conductivity
1
length scale which decreases with increasing W by multiplying e/h. The total SHC is total yx = 0.9  ,
(Chen et al., 2005b). Various other aspects of the which reproduces well the order of magnitude for the
1
impurity effects are studied (Arii et al., 2007; experimental value total
yx = 0.5  (Kato et al., 2004).
Bleibaum, 2005, 2006; Engel et al., 2007; Hu and We note that the sign of the above experimental value
Huang, 2006; Lin et al., 2006; Liu et al., 2007b; Liu is somewhat uncertain. Considering that the two con-
and Lei, 2006; Liu et al., 2006b; Maytorena et al., tributions have opposite signs, together with a number
2006a,b; Rashba, 2004b; Sinitsyn et al., 2006; Wang of approximations made in this theoretical evaluation,
and Li, 2008; Xing et al., 2008; Xiong et al., 2006; the definite sign of the total SHC cannot be determined
Mal’shukov and Chu, 2007; Dimitrova, 2004b). within this theory at the present stage.
The extrinsic SHE is also studied in the Green’s
function method (Tse and Das Sarma, 2006). The
1.07.2.3.2 SO coupling modified by velocity operator is
impurities
Because the SO coupling is of the form (  rV) ? k, i 1 e 
v ¼ ½H ; x  ¼ hk – A –
ð  rV ðxÞÞ ð35Þ
the impurity potential gives an additional term. The h m c
Hamiltonian is the simple one-band Hamiltonian: while the spin current operator is given as
h2 k2 1 1  e 
H¼ –
ð  rV ðxÞÞ?k þ V ðxÞ ð31Þ js ¼ fsz ; vg ¼ hk – A z –
ðẑ  rV ðxÞÞ ð36Þ
2m 2 2m c
236 Spin Hall Effect

The diagrams contributing to the SHE are shown in is studied with the Kubo formula. By including ver-
Figure 7. These diagrams are classified into the SJ and tex corrections, the SS vanishes and the SJ
the SS in the similar way as in the AHE (Crépieux and contribution is reduced to
Bruno, 2001). The spin current operator has a term
involving V(x), which gives rise to the SJ (Figure 7(c)). SJ
s ¼ e
n=2 ð40Þ
The other contribution comes from the impurity term which is a half of the value (37) where the SO
V(x) itself in the Hamiltonian, corresponding to the SS coupling of the impurities is neglected. This remains
(Figure 7(d)). The resulting formula is true when
R ! 0, meaning that the resulting SHC
for
R ! 0 is a half of the value at
R = 0. Thus, the
SJ
s ¼ e
n ð37Þ
SHC is nonanalytic at
R = 0 (Tse and Sarma, 2006).
for the SJ and The cubic Rashba model is treated in the same way.
( In accordance with the previous results on the intrin-
1=3 :3D sic SHE, the vertex correction vanishes, and the
SS
s ¼ – 4e
"F =h ð38Þ
1=2 :2D result is additive in the lowest order for the intrinsic
and extrinsic parts (Tse and Sarma, 2006). This ana-
for the SS. The ratio between the two contributions is
lysis shows a rather peculiar feature of the (linear)
SJ =SS  ðh=Þ="F which is smaller for cleaner sam- Rashba model.
ples. For   1013–1012s and "F  1–10 meV, for
example, they are of the same order.
For 3D n-type semiconductors, the resulting value of
1 1 1 1
the SHC is SJs = 0.75  m andpffiffiffiSJ
s 6  m mula results (Tse and Sarma 2006). It is not usually
with nominal values of parameters: 2
¼ 4:7Å, n = 3 easy to trace the reason for the difference in the
 1016 cm3, and xx = 3  103 1m 1. The sum is
s = 5.2 1 m1. It reproduces the order of magnitude
for the experimental value 0.7 1m 1, obtained in an
experiment in Kato et al. (2004), although we took the
simplest model and picked up only the lowest-order
i, while it may not be always true when the
diagrams. For 2D p-type semiconductors with the para-
meters p = 2  1012 cm2 and xx  1.09  1013 1,
as in the experiments by Wunderlich et al. (2005),
8 1
the SHC is evaluated as SJ s = 3.10  10  Wu (2008), Chudnovsky (2007), Grimaldi et al.
SS 6 1
and s = 2.72  10  . The total SHC is
2.68  106 1. In this case the ratio jSJ SS
s /s j is as
2
small as 2  10 , because the sample is relatively clean.
The results of Engel et al. (2005) and those in Tse and
Das Sarma (2006) qualitatively agree with each other.
When both types of the SO coupling, namely that
of the bulk and that at the impurities, coexist, the
problem becomes much more complicated. This
problem is studied in Tse and Sarma (2006) for
Rashba and cubic Rashba models, and it was
revealed that the Rashba model shows a peculiar
interplay between the intrinsic and the extrinsic
parts, whereas in the cubic Rashba model extrinsic
and intrinsic parts are additive in the lowest order.
The Rashba Hamiltonian with SO-coupled
impurities
h2 k2
H¼ þ
R ðx ky – y kx Þ þ V ðxÞ –
ð  rV ðxÞÞ?k
2m
ð39Þ
We note that the same problem is studied in Hu
et al. (2006) with the Boltzmann transport theory. The
results look somewhat different from the Kubo for-
results with Kubo formula and Boltzmann transport
theory. Nevertheless, one of the reasons may lie in
the fact that in Hu et al. (2006) the distribution func-
tion is considered to be diagonal in the chirality basis
jk
external field is present, as studied in Shytov et al.
(2006). The readers are referred also to Hankiewiez
and Vignale (2006, 2008), Tse et al. (2005), Cheng and
(2006a), and Sherman et al. (2006) for related subjects.
1.07.2.3.3 SHE in the hopping regime
The SHE in strongly disordered systems is governed
by hopping conduction. In Beckmann et al. (2005),
Damker et al. (2004), and Entin-Wohlman et al.
(2005), the SO coupling is included in the hopping
amplitudes, and interference effect between hopping
paths is studied. The effect of the SO coupling
appears in the third order in hopping amplitudes;
for three sites i, l, and m, the interference occurs
between the direct path i ! l and the indirect path
i ! m ! l. Because of this interference, when an
external electric field is applied, the transverse spin
current calculated as a time derivative of the spin
polarization becomes nonzero. In Beckmann et al.
(2005) and Damker et al. (2004), only the Rashba SO
coupling is studied in terms of the rate equations in
the Markovian limit. In Entin-Wohlman et al. (2005),
the Rashba and Dresselhaus SO coupling are

included in the hopping amplitudes, and this SHE is
proportional to !2, where ! is the frequency of the
external electric field (Entin-Wohlman et al., 2005).
We note that the way to calculate the spin current as
a time derivative of the spin polarization was adopted
in several works (Entin-Wohlman et al., 2005; Shi
et al., 2006) as discussed in Section 1.07.2.6.1
1.07.2.4 Mesoscopic SHE
In this subsection, we discuss various calculations on
SHE in small systems. This includes (1) the calcula-
tions based on Kubo formula and (2) the calculations
by the Landauer–Büttiker formalism. We discuss
these two types of calculations separately.
The Kubo formula calculation for small-size sys-
tems (<100 sites) of 2DEG has been done (Sheng
et al., 2005a; Moca and Marinescu, 2007a). The result-
ing SHC strongly fluctuates as a function of the
Fermi energy EF. Nevertheless, by averaging over
the twisting angle in the boundary conditions, the
SHC becomes a smooth function of EF. We note that
this trick has been adopted for numerical calculation
of Hall conductivity in the QHE. As a function of the
system size, the SHC is s  0.48(e/4) for a clean
system, while s for disordered systems exponen-
tially decays as a function of the system size
hsi _ exp(L/s), with a characteristic length s
(Sheng et al., 2005a; Moca and Marinescu, 2007a).
This is consistent with the above-mentioned result
that the SHC in disordered Rashba models is zero.
In Chen et al. (2005a), the 2DHG is investigated
numerically with the Kubo formula. The model is a
discretized version of the Luttinger–Rashba model.
The SHC is calculated with the Kubo formula in a
finite-size sample, with the imaginary part  set to
zero. In a clean system, the SHC is of the order of
11e/8, as long as the EF is near the band bottom.
When the system size is not large (around L = 20–30),
zxy largely fluctuates by changing disorder config-
uration. This fluctuation is strongly suppressed when
an average over the twisting angle in the boundary
condition is performed, as in the electron systems.
The resulting value agrees quite well with a result in
a large system L = 1000; hence, one can regard that
this averaging over the boundary conditions removes
a finite-size effect efficiently. As one introduces the
disorder gradually by changing W, the SHC is mono-
tonically suppressed. The SHC almost vanishes
when W  5t.
The Landauer–Büttiker formalism has been applied
to many types of systems. In fact, the SHE in the
Spin Hall Effect 237
Rashba model for a four-terminal geometry was first
numerically studied by Bulgakov et al. (1999), prior to
the theoretical proposals of the intrinsic SHE
(Murakami et al., 2003; Sinova et al., 2004). In
Bulgakov et al. (1999), the scattering-wave formalism
is applied to the four-terminal (continuum) Rashba
model without disorder. For example, without the SO
coupling whose eigenstates are plane waves are
attached to the system. One can calculate the transition
probabilities that an incoming wave goes into an out-
going wave in other leads. It was numerically obtained
that a left–right asymmetry occurs in the transmission
probability into the transverse channels, because of the
Rashba SO coupling. When the incoming electrons are
not polarized, the outgoing electrons in the transverse
channel are spin polarized, which we can call the SHE.
On the other hand, polarized incoming electron gives
rise to a transverse voltage, associated as an inverse
SHE (ISHE) (Bulgakov et al., 1999).
This problem was then studied in the four-terminal
Landauer–Büttiker formalism (Nikolić et al., 2005b;
Sheng et al., 2005b). In this formalism, the authors
used a tight-binding Hamiltonian with Rashba SO
coupling on a square lattice. The random on-site
energy, "i, is set to be a random variable within
[W/2, W/2] when disorder effect is considered.
When we consider a square sample with the size
L  L, and attach the leads with no SO coupling at
the four edges, we can apply the four-terminal
Landauer–Büttiker formalism. The current is driven
through the lead 0 to 1 in the inset of Figure 8. Nikolić
et al. (2005b) and Sheng et al. (2005b) studied systems
with size up to 100  100. The SHE without any
disorder is studied by changing the system size and the
SO coupling. The SHC with spin along the z-axis, Gz,
is of the order of e/4, but not exactly equal to the
universal value e/8 calculated from the Kubo for-
mula in the clean system. This SHC Gz depends on
the system size L or the SO interaction VRSO. As the SO
coupling VRSO increases, the SHC increases (Sheng et al.,
2005b). The SHC with spins along the x-direction,
Gx, is also nonzero, which is not the case for the
Kubo formula calculation in a system with infinite
size. The spin Hall current for both edges of the
sample has the opposite sign for the x- and z-direction.
When the size of disorder W is increased, the SHC is
gradually suppressed, and when W  5t the SHC
becomes vanishingly small. With the system size
L 100, the size dependence of Gx and Gz depends
on the SO interaction. There also arises a spin com-
ponent along the y-direction, and it has the same sign
for both edges of the sample. It corresponds to the
238 Spin Hall Effect
1.2
W=0
0.8 W = 1t
W = 2t
0.4
GsH (e/4π)
0.0
3
L –0.2
–0.4
0 L 1 0.08
y 0.04
–0.8
2 0.00
x
–1.2
–4 –2 0 2
E/t
Figure 8 Landauer–Büttiker calculation. From Sheng L,
Sheng DN, and Ting CS (2005) Spin-Hall effect in two-
dimensional electron systems with Rashba spni–orbit
coupling and disorder. Physical Review Letters 94: 016602.
current-induced spin polarization (CISP) studied the-
oretically (Edelstein, 1990; Aronov et al., 1991; Inoue
et al., 2004) and experimentally. A similar system with
and the system size L.
the Rashba coupling also in the leads is studied by
Wang and Chan (2005). Qualitatively similar results
with the previous cases of leads without SO coupling
are obtained, whereas the existence of the SO coupling
in the leads makes the definition of the spin current
somewhat ambiguous (Figure 9).
The reciprocal effect of the SHE can be studied
by the Landauer–Büttiker formalism (Hankiewicz
et al., 2005a). In the Landauer–Büttiker formalism,
the lead has no SO coupling, and the spin current is
uniquely defined, thanks to the spin conservation.
This conservation of spin automatically ensures the
Onsager relation
xy yx
GSC ¼ – GCS
This relationship holds for disorder-averaged con-
ductances, because its proof uses the inversion
symmetry on the x–y plane (Hankiewicz et al.,
2005a). This relationship can be directly checked
numerically. The 2DEG as well as the 2DHG are
studied. The 2DEG is described by the Rashba
model, and the 2DHG by a cubic Rashba model
p2 i
3 þ 3 –
H¼ þ ðp  – pþ  Þ, where  = x  iy.
2m 2 –
The resulting SHC (which is equal to the GyxCS) is
0.0050
0.0025 G xsH
0.0000
–0.0025 tSO = 0.01to
–0.0050
0.2
0.1 60 × 60
Spin conductance (e/4π)
0.0
–0.1 G ysp
G zsH
–0.04 EF = –3.8to
–0.08
4
–4 –3 –2 –1 0 1 2 3 4
Fermi energy
Figure 9 Landauer–Büttiker calculation. From Nikolić BK,
Zârbo LP, and Souma S (2005b) Mesoscopic spin Hall effect
in multiprobe ballistic spin–orbit-coupled semiconductor
bridges. Physical Review B 72: 075361.
larger for the 2DHG than that for the 2DEG in
general. Nonetheless, they are of the order e/8 and
depend unmonotonically on
An effect of impurity SO coupling is studied by
Pareek (2004) in a Y-shaped geometry. Here a charge
current is passed between two terminals, while the
third terminal works as a voltage probe without any
charge current. A pure spin current is then produced
in the third probe, and it can be regarded as a result of
an extrinsic SHE.
Nonequilibrium spin accumulation has been stu-
died in a two-terminal geometry, namely in a
quantum wire geometry (Nikolić et al., 2005a; Wang
et al., 2006b). The Keldysh nonequilibrium Green’s
function is combined with the Landauer formalism to
study numerically the spin accumulation. The tight-
binding model studied by Ando (1989) is used for the
ð41Þ calculation. The spins accumulate at both the edges,
with their directions along the z-axis and the x-axis
opposite for the two edges, in accordance with the
calculation of the spin current by the Landauer–
Büttiker formalism in the previous section (Nikolić
et al., 2005b; Sheng et al., 2005b). In Nikolić et al.
(2005a), the leads are without the SO coupling,
whereas in Wang et al. (2006b) the leads include the
SO coupling in the leads as well, which changes the
spin-dependent scattering between the leads and the
sample. In Wang et al. (2006b), the spin accumulation

oscillates along the wire, while this feature seems
absent in Nikolić et al. (2005a). This might be because
in Wang et al. (2006b) the nonlinear region (strong bias
voltage eV  EF) is studied whereas the system in
Nikolić et al. (2005a) is closer to the linear region
(weak bias voltage eV  EF). It is also shown that the
spin Hall current can really inject spin into the leads
(Nikolić et al., 2005a). In contrast, the spin accumula-
tion along the y-axis is the same for the two edges,
resulting from the CISP (Nikolić et al., 2005a; Wang
et al., 2006b).
In Hankiewicz et al. (2004), an H-shaped structure is
proposed for a measurement of the SHE through de-
transport properties. This structure follows the same
spirit as the structure proposed by Hirsch (1999); in
order to measure the spin current due to the SHE, one
uses the inverse effect of the SHE to convert the spin
current to a voltage signal. In Hankiewicz et al. (2004),
the device size is set to be of the order of 100 nm, and
one passes the current 10 nA into the lower arm as
shown in Figure 10. When the Rashba coupling
R is Hattori and Okamoto, 2006; Hu et al., 2003c; Huh
changed from 0 to 80 meV nm, the voltage change
between the voltage probes (10) becomes 2–8 mV as
shown in Figure 11 (Hankiewicz et al., 2004).
By using the Landauer–Büttiker formalism, the
SHC in a ring geometry is calculated with realistic
parameters. In Souma and Nikolić (2005), the
Landauer–Büttiker formalism is applied to a meso-
scopic ring with Rashba SO coupling with four
terminals attached. If the ring is smaller than the
dephasing length, the SHC is affected by an interfer-
ence of two paths, due to the Aharanov–Casher phase
around the ring. Indeed, the SHC has a
quasi-oscillatory behavior as functions of the Fermi
energy or the Rashba SO coupling. A 1D mesoscopic
ring with the Rashba and Dresselhaus SO coupling is
studied (Moca and Marinescu, 2005), and similar
oscillatory behavior of the SHC is found as a function
of the SO coupling. Disorder reduces the size of the
SHC and the amplitude of the oscillation (Moca and
Marinescu, 2005). Nonequilibrium spin accumulation
for a 1D mesoscopic ring with Rashba coupling is
studied (Zhang, 2006), and a similar quasi-oscillatory
behavior is observed, depending on whether the beat-
ing pattern of the spin accumulation matches with the
ring circumference. There are many other publica-
tions on the various aspects of the mesoscopic SHE
to which the readers are referred (Adagideli and
Bauer, 2005; Bardarson et al., 2007; Bellucci and
Onorato, 2007a,b, 2008; Brusheim and Xu, 2006,
2007; Chen et al., 2007; Erlingsson and Loss, 2005,
2006; Galitski et al., 2006; Hankiewicz et al., 2005b;
Spin Hall Effect 239
(a) V5
Itot = 0
V4
V3 Itot = 0
Itot = 0
V1 V2 = 0
Itot = 1 Itot = –1
V6
Itot = 0
(b)
a0
Figure 10 (a,b) Schematic picture for the H-shaped device
for detection of the SHE. From Hankiewicz EM, Molenkamp
LW, Jungwirth T, and Sinova J (2004) Manifestation of the
spin Hall effect through charge-transport in the mesoscopic
regime. Physical Review B 70: 241301.
et al., 2007; Jiang and Hu, 2007; Levitov et al., 1985;
Liu et al., 2007a; Mal’shukov et al., 2007, 2005b; Moca
and Marinescu, 2005, 2007b; Moca et al., 2008; Nikolić
and Zârbo, 2006; Nikolić et al., 2006, 2005c; Ohe et al.,
2008; Onoda and Nagaosa, 2005a; Pareek, 2007; Qiao
et al., 2007, 2008; Ren et al., 2006; Reynoso et al., 2006;
Schliemann, 2007; Sheng and Ting, 2006a, b; Souma
and Nikolić, 2005; Wu and Zhou, 2005; Xing et al.,
2006a, b; Zyuzin et al., 2007; Mal’shukov and Chu,
2006; Mal’shukov et al., 2005a; Pershin and Di
Ventra, 2008; Sun et al., 2005; Xing et al., 2007; Zhou
et al., 2007).
1.07.2.5 Experimental Observation of SHE
in Semiconductors
The SHE in semiconductors was recently observed
experimentally (Day, 2005). There are two types of
measurements, that is, the KR and the LED, each of
which is reviewed below.
1.07.2.5.1 Measurement of SHE in
semiconductors by KR
When the SHE occurs in a semiconductor sample,
the induced spin current will eventually reach the
sample edge, and they will accumulate, balancing
with the spin diffusion and spin relaxation. Such
spin accumulation is measured by KR in a series of
experiments by Awschalom et al. (Kato and
Awschalom, 2008; Sih and Awschalom, 2007). In
their experiments, laser beam with linear
240 Spin Hall Effect

L = 90 nm, N1= 36, 4 leads

L = 90 nm, N1= 42, 4 leads
2 L = 120 nm, N1= 42, 4 leads
L = 120 nm, N1= 48, 4 leads

ΔV34(λ) – ΔV34(0) (μV) 100

–2 |ΔV12(λ) – ΔV12(0)|/|ΔV12(0)|

|ΔV (λ) – ΔV(0)|/|ΔV (0)|

10 |ΔV34(λ) – ΔV34(0)|/|ΔV34(0)|
1
–4
0.1

0.01
–6
0.001

0.0001
–8 0 20 40 60 80
λ (me V nm)

0 20 40 60 80
λ (meV nm)

Figure 11 Calculated voltage drop between terminals 3 and 4 in the H-shaped device. From Hankiewicz EM, Molenkamp
LW, Jungwirth T, and Sinova J (2004) Manifestation of the spin Hall effect through charge-transport in the mesoscopic regime.
Physical Review B 70: 241301.

polarization, focused to 1 mm size, is incident onto the experimental data. It can also account for the absence
sample, and they measured the rotation angle of the of dependence on crystal orientation. Thus, the
polarization plane upon reflection. The rotation quantitative explanation of the observed SHE is still
angle is proportional to the spin polarization perpen- to be resolved.
dicular to the plane. When a static magnetic field is Further experiments using the spin mapping by the
applied, the magnetization will precess around the KR have been done by the same group. Sih et al. (2005)
magnetic field, and decays as A?ð1=½ð!L s Þ2 þ 1Þ by investigated the SHE and CISP in (110) AlGaAs QWs
the Hanle effect, where !L ¼ gB B=h is the Larmor with various direction of electric field. In the (110)
frequency and  s is the spin coherence time. By QW, the Dresselhaus field is perpendicular to the
measuring the field dependence of the angle, one plane, while the Rashba field is in-plane; thereby, the
can determine  s. separation between the two fields is possible. For
Kato et al. (2004) observed the SHE in n-type Ejj[001], the CISP due to the Dresselhaus field
semiconductors by measuring spin accumulation at vanishes, and the total CISP is in-plane. Thus, the
the edges of the sample by KR (Bauer, 2004). The CISP is absent in the KR signal, because the KR
spin accumulation is uniformly distributed along both detects the spin component perpendicular to the
the edges, while away from the edges there is no spin plane. Therefore, the out-of-plane spin is accumulated
accumulation, as can be seen from Figure 12. From only at the two edges of the sample. On the other
experimental data they evaluated the amount of spin hand, for other orientations of the electric field such as
accumulation and spin lifetime as a function of an ½110 and ½112, the CISP has an out-of-plane compo-
external magnetic field. The measured SHC is nent, and appears in the whole sample, in addition to
5  103 1 cm1. They concluded the observed the SHE signal at the edges.
SHE to be extrinsic for the following reasons: (1) Sih et al. (2006) also investigated the device with
spin splitting is negligibly small in the sample and (2) side arms, in order to see whether the observed spin
the effect has no dependence on crystal orientation. accumulation at the edges is due to a spin current, or
Nevertheless, Bernevig and Zhang (2004) argued due to other edge effect. The measurement was done
that the observed SHE can be intrinsic, coming from for 3D n-GaAs (2 mm thick) with a Si doping with
the dresselhaus term representing bulk inversion- n = 3  1016 cm3 at T = 30 K. The observed profile
symmetry breaking. They showed that even if the of spin distribution is well fitted by assuming that the
spin splitting due to the Dresselhaus term is negligi- spins are generated through the SHE in the main
bly small, the SHE can be as large as the channel, and flow into the side arm.
 Spin Hall Effect 241

ns (a.u.) that the SO interaction is weaker in ZnSe compared

–2 –1 0 1 2 with GaAs, and is encouraging for the applications.
The in-plane CISP in n-type ZnSe is also measured
150 at room temperature (Stern et al., 2006). The spin
accumulation due to the CISP obtained from the
KR is 12 spins mm3 at 20 K, which is comparable to
100 that in n-GaAs, although the SO coupling is con-
sidered to be much weaker in n-ZnSe than in
n-GaAs.
50 Another interesting recent development is the
time-resolved dynamics of the SHE observed in
Position (μm)

GaAs. By using the electrically pumped time- and

0 space-resolved KR spectroscopy, they could see the
time–space dependence of the spin accumulation
after the voltage pulse (Stern et al., 2008). With the
–50 voltage applied along x-direction, we expect the
spin current to flow along y-direction with the spin
polarization along z-direction, and the spin accu-
–100 mulation of that polarization near the edge at y = L
with L being the half of the dimension of the sample
measured from the center. The dynamics of the spin
–150 density s(y, t) is described by the following equation:
–40 –20 0 20 40 qjyi
qs i s i ðy; t Þ
Position (μm) ðy; t Þ ¼ – ðy; t Þ – þ ðgB =hÞ½B  sðy; t Þi
qt qt 
Figure 12 Experimentally observed spatial profile of the ð42Þ
spin accumulation. The electric field is in the vertical
direction. Red and blue represent the opposite directions of
the out-of-plane spin polarizations. From Kato YK, Myers
RC, Gossard AC, Awschalom DD (2004) Observation of the
spin Hall effect in semiconductors. Science 306: 1910.
Stern et al. (2006) reported the SHE in ZnSe
which persists even at room temperature. With the
sample of the n-type Cl-doped ZnSe with the car-
rier concentration n = 9  1018 cm3, they used the
where  is the spin decoherence time, B is the mag-
netic field, and jiy is the spin current given by
jiy = Dqysi  sEi,z. This equation can be solved by
imposing the appropriate boundary condition rele-
vant to the experimental situation, and excellent
agreements between the data and the calculation
have been obtained as shown in Figure 13, which
established the SHE as the origin of the spin accu-
mulation near the edge, and also gave a reliable
KR spectroscopy, where the the pump-probe tech-
nique with the normally incident beam focused to a
15 mm spot. The time-resolved KR measurement
determined the spin coherence time of 0.5 ns for
n = 9  1018 cm3. At T = 20 K, the spin density
peak n0 at the edge of the sample is found to be
n0 > 16 spins/mm3 under the electric field of
3 mV mm1. With the fitting to solution of the
drift-diffusion equation, the spin diffusion length is
estimated as Ls = 1.9  0.2 mm at T = 20 K and the
estimated SHC is s = 3  1.5 1 m1/jej at T = 20.
The temperature dependence of s has also been
measured and even at room temperature s > 0.5
1 m1/jej. The measured sign and magnitude of
s is consistent with the extrinsic mechanism (Engel
et al., 2005). This is a surprising result considering
estimate of various physical quantities as  = 4.2 ns
and the spin diffusion length Ls = 3.9 mm.
1.07.2.5.2 Measurement of SHE in
semiconductors by spin LED
Wunderlich et al. (2005; Kaestner et al., 2006)
observed the SHE in a 2D p-type system, using a
p–n junction LED. They applied an electric field
across the hole channel, and observed a circular
polarization of the emitted light, whose sign is oppo-
site for the two edges of the channel as shown in
Figure 14. The circular polarization is 1% at max-
imum. This circular polarization is attributed to the
recombination of electrons and spin-polarized holes
produced at the p-type channel through the SHE.
They argued that it is near to the clean limit, and the
242 Spin Hall Effect

(a) 0.2 (b) 0.2

Data Model

B (T)

B (T)
0 0

θK (μrad)

–4 8
–0.2 –0.2
0 10 20 0 10 20
t (ns) t (ns)
Figure 13 Experimental setup for the time-resolved measurement of SHE. From Stern NP, Steuerman DW, Mack S,
Gossard AC, and Awschalom DD (2008) Time-resolved dynamics of the spin Hall effect. Nature Physics 4: 843.

obtained SHE is mostly intrinsic. More refined argu-
ment, by showing vanishing vertex correction, also
supports this conclusion (Bernevig and Zhang, 2005).
Nomura et al. (2005c) studied numerically the SHE-
induced edge-spin accumulation in a 2DHG with
strong SOs (Figure 15). They found it is indepen-
dent of the strength of disorder scattering suggesting
the intrinsic nature of the effect, and obtained the
similar phenomenological aspects as compared with
the experiment (Wunderlich et al., 2005).

(a) Ip
LED 1
+Ip
1

LED 1
0
p n
y
1.5-mm x
n
CP (%)

channel z –1
–Ip
LED 2 (b)

9 +Ip 1
LED 1
2.5
(d)

1.5 0
(meV)

0.5 LED 2
(c) –1
1
10 20 30 1.505 1.510 1.515 1.520
P2D (1011 cm–2) E (eV)

Figure 14 (a) The device setup for the spin LED, (b) circular polarizations measured for the opposite directions of current,
(c) circular polarizations measured at LED1 and LED2, and (d) fit with the theory. From Wunderlich J, Kaestner B, Sinova J,
and Jungwirth T (2005) Experimental observation of the spin-Hall effect in a two-dimensional spin–orbit coupled
semiconductor system. Physical Review Letters 94: 047204.
 Spin Hall Effect 243

8
(a) Spin-density profile (c) Edge-spin density

Szedge/E (e /4πvF)
10
Sz (x)/E (e /4πvF)
4

0
5
–4

–8 0
8 (b) Spin-current profile (b) Bulk-spin current
10

jxzbulk/E (e /8π)
jxz(x)/E (e /8π)

4
5
2

0 0
0 10 20 30 40 50 0 2 4 6 8 10 12 14
X (kF–1) EF (h/τ)

Figure 15 Spatial dependence of the spin accumulation and spin current in a model for the 2D hole gas. From Nomura K,
Wunderlich J, Sinova J, Kaestner B, MacDonald AH, and Jungwirth T (2005c) Edge-spin accumulation in semiconductor two-
dimensional hole gases. Physical Review B 72: 245330.

A theoretical study on the spin accumulation by the One can adopt the symmetrized product
electric field can also be found in Kleinert 1
ðvi s j þ s j vi Þ between the velocity v and the spin s
et al. (2005). 2
as a definition of the spin current as in Sinova et al.
(2004). The result given by the Kubo formula with
1.07.2.6 Various Issues on the SHE this definition is in general different from that by the
semiclassical theory described above (Murakami
1.07.2.6.1 Definition of the spin current
et al., 2004b). This difference comes from noncom-
In the presence of the SO coupling, the total spin is
mutability between the spin S and the velocity v. In
not conserved. Hence, there is no unique way to
other words, this comes from the nonuniqueness of
define a spin current. Naively we expect that the
the definition of spin. One can modify the semiclas-
spin current js should satisfy the equation of continu-
sical theory to give the same result as the Kubo
qs i
ity þ r?Jsi ¼ 0; this relationship requires the formula by adding three contributions: spin dipole,
qt torque moment, and change of wavepacket spins due
conservation of total spin, namely
to electric field (Culcer et al., 2004).
Z Z

q An alternative way is to separate the spin s into

0¼ s i dd x ¼ – i
qt
In the cases relevant for the SHE, the SO coupling
violates this conservation of total spin. In other
words, due to the nonconservation of spin,
Noether’s theorem is not applicable for a definition
of spin current.
The conventional definition of the spin cur-
rent, (21) or (36), is usually adopted. However,
its mathematical meaning as a current is ill-
defined. A current is always associated with a
corresponding conserved quantity. The conven-
tionally defined spin current is not conserved for
the Luttinger Hamiltonian due to the SO
coupling.
s i dd x; H ð43Þ
conserved (intraband) part s(c) and nonconserved
(interband) part s(n) (Murakami et al., 2004b). As
[s(c), H] = 0, spin current can be uniquely defined
for s(c). The resulting spin current is
e
jij ¼ ðkH – kL Þ"ijl El ð44Þ
62 F F
which is different from Equation (13), and this dif-
ference is considered as a quantum correction to
Equation (13).
Another attempt for defining conserved spin cur-
rent is done by introducing torque dipole moment
(Entin-Wohlman et al., 2005; Shi et al., 2006). A con-
tinuity equation for the spin can be written as
244 Spin Hall Effect

qs z and for the cubic Rashba model

þ r?Js ¼ Tz ð45Þ
qt
9e 9e 9e
where Tz X dsz/dt is the torque density. This torque ð0Þ
s ¼ ; ðÞ
s ¼ – ; ðcÞ
s ¼ – ð53Þ
8 4 8
density describes a spin precession due to local mag-
netic field of the SO coupling. If this torque density is The results for the conventional and the conserved
zero, it describes the spin conservation that the total spin currents have different sign; hence, the sign of
increase of the spin in a certain region of the system is the SHC in experiments or numerical simulations
equal to a net in-going spin current js; hence, the spin might be a simple test to distinguish between the
current is measurable as a spin accumulation. On the conserved spin current and the conventional one.
other hand, if the torque density Tz is nonzero, the This definition ensures the Onsager relation
spin current is not directly connected with a spin between the SHE and its reciprocal effect. In the
accumulation. reciprocal effect, a spin force Fs, which is a gradient
If the average of the torque over the entire system of a spin-dependent chemical potential or that of the
vanishes due to some symmetry reasons, that is, Zeeman field, induces a charge current transverse to
Z the gradient (Zhang and Niu, 2004). This reciprocal
1 effect can be evaluated in the semiclassical theory
dV Tz ¼ 0 ð46Þ
V where the Berry phase in a mixed position-momen-
one can define another conserved spin current, tum space, xk, plays a central role for the effect
which is directly related with the spin current. (Zhang and Niu, 2004). The total response with SO
Provided Equation (46) holds, the torque density coupling is written as
term can be written as ! ! !
Js ss sc Fs
Tz ¼ – r?P ð47Þ ¼ ð54Þ
jc cs ss E
where P is called a torque dipole density. Hence,
The Onsager reciprocity is then written as
we get
sc cs
 ¼ –  ð55Þ
qs z
þ r?Js ¼ 0 ð48Þ
qt which is explicitly shown in the semiclassical theory
where (Zhang and Niu, 2004). This reciprocity manifests
that the conserved spin current Js is a time derivative
J s ¼ Js þ P  ð49Þ of an operator xsz, which is conjugate to the spin
is called a conserved spin current. In order to calcu- force Fs. This reciprocal effect was discussed earlier
late the torque dipole moment, P , in the bulk in
response to an external electric field E, it is
convenient to consider an electric field at a finite
wavevector q. The torque dipole density at finite
q, Tz(q) = (q) ? E(q) is calculated, and from
Equation (47) we get
in a context of extrinsic effect (Hirsch, 1999).
Because there is no unique definition for the spin
current, we have to choose one definition which
matches the considered experimental setup to mea-
sure the spin current.
One possible test to see which definition of spin
current is relevant is to measure the spin accumula-
P ¼ i½rq ðqÞq¼0 ?E ð50Þ
tion. To this purpose, spin accumulation as well as
from which the SHC can be calculated. Let us write conventional spin current are calculated numerically,
by varying disorder. The calculation uses the Kubo
ðcÞ ð0Þ ðÞ
s ¼ s þ s ð51Þ formula both in the strip geometry for the 2DHG and
where (c)
s , (
s ,
)
and (0)
are the SHC for the con-
s
2DEG (Nomura et al., 2005c). The resulting spin
served spin current Js, the conventional spin current accumulation can be fitted by the conventional spin
js, and the torque dipole density P . In Shi et al. current rather well. The readers are referred to the
(2006), the SHC for the conserved spin current is further references on the spin current issues (Chen
calculated for Rashba model, cubic Rashba model, et al., 2006; Fu et al., 2007b; Jin and Li, 2008, 2006; Jin
and Luttinger model. For Rashba model et al., 2006; Leurs et al., 2008; Shen et al., 2006; Sun and
Xie, 2005; Wang et al., 2006c; Wang and Zhang, 2007;
e e e Yang and Chang, 2006; Zhang et al., 2008b; Li and
ð0Þ
s ¼ ; ðÞ ¼ – ; ðsÞ ¼ – ð52Þ
8 s 4 s 8 Tao, 2007; Wong et al., 2008).

1.07.2.6.2 Ab initio calculations
On the other hand, the intrinsic SHE is calculated for
Si, GaAs, W, and Au for various values of the Fermi
energy (Guo et al., 2005). For p-type GaAs the pre-
dicted value is maximally 300 1 cm1, which is of
the same order of magnitude as that from the
Luttinger model (Zhang and Yang, 2005). The
p-type Si has somewhat smaller value, 50 1 cm1,
which is due to smaller SO coupling than GaAs. For
n-type GaAs, the size of the SHC is 50 1 cm1
and undergoes a sign change as a function of carrier
density, and n-type Si is found to have a negative
SHC ( 50 1 cm1). It is found that even without
doping, GaAs and Si show a small but finite SHE (43
and 7 1 cm1, respectively). It is due to a small
hybridization. In this sense, these undoped semicon-
ductors are SHI. In the metallic systems such as W
and Au, the SHC is calculated to be 1390 and
731 1 cm1, respectively, and is rather robust
against disorder (Yao and Fang, 2005). These ab initio
calculations are done by calculating only the bare
vertex diagram (Figure 5) in the Kubo formula.
Nevertheless, analytic calculations revealed that the
vertex correction can be of the same order as the
intrinsic SHE, and an effect of vertex correction on
such ab initio calculations remains to be unsettled.
For applications to spintronies (Žutić et al., 2004),
the SHE may potentially be used as an effective
means to inject spins into semiconductor spintronics
devices. There have been many proposals for semi-
conductor spintronics devices such as Datta–Das spin
transistor (Datta and Das, 1990). Nevertheless, an
effective spin injection into semiconductors is one
of the elusive issues, because spin injection from a
ferromagnetic metal suffers from conductance mis-
match (Schmidt et al., 2000). There have been many
kinds of attempts to overcome this difficulty, and the
SHE might be one of the way out toward effective
spin injection into semiconductors. In particular, one
of the merits of the SHE is that it does not require
magnetic field or magnetism. The main obstacle for
the SHE toward application is its smallness. Ab initio
calculations would be important for searching sys-
tems with large enough SHC.
1.07.3 SHE in Metals
sf, the spin
1.07.3.1 Experiments of SHE in Metals
Up to now we have focused mainly on the semicon-
ductor systems with small carrier concentration. The
local band structure in momentum bfk-space is well
Spin Hall Effect 245
characterized by, for example, k ? p theory, and the
theory can be rather well controlled. However, it has
the following disadvantages. (1) due to the small
number of carriers, the conductivity itself is small,
and correspondingly the SHC is even smaller; (2)
the interface with magnetic materials, which are
mostly metals, suffers from the impedance mismatch
(Schmidt et al., 2000); and (3) the systems are rather
fragile against disorder and thermal agitation. These
disadvantages are overcome by the metallic systems.
For example, (1) the SHC is much larger than that of
doped semiconductors typically by the factor of 102–
105; (2) the junction with ferromagnetic metals is
simple and techniques in metallic spintronics such as
the spin injection (Johnson, 1993; Johnson and Silsbee,
1985), spin diffusion (Shchelushkin and Brataas,
2005a,b), and nonlocal effect can be used; and (3)
the quantum coherence is much more robust against
disorder and thermal agitation due to the large Fermi
energy, and hence the operation at room temperature
is possible. These advantages make the metallic
systems more promising candidates for the real appli-
cations of the SHE in spintronies.
In semiconductors, the optical detection of the
spin accumulation such as the KR has been used to
detect SHE, since the spin diffusion length is much
larger than the spot size of the laser beam of the order
of 1 mm. In metals, on the other hand, the spin diffu-
sion length is much shorter, and the electrical
detection is used (Huh et al., 2008). There are two
ways to study the SHE in metals. One is to use the
nonlocal spin diffusion due to the injection of the
spin-polarized current from the ferromagnet
(Takahashi and Maekawa, 2003, 2007, 2008a,b). An
early experiment on the SHE in Al (Valenzuela and
Tinkham, 2006) uses CoFe as the ferromagnet. A thin
Al Hall cross is oxidized and contacted with the
ferromagnetic electrodes as shown in Figure 16.
When the current flows from the ferromagnetic elec-
trode to Al Hall bar, the spin diffusion occurs to the
other side of the bar, where the Hall voltage is mea-
sured. This is the reciprocal effect to the SHE in
which the charge current induces the spin current.
This is called the ISHE, and is now widely used to
measure the SHC in metals. As shown in Figure 16
the spin transistor configuration with two ferromag-
netic electrodes FM1 and FM2 has been used to
characterize the spin diffusion length
polarization P, and the angle  between the magne-
tization m and the electrode axis. The chemical
potential difference between up- and down-spins
decays as the distance x from the distance from the
246 Spin Hall Effect

(a) where s is the SHC, c is the conductivity of Al, and

B⊥ LSH is the distance between the FM1 and the voltage
2 M terminal. By plotting RSH as a function of LSH, they
FM
estimated the
sf and s as
sf = 735 nm for
θ
tAl = 25 nm and
sf = 490 nm for tAl = 12 nm in good
FM1 agreement with the above estimate by the spin tran-
sistor configuration. The SHC is obtained as
s = (2.7  0.6)  101 1 cm1 for tAl = 25 nm, and
AI s = (3.4  0.6)  101 1 cm1 for tAl = 12 nm. This
corresponds to the spin Hall angle SH = s/
c = (1–3)  104, which is a bit smaller than the
500 nm
typical value of the anomalous Hall angle 103.
(b) B⊥ (d) BI Later, Kimura et al. (2007) observed the SHE in Pt
+
V metal at room temperature. They used the device
–
+ structure as shown in Figure 18 where the Cu metal
I VSH
–
is bridging the ferromagnet (Py) and Pt. With this
configuration, they could observe both the SHE and
FM1 FM2 FM1
LSH LFM ISHE. For example, when the spin-dependent elec-
(c) (e) trochemical potential is induced in Cu and also Pt by
μ μ the spin injection from Py, the spin current is intro-
duced and the charge current in Pt is induced by the
ISHE. When the voltage is applied to Pt and the
charge current flows, on the other hand, the SHE
Js Js induces the spin current in Cu and Py, producing the
voltage change in Py. These two effects are related
0 0
by the Onsager’s reciprocal relation, which is quanti-
tatively confirmed in this experiment. The obtained
–1 0 1 2 2 1 0 –1 value for the SHC s in Pt at room temperature is
x/λ sf x/λ sf 2.4  102 1 cm1, and the spin Hall angle is
SH = s/c = 3.7  103.
Figure 16 (a–e) Experimental setup for the measurement
of SHE in Al. From Valenzuela SO and Tinkham M (2006) Recently, even larger SHE has been reported in
Direct electronic measurement of the spin Hall effect. FePt/Au devices at room temperature (Seki et al.,
Nature 442: 176. 2008). As shown in Figure 19, the Au Hall cross is
attached to the FePt injector in their devices. The
resistivities () of Au and FePt at room tempera-
ferromagnet, and the spin diffusion length
sf is esti- ture are 2.7 m cm and 36 m cm, respectively.
mated from the exponential decay of the resistance With this small value of  for Au, the main
change due to the spin transistor action as a function mechanism of the SHE/ISHE is considered to be
of x. The measurement has been done at low tem- the extrinsic SS. The spin diffusion length,
Au, of
perature (4.2 K), and it turned out that
sf depends on Au is estimated as
Au = 86  10 nm at room tem-
the Al film thickness tAl; that is,
sf = 705 nm for perature, which is much larger than that of Pt.
tAl = 25 nm and
sf = 455 nm for tAl = 12 nm from They also measured both SHE and ISHE, and the
the data shown in Figure 17(b). With the configura- obtained value of the spin Hall angle SH is 0.113
tion in Figure 16(b), the spin Hall resistance from the data in Figure 19, which is very large
RSH = VSH/I is expressed as compared with the values obtained so far.
Another method to inject the spin current is to
RSH use the ferromagnetic resonance. This method is
RSH ¼ sin  ð56Þ
2 the so-called spin battery or spin pumping, and is
with shown schematically in Figure 20. The ferromag-
netic metal is attached to the nonmagnetic metal,
Ps and the microwave magnetic field is applied to the
RSH ¼ expð – LSH =
sf Þ ð57Þ
tAl 2c ferromagnetic metal. The magnetization precesses
 Spin Hall Effect 247

(a) (b)
FM2
FM1 λsf = 705 nm
V– 10

ΔR (mΩ)
I– 1 λsf = 455 nm

I– 0.1 tAI = 12 nm
tAI = 25 nm
I+ V+
1 2 3 4
LFM (μm)

(c) (d)
LFM = 2 μm 1
2 B⊥ (T)
• sin θ
–0.4 –0.2 0.0 0.2 0.4
V/I (mΩ)

sin θ
0 0
2 B⊥
V/I (mΩ)

0 M
–2 θ
–2
–1
0 1 2 3 –3 0 3
B⊥ (T) B⊥ (T)

Figure 17 (a–d) Experimental data for the SHE in Al. From Valenzuela SO and Tinkham M (2006) Direct electronic
measurement of the spin Hall effect. Nature 442: 176.

y Pt Cu z
y
Cu
x x Pt
Cu 1 2 3
Cu 1 2 3 Py
Py

(a) Cu

Is
(b) (c)

Ie s

Is

Is
Py Cu Pt
1 2 3 Ie

Is
(e)
(d)

Is
Is Ie
Py Cu Pt
1 2 3 s Ie

Figure 18 (a–e) Experimental setup for the measurement of SHE and ISHE in Pt. From Kimura T, Otani Y, Sato T, Takahashi
S, and Maekawa S (2007) Room-temperature reversible spin Hall effect. Physical Review Letters 98: 156601.
 (a) z (b)
F
y
200 nm 150 nm
FePt injector x
d
M
C

B Au E
V
Au hall cross D
Fept
A

(c) –31.0 (d)

300 V–
I = +0.5 mA I = +0.5 mA
–19.0 M
⏐ΔV⏐ (μV)

0.5
200 +
–31.5
V
ΔV –
–19.5
0 100
0 0.5 e–
RISHE (mΩ)

RLHE (mΩ)
–32.0

V (μV)
I(mA) V+
ISHE I = –0.5 mA V+
0
LHE
20.0 M
–32.5
+
–100
e– V
ΔV
19.5 –
–33.0
–200
V–
–10 –5 0 5 10 15 –8 –4 0 4 8
H (k0e) H (k0e)
Figure 19 (a–d) Experimental setup and results for the measurement of ISHE in Au. From Seki T, Hasegawa Y, Mitani S, et al. (2008) Giant spin Hall effect in perpendicularly
spin-polarized FePt/Au devices. Nature Materials 7: 125.

(a) Microwave
V strength of the resonance microwave magnetic field
H
Ni81Fe19 θ is HFMR = 130 mT, and the resonance line shape is
Pt
Magnetization
Magnetization
Ni81Fe19
(b)
Spin pumping
Pt σ Jc
Js
σ
+ the applied static magnetic field (the direction
Jc
Jc – drop V(H) measured for Pt. The line shape of V(H) is
Figure 20 (a,b) Experimental setup for the spin pumping
and the measurement of ISHE in Pt. From Saitoh E, Ueda M,
Miyajima H, and Tatara G (2006) Conversion of spin current
into charge current at room temperature: Inverse spin-Hall
effect. Applied Physics Letters 88: 182509.
around the magnetic field with the Gilbert
damping. More explicitly, the EOM for the mag-
netization reads
dm dm
¼ m  H eff þ m 
dt dt
where the last term on the right-hand side represents
the Gilbert damping, and  is typically 103–101.
This Gilbert damping drives the magnetization pre-
cession amplitude smaller and smaller and the
magnetization eventually turns the direction of the
effective magnetic field Heff. From the viewpoint of
the conservation of the angular momentum, the spin
angular momentum dissipates to the environment
from the ferromagnet, that is, the flow of the spin
current is produced from the ferromagnet to the
reservoir. In the present configuration, the reservoir
is the nonmagnetic metal. To summarize, the spin
current with the polarization direction  parallel to
the averaged magnetization is injected to the non-
magnetic metal from the ferromagnet by the
ferromagnetic resonance. This injected spin current
will produce the charge current jc in the nonmagnetic
metal through the ISHE as expressed by
jc ¼ DISHE js  
where DISHE is a coefficient for ISHE efficiency. In
the original experiment by Saitoh et al. (2006) and
Inoue et al. (2007), Ni81Fe19/Pt sample with the
Spin Hall Effect 249
thickness of 10 nm for NiFe layer and 7 nm for Pt
layer, respectively, was used to detect the ISHE. The
broadened when Pt is attached compared with the
case of NiFe only. This is the evidence for spin
pumping. They observed the voltage drop at the
edge of Pt which is consistent with the angle depen-
dence expected for the ISHE. The thickness of Pt
layer is of the order of 1 nm, which is within the
decay length of the spin or spin current due to the
strong SO interaction in Pt. Figure 21 shows
the dV(H)/dH curves for various angle  between
of the magnetization) and the direction of the voltage
fitted by
2
V ðH Þ ¼ IISHE
ðH – HFMR Þ2 þ 2
– 2ðH – HFMR Þ
þ IAHE ð60Þ
ðH – HFMR Þ2 þ 2
where  is the relaxation rate. The second term
represents the contribution from the AHE in NiFe
system. Taking the derivative dV(H)/dH, the ISHE
contribution is odd with respect to H  HFMR while
ð58Þ AHE contribution is even. Therefore, it is clear
from the data in Figure 21 that the ISHE contri-
bution is dominant. Another test of ISHE is the
angel dependence. From (58), the signal is
expected to be proportional to sin  ( is the
angle between the external magnetic field and the
charge current), which is also consistent with the
data. These experimental results provide rather
firm evidence for the ISHE in Pt metal, but the
magnitude of the SHC could not be derived
(Saitoh et al., 2006). Recently, an extension of this
experiment has been done by the same group using
similar devices (Ando et al., 2008a,b). In this experi-
ment, the magnetization relaxation in NiFe is
controlled by the spin current injection from Pt
by the SHE. They have carefully studied the
change in the ferromagnetic resonance signal,
dI(H)/dH, due to the charge current Jc in Pt
layer. The idea here is just opposite to that in
the above experiment. For example, the injected
ð59Þ
spin current to NiFe will modify the Gilbert
damping, which depends on the direction of the
spin current polarization. They studied the reso-
nance lineshape for different values of the current
in Pt. Note that the change in the spectra is
250 Spin Hall Effect

(a) FMR θ = 90° (b) θ = 90°

H

d/(H)/dH (a.u.)
Ni81Fe19/Pt
10–4V/T

dV (H )/dH
0 0

Ni81Fe19
Ni81Fe19/Pt
100 150 100 150
H (mT) H (mT)
(c)
ISHE (d) Ni81Fe19 (e) Ni Fe /Pt
81 19
dV/dH HFMR H 10–5V/T 10–4V/T
calc.

dV (H)/dH
exp.

AHE
0
dV/dH H
0 = 90°
HFMR
100 150 120 140
H (mT) H (mT)
Figure 21 (a–e) Experimental data for the ISHE in Pt. From Saitoh E, Ueda M, Miyajima H, and Tatara G (2006)
Conversion of spin current into charge current at room temperature: Inverse spin-Hall effect. Applied Physics Letters
88: 182509.

symmetric for positive and negative direction of
the current for  = 0 ( is the angle between the
external magnetic field and the charge current)
suggesting that the heating effect is the dominant
contribution. When  = 90 , on the other hand, the
spectral change is clearly different for the different
direction of the charge current. By examining the
asymmetric part, that is, dI(H,jc)/dH  dI(H,jc)/
dH, they could estimate the change of the Gilbert
damping coefficient  due to the charge current
jc through the SHE. Considering the values of spin
diffusion lengths
Pt = 7 nm,
Py = 3 nm, and
1
the conductivities Pt c = 0.064(m cm) and
Py 1
c = 0.065(mcm) , they obtained the spin Hall
angle for Pt as 0.08, which is much larger than
0.0037 obtained by Kimura et al. (2007).
The ISHE has been recently applied to the
experimental observation of the spin Seebeck effect
(Uchida et al., 2008). With the magnetic field
applied also along the x-direction, the spin current
is produced by the difference of the chemical
potentials " and # for up- and down-spins,
respectively. In the attached Pt metal, where the
decay of the chemical potential difference,  =
"  #, occurs along the z-direction, the ISHE
occurs and results in the electric field ESHE or the
voltage drop along the y-direction. This voltage
drop due to ESHE is measured as a function of the
temperature difference, T, between the two ends
of the sample, the applied magnetic field H, and
also the position xp of the attached Pt metal mea-
sured from the center of the sample. Results
showed that r is almost constant along the x-
direction, which suggests that the temperature gra-
dient term, that is, the second term, gives
the dominant contribution to r in the expres-
sion r = (qc/qn)rn + (qc/qT)rT  er
(c: spin-dependent chemical potential for spin ,
: scalar potential). It has been argued that the
contribution from rn decays quickly within the
length scale of the spin diffusion length (5 nm)
much shorter than the size of the sample (6 mm),
and does not contribute to the bulk of the sample.
From this measurement, the estimated spin
Seebeck coefficient for Ni81Fe19 is
S spin > 2 nV K1 at T = 300 K, which is orders of
magnitude smaller than the usual Seebeck coeffi-
cient S > 20 mV K1. In addition to the studies
mentioned above, the increasing number of publi-
cations address the metallic SHE (Fan and Eom,
2008; Harii et al., 2008; Kent, 2006; Ma et al., 2008;
Otani and Kimura, 2008; Song et al., 2006a; Stern
et al., 2007, 2008; Valenzuela and Tinkham, 2007;
Vila et al., 2007).
 Spin Hall Effect 251

1.07.3.2 Theories of SHE in Metals
Theoretically, both the intrinsic and extrinsic
mechanisms can contribute to the SHE in metals as
in the case of semiconductors. From the studies on the
AHE, the microscopic mechanism depends strongly
on the degree of disorder characterized by the long-
itudinal resistivity  or conductivity c (Onoda et al.,
2006b; Miyasato et al., 2007). For very clean system
where c is larger than 106 1 cm1, the extrinsic
SS is expected to be dominant where the spin Hall
angle is the proper quantity. In the intermediate
region where c lies between 104 and 106 1
cm1, the intrinsic contribution is the dominant one,
where s is of the order of 103 1 cm1. This value
of 103 1 cm1 corresponds to e2/ha with a > 5 Å
as the lattice constant, representing the QH conduc-
tivity in 3D. Therefore, it is reasonable to assume the
intrinsic mechanism for Pt metal since the conductiv-
ity of Pt at room temperature is of the order of
105 1 cm1. The first-principles band structure cal-
culation for the intrinsic contribution has been done
(Guo et al., 2008). Note that the SHE does not simply
scale with the SO interaction strength, which suggests
that the perturbative treatment of SO interaction is
not valid. Pt shows particularly large SHE surviving
even up to room temperature among the 5d elements
with the similar SO interaction strength. The band
structure of Pt is calculated using a fully relativistic
extension of the all-electron linear muffin-tin orbital
method based on the density functional theory with
local density approximation. Figure 22 shows the
relativistic band structure of Pt, and also the SHC
s, as a function of EF. The 6s bands are extending
broadly from 10 eV to higher energy, while the 5d
bands are within the range of 7 eV < " < 1 eV.
Therefore, the electronic states near EF = 0 are the
mixture of the 6s and 5d bands. The situation is
different for Au, where one extra electron is added
compared with Pt, and the Fermi energy is shifted
upward. The electronic states near the Fermi energy
are mostly 6s and 6p bands in this case. Therefore, we
need to look at the electronic structure in more detail
to understand the mechanism of SHE. As shown in
Figure 22 the SHC s peaks at the true Fermi level
(0 eV), with a large value of 2200 1 cm1. This
gigantic value of the SHC is orders of magnitude
larger than the corresponding value in p-type semi-
conductors such as Si, Ge, GaAs, and AlAs.
Furthermore, the calculated SHC in simple metal Al
is only 17 1 cm1, being two orders of magnitude
smaller than that of Pt.
One important point is the degenerate band struc-
ture at L- and X-points near EF in the scalar-
relativistic band structure (i.e., without the SO
coupling). These double degeneracies are lifted by
the SO coupling, with large SO splittings (0.66 and

4 4
3 3
SOC
2 noSOC 2
1 1
0 0
–1 –1
–2 –2
Energy (eV)

–3 –3
–4 –4
–5 –5
–6 fcc Pt –6
–7 –7
–8 –8
–9 –9
(a) (b)
–10 –10
–11 –11
W L Γ X W Γ –20 0 20
σxyz (102 Ω–1cm–1)

Figure 22 Band structure and SHC as a function of Fermi energy for Pt. From Guo GY, Murakami S, Chen TW, and
Nagaosa N (2008) Intrinsic spin Hall effect in platinum: First-principles calculations. Physical Review Letters 100: 096401.
252 Spin Hall Effect
0.93 eV, respectively). As has been discussed for
p-type GaAs, the magnetic monopoles contribute
resonantly to the SHC, and this structure is realized
at L-and X-points. This is confirmed by the momen-
tum-resolved contribution to the SHC as shown in
Figure 23 where the contribution from the region
near L- and X-points are dominant. It has been also
found that the SHC decreases monotonically as the
temperature T is raised, as shown in the inset of
Figure 23. This rather strong temperature depen-
dence is also due to the near degeneracies since the
small energy scale is relevant to the SHC.
Nevertheless, the SHC s > 240 1 cm1 at
T = 300K is still large and is close to the measured
value (>200 1 cm1). The calculated SHC for Al
at T = 4 and 300 K is 17 and 6 1 cm1, respec-
tively. The former value is similar to the
experimental values (27, 34) at 4.2 K.
To understand the microscopic mechanism of
the SHE, the effective Hamiltonians H(k) for the
two doubly degenerate bands at X- and L-points
have been constructed. This 4  4 matrix can be
written as the linear combination of  matrices,
which is similar to the Luttinger model. The pre-
vious analysis for the p-type semiconductors can be
equally applied to the present case. An important
issue is whether the contributions from conduction
band and valence bands cancel or not. For example,
the contribution to the SHC becomes zero or finite
when the Fermi energy is within the gap between
the two bands. This issue has been discussed in the
context of SHI, and the inverted band structure as in
the case of HgTe has the finite SHC even if the
Fermi energy is within the gap, while it vanishes in
the usual band structure as in the case of GaAs. The
present case of Pt corresponds to the former one,
300
Ωz(k) (atomic units)
200
100
0
W L
Figure 23 Momentum-resolved contribution to the SHC. Inset: The temperature dependence of the SHC. From Guo GY,
Murakami S, Chen TW, and Nagaosa N (2008) Intrinsic spin Hall effect in platinum: First-principles calculations. Physical Review
Letters 100: 096401.
and hence the SHC shows the maximum when EF
lies within the gap. One can also argue from this
effective Hamiltonian that the intrinsic SHE is
robust against impurity scattering since the vertex
corrections for the SHC from the short-ranged
impurity scattering vanish in the clean limit due to
the symmetry H(k) = H(k). Therefore, the intrin-
sic contribution in Pt is expected to be robust
against the disorder potential, and the observed
SHE is most probably of the intrinsic origin.
A related work has been done by Kontani et al.
(2008) using the tight-binding Hamiltonian for the
t2g orbitals. Sr2MO4 (M = Ru,Rh,Mo) has been
explicitly considered, and the large SHC of the
order of 700 1 cm1 was obtained for Sr2RuO4
(Kontani et al., 2007, 2008). They also calculated
the orbital Hall conductivity corresponding to the
orbital current. Tight-binding model is convenient
to draw an intuitive picture in the real space. The
transfer integrals among the t2g orbitals become
complex in the presence of the SO interaction as
has been discussed in the context of the AHE by
Onoda and Nagaosa (2002). This phase of the trans-
fer integral can be regarded as the Peierls phase for
the fictitious magnetic field, and induces the
Aharonov–Bohm effect in the crystal. A related
paper by Tanaka et al. (2008) considered the SHE
and the orbital Hall effect in 3D 4d and 5d transition
metals. The vertex correction relevant to the SS
contribution has not been considered in this work.
Therefore, the obtained results are for the intrinsic
mechanism only.
As for the giant SHE observed in Au by Seki et al.
(2008), the role of local electron correlation has been
considered by Guo et al. (2009). They considered the
vacancy, Fe, and Pt as the possible defects in Au and
2
σ (103 Ω-cm–1)
1
0
0 150 300
T (K)
Γ X W Γ

calculated the local density of states for each case.
Only in the case of Fe in Au, there appears the
resonant electronic states at the Fermi energy which
can contribute to the enhanced SS. Fe in Au has been
known as a representative Kondo magnetic impurity
with a low Kondo temperature TK = 0.4 K. Therefore,
naively, it is not relevant to the giant SHE observed at
room temperature. However, the detailed first-princi-
ples calculation has shown that the Kondo effect in Fe
is orbital-dependent in nature. Previously, the crystal
field splitting between eg and t2g orbitals is around
0.1 eV, which is much smaller than the hybridization
energy  > 1 eV, and has been neglected. On the
other hand, the LDA + U calculation shows that the
electron correlation induces the large orbital polariza-
tion and the energy splitting between eg and t2g orbitals
is of the order of 2 eV. This means that the spins in eg
orbitals are in the Kondo limit, while the electrons in
t2g orbitals are in the mixed-valence region. The for-
mer ones lead to the Kondo effect at low temperature,
while the latter can contribute to the large SHE since
the SO interaction is active in the t2g orbitals while it is
quenched in eg orbitals. Another scenario for the
Kondo effect of Fe in Au has been recently proposed
by Costi et al. (2009).
Actually, taking into account the SO interaction in
the first-principles calculation, the energy splitting
between the effective m = 1 and m = 1 states occurs
(m: in the z-component of the orbital angular
momentum). According to Engel et al., (2005), the
spin Hall angle S = s/xx due to the SS is given
by the formula
Z order of the bands is inverted from LH–HH–CB to
dI ðÞSðÞsin
S ¼ Z ð61Þ
dI ðÞð1 – cosÞ
where  is the angle between the incident and scat-
tered waves,  is the solid angle, S() is the skewness
function, and I() is the strength of the scattering. S()
and I() are given by the spin-dependent phase shifts
of the scattering, and the large energy splitting
between m = 1 states suggests that S can be as
large as  0.1. The reason why S cannot be larger
than  0.1 is that the phase shift 1 for the p-wave
scattering is needed as first noted by Fert and Jaoul
(1972). The SHE due to the SS by Ce and Yb impu-
rities has also been considered recently (Tanaka and
Kontani, 2008), and it is concluded that the spin Hall
angle S is given by 8 sin(2/7), expecting the
giant SHE.
Spin Hall Effect 253
1.07.4 Quantum Spin Hall Effect
The QSHE and the topological insulator have been
theoretically proposed and experimentally con-
firmed. In the present section, we review these
recent developments.
1.07.4.1 Inverted Band Structure and SHI
From the systems discussed so far, we can extend
our discussion to insulators. We can see that the
SHE can be nonzero in some classes of insulators,
which we call SHIs in Murakami et al. (2004a).
The reason why the SHI arises can be understood
in terms of band structure. The SHE is caused by
the SO coupling. In terms of the band structure,
the respective bands are classified into multiplets
of the angular momentum. SHE appears if the
fillings of the bands within the same multiplet
are different. Instead, the bands within the same
multiplet are all empty or all occupied, and their
contribution to the SHE cancels each other. In the
Luttinger model representing the valence bands of
cubic semiconductors, the J = 3/2 multiplet con-
tains the LH and HH bands; the SHE appears
because the fillings of the HH band and the LH
band are different.
In the semiconductors such as -Sn, HgTe, HgSe,
and -HgS, the band structure is inverted from the
cubic semiconductors such as GaAs (Figure 24(a)).
In the inverted band structure (Figure 24(b1)), the
CB–HH–LH. The mathematical structure of the
Hamiltonian is essentially the same with the cubic
semiconductors. The only change is that the energy
difference at the  point between 6 (CB) and 8
(LH and HH) bands has a different sign. Thus, the
original LH band and the CB become a CB and the
valence band in the inverted semiconductors, respec-
tively. Hence, in the hole picture the LH band is fully
occupied and the HH band is empty, and the result-
ing SHC is nonzero even for the band insulators. In
these semiconductors with inverted band structure,
the bandgap is zero, which comes from the degener-
acy at the  point due to the cubic symmetry. When
one breaks the cubic symmetry by uniaxial strain, for
example, there opens a finite gap, while the SHC
remains nonzero (Figure 24(b2)). This nonzero
SHC is a result of the nature of the gap; the gap is
opened by the SO coupling.
254 Spin Hall Effect
(a) Conventional (b1) Zero-gap
(GaAs) (HgTe)
CB
LH
EF EF
HH
HH
LH
CB
k=0 k k=0 k k=0
Figure 24 Band structures of (a) Cubic semiconductors such as GaAs, zero-gap semiconductors (b1) without strain and
(b2) with uniaxial strain along z-axis, and (c) narrow-gap semiconductors such as PbTe. The LH, HH, and CB in (a) stand for
the light-hole, heavy-hole, and conduction bands. The LH, HH, and CB correspond to the LH, HH, and CB bands in (a).
Narrow-gap semiconductors such as PbTe, PbSe,
and PbS are also SHI. The bandgap in these narrow-
gap semiconductors is also caused by the SO
coupling, and the SHC is nonzero. The crystal struc-
ture is that of the rocksalt. The direct gap of the size
0.15–0.3 eV is at the four L-points (Figure 24(c)).
The SHC for these compounds is around 0.04e/a,
where a is the lattice spacing (Murakami et al., 2004a).
In the SHI described above, as in contrast with the
QSH system discussed later, there are no gapless
edge channels. It is then a question of how the spin
current flows in the SHI. The nature of the spin
current in the SHI was numerically studied using
the Keldysh formalism (Onoda and Nagaosa,
2005b). It is revealed that the spin current flows
along the edge only when an electrode is attached
along the edge. This may imply that by providing the
edge channel from the electrode, the SHI can carry
the spin current.
1.07.4.2 QSHE and Z2 Topological
Invariants in 2D and 3D
The QSHE is theoretically proposed as the spin
analog of the QHE (Kane and Mele, 2005a,b;
Bernevig and Zhang, 2006; Fu et al., 2007a; Fukui
and Hatsugai, 2007a; Hatsugai et al., 2006; Sheng
et al., 2005c). The QSH phase is possible both in 2D
and 3D. We first consider the 2D QSH phase. In the
phase, the bulk is gapped while the edge is gapless
carrying a spin current.
The simplest version of the 2D QSH can be con-
structed as a superposition of two QH subsystems with
opposite spins (see Figure 25). For the 2D up-spin
subsystem, we apply an external perpendicular
magnetic field (jj + ẑ ), realizing the QH state with
(b2) Zero-gap + Uniaxial strain (c) Narrow-gap
(HgTe) (PbTe)
LH
EF EF
HH
CB
π (111)
k= a
k k
"xy = e2/h. Meanwhile, for the 2D down-spin subsys-
tem, the magnetic field is opposite, and #xy = e2/h.
They have gapless chiral edge states having opposite
sense of rotations. Superposition of these two subsys-
tems then results in two gapless edge states which have
opposite spins and flow directions, thus carrying a spin
current. This phase realizes topological order, as is
similar to the QH phase. This QSH phase is character-
ized by the Z2 topological number, as we discuss below.
The whole system preserves the time-reversal
symmetry. This state requires a field, which acts as
+ẑ magnetic field for up-spin and ẑ magnetic field
for down-spin. It is not achievable by an external
magnetic field, but instead it is effectively achieved
by the SO coupling, which preserves time-reversal
symmetry. In some materials the SO coupling is
strong enough to realize this topological phase, as
we discuss subsequently. There is one important
aspect of the QSH system QSHS, which is absent in
the QH system; the above example with two QH
subsystems conserves the spin sz, while the SO cou-
pling does not conserve sz in general, hybridizing the
two subsystems together. The question is whether
there is still some interesting physics even in the
absence of sz conservation. Remarkably, the answer
is positive; the edge states are robust against pertur-
bations which do not break the time-reversal
symmetry, such as nonmagnetic impurities or inter-
action (Wu et al., 2006; Xu and Moore, 2006). This
shows the peculiarity of the edge states.
The key concept of the QSHS is the time-reversal
symmetry, which gives rise to the Kramers degener-
acy between k and k. In the band theory, the wave
numbers satisfying k X k (mod G) play an important
role. Such momenta are called the time-reversal-
invariant momenta (TRIM), and are expressed in 2D

Quantum Hall system
(B > 0 for up-spin)
Quantum spin Hall system
Figure 25 Realization of the QSH system as a superposition of two QH subsystems.
1
as k = i where i¼ðn1 n2 Þ ¼ ðn1 b1 þ n2 b2 Þ with n1,
2
n2 = 0, 1 and b1, b2 are reciprocal lattice vectors
(Kane and Mele, 2005a; Fu and Kane, 2006; Fu
et al., 2007a). The degeneracy is different depending
on the presence or absence of the spatial inversion
symmetry I. In I-asymmetric systems the Kramers the-
orem implies double degeneracy only at the TRIM,
and at other wave numbers k the eigenenergies are free
from degeneracies. On the other hand, in I-symmetric
system the eigenenergies are degenerate at all k.
The QSH phase is characterized by the Z2 topo-
logical number  taking only two values  = 0 and
 = 1. In some literature they are called as  = even
and  = odd, respectively, or  X (1) = 1. When
 = odd (or  = 1), the system is in the QSH phase,
and when  = even (or  = 0), the system is an ordin-
ary insulator. It is worth noting that  is calculated
from the Bloch wave function in the bulk as
explained in the next section.
The Z2 topological number  in noninteracting
clean systems is defined in the following way (Fu and
Kane, 2006; Fu et al., 2007a). Let N denote the num-
ber of Kramers pairs below EF. First, we define a
(2N)  (2N) matrix w, defined as
 
wmn ðkÞ ¼ u – k;m h j U juk;n
where U is the time-reversal operator represented as
U = iyK, with K being complex conjugation. uk,m is
the periodic part of the mth Bloch wave function
(m = 1, 2, . . ., 2N). This matrix w(k) is unitary at any
k, and is also antisymmetric at k = i. Then, for each
TRIM we define the index i as
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
det wði Þ
i X
Pf wði Þ
Spin Hall Effect 255
B B
Quantum Hall system
(B < 0 for down-spin)
Spin
for I-asymmetric systems (Fu and Kane, 2006).
Here, w depends on the U(1) phase of the Bloch
wave function; the phase should be chosen to be
smooth over the whole Brillouin zone. On the
other hand, for I-symmetric systems, due to double
degeneracy of each state, the calculation of i
involves the SU(2) gauge choice of juk,mi. In fact,
however, for I-symmetric systems the formula for
the index i is even simpler (Fu et al., 2007a):
Y
N
i X 2m ði Þ ð64Þ
m¼1
where 2m(i)(=1) is the parity eigenvalue of the
Kramers pairs at each of these points for I-symmetric
systems. This shows a crucial role of the I-symmetry
in the theory of the QSHSs. This is because the I
symmetry relates between k and k, as does the
time-reversal symmetry. The Z2 topological number
 in 2D is defined as
Y
ð – 1Þ ¼ i ð65Þ
i
where the product over i runs over the four TRIMs in
the 2D Brillouin zone. The Z2 topological number
allows various equivalent expressions. For example, in
ð62Þ the I-asymmetric systems, the Z2 topological number
can define how the wave functions are glued together at
the TRIMs (Fu and Kane, 2006; Moore and Balents,
2007; Roy, 2006a). We classify the wave functions
below EF into two classes juk,2j  1i (j = 1, 2, . . ., N),
and juk,2ji (j = 1, 2, . . ., N). When the Z2 topological
number  is trivial ( = 0), by a judicious unitary trans-
formation, one can make these states to satisfy
       
ð63Þ uk;2j ¼ Uuk;2j – 1 ; uk;2j – 1 ¼ – Uuk;2j
ð66Þ
256 Spin Hall Effect
We note that U2 = 1. When  = 1, in contrast, it is
not possible for (66) to hold, but there should neces-
sarily appear additional phase factors. Notice that
the wave functions are degenerate only at the
TRIMs. The nontrivial Z2 topological number
works as an obstruction for the wave functions to
be glued at the TRIMs in the simple way given in
(66) (Fu and Kane, 2006; Moore and Balents, 2007;
Roy, 2006b). because the topological order survives
perturbations, such as nonmagnetic disorder and
interactions, the definition of the Z2 topological
number can be further extended (Qi and Zhang,
2008) to systems with nonmagnetic disorder (Kane
and Mele, 2005b) and those with interactions (Lee
and Ryu, 2008).
To illustrate the relationship between Z2 topolo-
gical number and the edge states, we calculate the
bandstructure for geometries with edges in the
Kane–Mele model (Kane and Mele, 2005a,b), which
is the 2D tight-binding model showing the QSH and
insulator phases by changing some parameters (for
details, see Section 1.07.4.4). Let us consider a ribbon
geometry, which is finite in one direction and is
infinite in the other. The phase diagram is in the
inset of Figure 26, where
R,
SO, and
v are The analogous phase is also possible in 3D (Moore
model parameters. The QSH and I in the phase
diagram represent the QSH and insulator phases,
respectively. In the QSH phase (Figure 26(a)),
there exists gapless edge states, irrespective of the
geometry. In contrast, for the insulator phase
(Figure 26(b)) there are no gapless edge states. In
fact, there are edge states, but they do not go across
the gap. In some cases, in general, these edge states in
the insulator state may cross the Fermi energy;
nevertheless, even if they cross the Fermi energy, it
is not an intrinsic property, and the crossing can
disappear by perturbations preserving time-reversal
symmetry. On the other hand, the bulk bandstructure
1
E/t
5 λ R / λ so
0 0
–5
(a)
–1
0 π ka
Figure 26 Band structures of the Kane–Mele model on a ribbon geometry, for parameters in (a) the QSH phase and (b) the
insulator phase. Inset: phase diagram of the Kane–Mele model. From Kane CL and Mele EJ (2005) Z2 topological order and
the quantum spin Hall effect. Physical Review Letters 95: 146802.
is gapped for both cases and looks similar. The topo-
logical order, which is not evident in the bulk
bandstructure, appears as the existence of the robust
edge states. The correspondence between the bulk
and the edge is as follows:
• bulk: Z2 topological number is  = 1 ( = 0) and
• edge: there are odd (even) numbers of Kramers
pairs of gapless edge states.
Because an odd number cannot be zero, the system
with  = 1 should have at least one Kramers pair of
gapless edge states. This bulk–edge correspondence
can be shown by the argument similar to the well-
known Laughlin’s gedanken experiment (Fu and
Kane, 2006). Suppose that we consider the system
on a ribbon, with two opposite ends attached
(Figure 27). In one direction the system is periodic,
while in the other there are edges. Then, when we
increase the flux penetrating the hole from zero to
half the flux quantum, the change of the system
characterized by the time-reversal polarization (Fu
and Kane, 2006) depends on the Z2 topological num-
ber, and it is also related with the number of Kramers
pair of edge states.
and Balents, 2007; Fu et al., 2007a; Roy, 2006b). In this
phase in 3D, the system is an insulator in the bulk and
supports gapless surface states carrying spin currents.
In 3D, the Z2 topological numbers are defined
in the following way. The TRIMs are
i¼ðn1 n2 n3 Þ ¼ 1=2ðn1 b1 þ n2 b2 þ n3 b3 Þ with n1, n2,
n3 = 0, 1 in 3D. There are four Z2 topological numbers
 j (j = 0,1,2,3) (Moore and Balents, 2007; Fu et al.,
2007a; Teo et al., 2008), given by
Y
8 Y
ð – 1Þ0 ¼ i ; ð – 1Þk ¼ i¼ðn1 n2 n3 Þ ð67Þ
i¼1 nk ¼1;nj 6¼k ¼0;1
I
QSH
λ V / λ so
–5 0 5 (b)
2π 0 π ka 2π

y We consider a time-reversal symmetric system
Φ∼ky
x
Figure 27 Laughlin’s gedanken experiment. The flux 
plays the role of the wave number ky.
Each phase is expressed as  0; ( 1 2 3), which distin-
guishes 16 phases. Among  i,  0 is the only topological
number robust against nonmagnetic disorder, and
hence the phases are mainly classified by  0. When
 0 is odd, the phase is called the strong topological
insulator (STI), while it is called the weak topological
insulator (WTI) for the even case. The other indices
 1,  2, and  3 are used to distinguish various phases in
the STI or WTI phases, and each phase can be asso-
ciated with a mod 2 reciprocal lattice vector
G 1 23 =  1b1 +  2b2 +  3b3, as was proposed in Fu
et al. (2007a). These three topological numbers
( k(k = 1,2,3)) are meaningful only for a relatively
clean sample (Fu et al., 2007a). (However, a recent
paper proposes that the 1D helical edge channels
along dislocation are protected by  k (k = 1, 2, 3), and
hence the WTI is also topologically nontrivial
(Ran et al., 2008b).) These topological numbers in 3D
determine the topology of the Fermi curve of the
surface states for arbitrary crystal directions (Fu et al.,
2007a; Teo et al., 2008). It is an example of the bulk–
surface correspondence. Further discussion on the
correspondence between bulk topological numbers in
3D and surface states can be found in Teo et al. (2008).
The nature of the Z2 topological numbers can be
revealed through the study of phase transitions
between the QSH and the insulator phases, involving
a change of the Z2 topological number (Murakami
et al., 2007; Murakami, 2007; Murakami and Kuga,
2008). The Z2 topological number is preserved as
long as the gap remains open. Suppose that the system
transforms from the insulator to the QSH phase by
changing some parameter of the system. Then, the gap
should close somewhere in between. Whether or not
the gap closes as the parameter is varied reflects the
topological properties of the system. The criterion for
the occurrence of the phase transition has been studied
by Murakami et al. (2007), Murakami (2007), and
Murakami and Kuga (2008). The idea is that the
specification of each phase requires information over
the entire first Brillouin zone, whereas the change of
the Z2 number across the transition can be discussed in
terms of the local information near the gap closing
point in the momentum space.
Spin Hall Effect 257
with a bulk gap, and assume that it depends on an
external parameter m. We assume here that the
Hamiltonian itself is generic, and all the terms allowed
by symmetry are nonzero in general. When the para-
meter m is changed, the gap can close in some cases,
whereas in other cases the gap closing is impossible
because of level repulsion. The condition for the gap
closing by varying a single parameter is obtained as
follows. In I-symmetric systems, all the bands are
doubly degenerate and the level repulsion is strong.
In this case, the gap can close only at one of the TRIM
k = i , and only when the valence and conduction
bands have opposite parities. In I-asymmetric systems,
the gap can close at a generic k in 2D at a single value
of m. In 3D I-asymmetric systems, there necessarily
appears a gapless phase between the QSH and the
insulator phases, when m is changed. This gapless
phase occurs because of the topological nature of the
gapless points in 3D (but not in 2D). To summarize,
the universal phase diagrams involving the QSH and I
phases in 2D and in 3D are given in Figure 28
(Murakami, 2007; Murakami et al., 2007; Murakami
and Kuga, 2008).
1.07.4.3 Helical Edge Modes in QSH
systems
As we assume the time-reversal symmetry in the
QSH phase, the edge states consist of pairs, in each
of which the states are related by the time-reversal
symmetry. Such pairs are sometimes called Kramers
pairs. The gapless helical edge states consist of
Kramers pairs of states with opposite spins, propagat-
ing in the opposite directions (see Figure 29). As
stated previously, the edge states remain gapless
even with nonmagnetic impurities or interaction
(Wu et al., 2006; Xu and Moore, 2006). However,
the two-particle scattering terms such as
Z
H9 ¼ g dx y y
ð68Þ
R" R" L# L#
are allowed. These terms give rise to the Tomonaga–
Luttinger liquid effect and also the Umklapp term
among them leads to the spontaneous symmetry
breaking, most probably the magnetic ones. The
readers are referred to the original papers (Xu and
Moore, 2006; Wu et al., 2006). We note that another
proposal to obtain the similar helical edge modes in
graphene has been made (Abanin et al., 2006).
On the other hand, if we break the time-reversal
symmetry by a magnetic field, the helical edge states
258 Spin Hall Effect

(a) (b)
Gapless

Inversion Inversion
symmetric symmetric

I QSH I QSH

δ δ

Gapless
m m

Figure 28 Universal phase diagram between the QSH and the insulator (I) phases in (a) 3D and (b) 2D (Murakami, 2007;
Murakami et al., 2007; Murakami and Kuga, 2008).

V I 0

Figure 29 Schematic of the helical edge states. From Kane CL and Mele EJ (2005a) Quantum spin Hall effect in graphene.
Physical Review Letters 95: 226801.

open a gap. It is demonstrated experimentally in
CdTe/HgTe/CdTe QW that the two-terminal con-
ductance decreases rapidly when the magnetic field
is increased (König et al., 2007, 2008). A fractional
charge appears when the time-reversal symmetry is
broken by magnetic domains put on the edge, as
discussed in Section 1.07.4.6.1. It is proposed theore-
tically that the proximity effect to the ferromagnets
with the helical edge channels introduces the mag-
netic domain wall and a fractional charge e/2,
which can be detected as the shift of the Coulomb
blockade periodicity (Qi et al., 2008b).
1.07.4.4 Models and Candidate Materials
for QSHE
The QSHE was first discovered in a model for gra-
phene by Kane and Mele (2005a,b). This model is
given as
X X
HKM ¼ t ciy cj þ i
SO ij ciy sz cj
ði;j Þ hhi;j ii
X X
þ i
R ciy ðs  b
kij Þz cj þ
v i ciy ci ð69Þ proposed by Fu et al. (2007a). It is the tight-binding
hi;j i
where hi,ji runs through the nearest-neighbor pairs
(i,j), and hhi,jii runs through the next nearest-neighbor
SO =a2 Þ ciy s?ðd1ij  d2ij Þcj ð70Þ
pairs (i,j). bkij is the unit vector along the nearest-
neighbor bond from i to j.  ij takes the value 1
depending on whether the next-nearest-neighbor
hopping from j to i is clockwise or counterclockwise.
i takes the value 1 for the A and B sublattices,
respectively. The phase diagram is as shown in the
inset of Figure 26. We note that there are other
tight-binding models showing the QSH phase
(Onoda and Nagaosa, 2005b; Qi et al., 2006a,b). This
model shows the QSH and the insulator phases, by
changing the model parameters. The phase diagram
is shown in the inset of Figure 28.
A theoretical proposal of the 2D QSH on the
cubic semiconductor with strain gradient has been
made (Bernevig and Zhang, 2006). In this setup, the
strain gradient plays a role of a spin-dependent
effective magnetic field through the SO coupling,
and gives rise to the spin-dependent QH effect, that
is, the QSH effect. In this proposal, the Landau
levels are formed, and in the presence of interaction,
there might be a chance to have exotic states similar
to the fractional QH states.
The 3D QSH phase is realized in the model
i
model on a diamond lattice:
X X
H ¼t ciy cj þ ið8
hij i ðhij iÞ
 Spin Hall Effect 259

where t represents the nearest-neighbor spin-indepen- (a)

dent hopping, and
SO represents the SO coupling, E (eV)
exemplified as a next-nearest-neighbor hopping, and a 0.04
is the size of the cubic unit cell. The vectors d1ij and d2ij
denote those for the two nearest-neighbor bonds 0.02
E1
involved in the next-nearest-neighbor hopping. This dC
four-band model is I-symmetric, and we assume the 50 60 70 80 d (Å)
Fermi energy to be between the upper and lower –0.02 H1
doubly degenerate bands. The gap between the
doubly degenerate CB and valence bands vanishes at –0.04
three X-points. In order to realize the QSH phase, we (b)
need to open the gap. It is achieved by making the
hopping amplitudes for the four different bond direc-
tions to be different. For example, by making one bond
stronger than the other three, it becomes the STI,
while by making it weaker, it becomes the WTI.
This phase change can be attributed to different Figure 30 Change of the bandstructure of CdTe/HgTe/
signs of masses at the direct gaps at the X-points. f0150 CdTe quantum-well as a function of well width d.
Because the QSH phase is caused by the SO From Bernevig BA, Hughes TL, and Zhang S-C (2006)
coupling, one may wonder if there are real materials Quantum spin Hall effect and topological phase transition in
HgTe quantum wells. Science 314: 1757.
which have a sufficiently strong SO coupling to
realize this phase. In order to be in the QSH
are described in the next subsection, in conjunction
phase, the system should satisfy the following two
with the experimental results (König et al., 2007).
necessary conditions: (1) nonmagnetic insulator and
Next, we consider the 3D QSH phase. Because the
(2) odd Z2 topological number. These conditions
bulk bismuth is a semimetal, one possibility to make
mean that the gap is opened by the SO coupling.
it nonmagnetic insulator is to dope antimony. Indeed,
One criterion to see whether the gap is opened by
the alloy Bi1  xSbx with 0.07 < x < 0.22 becomes an
the SO coupling is to focus on the magnetic suscept-
insulator. The Z2 topological numbers are calculated
ibility (Murakami, 2006). In insulators and
from the parity eigenvalues, and it is proposed to be
semimetals, when the SO coupling has a large
the 3D QSH phase (Fu and Kane, 2007; Fu et al.,
matrix element between the valence and the con-
2007a). Related subjects are discussed in Fukui and
duction bands, the magnetic susceptibility is
Hatsugai (2007), Fukuyama (2006), Kane (2007),
enhanced. This has been established through the
Kane and Mele (2006), Liu et al. (2008), Min et al.
study of bismuth and bismuth–antimony alloy.
(2006), Nagaosa (2007), and Yang et al. (2008).
Therefore, bismuth and bismuth–antimony alloy
might be good candidates for the QSH phase. For
2D QSH phase, we consider a thin-film bismuth. By
1.07.4.5 Experimental Observation of
making a ultrathin film, like (111) 1-bilayer film, it
QSHE
becomes an insulator (Koroteev et al., 2008). This
lattice structure is inversion symmetric, and we can So far, there are several experimental reports for the
easily calculate the Z2 topological number from the QSH phase in 2D (König et al., 2007, 2008) and in 3D
parity eigenvalues. Indeed, it is theoretically pro- (Hsieh et al., 2008; Xia et al., 2008). One is on the
posed to be the 2D QSH phase (Murakami, 2006). (Cd,Hg)Te/HgTe/(Cd,Hg)Te QW, realizing the
Another system is CdTe/HgTe/CdTe QW 2D QSH phase. By changing the width d of the
(Bernevig et al., 2006; König et al., 2007, 2008 HgTe QW, the phase changes from the ordinary
(Figure 30)). This idea is based on the fact that insulator (d < dc  64 nm) to the QSH phase (d > dc).
HgTe has an inverted bandstructure from the usual For the narrow QW (da < dc) the bandstructure is like
cubic semiconductors such as CdTe. Thus, by increas- that of CdTe, where the CB is 6 and is s-like. For
ing the QW width, the electronic states change from the wider QW (d > dc), on the other hand, the
the conventional ones to the inverted ones. This change bandstructure is more like that of HgTe, where the
of character in the electronic states correspond to the CB is 8 and is p-like. When the thickness is larger
transition from the insulator to the QSH phase. Details than the critical value, dc, the p-like and s-like bands
260 Spin Hall Effect

touch at k = 0. Thereby the parity of the valence
band and the Z2 topological number changes have
been predicted theoretically in advance (Bernevig
et al., 2006). In the experiments (König et al., 2007,
2008) the charge conductance, G, is measured in a
two-terminal setup, and found to be G  2e2/h when
d > dc and G  0 when d < dc. An effect of the external
magnetic field has also been studied. As the QSHE is
fragile to perturbations which breaks time-reversal
symmetry, the charge conductance G shows a rapid
decrease when the magnetic field is applied. This
means that in the presence of magnetic field, there
appears a gap in the helical edge channel to suppress
the conductance (Figures 31 and 32).
The 3D QSH phase has also been observed experi-
mentally in the alloy Bi0.9Sb0.1 (Hsieh et al., 2008). This
alloy is proposed to be the 3D QSH phase, that is, the
STI (Fu and Kane, 2007; Fu et al., 2007a). The angle-
resolved photoemission spectroscopy (ARPES) is used
for this alloy, and the Fermi surface of the surface state
 and  –
crosses the M line five times (see Figure 33).
From the bandstructure calculation, the indices i at
 and –
M are opposite in sign as predicted theoretically
(Fu and Kane, 2007). This means that there should be
 and –
odd number of Fermi points between M . Thus,
–
 and  indicate that it is
the five crossings between M
indeed the 3D QSH phase (Hsieh et al., 2008). Further
relevant references in this regard are Dai et al. (2008),
Day (2008b), Hirahara et al. (2006), König et al. (2008),
and Koroteev et al. (2008).
Another experiment on the 3D QSH is carried out
on Bi2Se3 (Xia et al., 2008). The ARPES measurement

16
14
R = h/(2e2)
12
10
Rxx / kΩ

8
6
4
2 1 μm × 1 μm, 1.8 K
1 μm × 0.5 μm, 1.8 K
0 1 μm × 1 μm, 4.2 K
–1 0 1 2
(Vg – Vth) / V

Figure 31 Conductance as a function of gate voltage. From König M, Buhmann H, Molenkamp LW, et al. (2008) The
quantum spin Hall effect: Theory and experiment. Journal of the Physical Society of Japan 77: 031007.

0.14 0°
0°
(B|| x)
0.12
15°
30°
0.10 45°
60°
G (e 2/h)

0.08 75°
90°
0.06 (B|| z)

0.04
x
0.02 I
y z
0.00 90°
–0.10 –0.05 0.00 0.05 0.10
B (T)
Figure 32 Conductance as a function of external magnetic field. From König M, Buhmann H, Molenkamp LW, et al. (2008)
The quantum spin Hall effect: Theory and experiment. Journal of the Physical Society of Japan 77: 031007.

0.1
Topological Hall insulator
1 2
0.0
EB (eV)
–0.1
0.0 0.2
Γ –kx (Å–1)
Figure 33 ARPES data for Bi0.9Sb0.1. From Hsieh D, Qian D, Wray L, et al. (2008) A topological Dirac insulator in a
quantum spin Hall phase. Nature 452: 970.
showed that in Bi2Se3 the surface states traverse the
bulk gap. The dispersion of the surface states forms a
single Dirac fermion at the  point, meaning that
Bi2Se3 is the STI if it is insulating in the bulk.
Nevertheless, in reality the material is n-doped in
nature, and it is not even insulating in the bulk. If the
carriers are compensated and the material becomes
insulating in the bulk, it will become the STI. First-
principles calculations have been done on this and
related materials (Zhang et al., 2009), and it was pre-
dicted that Bi2Se3 is really the STI. In addition,
Sb2Te3 and Bi2Te3 are also predicted to be STI,
while they have a smaller gap than Bi2Se3.
1.07.4.6 Further Developments in the QSHE
QSHS and topological insulator are the subject of
intensive studies, and constitute a growing field. We
mention here some of the interesting recent devel-
opments and future directions.
1.07.4.6.1 Spin-charge separation and
charge fractionalization
The simplest example of the spin-charge separation
is the soliton excitations in the conjugate polymer
model such as polyacetylene. Suppose we have the
tight-binding model (Niemi and Semenoff, 1986)
X
H¼ – ðt þ ð – 1Þj dj Þðcjy cj þ1 þ h:c:Þ
j and Semenoff, 1986). In the continuum approxima-
where there is one orbital at each atom j, coupled to
the atom at j + 1 by the transfer integral t + (1)jdj,
with dj being the dimerization. We assume that the
average electron number is 1/2 per atom, that is,
Spin Hall Effect 261
3 4, 5
0.4 0.6 0.8 1.0
M
half-filled. In the ground state, dj = d is uniform,
which opens the gap. In the real space, this corre-
sponds to the periodic array of dimers. For each
dimer, there are bonding and antibonding orbitals
and an electron occupies the bonding orbital.
Therefore, the electron number per atom is 1/2.
There is an energy gap corresponding to the energy
splitting between the bonding and antibonding
states. Now, we consider an isolated atom separated
from the dimers. This can be regarded as the kink or
domain wall between the two degenerate dimeriza-
tion patterns, and called a soliton. Because the
isolated atom has one orbital decoupled from
the other atoms, it has the energy between those of
the bonding and antibonding orbitals in the dimers.
Let us define here the charge of the soliton. An
important remark here is that the charge is measured
from that of the ground state. For example, we count
the charge of the soliton from that of the ground-state
configuration. As noted above, there is half electron
per atom in the ground state, that is, e/2 charge.
Therefore, the charge of the soliton q is defined as
q = (e)  (e/2) = e/2 if an electron occupies the
soliton site, while q = 0  (e/2) = e/2 if the soliton
site is empty. This means that the soliton charge is a
fraction (half) of the unit charge e. This corresponds to
the case of jdjj = t, but the physics remains qualita-
tively the same also in the limit of jdjj << t. In this case,
ð71Þ the field theoretical methods can be applied (Niemi
tion, the Hamiltonian reads
Z
H¼ dx y
ðxÞ½z qx þ x mðxÞ ðxÞ ð72Þ
262 Spin Hall Effect
where (x) = t( 1(x), 2(x)) is the two-component
field operator for the right-going and left-going elec-
trons, and m(x) is the mass term. With the sign change
of the mass m(x) between the two limits x ! 1, a
mid-gap state is topologically guaranteed (Niemi and
Semenoff, 1986). This is the simplest example of the
fractionalization but can be generalized to many
situations in a straightforward way.
Now, we consider the spinfull electrons. Each
atom can accommodate two electrons, that is, up-
spin and down-spin electrons. Then, there is one
electron per atom in the ground state. There are
four possibilities of the soliton in this case: (1)
vacancy, (2) double occupancy, (3) up-spin electron,
and (4) down-spin electron. Let us count the charge q
of the soliton for each of (1)–(4) states. It reads (1):
q = 0  (e) = e, (2): q = (2e)  (e) = e, (3):
q = (e)  (e) = 0, and (4): q = (e)  (e) = 0.
Therefore, the soliton with (1) or (2) configuration
is positively and negatively charged, respectively,
and is called charge soliton. On the other hand, the
soliton with (3) or (4) configuration is neutral. When
we consider the spin quantum number S, it is 1/2 for
the configuration (3) and (4), while (1) and (2) and
also the ground state are the spin singlet. Therefore,
the (3) and (4) forms the spin-doublet pair and is
called the spin soliton. Summarizing the above con-
sideration, the charge and spin are carried by the
different kinds of soliton, and this phenomenon can
be called spin-charge separation. We have shown that
even though the constituent particle have both unit
charge and spin, the excitation in the many-body
state could have fractional quantum numbers and
also the spin-charge separation.
This idea has been applied to the QSHS. As
already noted in Section 1.07.4.3, the helical edge
modes in QSHS separate the right-going and left-
going branches of the dispersion at the two edges of
the sample for up- and down-spin electrons, respec-
tively. Therefore, the degrees of freedom are reduced
to half at each edge, leading to the fractionalized
charge. The effective Hamiltonian for the helical
edge modes at one edge can be written as (72) with
1(x) ( 2(x)) corresponding to the right-going up-
spin electron (left-going down-spin electron), while
the mass m(x) corresponds to the magnetic order
parameter. Therefore, at the magnetic domain wall
where m(x) changes sign, one expects the fractional
charge e/2 as discussed in Section 1.07.4.3 (Qi et al.,
2008b).
In the bulk of the QSHS, there are both up- and
down-spin states, and the situation is similar to the
spinfull electron model discussed above. The only
difference is that the system is 2D and the soliton is
replaced by the vortex with the flux . The phase
winding around this vortex guarantees the existence
of the mid-gap state in the QSHS, and the occupancy
of that mid-gap state determines the charge and spin
quantum numbers quite analogous to that in the spin
and charge solitons (Ran et al., 2008a,b; Qi et al.,
2008b; Moore, 2008). Therefore, QSHS offers the
first explicit model showing the spin-charge separa-
tion in 2D, which has been examined for many years
in the context of the theory of high temperature
superconductors (Lee et al., 2006).
1.07.4.6.2 Effective theory and quantized
magneto-electric effect
In the case of QH systems, the effective theory, that
is, the Chern–Simons theory, describes the low-
energy phenomena. Therefore, it is desirable to
develop an effective field theory for the QSHS also.
Recently, an interesting work has been done in this
direction (Qi and Zhang, 2008). The idea is to define
the fundamental time-reversal invariant (TRI) insu-
lator in (4 + 1)-dimensions, described by the (4 + 1)-
dimensional Chern–Simons theory and characterized
by the second Chern number. Due to the time-rever-
sal symmetry, the coefficient of the Chern–Simons
term is restricted to be 0 or , which corresponds to
the Z2 topological number discussed in Section
1.07.4.2. By dimensional reduction, this state is
related to the QSH system in (2 + 1)-dimensions
and the topological insulator in (3 + 1)-dimensions.
As an explicit application of this effective theory, the
quantized magneto-electric effect was predicted,
where an electric field produces the magnetization
in the same direction, with a universal constant of
proportionality quantized in odd multiples of the
fine-structure constant  ¼ e 2 =hc.
1.07.4.6.3 Superconducting QSHSs
The topological concept related to the time-reversal
symmetry has been generalized to the superconduc-
tors. In particular, the superconducting proximity
effect between the surface of the (3 + 1)-dimensional
STI and the usual s-wave superconductor has been
discussed (Fu and Kane, 2008). The Hamiltonian
reads
Z
H¼ dx½ y
ð – iv?r – Þ þ  y y
þ h:c: ð73Þ
" #

where = t( " #) is the two-component spinor cor-
responding to the surface Dirac fermion dictated by
the topology of the bulk state, while  is the super-
conducting order parameter induced by the
proximity effect. This Hamiltonian can be diagona-
lized to result in a superconducting state resembling
the chiral p + ip spinless pairing state. Therefore, a
novel vortex satisfying the non-Abelian statistics
(Read and Green, 2000; Ivanov, 2001), and the chiral
edge modes (Buchholtz and Zwicknagl, 1981;
Matsumoto and Sigrist, 1999; Read and Green,
2000) carrying Majorana fermions are expected. Fu
and Kane (2008) considered the geometry of the two
superconductors with the order parameter 0 and
0ei attached to the topological insulator with the
separation W. Then, the energy dispersion of the
Andreev bound state is given by
E(q) = [v2q2 + 0  2 cos2(/2)]1/2, with q being
the wave number along the edge. The fermion opera-
tor for this bound state constitutes the Majorana wire,
and the circuit of this wire can be used to create,
manipulate, and fuse Majorana bound state (Fu and
Kane, 2008).
On the other hand, one can consider the (p  ip)-
pairing state as the superconducting analog of the
QSH state in parallel to the spinless chiral (p + ip)-
pairing state which can be regarded as the super-
conducting QH system (Qi et al., 2008a,c; Goryo
et al., 2008; Grover and Senthil, 2008; Roy, 2006c;
Sengupta et al., 2006). In the (p  ip)-pairing state, the
helical edge modes appear as the Andreev bound
states. However, because the negative and positive
energy states are redundant in the Bogoliubov–de
Gennes Hamiltonian, only the half of the fermion
degrees of freedom should be taken. This means that
the Bogoliubov quasi-particles at the helical edge
modes are Majorana fermions. In the case of a vortex,
a pair of the Majorana fermion states at the core of
the vortex appears. On this low-energy state, the
time-reversal symmetry operation acts as the super-
symmmetry operation changing the even/odd of the
fermion number. This leads to a nontrivial nonlocal
correlation of some order parameter. They also pro-
pose the BW-phase of 3He as the (3 + 1)-dimensional
superfluid analog of the topological insulator
(Qi et al., 2008c).
Recently Tanaka and Kontani (2008) have pro-
posed that the noncentrosymmetric superconductors
can be a candidate for the superconducting QSHS. In
the presence of the SO interaction, the singlet and
triplet pairing states are mixed, and one cannot
define the spin Chern number. However, the Z2
Spin Hall Effect 263
number can still be defined, and the helical edge
modes as the Andreev bound states appear when
the order parameter p for the p-wave pairing is
larger than that for the s-wave pairing s. An inter-
esting spin-transport property is found in the
Andreev reflection at the junction of the normal
metal and the noncentrosymmetric superconductor.
Another recent development of this field is the math-
ematical classification of the possible topological
classes including both the insulators and supercon-
ductors. It is concluded that there are five classes
according to the time-reversal symmetry and chiral
symmetry. The readers are referred to the recent
papers (Roy, 2006a,b; Schnyder et al., 2008).
1.07.4.6.4 Localization problem related to
the QSHS
The effect of disorder on the electronic states is an
important issue in condensed matter physics. In par-
ticular, it is known that the dimensionality,
symmetry, and topological properties of the system
determine the localization/delocalization behavior
of the wave functions (Lee and Ramakrishnan,
1985). There are basically three universality classes,
that is, (1) orthogonal, (2) symplectic, and (3) unitary
classes, which corresponds to the (1) spinless time-
reversal system, (2) time-reversal system with SO
interaction, and (3) system with broken time-reversal
symmetry. It is remarkable that all the states are
localized in 2D however weak the disorder strength
is in (1) and (3), while the metal–insulator transition
occurs in (2). The integer QH system, which corre-
sponds to the case (3) but also is characterized by the
topological number called Chern number related to
the quantized Hall conductance, has distinct locali-
zation properties. For example, there remain
extended states at the center of each Landau level
(Girvin and Prange, 1987). Therefore, it is an intri-
guing problem if the similar modification of the
localization properties due to the Z2 topological
numner occurs also in the QSHS, which belongs to
the symplectic class (2). Concerning this problem,
Onoda et al. (2007) numerically studied the localiza-
tion length and its scaling behavior of the
Kane–Mele model (Kane and Mele, 2005a,b). The
exponent  describes the divergence of the localiza-
tion length as a function of energy difference from
the mobility edge,  _ jE  Ecj . By numerical cal-
culation, it is found to be   1.6, which is different
from the symplectic value   2.7 (Onoda et al.,
2007). On the other hand, the QSH phase is studied
by extending the network model (Obuse et al., 2007).
264 Spin Hall Effect
The result is consistent with the symplectic value
(Obuse et al., 2008a,b).
For the 3D QSHS, the localization of the (2 + 1)-
dimensional Dirac fermion at the surface is an inter-
esting issue. A model of a single 2D Dirac fermion is
studied by constructing an effective theory includ-
ing a nontrivial topological term, which is
responsible for the protection of the extended states
(Ostrovsky et al., 2007; Ryu et al., 2007). Therefore,
the localization is prohibited by the topology in the
case of the surface states of the STI. From the view-
point of the nonlinear sigma model approach, the
topological terms are classified by the homotopy
consideration of the target space, which is deter-
mined by the symmetry of the problem, and are
restricted to the two cases: (1) there is no topological
term and (2) the topological sectors are classified by
Z2 number. The former corresponds to the usual
symplectic class and also the 2D topological insula-
tor, while the latter to the surface Dirac fermion of
the 3D STI. The readers are referred to some
further references on this issue (Sheng et al., 2006;
Essin and Moore, 2007; Obuse et al., 2008a,b;
Shindou and Murakami, 2009).
1.07.4.6.5 SHE in strongly correlated
systems
One of the most important issues to be studied in the
future is the role of electron correlation in SHE
(Raghu et al., 2008). Concerning this issue, an inter-
esting material has been reported, that is, Sr2IrO4
(Kim et al., 2008). As the atomic number increases
from 3d, 4d to 5d, SO interaction increases while the
electron correlation decreases since the extent of the
d-orbitals gets larger and larger. In the case of 5d
orbitals, the SO interaction and the correlation
energy U are of the order of 0.5 eV, both of which
play important roles, while the crystal field splitting
between eg and t2g orbitals is much larger. In Sr2IrO4,
Ir4+ ion has d5 configuration, and one hole occupies
the t2g orbitals. Because the orbital angular moment is
active in t2g orbitals, the strong SO interaction mixes
the spin and orbital states, leading to the effective
Jeff = 1/2 states and Jeff = 3/2 states. The single hole
occupies one of the doubly degenerate Jeff = 1/2
states, and the Coulomb interaction U leads to the
Mott insulating state (Kim et al., 2008). This experi-
ment opens a promising route of the SHE in oxides
because the effective Hubbard model for Jeff = 1/2
states contains the spin-dependent complex transfer
integrals due to the SO interaction. Actually, a tight-
binding analysis on a related material, Na2IrO3, with
the honeycomb lattice structure concludes that the
system is a QSHS at room temperature (Shitade et al.,
2009). Due to the electron correlation, the novel
antiferromagnetic state is expected at lower tempera-
ture. Further studies on the interplay between the
electron correlation and SHE are extremely impor-
tant especially in correlated oxides, which have many
advantageous features such as the systematic control
of the band width, carrier doping, and the high
energy scales.
1.07.5 Summary and Perspectives on
SHE
1.07.5.1 Comparison between AHE and
SHE
SHE is closely related to the AHE in metallic ferro-
magnets as discussed in Section 1.07.1. Both are
driven by the relativistic SO interaction, and intrinsic
and extrinsic mechanisms are considered. More
explicitly, one may regard the SHE as the two copies
of AHE for up- and down-spins. This analogy is
correct in the zeroth order approximation, but there
are several differences as described below.
One important difference is that the charge is a
conserved quantity and the charge current in AHE is
well defined as the Noether current associated with
the U(1) gauge symmetry, while the spin is not con-
served in the presence of the SO interaction and
correspondingly the continuity equation for the
spin and spin current cannot be derived in generic
situations. Therefore, the definition of the spin cur-
rent is somewhat arbitrary, and the direct observation
of the spin current is much more difficult than that of
charge current, as discussed earlier. This is why the
experimental observation of the SHE has been rather
indirect, by measuring the consequent spin accumu-
lation near the edge of the sample, for example. In
that case, the analysis of the spin diffusion equation
including the decay of the spin density due to the SO
interaction, which is phenomenologically intro-
duced, should be performed.
More direct detection of the spin current is in
terms of the voltage drop perpendicular to it. This
effect is the so-called Aharonov–Casher effect in the
vacuum, but is very small because the magnitude of
the effect in the vacuum contains the rest mass of the
electron mc2 in the denominator. In solids, the effec-
tive SO interaction can be tremendously enhanced
by the factor of mc2/E with E being the bandgap.
This factor can be as large as 106, and hence the

detection of the spin current in solids is much easier.
This idea has been already pursued in the ISHE as
discussed in Section 1.07.3 for metallic SHE.
/ > 0.1 and 1 > 0.1 are possible but
In the case of AHE, the theoretical studies on the
cross-over between the extrinsic and intrinsic domi-
nated regions have been developed, taking into
account the band crossing near the Fermi energy
which resonantly enhances the AHE (Miyasato
et al., 2007; Onodaet al., 2006b). The representative
model system is the Rashba Hamiltonian with the
spin polarization. For example, the cross-over from
the very clean metal, where the SS is dominant, to
the usual metallic region, where the intrinsic contri-
Spin Hall Effect 265
and 1 is the phase shift for the p-wave scattering
(Fert and Jaoul, 1972). This can be of the order of
102 since
not larger. Therefore, the giant SHE observed in Au
(Seki et al., 2008) suggests an essential difference
between the AHE and SHE. For example, the SHE
is not a simple two copies of AHE for up- and down-
spins. This is natural since the x and y components of
the spin operator play some role in the quantum
fluctuation, which leads to the singlet formation in
the Kondo effect as discussed in Section 1.07.3.2 (Guo
et al., 2009; Tanaka et al., 2008). This can be the
mechanism of the enhanced SHE compared with
bution determines H, occurs at h=> where  is
the transport lifetime, and  is the SO energy. At this
cross-over, the longitudinal conductivity xx is much
larger than e2/h, that is, xx > (e2/h)("F/). If one
increases the disorder strength furthermore, the sec-
AHE. In any case, the role of the electron correlation
and the quantum fluctuation of the spins will be an
important issue in the future.
1.07.5.2 Comparison between Integer QHE
ond cross-over occurs at h=ð"F Þ  0:1 to the region
where a new scaling law H _ (xx) with the expo-
nent  > 1.6 holds. This theoretical prediction
(Onoda et al., 2006b), when translated to the 3D
systems by replacing e2/h by e2/(ha) > 103 (Ohm
cm)1 (where a is the lattice constant assumed to be
around 4 Å), is in agreement fairly well with the
recent experimental studies over the many decades
of the disorder strength (Miyasato et al., 2007).
and QSHE
The QHE and the QSHE have many aspects in
common. They come from topological orders in
gapped systems. The QH system is represented
by the topological number (the Chern number) 
taking any integers:  = . . ., 2, 1, 0, 1, 2,. . . . This
is because the underlying symmetry is the contin-
uous U(1) symmetry associated with the charge
Therefore, h=ð Þ and hence the absolute value of
the longitudinal conductivity is a key parameter to
control the behavior of the AHE, which resolves the
long-standing controversy.
From the viewpoint of the above results, the SHE
in semiconductors is all in the strongly disordered
region where the 1.6-power law is expected, but
detailed study of the xx-dependence of s has
never been done. In the case of metals, on the other
hand, the vital role of the band crossings is common
which leads to the enhanced intrinsic SHE in the
usual metallic systems as discussed in Section
1.07.3.2. If the disorder is further reduced, the extrin-
sic SS contribution is dominant, and the SHC s is
proportional to the diagonal charge conductivity xx,
and the spin Hall angle S = s/xx characterizes the
spin Hall response. The anomalous Hall angle is also
defined in a similar way, that is, = s/xx. The
typical value of is of the order of 103, correspond-
ing to the ratio of the SOI and the Fermi energy.
When the resonant scattering by the virtual bound
state of d-orbitals is active, is of the order of
(
/)1 where
is the SOI energy,  is the hybri- topological numbers is reduced to only two classes,
dization energy between the d-orbitals and the
s-bands, that is, the width of the virtual bound state,
conservation. This Chern number is equal to the
number of chiral edge states, and also appears as
the quantized Hall conductance xy = e2/h. In the
2DEG in a strong magnetic field, this number  is
equal to the number of Landau levels below the
Fermi energy. On the other hand, QSHE is related
to the discrete symmetry, that is, the time-reversal
symmetry, which is not related to the conservation
of a physical observable. Correspondingly, QSHS is
characterized by the Z2 topological number taking
only two values,  = even and  = odd, that is,
(1) = 1. As stated earlier, the simplest example
of the QSHS is realized as a superposition of two
QH systems of opposite effective magnetic fields
for opposite spins. Only for such kinds of the
QSHSs, the corresponding topological number is
the spin Chern number:  s =  "   # = . . ., 4,
2, 0, 2, 4, . . . . In this criterion, Z2 even (odd)
corresponds to  s = 0(2)(mod 4). Nevertheless, gen-
eric QSHSs allow terms which break spin
conservation preserving the time-reversal symme-
try. With such spin-nonconserving terms, the set of
odd and even. This is the Z2 topological number,
which characterizes the QSHS.
266 Spin Hall Effect
The edge states are also similar, whereas the
spin-nonconserving terms make the QSH different
from a mere superposition of two QH systems.
The QH system has chiral edge states whose num-
ber is equal to the Chern number. They are
immune to backscattering from impurities, since
the modes with different chiralities are separated
by the sample width. The QSHS has helical edge
states, which consist of pairs of Kramers-degener-
ate edge states. When the spin, sz, is conserved, the
number of edge states is equal to the spin Chern
number of the original QH system. When the spin,
sz, is no longer conserved (but time-reversal sym-
metry is preserved), some edge states may open a
gap; nevertheless, if the Z2 topological number is
odd, at least one Kramers pair of edge states
remains gapless.
An important difference between the QH and
QSHSs is that the QHE usually requires a strong
magnetic field, while the QSHE is realized in the
absence of the magnetic field. In fact, the QHE
requires breaking of the time-reversal symmetry,
but not the uniform magnetic field; the QHE can
arise from external staggered magnetic field
(Haldane, 1988). However, in real systems thus far,
QHE arises only in external uniform magnetic field.
In 2D systems it can be realized because of the
cyclotron motion in the plane perpendicular to the
magnetic field. Due to the Landau level formation by
the strong magnetic field, the motion perpendicular
to the magnetic field opens a gap. In 3D, on the other
hand, the motion along the magnetic field usually
remains gapless; this means that the system cannot
be the QH phase in most 3D systems. On the con-
trary, the QSHS is realized in the absence of the
magnetic field; there is no fixed direction for the
magnetic field, and the QSH phase can be realized
in 3D as well as in 2D. More deeply, the QSHS or the
topological insulator in 3D has no correspondence to
the QH system.
1.07.5.3 Generalization of SHE and Future
Directions
1.07.5.3.1 Optical SHE
The concept of the SHE can be generalized in many
directions. One example is the optical SHE, that is,
the SHE of light (Fedorov, 1955; Pancharatnam,
1956; Imbert, 1972; Chiao and Wu, 1986; Tomita
and Chiao, 1986; Berry, 1987a,b; Onoda et al., 2004,
2006a; Kavokin et al., 2005; Bliokh and Bliokh, 2006;
Day, 2008a; Duval et al., 2006; Glazov and Kavokin,
2007; Wang and Li, 2007; Yao and Niu, 2008; Zhang
et al., 2007). In this case the spin of light is nothing but
the circular polarized states of light. One can derive
the EOM for the center of mass position rc and
momentum kc of the wavepacket of light including
the lowest-order correction due to the finite wave-
length. It reads as
dxc kc
¼ vðxc Þ þ k̇c  ðzc jkc jzc Þ ð74Þ
dt kc
dk c
¼ – ½rvc ðxc Þkc ð75Þ
dt
d jzc Þ
¼ – k̇c ?kc jzc Þ ð76Þ
dt
where v(x) = 1/n(x) (n(x): refractive index) is the
velocity of light, and jz) = [z+, z] represents the
polarization state of light. kc and kc are the SU(2)
connection and curvature matrices, which corre-
spond respectively to An(k) and Bn(k) in the
Berry-phase theory of electron transport. The sec-
ond term on the right-hand side of (74) is the
anomalous velocity due to the Berry curvature.
This term will induce the shift of the trajectory of
light once the force, that is, the spatial gradient of
the refractive index rn(x) is applied. As shown in
Figure 34 this leads to the Hall effect of light at the
refraction at the spatial change of n (Onoda et al.,
2004, 2006a). If we make the spatial change of n to be
abrupt, it reduces to the case of interface refraction/
reflection, which is described by the famous Snell’s
law. The new finding is that once the light beam is
injected to the interface, the shift of the refracted
and reflected beams occurs perpendicular to the
plane of incident light typically of the order of a
fraction of the wavelength. This phenomenon has
Anomalous velocity
k (z c | Ω kc|z c )
Small n
Berry curvature
(z c | Ω kc|z c )
k
Large n
Figure 34 Schematic of the optical SHE at refraction. The
polarization is left circular. The gradient of the refractive
index induces a transverse anomalous velocity due to Berry
curvature.

been known as the Imbert shift (Fedorov, 1955;
Imbert, 1972) since long ago, whereas it is surprising
that it shares the similar mechanism with the SHE in
electrons. This transverse shift has been reconsid-
ered by Bliokh in the case of Gaussian beam (Bliokh
and Bliokh, 2006). Because the semiclassical EOMs
(74)–(76) assumes slow spatial variation of n, in a
strict sense they cannot be applied for the abrupt
interface; as a result, in the abrupt interface the shift
depends on the detail of the beam, for example,
whether it is a Gaussian beam (Bliokh and Bliokh,
2006; Onoda et al., 2006a).
Recently, this transverse shift has been observed
experimentally by using the weak measurement
(Hosten and Kwiat, 2008). With the setup shown in
Figure 35 the transverse shift at the interface refrac-
tion is measured to the accuracy of 1 nm, and the
result shows good agreement with the theory, as
shown in Figure 36. The readers are referred to the
original papers for more details. Optical SHE in exci-
ton-polariton system due to the precession of the spin
state by the k-dependent Zeeman field has been dis-
cussed and observed experimentally (Kavokin et al.,
2005; Leyder et al., 2007). This mechanism is distinct
from that due to the Berry curvature discussed above.
Note that the SHE of excitons due to the Berry
curvature has been proposed by Yao and Niu (2008)
and Kuga et al. (2008) recently.
1.07.5.3.2 Multiferroics
Another generalization of SHE is to the magnetic
insulators. The charge transport is forbidden in the
insulator, but the spin current can be nonzero once
the magnetism is there. For example, the spin cur-
rent is associated with the spin wave propagation
VAP
θw
θI
θT
HWP
L1
Figure 35 Experimental setup for the measurement of optical SHE. From Hosten O and Kwiat P (2008) Observation of the
spin Hall effect of light via weak measurements. Science 319: 787.
Spin Hall Effect 267
due to the spatial variation of the spin directions
(Meier and Loss, 2003). This is more promising
when one wants to suppress the dissipation, com-
pared with the metals and semiconductors. The
design of the QSHE has been developed along this
line as discussed in Section 1.07.1 but Mott insulat-
ing magnetic systems are more common and usual.
In the presence of the SO interaction, one expects
the coupling between the spin current and the
electric polarization/electric field as a natural gen-
eralization of SHE.
Let us start with the commutation relationship
among the components of the spin operator, that is,
½s a ; s b  ¼ ih"abc s c ð77Þ
z
which can be translated into that of s and the angle 
within the xy-plane (s+ = sx + isy  ei) as
½; s z  ¼ ih ð78Þ
This relation is analogous to the commutation rela-
tion between the phase j and the particle number n
of the bosons.
In this language, the magnetic ordering can be
regarded as the superfluidity of the spin current,
and once difference of the phases i and j occurs
between the neighboring sites i and j, the Josephson
super spin current is induced, which then produces
the electric polarization. In this scenario, the electric
polarization P produced by the two spins si and sj is
given by (Katsura et al., 2005)
P ¼ eij  ðsi  sj Þ ð79Þ
with  being a constant proportional to the SO inter-
action. Here, the spin current is related to the vector
spin chirality si  sj.
zI
PS
xI P2 L2
y
P1 VAP
268 Spin Hall Effect
46
70
44
42
60
40
38
y-Displacement (nm)
50
36
34
40
0 20
γI(degrees)
30
20
10
0 20
Figure 36 Experimental results of optical SHE. From Hosten O and Kwiat P (2008) Observation of the spin Hall effect of light
via weak measurements. Science 319: 787.
According to this consideration, one expects the
ferroelectric state for the cycloidal helimagnets,
that is, when the spin rotation plane includes the
direction of the helical wavevector. Experimentally,
the multiferroic behavior of RMnO3 has been
discovered earlier by Kimura et al. (2003) indepen-
dently of the theoretical works mentioned above,
and the magnetic structure in the ferroelectric
phase was shown to be the incommensurate cycloid
later (Kenzelmann et al., 2005; Arima et al., 2006)
supporting the theoretical proposal. The origin of
the ferroelectricity in several other multiferroic
materials is now shown to be the spin current
mechanism (Katsura et al., 2005). In any case, the
generalization of the spin Hall idea to the insulating
magnetic insulating materials offers an interesting
route to the dissipationless spintronics.
1.07.5.3.3 Future directions
The future of the studies on SHE is briefly discussed
here. One can imagine two directions for the future
developments. One direction is to consider the var-
ious kinds of current instead of the spin current such
as the heat current and orbital current. In particular,
the heat current is an important issue also from the
viewpoint of applications, and the interplay between
this current and the spin current is an interesting
problem. Temperature gradient, magnetic field
θI = 64°
δH
40 60 80
δV
λ = 633 nm
40 60 80
θI(degrees)
gradient, and the voltage drop are the external forces
to drive the heat, spin, and charge currents, respec-
tively, and one can consider various kinds of off-
diagonal responses among these. In particular, the
Hall responses have the topological aspects as
described above, which needs to be explored in the
future. Orbital current, on the other hand, is rather
subtle since the information of the shape of the wave
function is lost once the current is taken out of the
sample to the leads. However, one can develop var-
ious analogies between the spin current and orbital
current. Similar ideas have been discussed in the
physics of graphene recently, where the valley
degrees of freedom is analogous to those of spin,
and valleytronics might be an interesting subject
(Rycerz et al., 2007).
Another direction is to consider the electron–
electron and electron–phonon interactions in SHE.
As we discussed above, the d-electrons can be a
promising candidate for future spintronics, where
the electron correlation plays a crucial role. The
enhanced SHE by local correlation by Fe impurity
has been discussed in Section 1.07.3. SHE with 5d
electrons was mentioned in Section 1.07.6.5. The
many-body effects combined with the nontrivial
topology is a vast field of research as represented by
fractional QHE. Whether the analogous fractiona-
lized state exists or not for QSHE is an open

question, although the quenched kinetic energy by
Landau level formation is missing in the case of QSHE.
From the viewpoint of the materials, it started
with the semiconductors and now extends to metals,
band insulators, Mott insulators, and even supercon-
ductors. Accordingly, the concept of the spin current
and SHE is generalized. The condition is that the SO
interaction is effective, which generally requires
heavy elements. It is very important to consider the
possible mechanisms to enhance the SO interaction.
An interesting proposal has been made (Huertas-
Hernando et al., 2006): the curvature in graphene,
fullerenes, nanotubes, and nanotube caps induces
the new term of SO interaction. This kind of theore-
tical design will be useful to extend the horizon of
the SHE. Various other issues such as the role
of correlation (Hu et al., 2003b; Kou et al., 2005;
Dimitrova, 2004a), electron–phonon coupling
(Grimaldi et al., 2006b), the enhancement by bilayer
effect (Jin and Li, 2007), and SHE in atoms (Liu et al.,
2007c; Zhu et al., 2006) are left for future studies.
(See Chapters 1.01, 1.02, 1.05 and 1.06).
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 1.08 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
W R Clarke and M Y Simmons, University of New South Wales, Sydney, NSW, Australia
C-T Liang, National Taiwan University, Taipei, China
ª 2011 Elsevier B.V. All rights reserved.

1.08.1 Introduction 281

1.08.1.1 Important Length Scales and Mesoscopic Systems 282
1.08.1.1.1 Important length scales 282
1.08.1.1.2 Mesoscopic transport 283
1.08.1.2 2D Systems 284
1.08.1.3 1D Systems 285
1.08.1.3.1 Quantum transport in 1D systems 285
1.08.1.3.2 QPCs and saddle point potentials 287
1.08.1.4 Observing Conductance Quantization 288
1.08.2 Ballistic Conduction in n-type GaAs-Based 1D Systems 289
1.08.2.1 Introduction 289
1.08.2.2 The SG Technique and the First Observations of Quantized Conductance 289
1.08.2.3 Other Methods to Fabricate 1DEGs 291
1.08.2.3.1 Shallow etching techniques 292
1.08.2.3.2 Cleaved-edge overgrowth wire 292
1.08.2.3.3 V-groove quantum wires 293
1.08.2.3.4 Gated, undoped (induced) heterostructures 293
1.08.2.4 Energy-Level Splitting and the 1D g-Factor 295
1.08.2.4.1 Zeeman splitting in 1D electron systems 295
1.08.2.4.2 Source–drain bias spectroscopy 295
1.08.2.4.3 Determination of the g-factor in 1D 296
1.08.2.5 Many-Body Physics in 1D – The 0.7 Structure 297
1.08.2.5.1 Identifying the 0.7 structure 297
1.08.2.5.2 In-plane magnetic field behavior of the 0.7 feature 298
1.08.2.5.3 Temperature dependence of the 0.7 structure 301
1.08.2.5.4 Density dependence of the 0.7 feature 302
1.08.2.5.5 Source–drain bias dependence of the 0.7 feature 303
1.08.2.5.6 Thermopower, thermal conductance, and shot noise dependence of the 0.7 feature 304
1.08.2.6 The Kondo Model and Zero-Bias Anomaly 305
1.08.2.6.1 Overview 305
1.08.2.6.2 Experimental and theoretical evidence for a Kondo model 306
1.08.3 Ballistic Transport in p-Type GaAs-Based 1D Systems 309
1.08.3.1 Introduction 309
1.08.3.2 The Hole Band Structure 310
1.08.3.3 Fabricating Stable 1D Hole Systems 312
1.08.3.3.1 Etched quantum wires 312
1.08.3.3.2 Surface gate-depleted quantum wires 313
1.08.3.3.3 Local anodic oxidation 313
1.08.3.3.4 Bilayer quantum wires 314
1.08.3.3.5 Electrostatically induced quantum wires 315
1.08.3.3.6 Cleaved-edge overgrowth hole wires 315
1.08.3.4 Ballistic Transport in Hole Quantum Wires 316
1.08.3.4.1 Source–drain bias spectroscopy 316
1.08.3.4.2 Zeeman splitting and the g-factor anisotropy 317

279
280 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
1.08.3.5 The 0.7 Structure in 1D Hole Systems
1.08.3.5.1 Characterizing the 0.7 structure
1.08.3.5.2 g-Factor anisotropy of the 0.7 structure and zero-bias anomaly
1.08.3.5.3 Spin polarization near the 0.7 structure
1.08.4 Summary
References
Glossary
Band-gap engineering The process of controlling
or altering the band gap of a material by controlling
the growth and composition of layers of different
semiconductors, such as GaAs, AlGaAs, InGaAs,
and InAlAs.
Chemical potential The chemical potential of a
thermodynamic system is the amount by which
the energy of the system would change if an
additional particle was introduced, with the
entropy and volume held fixed. If the chemical
potential of a source lead of a quantum wire is
greater than the chemical potential of the drain
lead, then the electrons will flow from source to
drain.
Density of states The number of states at each
energy level of a system.
Drude conductivity The conductivity of an
electronic system at zero temperature predicted by
the classical Drude model.
Effective mass A value of the mass assigned to an
electron traveling in a periodic lattice that allows the
electron to be treated as a particle traveling in free
space.
Einstein’s relation Also known as Einstein–
Smoluchowski relation, it states that the mobility of
charges in a semiconductor is proportional to a
diffusion coefficient D and inversely proportional to
the product of the Boltzmann constant and the
absolute temperature.
Elastic scattering A form of scattering event in
which the energy of the incident particles is
conserved, only their direction of propagation is
modified.
Fermi energy The energy in a solid below which all
energy states are occupied at zero temperature
and above which all states are unoccupied at zero
temperature.
Fermi velocity The velocity of particles having
kinetic energy equal to the Fermi energy.
Fermi wavelength The de Broglie wavelength of a
quantum wave packet with kinetic energy equal to
the Fermi energy.
318
319
319
321
322
322
Four-terminal configuration A measurement
configuration for measuring the resistance of a
device in which the current at the source and drain
and the voltage at two points along the device are
measured simultaneously. With this information, it
is possible to determine the resistance of the
device between the two voltage probes and
eliminate contact resistance.
g-Factor A dimensionless quantity which
characterizes the magnetic moment and
gyromagnetic ratio of a particle. The g-factor
determines how strongly the particle will couple to
an external magnetic field.
g-Factor anisotropy The extent to which the
measured g-factor of carriers changes as the
direction of the magnetic field changes.
Group velocity The velocity of the envelope of a
group of interfering waves having slightly different
frequencies and phase velocities.
Heterostructure A single crystal made up of
layers of different crystalline materials such as
GaAs, AlGaAs, and AlAs.
Inelastic scattering A form of scattering event in
which the energy of the incident particles is not
conserved.
Low-dimensional system Systems of electrons
or holes that are confined to approximately one
Fermi wavelength in one or more directions.
Many-body phenomena Phenomena that can
only be described by including the interactions
between particles and cannot be described by a
single-particle model.
Mean free path The average distance an electron
travels before being scattered.
Mesoscopic Pertaining to a size regime,
intermediate between the microscopic and the
macroscopic, that is characteristic of a region
where a large number of particles can interact in a
quantum-mechanically correlated fashion.
Mobility The average drift velocity of carriers per
unit electric field in a homogeneous
semiconductor. Mobility is determined by the
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
number of scattering events and therefore is often
quoted as a measure of purity of the system.
Modulation doping A technique used in molecular
beam epitaxy in which successive heterostructure
layers are grown with different types and amounts
of dopants.
Momentum relaxation time The characteristic
time for the momentum distribution of electrons in a
solid to approach or relax to equilibrium after an
external influence is removed.
Phonon The quantum of acoustic or vibrational
energy, considered a discrete particle and used
especially in models to calculate thermal and
vibrational properties of solids.
Quantum point contact A quasi-1D system in
which the length of the channel approaches zero.
Scattering time The time between scattering
events of an electron.
Spin–orbit coupling In an atom, it is the interaction
between a particle’s spin and its orbital angular
momentum. In a semiconductor, the spin–orbit
coupling refers to the coupling of the spins to the
orbital angular momentum of the bands in which
they travel. The orbital angular momentum of the
band derives from the atomic orbitals from which it is
formed. In GaAs, the conduction band derives from
s-orbitals and therefore has l ¼ 0. The valence band
derives from p-orbitals and therefore l ¼ 1.
Transconductance The derivative of the current
through a device as a function of source–drain voltage.
1.08.1 Introduction
For the past four decades, the semiconductor indus-
try has consistently managed to double the number of
transistors on a silicon chip roughly every 18 months
to 2 years. While this effort is to satisfy the ever-
increasing demand for faster and smaller computers,
it has also opened up completely new areas of
research in condensed matter physics. In particular,
the continued miniaturization of devices and
increased purity of semiconductor materials has
allowed the study of novel quantum phenomena in
systems where charge carriers are confined spatially
to lower dimensions. This has resulted in important
fundamental discoveries in quantum physics, includ-
ing the integer and fractional quantum Hall effects in
281
Weak localization A quantum mechanical
property of 2D systems characterized by an
enhanced resistance at zero magnetic field that
rapidly falls away with the application of a
perpendicular field. The enhanced resistance at
zero field arises due to time-reversal symmetry.
For each particle with a probability to travel a
closed loop, there is an equal probability that the
particle will travel the same closed loop in the
opposite direction. These two probability
pathways constructively interfere, increasing the
probability that the particle will be trapped in this
closed loop and unable to take part in conduction.
The size of these localizing pathways is dependent
on the phase coherence length and therefore
weak localization is most apparent at low
temperature where the phase coherence is
enhanced. Applying a magnetic field breaks the
time-reversal symmetry and thereby causes a
decrease in the resistance.
Zeeman splitting The breaking of spin
degeneracy by the application of an external
magnetic field.
Zero-bias anomaly In 1D systems, the zero-bias
anomaly refers to an enhanced conductance at
zero source–drain bias that falls away rapidly as the
source–drain bias is increased. The effect draws its
name from an analogous effect seen in quantum-
dots due to the Kondo effect in 0D.
two-dimensional (2D) systems, conductance quanti-
zation in 1D quantum wires and a host of spin and
charge phenomena in 0D quantum-dots.
In this context, gallium arsenide (GaAs) has
emerged as an important material system for study-
ing quantum phenomena in low-dimensional
systems. This is because it contains high-quality,
epitaxial interfaces in combination with modulation
doping, which provide an ultralow disorder environ-
ment. The very high purity of GaAs heterostructures
allows low-dimensional GaAs devices to easily access
the ballistic transport regime in which the mean free
path of the carriers is longer than the device itself. As
a consequence, carriers can pass through the device
without scattering from impurities. Electron trans-
port in the ballistic regime is very different from
282 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
conventional diffusive transport, where the electrons
are scattered many times by impurities as they make
their way through the device. Interestingly, funda-
mental research in these high-purity GaAs-based
devices has been incorporated back into the semi-
conductor industry, which now uses them in high-
speed applications such as monolithic microwave
integrated circuits (MMICs).
In this chapter, we study the unique properties of
ballistic transport in GaAs devices. In particular, we
examine the intriguing effects that appear in ballistic,
1D quantum wires. The truly quantum nature of
ballistic 1D wires was first demonstrated by two
groups independently. In 1988, van Wees et al.
(1988) and Wharam et al. (1988) both showed that
the conductance of a ballistic 1D channel was quan-
tized in units of G ¼ 2e2/h. This seminal discovery
could be explained by a simple single-particle model.
However, subsequent experiments revealed the
appearance of new features with no single-particle
analog. Most notable has been the discovery of a
small conductance plateau at the oddly unquantized
value of G ¼ 0.7(2e2/h). This so-called 0.7 structure
reveals a plethora of many-body effects, the origin of
which continues to be a source of contention in the
field of mesoscopic physics.
The chapter will proceed with a brief introduction
to transport in mesoscopic systems with important
length scales in Section 1.08.1.1. Since all 1D devices
are derived from 2D systems, we will present a brief
introduction to 2D systems in Section 1.08.1.2. Then,
in Section 1.08.1.3, we introduce the fundamental con-
cepts of conduction in 1D, which includes an
introduction to the density of states and to the
Landauer formula for transport in 1D systems, quan-
tum point contacts, and the saddle point potential. In
Section 1.08.2, we provide a historical account of the
discovery of conductance quantization in n-type GaAs
heterostructures. This includes an introduction to the
split-gate technique (Section 1.08.2.2) and several other
methods to fabricate 1D systems (Section 1.08.2.3),
including shallow etching techniques, cleaved-edge
overgrowth, V-groove quantum wires, and gated,
undoped heterostructures. We then review the out-
comes for the quantized conductance plateau in both
magnetic field and as a function of source–drain bias in
Section 1.08.2.4. This allows us to measure energy-level
subband spacings and the g-factor in 1D systems. In
Section 1.08.2.5, we review the appearance of a feature
at 0.7(2e2/h) seen in high-quality electron systems,
before finishing with a discussion of the Kondo
model and zero-bias anomaly (Section 1.08.2.6).
In Section 1.08.3, we mirror the discussion on electron
systems by considering ballistic transport in 1D hole
systems. In particular, we highlight the important role
that spin–orbit coupling and the large effective
mass have on both the single-particle properties and
many-body effects in ballistic hole channels.
1.08.1.1 Important Length Scales and
Mesoscopic Systems
As semiconductor devices scale down in size, there
reaches a limit where device behavior no longer
scales with dimension but novel effects start to
occur. These effects come into play when the dimen-
sions of the device become comparable to an
important length scale, such as the mean free path
or the Fermi wavelength. At this point, the system
enters what is called the mesoscopic regime, where
the wave character of the charge particle comes into
play and the kinetic energy becomes quantized. This
quantization comes about purely from the spatial
confinement of the charge carriers. This confinement
can occur in just one spatial dimension to form a 2D
film or in two spatial dimensions to form a 1D wire or
in all three spatial dimensions to form a quantum-dot
or an artificial atom. In each case, the dimensionality
of charge motion is the number of spatial directions
in which the electron eigenstates are free to evolve
and thereby to transport charge. Understanding
mesoscopic systems requires an understanding of
several key length scales. These are summarized as
follows.
1.08.1.1.1 Important length scales
The three most important length scales in meso-
scopic systems are: the Fermi wavelength, the mean
free path, and the phase coherence length.
Fermi wavelength, F: The Fermi wavelength for 2D
systems, F, is the de Broglie wavelength of electrons
at the Fermi energy and is given by
rffiffiffiffiffi
2 2 h
F ¼ ¼ ¼ pffiffiffiffiffiffiffiffiffiffiffiffi
kF ns 2m EF
where kF is the Fermi wave number, ns is the sheet
carrier concentration, m is the effective mass, and EF
is the Fermi energy. At low temperatures, current in
devices is passed by carriers having an energy close
to the Fermi energy, so that the Fermi wavelength
becomes the relevant wavelength. Carriers with less
energy have longer wavelengths, but they do not
contribute to the conduction. The lowest energy
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures 283

mode in a quantum wire is half the Fermi wave-
length; therefore, a wire must be at least this wide
in order to see conductance quantization. In GaAs/
AlGaAs heterostructures F  400 Å for an electron
concentration of ns  3  1011 cm2. For 1D systems
kF is given by ns.
Mean free path, lmfp: A simple explanation of the
mean free path is the average distance a carrier
travels before it gets scattered into a different wave-
vector direction. If we consider an electron moving
through a perfect crystalline lattice, the electron
moves as if it were in vacuum, but with a different
mass. However, if there is any deviation from perfect
crystallinity either caused by defects or impurities in
the lattice or, from thermal vibrations, then the elec-
tron’s path is scattered and it changes its momentum.
The mean free path lmfp is given by
lmfp ¼ vF 
where vF is the Fermi velocity and  is the momen-
tum relaxation time. The Fermi velocity is given by
hkF
VF ¼
m
The mean free path dictates the length a quantum
wire must be before ballistic transport is observed.
Ideally, the length of the wire should be less than the
mean free path. Typically, for high-mobility, modu-
lation-doped GaAs/AlGaAs heterostructures, with
sheet carrier densities of 3  1011 cm2, and mobi-
lities of 5  106 cm2 V1 s1, the mean free path can
be as long as 100 mm at low temperatures. At room
temperature, this value can decrease considerably
due to the large amount of electron–phonon scatter-
ing. The consequence of such long mean free paths at
low temperatures is that it is easy to create devices
where the device size has comparable dimensions to
the mean free path and the system becomes ballistic.
Phase coherence length, l : When electrons are con-
fined spatially, we need to consider the electron as a
wave packet with a phase coherence length. Electron
motion can no longer be described by a single
Schrödinger equation but can interact with many
other degrees of freedom and exchange their energy.
The phase-coherence length is essentially the dis-
tance the charge carrier can travel before its phase
becomes uncorrelated with its original value. The
phase-coherence length can only be destroyed by
inelastic scattering events – ones that cause phase
randomizing collisions. Typically, this is caused by
fluctuating scatterers. Some examples of this include
electron–electron interactions, where the mutual
Coulomb repulsion of electrons causes them to con-
tinually move and act as scattering sites. Phonons or
lattice vibrations also cause dephasing, but these
typically reduce considerably at low temperatures.
Indeed, both electron–electron and electron–phonon
scattering decrease at low temperatures. Impurity
scattering can also be phase-randomizing if the
impurity has an internal degree of freedom that can
fluctuate with time, such as magnetic impurities
where the spin fluctuates with time. The weak
localization correction is only significant when
l > lmfp.
1.08.1.1.2 Mesoscopic transport
Transport in mesoscopic systems can be divided into
three distinct regimes depending on the relative
magnitude of the size of the system, L, mean free
path, lmfp, and the phase coherence length, l, (see
Table 1). In the diffusive regime, the sample size is
much larger than the mean free path and the trans-
port is essentially independent of the form of the
system. In the quantum coherent regime, the sample
size is similar to the mean free path; therefore classi-
cal transport begins to break down as edge and

Table 1 Trends in g-factor with increasing ID confinement for quantum wires oriented along different crystallographic axes
in parallel and perpendicular magnetic fields.

Important
Regime length scales Impact on electrical conduction

Diffusive regime l < L Quantum corrections to the conductivity can exist due to phase coherence within
regions of size lø
Quantum lmfp < L < l Classical theories of conduction breakdown and the device becomes a more
coherent complex quantum system
regime
Ballistic regime L< lmfp Electrons move through the device like billiard balls on a table and the system
behaves in a more simple purely quantum mechanical way.

Reproduced from Koduvayur, (2008).

284 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
boundary effects start to dominate. However, in the
ballistic regime, the electron makes a ballistic motion
in the system and the system boundary plays the role
of the scatterer instead of impurities. Metallic sys-
tems are typically diffusive since their mean free
paths are of the order of 100 Å and Fermi wave-
lengths of 1–2 Å, such that quantization of the
electron energy levels is not so important.
However, for semiconductor systems where mean
free paths can be 50 mm long and the Fermi wave-
lengths are large, 500 Å, both the boundaries and
quantization of the system play important roles.
Before introducing conduction in ballistic 1D sys-
tems, it is important to briefly consider the 2D
systems from which they are typically formed.
1.08.1.2 2D Systems
Two-dimensional electron gases (2DEGs) are
important since they represent the conducting
layer that is subsequently confined laterally to cre-
ate 1D systems. A 2DEG occurs when electrons are
confined to an interface between two different
materials, such as the interface between a thin sili-
con and silicon dioxide insulating layer or the
interface between GaAs and AlGaAs. Here, the ver-
tical confinement of the electron gas means that the
spacing of all the energetically accessible particle-
in-a-box energy levels for modes in the z-direction
is greater than the level broadenings and kBT. The
density of states in the z-direction is measurably
discrete and the z-component of the wave function
has a standing wave form. Therefore, the electron
cannot move classically in the z-direction and the
transport is 2D.
The dimension at which this vertical confinement
occurs is system specific but is usually of the order of
the Fermi wavelength, F, and in a metal-oxide
semiconductor field effect transistor (MOSFET) or
high-electron-mobility transistor (HEMT) is typi-
cally hundreds of angstroms at low temperatures.
The most authoritative text on 2D systems is that
by Ando et al. (1992). However, a brief summary as to
how they are formed will be given here before we
consider 1D systems.
A 2DEG can be formed in GaAs with the impor-
tant advantage that it is formed at a crystalline GaAs/
AlGaAs heterointerface. GaAs can be considered as a
special case of the more general group of ternary
compounds AlxGa1xAs, where x represents the Al
mole fraction. As a result, the variation in lattice
constant a is very small, with a ¼ 5.6533 þ 0.0078x
(Adachi, 1985), minimizing strain and scattering at
GaAs/AlGaAs interfaces. This is in stark contrast
to the crystalline-amorphous Si–SiO2 interfaces in
Si-MOSFETs.
Confining the carriers to a 2D plane is made
possible through band-gap engineering. While the
lattice spacing in GaAs (5.653 Å) is very similar to
AlAs (5.660 Å), the band gap between them is very
different. If we replace a fraction, x, of the Ga atoms
with Al atoms in AlxGa1xAs, we can span a whole
range of band gaps from Eg ¼ 1.424 þ 1.247x eV at
room temperature. With the use of techniques such
as molecular beam epitaxy (MBE), it is possible to
engineer the band gap by growing a series of layers
with different doping and mole fractions x to form
heterojunction devices.
When a layer of AlGaAs is grown on top of a layer
of GaAs, discontinuities in the conduction and
valence bands form. It is possible to trap carriers
and thereby form a 2D sheet of carriers at the
AlGaAs/GaAs interface. However, by a technique
called modulation doping, it is possible to position
donors in an AlGaAs layer some distance away from
the interface where the 2DEG is formed. The elec-
trons from these donors tunnel to the lower energy
state at the interface leaving behind ionized impurity
states. Since the electron gas formed is spatially
removed from these ionized donors, the scattering
from these charged impurities is reduced and the
mean free path increases.
When the doped layer is n-type, the Fermi energy
in this layer is shifted toward the conduction band in
analogy to a positively biased surface gate. This
forces the bands in the intrinsic layers to bend
upward in order to balance the internal electric
field and creates a triangular quantum-well in the
conduction band at the GaAs/AlGaAs heterointer-
face. This is shown schematically in Figure 1(a).
Conversely, if the doped layer is p-type, the bands
in the intrinsic layers bend down, forming a
quantum-well in the valence band in which holes
accumulate to form a 2D hole system (2DHS) as
shown in Figure 1(b).
A big advantage of GaAs systems over silicon-
based devices is that it is possible to produce sam-
ples where the electron mean free path is much
larger than that of bulk materials with the same
carrier concentration. This makes the ballistic
regime readily accessible in GaAs devices. Lower-
dimensional systems can then be created by using
etching or surface gates to confine the 2D system to
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures 285

(a) (b)
n-AIGaAs AIGaAs GaAs p-AIGaAs AIGaAs GaAs

EF
2DEG

2DHG
EF

Figure 1 a) Band diagram of a GaAs/AlGaAs heterostructure with an n-type doping layer and intrinsic AlGaAs spacer layer
forming a two-dimensional election gas (2DEG) at the GaAs/AlGaAs interface. b) The analogous band diagram for p-type
doping to form a two-dimensional hole gas (2DHG).

one or zero dimensions. This brings us to a more (a) Diffusive

extended discussion of the background theory of 1D
systems. W

lϕ
1.08.1.3 1D Systems
(b)
When the width of the 2D system is confined later- Ballistic
ally to a length scale that is comparable to the Fermi
wavelength, then we form a quasi-1D system. Again, W
we can experience diffusive or ballistic transport
depending on the comparison between the length of
L << lmfp
the wire and the mean free path. In the case where
the length of the wire is longer than the mean free
(c) Quantum point contact
path, the electrons suffer many elastic scattering
events and the wire is diffusive (see Figure 2(a)). If
however the length of the wire becomes comparable W
to the mean free path, the wire becomes ballistic (see
Figure 2(b)). There is also a situation where the W ≈ L « lmfp
width is comparable to the length and is much less
than the mean free path, and this corresponds to a Figure 2 Electron trajectories in the (a) diffusive and
quantum point contact (QPC) see Figure 2(c). (b) ballistic regimes and in (c) a quantum point contact. Here
W is the width of the constriction, L is the length l is the phase
In ballistic wires or QPCs, the constriction in the coherence length, and lmfp is the mean free path. Modified
2DEG is narrow enough that the electron wave from van Wees BJ, van Houten H, Beenakker CWJ, et al.
functions form 1D subbands. In an ideal case, the (1988) Quantized conductance of point contacts in a two-
longitudinal momentum is conserved and no dissi- dimensional electron gas. Physical Review Letters 60: 848.
pation takes place in the semiconductor. The
conductance of such a 1D conductor does not 1.08.1.3.1 Quantum transport in 1D
depend on the length of the channel but only systems
depends on the number of 1D modes in the channel. The Schrödinger equation for a quasi-1D system is
Here, we can no longer define a local conductivity given by
as in the diffusive case and we can no longer directly  
P2
use Einstein’s relation between the conductivity and þ V ðyÞ  ¼ E
2m
the diffusion constant. Instead, however, we must
use the Landauer formula, which connects the con- where V(y) is the lateral confinement potential. The
ductance of a ballistic conductor with a Fermi-level electron wave function within the quasi-1D conduc-
property of such a system. tor can be written as
286 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures

k ðx;nÞ ¼ eikx n ðyÞ to the conductance of the quasi-1D system, where n is

the degeneracy of the subband. For GaAs, n ¼ 2 due
where motion along the wire is described by a plane
to the degeneracy of spin-up and spin-down modes.
wave. In real quantum wires, V(y) can be approxi-
Landauer (1957) showed that the conductance of
mated by the general form:
an ideal conductor (see Figure 4) could be expressed
V ðyÞ ¼ Ajy j in terms of the transmission and reflection probabil-
ities of electron waves at a barrier, connected on
where  ¼ 2 for a simple harmonic oscillator poten-
either side by ideal leads. Here, the nature of trans-
tial or  ! 1 for a square well potential. In the case
port is discussed in terms of the incident carrier flux
of the harmonic oscillator potentials, the quantized
from randomizing reservoirs. The conductance is
energy levels are equally spaced and have the eigen-
given by
functions shown in Figure 3(a). For  > 2 the energy
levels become increasingly far apart as their energy 2e 2 T
increases, whereas for  < 2 the energy-level spa- G¼
h R
cings become smaller. These energy levels form the
where T is the transmission coefficient and R ¼ 1  T
subbands of the 1D system.
is the reflection coefficient. Here, we assume the leads
For an arbitrary potential V(y), the energy-level
are weakly coupled to the reservoirs and hence the
spacings are given by
chemical potentials considered are those of the leads,
h2 kx2 A and B, respectively, giving an infinite conduc-
Ekx ;n ¼ E0;n þ tance for perfect transmission T ¼ 1 and R ¼ 0.
2m
However, in an experiment, the leads are connected
From this relation, we see that the energy-level spa-
to reservoirs where the chemical potentials S and D
cing is inversely proportional to m. Because of this, it
are actually measured. The conductance is then given
is more difficult to observe conductance quantization
by the modified Landauer formula (Imry, 1997)
in p-type GaAs systems due to the fact that the
effective mass of holes in GaAs is 5–6 times greater I 2e 2 T
G¼ ¼
than the effective mass of electrons. S – D h
We can treat each subband as an independent 1D
Here, the conductance takes a finite and universal
system. As a result, the density of states is simply the
value for T ¼ 1 defined as the contact conductance.
sum of the density of states for each subband.
Typically, however, the electrons flow out of one
Figure 3(b) shows the density of states for a square
reservoir into the other and as such the chemical
well potential. Moreover, each occupied subband
potentials in the reservoirs are not well defined. As
contributes exactly
a consequence, four-terminal measurements are gen-
ne 2 erally made experimentally, two terminals for
G¼
h supplying current and two terminals for measuring

|ψ(y )|2 1.0

n=3 0.8
ID DOS (a.u.)

0.6
n=2

0.4
n=1

0.2
n=0
0.0
y 0 1 2 3 4 5 6
E (meV)
Figure 3 One-dimensional (1D) subbands: (a) eigenfunctions of a simple harmonic oscillator and (b) density of states for a
1D system with a square well potential.
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures 287

1D conductor where N is the number of 1D channels. This result,

which comes about due to the perfect cancellation of
μ μA μB μD
the 1D density of states gN(E) and group velocity
vN(E), has been most clearly seen in short (<1 mm)
ballistic channels. To date, numerous experimental
Figure 4 A schematic representation of a one-dimensional
(1D) conductor with source and drain reservoirs with their
systems have reported 1D ballistic transport and
respective chemical potentials. those in high-quality GaAs/AlGaAs heterostructures
are summarized in Sections 1.08.2 and 1.08.3.
the voltage. When these reservoirs are weakly It is interesting to note that while theoretically
one might expect to observe conductance quantiza-
coupled to the system, the universal conductance is
tion in longer channels, it has been shown that
recovered. Indeed, in early measurements, where the
typically channels longer than 10 mm in length do
mean free path was much larger than the constriction
not show ballistic quantization. This arises because
length, quasi-four-terminal measurements revealed
the elastic scattering length in the constriction is
quantized conductance plateau and only a small ser-
different from the lmfp of the 2DEG. As the constric-
ies resistance arising from the 2DEG contact regions
tion narrows and the carrier density decreases, the
needed to be subtracted (Wharam et al., 1988).
Fermi wave vector, kF becomes shorter and the
If we now consider the conductance of a ballistic
screening of the Coulomb impurities in the doped
1D system under an applied bias, we can write an
layer by the electron gas becomes less effective.
expression for the current flow. First, we assume that
Consequently, the elastic scattering length may be
the voltage applied is small in comparison to the
reduced because the confined electron gas ineffec-
Fermi energy and to the subband spacing of the 1D
tively screens the potential fluctuations.
channel – the linear response regime. The current is
then calculated for a simple 1D conductor connected
1.08.1.3.2 QPCs and saddle point
to source and drain reservoirs, which are at the che-
potentials
mical potentials S and D. At zero bias, S ¼ D and
The above discussion suggests that the conductance
the net current flow will be zero. If a voltage is
through an ideal 1D system increases as a series of
applied, the net current will be
perfect step functions as the subbands are occupied.
X Z1 In reality, the conductance plateaus are connected by
I ¼ egN ðEÞvN ðEÞf ðL ;E ÞdE smooth, monotonic risers. While it is tempting to
n attribute this to thermal or disorder broadening of
0
Z1  the discrete energy levels, it is in fact the result of
– egN ðEÞvN ðEÞf ðR ;E ÞdE quantum tunneling and gives important information
0 about the shape of the potential in the wire. This can
where the first term represents electrons moving from be understood most clearly by considering a quantum
source reservoir to drain reservoir and the second wire with zero length, that is, a QPC.
term is the current from drain to source, gN(E) is the In a QPC, the potential varies smoothly along
1D density of states, and vN(E) is the group velocity. At the length of the QPC and can be well approxi-
zero temperature, the Fermi–Dirac distribution is a mated by a saddle point potential (see Figure 5(a))
step function. The product of the density of states given by
g(E)¼1/(dk/dE) and the velocity v¼(1/h–)dE/dk 1 1
V ðx;yÞ ¼ V0 – m !2x x 2 þ m !2y y 2
gives a constant 2/h. Therefore, I becomes 2 2
0 1
X 2e Z ZD
S
2e X 2e
I ¼ @ dE – dE A ¼ ð S –  D Þ where V0 is the electrostatic potential at the center of
n
h h n
h
0 0 the saddle point. This equation assumes that modes
X 2e
¼  eV between V0 and EF are perfectly transmitted while all
n
h other modes (i.e., those above EF and below V0) are
The differential conductance, G, is then given by perfectly reflected. However, this is not true as quan-
tum mechanical tunneling and reflection introduces
dI 2e 2 the possibility of partially transmitted modes. As a
G¼ ¼ N
dV h result, the conduction of a single mode through the
288 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures

4.0

10 3.0

G /e 2/h
0z
2.0

–10
–4 0 1.0
–2 4 ωy
2
0 2 ωx
x 0 4
2 0.0
–2 y –2 0 2 4 6 8
4 –4 (E –Vo)/ hωx

Figure 5 (a) Schematic diagram of a symmetric saddle point potential. (b) Calculated conductance of a quantum point contact
(QPC) as a function of energy E relative to the energy of the longitudinal harmonic oscillator energy, h!x/2 plotted for differently
shaped saddle potentials parametrized by the ratio !x/!y (Büttiker, 1990). Here, spin degeneracy has not been included and as a
result the conductance quantization is in units of e2/h. Reproduced with permission from Büttiker M (1990) Quantised
transmission of a saddle point constriction. Physical Review B 41: 7906. Copyright (1990) by the American Physical Society.

wire will depend on a transmission probably matrix
Tn,m so that
e2
G¼  Tn;m
h
where Tn,m depends exponentially on the energy of
the mode ("n) and is given by
Tn;m ¼ n;m 1=ð1 þ e – "n Þ
The total conductance is therefore given by
e2 X e2
G¼N Tm;n ¼ N T
h h
As a result, the shape of the saddle point potential plays
an important role in determining the shape of the
conductance quantization plateaus. For very short
quantum wires (!y/!x < 1), there is very little evidence
of conductance quantization. Where the confinement is
symmetric (!y/!x ¼ 1), plateaus develop in the con-
ductance and as this ratio increases, the plateaus
become flatter and longer (Büttiker, 1990).
1.08.1.4 Observing Conductance
Quantization
From the above discussion, it is evident that many
factors influence whether or not conductance
quantization can be observed in 1D systems.
These include disorder, confinement potential,
temperature, and effective mass and are summarized
briefly here for clarity.
Disorder plays a pivotal role by determining all
the important length scales. It can be directly corre-
lated to the mobility of the system and therefore the
mean free path. Disorder also sets the phase coher-
ence length as a larger number of scattering events
increases the probability of a carrier losing its phase
memory. However, disorder also influences the
Fermi wavelength. This is because disorder deter-
mines the minimum density at which a mesoscopic
system can operate and hence the maximum Fermi
wavelength. As a result, the disorder of a mesoscopic
system sets the upper limits of both the length and
width of a quantum wire.
Confinement potential is also a crucial factor. As we
have seen, the relative curvature of the confinement
potential parallel and perpendicular to the wire will
influence the shape of the conductance plateaus – the
length of the steps and the sharpness of the risers. The
shape of the confinement potential (i.e., parabolic or
square well) determines the relative spacing between
energy levels while the strength of the confinement
potential will determine the absolute energy-level spa-
cing. The energy-level spacing is also affected by the
effective mass of the carriers. Having a small effective
mass increases the energy-level spacing.
Maximizing the energy-level spacing is particu-
larly important for the observation of conductance
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
quantization to mitigate the effects of thermal broad-
ening, which smears out the plateaus. It follows that
lower temperatures are also preferable for the obser-
vation of conductance quantization.
Today, conductance quantization is readily obser-
vable in GaAs due to the development of high-purity
heterostructures, nanolithography techniques, and
milli-Kelvin measurements. In the next section we
review the development of some of these techniques
and the insight into 1D ballistic transport that has
been gained as a result.
1.08.2 Ballistic Conduction in n-type
GaAs-Based 1D Systems
1.08.2.1 Introduction
Ballistic transport was first observed in 1D devices
based on GaAs/AlGaAs n-type heterostructures. One
of the reasons for this is that GaAs-based heterojunc-
tions have long mean free paths and are generally
easier to fabricate. In addition, the smaller effective
mass of electrons increases the subband spacing,
thereby enhancing quantization effects. Today, advan-
cing growth and fabrication techniques have made it
possible to readily achieve long mean free paths and
hence obtain 1D ballistic conductance quantization.
Moreover, high-purity 1D systems have become a
fertile playground for the study of unique many-
body phenomena indicative of spontaneous spin polar-
ization at zero magnetic field and Kondo-like physics.
In Section 1.08.2.2, we describe the developmental
steps that lead to the first observations of ballistic
conductance plateaus. In Section 1.08.2.3, we survey
several of the most commonly used techniques for
fabricating ballistic 1D systems, while the effect of a
source–drain bias and in-plane magnetic field will be
reviewed in Section 1.08.2.4. Many-body physics in
1D systems will be addressed in the Sections 1.08.2.5
and 1.08.2.6 is where we take a detailed look at the
0.7 structure and zero-bias anomaly and review the
theories that have emerged to explain their origins.
1.08.2.2 The SG Technique and the First
Observations of Quantized Conductance
Initial attempts to laterally confine transport in a 2D
system to fabricate 1D systems were in silicon in the
1980s by Fowler et al. (1982). These experiments were
guided by earlier GaAs experiments by Pepper (1978) in
which a Schottky gate had been reverse biased to reduce
the thickness of channel, thereby observing a change in
289
the dimensionality from 3 to 2 dimensions. Fowler used
an n-type silicon MOSFET, with two p-type implanted
regions patterned either side of a 1 mm channel covered
by a metal top gate. The p-type implanted regions fully
depleted the lightly doped n-type channel. However, by
applying a positive bias to the top gate, it was possible to
induce a 1D conducting channel. The devices, however,
were highly disordered and the authors were restricted
to looking at the transition from 2D to 1D variable
range hopping. Since that time, there have been many
investigations of how to controllably confine the width
of the conducting channel.
The first variable width system was demonstrated
in GaAs-based heterostructures by Thornton et al.
(1986). Here, they were able to look at the transport
characteristics of a 2DEG in a narrow channel formed
by the split gate of a GaAs–AlGaAs heterojunction
field effect transistor, as shown in Figure 6. A split
gate (SG) is literally a gate that has a gap in it so that
the two sides can be biased independently. By applying
a negative voltage to these gates, they first deplete
the carriers underneath them and then start to deplete
the carriers laterally.
In this way, the width of the 1D channel could be
varied from 0.4 mm down to 0 mm. Thornton et al.
investigated the conductance in the channel as a
function of magnetic field for different temperatures,
as shown in Figure 7. They were able to show that, at
small sample widths, the magnetic field behavior did
not fit standard models of 2D conductance but did fit
1D models. As such, they were able to demonstrate a
transition from 2D to 1D conductance as they
reduced the width of the conducting region.
However, since the dimensions of their device were
still relatively large (0.6 mm wide and 16 mm long)
compared with the mean free path, they did not
observe ballistic transport through their 1D system.
Split-gate electrodes
2DEG
Figure 6 A schematic of a split-gate (SG) device showing
how applying a negative voltage to surface gates called split-
gate electrodes depletes the underlying 2D electron gas
(2DEG) to form a one-dimensional (1D) channel. Initially the
gate voltage depletes the 2D until a 1D channel is formed.
290 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures

0.41 K
0.46 K
4.0 × 10–7

0.56 K
0.6 × 15μ Gap

3.0
0.6 K

G(B) – G(0) (Ω–1)

1.0 K

2.0

1.0

0.0
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14
Magnetic field (T)
Figure 7 Conductance as a function of magnetic field indicated by crosses. The solid lines indicate the best fit to
one-dimensional (1D) weak localization theory at different temperatures. The inset shows the gate defining the narrow channel
in the underlying heterojunction. From Thornton TJ, Pepper M, Ahmed H, Andrews D, and Davis GJ (1986) One dimensional
conduction in the two dimensional electron gas of a GaAs-AlGaAs heterojunction. Physical Review Letters 56: 1198, Fig. 1.

Following these initial results, two groups pur-
sued this technique to make 1D systems in materials
in which the elastic mean free path was much longer
than both the length and the width of the 1D chan-
nel. As a result, the first evidence for ballistic
conductance quantization was independently
observed by both the Delft–Philips group led by
van Wees et al. (1988) and the Semiconductor
Physics group, Cambridge University led by
Pepper and co-workers (Wharam et al., 1988). Both
of these results will be discussed here for
completeness.
In the Wharam paper (Wharam et al., 1988), the SGs
defined a channel that was 0.4 mm long and 0.5 mm wide
and 0.7 mm below the surface. Due to the spreading
resistance of the electric fields below the gates and the
negative voltage applied to the SG, it was possible to
reduce the width of the channel and therefore depopu-
late the 1D subbands. The mobility of the 2DEG was
between 2.5  105 and 1  106 cm2 V1s1 for carrier
concentrations between 2 and 5  1011 cm2. At low
temperatures, the elastic mean free path is given by
pffiffiffiffiffiffiffiffi
h 2n
lmfp ¼
e the 1D channel. It is worth mentioning, however, that
So, for these samples, this corresponded to a mean
free path in excess of 2 mm with a Fermi wavelength
of 50 nm. At low temperatures, the longitudinal
resistance showed quantized conductance steps as
the voltage on the SG was made more negative (see
Figure 8):
h 2e 2 N
R¼ ; G¼
2e 2 N h
where N is the number of 1D subbands in the constric-
tion. As the split-gate voltage was made increasingly
negative, the plot showed an initial rise of the resis-
tance at Vg ¼ 0.4 V due to the depletion of the
electrons under the gate to create the narrow channel.
This was then followed by the continual depopulation
of the 1D channels giving steps in the resistance on the
order of h/2e2. The measurements were taken in a
quasi-four-terminal configuration with the contacts
several microns away. As a result, the resistance of
the 2DEG regions at either end contributed a series
resistance to the overall resistance of the sample. When
the series resistance was subtracted, the plateaus were
found to be quantized to within 1%.
Generally, the advantage of using a four-terminal
resistance measurement is that one can minimize the
resistance of the 2DEG region, which is in series with
at present quantized conductance steps cannot be
used as a conductance standard. One of the key
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures 291

1/3
R (h/2e 2 ) 4

R (kΩ)
1/4
3
1/5
1/6
1/7 2
1/8
1/9
1/10
1

0
–3 –2 –1
Vg(V)

Figure 8 The channel resistance as a function of split-gate voltage for two different carrier concentrations in a high-mobility two-
dimensional electron gas (2DEG), showing quantization of the resistance in units of h/2e2. The dimensions of the SG were 0.5 mm
wide and 0.4 mm long and measurements were taken at T  0.1 K. Different carrier concentrations were achieved by illumination.
The inset shows a schematic diagram of the device used in this work. From Wharam DA, Thornton TJ, Newbury R, et al. (1988)
one-dimensional transport and the quantisation of the ballistic resistance. Journal of Physics C: Solid State Physics 21: L209, Fig. 1.

reasons for this is that the resistance of the 2DEG

contact regions always needs to be considered, unlike 10
Conductance, e 2/πh

in the case of the quantized Hall resistance observed

in 2D GaAs/AlGaAs heterostructures.
The importance of having a long mean free path was
also highlighted in the point contact devices made by
the van Wees group (van Wees et al., 1988), who used a
2DEG with an electron density of 3.6  1011 cm2 and
a mobility of 8.5  105 cm2 V1 s1 giving a mean free
path of 8.5 mm and Fermi wavelength of 42 nm. Their
devices were 250 nm wide and they also observed
conductance plateaus (see Figure 9). At Vg ¼ 0.6 V,
the electron gas underneath the gate was depleted and
then conduction was only observed through the point
contact until Vg ¼ 2.2V where the channel was com-
pletely pinched off. Again, a series resistance (400 )
was subtracted to reveal clear plateaus at integer multi-
ples of 2e2/h. Both these results are well understood as
the transmission of spin-degenerate 1D subbands
(Landauer, 1957; Imry, 1997).
The experimental realization of the SG technique
marked an important milestone in the field of meso-
scopic physics. Using Schottky gates fabricated on top
of a GaAs/AlGaAs heterostructure, one is able to
pattern the underlying 2D electron system into any
desired shape such as a 1D channels, quantum-dots,
quantum billiards, and many others.
8
6
4
2
0
–2 –1.8 –1.6 –1.4 –1.2 –1
Gate voltage (V)
Figure 9 The conductance as a function of gate voltage
for a quantum point contact defined in a high-mobility
two-dimensional electron gas (2DEG), showing quantized
plateaus in units of e2/h. The measurement temperature T
is 0.6 K. From van Wees BJ, van Houten H, Beenakker
CWJ, et al. (1988) Quantized conductance of point
contacts in a two-dimensional electron gas. Physical
Review Letters 60: 848, Fig. 2.
1.08.2.3 Other Methods to Fabricate 1DEGs
Several other methods have been shown to produce
ballistic 1DEGs providing more information on
the importance on the geometric nature of the
source and drain contacts to the wires. They
include shallow etching techniques, cleaved-edge
292 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures

overgrowth wires, V-groove quantum wires, and
electrostatically induced 1D systems, and are briefly
reviewed here.
1.08.2.3.1 Shallow etching techniques
Another method for the fabrication of 1DEGs
was developed by Scherer et al. (1987). Here, they
laterally patterned a 2DEG with low-energy
ion-beam-assisted etching to form channels as low
as 75 nm wide. They noted that there was no loss in
electron mobility by the creation of the wires and
that this technique would permit investigation of
devices where the wave nature of electron transport
would be dominant. Kristensen and co-workers then
went on to use shallow-etching techniques to form
three different types of quantum point contacts (see
Figure 10). In their type-I sample, the 1D constric-
tion was formed by shallow wet etching as shown in
Figure 10(a). The etched constriction was then cov-
ered by a 10-mm-wide, 100-nm-thick Ti/Au top gate.
Negatively biasing the top gate simultaneously
reduced the density in the wire and laterally confined
the wire. In their type-II and type-III devices
(Figure 10(b)), etched trenches define the quantum
point contact within two large areas of 2DEG. In this
case, the 2DEG region can be used as side gates to
alter the width of the conducting channel. In type II
(III) devices, the trenches were etched 60 nm (90 nm)
to remove the donor layer.
Interestingly, the confinement strength of these
shallow-etched samples is much larger than that of
a typical SG device, resulting in large 1D subband
spacings of 20 meV. In these devices, therefore,
the 1D conductance plateaus were observed to
persist up to a relatively high temperature of 30 K.
These shallow-etched QPCs form a very good sys-
tem for studying both quantized 1D conductance
plateau and the 0.7 structure at elevated tempera-
tures (see Section 1.08.2.5).
1.08.2.3.2 Cleaved-edge overgrowth wire
Yacoby and co-workers (Yacoby et al., 1996) pio-
neered a new technique to fabricate 1D wires
using cleaved-edge overgrowth by MBE and a
novel in situ contacting scheme. They first grow a
modulation-doped GaAs quantum-well embedded
between two thick AlGaAs layers with a doped
GaAs top layer as shown in Figure 11(a) . In this
case, the resulting 2DEG is 500 nm below the top
surface. A long and narrow tungsten stripe is then
evaporated over the top of the heterostructure that
is ultimately used to gate the wire. The quantum
wire itself is prepared by cleaving the sample in
ultrahigh vacuum as shown in Figure 11(a) and
then overgrowing the smooth cleavage plane
with a second modulation doping scheme (see
Figure 11(b)). As shown in Figure 11(b), electrons
are introduced at the edge of the quantum-well,

(a) (b)

500 nm

AlGaAs Si donors
AlGaAs Ti/Au top gate

GaAs Quantum wire Si donors GaAs Quantum wire Side gate

Figure 10 (a) Scanning electron microscopy (SEM) pictures of the shallow-etched quantum point contacts. (a) Type I devices.
The quantum point contact (QPC) is formed by shallow wet etching, 60 nm deep. The etched walls are shaped as two back-to-
back parabolas. The picture was recorded before covering the etched constriction with a 10-mm-wide, 100-nm-thick Ti/Au
top gate. (b) Type II and III devices. Two semicircular-shaped, etched trenches define the QPC and two large areas of
two-dimensional electron gas (2DEG), which are used as side gates. In type II devices, the trenches are etched 60 nm deep to
remove the donor layer. In type III devices, the trenches are etched 90 nm to the AlGaAs/GaAs heterointerface, and subsequently
covered with AlGaAs by molecular beam epitaxy (MBE) regrowth. From Kristensen A, Bruus H, Hensen AE, et al. (2000) Bias
and temperature dependence of the 0.7 conductance anomaly in quantum point contacts. Physical Review B 62: 10950, Fig. 1.
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
Cleave
W gate
(a)
Z group solved this puzzle by demonstrating that the
X
Y were caused by electron scattering across the 2D–1D
(b) Vτ = 0V T interface (de Picciotto et al., 2000).
S S
T (d)
Vτ = VD
V pioneered the fabrication of V-groove quantum wires
(c) (e)
I DS Vτ
Vτ > VD
V DS
(f)
Figure 11 Fabrication procedures of preparing cleaved-
edge overgrown wires. (a) A GaAs heterostructure with a
buried two-dimensional (2D) electron system and tungsten
surface gate is cleaved in situ. (b) A second modulation-
doped heterostructure scheme is then grown with
molecular beam epitaxy (MBE) on the cleaved edge. (c) The
1D system is formed in the quantum-well along the cleaved
edge by using the tungsten gate to deplete the 2D electron
system while maintaining the 1D modes along the edge as
shown in (d)–(f). The 2DESs either side of the depleted
region act as source and drain contracts to the 1D wire.
From Yacoby et al. (1996), Fig.1.
with one and more confined edge states along the
cleavage. However, there is strong overlap between
the 2DEG and the edge states coupling both systems
along the entire edge as shown in Figure 11(c). The
tungsten gate (T) is then used to decouple the edge
states from the 2DEG. By negatively biasing the top
gate (T), the 2DEG directly below it is depleted
while the edge states remain. The 2DESs either side
of the top gate then act as source and drain contacts
to the edge states to the 1D wire. The side gate (S)
is primarily used to vary the electron density along
the edge. Figures 11(d)–11(f) show a sequence of
schematic cross sections of charge distribution in the
wire region for different top-gate voltages, VT. As
VT is biased increasingly negative, the 2DEG is
separated from the 2D sheets that connect, through
the edge states, to the 1D wire. At this point, the 1D
wire becomes strongly confined in two dimensions.
293
Preliminary measurements of the two-terminal
conductance of a cleaved-edge-overgrown 1D wire
showed deviation from multiples of the universal
values of 2e2/h by as much as 25%. For a long time,
it was not clear what caused this deviation. However,
in 2000, de Picciotto and co-workers from the same
observed nonuniversal quantized conductance steps
1.08.2.3.3 V-groove quantum wires
Another unique route to fabricating ballistic, 1D wires
was taken by the Kapon group (Dwir et al., 1999), who
using organo-metallic vapor deposition on corrugated
substrates. Figure 12(a) shows a cross-sectional trans-
mission electron microscopy (TEM) image of such a
quantum wire device. The charge distribution due to
the modulation doping is shown by the white crosses. In
this structure, a top quantum-well and sidewall quan-
tum wires are present. To measure the conductance of
the quantum wire, an S-shaped mesa was developed, as
shown in Figure 12(b). Here, the groove sidewalls are
used as electron reservoirs. To isolate the V-groove
quantum wire section between the source and drain
contacts, two negatively biased Schottky metal gates of
length 2 mm are deposited so that one (left) depletes
only the sidewalls whereas the second (right) depletes
both the sidewalls and the quantum wire. The conduc-
tance was shown to display a step-like dependence on
gate voltage but with deviations from the universal
quantized conductance values. Using this V-groove
architecture, the authors were able to control the
strength of the lateral confinement of the wire, thus
allowing a comparison between nearly adiabatic and
more abrupt transitions from the wire to the reservoirs.
They were able to show that in the limit of strong
confinement, there was poor coupling between the
1D state of the wire and the 2D states of the electron
reservoirs, which lead to the suppression of the
conductance steps from 2e2/h (Kaufman et al., 1999).
1.08.2.3.4 Gated, undoped (induced)
heterostructures
Kane et al. (1998) demonstrated that semiconductor–
insulator–semiconductor field effect transistor
(SISFET) heterostructures can be used to fabricate
ultra-low disorder n-type quantum wires. The
heterostructure has an AlGaAs layer grown on top
of an intrinsic GaAs substrate. The structure is
then capped with a highly doped layer of GaAs
294 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures

(a) + Ionized impurities (b)

– Eelectrons Sidewalls Gate1: Sidewall

Source

QWR

50 nm Drain
QWR Gate2: Sidewalls with QWR

Figure 12 (a) Cross-sectional transmission electron microscopy (TEM) images of the quantum wire ridge region, charge
distribution due to doping is schematically shown. Taken from Fig. 1 in Electron transport in AlGaAs/AlGaAs V-groove
quantum wires. (b) A tilted scanning electron microscopy (SEM) image of the S-shaped device. Black arrows indicate the
trajectory of the current flow. Two metallic gates of 0.25 mm width each are deposited, one on the sidewall area and the other
on the full sidewall–wire–sidewall path. Taken from Fig. 1 (b) in Conductance quantization in V-groove quantum wires,
(a) From Dwir B, Kaufamn D, Berk Y, Rudra A, Paleski A, and Kapon E (1999) Electron transport in GaAs/AlGaAs V-groove
quantum wires. Physica B 259–261: 1025. (b) From Kaufman D, Berk Y, Dwir B, Rudra A, Palevski A, and Kapon E (1999)
Conductance quantization in V-groove quantum wires. Physical Review B 59: R10433.

that can act as an in situ top gate. Positively biasing
the gate induces an electron gas at the intrinsic
GaAs–AlGaAs interface. A quantum wire can be
formed by patterning the in situ top gate into three
distinct regions as shown in Figure 13. This is
usually done by a combination of electron-beam
lithography and wet-etching techniques. In this
way, the central region of the top gate can be used
to induce a 1D electron system while the outer
regions can be biased negatively to control the
lateral confinement of the wire.
The key advantage of induced, undoped quantum
wires is that they have ultra-low levels of disorder.
The fact that there is no modulation doping means
that scattering from remote-ionized impurities is
essentially eliminated and the epitaxial GaAs–
AlGaAs interface minimizes interface roughness
scattering.
Several groups have used the undoped hetero-
structure to understand quantum transport in low-
disorder quantum wires. Reilly et al. (2001) used
induced quantum wires to study many-body effects
as a function of wire length. Typically, they noted
that for these induced architectures, a change in
density always coincided with a change in the shape
of the quantum-well and it was difficult to disentan-
gle the contributions from each effect. More recently,
Sarkozy et al. (2009) have also used induced hetero-
structures to study many-body effects in low-
disorder quantum wires. In particular, they looked

(a) Side gates: Vs < 0

Top gates: (b)

VT > 0

+ + +
Barrier

Wire
Figure 13 (a) Schematic cross section of an semiconductor–insulator–semiconductor field effect transistor (SISFET)
quantum wire device. The metallically doped cap is patterned into three regions that act as independent surface gates.
Positively biasing the middle gate induces a one-dimensional interacting election system (1DES) directly beneath the gate at
the GaAs/AlGaAs interface while a negative bias on the outer gates controls the lateral confinement potential. (b) Scanning
electron micrograph of an induced quantum wire device fabricated by electron beam lithography and wet etching. From Kane
BE, Facer GR, Dzurak AS, et al. (1998) Quantized conductance in quantum wires with gate-controlled width and electron
density. Applied Physics Letters 72: 3506.
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
at the zero-bias anomaly, which is believed to result
from Kondo-like physics (see Section 1.08.2.6).
1.08.2.4 Energy-Level Splitting and the 1D
g-Factor
1.08.2.4.1 Zeeman splitting in 1D electron
systems
In Section 1.08.2.2, we introduced the first observa-
tion of ballistic conductance in 1D systems. At zero
magnetic field, the conductance steps are quantized
in units of 2e2/h, where the factor 2 comes from
electron spin degeneracy. When a large magnetic
field is applied in the plane of the 1D channel, the
electron spin degeneracy is lifted and the conduc-
tance plateaus become quantized in units of e2/h.
This effect is called Zeeman splitting in 1D electron
systems. The first Zeeman splitting in a 1D electron
system was observed by Wharam et al. (1988), as seen
in Figure 14. Here a magnetic field of 13.6 T was
applied in the plane and parallel to the 1D subbands
of a high-mobility 1  106 cm2 V1 s1 2DEG at
T 0.1 K. The magnetic field lifted the spin degen-
eracy, doubling the number of plateaus observed
in the quantized resistance. These steps occur at
R ¼ h/2(N þ 1/2)e2.
Patel et al. (1991a) extended the parallel field work
of Wharam et al. (1988) and measured the transcon-
ductance dG/dVg of a 1D channel as a function of SG
voltage at various magnetic fields and at various
source–drain biases, as shown in Figure 15. The
positions of the peaks correspond to the Fermi
1500
1/9
1400
Resistance (Ω)
R(h/2e 2)
1/10 1300
1200
1/11
1100
1000
–1.5 –1.0 –0.5
Vg(V)
Figure 14 The channel resistance of a 1D electron system
as a function of applied gate voltage when a magnetic field
of 13.6 T is applied parallel to the channel. The
measurement temperature T is 0.1 K. The spin splitting
gives rise to additional quantized plateaus at R ¼ h/(21e2), h/
(23e2), and an incipient plateau at h/(19e2). From Wharam
DA, Thornton TJ, Newbury R, et al. (1988) One-dimensional
transport and the quantisation of the ballistic resistance.
Journal of Physics C: Solid State Physics 21: L209, Fig. 1.
295
energy crossing the spin-split subbands. By measur-
ing the transconductance, it is possible to get a more
accurate position of the conductance steps. If we
consider the lowest trace for Figure 15(a), we see
the transconductance of the 1D channel versus gate
voltage for B ¼ 0. The position of the n ¼ 1 and n ¼ 2
conductance plateaus occur when dG/dVg is zero. As
a parallel magnetic field is applied to the current
direction, a linear splitting of the transconductance
peaks becomes apparent.
1.08.2.4.2 Source–drain bias
spectroscopy
The quantized conductance plateaus also split lin-
early with the application of a large bias between
source and drain. The effects of a source–drain bias
on 1D subbands were also investigated by Patel
et al. (1991a, 1991b), as shown in Figure 15(b).
They measured a linear splitting of the transcon-
ductance peaks both with increasing magnetic field
and for increasing source–drain bias. Increasing
the source–drain voltage lifts the momentum
degeneracy and splits each conductance plateau
(in the differential conductance vs. gate voltage
trace) into two. Again, a linear splitting in the
transconductance peaks is observed, this time as
Vsd increases.
Source–drain bias spectroscopy is based on a
model developed by Glazman and Khaetskii (1989)
and is now a standard method for measuring subband
spacings in 1D systems . The method adds a direct
current (DC) bias to the alternating current (AC)
excitation voltage in order to change the relative
chemical potentials, , at the source and the drain
of the quantum wire. When no DC bias is applied, the
differential conductance follows the standard quan-
tized conductance relation
XN
dI e2
G¼ ¼ 2n
dV h
n¼0
where N is the number of subbands occupied.
However, when a DC bias equivalent to the subband
energy spacing is applied, the differential conduc-
tance becomes
dI XN
e2
G¼ ¼ ð2n þ 1Þ
dV n¼0
h
Applying a source–drain bias is known to select dif-
ferent numbers of channels from the source and
drain, and is expected to give rise to a half-integer
plateau in zero magnetic field. In other words, the
296 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
(a) 12
10 B = 15T
dG /dVg (a.u.)
8
B = 10T
6
B = 5T
4
2 2
B = 0T
n=1 n=2
0 0
–3.6 –3.4 –3.2 –3 –2.8 –2.6 –2.4
Vg (V)
Figure 15 (a) Transconductance as function of gate voltage at different magnetic fields. (b) Transconductance as a function of
gate voltage at different source drain biases for B ¼ 0 T. From Patel NK, Nicholls JT, Martin-Moreno L, et al. (1991a) Properties of
a ballistic quasi-one-dimensional constriction in a parallel high magnetic field. Physical Review B 44: R10973, Fig. 2.
conductance is quantized in odd integer multiples of
e2/h. Therefore, by measuring at what DC bias the
conductance plateau becomes quantized in odd inte-
ger multiples of e2/h, it is possible to determine the
subband energy spacing for each subband. By tuning
the source–drain voltage, one can then probe the 1D
subband spectrum. It is important to note that
these half-integer plateaus at high Vsd are still spin
degenerate. Further application of a magnetic field
results in the formation of quarter-integer plateaus
at 1.25(2e2/h), 1.75(2e2/h), 2.25(2e2/h), 2.75(2e2/h),
3.25(2e2/h), . . . .
Thomas et al. (1998b) went on to show that in
finite source–drain bias experiments where well-
resolved integer and half-integer plateaus were
observed quarter-integerplateaus were also seen for
every subband even at zero magnetic field.
1.08.2.4.3 Determination of the g-factor
in 1D
The extent to which the spins couple to an external
magnetic field is determined by the g-factor, which
can be measured by finding the source–drain voltage
at which the splitting of the transconductance peaks
is equal to the Zeeman splitting in an in-plane mag-
netic field. At this point, the g-factor is given by the
relation
eVsd ¼ 2gB SB
where B is the magnetic field, B is the Bohr magne-
ton, and S ¼1=2.
As shown in Figure 15, a linear splitting of the
transconductance peaks was observed for both
increasing magnetic field and for increasing
source–drain bias. By comparing the data at high
(b) 10
B = 0T
8 Vsd (mV)
dG /dVg (a.u.)
6 1.5
4 1.0
0.5
n=1 n=2
0.0
–3.6 –3.4 –3.2 –3 –2.8 –2.6 –2.4
Vg (V)
magnetic fields with those in the presence of
source–drain biases, Patel et al. found that for the
second and third subband edge, the 1D g-factor was
1.1 – significantly enhanced over the bulk g-factor
0.4. This large discrepancy was attributed to an
enhancement of the g-factor due to exchange and
correlation mechanisms. This pioneering experi-
ment did not require a perpendicular field as is
normally required for the determination of the
g-factor for 2DEGs.
Thomas et al. (1996) further extended the work of
Patel and co-workers and were able to measure the
g-factor when the current is either perpendicular or
parallel to the applied in-plane magnetic field.
Their experimental results are reproduced in
Figure 16. For Vg < 4 V, additional spin-split pla-
teau are observed interleaved between those at zero
field. For Vg > 4 V, the Zeeman energy is compar-
able to the subband spacings and both sets of spin-
split plateaus cannot be easily resolved. From the
inset (b), we can see gk and g? for all 26 subbands,
and it is evident from these results that the g-factor
is almost isotropic. It is worth pointing out that
when the number of occupied 1D subbands was
high, the absolute value of the g-factor was found
to be 0.4, that is, close to the bulk value of GaAs.
For the last few occupied subbands of the channel,
the anisotropy of the confinement potential can be
described by a saddle point (Martin-Moreno et al.,
1992) and little anisotropy of the in-plane g-factor is
observed. However, as the number of 1D subbands
decreases, the g-factor was observed to increase
gradually. It was suggested that the enhanced
g-factor (1) over its bulk value was due to elec-
tron–electron interaction effects as the constriction
became narrow.

20
1.5 (b)
g-factor
1 •
15
0.5
G (in units of 2e 2/h)
0
10
0 10
Subband Index
Sample A
T = 60 mK
5 0.5
0 Although the 0.7 structure was observed in some of
–6 –5
Gate voltage Vg (V)
Figure 16 (I) Gate voltage characteristics at B ¼ 0. (II) The
gate characteristics (offset by 0.3 V for clarity) in a magnetic
field of 11 T. Insets: (a) detail of the structure at 0.7 2e2/h; (b)
the in-plane g-factors as a function of subband index, as
obtained from the Zeeman splitting at 8.2 T. From Thomas KJ,
Nicholls JT, Simmons MY, Pepper M, Mace DR, and Ritchie
DA (1996) Possible spin polarization in a one-dimensional
electron gas. Physical Review Letters 77: 135, Fig. 1.
1.08.2.5 Many-Body Physics in 1D – The 0.7
Structure
In a very clean 1D channel, a clear plateau-like
structure close to (0.7  2e2/h) has been observed at
zero magnetic field, which can be seen in the inset
(a) to Figure 16 (Thomas et al., 1996). This feature is
now well known as the 0.7 structure or 0.7 anomaly,
whose conductance value is placed between the
spin-degenerate conductance plateau at 2e2/h and
the spin-split conductance plateau at e2/h, and can-
not be explained within a single–particle picture.
The 0.7 structure has been observed in numerous
1D systems with different sample designs establish-
ing that it is a universal effect. Its origin remains the
subject of intense experimental and theoretical
debate and has focused on zero-field spin polariza-
tion (Thomas et al., 1996; Spivak and Zhou, 2000;
Bruus et al., 2001; Starikov et al., 2003), spin-density
wave formation (Reimann et al., 1999), pairing of
electrons (Flambaum and Kuchiev, 2000), singlet–
triplet formation (Rejec et al., 2000), Kondo-like
interactions (Cronenwett et al., 2002; Meir et al.,
2002; Lindelof, 2001), and electron–phonon effects
(Seelig and Matveev, 2003).
There are some general features of the 0.7 struc-
ture that make it unique and intriguing:
Ballistic Transport in 1D GaAs/AlGaAs Heterostructures 297
g⊥
• The conductance tends toward 0.5(2e2/h) in a par-
allel magnetic field (Thomas et al., 1996).
The conductance has been observed to tend
toward 0.5  2e2/h with both increasing (Reilly
et al., 2001) and decreasing density (Thomas
I
II et al., 1998a, 2000; Pyshkin et al., 2000).
20
• The feature is activated with temperature.
Typically, it strengthens with temperature and
evolves downward from the 2e2/h plateau as
G (2e2/h) 1 (a) temperature increases (Thomas et al., 1998a).
T = 600 mK
• It is often accompanied by a peak in the conductance
at zero source–drain bias (Cronenwett et al., 2002).
0
–5.8 –5.6
Vg (V) 1.08.2.5.1 Identifying the 0.7 structure
–4 –3
the earliest experiments of conductance quantiza-
tion in 1D, it was not appreciated as a phenomenon
in its own right until Thomas et al. (1996) performed
a detailed study of the anomalous plateau. The
initial oversight is likely to be due to the fact that
disorder within the channel can cause resonant
backscattering and produce similar features at arbi-
trary conductances. It is therefore necessary to first
distinguish the 0.7 structure from these resonances.
This is possible because, unlike the 0.7 structure,
resonances will change on successive cool-downs,
get weaker with temperature, appear in the risers at
higher subband indices with increasing amplitude,
and will disappear when the channel is shifted lat-
erally. Therefore, it is important when investigating
the 0.7 structure to measure not only the tempera-
ture and magnetic field dependence but also the
ability to laterally shift the channel on the same
sample.
Liang et al. (2000) performed such a study using a
multi-layered gated 1D structure as shown in
Figure 17(a). Here, a cross-linked PMMA layer sits
between the SG labeled in black and three finger
gates (F1, F2, and F3) labeled in gray and acts as an
insulating layer, so that by biasing the finger gate
voltages, it is possible to control the strength of
lateral confinement of the 1D channel.
As shown in Figure 17(b), with decreasing nega-
tive finger gate voltage, VF2, the 1D conductance steps
become less pronounced and finally disappear due to
weakening of the lateral confinement strength. The
energy separation of the 1D subbands was determined
from source–drain bias experiments at various VF2 and
demonstrated a good linear fit in Figure 17(c). As the
finger gate voltage, VF2 was made more negative the
energy spacing between the first and second subband,
E1,2 (VSG) decreased, giving rise to the reduction in
298 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures

(b) Device A
First cooldown
4
T = 1.2 K

G (in units of 2e 2/h)

(a)
3
SG VF2 = 0 V
2

1
0.05 μm VF2 = –1.8 V
0
–1.2 –1 –0.8 –0.6 –0.4
VSG (V)
0.3 μm 0.6 μm
(c)
2.4

2.1
ΔE12 (mV)

F1 F2 F3 1.8
SG

0.8 μm 1.5

–1.5 –1.2 –0.9 –0.6 –0.3

VF2 (V)

Figure 17 (a) A schematic diagram showing a multi-layer-gated structure. The black areas represent the split-gate (SG). The
gray lines correspond to three overlaying finger gates F1, F2, and F3. There is a layer of crosslinked polymethylmethacrylate
(PMMA) in between SG and F1, F2, and F3 to act as a gate dielectric. (b) Conductance measurements as a function of SG
voltage VSG at various finger gate voltages VF2. From left to right VF2¼ 0 to 1.8 V in 0.3 V steps. (c) Measured subband
spacing at various VF2. (a) From Liang, (1999), Fig. 1(a). (b) From Liang (1999), Fig. 2(a). (c) From Liang, (1999), Fig. 2(b).

flatness of the conductance plateaus. Using the saddle
point potential model (Buttiker, 1990), they estimated
the change in lateral confinement strength by a factor
of 2 over this range. Therefore, the 0.7 structure per-
sists despite a change in lateral confinement strength
by a factor of 2, while the 1D ballistic conductance
plateau disappears. This result showed compelling
evidence that the 0.7 structure is an intrinsic property
of a clean 1D channel and persists over a wide range of
lateral confinement potentials.
1.08.2.5.2 In-plane magnetic field
behavior of the 0.7 feature
Historically, the 0.7 structure was observable in some
of the earliest experiments (van Wees et al., 1988) and
first commented on by Patel and co-workers (Patel
et al., 1991a). In Figure 15, Patel et al. observed an
additional shoulder-like structure at around
Vg¼3.4 V in the transconductance of a high-mobility
1D channel. With increasing applied source drain bias,
the shoulder-like structure appeared to split into two.
While the structure was observed, its origin could not
be explained. It was not until 1996 when Thomas and
co-workers performed a systematic study of an ultra-
clean 1D channel in an in-plane magnetic field that
the 0.7 structure was investigated thoroughly.
In this work, Thomas et al. used a high-quality
2DEG with a mobility of 4.5  106 cm2 V1 s1 at a
carrier density of 1.8  1011 cm2 showing nearly 30
quantized plateaus and a well-defined structure at
0.7(2e2/h). The 0.7 structure was observed to be repro-
ducible on thermal cycling, ruling out the possibility
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
Sample B
T = 60 mK
1
G (in units of 2e 2/h)
B=0T
0.5
B = 13 T
0 (Bagraev et al., 2002), GaN (Chou et al., 2005), and
–6.8 –6.6 –6.4
Gate voltage Vg (V)
Figure 18 Conductance measurements as a function of
gate voltage at various in-plane magnetic fields. From left to
right: B ¼ 0–13 T in 1 T steps. Curves have been horizontally
offset for clarity. From Thomas KJ, Nicholls JT, Simmons
MY, Pepper M, Mace DR, and Ritchie DA (1996) Possible
spin polarization in a one-dimensional electron gas.
Physical Review Letters 77: 135, Fig. 3.
of a universal conductance fluctuation or a scattering
effect. Using such a device, Thomas et al. investigated
the evolution of the 0.7 structure with increasing in-
plane magnetic field as shown in Figure 18. The left-
most trace shows a clear structure at 0.7(2e2/h), which
by 11 T on the right-hand side has moved down to
0.5(2e2/h). The evolution of the 0.7 structure into the
spin-split plateau at e2/h led them to speculate that
there could be a possible spin polarization in zero
magnetic field. The conclusion that the 0.7 structure
was related to spin polarization in the channel was
reinforced by the presence of an incipient spin split-
ting also observed just below the 4e2/h plateau (the 1.7
structure) (Thomas et al., 2000) and an enhancement
of the Landé g-factor as the carrier density decreased
and the 1D bands were depopulated.
There were two problems with this proposition.
First, the possible existence of a spin-polarized
ground state in 1D contradicted a long-standing the-
ory that showed it was impossible to have a spin-
polarized ground state in a strictly 1D system (i.e.,
one that has no 2D leads and where the second 1D
subband is infinitely high in energy above the first)
(Lieb and Mattis, 1962). However, real quantum
point contacts and quantum wires are not strictly
1D, but have finite length and width. In addition,
the subband spacing is also finite and they are
299
connected via 2D reservoirs. It has been more
recently shown that, for such realistic conditions, a
spin-split ground state is possible (Spivak and Zhou,
2000; Starikov et al., 2003). This brings us to the
second problem of explaining the 0.7 structure – a
complete spin polarization would produce a struc-
ture at 0.5(2e2/h). To date, a quantitative explanation
of the higher fractional value observed experimen-
tally remains elusive. However, the 0.7 structure has
now been widely observed in 1D systems defined in
cleaved-edge overgrowth structures (de Picciotto
et al., 2004, 2005), induced GaAs electron (Pyshkin
et al., 2000), GaAs hole (Danneau et al., 2006b), Si
–6.2 InGaAs (Simmonds et al., 2008), proving the universal
nature of this effect.
Hartree–Fock calculations of electrons confined
to a cylindrical wire showed that at low electron
densities exchange interactions would drive a spon-
taneous spin polarization (Gold and Calmels, 1996).
However, this would give rise to an extra plateau in
the conductance at e2/h rather than 0.7(2e2/h). Other
theories based on the idea of a spin-split ground state
also predicted a plateau at G ¼ 0.5(2e2/h) (Wang and
Berggren, 1996). Two groups attempted to use
coupled spins to rationalize the fact that the plateau
is observed at 0.7(2e2/h) rather than 0.5(2e2/h) by tak-
ing a statistical approach (Flambaum and Kuchiev,
2000; Rejec et al., 2000). Both groups developed the-
ories that suggested the electrons couple to form
singlet and triplet pairs with different transmission
barriers. Since there are three triplet configurations
and only one singlet configuration, there is a 3 to 1
probability that a triplet is formed over a singlet. This
predicts a plateau at G ¼ 0.75(2e2/h) corresponding to
triplet conduction band edge and a second plateau at
G ¼ 0.25(2e2/h) corresponding to singlet conduction
band edge. Interestingly, plateaus at G  0.25(2e2/h)
have been also observed when a source–drain bias is
applied and this will be discussed further in Section
1.08.2.5 (Patel et al., 1991b; Thomas et al., 1998b; de
Picciotto et al., 2004; Ramsak and Jefferson, 2005;
Graham et al., 2006).
To further study the role of spin in 1D systems
Graham et al. (2003) investigated the behavior of the
Zeeman split 1D subbands of different indices in a
high parallel magnetic field (see Figure 19). They
observed that, as expected, each spin degenerate 1D
subband splits into two (see P in the inset) with new
conductance plateau appearing at half-integer values
of 2e2/h. As Bk increased these half-integer plateaus
strengthened while the integer plateaus weakened,
300 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
T = 100 mK
3 α2
Sample A
G (in units of 2e 2/h)
B
2
1
Energy
0
–1.4 –1.2
Gate voltage Vg (V)
Figure 19 Differential conductance G(Vg) traces for
different parallel magnetic fields from 0 to 15.6 T in steps of
0.6 T. The traces are offset for clarity. Inset: Schematic
energy diagram for a linear Zeeman splitting of one-
dimensional (1D) subbands and subsequent crossings.
From Graham AC, Thomas KJ, Pepper M, Cooper NR,
Simmons MY, and Ritchie DA (2003) Interaction effects at
crossings of spin-polarized one-dimensional subbands.
Physical Review Letters 91: 136404, Fig. 1.
until the point where the Zeeman energy was equal
to the subband spacing and the integer plateaus dis-
appeared. This happened at a crossing point, such as
Q in the inset. Finally, the half-integer plateaus wea-
kened again as Bk increases further and the integer
plateaus reappeared after this crossing (see R in the
inset). They considered that the appearance of the
1.5(2e2/h) plateau, which weakened and then evolved
into the 2e2/h plateau before reappearing for Bk > 8 T,
resembled the evolution of the 0.7 structure to
0.5(2e2/h) with increasing Bk. As a consequence, they
have named the 1.5 (2e2/h) plateau, the 0.7 analog.
The reappearing 2e2/h plateau carried the opposite
spin than before the crossing, while the lowest sub-
band, which does not encounter a crossing, does not
change its spin.
The evolution of these conductance characteris-
tics is more clearly seen in gray-scale plots of the
transconductance as a function of Bk and Vg, as shown
in Figure 20. White regions represent the plateaus in
conductance and the dark regions correspond to the
transitions between plateaus. As Bk was increased
from zero, a splitting of the 1D subbands of opposite
spin was observed, as shown in Figure 21 for point P.
At Bk ¼ 0, the first white plateau, 0, corresponding
(a)
α1 β
10
B (T)
B
N+1
Q
R
N P
N–1
Magnetic Field α0
–1
–1.25 –1.2 –1.15
Gate voltage Vg (V)
Figure 20 Gray-scale plots of the transconductance,
dG/dVg,as a function of Vg and Bk The labels 1, 2, and
show the 0.7 analogs at the Zeeman crossing between
spin levels 1" and 2#, 1" and 3#, and 2" and 3#,
respectively. From Sfigakis F, Graham AC, Thomas KJ,
Pepper M, Ford CJB, and Ritchie DA (2008b) Spin Effects in
One Dimensional Systems. Journal of Physics C 20: 164213.
Fig. 6.
to the 0.7 feature is visible. As Bk was increased, this
plateau evolved into the 0.5(2e2/h) and the white
region broadened. By Bk ¼ 11 T, the first (N ¼ 1")
and second subbands (N ¼ 2#) crossed. After the
crossing, the N ¼ 1" showed a discontinuous shift
from the crossing point, marked 1. This discontinu-
ity corresponds to the 0.7 analog. This discontinuous
shift was also observed at the crossing of the N ¼ 2"
and the N ¼ 3# lines marked by , and the N ¼ 1"
and the N ¼ 3# lines marked by 2. Interestingly, at
these points, there was no anti-crossing of the sub-
bands, but a gap formed abruptly after the crossing.
Graham et al. argued that this 0.7 analog is a conse-
quence of the strong exchange interactions and
where there is a lifting of the zero-field spin degen-
eracy in the 0.7 structure, there is also a lifting of the
degeneracy of the crossing point for the 0.7 analog
(Graham et al., 2003; Graham et al., 2004). In further
works using DC bias spectroscopy, they showed that
the 0.7 structure and its analogs were caused by the
highest energy spin-up subband pinning to the che-
mical potential, as predicted by Kristensen et al.
(2000), together with an abrupt rearranging of
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
1.5
1.0
G (2e2/h)
0.3K
1.5K
0.5
2.7K
5.1K
0.0
0.28 0.30 0.32 0.34
Vgs (V)
Figure 21 Conductance as a function of gate voltage Vgs
at various temperatures for the first quantized plateau. As the
temperature is raised the 0.7 structure emerges. Kristensen
A, Bruus H, Hensen AE, et al. (2000) Bias and temperature
dependence of the 0.7 conductance anomaly in quantum
point contacts. Physical Review B 62: 10950, Fig. 7.
spin-up and spin-down subbands (Graham et al.,
2007). The 0.7 analog has since been shown to share
the same DC bias, magnetic field, and temperature
dependence as the 0.7 structure highlighting the need
for a theoretical description of this unusual state that
is valid for both features at zero magnetic field.
1.08.2.5.3 Temperature dependence of
the 0.7 structure
The 0.7 structure has a characteristic temperature
dependence, strengthening as the temperature is
increased in contrast to the 2e2/h plateaus (see
Figure 21). The 0.7 structure can appear weak at
very low temperatures, but typically becomes stronger
as the temperature is increased. As the temperature is
increased further, the strength of the state stabilizes
and then weakens once more, but only after all higher
plateaus have been thermally smeared.
Kristensen et al. studied the temperature depen-
dence of the 0.7 structure using shallow-etched
QPCs described in Section 1.08.2.3.1 (Kristensen
et al., 2000). These are ideal for temperature
dependence studies of the 0.7 structure since the
large 1D subband energy separation in shallow-
etched QPCs allows studies up to the relatively
high temperature of 5 K without appreciable ther-
mal smearing of the quantized conductance steps.
301
At the lowest temperature, the first conductance
plateau was broad and flat. With a 1D subband
energy separation of 6.5 meV, the thermal smearing
of the plateau should be negligible. As the tem-
perature was raised, the conductance plateau
remained flat; it however weakened as the tem-
perature was further increased. In contrast, a
plateau-like structure emerged and strengthened
around the conductance value of 0.7(2e2/h).
Following on from this, Kristensen et al. went on
to plot the relative conductance suppression.
Figure 22(a) shows the graph between 1 – G(T)/G0
and 1/T at the given fixed gate voltage. Interestingly,
the linear dependence in the semilogarithmic
Arrhenius plot indicates an activated behavior.
Figure 22(b) shows the measured activation energy
TA as a function of gate voltage. We can see that TA
increases from zero to a few Kelvin in the middle of
the conductance step. This suggested that the 0.7
structure is associated with thermal depopulation of
a subband, which has a gate-voltage-dependent sub-
band edge. Kristensen concluded that these
observations ‘‘indicate the importance of interaction
effects beyond the simple single-particle subband
picture, presumably related to spin polarization.’’
Spontaneous spin-split ground-state models have
difficulty in explaining the temperature dependence
of the 0.7 structure. The fact that the 0.7 structure
may become stronger with temperature suggests that
it is not a ground state with a single-particle energy
gap, but an activated process with an activation tem-
perature TA. To explain this within the spontaneous
spin-splitting paradigm, Starikov et al. (2003) pro-
posed a model in which the polarized ground state
is accompanied by metastable states with lower con-
ductivity. Therefore, thermal activation of carriers
into the metastable states causes a depression of the
conductance plateau at G ¼ 2e2/h to form the anom-
alous plateau at G ¼ 0.7(2e2/h).
Other authors have suggested that the tempera-
ture dependence of the 0.7 structure indicates that
spontaneous spin splitting is not the underlying
mechanism and have looked for an alternative
explanation. Seelig and Matveev (2003) proposed
a theory based on electron–phonon scattering in
the 1D channel. They showed that a significant
negative correction to the quantized conductance
could occur due to the effect of backscattering of
electrons in QPCs by acoustic phonons. In 1998,
Kristensen et al. (1998b) also suggested a mechan-
ism whereby scattering from thermally activated
plasmons decreased the conductance of the
302 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
(a) –0.4
Vgs = 0.305 V
TA = 0.28 K
–0.8
In(1–G/G0)
–1.2
Vgs = 0.309 V
–1.6 TA = 1.11 K
–2.0
0.0 0.5 1.0 1.5 2.0
1/T (K–1)
Figure 22 (a) Temperature dependence of the conductance suppression G0-G(T) at fixed gate voltages Vg ¼ 0.305V and
0.309 V, measured on device A. The data show Arrhenius behavior, G(T)/G0 ¼ 1-Cexp(TA/T),with an activation temperature TA.
(b) Measured activation energy as a function of gate voltage. (a) From Kristensen A, Bruus H, Hensen AE, et al. (2000) Bias and
temperature dependence of the 0.7 conductance anomaly in quantum point contacts. Physical Review B 62: 10950, Fig 8(a).
(b) from Kristensen, (2000), Fig 8(b).
G ¼ 2e2/h plateau to form the anomalous plateau at
G ¼ 0.7(2e2/h).
Cronenwett et al. (2002) noted that the tempera-
ture dependence of the 0.7 structure is reminiscent of
the Kondo effect in quantum-dots with one unpaired
electron. Extending this analogy, they performed
temperature dependence and source–drain bias stu-
dies and found several other conspicuous similarities.
These included a conductance peak at zero source–
drain bias. In addition, plots of the conductance along
the 0.7 plateau as a function of T collapse onto a
single function of empirical Kondo-like form using a
single scaling parameter designated the Kondo tem-
perature, TK. Since then, several theories have been
developed based on a Kondo explanation for the 0.7
structure, which explain many of the experimental
observations (Meir et al., 2002; Hirose et al., 2003;
Schmeltzer et al., 2005) (see Section 1.08.2.6).
However, Kondo models require that an unpaired
electron can become localized in the 1D region to
act as a form of magnetic impurity. While it has been
shown that such a state is theoretically possible under
certain assumptions (Meir et al., 2002), other density
functional (Starikov et al., 2003) and Hartree–Fock
(Sushkov, 2003) calculations did not confirm a loca-
lized spin state in real QPC devices.
1.08.2.5.4 Density dependence of the 0.7
feature
Studies of the carrier density dependence of the 0.7
structure are not straightforward. Initial experiments
showed that lowering the carrier concentration from
(b) 20
15
TA (K)
10
5
0
2.5 0.30 0.31 0.32 0.33
Vgs (V)
1.3  1011 to 3  1010 cm–2 shifted the 0.7 structure to
0.5(2e2/h) (Thomas et al., 2000), indicating a complete
spin polarization (Wang and Berggren, 1996; Gold
and Calmels, 1996). However, subsequent work on
induced electron gases showed that the conductance
of the 0.7 structure tended toward 0.5(2e2/h) at both
the highest and lowest densities, with further reports
in an induced 1D wire of length 2 mm showing that
the 0.7 structure evolved continuously to 0.5(2e2/h)
with increasing 1D density (Reilly et al., 2001). Reilly
(2005) showed that the position and strength of the
0.7 structure did not depend on the absolute value of
the carrier density but on the relative difference
between the potentials in the 1D and 2D regions.
Wirtz et al. (2002) performed interesting studies
on the hydrostatic effect on the 0.7 structure. Using
both pressure and illumination, the electron density
in the 2DEG was reduced from 2.14  1011 to
0.61  1011 cm2, and a shift in the conductance of
the 0.7 structure toward the spin-split value of e2/h
was observed (see Figure 23). The electron density
below the SG is lower than in the 2DEG, so it is
possible that the exchange energy could be signifi-
cantly enhanced with the Hartree term being
completely collapsed inside the constriction.
Theoretically, such an enhancement could lead to a
spin polarization. Theoretical results by Bruus et al.
(2001) suggested that an increase of the spin gap
between the up and down states should result in a
shift of the 0.7 structure toward e2/h.
Using a cleaved-edge overgrown 1D wire, de
Picciotto et al. (2004) observed a 0.7 structure in the
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures 303

Decreasing 2DEG electron density electron–electron interactions play an important

role in the 0.7 structure observed in their 1D wires.
1.0 More recent studies of very long 1D wires fabri-
cated by cleaved-edge overgrowth postulated that
0.8 the 0.7 structure is a property of long wires, where
there is both a large aspect ratio and where there are
G (2e2/h)

0.6 numerous electrons in the wire (up to 100) (de

0.4
0.2
0.0
–2.50 –2.45 –2.40
Vg (V)
Figure 23 Conductance measurements at various
two-dimensional electron gas (2DEG) densities. From left
(ne ¼ 2.14  1011 cm2) to right (ne ¼ 6  1010 cm2). The
position of the 0.7 structure is indicated by an open circle in
each curve. From Wirtz R, Newbury R, Nicholls JT, Tribe
WR, Simmons MY, and Pepper M (2002) Tuning the electron
transport properties of a one-dimensional constriction using
hydrostatic pressure. Physical Review B 65: 233316, Fig. 4.
differential conductance measurements as shown in
Figure 24. It was found that the 0.7 structure existed
whenever the kinetic energy provided to the carriers
exceeded the Fermi energy. In this regime, the mea-
sured conductance exceeded the value calculated
from a noninteracting model, suggesting that
–3.4
Gate voltage (V)
Picciotto et al., 2008). In this study, the authors argued
that it is the charge density in the wire that mainly
affects the appearance of the 0.7 structure and not the
length of the channel. The 0.7 structure was observed
to occur at densities low enough such that Fermi
energy was lower than the temperature.
In general, it is difficult to make a definitive state-
ment about the density dependence of the 0.7
structure and how it fits in with current models.
One of the complications in understanding how the
0.7 structure changes with density is to understand
experimentally exactly how the density of the 1D
region is changed. Typically, a gate is used to change
the density within the wire, but this is very sample
specific depending on the gate geometry and is also
likely to change the shape of the confinement poten-
tial and the mismatch between the potential of the 1D
and 2D regions.
1.08.2.5.5 Source–drain bias dependence
of the 0.7 feature
The effects of a source–drain bias on 1D subbands
were discussed in Section 1.08.2.4.2. Increasing the
source–drain voltage lifts the momentum degeneracy
and splits each conductance plateau (in the differen-
tial conductance vs. gate voltage trace) into two. For
4
G  2e2/h in zero magnetic field, half-integer plateaus
3
were observed for every subband. However, Patel

–3.6 2 et al, also reported that as the source–drain bias was

–3.8 g∼1 1 increased, the 0.7 structure evolved into a structure at
–4 0 0.8–0.85(2e2/h) with another plateau appearing at
–4.2 g ∼ 0.25
–1 0.2(2e2/h) at even higher biases. Initially, this led to
–2 suggestions that these additional plateaus were due to
–4.4
g ∼ 0.7 g=0 –3 a spin degenerate 0.5(2e2/h) feature but with its con-
–4.6
–4 ductance reduced by some mechanism (Kristensen
–20 –10 0 10 20 Δ(g/g ) et al., 2000; Cronenwett et al., 2002; Reilly et al., 2002;
0
(V–1)
Source voltage (mV) ΔVg de Picciotto et al., 2004; Kothari et al., 2008).
Figure 24 Transconductance of a one-dimensional (1D) Alternatively, it has been described as a fully spin-
channel as a function of gate voltage and direct-current (DC) polarized quarter plateau (Graham et al., 2006;
bias: The numerical derivative of the differential Simmonds et al., 2008).
conductance with respect to gate voltage as a function of Thomas et al. (1998b) went on to show that in
gate voltage and DC bias, in a color plot format. The 0.7
finite source–drain bias experiments where well-
structure is indicated by g  0.7. From de Picciotto R,
Pfeiffer LN, Baldwin KW, and West KW (2004) Nonlinear resolved integer and half-integer plateaus were
response of a clean one-dimensional wire. Physical Review observed, quarter-integer plateaus were also seen
Letters 92: 036801, Fig. 2. for every subband even at zero magnetic field. The
304 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
appearance of these quarter-integer plateaus did not
change with increasing magnetic field, further sup-
porting the concept of spin polarization at zero
magnetic field. More recently, plateaus at 0.25 (2e2/h)
and 0.75 (2e2/h), nearly identical to those observed in
GaAs quantum wires, have also been observed in
nonequilibrium transport studies in In0.75Ga0.25As
quantum wires (Simmonds et al., 2008). Their appear-
ance has also been attributed to zero-field
spin-polarized quarter-integer plateaus.
Sfigakis et al. (2008a) considered that in a single
particle picture, the quarter-integer plateau for a
given subband should appear at the same time when
sweeping the source–drain bias. For the high index
subbands, this appeared to be the case. However, as
the subband index decreased, the (N þ 0.25) 2e2/h
plateau appeared at increasingly higher bias than
the (N þ 0.75) 2e2/h. The late formation in source–
drain bias voltage of the 0.25(2e2/h) plateau with
respect to the formation of the 0.75(2e2/h) plateau
was shown to be consistent with the predictions from
a spin-gap model. Here, self-consistent calculations
with a saddle point model and a density-dependent
energy gap between spin subbands were shown to
exhibit the same characteristics (Sfigakis, 2005).
, and electrical con-
1.08.2.5.6 Thermopower, thermal
conductance, and shot noise dependence
of the 0.7 feature
In addition to conventional transport measurements,
the 0.7 structure has also been observed in studies of
the thermopower, thermal conductance, and shot
noise experiments. While not comprehensive, the
following section briefly reviews these experiments.
The thermopower of a 1D system, S, is related to
the conductance, G:
V  2 kB2 qð1nGÞ
S¼  ¼ – ðTe þ Tl Þ
Te – Tl I ¼0 3e qm
by the Mott formula (Mott, 1963), where  is the
chemical potential of the contacts relative to the 1D
subbands, Te is the electron temperature, Tl is the
lattice temperature, and V is the voltage measured
across the constriction. Initial thermopower experi-
ments used a 1D constriction to measure the electron
temperature (Appleyard et al., 1998). Here, electrons
were heated on one side of a 1D constriction by the
application of an electric current. However, the hot
electrons are prevented from passing through to the
other side by the 1D constriction and a temperature
difference is established across the channel. This
results in a potential difference that can be measured.
The authors showed that, in a ballistic 1D system, the
steps in the conductance between the quantized
values gave rise to peaks in the measured thermo-
power. By measuring the height of the thermopower
peaks, it was possible to determine the temperature
of the hot electrons in the heating channel.
Appleyard et al. (2000) also went on to show the
presence of a small shoulder in the thermopower
near the 0.7 structure. Application of a magnetic
field converted the 0.7(2e2/h) to the spin polarized
0.5(2e2/h) value, accompanied by a decline in the
thermopower signal to zero. The observed thermo-
power signal at 0.7(2e2/h) is consistent with the first
subband being split, with the spin# subband being
transmitted, and the other pinned near the chemical
potential. Since a fully transmitted channel leads to a
zero thermopower, the 0.7 structure could be
explained by partial transmission of the minority
spin" subband. While the Mott formulation does
not predict a peak in G at 0.7(2e2/h), it is likely that
in the regime of strongly interacting electrons an
additional mechanism is required to explain the finite
measure thermopower coincident with 0.7 structure.
The thermal conductance,
ductance, G, of noninteracting electrons in quantum
wires are known to be related by the Wiedemann–
Franz equation
2 kB2 T
K ¼ – G
3e 2
As a consequence, if the conductance is quantized in
units of 2e2/h, then the thermal conductance will be
quantized in units of 2kB2 T =3h. Below 2e2/h, the
Wiedemann–Franz equation no longer holds, but at
gate voltages near the 0.7 structure, a half plateau in
the thermal conductance was observed by Chiatta
et al. (2006).
Finally, shot noise experiments in a QPC in the
regime of the 0.7 structure were also performed. Shot
noise is the temporal fluctuation of current resulting
from the quantization of charge. DiCarlo et al. (2006)
reported simultaneous measurements of the shot
noise and DC transport in a QPC. In particular,
they focused on the 0.7 structure and its evolution
in a parallel magnetic field. They observed a suppres-
sion of the noise, compared with that expected for
spin degenerate transport, near 0.7(2e2/h) in zero
magnetic field in agreement with earlier results by
Roche et al. (2004). With increasing Bk, this suppres-
sion was observed to evolve into the signature
of a spin-resolved transmission. They found
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
quantitatively good agreement between their noise
data and the phenomenological model for density-
dependent level splitting (Reilly, 2005).
Since the first reported observation of the 0.7 struc-
ture, its origin has been intensely debated.
Throughout the deliberations, both Coulomb and
exchange energies have been shown to be very impor-
tant in quasi-1D systems since they can cause a
spontaneous spin polarization. Indeed, the concept of
a spin gap has been fairly successful in explaining most
of the experimental results of the 0.7 structure
(including the temperature dependence, magnetic
field, and bias dependence) (Wang and Berggren,
1996; Spivak and Zhou, 2000; Kristensen et al., 2000;
Reilly et al., 2002; Berggren and Yakimenko, 2002;
Graham et al., 2005; Lassl et al., 2007; Graham et al.,
2007). Central to this interpretation is the concept that
the spin gap must depend on carrier density (gate
voltage), otherwise a quantized plateau at 0.5(2e2/h)
would be observed. To date, however, none of the
SG models have addressed the appearance of a peak
in the differential conductance of the quantum wire
for G < 2e2/h at very low temperatures (Cronenwett
et al., 2002). This is discussed in the next section.
1.08.2.6 The Kondo Model and Zero-Bias
Anomaly
1.08.2.6.1 Overview
Although a spontaneous spin-splitting model explains
many of the salient features of the 0.7 structure, there
sometimes exists a peak in the conductance around
Vsd ¼ 0 that cannot be explained within the spin-split
paradigm. This conduction peak has been termed the
zero-bias anomaly, in analogy to the zero-bias anomaly
observed in quantum-dots. The zero-bias anomaly has
led to a Kondo-like description of the 0.7 structure that
also describes many of its properties – in particular, its
unusual temperature dependence.
The Kondo model predicts that near pinch-off
(Meir, 2008), a 1D system contains a bound state that
acts as a magnetic impurity. Without electron–elec-
tron interactions, the bound state would block carriers
of the same spin from passing through the 1D channel
– limiting transport to a single spin channel and redu-
cing the conductivity to 0.5(2e2/h). However,
electron–electron interactions cause the bound state
to polarize electrons in the leads and thereby screen its
effect. At T ¼ 0, the magnetic impurity is screened
perfectly by the carriers in the leads and the conduc-
tivity reaches the unitary limit, 2e2/h. As the
temperature is increased, the magnetic impurity is
305
less efficiently screened, and the conductance is
reduced toward its high-temperature limit of 0.5(2e2/
h). This gives rise to the 0.7 structure and provides an
explanation for why the plateau at 0.7(2e2/h) is
stabilized by temperature.
A critical assumption of the Kondo model is that
an open 1D system is able to support a bound state.
This assumption appears to be robust according to
recent spin-density functional theory calculations
(Meir et al., 2002; Hirose et al., 2003; Rejec and
Meir, 2006) and tunneling spectroscopy measure-
ments between parallel quantum wires (Auslaender
et al., 2005; Yoon et al., 2007). From this assumption it
follows that (Meir, 2008):
1. The bound state will blockade the current, result-
ing in a reduced conductance between 0.5(2e2/h)
and 2e2/h.
2. As the Fermi level is increased, the Coulomb
blockade energy is overcome and the universal
value of 2e2/h is recovered.
3. In the presence of a magnetic field, the energy of
the localized state splits and the conductance is
reduced to 0.5(2e2/h).
4. There is a reduction in shot noise around the 0.7
plateau due to charge being carried by two spin
channels, one of perfect transmission and the other
with reduced transmission.
These predictions are consistent with experimental
observations.
However, the greatest strength of the Kondo
model is arguably its ability to explain the zero-bias
anomaly. The zero-bias anomaly was originally stu-
died by Cronenwett et al. (2002), who showed that the
1D zero-bias anomaly shared many of the features of
its 0D counterpart including:
1. the collapse of G(T) curves onto a single function
with a single scaling parameter designated the
Kondo temperature, TK;
2. an exponential dependence of TK on VG;
3. a correlation between zero-bias peak width and
TK; and
4. splitting of the zero-bias peak in a parallel mag-
netic field.
Subsequent experiments have confirmed the exis-
tence of the zero-bias anomaly as a fundamental
property of quantum wires but have found less cor-
respondence with the 0D zero-bias anomaly (Sfigakis
et al., 2008a; Sarkozy et al., 2009). In particular, the 1D
zero-bias anomaly does not always split with parallel
306 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures

magnetic field and the observed splitting is often less
than predicted (Chen et al., 2009).
Today, there is a growing consensus that bound
states can and do exist in quantum wires resulting in
Kondo-like physics. However, whether or not this is
the origin of the 0.7 structure is still a point of con-
tention as there is mounting evidence to suggest that
the 0.7 structure and Kondo-like phenomena co-exist
as separate and distinct effects (Sfigakis et al., 2008a).
1.08.2.6.2 Experimental and theoretical
evidence for a Kondo model
The detailed studies of the zero-bias anomaly per-
formed by Cronenwett et al. (2002) preceded a
concrete theory of Kondo-like physics in 1D and
spin-density functional theory calculations demon-
strating a stable bound state in QPCs (Meir et al.,
2002; Hirose et al., 2003; Rejec and Meir, 2006; Meir,
2008). Cronenwett et al. used surface gate depletion
to define a 1D channel in a 2DES and performed
source–drain bias measurements on the first three
subbands. Figure 25(a) shows the nonlinear differ-
ential conductance as a function of source–drain bias
for a range of surface gate voltages at base tempera-
ture and zero magnetic field. Bunching of the lines
along Vsd ¼ 0 indicates the familiar plateaus in the
linear conductance at 2e2/h and 2(2e2/h). These pla-
teaus split to form half-plateaus at 1.5(2e2/h) and
2.5(2e2/h) that trend upward as Vsd is shifted away
from zero (Glazman and Raikh, 1988; Ng and Lee,
1988; Patel et al., 1991b).
Below 2e2/h, however, they observed a lot more
structure in the nonlinear conductance. The data
showed a clear zero-bias peak – the so-called zero-
bias anomaly. Importantly, there was no bunching of
lines along Vsd ¼ 0 and hence, no plateau at 0.7(2e2/h)
was observed in the linear conductance. At this low
temperature, the zero-bias anomaly appeared to
enhance the conductance at Vsd ¼ 0 and wash out
the 0.7 structure. Nonetheless, as Vsd was moved
away from zero, two distinct plateaus formed at
0.8(2e2/h) and 0.2(2e2/h), which are believed to result
from the splitting of spin bands.
As the temperature was increased to 600 mK,
the zero-bias peak was suppressed as shown in
Figure 25(b). Now, a clear bunching of lines at
0.7(2e2/h) around Vsd ¼ 0 is observed. This is a
strong indication that the formation of the 0.7
structure coincides with the destruction of the
zero-bias anomaly with temperature. The strong
correlation between the zero-bias anomaly and 0.7
structure was further exemplified at high-parallel
magnetic field. Figure 25(c) shows source–drain
bias measurements performed at base temperature
and Bk ¼ 8 T. In this case, the zero-bias peak was
completely destroyed and the spin-split plateau

(a) T = 80 mK, Bll = 0 T (b) T = 600 mK, Bll = 0 T (c) T = 80 mK, Bll = 8 T
3

5/2
5/2

2 2 2
G (2e2/h)

3/2
3/2

1 1 1 1
0.8
0.7
1/2
1/2
0
–1 0 1 –1 0 1 –1 0 1
Vsd (mV) Vsd (mV) Vsd (mV)

Figure 25 Nonlinear differential conductance as a function of source–drain bias at various surface gate voltages for the first
three subbands of a quantum wire. (a) At base temperature and zero parallel magnetic field, there is a strong zero-bias peak in
the nonlinear conductance below (2e2/h) – the zero-bias anomaly. (b) Raising the temperature suppresses the zero-bias
anomaly and reveals a bunching of lines near 0.7(2e2/h) due to the 0.7 structure. (c) At base temperature and B|| ¼ 8 T, the
zero-bias anomaly has vanished and there is a strong spin-split plateau at 0.5(2e2/h). These results demonstrate the intimate
relationship between the 0.7 structure and the zero-bias anomaly. Modified with permission from Cronenwett SM, Lynch HJ,
Goldhaber-Gordon D, et al. (2002) Low-temperature fate of the 0.7 structure in a point contact: A Kondo-like correlated state
in an open system. Physical Review Letters 88: 226805. Copyright (2002) by the American Physical Society.
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures 307

at 0.5(2e2/h) is clearly visible. Again, the appear-
ance of the spin-split subband coincides with
the destruction of the zero-bias anomaly with
magnetic field.
Cronenwett et al. went on to study the tempera-
ture dependence of the zero-bias anomaly in detail
and showed important similarities between the 1D
zero-bias anomaly and Kondo physics observed in
quantum-dots (Goldhaber-Gordon et al., 1998;
Cronenwett et al., 1998; van der Wiel et al., 2000).
Figure 26(a) shows the temperature dependence of
zero-bias peaks for five different gate voltages.
Plotting the peak height as a function of tempera-
ture over a range of gate voltages produced the
curves shown in the inset of Figure 26(b).
Cronenwett et al. found that these curves could
be scaled onto one function using a single scaling
parameter TK as shown in the main panel of
Figure 26(b). The functional form of the scaled
curve agrees with a modified expression of the
Kondo conductance:
 
2e 2 1 1
G¼ þ
h 2f ðT =TK Þ 2
where f(T/TK) is a universal function for the Kondo
conductance. This provided compelling evidence for
a Kondo explanation of the zero-bias anomaly and
hence the 0.7 structure. Moreover, it was found that
TK scaled exponentially with gate voltage as shown
in Figure 26(c). This is also consistent with TK in
quantum-dots, which depends exponentially on the
energy of the bound spin ("0) relative to the Fermi
energy in the leads ("0 þ U) according to
 
"0 ð"0 þ U Þ
TK  exp
GU
where G is the energy broadening (Haldane, 1978).
Moreover, Cronenwett et al. found that the zero-
bias peak splits with magnetic field and that between
0.7(2e2/h) and 2e2/h, the peak widths increase like
2kTK/e. Both of these observations are consistent
with Kondo physics in quantum-dots. However,
more recent experiments have shown that the zero-
bias peak does not always split with magnetic field
and that any observed splitting is significantly less
than predicted (Chen et al., 2009). Sarkozy et al. (2009)
also performed a detailed study of the zero-bias
anomaly as a function of magnetic field and tempera-
ture and found further discrepancies between the
behavior of the zero-bias anomaly and 1D Kondo
physics model, namely:
1. a nonmonotonic increase of TK with surface gate
voltage;
2. the FWHM of the zero-bias peak did not scale
with Gmax of the peak; and
3. a linear peak splitting with gate voltage at fixed
magnetic field.

(a) (b) (c)

1.0 80 mK 320 mK 1.0 1
100 mK 430 mK
210 mK 560 mK
670 mK 10
0.9
G (2e2/h)
G(2e2/h)

G(2e2/h)

0.8
TK (K)

0.5 –466 mV
1.0 1
0.7
G (2e2/h)

0.6
–488 mV
0.5
0.1 1 T (K)
0.5 0 0.1
0
–1 0 1 0.01 0.1 1 10 –492 –462
Vsd (mV) T/Tk Vg

Figure 26 Temperature dependence data of the zero-bias anomaly by (Cronenwett et al. 2002). (a) Temperature
dependence of the zero-bias anomaly at five different surface-gate voltages. As the temperature is increased from 80 to 670
mK, the zero-bias anomaly is destroyed. (b) Zero-bias anomaly peak conductance as a function of temperature for various
gate voltages and scaled onto a single functional form using the scaling parameter TK. The inset shows the unscaled data. (c)
TK as a function of surface gate voltage, Vg, showing an exponential correspondence between TK and Vg. The plot also shows
the linear conductance of the first subband as a function of Vg for 80 mK (solid), 210 mK (dotted), 560 mK (dashed), and 1.6 K
(dot-dashed) showing the emergance of the 0.7 structure as the zero-bias anomaly is suppressed.
308 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures

While these discrepancies may suggest that the 1D
Kondo model is incomplete, the model is still more
effective at describing the zero-bias anomaly com-
pared to a spin-split model, which cannot account for
the occurrence of the zero-bias anomaly.
Guided by the strong experimental evidence,
Meir and co-workers developed a comprehensive
model for the 0.7 structure based on Kondo physics
(Meir et al., 2002; Hirose et al., 2003; Rejec and
Meir, 2006; Meir, 2008). A key prerequisite of the
theory is the formation of a quasi-bound state in
the QPC. This localized state is generated by
multiple reflections between the edges of a poten-
tial barrier. In the case of a square potential
barrier, a particle with higher energy can be
reflected as it enters and exits the barrier.
Resonant reflections between these two interfaces
lead to a quasi-bound state localized within the
barrier region. Interestingly, spin-density functional
theory calculations indicate that this remains true
even for the smooth potential of a QPC, thereby
producing a narrow quasi-bound state that may act
as a single magnetic impurity.
Although the calculations by Meir et al. were
perturbative and therefore only semi-quantitative,
they provided a good qualitative description of
many of the important features of the 0.7 structure.
Figure 27(a) shows the conductance of the first
subband as a function of the Fermi energy ("F)
relative to the energy of the bound state ("0) calcu-
lated at four different temperatures (Meir et al.,
2002). As the temperature increases, a distinct pla-
teau forms at 0.7(2e2/h), in excellent agreement with
the experimental data shown in the inset of
Figure 27(a).
The calculations also show the formation of a
strong plateau with increasing parallel magnetic
field as shown in Figure 27(b). While this is in
qualitative agreement with experimental data
shown in the inset, the position of the calculated
plateau is significantly lower than that observed
experimentally. However, Meir et al. (2002) attribute
this quantitative disagreement to the perturbative
approach used in their calculations rather than a
fundamental difference in the underlying physical
mechanism.
The Kondo model also provides a very good
description of the evolution of the zero-bias anomaly
as a function of temperature and magnetic field as
shown in Figure 28(a) and Figure 28(b),

1.0
(a)

Data
1.0
0.5
Conductance (2e2/h)

0.5

VG
1.0
(b)
Data
1.0
0.5

0.5
VG
0.0
0.0 0.2 0.4 0.6 0.8
εF/lε0l

Figure 27 Linear conductance of the first subband as a function of the Fermi energy "F relative to the energy of the
quasi-bound state "0. The calculations by Meir et al. are based on spin-density functional theory calculations of a Kondo
model (Meir, 2002). (a) The calculated conductance at 50, 100, 200 and 600 mK. The results agree both qualitatively and
quantitatively with the experimental observations of Cronenwett et al. shown in the inset (Cronenwett 2002). (b) The calculated
conductance of the first subband in parallel magnetic fields of 0 T, 0.07, 0.12, and 0.4 T (from top to bottom, respectively).
The calculations agree qualitatively with experimental observations shown in the inset, and quantitative discrepancies are
attributed to the perturbative nature of the calculations. Reproduced with permission from Meir Y, Hinose K, and Wingreen
NS (2002) Kondo model for the ‘‘0.7 anomaly’’ in transport through a quantum point. Physical Review Letters 89: 196802
Copyright (2002) by the American Physical Society.
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures 309

1.0 1.0
(a) (b)
Data
Conductance (2e2/h)

Conductance (2e2/h)
1.0

0.5 0.5 Data

1.0
0.5

0.5

V V
0.0 0.0
−0.5 0.0 0.5 −0.5 0.0 0.5 0
Bias voltage V/lε0l
Bias voltage V/lε0l

Figure 28 Calculations of the nonlinear conductance and zero-bias anomaly based on spin-density functional theory
calculation of a Kondo model (Meir, 2002). (a) Calculated zero-bias anomaly at for Fermi energies "F ¼ 0.1, 0.03, and 0.01 from
top to bottom respectively at four different temperatures T ¼ 60, 100, 200, and 400 mK. The calculations agree both
quantitatively and qualitatively by the experimental data taken by Cronenwett, shown in the inset (Cronenwett, 2002).
(b) Zero-bias anomaly near the 0.7 structure for different parallel magnetic fields corresponding to a Zeeman splitting of  ¼ 0,
0.04, 0.07, and 0.1, where  ¼ 0.04. Again, the data agree with the splitting of the zero-bias anomaly peak observed
experimentally shown in the inset (Cronenwett, 2002).

respectively. Through this work, combined with
experimental studies, there is growing consensus
that 1D systems (1.) can support a quasi-bound
state, (2.) do display Kondo-like physics, and
(3.) the zero-bias anomaly and 0.7 structure are
intimately related phenomena based on spin.
However, it does not necessarily follow that the 0.7
structure has its origins in Kondo-like physics. There is
evidence to suggest that while the zero-bias anomaly
and 0.7 structure coexist, their underlying mechanisms
are separate and distinct. Using etched channels
Sfigakis et al. (2008a) formed open quantum-dot struc-
tures that displayed enhanced Kondo behavior while
retaining many of the features of the 0.7 structure .
These 0D–1D hybrid structures allowed Sfigakis et al.
to study the temperature dependence of the 0.7 struc-
ture and zero-bias anomaly independently. They
found that the two features appeared at different
energy scales with the 0.7 structure appearing after
the zero-bias anomaly had been destroyed by increas-
ing temperature.
In summary the origin of the 0.7 structure
remains one of the most intriguing and challenging
puzzles in the field of 1D ballistic transport. Many of
its properties indicate the presence of spontaneous
spin polarization – such as its behavior in magnetic
field and source–drain bias and density depen-
dences. However, other properties such as the
zero-bias conductance peak and temperature depen-
dence are more commensurate with a Kondo-like
model. These conflicting properties suggest that the
physics is more complicated than first thought and
that perhaps two separate and distinct phenomena
exist near 0.7(2e2/h) concomitantly. In the next
section, we review the experiments performed in
p-type 1D systems. The unique properties of the
valence band provide a different system to probe
the 0.7 structure.
1.08.3 Ballistic Transport in p-Type
GaAs-Based 1D Systems
1.08.3.1 Introduction
Studying ballistic transport in p-type 1D systems
brings with it the advantages of a larger effective
mass, strong spin–orbit coupling, and spin 3/2 com-
pared with spin 1/2 for electrons. The large effective
hole mass m ¼ 0.2 – 0.4me leads to enhanced many-
pffiffiffiffi
body interactions as parametrized by rs _ m = ns .
While 2D electron systems are limited to rs < 5,
hole systems can readily achieve rs >> 10. This lar-
ger value of rs allows a study of the importance of
interaction effects in 1D.
The strong spin–orbit coupling makes it possible
to manipulate the hole spin with an applied electric
field. In addition, the total angular momentum j ¼ 3/2
gives low-dimensional hole systems a much richer
spin physics than their electron counterparts
(Winkler, 2003). The strong spin–orbit coupling
and anisotropic Zeeman splitting in these systems
also give important insights into the origin of the
0.7 structure and zero-bias anomaly. The study of
hole quantum wires in GaAs is still relatively new
310 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
compared to the broad spectrum of literature on 1D
electron systems. However, their complex spin prop-
erties and ability to be tuned with external electric
and magnetic fields allow unique insights into the
spin properties of 1D systems.
Progress in the study of 1D GaAs hole systems has
been slower for two main reasons. First, the higher
effective mass in p-type systems results in smaller
subband spacings that require lower temperatures to
resolve clear conductance quantization. Second, and
most important, fabricating stable ballistic p-type
hole wires has proved to be significantly more chal-
lenging than is the case for n-type electron wires
(Zailer et al., 1994; Daneshvar et al., 1997; Rokhinson
et al., 2006). However, recent developments in device
fabrication technology and high-purity heterostruc-
tures have allowed the fabrication of 1D hole systems
that demonstrate clear conductance quantization.
This has led to a rapid development in our under-
standing of both single-particle and many-body
phenomena in ballistic 1D channels.
In this section, we review the importance of the
hole band structure before going on to discuss how
different fabrication techniques have allowed pro-
gressively more stable and reliable 1D hole systems
in Section 1.08.3.2. In Section 1.08.3.3 we review
the observation of ballistic transport in 1D hole
wires, including measurements of the subband spa-
cing, Zeeman splitting, and measurements of the
g-factor anisotropy. Finally, in Section 1.08.3.4 we
E E
(a)
Conduction
band
Eg K Eg
Valance band
HH
Δ0 ±3/2
j = 3/2
LH
±1/2
SO } j = 1/2
Figure 29 (a) Schematic band diagram for bulk GaAs, showing the split-off (SO), light-hole (LH), heavy-hole (HH), and
conduction bands. (b) Schematic band diagram for a two-dimensional (2D) hole system (2D HS) where the HH–LH
degeneracy is lifted at k ¼ 0 due to the 2D confinement.
discuss the 0.7 structure and the zero-bias anomaly
in the context of p-type systems.
1.08.3.2 The Hole Band Structure
The structure of the valence band in bulk GaAs
systems is more complex than the simple parabolic
conduction band for electrons (see Figure 29). In
the conduction band, transport is described well by
the effective mass approximation due to the fact that
the conduction band is, to a good approximation,
parabolic and therefore d2E(k)/dk2 is a constant. In
contrast, the definition of m in the valence band is
complicated by the fact that the bands are nonpara-
bolic and anisotropic around k ¼ 0 (Winkler, 2003).
Furthermore, the curvature of the valence band is
negative, resulting a negative m. This concept is
nonphysical and so we treat these carriers as
positively charged particles with a positive mass.
Conduction band electrons originate from s-like
l ¼ 0 states with spin 1/2, with a quantized projection
in any direction of ms ¼ h/2. In contrast, there are
three valence band states. In a tight-binding picture,
these band states are derived from the three
p-orbitals px, py, and pz, and therefore have an orbital
angular momentum l ¼ 1. The spin–orbit interaction
lifts the sixfold degeneracy of the valence band states
at k ¼ 0 leading to a splitting of the valence band
states to give four degenerate states of total angular
momentum j ¼ 3/2, separated from two degenerate
(b)
Conduction
band
K
Valance band
HH
Δlh-hh ±3/2
LH
±1/2
SO
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
states of lower energy with j ¼ 1/2. The doubly
degenerate states are known as the spilt-off band
and have m ¼ 0.17 (Kittel, 1996). The fourfold
degenerate states form two band masses, heavy
holes (m ¼ 0.5me) with z-component of the angular
momentum jz ¼ 3/2 and light holes (m ¼ 0.087me)
with jz ¼ 1/2.
Confining the GaAs system to 2D lifts the fourfold
degeneracy of the heavy hole (HH) and light hole
(LH) bands, as depicted Figure 29(b), so that the HH
(mJ ¼ 3/2) band becomes the highest energy hole
band. Two ladders of energy states are formed as a
result of the different effective masses of the bands
(Winkler and Nesvizhskii, 1996). However, much of
this substructure is hidden from magneto-transport
measurements of 2DHSs, which are described
primarily by transport through only the highest
energy band – typically HH1. In these systems, the
Fermi energy is small (EF  1 meV), significantly
less than the light-hole heavy-hole splitting
(lhhh  10 meV), so that only the heavy-hole
band is occupied.
Eisenstein et al. (1984) showed that, in 2D asym-
metric quantum-wells, a lifting of the spin
degeneracy of the HH1 band results in two effective
masses, which appear as two distinct frequencies in
Shubnikov de Haas oscillations. In contrast, the states
in symmetric, square quantum-wells remain doubly
degenerate and only one effective mass is present.
Even so, assigning an effective mass to 2D GaAs hole
systems is nontrivial due to the fact that m is depen-
dent on both the symmetry of the device (Eisenstein
et al., 1984; Iye et al., 1986; Pan et al., 2003) and the
density (Pan et al., 2003; Noh, 2005).
Historically, transport measurements of 2DHSs
have been performed on silicon-doped GaAs-
AlGaAs heterostructures grown on a (311)A-oriented
GaAs substrate. The hole mobility in these structures
depends on the direction of the current path and is at
a maximum for currents parallel to the [233] direc-
tion (the fast direction). Between this direction and
the [011] direction (the slow direction), the mobility
may change as much as 20% (Davies, 1991;
Heremans and Santos, 1994). This anisotropy must
also be taken into account when calculating transport
properties. Recent developments in MBE have
allowed the growth of high-quality p-type hetero-
structures on (100)-oriented GaAs substrates.
However, their 1D transport properties are largely
unexplored.
Further confining the valence band to just one
dimension causes a mixing of the HH and LH states
311
(Zülicke, 2006). We can consider two limiting case. In
the case of very narrow wires, the mj ¼ 1/2 light-hole
band becomes higher in energy than the mj ¼ 3/2
heavy-hole band. The other limit is where the 2D
confinement from the quantum-well is stronger than
the lateral quantum wire confinement. In this case,
the ground state remains predominantly mj ¼ 3/2
HH-like. This has important implications for how
the holes couple with an external magnetic field as
the confinement strength varies.
Figure 30 shows the calculated change in g-factor
during the 2D-to-1D cross-over for a square wire
parallel to the [233]crystallographic axis. In this fig-
ure, Wz/Wx is the ratio of the height of the quantum
wire (Wz) relative to the width Wx. In the 2D limit,
the g-factor for the low-symmetry [311] GaAs is also
highly anisotropic. The holes are strongly coupled to
an external magnetic field perpendicular to the [311]
plane with gz  7. In contrast, holes coupled to a
magnetic field in the plane and parallel to the wire
have gy  0.6. The holes are even more weakly
coupled to a magnetic field in the plane and perpen-
dicular to the wire, with gx  0.2.
2D limit 1D limit
7
g∗z
6 z
5
x g∗x
g ∗x,y,z 4
3 y
2 g∗y
1
0
0 0.2 0.4 0.6 0.8 1
Wz / Wx
Figure 30 Calculated g-factors for a rectangular hole
quantum wire oriented along [233] as a function of one-
dimensional (1D) confinement.¯ The g-factors gx and gy
correspond to in-plane magnetic fields orthogonal and
parallel to the wire, respectively, while gz corresponds to
magnetic fields perpendicular to the plane. The 1D
confinement is characterized by the ratio of the quantum-
well height (Wz) to the width of the wire (Wx). When Wz/Wx ¼
0, the system is in the 2D limit but tends towards the 1D limit
as Wz/Wx ! 1. The calculations predict that increasing the
1D confinement will reduce the out-of-plane g-factor while
simultaneously increasing the inplane g-factors, gx and gy.
The 1D confinement also affects the g-factor anisotropy.
Below Wz/Wx ¼ 0.4 spins couple most strongly to fields
parallel to the wire. However, when Wz/Wx > 0.4, fields
orthogonal to the wire couple more strongly. From Zülicke U
(2006) Electronic and spin properties of hole point contacts.
Physica Status Solidi (c) 3: 4354.
312 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
The data in Figure 30 show that the g-factors and
the g-factor anisotropy change as the hole system
approaches the 1D limit. This occurs because the
confinement reduces the separation between the
HH and LH subbands and allows mixing of these
two bands. Most importantly, we see that when
Wx > 2Wz, there is a cross-over of the in-plane aniso-
tropy, that is, gx > gy. This cross-over is a result of
the LH subband becoming the highest-energy sub-
band and therefore the subband that dominates the
transport properties. It is worth noting that here
the traditional nomenclature becomes confused as
the holes occupying the light-hole subband (charac-
terized by jz ¼ 1/2), in fact, have the greater
effective mass in this regime.
1.08.3.3 Fabricating Stable 1D Hole
Systems
The enhanced m in the valence band implies that
resolving conductance plateaus in p-type systems is
intrinsically more difficult than for n-type systems.
The problem is twofold. First, increasing m reduces
the subband energy spacing. As a result, p-type sys-
tems must be measured at much lower temperatures
to remove the effect of thermal broadening, which
smears out the conductance plateaus. Second, increas-
ing m reduces the Fermi velocity and, hence, the
mobility of 2DHSs. This makes it more difficult to
achieve conduction at low carrier densities, which, in
turn, limits the Fermi wavelength. As a result, p-type
quantum wires must be made thinner and shorter
before conductance quantization can be observed.
This has led to ballistic hole transport to be studied
primarily in QPCs, that is, quantum wires in which
the length tends to zero.
However, the need for low measurement tem-
peratures and small quantum wires does not put a
practical limit on our ability to fabricate and measure
1D hole systems. Instead, the main hurdle has been
obtaining stable currents through the 1D channel.
Recently, there has been as significant improvement
in the stability of p-type quantum wires, which has
opened up the possibility for more detailed studies of
the single-particle and many-body phenomena in
these systems. As a general rule, the stability of 1D
hole systems improves with the mobility of the
2DHS from which they are formed. However, there
is increasing evidence to suggest that limiting the
scattering caused by remote ionized dopants also
improves device stability (Hamilton et al., 2008).
1.08.3.3.1 Etched quantum wires
The first observation of conductance quantization in
a 1D hole system was made by Zailer et al. (1994).
Original data from this work and a schematic of the
device structure are shown in Figure 31. In these
experiments, Zailer et al. used wet-etching to define
two parallel wires in a 2DHS of peak mobility
320 000 cm2 V1 s1 at 50 mK. Using electron beam
lithography, Zailer et al. were able to etch two 300-
nm-wide trenches separated by a 1100-nm gap. A
300-nm dot was then etched between the two
trenches to divide the gap into two, 400-nm wide
1D channels. By depositing metal into the etched
regions, Zailer et al. formed self-aligned depletion
gates that could be used to tune the width of each
wire independently. By using the depletion gates to
completely pinch off one channel and vary the width
of the other channel, Zailer et al. were able to explore
the current quantization through a single channel.
The wet-etch technique has been used success-
fully to fabricate n-type quantum wires with very
large subband spacings and high stability. However,
Zailer et al. found that the current through their
p-type devices suffered from random telegraph
8
B = 0T
6
G (e2/h)
Split ga
te
1DHS
1DHS
Split ga
4 te
2
B = 3T
0.4 0.6 0.8 1 1.2
Vg (V)
Figure 31 Original data from Zailer et al. showing current
quantization in etched one-dimensional (1D) hole systems
after averaging over 40 traces. The application of a 3T
magnetic field splits the first subband into well-defined
steps at e2/h and 2e2/h (Zailer, 1994). (Inset) Schematic of
the etched quantum wire device used by Zailer et al. Etched
regions define two parallel one-dimensional hole systems
(1DHSs), while metal deposited into the etch regions as side
gates that can independently control the current through the
1D channels. With permission from, Zailer I, Frost JEF, Ford
CJB, et al. (1994) phase coherence, interference and
conductance quantization in a confined two-dimensional
hole gas. Physical Review B 49: 5101. Copyright (1994) by
the American Physical Society.
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
signals. As a result they were forced to average
data taken over 40 traces. Nonetheless, they were
able to resolve conductance plateaus at G ¼ 2e2/h
and 3(2e2/h).
1.08.3.3.2 Surface gate-depleted
quantum wires
Daneshvar et al. (1997) fabricated p-type QPCs
from a 2D system with a higher mobility:
 ¼ 1 200 000 cm2 V1 s1 at 1.5 K. These devices
used the surface gate-depletion method to define
the 1D channel – a method that has also been used
with great success in n-type systems. A schematic of
the device structure and original data from
Daneshvar et al. is shown in Figure 32. Three metal
gates were patterned on the surface of the GaAs
heterostructure – two SGs separated by a small dis-
tance and a third gate that runs between them.
Applying a positive bias to the SGs locally depletes
the 2DHS directly beneath them and forms a 1D
channel. Increasing the bias on the SG constricts
and eventually pinches off the 1D channel. The mid-
dle gate can be used to vary the density in the 1D
channel without affecting the width of the channel.
Similar techniques are used routinely in n-type
systems to define 1D electron systems with high
stability and clear conductance quantization (cf. van
Wees et al., 1988). In contrast, Daneshvar et al. were
only able to resolve inflections in the conductance up
to 5(2e2/h). The ballistic transport was facilitated by
the application of an in-plane magnetic field, which
lengthened the inflections to form well-defined pla-
teaus and provided a good estimate of the 1D g-factor
as a function of subband index.
1.08.3.3.3 Local anodic oxidation
In the five years that followed, there was very little
work done in this field. However, Rokhinson et al.
(2002) fabricated a 1D channel that showed clear
but irregular conductance plateaus up to 9(2e2/h). A
schematic of the device structure and data from this
work are shown in Figure 33. In this device, local
anodic oxidation was used to form a 1D constriction
in a 2DHS situated just 35 nm from surface. The
local anodic oxidation technique uses a biased
atomic force microscope (AFM) tip to locally
induce an oxidation reaction between the GaAs
and native water film. In this way, the AFM tip
can be used to oxidize lines in the GaAs substrate
down to 10 nm resolution. Rokhinson et al. used the
local anodic oxidation technique to pattern their
2DHS into three separate regions. The central
313
12
10
8
G (e2/h)
6
B=0
4
2
B⊥ = 0.7T
0
2.5 2.75
Side gate voltage (V)
Figure 32 Original data from Daneshvar et al. showing
quantized inflections in the conductance up to 5(2e2/h) in a
surface gate-depletion quantum wire (Daneshvar, 1997). A
small magnetic field enhances the ballistic transport
through the device to produce well-defined and well-
quantized conductance plateau. (Inset) Schematic of the
surface gate-depletion device architecture used by
Daneshvar et al. on a single-layer hole system. The two side
gates define and confine the one-dimensional (1D) channel
while the middle gate controls the density in the wire.
Reproduced with permission from Daneshvar AJ, Ford CJB,
Hamilton AR, simnons MY, Pepper M, and Ritchie DA (1997)
Enhanced g factor of a one-dimensional hole gas with
quantized conductance. Physical Review B 55: R 13409.
Copyright (1997) by the American Physical Society.
region formed the source and drain that taper
down to the 1D constriction. The 2DHSs either
side of the constriction then acts as in-plane gates.
Applying a positive bias to these 2DHSs allows the
1D channel to be confined and even completely
pinched off.
However, the 2D system must be kept close to the
surface because the oxidation does not penetrate
deeply into the heterostructure. Due to the close
proximity to the surface, the mobility of the 2DHS
( ¼ 500 000 cm2 V1 s1 at 0.3 K) was less than half
that of Daneshvar et al. Nonetheless, Rokhinson et al.
(2004, 2006) used this technique to fabricate 1D
hole systems that show well-defined and stable
314 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
10
8 In-plane
gate
1 DHS
In-plane
gate
G (2e2/h)
6 4
4 2
2 2.8
0 Figure 34 Conductance quantization observed in a
–0.8 –0.6 –0.4 –0.2 0.0 0.2
Vg1 = Vg2 (V)
Figure 33 Original data from Rokhinson et al. showing
irregular conductance quantization plateaus up to 9(2e2/h).
(Inset) Schematic of the device architecture used by
Rokhinson et al. Using local anodic oxidation, a shallow
two-dimensional hole system (2DHS) is pattern into three
separate regions. The middle region forms the one-
dimensional (1D) channel while the 2DHSs either side of the
channel act as in-plane gates to control the current through
the channel. From Rokhinson LP, Tsui DC, Pfeiffer LN, and
West KW (2002) AFM local oxidation nanopatterning of a
high-mobility shallow 2D hole gas. Superlattices and
Microstructures 32: 99.
conductance plateaus at 2e2/h and 2(2e2/h) and have
even used these devices to perform systematic stu-
dies of the 0.7 structure and the zero-bias anomaly.
They have also extended the technique to develop
spin filters, which have revealed important informa-
tion about the origins of the 0.7 structure and are
discussed in Section 1.08.3.4.3.
1.08.3.3.4 Bilayer quantum wires
In 2006, Danneau et al. applied the surface gate-
depletion method to form two hole wires in a
modulation-doped double quantum-well. In these
heterostructures, two sheets of high-mobility holes
are formed in 20–nm-wide GaAs quantum-wells
separated by a 30-nm AlGaAs barrier. The barrier
is sufficiently thick so that there is no tunneling
between the two 2D hole layers. The as-grown
hole densities in the two wells were
1  1011 cm2
, with peak mobilities in excess of
106 cm2 V1 s1. Ohmic contacts were made to
both 2DHSs in parallel, and an overall back-gate
was used to control the hole density in the lower
quantum-well. Two parallel quantum wires are
defined along the [233] direction by three surface
10
8
G (2e2/h)
6
0
3.2 3.6 4.0
Split gate bias (V)
0.4 0.6
bilayer one-dimensional hole system (1DHS) by Danneau
et al. (Inset) Schematic of the surface gate-depletion
architecture used by Danneau et al. to define the quantum
wires in the bilayer 2DHS. This device was fabricated on a
metallically doped substrate that could be used as an in situ
back-gate to vary the density in the lower layer. From
Hamilton AR, Danneau R, Klochan O, et al. (2008) The 0.7
anomaly in one-dimensional hole quantum wires. Journal of
Physics: Condensed Matter 20: 164205.
gates, as shown in Figure 34. A combination of
front- and back-gate biases allows the transport
properties of the top or bottom quantum wire to
be measured independently.
A positive bias applied to the two side gates
defines the 1D channels in the two quantum-wells.
The central top-gate is used to control the density
in the upper quantum wire, and the back-gate con-
trols the density in the lower quantum wire. Thus,
the top quantum wire can be measured in isolation
by depleting the lower wire with the back-gate. In
addition, a forth surface gate (not shown) could be
used to stop the current flow in the top quantum
wire without it being depleted. This allows the
lower quantum wire to be measured without having
to deplete the upper wire, and can be used to
measure the compressibility of 1D systems
(Danneau et al., 2006a, 2006b).
Using this bilayer heterostructure, Danneau
et al. were able to form highly stable and repro-
ducible conductance quantization for the first 11
subbands and a strong 0.7 structure. Figure 34
shows the conductance of the quantum wire in
the upper quantum-well as a function of the
side-gate bias without any of the resonances that
hampered previous studies of lower-mobility hole
devices.
The bilayer device design has been particularly
successful. Danneau et al. subsequently performed
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
detailed studies of the subband energy spacings and
g-factor anisotropy in their bilayer 1D hole systems.
In addition, the enhanced stability of these devices
allowed for the first time an in-depth look at the
temperature- and magnetic-field dependencies of
the 0.7 structure and the associated zero-bias anom-
aly (Danneau et al., 2008).
However, it is still unclear why the bilayer
device design has been so successful compared to
single-layer devices that have also used surface
gate depletion to define the 1D channel. Indeed,
the peak mobility of each of the two layers of the
bilayer devices is significantly lower than the
mobility of the single-layer 2DHS of Daneshvar
et al. One possibility is that remote ionized dopants
cause instabilities in the 1D channel. In the devices
of Daneshvar et al., the quantum-well was symme-
trically doped – with the 2DHS sandwiched
between two layers of remote ionized dopants.
The bilayer system is also symmetrically doped;
however, the top 2DHSs screens the lower
2DHSs from the upper band of remote ionized
dopants and vice versa. This effectively halves the
impact that the remote ionized dopants have on
each layer.
It is not possible to rule out that geometric prop-
erties of the wire (such as the dimensions of the 1D
channel and the 2D-to-1D transition) may have con-
tributed to the enhancement of the channel stability.
However, recent experiments by Klochan et al. (2006)
have confirmed that by completely removing remote
ionized dopants, the stability of the 1D channel is
improved dramatically.
1.08.3.3.5 Electrostatically induced
quantum wires
Klochan et al. removed the need for dopants by
electrostatically inducing a 1D hole system in a
GaAs SISFET (Clarke et al., 2006; Klochan et al.,
2006) (see Figure 35). This is simply an induced
single heterojunction in which the holes are intro-
duced by a negative bias applied to a degenerately
doped pþ-GaAs gate electrode, instead of by
modulation doping the AlGaAs layer. This
approach avoids unwanted scattering from remote
ionized impurities. The holes are confined in a
triangular potential well, with densities from
1.6  1010 to 1.9  1011 cm2 and mobilities up to
700 000 cm2 V1 s1. To define a quantum wire, the
pþ-GaAs layer is divided into three electrically
separate gates using electron beam lithography
and a shallow wet etch. The hole density in the
315
G
at
e Mid
dle
8 lit Ga
Sp te
6 1D at
e
HS G
G (2e2/h)
lit
Sp
4
2
0
0.0 0.4 0.8 1.2
Side gate bias (V)
Figure 35 Conductance quantization observed in an
electrostatically induced 1DHS by Klochan et al. (Inset)
Schematic of the one-dimensional (1D) semiconductor–
insulator–semiconductor field effect transistor (SISFET)
device architecture. Electron beam lithography was used to
pattern the metallically doped capping layer into three
independent surface gates. The middle gate is negatively
biased to form the 1D channel while the side gates are used
to control the 1D confinement. From Hamilton AR, Danneau
R, Klochan O, et al. (2008) The 0.7 anomaly in one-
dimensional hole quantum wires. Journal of Physics:
Condensed Matter 20: 164205.
1D quantum wire and the 2D reservoirs to the left
and right of it are controlled with a negative bias
applied to the central top-gate. At the same time, a
positive bias applied to the two side gates controls
the effective width of the 1D wire formed 200 nm
below the gate.
As a result, they were able to fabricate a 1D hole
system with remarkable stability – even very close
to pinch-off. The device shows seven clean con-
ductance steps, with additional structure below the
first plateau. These devices were found to be
exceptionally stable, without the hysteresis or
instabilities that occur in most modulation-doped
devices. Remarkably, Klochan et al. demonstrated
that the current through their 1D channel
remained constant – even for conductances as low
as 0.3(2e2/h).
1.08.3.3.6 Cleaved-edge overgrowth hole
wires
To date, almost all experiments on ballistic 1D hole
systems have been performed on QPCs fabricated in
heterostructures grown on the (311)A GaAs. A
notable exception to this trend are the p-type wires
produced by Pfeiffer et al. (2005), who used cleaved-
edge overgrowth to fabricate 2-mm-long, p-type
316 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures

ce
4 Finger gate urfa
)S
10
(1

Conductance (2e2/h)
QW

1DHS Doped AlGaAs

3 gexp
2

2 gexp

gexp

0
1.5 2 2.5
Gate voltage (V)
Figure 36 Conductance quantization observed in a 2-mm-long quantum hole wire fabricated using cleaved-edge over-
growth by Pfeiffer et al. In this case the conductance is quantized in units of 0.77(2e2/h) as a result of 1D–2D wave function
mismatch (Peiffer, 2005). (Inset) Schematic of the cleaved-edge overgrowth quantum wire. A quantum-well heterostructure
grown in [100] GaAs is cleaved along the [110] crystallographyic plane. Additional layers of modulation-doped AlGaAs are
grown on the newly cleaved surface, creating an enhancement in the carrier density in the quantum-well along the cleaved
edge. Surface gates are then biased such that the two-dimensional hole system (2DHS) in the quantum-well is depleted but a
2-mm-long 1D channel remains along the cleaved edge. Reproduced with permission from Pfeiffer LN, de Picciotto R, West
KW, Baldwin KW, and Omony CHL (2005) Ballistic hole transport in a quantum wire. Applied Physics Letters 87: 073111, of
American Institute of Physics.

quantum wires from a carbon-doped heterostructure
grown on a (100) GaAs substrate.
A schematic of the device and the conductance
plateau observed is shown in Figure 36. A high-
mobility ( ¼ 1 500 000 cm2 V1 s1) 2DHS was
grown on a (100) GaAs substrate. A series of 13
parallel metallic finger gates were then patterned
on the surface of the heterostructure – each gate
being 2 mm wide and separated from each other by
2 mm. The heterostructure was then cleaved through
the finger gates such that a clean [011] surface was
formed along the cleaved edge. A second MBE
growth step was then used to grow a modulation-
doped AlGaAs heterostructure on the [011] surface –
perpendicular to the original 2DHS quantum-well.
The additional doping along this edge increases the
electron density in the quantum-well near the
cleaved-edge interface. As a result, applying a posi-
tive bias to a finger gate-depletes the 2DHS directly
beneath it, but leaves a 2 -mm-long, 1D conducting
channel along the cleaved-edge interface. Increasing
the bias on the finger gate constricts the wire and
ultimately pinches off the channel.
These devices showed well-defined and reprodu-
cible conductance plateaus for the three lowest
subbands. However, the plateaus were quantized in
units of 0.77(2e2/h) as opposed to 2e2/h. de Picciotto
et al., (2000, 2001) explained this discrepancy as
a competition between 1D–2D wave function
mismatch and the inevitable residual disorder along
the ungated regions.
1.08.3.4 Ballistic Transport in Hole
Quantum Wires
In recent years, the marked improvement in the
stability of p-type quantum wires and QPCs has
allowed single-particle and many-body phenomena
in 1D hole systems to be explored in much greater
detail.
1.08.3.4.1 Source–drain bias spectroscopy
One of the defining factors regarding the clarity of
the conductance plateau is the energy spacing
between the 1D subbands, which is related to the
strength of the confinement potential. We have seen
that experiments on n-type wires defined by wet
etching tend to have a very strong confinement
potential (Kristensen et al., 1998a, 2000; Skaberna
et al., 2000; Ramvall et al., 1997; Regul et al., 2002).
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
This results in large subband spacings, up to 20 mV.
As a result, conductance quantization can be
observed in these devices at temperatures up to tens
of kelvin (Kristensen et al., 1998a, 2000; Skaberna
et al., 2000; Ramvall et al., 1997) before thermal broad-
ening destroys the conductance plateaus.
On the other hand, 1D wires defined by surface
gate depletion exhibit subband spacings of the order
of 1 or 2 mV and so require much lower measure-
ment temperatures to resolve the conductance
plateaus (Daneshvar et al., 1997; Thomas et al., 1995;
Pyshkin et al., 2000; Cronenwett et al., 2002). Another
distinguishing feature is that the subband spacings in
etched QPCs show little variation between energy
levels (Kristensen et al., 2000; Regul et al., 2002),
whereas the subband spacings in surface-gated sys-
tems tend to decrease rapidly for higher energy levels
(Daneshvar et al., 1997; Thomas et al., 1995; Pyshkin
et al., 2000; Cronenwett et al., 2002).
To date, there have been only two studies to mea-
sure the subband energy spacing in 1D hole systems
using source–drain bias spectroscopy. One study con-
sidered a single hole wire and the other a bilayer hole
system. Daneshvar et al. (1997) applied the source–
drain bias spectroscopy technique to their single 1D
hole system defined by surface gate depletion. The
subband energy spacings measured were observed to
decrease from 0.27 mV to 0.09 mV for the first five
subbands. These spacings are significantly smaller than
the subband energy spacings measured in n-type
devices defined by the same technique. However, this
is consistent with the fact that the effective mass of
holes is approximately 6 times larger than that of
electrons and therefore we expect the subband energy
spacing to be reduced by a factor of 6 for p-type
systems.
Danneau et al. (2006a, 2006b) also measured the
subband spacings of a p-type bilayer QPC using
source–drain bias spectroscopy. They found that in
the bilayer device, the subband spacing ranged from
E1,2 ¼ 0.41 mV to E5,6 ¼ 0.28 mV for the first five
subbands, with very little variation in the three high-
est subband spacings. The larger subband spacings,
and the small variation between energy levels in the
bilayer devices is more consistent with that observed
in etched QPCs than in surface-gated devices. This
may indicate a stronger confinement potential set up
by the two QPC gates, the midline gate and the in situ
back gate. Despite the fact that both devices used
surface gate depletion, the source–drain bias spectro-
scopy revealed that the bilayer system had a much
stronger confinement potential, which is consistent
317
with the observation of very well-defined conduc-
tance plateaus in these bilayer systems.
1.08.3.4.2 Zeeman splitting and the
g-factor anisotropy
For hole quantum wires, the Zeeman splitting of the
1D subbands is highly dependent on the orientation
of the magnetic field. For quantum wires fabricated
on (311)A heterostructures, the interplay of the con-
finement potential and the crystal anisotropy implies
that the Zeeman splitting is much larger when the
magnetic field is applied parallel to the quantum wire
(along [233]), than when it applied perpendicular to
the quantum wire (along [011]). This is quite differ-
ent to 1D electrons, where the Zeeman splitting has
been shown to be isotropic and independent of the
direction of the in-plane field.
The way in which 1D hole systems couple with an
in-plane magnetic field is dependent on both the
direction of the magnetic field and the orientation
of the wire relative to the [233] and [011] crystal-
lographic axes. This means that there are four
possible g-factors that must be considered:
1. Wire k [233]and B k [233];
2. Wire k [233]and B k [011];
3. Wire k [011]and B k [233]; and
4. Wire k [011]and B k [011].
As early as 1997, it was shown that the g-factor in a
1D hole systems increases with 1D confinement
(Daneshvar et al., 1997). However, it was not until
very recently that the g-factor anisotropy was studied
in detail along the two major orthogonal directions.
Danneau et al. (2006a) studied the g-factor aniso-
tropy in a quantum wire oriented parallel to the [233]
axis and found that increasing the 1D confinement
increased the g-factor for in-plane magnetic fields
oriented both parallel and perpendicular to the
wire. For magnetic fields parallel to the wire, there
was a dramatic 40% increase in g-factor as the wire
was confined to a single subband. For fields perpen-
dicular to the wire, the g-factor showed a more
modest 15–20% increase. Danneau et al. suggested
that the enhanced sensitivity to in-plane magnetic
fields was due to the the 1D confinement causing
the total angular momentum quantization axis to
rotate into the plane and parallel to the wire. As a
result, the spins couple more strongly to in-plane
magnetic fields and in particular to fields parallel to
the wire.
However, experiments by Koduvayur et al. (2008)
suggested that the total angular moment quantization
318 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
Table 2 Important length scales in mesoscopic systems

Bk[233]

Wire k [233] Nonmonotonic increase

Wire k [011] 100% increase
axis always rotates toward [233], regardless of the
orientation of the wire. In these experiments, they
compared the g-factor anisotropy for all four combi-
nations of wire and magnetic field orientations. Their
results are summarized in Table 2.
For a quantum wire oriented along the [233] direc-
tion Koduvayur et al. observed that for fields parallel to
the wire, the g-factor increased rapidly as the number
of subbands in the wire decreased from 6 to 4 but then
dropped abruptly for the third subband. Conversely,
for fields perpendicular to the wire, Koduvayur et al.
recorded g-factors very close to zero that showed no
significant change with increasing 1D confinement.
This result disagrees with recent theoretical results
(Zülicke, 2006) that predict that the 2D g-factor
along the [011] direction (which has a finite value of
g  0.3) will only increase with 1D confinement.
For a quantum wire oriented along the [011]
direction, the observations are consistent with
experiment. For magnetic fields oriented along the
[233] direction, the g-factor increases monotonically
as the number of subbands decreases. In addition, for
fields parallel to the [011] direction, Koduvayur et al.
observed a constant but finite value g ¼ 0.3 – very
close to the g-factor expected in the 2D limit. These
results indicate that even when the wire is oriented
along the [011] axis, 1D confinement causes the
quantization axis to align itself along the [233] direc-
tion, leading Koduvayur et al. to conclude that ‘‘. . .g-
factor anisotropy is primarily determined by the
crystalline anisotropy of spin–orbit interactions.’’
This rational may also explain the unusual non-
monotonic behavior of the g-factor in the wires
oriented along the [233] direction. However, it is not
clear why this random fluctuation in g-factors has not
been observed previously. Although, it has been pre-
dicted by Csontos and Zülicke (2007) that spin–orbit
coupling may introduce large and apparently random
variations in the g-factor for different subbands. These
theoretical predictions of Csontos et al. are based on
perfectly cylindrical or square-shaped wires as
opposed to the square well and saddle potentials in
practical devices. Moreover, the theory calculates the
g-factors for wires of constant width, while for

Bk[011]
Little to no increase (g  0)
Little to no increase in g-factor
transport measurements, accessing a different subband
requires a change in the confinement potential.
Despite a series of investigations, there is still
much to be understood about the g-factor in 1D
hole systems, how it changes with a magnetic field,
and how it can be tuned with 1D confinement and
spin–orbit coupling.
1.08.3.5 The 0.7 Structure in 1D Hole
Systems
One of the most direct benefits of improved device
stability in 1D hole systems has been the ability to
resolve and study the 0.7 structure in 1D holes – one
of the most intensely studied many-body phenomena in
n-type 1D systems. One might expect to see a significant
qualitative or quantitative difference between the n-
and p-type 0.7 structures given that holes have much
greater effective mass, particle–particle interaction
strength, spin–orbit coupling, and effective spin-3/2.
However, to date, experiments have shown that the
0.7 structure in 1D hole systems behaves almost identi-
cally to the analogous structure in n-type systems.
In particular, the anomalous 0.7 plateau:
1. appears at a conductance value of 0.7(2e2/h);
2. shows activated behavior, becoming stronger with
increasing temperature;
3. typically coincides with a zero-bias anomaly; and
4. moves toward 0.5(2e2/h) in the presence of an in-
plane magnetic field.
Interestingly, the behavior of the plateau in a mag-
netic field shows the same anisotropy as the
conductance plateaus at higher subbands, providing
further evidence that the origin of the 0.7 structure is
fundamentally spin-based. Furthermore, it was found
that the zero-bias anomaly mirrors the 0.7 structure
anisotropy – disappearing in an in-plane magnetic
field at the same time the 0.7 structure is reduced to
0.5(2e2/h). This highlights a close interdependence of
these two phenomena. Recent experiments have used
spin–orbit coupling to probe the level of spin-polar-
ization around 0.7(2e2/h). The results from these
experiments indicate that the anomalous plateau at
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures 319

0.7(2e2/h) does indeed coincide with spontaneous (a)

spin-polarization (Danneau et al., 2006b, 2008; 2.0

Rokhinson et al., 2004). T = 20 mK
T = 200 mK
1.5
T = 320 mK
T = 550 mK

G (2e2/h)
T = 650 mK
1.0
1.08.3.5.1 Characterizing the 0.7 structure
One of the main differences between electron and 0.5

hole quantum wires is the much larger effective

0.0
interaction strength rs in holes, which might be 3.5 3.6 3.7 3.8

expected to have implications for the 0.7 structure. Vsg (V)

(b) (C)
In contrast to n-type systems, there have been rela-
tively few studies of the 0.7 structure in p-type 1D
systems. However, Danneau et al. (2006b) performed
1.0
a comprehensive study of the properties of the 0.7

structure observed in bilayer 1DHSs. These studies
showed that despite rs in the electron and hole
samples differing by a factor of 5 or more, many of
the zero-field properties of the 0.7 structure were
identical and, therefore, were independent of carrier
type. This suggests that the 0.7 structure may be
more sensitive to the potential landscape and/or
the disorder environment than to the strength of the
interactions.
The temperature dependence of the 0.7 structure
was observed to be very similar to that in n-type
quantum wires. Danneau et al. showed an enhance-
ment of the 0.7(2e2/h) plateau with increasing
temperature up to 650 mK (see Figure 37(a)). In
contrast to the single particle plateaus, the 0.7 struc-
ture became more prominent as the temperature
was increased, and moved closer to 0.5(2e2/h). As
the temperature was increased further, the strength
of the state weakened once more, but only after all
the single-particle plateaus had been thermally
smeared.
This activated behavior was studied in detail in
n-type systems where it was shown by Cronenwett
et al. (2002) to have similarities to the 0D Kondo
effect. The Kondo model was also used to explain
another peculiar feature of the 0.7 structure – a
peak in the conductance around zero source–drain
bias, also known as the zero-bias anomaly.
Danneau et al. confirmed the existence of the
zero-bias anomaly in 1D hole systems, as shown
in Figure 37(b). Moreover, it was shown that in
analogy to n-type systems, the p-type zero-bias
anomaly was also destroyed with increasing tem-
perature and correlated well with the simultaneous
enhancement of the 0.7(2e2/h) conductance plateau.
This is evident from the missing zero-bias peak in
Figure 37(c).
G (2e2/h)
0.5
T = 20 mK
T = 320 mK
B=0T
0.0
–0.5 0.0 0.5 –0.5 0.0 0.5
Vsd (mV) Vsd (mV)
Figure 37 (a) Evolution of the 0.7 structure in a bilayer
quantum wire as a function of temperature. The data show
that the 0.7 structure has the same activated behavior as
observed in n-type systems – becoming more evident as the
temperature increases. Conversely, conductance plateaus
for higher subbands become less well defined as a result of
thermal broadening. b) Source–drain bias spectroscopy at
T ¼ 0 showing the presence of a strong zero-bias anomaly
below the first subband. c) Increasing the temperature
destroys the zero-bias peak. From Danneau R, Klochan O,
Clarke WR, et al. (2008) 0.7 structure and zero-bias anomaly
in ballistic hole quantum wires. Physical Review Letters 100:
016403.
1.08.3.5.2 g-Factor anisotropy of the 0.7
structure and zero-bias anomaly
The similarities between the 0.7 structure observed
in n- and p-type ballistic wires diverge with the
application of an in-plane magnetic field. It is
through this difference that we have gained valuable
information about the origin of the 0.7 structure.
Earlier, we showed that the Zeeman splitting of the
1D subbands in hole quantum wires is highly depen-
dent on the orientation of the magnetic field. This
extreme anisotropy of the spin splitting in 1D holes
can be used to probe the 0.7 structure: if it is related
to spin, then it should show an anisotropic response
to an in-plane magnetic field as well.
Danneau et al. (2008) used in-plane magnetic
fields to demonstrate that the 0.7 structure shared
the same g-factor anisotropy as that observed in
320 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures

higher 1D subbands. The fact that the 0.7 feature
always moves toward 0.5(2e2/h) at the same rate that
degeneracy of the higher subbands is lifted suggests
that the underlying mechanism is the same for both –
providing strong evidence that the 0.7 structure is a
spontaneous spin-split level. In these experiments,
Danneau et al. studied the magnetic field dependence
of the 0.7 structure formed in a bilayer 1DHS
oriented along the [233] crystallographic axis (see
Figures 38(a)–38 (d)). Danneau et al. found that for
magnetic fields oriented parallel to the wire, the spins
coupled strongly to the external magnetic field. This
was evidenced by the fact that the 0.7 structure
reacted rapidly to the applied field, reaching
0.5(2e2/h) at approximately 3.6 T. At the same time,
the higher subbands also experienced strong Zeeman
splitting, becoming fully spin split at 3.6 T.
However, for in-plane magnetic fields oriented
perpendicular to the wire (Figures 38(c) and 38(d))
the case was very different. In this case, the 0.7
structure showed very little change in its absolute
position – even at 3.6 T. Likewise, the higher sub-
bands showed no signs of Zeeman splitting at this
field. The fact that the 0.7 structure shares the same
g-factor anisotropy is an indication that the anoma-
lous plateau at 0.7(2e2/h) is the result of same form of
spontaneous spin polarization.
In electron systems, it has been shown that the 0.7
structure is accompanied by an enhanced conduc-
tance at zero source–drain bias, which falls away
rapidly as the magnitude of the source–drain bias is
increased. The resulting conductance peak at Vsd ¼ 0
is a characteristic signature of an anomaly in the
density of states at the Fermi energy, and shares

(a) (b) (e)

2
BII =
3.6 T
1.0

g (2e2/h)
g (2e2/h)

1
BII = 0.5
0T T = 20 mK
B = 3.6 T
II

0 0.0
3.4 3.6 3.8 4.0 4.2 4.4 4.6 0 1 2 3 4 –0.5 0.0 0.5
Vsg (V) BII (T) Vsd (mV)
(c) (d) (f)
2 B T
=4T
1.0
g (2e2/h)
g (2e2/h)

1
B T 0.5
=0T T = 20 mK
B = 3.6 T
T

0 T
0.0
4.0 4.2 4.4 4.6 4.8 5.0 5.2 5.4 5.6 0 1 2 3 4 –0.5 0.0 0.5
Vsg (V) B (T)
T Vsd (mV)

Figure 38 Conductance data from a bilayer quantum wire oriented along the [2 –33] crystallographic axis. (a) Conductance
quantization and the 0.7 structure as a function of an in-plane magnetic field parallel to the wire B||. (b) Gray scale of the
transconductance in the wire as a function of B||. The dark regions correspond to plateaus in the conductance. These data
show that the higher sub–bands couple strongly to B|| and that the 0.7 structure is also strongly coupled – moving to 0.5G0 at
3.6 T. (c) Conductance quantization and 0.7 structure as a function of in-plane magnetic field orthogonal to the wire, B?. (d)
Transconductance in the wire as a function of B? showing that B? has very little effect on the higher subbands and similarly
has no effect on the position of the 0.7 structure up to 3.6 T. (e) Source–drain bias spectroscopy at B|| ¼ 3.6 T showing that the
zero-bias anomaly has not been destroyed by the in-plane magnetic field. (f) Source–drain bias spectroscopy at B? ¼ 3.6 T
showing that the zero-bias anomaly has not been destroyed by the in-plane magnetic field. Reproduced with permission from
Danneau R, Klochan O, Clarke WR, et al. (2008) 0.7 structure and zero-bias anomaly in ballistic hole quantum wires. Physical
Review Letters 100: 016403. Copyright (2008) by the American Physical Society.
 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
many of the features of the zero-bias anomaly
observed in quantum-dots.
In their experiment, Danneau et al. went on to
investigate the g-factor anisotropy of the 0.7 structure
with the presence of a zero-bias anomaly peak.
Danneau et al. found that for fields parallel to the
wire, the zero-bias anomaly collapsed by Bk ¼ 3.6 T.
This field lifts the spin degeneracy of the 1D sub-
bands, and suppresses the zero-bias anomaly. As
shown in Figure 38(e), the destruction of the zero-
bias anomaly coincided with the point at which the
0.7 structure reached 0.5(2e2/h). However, if the same
magnetic field was applied perpendicular to the
quantum wire, the Zeeman splitting of the integer
1D subbands was much weaker as shown in
Figure 38(f), and the zero-bias anomaly was still
present. In summary, the zero magnetic field data
for electron and hole quantum wires are strikingly
similar, with a clear 0.7 structure that becomes stron-
ger with increasing temperature. However in
contrast to electron systems the results for p-type
systems strongly suggest that the destruction of the
zero-bias anomaly is spin related, and that the zero-
bias anomaly and 0.7 structure are intimately related.
1.08.3.5.3 Spin polarization near the 0.7
structure
The fact that the 0.7 structure moves toward
G ¼ 0.5(2e2/h) in a parallel magnetic field strongly
suggests that the origin of the anomalous plateau is
a spin-split state due to a spontaneous spin polariza-
tion at B ¼ 0. However as discussed for 1D electron
wires in Section 1.08.2.5, the origin of the 0.7 struc-
ture remains highly debated.
A further experiment in 1D hole systems that has
provided important information on the 0.7 structure
was performed by Rokhinson et al. (2004). In this
work two quantum point contacts were separated
by a small distance, d, as show in the inset of
Figure 39. A magnetic field was applied perpendi-
cular to the plane and used to focus the holes injected
through the first QPC into the second QPC. When
the magnetic radius of the holes was d/n2 (where
n ¼ 1,2,3, . . .) there was a peak in the voltage mea-
sured across the second QPC. However, as shown in
Figure 39, the first peak is in fact a doublet, corre-
sponding to spin states that have been split by spin–
orbit coupling. The doublet is most prominent
when both QPCs are gated to pass exactly one
spin-degenerate mode. The level of splitting can
also be tuned by changing the asymmetry of the
injecting QPC’s confinement potential. This is
321
Ginj 1
5 Gc
3
4
Magnetic
2 Gdet
Magnetoresistance (kΩ)
focusing
3 4
2
1
0
–1
–1.0 –0.5 0.0 0.5 1.0
B (T)
T
Figure 39 (Inset) AFM micrograph of a p-type spin filter
composed of two p-type QPCs separated by 0.8 mm. The
injector QPCs, with contacts 1 and 2, passes a current of 1
nA while the voltage is measured across the detector QPC
using contacts 3 and 4. The main panel shows the magne-
toresistance measured across the detector QPC as a
function of magnetic field perpendicular to the plane B?. For
B? < 0 holes passing through the injector QPC are focused
away from the detector QPC and as a result the magne-
toresistance is determined primarily by Subnikov-de-Haas
oscillations in the two-dimensional hole system (2DHS).
However, for B? > 0, holes are focused into the detector
QPC, resulting in peaks in the voltage across the QPC. The
first and sharpest peak is comprised of a doublet of peaks
separated by 36 mT – showing that the different spins in the
subbands are indeed resolved and that these devices can
be used as spin filters. Reproduced with permission from
Rokhinson LP, Larkina V, Lyanda YB, Pfeiffer LN, and West
KW (2004) Spin separating in cyclotron motion. Physical
Review Letters 93: 146601. Copyright (2004) by the
American Physical Society.
analogous to turning on spin–orbit coupling in
2DHSs by asymmetrizing the quantum-well confine-
ment potential.
Rokhinson et al. found that as the conductance
through the injector QPC approached 0.7(2e2/h),
the height of the second peak collapsed as shown
in Figure 40. This result indicates that the injector
current is predominately spin polarized near 0.7(2e2/h)
(Rokhinson et al., 2004). Interestingly, in 1D hole sam-
ples that did not show a well-defined 0.7 structure, the
doublet remained intact below 0.3(2e2/h).
In summary we have reviewed the 0.7 structure
and zero-bias anomaly in high-quality hole quantum
322 Ballistic Transport in 1D GaAs/AlGaAs Heterostructures
(a) (b)
Injector QPC1
1.0
0
Gi (2e 2 /h)
V (μV)
0.5
–2
0.0
0.10 0.15 0.20 0.1 0.2
Vg (v) B (T)
T
Figure 40 (a) Conductance through the injector quantum
point contact (QPC) below the first subband as a function of
gate voltage showing a well-defined 0.7 structure. The
vertical lines indicate the points at which spin-polarized
measurements were performed. (b) Voltage drop across the
detector QPC as a function of magnetic field for different
injector conductances. The data show that when the
conductance through the injector is equal to (2e2/h), the
voltage across the detector QPC registers two voltage
peaks indicating two closely spaced spin states whose
degeneracy has been lifted by spin–orbit coupling.
However, when the conductance in the injector QPC is
reduced to 0.7(2e2/h), the detector QPC registers only a
single voltage peak indicating a single spin state and hence
a spin-polarized current. The upper solid and dashed lines
compare these two cases directly. Reproduced with
permission from Rokhinson LP, Pfeiffer LN, and West KW
(2006) Spontaneous spin polarization in quantum point
contacts. Physical Review Letters 96: 156602. Copyright
(2006) by the American Physical Society.
wires. Despite the fact that interaction effects should
be much stronger in these systems, because of the
enhanced hole effective mass, the zero magnetic
field data for electron and hole quantum wires are
strikingly similar. However, unlike 1D electron sys-
tems the Zeeman splitting caused by an in-plane
magnetic field is highly anisotropic for 1D holes, due
to the strong spin–orbit coupling. Both the 0.7 struc-
ture and the zero-bias anomaly share this anisotropic
response to an in-plane magnetic field demonstrating
that they are linked, and spin related. Finally, ballistic
hole spin filters were used to study the spin polariza-
tion around G ¼ 0.7(2e2/h). These devices were able to
resolve two spin states in the 1D subbands. However,
near the 0.7(2e2/h) plateau, only one spin state was
resolved – indicating that the lowest subband is in
fact spin polarized at B ¼ 0. More work is needed to
understand the electronic and spin properties of holes
confined to 1D systems, but already it is clear that 1D
holes have unusual spin properties with no counter-
part in spin-1/2 electron systems.
1.08.4 Summary
Gi
(2e2/h) In this chapter we have reviewed the extensive and
0.97
growing literature on ballistic transport in 1D GaAs
0.96 heterostructures. Since the first realization of ballistic
0.97
0.92 transport in GaAs quantum wires by van Wees et al.
0.73
0.66
and Wharam et al., the field has blossomed over the
0.68 past two decades as new experiments, and in parti-
0.43
0.26 cular, the ability to create purer and smaller systems
has exceeded new length scales, allowing new device
0.3
architectures to be probed.
Nonetheless, there remains important questions to
be answered regarding the nature of transport
through these devices, in particular the role of spin
and interactions at very low densities. Most notably is
the 0.7 structure, whose origin is still a point of
contention. Although many experiments suggest
that the anomalous plateau originates from a sponta-
neous spin splitting at zero magnetic field, others
suggest that Kondo-like physics may govern the
underlying mechanism. It appears that at the date of
submission neither mechanism can explain all the
experimental observations. With the ability to fabri-
cate both ballistic electron and hole systems with
different spin states and phonon coupling, there is
still a lot more to learn from 1D systems.
Perhaps most importantly, the techniques used to
study ballistic transport in 1D have provided a solid
foundation for understanding other systems. For
example, the work on 1D systems in GaAs has
opened the door to studies of 0D structures allowing
the fabrication of artificial atoms and coupled
quantum-dots. These fields are now expanding to
include the study of quantum-dots as a possible
route to a solid-state quantum computer. The work
has also contributed to an increased understanding of
quantum transport in other material systems such as
nanowires and carbon nanotubes. (See Chapter 2.03).
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Ferry DK and Goodnick SM (1997) Transport in Nanostructures.
Cambridge: Cambridge University Press.
Heinzel T (2003) Mesoscopic Electronics in solid state
nanostructures. Weinheim: Wiley-VCH.
Ihn T (2004) Electronic Quantum Transport in Mesoscopic
Semiconductor Structures. New York, NY: Springer.
Imry Y (1997) Introduction to Mesoscopic Physics. New York,
NY: Oxford University Press.
Kelly MK (1995) Low dimensional physics. In: Low Dimensional
Semiconductors, ch. 4, pp. 76–101. New York, NY: Oxford
Science Publications.
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 1.09 Thermal Conductivity and Thermoelectric Power
of Semiconductors
I Terasaki, Nagoya University, Nagoya, Japan
ª 2011 Elsevier B.V. All rights reserved.

1.09.1 Introduction 326

1.09.2 The Boltzmann Equation 327
1.09.2.1 Equations for Conduction Electrons 327
1.09.2.2 Equations for Phonons 329
1.09.3 Thermal Conductivity 330
1.09.3.1 Single-Crystalline Semiconductors 330
1.09.3.2 Amorphous Solids and Glasses 333
1.09.3.3 Magnetic Semiconductors 334
1.09.4 Thermoelectric Phenomena 336
1.09.4.1 The Seebeck Effect 336
1.09.4.2 The Peltier and Thomson Effects 340
1.09.4.3 The Galvanomagnetic Effects 341
1.09.5 Thermoelectrics 342
1.09.5.1 Thermoelectric Devices 342
1.09.5.2 Thermoelectric Materials 345
1.09.5.3 Oxide Thermoelectrics 347
1.09.6 Nanostructured Materials 350
1.09.6.1 Superlattices 350
1.09.6.2 Nanowires 352
1.09.6.3 Nanostructured Bulk Materials 353
1.09.7 Summary and Outlook 355
References 356

1.09.1 Introduction In the course of recent developments in electronic

The history of mankind tells us that our ancestors
recognized the importance of fire from the very early
stage, and that they were civilized with one of the
important properties of fire, that is, heat. It is,
however, a rather recent event in the late nineteenth
century that the nature of heat was understood;
thanks to thermodynamics, we know that heat is a
kind of energy, and obeys the energy-conservation
law, known as the first law of thermodynamics.
Temperature is a kind of intensive variable for heat,
given entropy as the corresponding extensive
variable. Except for reversible processes, such as the
Carnot cycle, entropy will continue to increase,
indicating that heat cannot be fully converted into
work. This is known as the second law of
thermodynamics.
According to the second law of thermodynamics,
the more the work done, the more the heat increases.
technology, many semiconductor devices have been
produced, complied, and used, which finally generate
an enormous amount of unusable heat. Heat manage-
ment has thus become a serious issue these days, and
requires deep understanding of the thermal conduc-
tion process in solids. Aside from this, the heat flow
itself is a prototypical example of nonequilibrium
states of matter, which is of vital importance in the
development of nonequilibrium thermostatistical
physics.
Thermal conduction is a predominant process of
heat flow in solids, when compared with radiation
and convection and is facilitated by conduction
electrons and lattice vibrations (phonons). In certain
kinds of magnetic insulators, magnetic excitations
(magnons) can carry heat much better than the lattice
vibrations can, which can be controlled by external
magnetic fields. Electrons can carry electrical current
as well, so that there exists a finite coupling between

326
 Thermal Conductivity and Thermoelectric Power of Semiconductors
the thermal current and the electrical current. These
are known as the thermoelectric phenomena. By
making full use of the thermoelectric phenomena in
semiconductors, we are able to convert electric
power into heat, and vice versa. Such a technology
is called thermoelectrics.
In this chapter, we briefly review the thermal
conductivity and thermoelectricity of semiconduc-
tors. This subject has more than a 100-year history
since Drude established his kinetic theory of electron
gas in 1900. Partly because of the space constraint, we
focus on recent developments and show only
minimal set of old data (selected with the author’s
biased view). Obviously, the data shown here are far
from complete, particularly the old ones. Regretably,
it is almost impossible to cite all the preceding studies
in order from an enormous numbers of papers. Those
who wish to know this area more in detail can refer to
many textbooks and reviews available. A good
summary of Drude’s theory is given by Ashcroft
and Mermin (1976), from which one can grasp gross
features of the electron transport. Callen (1985) has
explained a basic treatment of nonequilibrium
thermodynamics in his unique framework of thermal
physics. A standard theory of the transport phenom-
ena in solids is concisely described by Ziman (1976).
Thermal conductivity of new complex materials is
extensively reviewed by Tritt (2004), and the current
status of the thermoelectrics is thoroughly compiled
by Rowe (2006).
The chapter is organized as follows: In Section
1.09.2, we discuss the Boltzmann equations for
electrons and phonons, and derive explicit expres-
sions for thermal conductivity. Then, we take a quick
look at the thermal conductivities of various
semiconductors in Section 1.09.3. We also discuss
the thermoelectric effects in Section 1.09.4, and the
thermoelectrics in Section 1.09.5. In Section 1.09.6,
the thermal and thermoelectric properties in
nanostructured materials are briefly introduced. We
show that they raise difficult questions to our
understanding of thermal conduction. Finally, we
briefly summarize this chapter in Section 1.09.7.
1.09.2 The Boltzmann Equation
1.09.2.1 Equations for Conduction
Electrons
In the framework of nonequilibrium thermodynamics
(see Callen, 1985), the electrical current density j and
the thermal current density q are written as functions
327
of the gradient of the chemical potential r and the
gradient of the inverse temperature Ñð1=T Þ:
1 1
j ¼ L11 Ñ þ L12 Ñ ð1Þ
T T
1 1
q ¼ L21 Ñ þ L22 Ñ ð2Þ
T T
where Lij’ s are called the transport coefficients (the
Onsager coefficients). The chemical potential con-
sists of an electrostatic part e ¼ eV and a chemical
part c, wher e (<0) is the electron charge. Then, the
electric field E is given by
1
E ¼ – ÑV ¼ – Ñð – c Þ ð3Þ
e
However, Ñc cannot be observed separately in
real experiments, and is considered to be included
in the observed E hereafter (Ashcroft and Mermin,
1976).
Boltzmann has given a formula to calculate the
distribution function f(k, r) of a particle subject to
external fields. f(k, r) should change from its
equilibrium value f0, but the deviation will be
small enough, if the external fields are weak.
In this weak limit, f  f0 can be expanded in
terms of external fields. To include the non-
equilibrium state, Boltzmann has introduced the
scattering term describing the change of f(k, r)
from f0 through a process that a particle with
momentum k is scattered to acquire a momentum
of k9.
Then, the deviation from the equilibrium should
be due to diffusion, external field, and scattering, as
expressed by

e @f 
vk ?Ñf þ E ? Ñk f ¼ ð4Þ
h @t scattering
where Ñk refers to the gradient by the momentum k.
The first and second terms on the left-hand side
correspond to the diffusion and the acceleration,
respectively. For the sake of simplicity, we omitted
the contribution from magnetic fields in Equation (4).
To find the expressions for electrons, we assume
the Fermi–Dirac distribution function for f0, that is,
 –1
ð" k –  Þ
f0 ¼ exp þ1 ð5Þ
kB T
where "k is the eigenenergy for the momentum k.
The scattering term is, in fact, very difficult to
handle strictly, so that the relaxation time approxi-
mation is often used, in which the scattering term can
328 Thermal Conductivity and Thermoelectric Power of Semiconductors

be written using the deviation from the equilibrium Note that Kˆn is a second-rank tensor through
distribution g ¼ f  f0 as 0 1
vkx vkx vkx vky vkx vkz
 B C
@f  1 1 B C
¼ – g ¼ – ðf – f0 Þ ð6Þ vk vk ¼ B C
@t scattering   B v ky vkx v ky vky v ky vkz C ð14Þ
@ A
where  is the scattering time which characterizes the vkz vkx vkz vky vkz vkz
timescale of the dissipation of the system. It is origin-
We also note that Equations (11) and (12) are iden-
ally defined in the form of the inverse number 1/ as
tical to Equations (1) and (2), and Onsager’s relation,
the probability per unit time that a particle with a
L12 ¼ L21, is readily satisfied in Equations (11) and
momentum k and an energy ! is scattered to one
(12). All the parameters are reduced to scalar quan-
with a momentum k9 and an energy !9.
tities for a cubic crystal, where the conductivity is
We further assume that f depends on r only
given by
through the space variation of temperature T ðrÞ.
Making use of the following expression of the  ¼ e 2 K0 ð15Þ
group velocity
The rest of the parameters are similarly given by
1
vk ¼ Ñk"k ð7Þ 1 K1
h S¼ ð16Þ
eT K0
we obtain
  K2
@f0 h "k –  i 9 ¼ ð17Þ
g¼ – vk  e Eþ ð – ÑT Þ ð8Þ T
@" "¼"k T
where S is the Seebeck coefficient (thermoelectric
and calculate the electrical current density as power or thermopower) and 9 the thermal conduc-
Z tivity in the absence of electric field. The electron
1 1 thermal conductivity is always measured for the
j¼ evk gd3 k ¼ evk f d3 k ð9Þ
43 43 open-circuit condition of j =0; thus, by eliminating
In deriving Equation (9), we used the fact that the E from Equation (12), we get
above integral gives zero for f ¼ f0, because the
q ¼ S 2 T ÑT – 9ÑT
electron moves in random directions. The prefactor  
of 1/43 ¼ 2/(2)3 represents the density of states for S2 ð18Þ
¼ 9 1 – ð – ÑT Þ
the momentum space times the spin degrees of 9
freedom. and the thermal conductivity of conduction electron
Next, we find the expression of the thermal in real experiments is given by
current density in the same framework. Recalling  
that the chemical potential and the eigenenergy are S 2
 ¼ 9 1 – ð19Þ
the free and internal energies per electron, respec- 9
tively, we can define the heat per electron as "k – ,
The second term is usually small, and we may often
and the thermal current density as
Z
neglect the difference between  and 9 unless we
1 treat thermoelectric materials (see Section 1.09.5).
q ¼ ð"k – Þvk gd3 k ð10Þ
43 Using , S, and 9, we eventually simplify
Substituting Equation (8) in Equations (9) and (10), Equations (11) and (12) as
we obtain
j ¼  Eþ Sð – ÑT Þ ð20Þ
e
j ¼ e 2 Kˆ0 E þ Kˆ1 ð – ÑT Þ ð11Þ q ¼ ST Eþ 9ð – ÑT Þ ð21Þ
T
1 ˆ
q ¼ e Kˆ1 E þ K2 ð – ÑT Þ ð12Þ where all the parameters , S, and 9 can be deter-
T mined by experiments.
where From Equations (15) and (17), one can find that
Z   the conductivity and thermal conductivity are
1 @f0 calculated from a similar integral for conventional
Kˆn ¼ 3 – vk vk ð"k – Þn d3 k ð13Þ
4 @" "¼"k metals, in which the Fermi energy EF is much larger
 Thermal Conductivity and Thermoelectric Power of Semiconductors 329

than the thermal energy kBT. By expanding @f0/@" in Then, we finally obtain the lattice thermal
terms of kBT/EF (the Sommerfeld expansion), one conductivity as
can derive K2 in terms of K1 or  as Z  
1 @N0
  ˆ ph ¼
 h!k vk vk  – d3 k ð27Þ
2 kB2 T 2 kB T 2 83 @" "¼h!
K2 ¼ ðE F Þ þ O ð22Þ
3 e2 EF
Let us consider the physical meaning of Equation
and obtain the Wiedemann–Franz law given by (27). For the sake of simplicity, we assume cubic
symmetry, in which the second-rank tensor of
T 2 kB2 Equation (14) is reduced to the scalar quantity of
¼ ¼ L0 ð23Þ
el 3 e2 vk 2 . If we further assume that the velocity and scat-
tering time are independent of k, we may rewrite
where we write el, instead of 9, to emphasize that the
Equation (27) as
thermal conductivity discussed here is due to conduc-
" Z   #
tion electrons, not due to phonons. The numerical value 1 1 @N0 3
of L0 is 2.4  108 V2 K2  (155 mV/K)2 is known as ph ¼ v,
3 83
h!k –
@" "¼h!
dk ð28Þ
the Lorentz number. This relation states that electrons
in solids can carry heat as well as electricity, or where we take the thermal average of the velocity as
equivalently, that a metal is a good conductor of
electricity and heat. Note that the Lorentz number vx2 ¼ vy2 ¼ vz2 ¼ v2 =3 ð29Þ
L0 is given only by the universal constants. This and introduce the mean free path , ¼ v. Noting that
justifies the Wiedemann–Franz law that the ratio of the quantity in the brace is the specific heat of phonons,
the thermal to the electrical conductivity at fixed one can approximate the thermal conductivity as the
temperatures is independent of material parameters. product of the sound velocity, the mean free path, and
This is known as one of the most remarkable successes the specific heat.
of Drude’s theory. First, we show the electron thermal conductivity
in the Drude model (Ashcroft and Mermin, 1976).
Drude regarded electrons in a metal as ideal gas
1.09.2.2 Equations for Phonons molecules, and developed a kinetic theory of such
gases. Suppose a metal rod is subject to a temperature
The Boltzmann equation can also be applied to the gradient (one-dimensional (1D) model). The elec-
lattice thermal conductivity, the contribution of pho- trons coming from the hot side have a larger
nons to the whole thermal conductivity. Since the
thermal energy and equivalently, a larger kinetic
phonon does not carry charge, we only consider the
energy of ", so that the net heat flow is given as
energy (heat) flow, in which the distribution function
at thermal equilibrium is given by the Bose–Einstein nvx
q¼ ½"ðT ½x – vx Þ – "ðT ½x þ vx Þ ð30Þ
distribution as 2
   –1 d"
h!k ¼ nvx ,ðT1 – T2 Þ ð31Þ
N0 ¼ exp –1 ð24Þ dT
kB T
where n is the carrier density and v(T) is the thermal
where !k is the phonon frequency for the wavevector velocity at temperature T. The factor of 1/2 repre-
k (note that the chemical potential is zero for sents that the half of electrons are moving toward the
phonons). Similarly in the case of electrons, we position x. We take the thermal average of the
write the thermal current density of phonons as velocity of Equation (29) and obtain the expression as
Z 1 1
1
q ¼ h!k N vk d3 k ð25Þ el ¼ Cel v2  ¼ Cel v,el ð32Þ
83 3 3

where N is the distribution function for phonons in where Cel ¼ nd"/dT and , are the electronic specific
the presence of temperature gradient. We take the heat per volume and the electron mean free path,
relaxation time approximation given by respectively. One may notice that this is a special
  form of Equation (28). The interpretation of this
@N0 equation is straightforward. A good conductor of
N – N0 ¼ – vk ð – ÑT Þ ð26Þ
@" heat should satisfy that (1) the number of the heat
330 Thermal Conductivity and Thermoelectric Power of Semiconductors
carrier is large (large Cel), (2) the speed for the heat
carrier is high (large v), and (3) the heat carrier
travels far (large  or ,). In fact, Equation (32) is
valid for phonons as well:
1 1
ph ¼ Cph vs2  ¼ Cph vs ,ph ð33Þ
3 3
in which Cel is replaced by the phonon-specific heat
Cph; vs and  are the sound velocity and the phonon
scattering time, respectively.
To step further, let us go back to Equation (27),
and discuss the relaxation time . By definition,  is a
function of the momenta of a phonon scattered from
k to k9. While the conduction electrons in metals
have nearly the same energy as EF, the phonons
may have different energy ranging from zero to
kBT. Thus, it is more reasonable to assume that  is
dependent on energy, or equivalently, frequency !
through k  k9. Eventually, the mean free path of
phonons may strongly depend on !, implying that
Equation (33) is often oversimplified.
It has long been discussed how the scattering time
of phonons depends on ! (see Yang, 2004). Usually,
we can assume that the scattering events from differ-
ent origins are additive in the form of scattering rates
given as
X from one Brillouin zone to another. Such scattering is
–1
total ¼ i – 1 ð34Þ
i (1964) proposed the following formula
This is known as Matthiessen’s rule in electric resis-
tivity, in which the total resistivity is given by the
sum of the resistivity due to impurity scattering and
that due to electron–phonon scattering (Ziman,
1976).
In the case of phonons, we usually consider three
to four kinds of scattering, as pointed out by
Callaway (Callaway, 1959; Callaway and v Baeyer,
1960). The first one is the boundary scattering corre-
sponding to the elastic scattering. This term is
independent of energy, expressed in terms of a
parameter L as
B – 1 ¼ v=L ð35Þ
L corresponds to a characteristic length of the
system, which can be the dimensions of the sample,
the size of the grains, etc. The second one is the
point-defect scattering corresponding to the impur-
ity scattering of electrons. Klemens (1960) pointed
out that this scattering time  PD is proportional
to !4, so that
PD – 1 ¼ A!4 ð36Þ
Steigmeier and Abeles (1964) calculated the para-
meter A in a solid solution system. According to
their calculation, A is given by
V X m  – mi  2
A¼ 3
fi ð37Þ
4v i 
m
where V is the volume per atom, fi the volume fraction
of the atom i, mi the mass of the atom i, and m  the average
mass. Thus, the parameter A is large, when the mass
 – mi is large. The third term is the phonon–
difference m
phonon (normal) scattering. Since the lattice in real
materials deviates from the ideal harmonic oscillator,
the restoring force can be nonlinear. In terms of pho-
nons, it corresponds to the phonon–phonon scattering.
(Recall that the anharmonicity corresponds to products
of four phonon operators like bky bk9y bq9 bq .) This scattering
is phenomenologically given as
N – 1 ¼ B!a T b ð38Þ
where a and b are some exponents of the order of
unity. These parameters are determined by fitting
the thermal conductivity measured in real materials.
The last scattering is the phonon–phonon Umklapp
scattering. At high temperatures where the momen-
tum change k – k9 is large enough to exceed a
reciprocal lattice vector, then phonons are scattered
called Umklapp scattering. Slack and Galginaitis
 
h 2 D
U – 1 ¼ !2
T exp – ð39Þ
Mv2 D 3T
where D is the Debye temperature and  the Grüneisen
parameter. Equations (38) and (39) have similar
temperature dependence except for the exponential
term in the latter, and thus the former is sometimes
ignored for the data fitting. At first glance, one may
wonder if the thermal conductivity is uniquely fit with
the above four scattering times. Fortunately, they affect
the curve differently, and the scattering times are
reasonably determined by fitting the experimental
data. We see how experimental data are explained
with these scattering times in the following section.
1.09.3 Thermal Conductivity
1.09.3.1 Single-Crystalline
Semiconductors
Figure 1 shows the thermal conductivity of pure and
doped silicon, silicon carbide, and diamond (Slack,
1964). Below around 20 K, the thermal conductivity

104
Thermal conductivity (W m–1 K–1)
3
10
102
SiC
101
100 Doped Si
–1
10
100
Figure 1 Thermal conductivity of pure and doped silicon,
silicon carbide, and diamond. From Slack GA (1964)
Thermal conductivity of pure and impure silicon, silicon
carbide, and diamond. Journal of Applied Physics 35:
3460–3466.
increases approximately in proportion to Tp
(3 > p > 2), takes a broad maximum around 20–80 K,
and decreases with temperature approximately
inversely proportional to T above 100 K.
The temperature dependence is qualitatively
understood as follows: according to Equation (33),
the thermal conductivity is given by the product of
the specific heat, the phonon mean free path, and the
sound velocity. In many cases, the sound velocity
does not change with temperature very much, and
the other two predominantly determine the tempera-
ture dependence of the thermal conductivity. As is
well known, the specific heat is expected to scale with
T3 for T  D, and to be 3NkB for T  D.
In contrast, the phonon mean free path is dominated
by impurity scattering at low temperatures, and
expected to be weakly dependent on temperature.
With increasing temperature, the phonon begins to
be scattered by other phonons and/or electrons.
In particular, Equation (39) indicates that the
phonon–phonon scattering rate is roughly propor-
tional to T for T  D, so that the mean free path
is inversely proportional to T at high temperatures.
Thus, the product of the specific heat and the phonon
mean free path is expected to be proportional to Tp
(2 < p < 3) for low temperatures and to 1/T for high
temperatures (see also Figure 2). The thermal
conductivity peak corresponds to the crossover
between the two temperature regions.
The magnitude of the thermal conductivity is
80 W m1 K1 at room temperature for doped silicon.
Since a typical value of thermal conductivity of metals
is 10–102 W m1 K1 (Ashcroft and Mermin, 1976),
this value is reasonably high for phonon conduction.
Thermal Conductivity and Thermoelectric Power of Semiconductors 331
104
Diamond 70
Thermal conductivity (W m–1 K–1)
Ge(99.99%) (M)
70
Ge(99.99%) (S)
70
Ge(96.3)
70
Ge
na
Ge1 (M)
na
Pure Si 103 Ge1 (S)
70/76
Ge
T3
102
101 102 103 T –1
Temperature (K)
1 10 100
Temperature (K)
Figure 2 Thermal conductivity of isotope-pure and
natural Ge. From Asen-Palmer M, Bartkowski K, Gmelin E,
et al. (1997) Thermal conductivity of germanium crystals
with different isotopic compositions. Physical Review B 56:
9431–9447.
The thermal conductivity of diamond is much higher,
owing to higher Debye temperature and higher sound
velocity. Because of this property, diamond is
expected to be used as a semiconductor wafer of
next generation.
As discussed in the previous section, the point-
defect scattering given by Equations (36) and (37)
depends on the mass difference. This means that the
isotope atom can be a scattering center of phonons.
Geballe and Hull (1958) found that the isotopically
enriched 74Ge (96%) has three times larger thermal
conductivity than natural Ge. Asen-Palmer et al.
(1997) successfully measured the thermal conductivity
of isotope-pure 70Ge (99.99%) as shown in Figure 2.
The observed thermal conductivity is eight times
larger at maximum than that of natural Ge crystal.
Figure 3 shows thermal conductivity of various
semiconductors with particularly low thermal con-
ductivity (Kurosaki et al., 2005). They are used for
thermoelectric materials, which are discussed in
Section 1.09.5. All the materials include heavy ions
such as Ag, Tl, Te, and Bi, and consequently have
low sound velocities. Other complex materials with
low thermal conductivity are summarized in a review
by Snyder and Toberer (2008). By comparing data
from Figures 1–3, we can say that the magnitude of
the thermal conductivity ranges from 101 to
104 W m1 K1. This dynamic range is significant,
but much smaller than that of electrical conductivity,
in which it ranges from 1020 to 106 S cm1. This
implies that neither ideal heat insulator nor heat
conductor is available in real materials.
332 Thermal Conductivity and Thermoelectric Power of Semiconductors

2.0 further written in terms of the mass difference

given by Equation (37). Figure 4 shows an example
Thermal conductivity (Wm−1 K−1)

+ + + to what extent Equation (40) explains the thermal

1.5 +
conductivity measured in skutterudite antimonides
(Yang, 2004). From Equation (40), one can under-
1.0 AggTITe5
stand that the second term corresponds to  _ Tp
AgTITe
Bi2Te3
(p > 2) at low temperatures, while the third term
+ TAGS-85 corresponds to  _ 1/T at high temperatures.
0.5
Thanks to the fact that the relevant temperature
range is different between the two, the fitting para-
0.0 meters of A, B, and L are fairly uniquely determined.
250 300 350 400 450 500 550 600 650 700 The boundary scattering is responsible for the
Temperature (K)
magnitude of the thermal conductivity at low
Figure 3 Thermal conductivity of various temperatures. With decreasing temperature, only
semiconductors. TAGS stands for (GeTe)x(AgSbTe2)1x. long-wavelength phonons with an energy of h!
From Kurosaki K, Kosuga A, Muta H, Uno M and Yamanaka
S (2005) Ag9TITe5: A high-performance thermoelectric bulk
smaller than kBT are excited, and consequently the
material with extremely low thermal conductivity. Applied second and third terms in Equation (40) do not
Physics Letters 87: 061919. contribute at T ¼ 0. Thus, a thermal conductivity
would diverge without L. In this respect, L roughly
gives an average phonon mean free path at low
As discussed in the previous section, the scattering temperatures, but cannot be predicted from a first-
time for phonons is described phenomenologically by principles calculation (Chen 1998; Takahata and
a sum of different scattering rates given as Terasaki, 2002). In contrast, the second term dom-
inates a saturated value and exponent in the
 – 1 ¼ v=L þ A!4 þ B!2 T e – D =T ð40Þ
intermediate temperature range. The coefficient A
The first term corresponds to the boundary scatter- can be evaluated using Equation (37), but is often
ing, while the second term is due to point-defect determined as a fitting parameter. Meisner et al.
scattering and the third term is due to phonon– (1998) evaluated the parameter A of filled skutterudite
phonon Umklapp scattering. The parameter A is Cey(Co.Fe)4Sb12 by regarding this as a solid solution

150
Thermal conductivity (W m–1 K–1)

100 Measured data

Boundary only
Boundary + point-defect
Umklapp

50

0
0 50 100 150 200 250 300
Temperature (K)
Figure 4 Lattice thermal conductivity of skutterudite antimonide. The contributions of three scattering mechanisms are
separately drawn. From Yang J (2004) Theory of thermal conductivity in crystalline semiconductors. In: Trit TM (ed.) Thermal
Conductivity. Kluwer.
 Thermal Conductivity and Thermoelectric Power of Semiconductors
of CoSb3 and CeCoFe3Sb12, in which the huge mass
difference results in a large A. The third term dom-
inates the decreasing thermal conductivity at high
temperatures. For T  D, all the phonon modes
are thermally excited, and the specific heat is
saturated as a classical value of 3NkB. In such condi-
tions, the contribution from !4 does not cause strong
temperature dependence; the phonon–phonon
scattering rate is proportional to T exp(D/T)  T.
1.09.3.2 Amorphous Solids and Glasses
The amorphous solids and glasses are materials in
which atoms have a short-range order, but no trans-
lational symmetry. As a result, no phonons are well
defined, or all the phonon modes are localized at each
atoms. Cahill et al. (1992) measured and analyzed the
thermal conductivity of various disordered crystals,
and showed minimum thermal conductivity, as was
originally proposed by Slack (1979).
Figure 5 shows the thermal conductivity of amorph-
ous solids ( -SiO2 and CdGeAs2) and disordered solids
(Or1Ab33An66 feldspar and Ba0.67La0.33F2.33). All the
curves have low magnitudes at room temperature (less
than 102 W cm1 K1 ¼ 1 W m K1), and weakly
dependent on temperature above 10 K. With decreasing
temperature below 10 K, the thermal conductivity
10–1
Or1 Ab33 An66
Thermal conductivity (W cm−1 K−1)
10–2
CdGeAs2
10–3
Ba0.67 La0.33 F2.33
–4
10
α-SiO2
10–5
10–6
0.1 1.0 10 100
Temperature (K)
Figure 5 Thermal conductivity of amorphous solids
( -SiO2 and CdGeAs2) and disordered solids
(Or1Ab33An66 feldspar and Ba0.67La0.33F2.33). From Cahill
DG, Watson SK and Pohl RO (1992) Lower limit to the
thermal conductivity of disordered crystals. Physical
Review B 46: 6131–6140.
333
decreases as T3. The temperature dependence is quali-
tatively understood as follows: in the present situation,
the mean free path is as short as the atomic distance, and
consequently independent of temperature. Although the
sound velocity cannot be defined in disordered mate-
rials, it is expected to be similar to that in crystals. Thus
the last term, the specific heat, is the origin of the
temperature dependence of the thermal conductivity.
Another feature to be pointed out is that all the curves
are reasonably close to one another, implying somewhat
universal behavior.
Cahill et al. (1992) proposed a theoretical expres-
sion for the thermal conductivity of disordered solids,
by assuming that the thermal energy of each atom is
lost during half the period of an oscillation of the
atom. Based on the Debye model, the minimum
thermal conductivity min is given by
 2 1=3 X  2 Z i =T 3 x
nL T x e dx
min ¼ kB vi ð41Þ
6 i
i 0 ðex – 1Þ2
where vi corresponds to three sound modes (two for
transverse and one for longitudinal). The cutoff
frequency i is given in temperature unit as
h
i ¼ vi ð62 nL Þ1=3 ð42Þ
kB
where nL is the density of atoms. Note that Equation
(41) contains no free parameters, because vi and nL
can be determined by different experiments.
Figure 6 shows the calculated min plotted against
thermal conductivity measured in various disordered
solids at room temperature (Cahill et al., 1992). The
consistency between the calculation and measure-
ment is surprisingly well. The figure shows that
there exists a lower limit for  in solids, and an
ideal heat insulator cannot be designed.
The concept of minimum thermal conductivity
resembles that of minimum electrical conductivity
min as suggested by Mott (1972) and by Ioffe and
Regel (Gurvitch, 1981), in which the electron mean
free path cannot be shorter than the unit cell length
or the interatomic spacing. It is now generally agreed
that there is no min in real materials, and the
electrical conductivity can be infinitesimally small
1000 at low temperature in the presence of disorder
(Rosenbaum et al., 1980). This is known as the
Anderson localization (see Kramer and MacKinnon,
1993), which is understood as an interference
between an electron and the corresponding back-
scattered hole. Similar mechanism is theoretically
predicted and experimentally observed in photons,
334 Thermal Conductivity and Thermoelectric Power of Semiconductors

50 At low temperatures, magnetic moments localized on

the ions show a long-range-ordered state such as
Calculated conductivity (mW cm–1 K–1)

ZrO2 : Y ferromagnetic, antiferromagnetic, and ferrimagnetic

20 SiO2 orders. The elementary excitations from such orders
NaCl:CN Si YB66
are known as magnons, which correspond to phonons
Ca,KNO3 in a perfectly ordered lattice. Thus, it should be
10
CaF2:La
natural to think that magnons can carry heat as
CdGeAs2
phonons do.
5 Feldspar
Ge Quasi-1D magnetic insulator is particularly
As2S3 BaF2:La important. Theoretically, the energy current opera-
Se KBr:CN tor commutes the Heisenberg Hamiltonian in 1D
2 (Niemeijer and Vianen, 1971; Zotos et al., 1997).
This means that the energy current is conserved,
1 and travels ballistically through the sample. In fact,
1 2 5 10 20 50 such materials are found to show anomalously high
Measured conductivity (mW cm–1 K–1) thermal conductivity along the spin chain. Figure 7
Figure 6 Minimum thermal conductivity calculated from shows the thermal conductivity of Sr2CuO3
Equation (41) plotted as the measured thermal conductivity. (Sologubenko et al., 2000a). As shown in the inset,
From Cahill DG, Watson SK and Pohl RO (1992) Lower limit
this insulating oxide includes a corner-shared CuO4
to the thermal conductivity of disordered crystals. Physical
Review B 46: 6131–6140. plane along the b-axis, and is regarded as a 1D
Heisenberg antiferromagnet. The local moment on
which is known as the localization of light (Albada the Cu2þ behaves as S ¼ 1/2, and the exchange
and Lagendijk, 1985). Thus, there is no reason to energy J is evaluated to be 1300 K for polycrystals
deny the possibility of the localization of phonons, (Ami et al., 1995), and 2000 K for single crystals
which may give a thermal conductivity much lower (Motoyama et al., 1995). Contrary to the large J, the
than min (Venkatasubramanian, 2000). antiferromagnetic transition occurs below 4 K, owing
to the strong quantum fluctuation of S ¼ 1/2. As
shown in this figure, the thermal conductivity is
extremely high along the b-axis at room temperature,
1.09.3.3 Magnetic Semiconductors
while the thermal conductivity along the a-axis is
As is exemplified in transition-metal oxides, semicon- nearly the same as that along the c-axis. This
ductors including d- or f-electrons show magnetism. indicates that the magnetic excitation is responsible
Thermal conductivity (W m–1 K–1)

100

Cu
b O
Sr
κs

a Chain
c
b
a c T –1
10

10 100
Temperature (K)
Figure 7 Anisotropic thermal conductivity of the 1D magnetic insulator Sr2CuO3 along the a-, b-, and c-axis directions.
From Sologubenko AV, Felder E and Giannò K, et al. (2000a) Thermal conductivity and specific heat of the linear chain cuprate
Sr2CuO3: Evidence for thermal transport via spinons. Physical Review B 62: R6108–R6111.
 Thermal Conductivity and Thermoelectric Power of Semiconductors
for this high thermal conductivity. Other 1D spin
chains such as Sr14Cu24O41 and SrCuO2 show
similarly large thermal conductivity along the chain
direction. (Hess et al., 2001; Kudo et al., 2001;
Sologubenko et al., 2000b).
Figure 8 shows the mean free path of the
magnetic excitation evaluated from the Drude-like
expression:
1
mag ¼ Cmag vmag ,mag ð43Þ
3
As pointed out in the previous section, the Drude-
like expression for  is oversimplified. However, in
the case of magnetic excitation, we do not know
anything about the scattering process, and are unable
to calculate scattering times. The evaluated mean
free path is as large as 100 nm at low temperatures,
which strongly suggests that magnetic excitations in
this material travel over 250 unit cells without scat-
tering. Note that the lattice thermal conductivity is
less anisotropic; the anisotropy is basically deter-
mined by the anisotropy of the sound velocity
(Crommie and Zettl, 1991). Even in chain-like mate-
rials such as Sr2CuO3, the chemical bonds
perpendicular to the chain are similar to those in
the chain. As a result, the restoring force will be
more or less isotropic. Even in the presence of van
der Waals coupling in one direction, the anisotropic
ratio of  remains around 5–7 (Terasaki et al., 2004).
In this respect, the 300-K anisotropy between a- and
b-axis directions is remarkable, which may be used as
a heat guide in solids. More anisotropic thermal
103
Is (Å)
102
20 40 60 80 100 200
Temperature (K)
Figure 8 Mean free path of magnetic excitation in
Sr2CuO3. From Sologubenko AV, Felder E and Giannò K
et al. (2000a) Thermal conductivity and specific heat of the
linear chain cuprate Sr2CuO3: Evidence for thermal
transport via spinons. Physical Review B 62: R6108–R6111.
335
conductivity is seen in the spin-ladder copper oxide
Ca9La5Cu24O41, in which the a-axis thermal conduc-
tivity is 20 times larger than the c-axis one at 170 K
(Hess et al., 2001).
If the magnetic excitation dominates the heat con-
duction in magnetic materials, one may easily
imagine that external fields will change the thermal
conductivity. Such thermomagnetic effects are
widely seen in magnetic materials such as CuGeO3
(Ando et al., 1998), R2CuO4 (Sales et al., 2004), and
(La,Ca)MnO3 (Chen et al., 1997). Figure 9 shows the
thermal conductivity of the layered vanadium oxide
K2V3O8 (Sales et al., 2002). This particular oxide is an
antiferromagnetic insulator with the local moment
on V ions aligned along the a-axis. This antiferro-
magnetic order exhibits a spin-flop transition, in
which the critical field is less than 1 T. The thermal
conductivity suddenly increases above the critical
field, suggesting that the spin orientation determines
the heat conduction to some extent.
Like spin-valve/giant magnetoresistance effects in
multilayered ferromagnetic films (Zutic et al., 2004),
the magnetothermal effect observed here may be
applied to a thermal spin valve (Sales et al., 2004). At
the moment, it is remarkable only at low temperatures
at high fields (larger than 1 T). Even if a large response
in the spin thermal conductivity were discovered at
room temperature, the lattice thermal conductivity
would remain unchanged, and overlap the magnetic
contribution. Thus, the magnetothermal conductivity
could not be large at room temperature, in comparison
with magnetoconductivity.
6.5
+gμH
H//a, Q//a
6
κa (W m−1 K−1)
5.5 − gμH
5 H //c, Q//a
H = 0.55 T
4.5
4
T = 3.7 K
H = 0.95 T
3.5
0 0.5 1 1.5 2 2.5 3 3.5 4
H (T)
Figure 9 Thermal spin valve in K2V3O8. From Sales BC,
Lumsden MD, Nagler SE, Mandrus D and Jin R (2002)
Magnetic field enhancement of heat transport in the 2D
Heisenberg antiferromagnet K2V3O8. Physical Review
Letters 88: 095901.
336 Thermal Conductivity and Thermoelectric Power of Semiconductors
1.09.4 Thermoelectric Phenomena
1.09.4.1 The Seebeck Effect
An electron in solids carries an electrical current as an
elementary particle with a negative charge of e (<0).
Since an enormous number of electrons are at thermal
equilibrium in solids, they carry heat and entropy at
the same time. Thus in the presence of temperature
gradient, they can flow from a hot side to a cold side to
cause an electrical current. This implies a coupling
between thermal and electrical phenomena, which is
known as the thermoelectric effects.
The Seebeck effect is a phenomenon in which
electric field (E ¼ – ÑV ) is induced in proportion
to applied temperature gradient (ÑT ), defined by
ÑV ¼ Sð – ÑT Þ
where S is called the Seebeck coefficient (thermoelec-
tric power, or thermopower). We first discuss the
physical meaning of the Seebeck effect with a classical
electron-gas model proposed by Drude. Consider a
metal rod subject to a temperature gradient, as shown
in Figure 10. Suppose that the temperature at the left
side is T1, and at the right side is T2 (T1 > T2). Since
the average electron velocity is larger at T1, electrons
begin to diffuse from left to right just after the tem-
perature difference is given. Owing to the charge
neutrality, the side at T1 is positively charged, whereas
the side at T2 is negatively charged. This implies that
the metal rod behaves like a capacitor in the presence
of temperature gradient, which is the origin of the
thermoelectric voltage V. In a steady state, the energy
per electron is equal everywhere in the system, that is,
"ðT1 Þ þ eV ðT1 Þ ¼ "ðT2 Þ þ eV ðT2 Þ
is realized, where "(T) is the electron energy at
temperature T. In the limit of T1 ! T2, the Seebeck
coefficient S ¼ dV/dT reduces to
d"
eS ¼
dT
d"/dT is equal to the specific heat per carrier, and
Equation (46) further states that the Seebeck
coefficient is the entropy per electron. Note that
Hot Cold
T1 T2
Figure 10 A metal rod subject to the temperature gradient.
Reprinted from Sorell CC, Sugihara S, and Nowotny J (eds.)
(2005) Materials for Energy Conversion Devices. Cambridge,
UK: Woodhead Publishing: Figure 13.4.
the electron specific heat Cel is linear in T
R(i.e., Cel ¼ T),
R where the entropy is equal to
Cel dT/T ¼ dT ¼ Cel. Since the right-hand side
is positive, the sign of S is equal to the sign of the
carrier, and thus S is negative (positive) for electrons
(holes).
The Boltzmann equations (11) and (12) give an
explicit expression for the Seebeck coefficient. For
the sake of simplicity, let us consider a cubic system
in which all the transport parameters are reduced to
scalars. In the absence of current density, we rewrite
j ¼ 0 as
e
j ¼ e 2 K0 Eþ K1 ð – ÑT Þ ¼ 0 ð47Þ
T
Then, the electric field E is proportional to the
ð44Þ temperature gradient ( – ÑT ) as
1 K1
ÑV ¼ – E ¼ ð – ÑT Þ ð48Þ
eT K0
The Seebeck coefficient is written by
1 K1
S ¼
eT K0
Z  
@f0
– v2 ð"k – Þd3 k ð49Þ
1 @" "¼"k k
¼ Z  
eT @f0
– v2 d3 k
@" "¼"k k
Here, we used the definition of K1 and K0 given by
Equation (13). From this equation, one can under-
stand generic features of the Seebeck coefficient.
First, this is independent of scattering time in the
lowest order approximation. The scattering time 
ð45Þ appears in the numerator and the denominator at the
same time, so that it is cancelled when the k depen-
dence of  is neglected. Second, the Seebeck
coefficient should be zero when the energy disper-
sion is symmetric below and above the chemical
potential, because the integrand in the numerator is
ð46Þ
proportional to "k – . Thus, the Seebeck coefficient
of conventional metals is small, because the chemical
potential is in the middle of the valence band where
electrons and holes are almost symmetric. Third, the
Seebeck coefficient is usually less anisotropic than
the electrical and thermal conductivities. The
anisotropy comes from the velocity vk , which simul-
taneously appears in the numerator and the
denominator. This is qualitatively consistent with
Equation (46); the entropy per carrier is a scalar
quantity by definition, and accordingly it should be
isotropic in the lowest approximation.
 Thermal Conductivity and Thermoelectric Power of Semiconductors 337

First, we apply Equation (49) to a degenerate CeCu2

noninteracting Fermi gas. Thus, we assume the 10 CeCu2Si2
CeAl2
energy dispersion as CeColn2
CePt2Si2
h2 k2 1 NaxCoO2
CeRu2Si2
"k ¼ "k ¼ ð50Þ
2m NbSe2 UPd2Al3
and perform the Sommerfeld expansion to O(EF/kBT)2. La-214 Sr RuO 2 4
Then, we get the explicit expression of the Seebeck 0.1

S/T (T = 0) (µV K−2)

coefficient as
2 kB kB T 2 kB2 Dð0Þ Cel 0.01
S¼ ¼ T¼ ð51Þ
2 e EF 3 e n ne
−0.01
where n is the carrier density and D(0) the density of
states at EF (Ashcroft and Mermin, 1976). This Cu Pd
expression is a special form of Equation (46), and −0.1 (ET)2Br
Bi-2201
again shows that the Seebeck coefficient is the
entropy per carrier. (ET)2Cu(NSC)2 YbCu2Si2
−1 YbAl3
Figure 11 shows the Seebeck coefficient of
URu2Si2 YbCu4.5
Sr1xLaxPbO3 (Terasaki and Nonaka, 1999). The
YbCu4Ag
perovskite oxide SrPbO3 is a narrow-gap semicon- −10
ductor or a semimetal (Itoh et al., 1992), in which UBe13
electrons can be doped through the substitution of 1 10 100 1000
trivalent La3þ for divalent Sr2þ. As shown in the γ (mJ mol–1 K–2)
figure, the Seebeck coefficient is linear in T at low
Figure 12 The T-linear term of the Seebeck coefficient
temperatures. Using Equation (51), the carrier (S/T) plotted as a function of electron specific heat
density is evaluated from the T-linear coefficient of coefficient for various metals. Reproduced from Behnia K,
S, which is consistent with calculated values from the Jaccard D and Flouquet J (2004) On the thermoelectricity
La content. of correlated electrons in the zero-temperature limit.
Journal of Physics: Condensed Matter 16: 5187–5198.
Figure 12 shows the T-linear term of the Seebeck
coefficient (S/T) plotted as a function of electron
specific heat coefficient  for various metals
other hand, materials with large  values show large
(Behnia et al., 2004). The magnitude of S/T is of the
Seebeck coefficients. Such materials are called
order of 102 mV K2 for small , because a universal
heavy-fermion compounds in which localized
value of kB/je j ¼ 86 mV K1 is reduced by a factor of
f-electrons and conduction electrons are coupled
kBT/EF as is seen in the electron specific heat. On the
with the Kondo effect (Coleman et al., 2001). At low
temperatures, the localized f-electrons move
0 coherently with conduction electrons, and the local
moments vanish to show the largely enhanced Pauli
Thermopower (μV K–1)

paramagnetism. In a thermodynamic point of view,

–50
magnetic entropy due to the f-electrons is attached to
conduction electrons. Thus, the entropy per conduc-
x
–100 0.020 tion carrier is enhanced to cause the large Seebeck
0.012
0.010 coefficient. Figure 12 suggests that the electron
0.008 specific heat and the Seebeck coefficient are similarly
–150 0.006
0.004 enhanced, indicating close relationship between
0
0 100 200 300
the Seebeck coefficient and the thermodynamic
Temperature (K) quantities.
Phonon drag is a similar phenomenon to the
Figure 11 The Seebeck coefficient of Sr1xLaxPbO3.
From Terasaki I and Nonaka T (1999) Thermoelectric
enhanced Seebeck coefficient in heavy-fermion com-
properties of Sr1xLaxPbO3 (x < 0.02). Journal of Physics: pounds. At low temperatures, phonons and electrons
Condensed Matter 11, 5577–5582. are long-lived, and their distribution functions begin
338 Thermal Conductivity and Thermoelectric Power of Semiconductors

to be nonequilibrium in the presence of temperature than the bandwidth, it tends to zero as T ! 1. On

gradient, in which electrons and phonons can the contrary, the second term is rewritten with the
coherently move through the electron–phonon entropy s through an identity of thermodynamics as
interaction. As a result, the entropy of phonons over- follows:
laps the entropy of electrons, which enhances the  
 @s
thermoelectric power. Ziman (1976) called this – ¼ ð55Þ
T @N E;V
situation ‘thermoelectric power of lattice.’
In the case of metals in general, the integrand is Thus, the Seebeck coefficient is associated with the
finite only in the vicinity of the Fermi energy, thanks entropy per carrier, which is called the Heikes for-
to the Fermi statistics. By using the Sommerfeld mula written as
expansion, one can show that  kB @lng
  S¼ – ¼ ð56Þ
 2
@K0 eT e @N
K1 ¼ kB2 T 2 ð52Þ
3 @" "¼ where g is the total number of configurations
(Chaikin and Beni, 1976).
On the same assumptions, we may associate the
Let us calculate the Heikes formula for a simple
Seebeck coefficient with  as
conductor. Let the carrier number be N for N0 sites;
 
2 kB2 T @lnð"Þ then the total number of configurations g is equal to
S¼ ð53Þ
3 e @" "¼ N0 !
N CN0 ¼ ð57Þ
ðN0 – N Þ!N !
This is known as the Mott formula. Note that the
conductivity-like function (") in Equation (53) is a For macroscopically large number of N and N0, the
fictitious conductivity that a metal would show, if its Seebeck coefficient S of Equation (56) is
Fermi energy were equal to ". Do not forget that (")
kB N0 – N kB 1 – p
cannot be observed in real experiments. Thus, the S¼ ln ¼ ln ð58Þ
e N e p
Mott formula should be very carefully applied to
the analysis of real experiments (Ziman, 1976). where p ¼ N/N0 is the carrier concentration per site.
Nevertheless, this formula became quite popular, When the spin degrees of freedom are included, N0 is
and many experimentalists applied this to explain replaced by 2N0, and Equation (58) is modified as
the measured data without paying much attention kB 2N0 – N kB 2 – p
to the meaning of ("). Equation (53) includes S¼ ln ¼ ln ð59Þ
e N e p
logarithmic derivative of the density of states,
implying that the Seebeck coefficient is highly If the on-site Coulomb repulsion is strong, only one
sensitive to the shape of the Fermi surface; it can be electron can stand on each site. Then, the configura-
negative or positive depending on subtle change in tion from the spin degrees of freedom equals 2N, and
the curvature of the valence bands at EF. This is the Equation (58) is modified as
reason why this quantity has not been investigated kB N0 – N kB 2ð1 – pÞ
extensively in comparison with the Hall coefficient. S¼ ln 2 ¼ ln ð60Þ
e N e p
A complementary picture to the Mott formula is
the Seebeck coefficient in the high-temperature limit, There are a couple of features in the Heikes for-
where the one-electron energy is much smaller than mula. First, Equation (56) is independent of
the thermal energy. We can rewrite Equation (19) as temperature, because g is simply given by the combi-
nation of the sites on which the carriers exist. Second,
Z  
@f0 the Seebeck coefficient increases logarithmically with p
e 2 "k vk2  – d3 k
1 @" "¼"k  for p  1. This means that the Seebeck coefficient does
S¼ Z   – ð54Þ
eT @f 0 eT not change dramatically in comparison with conduc-
e 2 vk2  – d3 k tivity ( _ p). Third, we can derive Equation (56) in the
@" "¼"k
high-temperature limit, whenever one-electron energy
If we regard e 2 vk2 ð– @f0 =@"Þ as a weighting function, is defined. This means that the Heikes formula is
the first term will be reduced to h"ki/eT, where h. . .i correct, even if any types of interaction are present.
means the average with weights of e 2 vk2 ð– @f0 =@"Þ. Figure 13 shows the Seebeck coefficient of doped
Since the average of the one-electron energy "k is less pentacene films (Mühlenen et al., 2007). The numbers
 Thermal Conductivity and Thermoelectric Power of Semiconductors 339

600
104
2.8 × 1016 cm–3
Thermoelectric power (μV k–1)

500
103

–S (μV K–1)
400

102
300 1.7 × 1019 cm–3

200 101

100 1 3 5 7
2 4 6 8
0 Temperature (K)
180 200 220 240 260
Temperature (K)
Figure 13 The Seebeck coefficient of pentacene.
Reproduced from Mühlenen Av, Errien N, Schaer M, Bussac
M-N and Zuppiroli L (2007) Thermopower measurements on
pentacene transistors. Physical Review B 75: 115338.
in the figure represent different samples deposited on
different substrates. The Seebeck coefficient is
essentially independent of temperature, and the
magnitude is well understood from Equation (56).
The Seebeck coefficient of organic conductors is
reviewed by Kaiser (2001), in which lightly doped
organic conductors show temperature-independent
thermopower explained by the Heikes formula. The
Heikes formula also explains the Seebeck coefficient
of transition-metal oxide semiconductors such as
La1xSrxCrO3 (Karim and Aldred, 1979) and
La1xSrMnO3 (Palstra et al., 1997).
Let us consider the Seebeck coefficient in lightly
doped semiconductors. For a lightly doped semi-
conductor, the chemical potential is pinned near the
center of the band gap, and has a gap of 2Eg to the
bottom (top) of conduction (valence) band.
Substituting Eg for  in Equation (49), we get
n-type-doped SI
9
100
0 50 100 150 200 250 300
280 300
Figure 14 The Seebeck coefficients of lightly doped
silicon. From Weber L and Gmelin E (1991) Transport
properties of silicon. Applied Physics A 53: 136–140.
Gmelin, 1991). The Seebeck coefficient of the lightly
doped silicon is well described by Equation (62), in
which the Seebeck coefficient is linear in 1/T. The
magnitude is much larger than kB/jej ¼ 86 mV K1,
and the activation energy Eg evaluated with Equation
(62) is semiquantitatively consistent with the optical
band gap.
In the case of degenerate semiconductors, the
Seebeck coefficient is essentially the same as that of
a noninteracting Fermi gas given by Equation (51).
The Seebeck coefficient of the heavily doped silicon
shown in Figure 14 exhibits T-linear dependence
like those of metals. At high temperatures, minority
carriers are thermally excited to decrease the magni-
tude of the Seebeck coefficient, where the Seebeck
coefficient roughly obeys Equation (62). Figure 15
shows the Seebeck coefficient of the skutterudite
300
Seebeck coefficient (μV–1 K)

250 1212OB22
10OB22
1 K1 2NB13
S¼ 200 2NB9
eT K0
Z  
150
@f0 2
– v  ð"k Þ þ Eg Þd3 k ð61Þ
1 @" k
¼ Z   100
eT @f0 2 3
– v d k
@" k 50
p-type CoSb3
Eg 0
 ð62Þ
eT 300 400 500 600 700 800 900
Temperature (K)
In other words, each thermally excited electron will
acquire the activation energy, and carry large entropy. Figure 15 The Seebeck coefficient of the skutterudite
antimonide CoSb3. Reproduced from Caillat T,
Hence, the Seebeck coefficient is large compared with Borshchevsky A and Fleurial JP (1996) Properties of single
those of metals. Figure 14 shows the Seebeck coeffi- crystalline semiconducting CoSb3. Journal of Applied
cient of lightly and heavily doped silicon (Weber and Physics 80: 4442–4449.
340 Thermal Conductivity and Thermoelectric Power of Semiconductors
antimonide CoSb3 with various doping concentra-
tions (Caillat et al., 1996). At low temperatures,
the Seebeck coefficients decrease with decreasing
temperature, suggesting that the electrical conduc-
tion is dominated by degenerate carriers. In contrast,
the Seebeck coefficients have peaks and decrease
with increasing temperature at high temperatures,
showing that the minority carriers begin to be excited
thermally. The temperature at which the Seebeck
coefficients peak corresponds to a crossover from
the degenerate to intrinsic regions.
1.09.4.2 The Peltier and Thomson Effects
The Peltier effect is the reverse phenomenon of the
Seebeck effect; the electrical current flowing through
the junction connecting two materials will emit or
absorb heat per unit time at the junction to balance
the difference in the chemical potential of the two
materials. Thanks to this effect, an electronic refrigera-
tor can be made, which is known as the Peltier cooler.
The Peltier cooler has been applied to niche areas such
as infrared detectors, CPU coolers, wine cellars, etc.,
because the cooling power is lower than that of com-
pressor-based refrigerators. This technique is called
thermoelectrics, and is discussed in the next section.
Similarly to the Seebeck coefficient, the Peltier
coefficient  is defined as the coefficient of the ther-
mal current Q to the electrical current I, given by
Q ¼ I ð63Þ
or equivalently,  is defined as the coefficient of the
thermal current density to the electrical current
density
q ¼ j ¼ ð – ÑT Þ ð64Þ
where the current density is further expressed by the
electrical conductivity.
The Peltier coefficient is related to the Seebeck
coefficient. From Equations (11) and (12), we may
associate  with S as
 ¼ ST ð65Þ
This relationship is not specific to Equations (11) and
(12), but can be demonstrated from the first principle,
being known as Onsager’s reciprocal theorem.
Thanks to this relationship, the Peltier coefficient
has been rarely measured. The amount of heat is
difficult to measure precisely than the temperature
difference, so that the Seebeck coefficient is much
easier to measure.
The Harman method is known as a unique
technique to measure thermal conductivity using
the Peltier effect (Harman, 1958). Suppose that a
sample is hung by electrical leads in vacuum at a
temperature T. Upon a steady current I0, the Peltier
heat I0 is generated at one current contact to the
sample, and is absorbed at the other. As the sample is
in vacuum, that is, thermally isolated, the Peltier heat
is finally balanced by a back flow of thermal current
through the sample, and causes a temperature
difference T between the contacts to satisfy
K T ¼ I0 ð66Þ
where K is the thermal conductance of the sample.
If the Seebeck coefficient is measured in advance, the
Peltier coefficient will be given by  ¼ ST. Thus, K
can be obtained from the observed T. Figure 16
shows an example of T observed in the Harman
method (Satake et al., 2004). The temperatures at the
left side (TL) and those at the right side (TR) change
with external currents. As shown in the inset, the
antisymmetric part of the data is plotted to remove
the contribution from the Joule heating (which is
proportional to I0 2 ), which is linear in external
current, as expected from the Peltier effect.
The third thermoelectric effect is the Thomson
effect. In the presence of temperature gradient and
external current, thermal current generates in pro-
portion to the temperature gradient and external
current given as
@T
qx ¼ – T jx ð67Þ
@x
ΔT(l 0)−ΔT(–l 0) (K)
4
2
3
2 300 K
ΔT = TR − TL (K)
1 1
0
0 5 10 15
l 0 (mA)
0 100 K
−1
−10 0 10
Current l0 (mA)
Figure 16 The temperature difference by the Peltier effect
in the sample hung in vacuum. From Satake A, Tanaka H,
Ohkawa T, Fujii T and Terasaki I (2004) Thermal conductivity
of the thermoelectric layered cobalt oxides measured by the
Harman method. Journal of Applied Physics 96: 931–933.

where  T is the Thomson coefficient. This effect is
understood through the temperature dependence of
the Seebeck coefficient. Suppose that the tempera-
ture of the left half of a rod-like sample is T1, and that
of the right half is T2. This is equivalent to two rods
with different Peltier coefficients of T1S(T1) and
T2S(T2) welded at the edge. Then, the welded
junction will have the Peltier heat with respect
to external current. Eventually, the Thomson
coefficient is written as
T ¼ T
The measurement of the Thomson coefficient is
important, because the absolute Seebeck coefficient
can be obtained from  T. Note that the thermoelec-
tric voltage V is experimentally observed in the
open-circuit condition as
V ¼ Slead ðT0 – T1 Þ þ Ssample ðT1 – T2 Þ
þSlead ðT2 – T0 Þ
¼ ðSsample – Slead ÞðT1 – T2 Þ
where T0 is the ambient temperature, T1 and T2 are
the temperatures at the edges of the sample. Ssample
and Slead are the Seebeck coefficients of the sample
and the voltage leads, respectively. This indicates that
the Seebeck coefficient is always measured as the
difference from the Seebeck coefficient of the leads.
Figure 17 shows the Thomson coefficient of
various metals (Lander, 1948). As discussed above,
the Seebeck coefficient is an entropy per carrier.
20
Thomson coefficient (micro V K–1)
0 Au
−20
−40
−60
300 900
Temperature (K)
Figure 17 The Thomson coefficient of metals.
Reproduced from Lander JJ (1948) Measurements of
Thomson coefficients for metals at high temperatures and
of Peltier coefficients for solid–liquid interfaces of metals.
Physical Review 74: 479–488.
Thermal Conductivity and Thermoelectric Power of Semiconductors 341
Recalling that the entropy goes to zero at 0 K (the
third law of thermodynamics), we can assume that
the Seebeck coefficient also goes to zero at 0 K, and
calculate the absolute Seebeck coefficient from the
measured Thomson coefficient.
1.09.4.3 The Galvanomagnetic Effects
A conduction electron is coupled with external mag-
netic fields through the Lorentz force, and is
dS consequently deflected along the direction perpen-
ð68Þ dicular to both the current and magnetic field. The
dT
deflected electrons are accumulated to one side of
the sample to cause the transverse voltage, and cancel
the Lorentz force in the steady state. This is known as
the Hall effect, and the transverse voltage is called
the Hall voltage. Similarly to this, the electron in the
presence of temperature gradient will be deflected to
the direction perpendicular to both the temperature
ð69Þ gradient and the magnetic field, and eventually cause
the transverse voltage. This is known as the Nernst
ð70Þ effect, a typical galvanomagnetic effect. The Nernst
coefficient N is defined as
@T
Ey ¼ NBz ð71Þ
@x
where Bz is the external magnetic field applied along
the z-direction, and the temperature gradient is along
the x-direction.
The Nernst effect is exceptionally large in semi-
metals (Li and Rabson, 1970). This is a similar
situation of the classical magnetoresistance which
has a large magnitude in semimetals (Clayhold,
1996). In particular, the high-mobility semimetals
have the Nernst voltage as large as the Seebeck
Ag
voltage in magnetic fields of several teslas.
Cu +
Figure 18 shows the Nernst voltage of Bi1xSbx in
W – various magnetic fields (Li and Rabson, 1970). For
Mo small magnetic fields less than 1 T, the Nernst
Pt voltage exceeds 1 mV K1 at low temperatures.
Another class of materials exhibiting large Nernst
coefficients is a superconductor in the mixed state.
Needless to say, a superconductor is a material that
Pd
exhibits zero resistivity below the superconducting
transition temperature Tc. External magnetic field
above the lower critical field Bc1 can penetrate a
1500 2100
type II superconductor as quantized magnetic fluxes.
This state is called the mixed state, in which the
quantized fluxes form a triangular lattice. The flux
lattice is squeezed by external current through the
Lorenz force, and begins to flow above a critical
current density. Similarly to this, the flux can flow
342 Thermal Conductivity and Thermoelectric Power of Semiconductors

2.5 Nernst voltage is observed from the temperature

77 K above which the fluxes can move, to the temperature
2 below which the fluxes can exist. Xu et al. (2000)
found the large Nernst signal far above Tc in the
high-temperature superconductors, which they
NB (μV K–1)

1.5 114 K
ascribed to the phase fluctuation of the supercon-
188 K ducting order parameter far above Tc. A similar
1
large Nernst signal is observed in organic conductors
(Nam et al., 2007).
0.5
Te-doped Bi88Sb12 300 K

0 1.09.5 Thermoelectrics
0 0.2 0.4 0.6
B (T)
Figure 18 The Nernst voltage of the high-mobility
semimetal Bi1xSbx. From Li SS and Rabson TA (1970) The
Nernst and the Seebeck effects in Te-doped Bisingle bond
Sb alloys. Solid State Electronics 13: 153–160.
in the presence of temperature gradient (Huebener,
1995) from high- to low-temperature side. According
to Faraday’s electromagnetic induction, the voltage
will be generated in the direction of B  ð – ÑTÞ,
which is nothing but the Nernst voltage.
Figure 19 shows the Nernst voltage NB in the
mixed state of the high-temperature superconductor
YBa2Cu3O7 (Huebener, 1995). With increasing tem-
perature, the signal in a fixed field sharply rises above
a certain temperature, reaches a maximum, and then
decreases slowly. The external field enhances the
range in which the Nernst signal is observable. This
is qualitatively explained as follows: the quantized
fluxes are frozen at sufficiently low temperatures,
and cannot exist far above Tc. Consequently, the
0.8 1
1.09.5.1 Thermoelectric Devices
As discussed in the previous section, the Seebeck
and Peltier effects are cross-correlations between
electricity and heat carried by an electron in
solids. When the Seebeck coefficient and the
electrical conductivity are large in a material, such
a material can convert electric energy into heat and
vice versa. This is schematically illustrated in
Figure 20. A rod of a material subject to the
temperature gradient causes the thermoelectric
voltage V ¼ ST across the sample, where T is
the temperature difference between the edges of
the sample, and S is the Seebeck coefficient. If the
voltage V is sufficiently high, the rod works as a
battery, and generates electricity at an external
load connected to the rod. In this situation,
the thermoelectric voltage corresponds to the open-
circuit voltage of the battery, and the resistance of the
rod corresponds to the internal resistance of the

3
H=1T
H=2T
Current
H=3T
Ey/∇xT (μV K–1)

2 H=4T
H=6T
H=8T
H = 10 T
H = 12 T
1
Sample

0
70 80 90 100 110
Temperature (K)
Figure 19 The Nernst voltage of the high-temperature
superconductor YBa2Cu3O7 in the mixed state. Figure 20 A schematic picture of thermoelectric power
Reproduced from Huebener RP (1995) Superconductors generation. Reprinted from Narlikar AV (ed.) (2005) Layered
in a temperature gradient. Superconductor Science and Cobalt oxides as a thermoelectric material in Frontiers in
Technology 8: 189–198. magnetic Materials. pp 327–346. Springer: Berlin: Figure 1.
 Thermal Conductivity and Thermoelectric Power of Semiconductors 343

battery. Such a material is called a thermoelectric coefficient, and the net thermal conductance of the
material, and the device made from is called a ther- device, respectively. For the sake of simplicity, we
moelectric device. One can find a good review on assume that all the parameters of the device are
thermoelectrics given by Mahan (1997). independent of temperature. At the junction
Actually, Figure 20 is an oversimplified picture (cold side), the pumped heat per unit time QC is
for the thermoelectric device. Since the current lead given by
is usually a good conductor of heat, the heat applied
1
at the left edge will flow through the lead, and will QC ¼ STC I – RI 2 – K T ð72Þ
2
not generate sufficient temperature difference and,
in the worst case, may damage the load. To avoid where the second term is the Joule heat in the sample
this, one should make a pair of rods as shown in (we assume that a half of the heat goes to each side)
Figure 21. This structure is nothing but a thermo- and the third term is the back flow of the thermal
couple, and the heat applied at the junction now current by the temperature difference. Similarly, at
flows through the pair of thermoelectric legs. In this the hot side, the emitted heat per unit time QH is
given by
respect, the thermoelectric device is a thermocouple
with an ability to generate electricity, as shown in 1
QH ¼ STH I þ RI 2 – K T ð73Þ
Figure 21(b). Obviously, the pair should be a pair 2
of n- and p-type materials to maximize the Thus, the total work per unit time is given by
thermoelectric voltage. Another requirement is that
the thermal conductivity should be as low as possible W ¼ QH – QC ¼ ðST þ IRÞI ð74Þ
to maximize the temperature difference across Equation (74) means that the work to refrigerate is
the legs. equal to the voltage drop of the device in addition to
The thermoelectric device does not only generate the thermoelectric voltage.
electric power from heat, but also converts electric The heat balance at the hot and cold sides in the
power into heat through the Peltier effect, that is, it thermoelectric power generator shown in
cools the junction with external current, as shown Figure 21(b) is similarly given by
in Figure 21(a). This is known as thermoelectric
refrigeration or Peltier cooling. Thanks to the 1
QH ¼ STH I – RI 2 þ K T ð75Þ
Onsager relation of Equation (65), the Peltier 2
coefficient  is equal to the Seebeck coefficient 1
QC ¼ STC I þ RI 2 þ K T ð76Þ
multiplied by absolute temperature. Thus, materials 2
with the large Seebeck coefficient near or below By connecting an external load Rext ¼ xR, we find the
room temperature can be used for thermoelectric current I ¼ ST/(1 þ x)R. Then, the output power P
refrigeration. is equal to
We begin with the heat balance of the thermo-
electric cooling device shown in Figure 21(a). Let R, ðST Þ2 x
P ¼ IV ¼ ð77Þ
S, and K be the net resistance, the net Seebeck R ð1 þ xÞ2

(a) (b)
p-type

TC TH TH TC

xR

QC QH QH QC

n-type
Figure 21 A schematic picture of thermoelectric devices: (a) thermoelectric refrigerator and (b) thermoelectric power
generator. Reprinted from Sorell CC, Sugihara S, and Nowotny J (eds.) (2005) Materials for Energy Conversion Devices.
Cambridge, UK: Woodhead Publishing: Figure 13.2.
344 Thermal Conductivity and Thermoelectric Power of Semiconductors

pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
which takes a maximum Pmax ¼ (ST)2/4R at x ¼ 1, TC 1 þ ZT – TH
max ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ð86Þ
that is, Rext ¼ R. Pmax is determined by the following T ð 1 þ ZT þ 1Þ
material parameter:
S2 after some calculations. For the power generation,
¼ S2 ð78Þ

the efficiency  is given as
which is called the (thermoelectric) power factor. W
Here, we evaluate the maximum heat absorption ¼ ð87Þ
QH
of the cooling device under the conditions of
constant TH and TC. Then, a necessary condition of VI
¼ ð88Þ
dQC/dI ¼ 0 gives the optimum current I0 ¼ STC/R. STH I – RI 2 =2 þ K T
By substituting I0 into Equation (72), we have xT
¼ ð89Þ
2 ð1 þ xÞT þ ð1 þ xÞ2 =Z þ xT =2
ðSTC Þ
QCmax ¼ – K T ð79Þ
2R
  By taking d/dx ¼ 0, we find that the maximum
ðSTC Þ2 efficiency is
¼K – T ð80Þ
2RK pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
T ð 1 þ ZT – 1Þ
Then, we introduce the figure of merit Z defined by max ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ð90Þ
TH 1 þ ZT þ TC
S2 S2 S2
Z¼ ¼ ¼ ð81Þ
RK
  According to Equations (86) and (90), material
properties are associated with the conversion
and rewrite QCmax as
  efficiency through ZT. This is reasonable, because
ZTC 2 the conversion efficiency and ZT are both dimen-
QCmax ¼K – T ð82Þ
2 sionless quantities. In this respect ZT is the most
Thus, the maximum heat absorption is directly important parameter for thermoelectrics, and is
proportional to Z (or the power factor) for T ¼ 0. called the dimensionless figure of merit.
Next, we evaluate the lowest achievable tempera- We can take some notes on the above results.
ture TCmin under the conditions of constant QC and First, max given by Equation (86) and max given
TH. A necessary condition of dTC/dI ¼ 0 gives the by Equation (90) are reduced to the Carnot efficiency
optimum current I1 ¼ STCmin =R. By substituting I1 as ZT ! 1. This is reasonable, because thermoelec-
into Equation (72), we have tric energy conversion is a conversion through the
electron transport, which is an irreversible process
ðSTCmin Þ2 QC accompanying the Joule heat. Second, as shown in
T ¼ – ð83Þ
2KR K Figure 22, the efficiency  is larger for larger ZT and
The maximum temperature difference (i.e., lowest T. Considering that the conversion efficiency of a
achievable temperature) is again directly propor- solar battery is 10–15%, we think that a similar  is
tional to Z for QC ¼ 0. expected for practical use. For ZT̄ < 1, Equation (90)
In addition, we evaluate the maximum efficiency. can be expanded in terms of ZT̄. In the lowest order,
The energy conversion efficiency for a cooling max is
device is characterized by the coefficient of perfor-
mance (COP): max  ZðTH – TC Þ=4 ð91Þ

QC STC I – RI 2 =2 – K T
¼ ¼ ð84Þ Thus, Z(TH  TC) ¼ 0.4 is needed for 10%
W ðST þ IRÞI
efficiency. For a larger ZT, max tends to saturate,
Taking d/dI ¼ 0, we obtain the optimized current I2: and 10% corresponds to Z > 3  103 K1 for
T ¼ 300 K in Figure 22, which corresponds to
ST
I2 ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ð85Þ ZT ¼ 1.8 at 600 K. Third COP of a commercial
R 1 þ ZT – 1
refrigerator is 1.2–1.3, which corresponds to
where T ¼ ðTH þ TC Þ=2. By substituting I2 into , ZT ¼ 3–4. Thus, much improvement in ZT is needed
we find to replace a freon-gas refrigerator.
 Thermal Conductivity and Thermoelectric Power of Semiconductors 345

30  increases. The former is proportional to – ln n, while

Z TL = 300 K the latter is proportional to n. As a result, the carrier
1 × 10–3 K–1 TH = ΔT + TL concentration takes an optimum value for maximizing
2 × 10–3 K–1 the power factor S2. In other words, conventional
Efficiency (%)

20 3 × 10–3 K–1
4 × 10–3 K–1
10
0 materials are high-mobility semiconductors.
0 100 200 300 400
ΔT (K)
Figure 22 The conversion efficiency plotted as a function
of temperature difference. The cold temperature is set to
300 K. Reprinted from Sorell CC, Sugihara S, and Nowotny J
(eds.) (2005) Materials for Energy Conversion Devices.
Cambridge, UK: Woodhead Publishing: Figure 13.2.
1.09.5.2 Thermoelectric Materials
Thermoelectric materials are characterized by ZT,
that is, they show large Seebeck coefficient, high con-
ductivity, and low thermal conductivity at the same
time. Such requirements are difficult to be satisfied,
because the three parameters are functions of carrier
concentration, which cannot be tuned independently.
Figure 23 schematically shows how the three para-
meters depend on carrier concentration (Snyder and
Toberer, 2008). The Seebeck coefficient S decreases
with carrier concentration n, whereas the conductivity
1 700–800 K, and has been used for thermoelectric
S σ
ZT
Parameters (a. u.)
metals have very small Seebeck coefficient, while con-
ventional semiconductors have very low conductivity.
Hence, an optimum carrier concentration is evaluated
to be 1019–1020 cm3 that is a typical carrier concen-
tration of degenerate semiconductors. Once the carrier
concentration is set to be the optimum value, the only
way to maximize the conductivity is to maximize the
mobility. In fact, the state-of-the-art thermoelectric
500 600
In the case of degenerate semiconductors, the
lattice thermal conductivity is predominant to the
electron thermal conductivity. The electron thermal
conductivity is easily evaluated from the conductivity
through the Wiedemann–Franz law given by
Equation (23). Typical conductivity of thermoelectric
materials is 500–1000 S cm1 at room temperature,
which corresponds to el ¼ 0.4–0.8 W mK1. Good
thermoelectric materials show a low thermal conduc-
tivity of 2–3 W mK1, so that it has been a central
issue how to reduce the lattice thermal conductivity.
Figure 24 shows ZT for various thermoelectric
materials (Mahan, 1997). Thermoelectric materials
so far used for practical applications are Bi2Te3,
PbTe, and Si1xGex. They show ZT  1 at optimum
temperatures. n-Type BiSb is superior at low
temperatures, but has no p-type counterpart. Bi2Te3
shows the highest performance near room tempera-
ture, and is used for Peltier coolers commercially
available. PbTe shows the highest performance near
κ power generators operating at moderately high
temperatures. Si and Ge are poor thermoelectric
materials at room temperature because of the high

thermal conductivity. A solid solution effectively

reduces the lattice thermal conductivity, and ZT is
0.5 maximized above 1200 K. Si1xGex has been used for
the electricity source in space crafts, in which the
decay from Pu works as a heat source.
Above all, Bi2Te3 is a prototypical thermoelec-
tric material (Goldsmid et al., 1958). Reflecting the
high mobility, the resistivity is 1–2 m cm at room
0
temperature. It decreases with decreasing tempera-
1018 1019 1020 1021 ture, showing that the carrier concentration is in
Carrier concentration (cm–3) the range of degenerate semiconductors. The
Seebeck coefficient is basically linear in T, indicat-
Figure 23 Conductivity (), the Seebeck coefficient (S),
thermal conductivity (), and ZT plotted as a function of the ing that the electrons are degenerate to have the
carrier concentration. From Snyder GJ and Toberer ES (2008) Fermi energy larger than the thermal energy.
Complex thermoelectric materials. Nature Materials 7: 105–114. Above room temperature, in contrast, the Seebeck
346 Thermal Conductivity and Thermoelectric Power of Semiconductors
(a)
1 cage are named rattling, and rattler, respectively.
PbTe
Bi2Te3
Si1–x Gex
ZT
0.5
p-type
0 ZT >1, which is a prototypical success in the material
(b) BiSb Si1–x Gex
1 Bi2Te3
PbTe
ZT
0.5
n-type
0 CeFe3CoSb12, the two vacant subcells are filled with
0 500 1000
Temperature (K)
Figure 24 The dimensionless figure of merit ZT for various
thermoelectric materials. Reprinted from Sorell CC,
Sugihara S, and Nowotny J (eds.) (2005) Materials for
Energy Conversion Devices. Cambridge, UK: Woodhead
Publishing: Figure 13.5, and Narlikar AV (ed.) (2005) Layered
Cobalt oxides as a thermoelectric material in Frontiers in
magnetic Materials. pp 327–346. Springer: Berlin: Figure 3.
coefficient takes a maximum in magnitude, and
decreases with increasing temperature. The resis-
tivity also takes a maximum near the same
temperature. These results are understood in
terms of thermally excited minority carriers. The
Seebeck coefficient is 200 mV K1 at room tem-
perature, which is expected to give maximum ZT
at room temperature. The thermal conductivity is
2 W mK1 at room temperature, in which the
electron thermal conductivity is evaluated from
the Wiedemann–Franz law to be 20–30% of the
total. The low thermal conductivity comes from
the low sound velocity due to heavy atoms, and
point defect scattering due to solid solutions.
Motivated by the discovery of Bi2Te3 in mid-
1950s, many thermoelectric materials were synthe-
sized, but ZT did not exceed unity for 30 years or
more. The situations changed in the 1990s, since
Slack (1995) proposed a concept of phonon glass
and electron crystal (PGEC). When an atom is
weakly bound in an oversized atomic cage, it will
vibrate independently from the host to cause large
local vibrations. This vibration and the atom in the
Compound with such atoms will have a poor thermal
conduction like a glass and a good electric conduc-
tion like a crystal, in which ZT is evaluated to be 3–4
at maximum.
An experimental manifestation of PGEC is seen in
the filled skutterudite CexFe3CoSb12 (Sales et al.,
1997). This is the first unambiguous example of
search in the 1990s. The unit cell of the unfilled
skutterudite CoSb3 consists of the eight subcells
whose corners are occupied by Co atoms. Six subcells
out of the eight are filled with Sb plackets, forming the
valence band. According to the band calculation,
CoSb3 is a narrow-gap semiconductor with an indirect
gap of 0.5 eV (Singh and Pickett, 1994), and the hole
mobility of CoSb3 exceeds 2000 cm2 V1 s1 at 300 K
(Caillat et al., 1996). In the filled skutterudite
Ce. In order to compensate the charge valance, six Fe
atoms are substituted for the eight Co sites, because
Ce usually exists as trivalent. The most remarkable
feature of this compound is that filled Ce ions reduce
the lattice thermal conductivity by several times lower
than that for the unfilled skutterudite CoSb3 (Sales
et al., 1997), in which Ce ions seem to work as rattlers.
It is still controversial whether the rattling motion
really occurs in the filled skutterudite. Although a
localized phonon mode, like the Einstein mode, is
suggested from the specific heat measurement
(Keppens et al., 1998), neutron scattering shows that
a localized mode is not anharmonic (Viennois et al.,
2004). Geometrically, Ce is located in a wide space,
but recent band calculations suggest that the rare-
earth ions are considerably hybridized with adjacent
anions (Harima et al., 2002). The hybridization is
regarded to be an origin for unconventional physical
properties of this class of materials such as super-
conductivity in PrCo4Sb12 (Bauer et al., 2002).
The rattling motion is more clearly observed in
the clathrate compounds A6Ga16Ge30 (A ¼ Sr, Ba,
Eu) (Nolas et al., 1998). The crystal structure is
shown in Figure 25. The Ge and Ga ions form a
complicated network composed of face-shared poly-
hedra. The Ge–Ge bond angle is close to the angle of
sp3 orbitals (120 ), so that the electric properties are
expected to be similar to crystalline Ge. There exists
a large space in the polyhedron cage, in which Sr, Ba,
and Eu are filled to rattle. The neutron diffraction
experiment has revealed that Sr ions in the clathrate
compound have quadruple minimum in the cage, and
 Thermal Conductivity and Thermoelectric Power of Semiconductors 347

Ba8Ni6Ge40
Ba8Zn8Ge38 Type 1
2.0
Ba8Cu6Ge40 Ba8Al16Si30 clathrates

κ L (150 K) (W K−1m−1)
Ba8Ga16Ge30 Cs8Zn4Sn42

Cs8Sn44
1.5 Ba8Ga16Si30

Rb8Zn4Sn42
Rb8Ga16Sn38
Sr8Ga16Si30
Sr8Ga16Ge30
1.0
Ba8In16Ge30

n1 Ba8In16Ge28Sn2
β-Ba8Ga16Sn30 Eu8Ga16Ge30
p1
0.5
Figure 25 The crystal structure of the clathrate compound 1.2 1.3 1.4 1.5 1.6 1.7
A6Ga16Ge30. The large dots correspond to A ions, and the Guest free space (Å)
Ga and Ge ions form the face-shared polyhedral cages.
Figure 27 The thermal conductivity as a function of spacing
Reproduced from Suekuni K, Avila MA, Umeo K, et al. (2008)
in the rattling site. From Suekuni K, Avila MA, Umeo K, et al.
Simultaneous structure and carrier tuning of dimorphic
(2008) Simultaneous structure and carrier tuning of dimorphic
clathrate Ba8Ga16Sn30. Physical Review B 77: 235119:
clathrate Ba8Ga16Sn30. Physical Review B 77: 235119.
Figure 1(b).

the cage size is larger for larger x, one can conclude

the lattice dynamics is anharmonic (Zuric et al., 2004).
The lattice thermal conductivity is as low as that of
amorphous Ge, being much reduced from that of
crystalline Ge (Nolas et al., 1998). Thanks to this,
ZT reaches near unity at high temperature.
Figure 26 shows the lattice thermal conductivity of
the clathrate compound Sr6Ga16Si30xGex (Suekuni
et al., 2007). The lattice thermal conductivity system-
atically decreases with increasing Ge content, showing
the maximum at x ¼ 0 and the minimum at x ¼ 30.
This indicates that disorder from the solid solution
does not dominate the thermal conductivity. Since
that the degree of the intracage vibration of Sr reduces
the thermal conduction in this system.
Figure 27 shows the thermal conductivity plotted
as a function of the guest free space for various
clathrate compounds (Suekuni et al., 2008). The
guest free space is defined as Rcage  rhost  rion,
where Rcage is the radius of the cage, rhost is the
covalent radius of cage atom (Ga, Ge, Sn, Si, etc.),
and rion is the ionic radius of the rattler (Sr, Eu, Ba,
etc.). Regardless of the elements, the thermal
conductivity is roughly determined by this length.
This universal behavior strongly suggests that
rattling can be controlled in this system.

x=0
1.09.5.3 Oxide Thermoelectrics
κ L (W K–1 m–1)

1 5 As discussed above, the state-of-the-art thermoelectric

materials are Bi2Te3, PbTe, and Si1xGex, all of which
20
are degenerate semiconductors of high mobility. Since
Te is scarce in earth, toxic, and volatile at high tem-
26 perature, the application of Bi2Te3 and PbTe has to be
limited to a niche area. In contrast, oxides are chemi-
30 Sr8Ga16Si30–xGex cally stable at high temperature in air, and thus oxide
thermoelectrics is expected to be used in much wider
0.1 area. However, most of the oxide semiconductors
1 10 100
T (K) show very low mobility, and their use has been
thought to be out of the question.
Figure 26 The lattice thermal conductivity of the clathrate Since the large Seebeck coefficient and the low
compound Sr6Ga16Si30xGex. The dotted curves are the
resistivity in a NaCo2O4 (NaxCoO2) single crystal
fitting curves. Reproduced from Suekuni K, Avila MA, Umeo
K, and Takabatake T (2007) Cage-size control of guest were discovered (Terasaki et al., 1997), some kinds of
vibration and thermal conductivity in Sr8Ga16Si30xGex. oxides are found to be thermoelectric materials
Physical Review B 75: 195210. (Koumoto et al., 2006). Following NaCo2O4,
348 Thermal Conductivity and Thermoelectric Power of Semiconductors

Ca3Co4O9 (Funahashi et al., 2000), (Bi,Pb)2Sr2Co2O8
(Itoh and Terasaki, 2000), TlSr2Co2Oy (Hébert et al.,
2001), and (Pb,Co)Sr2Co2Oy (Maignan et al., 2002)
have been found to show good thermoelectric
performance. Some single crystals show even
ZT >1 at 1000 K. As shown in Figure 28, the
CdI2-type hexagonal CoO2 layer is common to
these cobalt oxides, which should be a key ingredient
for the unusually high thermoelectric performance of
the layered cobalt oxides.
Figure 29 shows the thermoelectric parameters of
the three kinds of the layered cobalt oxides. In the
upper panel the resistivity of the three cobalt oxides
along the in-plane direction is shown. The most-
conducting compound is NaxCoO2, where a low
special case of Equation (56).
of 200 m cm at 300 K decreases in a metallic-like
fashion with decreasing temperature down to 1.5 K.
This is as conductive as the superconducting Cu
oxides, meaning that the layered cobalt oxide is one
of the most conductive layered oxides. The other two
compounds show fairly large
of 1–10 m cm at 300 K reduced to
with an upturn below about 50 K. The Seebeck coeffi-
cient S of the three cobalt oxides along the in-plane
direction is shown in the middle panel. The magnitude
of S is as large as 100–150 mV K1 at 300 K, being
comparable with that of conventional thermoelectric
semiconductors. The thermal conductivity of the three
cobalt oxides along the in-plane direction is shown in
the lower panel. Clearly, a more complicated block
layer shows lower , implying that  is predominatly
determined by the block layer. High  was thus
far expected for oxides because of the light mass of
oxygen, which is not always true in the layered
cobalt oxides.
As an origin of the large Seebeck coefficient,
Koshibae et al. (2000) proposed an extended Heikes
formula for transition-metal oxides:
kB gA p
S¼ ln ð92Þ
Q gB 1 – p
where gA and gB are the degeneracy of the electron
configuration of A and B ions, Q is the charge differ-
ence between A and B ions, and p is the atomic
content of the A ion. Since
gA p
kB ln ð93Þ
gB 1 – p
is equal to the entropy per carrier, Equation (92) is a
Let us apply the above formula to NaCo2O4.
Assuming that Na and O exist as Naþ and O2 in
NaCo2O4, we expect that Co ions exist as Co3þ and
Co4þ with a ratio of Co3þ:Co4þ¼1:1. Then, p for
NaCo2O4 is equal to 0.5, and S for p  0.5 is simply
kB gA
S¼ ln ð94Þ
Q gB
Magnetic measurements reveal that the Co4þ and
Co3þ ions are in the low spin state in NaCo2O4.
The configuration of the low-spin-state Co3þ is
(t2g)6, whose entropy is zero. On the other hand,
the low-spin-state Co4þ has a hole in the t2g states,
which is sixfold degenerate (two from spin and
three from t2g orbitals) to carry large entropy of
kB ln6. Suppose that electric conduction occurs by
exchanging Co3þ and Co4þ. Then, a hole on Co4þ

Co

Co SrO

BiO
CaO

CaO BiO

Na0.5 CaO SrO

Co Co

NaCo2O4 Ca3CO4O9 Bi2Sr2Co2Oy

Figure 28 Crystal structures of the layered cobalt oxides. Reprinted from Sorell CC, Sugihara S, and Nowotny J (eds.) (2005)
Materials for Energy Conversion Devices. Cambridge, UK: Woodhead Publishing: Figure 13.8, and Narlikar AV (ed.) (2005)
Layered Cobalt oxides as a thermoelectric material in Frontiers in magnetic Materials. pp 327–346. Springer: Berlin: Figure 5.
 Thermal Conductivity and Thermoelectric Power of Semiconductors 349

103 temperature limit. NaCo2O4 shows good metallic

(a)
conduction, suggesting that the electronic states
102 should be discussed in an itinerant picture. Singh
Ca3Co4O9
ρ (mΩ cm)

101 (2000) pointed out that the large thermopower can

be explained from the band calculation. Kuroki and
100 Bi2Sr2CO2Oy
Arita (2007) showed that the band structure of
NaxCoO2 NaxCoO2 is special in the sense that the top of
10–1
the conduction band is flattened like a pudding
10–2 mold. Such structure breaks electron–hole symme-
(b) try at EF, and gives high Seebeck coefficient with
150 Ca3Co4O9
high conductivity. Takeuchi et al. (2004) showed
Bi2Sr2CO2Oy that the Seeback coefficient calculated from the
S (μV K–1)

100
observed photoemission spectra quantitatively
reproduces the experimental results. Ishida et al.
50 NaxCoO2
(2007) measured the temperature dependence of
the chemical potential from the photoemission
0
spectra, and found that the electronic states gradu-
8 (c) ally change from a high-temperature localized
NaxCoO2
picture to a low-temperature itinerant picture.
6
κ (W mK–1)

Although the layered cobalt oxides are good

4 Ca3Co4O9
2
Bi2Sr2CO2Oy
0 of Co2þ and Co3þ will be n-type, but such cobalt
0 100 200
T (K)
Figure 29 Resistivity (
), Seebeck coefficient (S), and Nagao et al., 2007).
thermal conductivity () of the layered cobalt oxides
(Koumoto et al., 2006).
can carry a charge of þje j with entropy of kB ln6,
which causes a large Seebeck coefficient of kB ln6/jej
(150 mV K1). This is close to the high-
temperature value of S. Note that carriers in semi-
conductors have no such internal degrees of freedom;
they can only carry entropy due to their kinetic
energy. In this sense, a hole in NaCo2O4 can carry
much larger entropy than a carrier in semi-
conductors, which leads to a new design for
thermoelectric materials.
Koshibae’s theory has successfully explained the
high-temperature Seebeck coefficient of NaCo2O4,
but the remaining problem is not trivial. The
Seebeck coefficient of NaCo2O4 is 100 mV K1 at
300 K, which is about two-thirds of kB ln6, which
means that the large amount of entropy of kB ln6 in
the high-temperature limit (104 K) survives down
to 102 K. We should also note that the resistivity is
expected to be a large, constant value in the high-
p-type thermoelectric oxides, they cannot be
n-type because the large Seebeck coefficient
comes from the combination of Co3þ and Co4þ
in the low spin state. We expect that the mixture
300 oxides are small polaron conductors to show poor
thermoelectric properties (Kobayashi et al., 2002;
The dielectric oxide SrTiO3 is a promising n-type
thermoelectric oxide. This material is a high-
mobility semiconductor with a large dielectric
constant. Okuda et al. (2001) showed that a partial
substitution of La for Sr supplies electrons to
cause a large Seebeck coefficient with low
resistivity. Unfortunately, the lattice thermal
conductivity is one order of magnitude higher
than that of conventional thermoelectric materials,
and ZT remains 0.1–0.2 at room temperature.
Ohta et al. (2005) showed that a partial substitution
of Nb for Ti improves the thermoelectric
properties, and that ZT reaches 0.37 at 800 K in
single crystals, thin films, and polycrystalline
samples.
Transparent oxides can also be good thermoelec-
tric materials. ZnO (Ohtaki et al., 1996) and In2O3
(Bérardan et al., 2008) show superior thermoelectric
properties above 1000 K. The high mobility of
these materials is based on the light effective mass,
and the Seebeck coefficient is small compared
with the state-of-the-art thermoelectric materials.
Another drawback is the high thermal conductivity
due to the light mass of oxygen atoms.
350 Thermal Conductivity and Thermoelectric Power of Semiconductors

1.09.6 Nanostructured Materials 1 1 @ 2 " a2

¼ 2 2 ¼ 2 tc cos ðkz aÞ ð97Þ
mc h @kz h
1.09.6.1 Superlattices
Accordingly, m c is proportional to 1/a2. S roughly
Superlattice films are prototypical examples of
increases with m ¼ ðm x m y m z Þ1=3 , and thus it
nanostructured materials in which different sub-
enhances as a2/3 for a ! 0. Figure 30 shows the
stances are epitaxially grown layer by layer. A great
calculation of the Bi2Te3 thin films. With decreasing
success of semiconductor superlattices is exemplified
layer thickness, ZT rapidly increases to reach ZT ¼ 6
by semiconductor lasers based on double-hetero
for a layer thickness of 1 nm.
and/or multiquantum well structures. In those
Thermoelectric superlattices have been extensively
devices, the layer thickness is controlled to be much
investigated since the proposal offered by Hicks and
smaller than the mean free path and the de Broglie
Dresselhaus (1993a). Venkatasubramanian et al. (2001)
length of doped carriers to make electronic states
succeeded in fabricating an extremely good thermo-
quasi-2D, in which the energy levels are quantized
electric device showing ZT ¼ 2.5. Their device shows
along the cross-plane direction. Concomitantly, the
a cooling temperature of 40 K without heat removal of
3D parabolic conduction band is split into subbands
heat sink at an external current of 3 A. This value is
shifted by the quantized levels along the cross-plane
about twice larger than the cooling temperature for a
direction, which enables to tune the emission
bulk device. They ascribed the high ZT to low thermal
frequency of photons strictly. This is called quantum
conductivity. Figure 31 shows room-temperature
confinement.
thermal conductivity of various thermoelectric thin
Hicks and Dresselhaus (1993a) theoretically
films (Venkatasubramanian, 2000). A minimum ther-
proposed that quantum confinement improves the
mal conductivity is observed for the superlattice period
thermoelectric figure of merit, when the layer
of 50 Å, which is significantly lower than the solid
thickness is comparable to a few nanometers. They
solution of BiSbTe3. They discussed this behavior in
assumed that the scattering time of doped carriers is
terms of the blocking of the low-frequency phonons,
independent of the layer thickness. If so, the sheet
that is, the interference of phonons between the super-
resistance will be independent of layer thickness.
lattice interfaces. Although the phonon blocking is not
Suppose that the layer thickness is reduced by x
clarified experimentally, the superlattice structure is
times. Since the sheet resistance remains unchanged,
effective to reduce the thermal conductivity in
the resistivity decreases by x, and the electron
other materials. Recently, extremely low thermal
thermal conductivity increases by x through the
conductivity has been reported in W/Se multilayers
Wiedemann–Franz law. Then, the figure of merit
ZT ¼ S2/
(el þ ph) is modified as

S2 S2
ZT ðxÞ ¼ ¼ ð95Þ

=xðxel þ ph Þ
ðel þ ph =xÞ
6.0
This corresponds to the fact that the lattice
thermal conductivity is effectively reduced by a
factor of x. 4.0
Z20T

The second effect is the enhancement of the (1)

Seebeck coefficient owing to the confinement.
Suppose that the tunneling process is dominant 2.0 (2)
along the cross-plane direction, while the carriers
are free along the in-plane direction. Then, the
energy dispersion of carriers in the multilayer can 0.0
0.0 20.0 40.0 60.0 80.0 100.0
be written as
a (Å)
h2 Figure 30 The calculated ZT as a function of the layer
"ðkÞ ¼ ðkx 2 þ ky 2 Þ – tc cos kz a ð96Þ
2m thickness. The curves (1) and (2) are ZT along the a- and
c-axis directions, respectively. Reproduced from Hicks LD
where a is the layer thickness, and tc the cross-plane and Dresselhaus MS (1993a) Effect of quantum-well
hopping energy. The effective mass along the structures on the thermoelectric figure of merit. Physical
cross-plane direction is then evaluated as Review B 47: 12727–12731.
 Thermal Conductivity and Thermoelectric Power of Semiconductors 351

0.8 10 bulk value. In the case of one unit-cell films, the

Sb2Te3
0.7 Seebeck coefficient reaches 500 mV K1. In this
8
)

0.6 oxide superlattice, a finite cover layer of SrTiO3

Imfp (Å) ( , , )
BiSbTe3 alloy
KL (W/m-K) ( ,

0.5 6 is necessary to confine the 2D electron gas. If this

0.4
0.3
0.2
0.1
0 0
0 40 80 120 160
Superlattice period (Å)
Figure 31 Thermal conductivity of various Bi2Te3/Sb2Te3
superlattice films. Reproduced from Venkatasubramanian R
(2000) Lattice thermal conductivity reduction and phonon
localization like behavior in superlattice structures. Physical
Review B 61: 3091–3097.
by Chiritescu et al. (2007). The magnitude is less than
the minimum thermal conductivity given by Equation
(41), and even lower than the thermal conductivity of
argon gas.
The enhancement of the density of states in
superlattices is also experimentally observed. Ohta
et al. (2007) showed that titanium oxide superlattice
films have a 2D electron gas at the interface, and
show five times larger Seebeck coefficient to give
ZT ¼ 2.5. Figure 32 shows the room-temperature
Seebeck coefficient of Sr(Ti0.8Nb0.2)O3/SrTiO3
superlattice films. When the thickness of the conduc-
tive Sr(Ti0.8Nb0.2)O3 layer is larger than four unit
cells, the Seebeck coefficient is the same as the
500
1 ML Sr(Ti0.8Nb0.2)O3/SrTiO3
thickness is included, an effective ZT remains lower
4
than unity.
2
The third effect of superlattice is energy filtering.
As mentioned in Section 1.09.4 the Seebeck coeffi-
cient is proportional to an average of the electron
200
energy from the chemical potential "k  , so that
it is small in the presence of the electron–hole
symmetry. The energy filtering is a theoretical
proposal that a tunneling barrier is introduced in
order that only electrons with higher energy should
propagate in the sample. This was originally given as
thermionic refrigeration by Mahan et al. (1998), and
many researchers tried to design such thermionic
devices. Vashaee and Shakouri (2004) showed that
the energy filtering is enhanced in the presence of
momentum-nonconserved scattering. Figure 33
schematically shows the momentum space for the
tunnelling process. An electron energy is distributed
between the two sphere shells with radii of kf
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
and kf þ 2mkB T =h2 . Suppose that an electron
with a lateral momentum k1 tunnels through the
kx
kf + (2m*kBT/h2)1/2 V2: k > kb
V1: kz > kb
kf

400 300 K kz
–S (μV K–1)

300
2 ML

200 kb
8 ML 16 ML

100 ky k2
4 ML
k1
0
0 1 2 3 4 5 6 7
Figure 33 Corresponding wave vectors in the k space, k1,
Sr(Ti0.8Nb0.2)O3 layer thickness (nm) k2, and kb correspond to cross-sectional planes and kf is the
radius of the Fermi sphere. V1 is the volume of the electrons
Figure 32 The Seebeck coefficient of Sr(Ti0.8Nb0.2)O3/ that participate in thermionic emission above the barrier if
SrTiO3 superlattice films as a function of thickness of the lateral momentum is conserved. V2 is that volume if the
Sr(Ti0.8Nb0.2)O3 layer at 300 K. From Ohta H, Kim S, Mune Y, lateral momentum is not conserved. Reproduced from
et al. (2007) Giant thermoelectric Seebeck coefficient of a Vashaee D and Shakouri A (2004) Electronic and
two-dimensional electron gas in SrTiO3. Nature Materials 6: thermoelectric transport in semiconductor and metallic
129–134. superlattices. Journal of Applied Physics 95: 1233–1245.
352 Thermal Conductivity and Thermoelectric Power of Semiconductors
neighboring layer to get a lateral momentum k2.
Then, the momentum space to conserve total
momentum is limited in V1, while the space to
allow the violation of the momentum conservation
is enlarged to V2. As a result, such momentum-
nonconserving filters will remain conductivity as
high as the bulk value, and enhance the Seebeck
coefficient significantly.
Zide et al. (2006) experimentally demonstrated
the enhancement of the Seebeck coefficient in
the superlattice. Figure 34 shows the in-plane and
cross-plane Seebeck coefficients in InGaAs/
InAlGaAs superlattices. Normally, Seebeck
coefficients are weakly anisotropic because the
anisotropic factor is cancelled in the calculation (see
Equation (49)). Contrary to this, the observed values
are unconventionally anisotropic: the cross-plane data
are three times larger than the in-plane ones, which is
essentially independent of doping levels.
Humphrey and Linke (2005) proposed a new
design of thermoelectric superlattice, and showed
that the conversion efficiency of this device reaches
the Carnot efficiency, which corresponds to ZT ! 1.
Their device consists of many quantum-wells, and a
small temperature gradient is applied in accordance
with implemented variation of chemical potential in
order that the electron distribution function
   –1
" – ðrÞ
f0 ¼ exp þ1
kB T ðrÞ
600
500
Seebeck coefficient (μV K–1)
Cross-plane
400
300
200 In-plane
100
0 0
0 2 4 6
Carrier concentration (1018cm–3)
Figure 34 The in-plane and cross-plane Seebeck
coefficient in the InGaAs/InGaAlAs superlattice films. From
Zide JMO, Vashaee D, Bian ZX, et al. (2006) Demonstration
of electron filtering to increase the Seebeck coefficient in
In0.53Ga0.47As/In0.53Ga0.28Al0.19 As superlattices. Physical
Review B 74: 205335.
is constant everywhere in the device. Under such
conditions, all the wells are in thermal equilibrium,
and the electron transfer is dissipationless.
1.09.6.2 Nanowires
Hicks and Dresselhaus (1993b) performed the same
calculation for 1D wires as they did for 2D films and
showed that ZT is enhanced with decreasing
diameter of the wire. They have further found
that the Bi wires change their ground state from
semimetal to semiconductor, because the quantum
confinement lifts the bottom of the conduction band
above the top of the valence band. Figure 35 shows
the electronic band diagram of Bi as a function of
wire diameter (Lin et al., 2000). For a diameter as
large as 200 nm, the band of the holes at the T point is
above electrons at the L point. The energy shifts to
higher values with respect to electron doping, and
electrons and holes coexist up to 40 meV. The energy
levels of the L electrons increase roughly in inverse
proportion to the wire diameter, while the energy
levels of the T holes rapidly decrease below 50 nm.
As a result, a transition from semimetal to semicon-
ductor occurs below 49 nm. Heremans et al. (2000)
have fabricated Bi nanowire bundles and clarified
that the electronic states of Bi nanowire can be
regarded as single-band semiconductor.
As discussed in Section 1.09.3, silicon is a good
conductor of heat, and hence the thermoelectric
ð98Þ
figure of merit ZT remains a low value of 0.005 at
100
80
Le− (A)
60 Le− (B, C) T holes
Energy (meV)
40
20 −Δ0 = 38
49.0 nm
0
L holes EgL = 15
−20
−40
50 100 150 200
8 10 Wire diameter (nm)
Figure 35 Calculated energy band diagram of Bi wire
plotted as a function of wire diameter. Below 49 nm, the
energy level of the holes at T point goes down below the
energy level of the electrons at L point. Reproduced from Lin
Y-M, Sun X, and Dresselhaus MS (2000) Theoretical
investigation of thermoelectric transport properties of
cylindrical Bi nanowires. Physical Review B 62: 4610–4623.
 Thermal Conductivity and Thermoelectric Power of Semiconductors
1.2
20-nm array (Boukai)
1
10-nm array (Boukai)
0.8
0.6
ZT
0.4
0.2
0 tivity of a single carbon nanotube, as shown in
50–nm wire (Hochbaum)
–0.2
50 100 150 200 250 300 350
Temperature (K)
Figure 36 Dimensionless figure of merit ZT of Si nanowire
samples. From Boukai AI Bunimovich Y, Tahir-Kheli J, Yu
J.-K, Goddard WA, III, and Heath JR (2008) Silicon
nanowires as efficient thermoelectric materials. Nature 451:
168–171; Hochbaum AI, Chen R, Delgado RD, et al. (2008)
Enhanced thermoelectric performance of rough silicon
nanowires. Nature 451: 163–167.
room temperature. This difficulty has been overcome
by fabricating nanowires. Figure 36 shows the figure
of merit of Si nanowires. Hochbaum et al. (2008)
prepared free-standing silicon wires with diameters
of 50–100 nm by self-organization technique based
on selective etching, and found that they exhibit a
low thermal conductivity of the order of 1 W mK1.
This value is 100 times lower than the bulk value,
and ZT increases by almost 100 times, and reaches
0.5 at room temperature. At the same time (in the
same journal), another research group reported
success in getting high ZT in silicon nanowire arrays.
Boukai et al. (2008) fabricated arrays of 20-nm-width
nanowires of silicon and measured the thermoelectric
properties. Their samples also show extremely low
thermal conductivity and some of them show ZT ¼ 1
at 200 K.
The 100-times lower thermal conductivity
observed in the two independent experiments awaits
a theoretical explanation. Obviously, the phonon
mean free path is of the order of 10–100 nm for
bulk Si, being comparable with the wire diameter in
the first experiment. Thus, it is highly nontrivial that
the mean free path is reduced to be of the order of
1 nm in nanowire.
Contrary to Si, nanowires of other elements
exhibit unconventionally high thermal conductivity.
Carbon nanotubes are nature-made nanowires (see,
Ebbesen, 1994 and Ando, 2005), and their physical
properties have been extensively investigated. They
have a large structure variation with different radii
353
and chiralities. Since the growth conditions are
nearly the same, the purification of a single structure
is extremely difficult. The physical properties
strongly depend on the structure, and samples can
be semiconducting, metallic, and even superconduct-
ing (Murata et al., 2008). Owing to this, different
values of thermal conductivity are reported from
sample to sample.
Kim et al. (2001) measured the thermal conduc-
Figure 37. They fabricated two microheaters of
400
10-mm2 area using Si3N4/Si-based technology, and
set the sample between them. The measured thermal
conductivity is 3000 W mK1 at room temperature.
This value is higher than that of diamond, and is
attractive for application. They further measured the
diameter dependence, and found that the thermal
conductivity increases with decreasing diameter. For
a 1-nm diameter, the thermal conductivity reaches
8000 W mK1, much higher than other bulk
semiconductors. The temperature dependence
suggests nearly ballistic conduction below 300 K,
which breaks owing to the Umklapp scattering above
300 K. The Seebeck coefficient is also measured for
the same sample, and is found to be 42 mV K1 at
300 K and roughly is linear in T. This suggests that
the electronic states are basically the same as in metals.
1.09.6.3 Nanostructured Bulk Materials
As discussed above, nanostructuring is a powerful
method to control thermal and thermoelectric
properties in semiconductors. However, heat is an
essentially macroscopic object, and cannot be
confined in nanospace. Thus, bulk materials are still
indispensable to practical applications for thermal
and thermoelectric management. It is thus important
to synthesize bulk materials with nanostructure
modification. Sharp et al. (2001) pointed out that the
mean free paths of phonons are more than one order
of magnitude larger than those of electrons, and
proposed that only the former can be reduced by
properly choosing the domain size of the material.
Poudel et al. (2008) succeeded in increasing ZT of
Bi2Te3 by 50% by reducing the lattice thermal
conductivity using nanostructured samples. Ohtaki
et al. (2007) included 100-nm-sized organic beads
with ZnO powder, and made ZnO ceramic samples
with 100-nm-sized voids by evaporating the beads
through sintering. The samples show lower thermal
conductivity, and ZT is substantially enhanced at
high temperatures.
354 Thermal Conductivity and Thermoelectric Power of Semiconductors

10–7

Thermal conductance (W K–1)

10–8

3000

κ (T) (W/m K)
2000

10–9 1000

0
100 200 300
T (K)

10 100
Temperature (K)
Figure 37 Themal conductivity of a single carbon nanotube. The sample mount is shown in the inset. The lower inset shows
the thermal conductivity of carbon nanotubes with different diameters. The solid, dashed, and dotted curves correspond to
diameters of 14.80, and 200 nm, respectively. Reproduced from Kim P, Shi L, Majumdar A, and McEuen PL (2001) Thermal
transport measurements of individual multiwalled nanotubes. Physical Review Letters 87: 215502.

Hsu et al. (2004) found that a PbTe-based new

material AgPb18SbTe20 (named LAST) has a high ZT
of 2.2 at 800 K. The mechanism of the high ZT is still
controversial, but they attributed this to a special tissue
of this material. In this material, nanometer-sized dro-
plets of an Ag–Sb rich phase are precipitated in the host
PbTe, and may work as quantum-dots. Preceding this
work, Harman et al. (2002) showed that quantum-dots
in PbTe-based superlattice enhance S and ZT.
Self-organized precipitation of nanosized particles
works to reduce the thermal conductivity in
GaAs-based semiconductor films. Kim et al. (2006) 5 nm
found that coevaporation of Er and Ga in As atmo-
sphere forms nanosized particles of ErAs in the GaAs
films. Figure 38 shows the self-grown ErAs dots Figure 38 Self-precipitated ErAs dots (dark dots) in
(shown as dark spots) in a (In,Ga)As film. Since the (In,Ga)As matrix. Scale ¼ 5 nm. Reproduced from Kim W,
particle diameter and the interparticle distance are Zide J, Gossard A, Klenov D, Stemmer S, Shakouri A, and
Majumdar A (2006) Thermal conductivity reduction and
approximately 1 and 10 nm, respectively, these struc- thermoelectric figure of merit increase by embedding
tures may effectively scatter long-wavelength nanoparticles in crystalline semiconductors. Physical
phonons. They measured the thermal conductivity Review Letters 96: 045901.
with and without ErAs particles, and found that the
lattice thermal conductivity is significantly reduced. (see Section 1.09.5.3). This class of materials has a
Another type of self-organized nanostructure layered structure consisting of the CdI2-type CoO2
modification is seen in the layered cobalt oxides layer and the NaCl-type block layer. This implies
 Thermal Conductivity and Thermoelectric Power of Semiconductors
160
CaBi
S300 K (μV K−1)
120 SrBt
BaBi SrCo
80 SrTI CaO2
Sr (this work)
RS
40 n=2
n=1 CoO2
n=0
0
0.50 0.55
Misfit ratio (=b2/b1)
Figure 39 Room-temperature Seebeck coefficient
plotted as a function of lattice misfit ratio b1/b2, where b1
and b2 are the b-axis lengths of the block layer and the
CoO2 layer, respectively. The inset shows a schematic
drawing of the crystal structure of the layered cobalt oxides.
Reproduced from Ishiwata S, Terasaki I, Kusano Y, and
Takano M (2006) Transport properties of the misfit layered
cobalt oxide [Sr2O2D]0.53CoO2. Journal of the Physical
Society of Japan 75: 104716.
that a new thermoelectric oxide can be designed by
properly combining the block layer, which is called
nanoblock integration by Koumoto et al. (2006).
A characteristic feature is that the CoO2 layer and the
block layer have a lattice mismatch along the b-axis,
and the interface is drastically modified by the misfit
structure. Maignan et al., (2002) first recognized that the
thermoelectric properties in a certain class of cobalt
oxides are controlled by the misfit structure. Ishiwata
et al. (2006) and Kobayashi and Terasaki (2006)
extended this concept to a whole family of the layered
cobalt oxides, and found that the Hall coefficient and
the Seebeck coefficient are determined by the lattice
ratio of the b-axis (b2) of the CoO2 layer to the b-axis (b1)
of the block layer. Figure 39 shows that the room-
temperature Seebeck coefficients of various layered
cobalt oxides plotted as a function of b2/b1 (Ishiwata
et al., 2006), in which all the data tend to increase with
b2/b1. Okada et al. (Okada and Terasaki 2005; Okada
et al., 2005) synthesized an isomorphic layered rhodium
oxide Bi-M-Rh-O, and found that the Seebeck coeffi-
cient is also dominated by b1/b2 (Terasaki et al., 2006).
1.09.7 Summary and Outlook
In this chapter, we have briefly reviewed the thermal
conductivity and thermoelectric power of various
semiconductors including amorphous solids, magnetic
355
oxides, and nanostructured materials. While Drude’s
CaCoPb kinetic theory of an electron gas unexpectedly works
well in element semiconductors, it does not cover more
complicated materials. In particular, localized phonon
CaCo
modes such as the rattling mode let perfect crystals to
be glass-like, which is named phonon glass by Slack
(1995). Nanostructuring effectively reduces the lattice
thermal conductivity of silicon, which can control
b1 heat flow in the nanowires. However, our theoretical
understanding of thermal conduction is far away from
b2 the goal, possibly owing to the fact that heat conduction
0.60 of phonons cannot be treated in quantum physics in a
strict sense. We do not fully understand the difference
between sound and heat, both of which are described
by lattice vibration. Although some theoretical trials
are being developed, the concepts of localization,
decoherence, confinement, quantum transport, and so
on for phonons are still premature, in comparison with
the corresponding ideas for electrons.
We have also reviewed thermoelectric phenom-
ena, which arise from the cross correlation between
electrical and thermal currents in solids. They can
be applied to energy conversion between heat and
electricity, which attracts renewed interest owing to
pressing needs for energy and environment issues.
This technology, called thermoelectrics, requires
materials having high thermoelectric power with
low thermal conductivity and resistivity. To get
high efficiency of thermoelectric energy conversion,
various complex materials are designed, synthesized,
and identified. For example, skutterudites and
clathrates show anomalously low thermal condu-
ctivity due to the rattling modes, and the layered
cobalt oxides have large thermoelectric power com-
ing from the degeneracy of the spin and orbital
configuration on the cobalt sites. Nanotechnology
has proved to be powerful for improving the
thermoelectric performance of bulk materials.
Semiconductor technology has been developed
with precise control of the electrical current of
doped carriers, whereas the thermal current has
been left uncontrolled. But now, through the recent
development of nanotechnology, we may be able to
control heat in the device; the thermal conductivity
of bulk materials can be reduced by 100 times, and
the thermoelectric power can be increased by several
times. Of course, we cannot make Maxwell’s daemon,
but we will be able to manage heat much better than
we do at present. In this respect, the author hopes
that semiconductor technology of next generation
will handle the electrical and thermal currents on
an equal basis.
356 Thermal Conductivity and Thermoelectric Power of Semiconductors
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 1.10 Electronic States and Transport Properties of Carbon
Crystalline: Graphene, Nanotube, and Graphite
Y Iye, University of Tokyo, Kashiwa, Chiba, Japan
ª 2011 Elsevier B.V. All rights reserved.

1.10.1 Introduction 359

1.10.1.1 Carbon Allotropes 359
1.10.1.2 Bond and Local Coordination 360
1.10.1.3 Dimensionality 361
1.10.2 Electronic Structures 361
1.10.2.1 Diamond 361
1.10.2.2 2D Graphite (Graphene) 361
1.10.2.3 Bilayer Graphene 365
1.10.2.4 Single-Wall Carbon Nanotubes 365
1.10.2.5 Graphene Nanoribbons 367
1.10.2.6 Bulk Graphite 368
1.10.3 Transport Properties of Graphene 369
1.10.3.1 Preparation of Graphene Samples 369
1.10.3.2 Transport at Zero Magnetic Field 369
1.10.3.3 Quantum Hall Effect 370
1.10.4 Transport Properties of Carbon Nanotubes 372
1.10.4.1 Electronic State in SWNTs 372
1.10.4.2 Electron Transport in SWNTs 372
1.10.4.3 Multi-Wall Nanotubes 374
1.10.5 Transport Properties of Graphite 374
1.10.5.1 Graphite Materials and Transport Characteristics 374
1.10.5.2 Semi-Classical Magneto-Transport 374
1.10.5.3 Magneto-Quantum Oscillations 376
1.10.5.4 Magnetic-Field-Induced Electronic Phase Transition 377
1.10.6 Concluding Remarks 380
References 380

1.10.1 Introduction carbon allotropes were discovered and created much

1.10.1.1 Carbon Allotropes
Carbon is one of the most ubiquitous elements on the
earth. It is the basic building ingredient of all the organic
molecules that constitute our own body and other bio-
logical systems. Indeed, the diversity of composition,
structure, and functionality of organic molecules is
truly rich and awesome. Carbon, however, is also unique
in that even as elementary substance it occurs in vastly
different forms. Diamond and graphite are just two allo-
tropes of carbon known since antiquity. Another well-
known allotrope is amorphous carbon materials which
are found, together with micro- or nanocrystalline mate-
rials of graphite or diamond, in coals and soot. During
the last quarter of a century, a few new members of
excitement in the research community.
Fullerene molecules C60 and C70 were discovered
by Kroto et al. (1985). These were initially identified
as distinct peaks in the time-of-flight mass spectro-
graph of carbon clusters evaporated from a graphite
target by laser irradiation. The high stability of a
cluster with exactly 60 carbon atoms led these
authors to propose the truncated dodecahedron or
soccer-ball structure. Owing to the small amount of
fullerene molecules that could be obtained by the
laser abrasion technique, research into fullerene was
not fully developed for the first few years after their
discovery, let alone investigation of the properties of
fullerene solids. The situation changed in 1990 when
Kretschmer and Huffman announced massive

359
360 Electronic States and Transport Properties of Carbon Crystalline
production of fullerene molecules by an arc dis-
charge method (Dresselhaus et al., 1996).
The arc discharge method yielded another, no less
important, family of allotropes, that is, carbon nanotubes.
Iijima (1991), while investigating under an electron
microscope the soot deposits on the cathode of his arc
discharge apparatus, discovered thin tubes made of gra-
phitic layers. Although one can spot in retrospect a few
earlier reports on similar substances (Oberlin et al., 1976),
it was the report by Iijima that triggered the subsequent
research activities on carbon nanotubes (Saito et al., 1998;
Dresselhaus et al., 2001). Whereas the initial discovery
was on multi-walled nanotubes, single-walled nano-
tubes were later prepared successfully (Iijima and
Ichihashi, 1993; Bethune et al., 1993).
A further surprise was brought about in 2004 by the
Manchester University group led by Geim (Novoselov
et al., 2004; Geim and MacDonald, 2007; Geim and
Novoselov, 2007). By an astonishingly simple peel-
and-stick technique, they prepared samples of a sin-
gle-layer sheet of graphite on an oxidized surface of
silicon wafer. Although cleavage was routinely done by
those who handled graphite samples, it came as a total
surprise that samples of single-layer graphite of semi-
macroscopic size can be obtained by such a method.
The discovery of these novel species of carbon
allotropes has vastly broadened the horizon of con-
densed matter physics. The exotic electronic
properties of nanotubes and graphenes and their
potential applications to future electronics are cur-
rently under vigorous study worldwide.
The carbon materials listed above and depicted in
Figure 1 are representative ones that have been most
extensively studied. There are many more exotic allo-
tropes, even limiting ourselves to those purely made of
carbon atoms. In addition to C60 and C70, there are so-
called higher-order fullerenes such as C84. The crys-
tals made of the fullerene molecules can take different
Figure 1 Carbon allotropes: diamond, graphite, C60 molecule, and carbon nanotube.
structures. Under appropriate conditions, fullerenes
can form dimers, trimers, and various polymers. One
of the most beautiful allotropes is carbon nanopea-
pods, that is, carbon nanotubes enclosing C60
molecules (Smith et al., 1998).
Exploring further beyond the boundary of pure
carbon territory, one finds a vast landscape of mate-
rials diversity. By using a metal-containing carbon
rod in the arc discharge process, metallofullerenes,
that is, fullerene molecules encapsulating metal
ion(s), can be produced. Nanotubes can accommo-
date various foreign species (including fullerenes as
mentioned above). Extensive studies have been made
on graphite intercalation compounds (GICs)
(Dresselhaus and Dresselhaus, 1981). A wide variety
of guest species (intercalant) can be inserted in the
interlayer spacing of graphite in a well-ordered fash-
ion. The resulting GICs are good examples of
synthetic metals.
1.10.1.2 Bond and Local Coordination
Carbon atom has four valence electrons in the 2s and
2p atomic orbitals. The carbon–carbon (C–C) bond
can be either sp3- or sp2-hybridized bond. The rich-
ness of carbon allotropes stems from various
combinations of the sp3- and sp2-hybridized bonds.
In diamond crystals, each carbon atom is tetra-
hedrally coordinated. Strong C–C bond is formed
with each of the neighboring four atoms by sp3-
hybridization. The C–C bond length in diamond is
0.154 nm. The crystal structure is cubic with lattice
constant 0.357 nm. The diamond lattice can be
viewed as consisting of two face-centered cubic
 
111
(f.c.c.) sublattices of which one is shifted by
444
relative to the other.
 Electronic States and Transport Properties of Carbon Crystalline
Carbon atoms in a graphitic sheet form a honey-
comb network so that each atom is trigonally
coordinated. Three of the four valence electrons are
used for the sp2-hybridized -bonds with the three
neighbors. The remaining one is in the -orbital and
can be easily delocalized. The C–C bond length in the
graphitic sheet is 0.142 nm. The three-dimensional
(3D) graphite is made of a stack of graphitic sheets.
The ordinary graphite (Bernal graphite) exhibits the
stacking order ABAB. . .. A thermodynamically
unstable variant called rhombohedral graphite has a
stacking sequence ABCABC. . ..
In the case of amorphous carbon, the C–C bonds
consist of mixture of sp3- and sp2-hybridized bonds.
Actually, one important parameter that characterizes
the amorphous carbon is the ratio of sp3- and
sp2-hybridized bonds. Materials that are high in
sp3-hybridized bonds are referred to as tetrahedral
amorphous carbon or as diamond-like carbon owing
to the similarity of many physical properties to those
of diamond. Raman spectroscopy provides a useful
means of characterization. The Raman spectrum of
diamond shows a sharp peak at ! ¼ 1332 cm1, while
the frequency of the Raman-active in-plane mode of
graphite is ! ¼1582 cm1. The Raman spectra of
amorphous carbon generally exhibit broadened mix-
ture of these two peaks.
1.10.1.3 Dimensionality
The line-up of carbon allotoropes introduced in the
previous section provides a set of model systems for
low-dimensional physics; that is, diamond (3D), gra-
phite (quasi-2D), graphene (2D), nanotube (1D), and
fullerene (0D). Dimensionality is a key ingredient
that profoundly affects transport and other electro-
nic properties. Indeed, phenomena intimately linked
to the dimensionality have been observed in these
systems. 2D electron system created at the semicon-
ductor heterointerface is an experimental stage of
many intriguing physics, including quantum Hall
effect (QHE) and electron localization. Up until
the advent of graphene, the experimental systems
were virtually limited to GaAs/AlGaAs and Si-
MOS. Graphene provides not just another 2D sys-
tem but a very unique one, as explained in later
sections. Carbon nanotubes are regarded as nearly
ideal 1D quantum wire. Some of the properties of
carbon nanotubes seem to corroborate the
Tomonaga–Luttinger liquid (TLL) behavior theo-
retically developed for interacting 1D electron
systems. Nanotube is also used in a device called
361
single electron tunneling (SET) transistor, in which
tunneling of individual electrons between the
quantum-dot and the leads can be controlled by a
gate voltage. A single fullerene molecule trapped in
the nano-sized gap between two electrodes can be
an ultimate quantum-dot. Thus, graphene, nano-
tube, and fullerene are regarded as wonderful
playgrounds for nanoscience and as precious parts
of nanotechnology.
In the subsequent sections, some of the basics
about the carbon-based electronic systems are
explained, and the excitement brought by the
research efforts since the late 1950s is conveyed.
This chapter mainly focuses on the transport
properties.
1.10.2 Electronic Structures
1.10.2.1 Diamond
Since this chapter is principally concerned with the
graphitic systems, we only briefly touch upon the
electronic structure of diamond. Diamond is a wide
gap semiconductor. Figure 2(a) shows the band
structure of diamond (Saslow et al., 1966; Saravia and
Brust, 1968), which is similar to that of silicon. The
conduction-band minima are located along the –X
lines of the Brillouin zone. The surfaces of equal
energy are ellipsoids with m1 ¼ 1.4 m0 and mt ¼ 0.36 m0.
The valence band top is located at the -point. The
effective masses of heavy and light holes
are mhh ¼ 2.12 m0 and m1h ¼ 0.7 m0. The split-off band
is   6 meV below the heavy and light hole bands
and the effective mass is m1h ¼ 1.06 m0. The indirect
gap is 5.47 eV and the direct gap at the -point
is 7.3 eV.
1.10.2.2 2D Graphite (Graphene)
Calculations of the electronic band of 2D version
of graphite (i.e., graphene in today‘s terminology)
have been made by many authors for over 50
years (Wallace, 1947; Coulson, 1947; Bassani and
Parravicini, 1967; Painter and Ellis, 1970; Zunger,
1978). Figure 2(b) shows the calculated band
structures of 2D graphite taken from Zunger
(1978). The Brillouin zone edges denoted by P
and Q in the figure correspond to K and M in the
today’s conventional notation. The s-orbital and
two in-plane p-orbitals form the sp2-hybridized
-bonds which make up the strong honeycomb
framework of graphene. The bonding -bands
362 Electronic States and Transport Properties of Carbon Crystalline

(a)
Δ1
Λ1 Δ2′
k2 20
Γ12′
Λ3 Δ5
l
Λ Λ3 Γ2
Γ k2 L3 Δ2′
10 Γ15
Δ Σ X1
k2 L1 Λ1
K
XZ W Δ1
Γ25′
0

E (eV)
L3′ Λ3 Δ5

X4
–10
Λ1 Δ2′

L1 C
X1
–20
L2′ Δ1
Λ1
Γ1
–30
(b) +
10 (a)
Q2v (b) (c)
+
Γ1v
–
P3+ –
Γ2g Γ2g
–
Γ2g Q2u
+
0 + +
P2 +
Qlu +
Γ3u Qlu
+
Γ3u Γ3u
+

–
Energy (eV)

Q2g
– Q2g +
Q2g
– P3–
–10
P3 P3– +
+
Γ3g – + Q2u
– Γ3g Q2u
–
Q2u Γ3g
+ +
– P1+ Γ2u Q2g
+ Γ2u +
Q2g Q2g
–
Γ2u P1+ +
–20 P1+ Qlu
+ +
+
P3+ + P3 Γlg +
P3+ Qlu Qlu Qlg
+ +
+ Qlg Qlg
Γlg +
Γlg
–30
P Γ Q P Γ Q P Γ Q

Figure 2 The Brillouin zone and electronic band of (a) diamond and (b) two-dimensional graphite. (a) Reprinted with permission
from Saslow W, Bergstresser TK, and Cohen ML (1966) Band structure and optical properties of diamond. Physical Review Letters
16: 354. Copyright (1966) by the American Physical Society. (b) Reprinted with permission from Zunger A (1978) Self-consistent
LCAO calculation of the electronic properties of graphite. I. The regular graphite lattice. Physical Review B 17: 626. Copyright
(1978) by the American Physical Society.

and antibonding 9-bands are shown by three As it constitutes the basis for the electronic struc-
solid curves in the lower part and another three ture of all graphitic systems, let us take a closer look
in the upper part of the band diagrams in at the graphene -band structure. The electronic
Figure 2(b). The dashed curves represent the structure of the graphene can be reasonably well
bonding -band and antibonding 9-band formed described by a simple tight-binding Hamiltonian for
by the remaining out-of-plane p-orbital. The the - and 9-bands. The notations here follow those
bonding -band and antibonding 9-band touch by Ando (2005).
with each other at the K-point, where the Fermi The honeycomb lattice of graphene consists of two
level of the undoped graphene resides. interpenetrating triangular sublatteices (referred to as
 Electronic States and Transport Properties of Carbon Crystalline 363

(a) (b)
4
z K
M
y
3
x Γ
2

Energy (units of γ0)

γ1
1

γ0 EF
0
Monolayer Bilayer
−1
(c)
ε ε −2

−3
κy κy K Γ M K
Wave vector
K K
κx κx

Monolayer Bilayer
Figure 3 (a) Left: Honeycomb lattice of graphene. Right: Stacking of bilayer graphene. (b) The - and 9-bands of graphene.
(c) Characteristic band structures at the K point for monolayer (left) and bilayer (right) graphene.

X X
A and B sublattices hereafter) as depicted in Figure 3(a) ðrÞ ¼ A ðrÞðr  RA Þ þ B ðrÞðr – RB Þ ð1Þ
with black and white atoms. Each atom of one sublattice RA RB

is surrounded by three atoms belonging to the other

sublattice, and vice versa. The primitive translation Here, ðrÞ is the pz-orbital of a carbon atom, and
vectors can be taken as a1 ¼ a(1,0) and RA ðRB Þ specifies the lattice point of the A- (B-) sub-
 pffiffiffi
1 3 lattice. We write the transfer integral between the
a2 ¼ a – ; , and the vectors connecting the nearest-neighbor carbon atoms as – 0 , and ignore
2 2
  the overlap integral between the A and B sublattices.
1
nearest neighbor carbon atoms are  1 ¼ a 0; pffiffiffi , Then the equation reads
    3
1 1 1 1 P
3
 2 ¼ a – ; pffiffiffi , and  3 ¼ a ; – pffiffiffi , where
2 2 3 2 2 3 " A ðRA Þ ¼ – 0 B ðRA – iÞ
pffiffiffi i¼1
a ¼ 0:142  3 ¼ 0:246 nm is the lattice constant. ð2Þ
pffiffiffi P
3
3 2 " B ðRB Þ ¼ – 0 A ðRB þ  i Þ
The unit cell area is 0 ¼ a . The corresponding i¼1
2
primitive reciprocal lattice vectors are Assuming A ðRA Þ ¼¼ fA ðkÞexpði k ? RA Þ and
   
 2 1  2 2 B ðRB Þ ¼¼ fB ðkÞexpði k ? RB Þ, Equation (2)
a1 ¼ 1; pffiffiffi and a2 ¼ 0; pffiffiffi , and the
a 3 a 3 becomes
area of the hexagonal first Brillouin zone is
  P
3
2 2 2 "fA ðkÞ ¼ – 0 fB ðkÞexpð – ik :  i Þ
0 ¼ pffiffiffi . i¼1
3 a ð3Þ
In the tight-binding model, the wave function is P
3
"fB ðkÞ ¼ – 0 fA ðkÞexpðþik :  i Þ
expressed as the sum of the atomic orbitals localized i¼1

at the lattice points: The eigenvalues of this equation are obtained as

364 Electronic States and Transport Properties of Carbon Crystalline

sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
pffiffiffi at the corners of the Brillouin zone as shown on the
 kx a 3ky a kx a
" ðkÞ ¼ 0 1 þ 4cos cos þ 4cos2 ð4Þ left of Figure 3(c). The corresponding density of
2 2 2
states reads
which is shown in Figure 3(b). Note that
" ðkÞ ¼ 0 at the K- and K9-points. In the Dð"Þ ¼
j"j
ð6Þ
vicinity of the K-points, the dispersion is linear; 2h2 vF2
that is,
This linear dispersion in the vicinity of the K-

" ðkÞ ¼ hvF jkjj ð5Þ and K9-points is what makes the graphitic
systems (graphene and nanotube) unique in
for a << 1, where k X k – K is the wave
pffiffiffi vector mea- their electronic properties, as will be seen in the
sured from the K-point and vF ¼ 30 a=2h is the following.
group velocity of the electrons (vF ¼ 1106 m s – 1 Within the effective mass approximation, the
for graphene). The same relation holds for the Schrödinger equation for graphene -band electrons
K9-point. This can be represented as cone structure can be written as

Ĥmono FðrÞ ¼ " FðrÞ

0 K 1 0 K 1 0 K 1
F ðrÞ FA ðrÞ FA ðrÞ
FðrÞ ¼ @ A; FK ðrÞ ¼ @ A; FK ðr Þ ¼ @ A
FK9 ðrÞ FKB ðrÞ FKB ðrÞ
0   1
0 hvF ˆ x – iˆ y 0 0
B C ð7Þ
B   C
B hvF ˆ x þ iˆ y 0 0 0 C
B C
Ĥmono ¼ B
B 
C
C
B 0 0 0 h
 v ˆ
 þ i ˆ
 C
B F x y C
@ A
 
0 0 hvF ˆ x – iˆ y 0
ð7Þ

Here, FAK ðrÞ, etc. are the slowly varying envelope
functions. The above matrix equation can be rewrit-
ten in the following more compact form:
( by Equation (5). This form is convenient for highlight-
hvF ðs?k̂ ÞFK ðrÞ ¼"FK ðrÞ
hvF ðs ?k̂ ÞFK9 ðrÞ ¼ "FK9 ðrÞ
 
Here, s ¼ x ;y is the pseudo-spin Pauli matrices
(the pseudo-spin corresponding to the A and B sub-
lattice), and k̂ ¼ – ir is the wave number operator.
Equation (8) is isomorphic to a relativistic Dirac equa-
tion for a particle with vanishing rest mass, known as
Wyle‘s equation. In this sense, electrons and holes in
monolayer graphene are often referred to as massless
Dirac fermions. Here, vF ¼ 1  106 m s – 1 plays the
role of the speed of light.
The quasi-particles in monolayer graphene can be
described by the effective Hamiltonian
0 ˆ x – i ˆ y
Ĥmono ¼ hvF
ˆ x þ i ˆ y
which operates in the pseudo-spin space that describes
the amplitude of electron waves on the A and B sub-
lattices. The eigenvalues of this Hamiltonian are given
ing the difference from the bilayer case to be discussed
ð8Þ
in the next subsection.
Although the concept of massless Dirac fermion in
solid state is not new but has been invoked in discussing
certain aspects of the electronic properties of graphite
(McClure, 1956) and other systems such as bismuth
(Fukuyama and Kubo, 1970) and HgTe, demonstration
of its genuine occurrence with all subtleties has been
first achieved in monolayer graphene. However, occur-
rence of genuine massless Dirac fermions in solid state
is not exclusive to graphene. Another example recently
elucidated is the zero-gap state in a molecular
conductor -(bis(ethylenedithia)tetrathiafulvalene
(BEDT-TTF))2I3 under pressure (Tajima et al., 2000),
! whose electronic structure can be described by a tilted
ð9Þ Weyl equation with anisotropic Fermi velocity
0 (Katayama et al., 2006; Kobayashi et al., 2009).
 Electronic States and Transport Properties of Carbon Crystalline 365

1.10.2.3 Bilayer Graphene the vertically aligned atoms gives rise to interlayer
coupling that changes the band structure of bilayer
In a graphene bilayer with Bernal (AB) stacking shown
graphene from the monolayer case.
on the right of Figure 3(a), one of the two sublattices
The Schrödinger equation for bilayer graphene
in the top layer comes right above a sublattice in the
(to be contrasted with Equation (7) for the monolayer
bottom layer, while the other sublattice does not find
case) can be written as
such a counterpart. The transfer integral 1 between

K
Ĥbi FK ðrÞ ¼ "FK ðrÞ
FK ðrÞ ¼ ðF1B ðrÞ; F1A ðrÞ; F2A ðrÞ; F2B ðrÞÞ
0   1
0 vF ˆ x þ iˆ y 0 0
B C
B   C ð10Þ
B vF ˆ x  iˆ y 0  0 C
K B 1 C
Ĥbi ¼ B
B 
C
C
B 0  0 v ˆ
 þ i ˆ
 C
B 1 F x y C
@ A
 
0 0 vF x  iy
ˆ ˆ 0
ð10Þ
together with a similar expression for the K9 valley.
This results in four valley-degenerate bands as estimated as m  0.034m. In contrast to the monolayer
shown on the right of Figure 3(c). A symmetric case, electrons and holes in bilayer graphene act as massive
pair of the higher penergy Dirac fermions as shown on the right of Figure 3(c).
ffiffiffiffiffiffiffi bands are separated by a
gap of magnitude 21 at  ¼ 0, which originates
from the interlayer coupling 1 . The effective
Hamiltonian for the lower energy band pair relevant
1.10.2.4 Single-Wall Carbon Nanotubes
to the transport and other low energy properties can
be written as Single-wall nanotubes (SWNTs) are formed by roll-
0 1 ing up a sheet of graphene into a nanometer-sized
vF2  2 cylinder. Electronic motion along the circumference
B 0 ˆ
 x – iˆ y C
B 1 C direction is then subjected to a periodic boundary
Ĥbi ¼ B C ð11Þ
@ v2   2 A condition that depends on how the sheet is rolled up.
F
ˆ x þ iˆ y 0 The way a graphene sheet is rolled up to make
1
SWNT is specified by a lattice translation vector,
which is to be contrasted with Equation (9) for the called chiral vector,
monolayer case. The energy eigenvalues of Equation
(11) are  pffiffiffi
1 3
L ¼ n1 a1 þ n2 a2 ¼ n1 ð1; 0Þ þ n2 – ;
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ! 2 2
1 2 1  pffiffiffi  ð13Þ
"ðkÞ ¼   þ ðhvF Þ – 1 2 1 3
4 1 2 ¼ n1 – n2 ; n2
ð12Þ 2 2
ðhvF Þ2 2
  as shown in Figure 4. The hexagons separated by L
12
in the original graphene sheet are rolled onto
Thus, the low energy bands of bilayer graphene are one another in the SWNT. The length of L is
quadratic and meets at k ¼ 0. This dispersion relation expressed as
can be written in the form of a massive
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
electron "ðkÞ ¼ h2 2 =2m , with the effective mass jLj ¼ jn1 a1 þ n2 a2 j ¼ n21 ja1 j2 þn22 ja2 j2 þ2n1 n2 a1 ? a2
m ¼ 1 =2vF2 , as opposed to the linear dispersion in the qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi  
monolayercase.Usingavalue 1  0.39 eVtakenfrombulk ¼ a n21 þ n22 – n1 n2 ,a1 ?a2 ¼ – a2 =2
graphite and vF  1106ms1, the effective mass is ð14Þ
366 Electronic States and Transport Properties of Carbon Crystalline

(a) ðr þ LÞ ¼ ðrÞ, or equivalently expðik?LÞ ¼ 1, to

y′
the graphene band. (For smaller diameter nano-
y b τ1 tubes, the curvature of the cylindrical surface
(ma, mb) η a τ τ3 becomes non-negligible so that mixing between
2
T A
B
the -bands and -bands has to be taken into
x
unit cell account.) The kx -component of the wave vector is
η x′ L
quantized to kx ¼ ð2=LÞs (s : integer), while the
(na, nb)
ky -component remains continuous, so that the
η a2 allowed values of k lie on a series of parallel straight
(0,0) a1 lines. The band structure of an SWNT critically
depends on whether these lines pass through the K
(b) Ky and K9-points of original graphene Brillouine zone.
K
Armchair (η = π/6)
When they do, the phase factor takes the following
K′ η
Kx form:
K Zigzag (η = 0)    
η 2 2
K′ expðiK?LÞ ¼ exp i ðn1 þ n2 Þ ¼ exp i
z B 3 3
K′ K (c) y    
2 2
x expðiK9?LÞ ¼ exp – i ðn1 þ n2 Þ ¼ exp – i
φ 3 3
L ð19Þ

Figure 4 Construction of a carbon nanotube from a where X ðn1 þ n2 Þðmod3Þ is an integer that takes a
graphene sheet. Chiral vector. Reproduced with permission value 0 or 1. If ¼ 0, the SWNT is metallic
from Ando T (2005) Theory of electronic states and transport because it has two bands crossing at the K- and
in carbon nanotubes. Journal of the Physical Society of
K9-points without gap. If ¼ 1, on the other
Japan 74: 777.
hand, there is a non-zero-gap so that the SWNT is
semiconducting.
An SWNT with a nonspecial L possesses a
helical (chiral) structure. There are two special
Since the chiral vector L becomes the circumference, categories of nonchiral SWNT: zigzag nanotubes
the diameter of the SWNT is with ðn1 ; n2 Þ ¼ ðm; 0Þ and armchair nanotubes
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi with ðn1 ; n2 Þ ¼ ð2m; mÞ. According to the above
L a n12 þ n22 – n1 n2 criterion for metallicity, zigzag nanotubes are
d¼ ¼ ð15Þ
  metallic when m is devisible by 3 and semicon-
Thus, every SWNT is specified by a set of two ducting otherwise. By contrast, all armchair
integers ðn1 ;n2 Þ. The primitive translation vector T nanotubes are metallic because n1 þ n2 ¼ 3m.
along the length of nanotube is written as The periodic boundary conditions for the envel-
ope function are
T ¼ m1 a1 þ m2 a2 ð16Þ
 
The condition L ? T ¼ 0 reads 2
FK ðr þ LÞ ¼ e – iK?L FK ðrÞ ¼ exp – i FK ðrÞ
3
  ð20Þ
m1 ð2n1 – n2 Þ þ m2 ð2n2 – n1 Þ – 0 ð17Þ 2
K9 – iK9?L K K9
F ðr þ LÞ ¼ e F ðrÞ ¼ exp i F ðrÞ
3
which can be solved as
The extra phase appearing here as an electron travels
n1 – 2n2 2n1 – n2
m1 ¼ and m2 ¼ ð18Þ around the cylinder corresponds to a fictitious
P P
magnetic flux of magnitude  ¼ – ð =3Þ0 for the
where p is the greatest common divisor of n1 – 2n2 K-point and  ¼ ð =3Þ0 for the K9-point (0 ¼ h=e
and 2n1 – n2 . The unit cell of an ðn1 ;n2 Þ nanotube is being the flux quantum) piercing the tube.
the rectangular region defined by T and L. The envelope wave function is given by a plane
The electronic bands of an SWNT is obtained wave FK ðrÞ_ exp – ikx x þ iky y . The kx -component
by imposing a periodic boundary condition is quantized to
 Electronic States and Transport Properties of Carbon Crystalline
2  
kx ¼ v ðnÞ ¼ n – ; n ¼ 0; 1; 2;    ;
L 3
while the ky-component is continuous. The energy
eigenvalues are expressed in terms of the quantum
number n that specifies the circumferential mode and
the wave number ky ð¼ kÞ for the 1D motion along
the length of the nanotube as
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
"ðn; kÞ ¼ hvF  ðnÞ2 þ k2
Figure 5 shows the band structure in the vicinity of
the K-point for ¼ 0 and ¼ þ1 (Ando, 2005). For
¼ 0, the n ¼ 0 subband has a linear dispersion and
other subbands are twofold degenerate with respect
to the positive and negative values of n. For ¼ 1,
on the other hand, the ðn ¼ 0Þ subband has a gap
"G
n¼0 ¼ "ð0;0Þ ¼ 4h vF =3L so that the system is
semiconducting. This sort of subband structure can
be probed by optical absorption spectroscopy.
Kataura et al. (1999) succeeded in preparing a series
of SWNTs with different diameters and demon-
strated systematic evolution of the subbands with
the nanotube diameter. It was subsequently demon-
strated that incorporation of Coulomb effects
(excitonic effects) is crucial (Ichida et al., 2002).
For a metallic SWNT with linear dispersion, the
density of states is given by
4 strip of graphene with a nanometer-size width,
Dð"Þ ¼
hvF
where the factor 4 comes from the spin and valley
degeneracy. This is in contrast to the case of
graphene (Equation (6)), that is, 2D system with a
linear dispersion, where the density of states vanishes
at " ¼ 0.
ε ε
n = +2, –2
n = +1, –1
n=0
k k
n = +1, –1
ν=0 ν = +1
Figure 5 Subbands of single-wall carbon nanotube for
metallic case, ¼ 0 (left), and semiconducting case ¼ 1
(right). Reproduced with permission from Ando T (2005)
Theory of electronic states and transport in carbon
nanotubes. Journal of the Physical Society of Japan
74: 777.
367
As mentioned above, the periodic boundary con-
ð21Þ
dition (Equation (20)) contains an extra phase that
can be viewed as arising from a fictitious magnetic
flux of magnitude ð =3Þ0 . When an external mag-
netic field is applied parallel to the nanotube axis,
the Aharonov–Bohm (AB) phase is added to the
periodic boundary condition. Equation (21) is then
modified to
 
ð22Þ 2 
kx ¼  ðnÞ ¼ n– þ ; n ¼ 0; 1; 2;   
L 3 0
ð24Þ
This poses an interesting possibility that the electro-
nic band structure of an SWNT can be tuned by an
AB flux due to an external magnetic field parallel to
the tube axis. As the AB flux is changed, the energy
gap oscillates between 0 and 2hvF =L with period
0 . Namely, a semiconducting nanotube can be
transformed metallic at appropriate values of the
AB flux where the gap vanishes either at K- or
K9-point.
1.10.2.5 Graphene Nanoribbons
Another family of carbon allotropes with a basic
structure intimately related with that of nanotubes
is graphene nanoribons. A graphene nanoribbon is a
ð23Þ
which can be viewed as an SWNT cut along the
length and opened flat. The dangling bonds that
occur in the carbon atoms on the side edges are
terminated, for example, with hydrogen. This
imposes different kinds of boundary conditions
than the periodic boundary conditions for SWNT.
In parallel with the corresponding categories for
SWNT, there exist different types of nanoribbons
depending on how (along which direction) the rib-
bon is cut out of the original graphene sheet. Two
n = +2 representative types are armchair and zigzag rib-
n = –1
bons, whose atomic arrangements along the edge
n = +1 are the armchair and zigzag patterns, respectively.
n=0
(It should be reminded that there is a difference in
n=0
nomenclature between nanotubes and nanoribbons.
n = +1
In the case of nanotubes, armchair or zigzag refers to
n = –1
the atomic arrangement along the chiral vector, that
is, along the circumference of the tube. Therefore, if
an armchair nanotube is cut along its length to make
a nanoribbon, the resulting one is a zigzag ribbon,
and vice versa.)
Many aspects of electronic properties of graphene
nanoribbons have parallels with nanotubes. For
368 Electronic States and Transport Properties of Carbon Crystalline

example, an armchair ribbon becomes metallic or - and 9-bands meet at the K- and K9-points.
semiconducting according to whether the width N Interlayer coupling gives rise to a finite overlap of
of the ribbon is N ¼ 3m – 1 ðm ¼ 1;2;3;   Þ or the - and 9-bands, so that 3D graphite is a semi-metal.
otherwise. One notable difference of nanoribbons The first Brillouin zone of graphite is a hexagonal
from nanotubes lies in the existence of edge states. prism shown in Figure 6. The -band structure of
In particular, the band calculations predict that a graphite in the vicinity of "F, that is, near the H–K–H
zigzag ribbon has a flat (dispersionless) band at zone edge, is described by the Slonczewski–Weiss–
" ¼ 0, so that the density of states has a sharp peak McClure (SWMcC) model (McClure, 1957;
at the Fermi level (Fujita et al., 1996). This is in Slonczewski and Weiss, 1958):
marked contrast with the bulk graphene whose den-
sity of states is zero at " ¼ 0. This flat band is due to 0 
1
E1 0 H13 H13
the edge states constructed from the nonbonding B C
orbitals of the atoms along the zigzag edge. Since B0 E2  C
H23 – H23
B C
H ¼B C ð25Þ
the weight of the edge states relative to the bulk B H13
 
H23 E3 H33 C
@ A
states increases with decreasing ribbon width, the  
H13 – H23 H33 E3
former plays an important role in nanometer-sized
ribbons. For example, the large density of states at the where
Fermi level would lead to a large Pauli paramagnetic
contribution to the magnetic suseptibility and may E1 ¼  þ 21 cosðkz c Þ þ 25 cos2 ðkz c Þ
even give rise to the so-called flat-band E2 ¼   21 cosðkz c Þ þ 25 cos2 ðkz c Þ
ferromagnetism.
E3 ¼ 22 cos2 ðkz c Þ
pffiffiffi
6 ð26Þ
H13 ¼ ð – 0 þ 24 cosðkz c ÞÞeij a
4
1.10.2.6 Bulk Graphite pffiffiffi
6
The global electronic structure of graphite is H23 ¼ ð0 þ 24 cosðkz c ÞÞeij a
4
given by the 2D graphite model described in pffiffiffi
H23 ¼ 33 cosðkz c Þeij a
Section 1.10.2.2. Graphite, however, is a 3D system
consisting of ABAB   stacking of graphene sheets with
the interlayer spacing c ¼ 0.335 nm. For the detailed If the parameter 3 which describes the trigonal
band structure near the Fermi level, interlayer coupling warping is neglected, the SWMcC model yields
plays an important role. In the case of 2D graphite, the the following four eigenvalues:

(a) (b)
E

A H
H′
H′ H K E1
Γ
K′ M K′
K
A H
H′ H′
H L
0 E3
EF
2γ2

E2

K K H H

Figure 6 The electron and hole Fermi surfaces of graphite located along the H–K–H (and H9–K9–H9) edges of the
Brillouin zone.
 Electronic States and Transport Properties of Carbon Crystalline
8 rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
>
> 1 1 3
> ð
<2 1 3E þE Þ ðE1 –E3 Þ2 þ ð0 –24 cosðkz c ÞÞ2 ðaÞ2
4 4
E¼ rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
>
>1
: ðE2 þE3 Þ 1 ðE2 –E3 Þ2 þ 3 ð0 þ24 cosðkz c ÞÞ2 ða Þ2
>
2 4 4
The -band near the H–K–H edge is illustrated in
Figure 6. There occur electron pockets centered at
the K- and K9-points and hole pockets at the H- and
H9-points. The bandwidth along the H–K–H edge is
4 1  1.56 eV and the band overlap that makes the
3D graphite a semimetal is 22  39meV.
Reflecting the quasi-2D structure of graphite, its
Fermi surfaces are highly elongated along the
kz -direction. The effective mass for motion within
the basal plane is me ¼ 0:057m for electrons and
mh ¼ 0:039mh for holes (Soule et al., 1964). (In the
early stage of the electronic structure study of gra-
phite, the assignment of the electron and hole pockets
was opposite to what was later established.) The effec-
tive mass for the out-of-plane motion is estimated to
be on the order of m? ¼ ð5 – 15Þm for both electrons
and holes. These values are inferred from the angular
dependence of the cyclotron mass mc fitted to the
following formula assuming ellipsoidal Fermi surfaces:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1 cos2
sin2
1.10.3.2
¼ þ
mc ð
Þ m2k mk m?
pffiffiffiffiffiffiffiffiffiffiffiffiffiffi
The anisotropy ratio m? =mk is 17 for the electron
Fermi surface and 12 for the hole Fermi surface (Soule
et al., 1964). Direct measurement of the effective masses
together with correct assignment of carrier pockets were
achieved by cyclotron resonance using circularly polar-
ized microwave (Suematsu and Tanuma, 1972).
Detailed studies of magneto-quantum oscilla-
tions suggest existence of additional small pieces
of Fermi surface. These are so-called minority
hole pockets residing at the H- and H9-points.
The minority hole Fermi surface is separated
from the narrow part (neck) of the Fermi surface
for majority holes by the spin–orbit splitting.
1.10.3 Transport Properties of
Graphene
1.10.3.1 Preparation of Graphene Samples
Graphene offers a totally new class of 2D electron
system (2DES) that exhibits novel properties to be
contrasted with those of conventional 2DES realized
369
in semiconductor heterointerfaces. Graphene samples
used in transport experiments are typically prepared
by pressing mechanically cleaved pieces of graphite
onto an oxidized surface of Si substrate (Novoselov
et al., 2005b). With enough skills and persistence, a few
ð27Þ
micron-sized ultrathin graphite pieces can be identi-
fied under an optical microscope. Electrical contacts
are made by standard lithographic techniques and
metal evaporation. With the underlying Si substrate
used as a back gate, the system constitutes a field-
effect-transistor (FET) structure. Figure 7 shows the
sheet resistance of a monolayer graphene sample as a
function of the back gate bias Vg . Positive (negative)
Vg induces electrons (holes) of density n ¼ Cg Vg =e in
the graphene sheet. For a typical thickness 300 nm of
the insulating SiO2 layer, the coefficient is
Cg =e  8  1014 m – 2 V – 1 . Thus, the system functions
as an ambipolar FET with carrier mobilities of the
order of   0:1 – 1m2 V – 1 s – 1 .
Another method to prepare graphene relies on gra-
phitization of the surface layer of a silicon carbide
crystal (Berger et al., 2006). The (0001) surface of a
4H-SiC wafer is vacuum heat treated to form an epi-
taxial layer of graphene. This technique has a potential
advantage of preparing a large area sample of graphene.
Transport at Zero Magnetic Field
ð28Þ
The unconventional nature of the electronic state in
graphene is reflected in various transport properties
(Geim and Novoselov, 2007; Castro Neto et al., 2009).
6
4
ρ (kΩ)
2
T=1K
B=0T
0
–60 –30 0 30 60
Vg (V)
Figure 7 Sheet resistance of a monolayer graphene as a
function of back gate bias Vg. Reproduced with permission
from Novoselov KS, Morozov SV, Mohinddin TMG, et al. (2007)
Electronic properties of graphene. Physica Status Solidi (b)
244: 4106. Copyright Wiley-VCH Verlag GmbH & Co. KGaA.
370 Electronic States and Transport Properties of Carbon Crystalline
The electronic dispersion in monolayer graphene is
characterized by the Dirac cones, that is, massless
chiral fermions. Indeed, graphene offers a unique
opportunity of exploring an analog of quantum elec-
trodynamics (QED) in solid state. Charge carriers in
bilayer graphene provide massive chiral fermions
that are no less exotic.
Massless Dirac fermion described by the
Hamiltonian, Equation (9), has a unique feature
that the electron state in the conduction band and
the hole state in the valence band are intercon-
nected, exhibiting properties analogous to charge-
conjugation symmetry in QED. For the case of
graphene, this symmetry arises from the honeycomb
lattice structure with A and B sublattices. The quasi-
particles are described by two-component wave
functions which is analogous to spinor wave func-
tion in QED, with pseudo-spin specifying the
sublattice playing the role of real spin in the latter.
The symmetry is such that an electron with energy
E propagating in one direction belongs to the same
branch of the electronic spectrum as the hole with
energy –E propagating in the opposite direction.
Electrons and holes belonging to the same branch
have pseudo-spin pointing in the same direction
(parallel to the momentum for electrons and anti-
parallel for holes). Chirality, which is defined as
projection of pseudo-spin on the direction of
motion, is positive for electrons and negative for
holes.
One of the most counterintuitive properties of
graphene is the so-called Klein paradox. It has been
theoretically predicted that a relativistic particle can
freely penetrate a potential barrier by transforming
itself to its antiparticle. In graphene, this is mani-
fested as reflectionless tunneling of charge carriers
through a potential barrier by unimpeded transfor-
mation between electron-like and hole-like quasi-
particles. Namely, an electrostatic potential cannot
backscatter a massless Dirac fermion. Another way to
understand the suppression of backscattering in gra-
phene is to invoke destructive interference between
one backscattering process and its time-revered
counterpart on account of Berry9s phase associated
with the rotation of pseudo-spin. This is analogous to
the anti-localization in the presence of a strong spin–
orbit interaction.
Charge carriers in graphene can indeed propagate
without scattering over large distances of the order of
micrometers. Carrier mobilities as high as
  1:5m2 V – 1 s – 1 are at room temperature and
  20m2 V – 1 s – 1 at helium temperature are cur-
rently reported. This means that carrier transport is
ballistic on submicron scale even at room tempera-
ture. Carrier mobilities currently achieved are
presumably limited by impurities, by structural dis-
order (corrugation of graphene sheet) and by
coupling with the substrate, and leave room for
improvement.
As seen in Figure 7, sheet resistance of gra-
phene increases as Vg ! 0, but remains on the
order of several kilo-ohm even right at the charge
neutrality point, where one naively expects the
system to become nonconducting owing to vanish-
ing carrier density. Conductivity on the order of
e 2=h per channel at the charge neutrality point has
been theoretically predicted (Fradkin, 1986; Shon
and Ando, 1998). This conduction without carriers
is yet another counterintuitive property of gra-
phene. The reason for the existing discrepancy
between experimentally observed values of the
minimum conductivity that scatters around  4e 2=h
and the theoretical value 4e 2=h is not clear at the
moment. Theoretically, proper treatment of strong
electron–electron interaction may be crucial. On
the other hand, the fact that a real graphene
sample at their charge neutrality point most likely
consists of puddles of electrons and holes may
significantly affect the experimental results
(Adam et al., 2007).
Theoretical prediction for the high-frequency con-
ductivity of Dirac fremion in graphene is  ¼ e 2=4h,
as opposed to 4e 2 =h for the DC conductivity. Optical
transmittance given by T X ð1 þ 2=c Þ – 2 becomes
 – 2  – 2
e2 1
T¼ 1 þ 2 ¼ 1 þ   1 –  ð29Þ
4hc 2
where  X e 2 =hc  1=137 is the fine structure
constant. The opacity of monolayer graphene is
given by ð1 – T Þ ¼   0:023. Visible light trans-
mission measurements on suspended graphene
membrane have proved that monolayer graphene
absorbs about 2.3% of the incident white light
(Nair et al., 2008).
1.10.3.3 Quantum Hall Effect
Application of magnetic field normal to the gra-
phene plane causes quantum oscillations of
resistance (Shubnikov–de Haas effect) which evolve
to QHE under higher fields (Novoselov et al., 2005a;
 Electronic States and Transport Properties of Carbon Crystalline 371

Zhang et al., 2005). The QHE in graphene is one of
the most conspicuous phenomena that reveal the
exotic nature of the system. Figure 8 shows the
characteristic QHE behavior in monolayer and
bilayer graphene (Novoselov et al., 2005a, 2006).
Here the Hall conductance xy and the longitudinal
N ¼ 0 and 1 LLs is E ¼ 400K  BðT Þ, which, in
conjunction with high mobility, makes it possible to
observe QHE even at room temperature. In moder-
ate magnetic fields, each LL has fourfold degeneracy.
The spin degeneracy of LL is lifted by a strong
magnetic field with g-factor somewhat smaller
resistance xx are plotted as a function of the charge
density controlled by the gate bias. In both cases, the
step of the Hall conductance xy is 4e 2=h. The factor
4 reflects the twofold spin degeneracy and the two-
fold valley degeneracy. For monolayer graphene,
the sequence of Landau levels is shifted by 1/2,
compared with the conventional QHE,
 so that the
Hall plateau values are xy ¼ 4 e 2=h ðjN j þ 1=2Þ,
than 2. For the N ¼ 0 LL, even the valley degener-
acy seems to be lifted under high magnetic fields
whose mechanism is yet to be elucidated (Zhang
et al., 2006).
Bilayer graphene has parabolic conduction and
valence bands that are degenerate at the charge neu-
trality point. The LLs of massive chiral quasi-
particles are given by
N being the Landau level (LL) index . The xx peak
at n ¼ 0 (Vg ¼ 0) implies that the N ¼ 0 LL which
stays at the charge neutrality point, E ¼ 0 is shared
equally by electrons and holes. This is a signature of
the massless Dirac fermion described by the hamil-
tonian, Equation (9). The shift by 1/2 is
alternatively viewed as arising from an additional
phase , known as Berry’s phase, gained by a quasi-
particle as it completes cyclotron motion with fixed
chirality.
The LL spectrum of a massless Dirac fermion
(linear dispersion) is
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
EN ¼ vF 2ehjN jB
to be contrasted with the ordinary
EN ¼ ðheB=mÞðN þ 1=2Þ for a massive particle (para-
bolic dispersion). Equation (29) implies large
separation of low-lying LLs. The gap between the
heB pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
EN ¼ N ðN – 1Þ ð31Þ
m
The QH plateau sequence is xy ¼ 4e 2=h  int
which is the same as the conventional 2DEG with
the same spin and valley degeneracy, except that the
lowest LLs of the valence and conduction bands
(N ¼ 0 and 1) are merged so that the plateau at
n ¼ 0 is missing.
The gapless electronic band of bilayer graphene is
modified by applying an electrostatic bias between
the layers. The resulting energy gap of the order of
0.1eV can be tuned by the field effect. In the presence
of nonzero gap, the above-mentioned anomaly in
ð30Þ
the QHE due to the degeneracy of the N ¼ 0 and 1
LLs disappears. To observe this splitting at finite
interlayer bias, the charge neutrality point has
to be shifted by additional chemical doping
(Castro et al., 2007).

(a) (b)
+7/2
Monolayer 4 Bilayer
+5/2 3
6
10 +3/2 2
σxy (4e 2/h)
σxy (4e 2/h)

1
ρxx (kΩ)
ρxx (kΩ)

+1/2
0 4
−1/2
−1
5
−3/2 −2
2
−5/2 −3

−7/2 −4
0 0
−4 −2 0 2 4 −4 −2 0 2 4
Charge density (1012 cm−2) Charge density (1012 cm−2)

Figure 8 Quantum Hall effect in (a) monolayer and (b) bilayer graphene. Reprinted with permission from Geim AK and
MacDonald AH (2007) Graphene: Exploring carbon flatland. Physics Today 60: 35. Copyright (2007) American Institute of
Physics.
372 Electronic States and Transport Properties of Carbon Crystalline

1.10.4 Transport Properties of
Carbon Nanotubes
1.10.4.1 Electronic State in SWNTs
As mentioned in Chapter 3.02, the electronic structure
of SWNT is determined by the chiral vector, that is,
how a hypothetical graphene sheet is rolled to make
the SWNT. An armchair SWNT which has an elec-
tronic structure similar to monolayer graphene is
metallic. Zigzag nanotubes are, by contrast, either
quasi-metallic or semiconducting depending on the
chiral vector. The difference in electronic structures
and their correlation with the chirality of nanotube has
been beautifully verified by spectroscopic measure-
ments using a scanning tunneling microscope (STM)
tip (Issi et al., 1995; Wildoer et al., 1998). Figure 9 shows
the calculated and measured spectra for metallic and
semiconducting SWNTs (Dekker, 1999). The spectra
show the characteristic van Hove singularities of 1D
subbands, and nonzero (zero) density of states at the
Fermi level for the metallic (semiconducting) SWNT.
As shown by Equation (23), the electronic structure
of an SWNT is profoundly affected by an AB flux
threading through the tube. Full conversion of a semi-
conducting nanotube to a metallic one (or vice versa)
is beyond experimental reach, because it will require
an extremely strong magnetic field in excess of 1000 T
for a typical nanotube diameter of 1 nm. Still, a pre-
cursory effect of AB flux on the band structure of
SWNT has been verified by observation of mag-
netic-field-induced splitting of the optical spectra
under magnetic fields up to 45 T (Zaric et al., 2004).
1.10.4.2 Electron Transport in SWNTs
For electrical transport experiments, it is necessary to
make electrical contacts. A usual way to achieve this
is to disperse or CVD-grow onto a substrate on which

Metallic Semiconducting
nanotube nanotube
(9,9) (11,7)
0.1 0.1
Density of states

Density of states

0.0 0.0
−1 0 1 0 1
−1
Energy (eV)
Energy (eV)

3
Differential conductance
Differential conductance

3
0
(normalized)
(normalized)

2 2

1 1

0 0
−1 0 1 −1 0 1
Voltage (V) Voltage (V)
Figure 9 Calculated (top panels) and measured (bottom panels) tunnel spectra of a metallic nanotube (left) and a
semiconducting nanotube (right). Reproduced with permission from Dekker C (1999) Carbon nanotubes as molecular
quantum wires. Physics Today 52: 21.
 Electronic States and Transport Properties of Carbon Crystalline 373

a large array of fine metallic electrodes has been
pre-patterned. After depositing the nanotubes, the
sample is scanned with an atomic force microscope
(AFM) to find nanotubes that by coincidence bridge
two or more electrodes. Another more controlled
method is to sprinkle nanotubes on an insulating
substrate, take a scanning image of the deposited
area with an AFM, and use that information to
make a suitable electrode pattern by electron beam
lithography. A problem here is that it is difficult to
prejudge whether the target nanotube is metallic or
semiconducting. The contact resistance varies widely
depending on the kind of metal used for the elec-
trode. Titanium and nickel are often used to achieve
low-resistance contacts, while gold and aluminum
tend to result in high contact resistance. The trend
seems to be correlated with the carbide formation
tendency of the respective metals.
The intrinsic conductance of armchair nanotube is
expected to be 4e 2 =h. Here, the factor 4 refers to the
spin and valley degeneracy. That a metallic SWNT
acts as a coherent quantum wire was first demon-
strated by Tans et al. (1997) and by Bockrath et al.
(1997). They observed and analyzed the Coulomb
blockade phenomenon at low temperatures, and
found that successively added single electrons are
carried by one additional molecular orbital, which
implied that electrons in SWNT were delocalized
over an appreciable length (a few mm).
Figure 10 shows the conductance of an SWNT
sample measured with highly transparent (low-
resistance) contacts achieved with titanium electro-
des (Kong et al., 2001). The value of conductance at
low temperatures is close to 4e 2 =h. The conductance
shows conspicuous fluctuations as a function of gate
bias which is attributed to Fabry–Perot-type inter-
ference of ballistic electrons repeatedly reflected at
the both ends (contacts) of the SWNT sample.
It is remarkable that metallic SWNT can remain
metallic at all, if one is reminded of intrinsic fragility
of 1D electron systems associated with Peierls
instability and strong tendency of localization. The
tubular structure of SWNT renders robustness
against Peierls distortion. The local defect potential
is effectively weakened because it is seen by electrons
as averaged over the circumference (White and
Todorov, 1998). Suppression of backscattering men-
tioned earlier in the graphene context also plays a
role here (Ando, 2005).
Once electron–electron interaction is switched
on, a 1D electron system is predicted to behave as a
so-called TLL rather than an ordinary Fermi liquid.
Signatures of TLL behavior are power-law depen-
dence of the conductance on temperature and bias
voltage, which are experimentally observed
by Bockrath et al. (1999). The TLL nature of
SWNTs is also corroborated by the photoemission
spectroscopy (Ishii et al., 2003).

2.0 I II III
25 K
20 K
1.5 50 K
Conductance (G0)

100 K

1.0 290 K

0.5

0.0
−20 −10 0 10 20 30
Vg (V)

Figure 10 Conductance of a nanotube sample as a function of gate bias at different temperatures. The conductance at low
temperatures is close to 2 G0 ¼ 4e2/h in value and exhibits random but reproducible fluctuations. Reprinted with permission
from Kong J, Yenilmez E, Tombler TW, et al. (2001) Quantum interference and ballistic transmission in nanotube electron
waveguides. Physical Review Letters 87: 106801. Copyright (2001) by the American Physical Society.
374 Electronic States and Transport Properties of Carbon Crystalline

1.10.4.3 Multi-Wall Nanotubes from 10 to 40 among kish graphite samples. Given

the change in carrier density with temperature
Multi-wall nanotubes (MWNTs) occur in a wide
stated above, the residual mobility ratio
variety, with respect to the number of wall, their
300K =4:2K is about 3 times as large. The values
morphology, and various defects including adsor-
of electron and hole mobility in best-quality sin-
bates. In general, adjacent tube sheets have different
gle-crystal samples at low temperatures exceed
chirality, so that electrons in a MWNT move in a
100 m2 V1 s1.
relatively strong random potential. This and other
The out-of-plane resistivity c tends to be even
source of disorder make the electron mean free path
more sensitive to the sample quality. The value of
in MWNTs much shorter than in SWNTs, so that
diffusive transport is usually observed in MWNTs.
1.10.5 Transport Properties of
Graphite
1.10.5.1 Graphite Materials and Transport
Characteristics
A type of graphite widely used in various experi-
ments is highly oriented pyrolytic graphite
(HOPG), which is synthesized by thermal crack-
ing of hydrocarbon and subsequent heat treatment
under pressure to improve the quality of c-axis
orientation of the crystallites. As they have a
variety of uses including monochrometers for
neutron diffraction and standard specimens for
scanning probe microscope, HOPGs are available
in various sizes. The in-plane structure of HOPG
is a randomly ordered collection of small (mm
size) crystallites. Another type of graphite is sin-
gle-crystal kish graphite obtained by
crystallization of carbon from molten steel. They
come in the form of thin flakes that contain fairly
large (mm size) single crystallites. As grown,
kish graphite contains fairly large amount of iron
segregates, which are subsequently removed by
chemical processing with chlorine.
As stated in Section 1.10.2.5, graphite is a semi-
metal with equal numbers of electrons and holes.
Owing to the small Fermi energy, the carrier
concentration shows a significant temperature
dependence; ne ¼ nh  1  1025 m – 3 at room tem-
perature, and  3  1024 m – 3 at helium
temperatures (Dillon and Spain, 1978). The basal
plane resistivity at room temperature is limited by
acoustic phonon scattering so that it is relatively
anisotropy ratio c =a at low temperature generally
falls between 103 and 105. (For reference, the effec-
tive mass ratio is estimated as m? =mk  102 .) It is
still unclear whether the lower or higher values of
the anisotropy ratio represent the intrinsic behavior.
On the one hand, less-well-oriented graphite crys-
tals tend to give lower values. On the other hand,
easy-to-cleave graphite crystals are vulnerable to
defects such as stacking faults and microcracks
which would give higher values. The out-of-plane
resistivity often shows a slightly negative (semicon-
ducting) temperature dependence from room
temperature down to 30 K and then turns to a
positive (metallic) one at lower temperatures. This
unusual behavior may be simply a combined effect
of the temperature-dependent carrier densities and
mobilities. On account of the materials problem as
stated above, however, full understanding of the
c-axis transport in graphite is still not yet reached
(Morgan and Uher, 1981; Brandt et al., 1988;
Matsubara et al., 1990; Kopelevich et al., 2003).
Recently, Kempa et al. (2002) invoke a field-induced
metal–insulator transition for the c-axis resistivity
based on their scaling analysis. However, given the
above-stated temperature dependence of carrier
density, the apparent metallic or insulating behavior
of resistivity cannot be taken literally. The validity
of proposed scaling analysis over a wide tempera-
ture range should be carefully accessed.
1.10.5.2 Semi-Classical Magneto-
Transport
Magneto-transport properties of graphite are charac-
terized by low carrier density, semi-metallic nature,
and high basal-plane mobility (small effective mass).
Figure 11(a) shows a magnetoresistance trace under
sample independent with a typical value   40 a magnetic field applied perpendicular to the basal
m cm. By contrast, the low-temperature resistiv- plane (Woolam, 1970). We first ignore the oscillatory
ity limited by defect scattering is much more part and focus on the overall magnetic field
sensitive to sample quality. The residual resistiv- dependence. The Lorentz force deflects electrons
ity ratio (RRR) defined as RRR ¼300K =4:2K is and holes to the same direction so that their Hall
typically 3–10 among HOPG samples, but ranges currents tend to cancel out. Since there occurs no
 Electronic States and Transport Properties of Carbon Crystalline 375

(a) (b)
θ
20 0°
19.8°
T = 1.22°K 29.8°
18

16
Magnetoresistance
–105 Δ:p 14 39.7°
50.1°
12

V,(mV)
–6 7.40 58.3°
10
n = 1 electron
6.60 63.5°
–4 8
68.2°
3.643
n = 1 hole 6
3.412
–2 2.952
2.936 n = 2 electron 73.3°
4
1.90 77.0°
0 80.0°
Magnetic field, T 2

0 90.0°

4 6 8 10 12 14 16 18 20 22 24
H (kg)

Figure 11 (a) Traces of longitudinal magnetoresitance xx (B) in a natural single crystal of graphite at T ¼ 1.1K showing the
Shubnikov–de Haas oscillations due to electrons and holes. (b) The magnetoresistance data at different field angles from the
c-axis indicate highly elongated electron and hole Fermi surfaces. (a) Reprinted with permission from Woolam JA (1970) Spin
splitting, Fermi energy changes, and anomalous g shifts in single-crystal and pyrolytic graphite. Physical Review Letters
25: 810. Copyright (1970) by the American Physical Society. (b) Reprinted with permission from Soule DE, McClure JW, and
Smith LB (1964) Study of Shubnikov–de Haas effet. Determination of the Fermi surfaces in graphite. Physical Review
134: A453. Copyright (1964) by the American Physical Society.

Hall voltage to counteract the Lorentz force, a very quadratic B-dependence for compensated metals, a
large positive magnetoresistance appears. In high- B-linear behavior over a wide range of magnetic
quality graphite crystals, xx ðBÞ=xx ð0Þ typically field (McClure and Spry, 1968; Woolam, 1970).
reaches 103 at B  1 T and 104 at 10 T. Since The linear increase of xx(B) tends to saturate at
xx xy , the diagonal magneto-conductivity is higher magnetic fields (Brandt et al., 1974; Lowrey
 
and Spain, 1977). For some samples, xx(B) even
xx ¼ xx = 2xx þ 2xy  1=xx at all magnetic
fields.
In a semi-classical transport model, the Hall
conductivity of a semi-metal in the high field
limit is ideally zero. In actual samples, it takes a
nonzero value that reflects a small imbalance
between the electron and hole densities,
starts to decrease at still higher fields (Iye, 1985;
Yaguchi and Singleton, 1998).
The characteristic B-linear behavior has been
interpreted as due to B-dependent screening of
ionized impurity potential which is thought to be
the dominant scattering mechanism at low tempera-
tures (McClure and Spry, 1968). The saturation of
xy ðBÞ  – ðne – nh Þje j=B. This imbalance is typi-
cally jne – nh j=ðne þ nh Þ  0:3 – 0:03%, and is due
to the presence of ionized impurities. For the major-
ity of graphite crystals, the imbalance goes toward
the electron excess side, that is, more donors than
acceptors.
Figure 12(a) shows traces of magnetoresistance
in single-crystal (kish) graphite at low temperatures
(Iye et al., 1985). The classical part of the diagonal
xx ðBÞ at higher field may be attributed to the so-
called magnetic freeze-out effect, that is, localization
of the excess carriers to the impurity sites, which is
known to occur for example in InSb (von Ortenberg,
1973). In the case of graphite, magnetic freeze-out
does not affect the total carrier density so much but
changes the ionized impurity scattering centers to
neutral ones. The two sets of data in Figure 12
represent two types of kish graphite samples in
resistivity xx(B) exhibits, instead of the standard terms of ionized impurity concentration. Type B
376 Electronic States and Transport Properties of Carbon Crystalline

Graphite
ρxx 150 mk
192
Type A 255
330
390
0.01 Ω cm 485
600

0 175 mk
257
335
ρxx Type B 390
465
0.01 Ω cm
620
0

0
0 50 100 150 200 250
B (kG)
Figure 12 Traces of longitudinal magneto-resitance xx (B) in single-crystal (kish) graphite at different temperatures. The
two set of data are obtained from samples with different ionized impurity concentrations (Iye, 1985).
sample contains an order of magnitude higher con-
centration of ionized impurities than type A. That
the resistivity saturation is more conspicuous in type
A sample seems to corroborate this picture. However,
genuine freeze-out that should diminish xy B to zero
is not observed in this field range, so that the resis-
tivity saturation may be interpreted as precursor of
the freeze-out effect.
from the c-axis (Soule et al., 1964).
1.10.5.3 Magneto-Quantum Oscillations
Since the early days of graphite research, the
dependence indicating
LL structure of graphite has been calculated (Nakao,
1976; Dresselhaus, 1974), and investigated by various
magneto-quantum oscillation measurements (Soule
et al., 1964; Woolam, 1970, 1971a) and magneto-optical
spectroscopy (Schroeder et al., 1971; Doezema et al.,
1979). Figure 13(a) shows a calculated LL structure
along the K–H edge of the Brillouin zone for
B ¼ 1 T.
The trace shown in Figure 11(a) contains two
series of Shubnikov-de Haas (SdH) quantum
oscillations: one due to the electron Fermi surface
and the other due to the hole Fermi surface
(Woolam, 1970). Due to the high carrier mobilities,
the SdH oscillations can be seen in graphite from
magnetic fields as low as 0.1 T. The SdH effect
appears as a series of sharp dips, whose shape
reflects that of the 1D density of states associated
with the motion parallel to the field. Figure 11(b)
shows magnetoresistance traces for different values
of field angle
The shift of the SdH oscillation pattern approxi-
mately obeys the cos
highly elongated electron and hole Fermi surfaces.
In magnetic fields higher than 3 T, the SdH dips
split into pairs, reflecting the Zeeman splitting
(Woolam, 1970). Minority hole pockets are also
identified (Woolam, 1971b).
More recently, direct probing of LL density of
states is made possible by the use of a low-temperature
scanning tunneling spectroscope (LT-STM) (Matsui
et al., 2005). Figure 14(a) shows the tunneling spec-
trum of graphite under perpendicular magnetic fields.
 Electronic States and Transport Properties of Carbon Crystalline 377

(a) (meV) (b)

12 c a
b
γ3 = 0 11 0.10
a
40 b n=1
10 c
H = 10 kG
0.08 σ=– H = 25 T
(H //c) 9 n=2
b
σ=+ H ||c
8
a 0.06
20 7
n=1
6 c σ=+
0.04 n=0
5 σ=–
a
0 4
c b 0.02
n=0

Energy (eV)
3
b c n = –1 σ=+
a
2 σ=–
b c c 0
1
–20 a
b 0 EF
c a EF
–1 1 2 3
a 45 –0.02
b 6 b
c 7
a n = –1
b c 8
n = –2 σ = +
a c –0.04
–40 9
b c
a 10 a b σ=–
a b c 11 b
a b c 12 –0.06
a b c c
c n=0
–60 13 a
–0.08 σ=–
b n=1
c
a σ=+
–0.10
0 0.1 0.2 0.3 0.4 0.5 0 0.1 0.2 0.3 0.4 0.5
(K) ξ (H) ξ = cokz /2π

Figure 13 (a) Landau levels of graphite in a magnetic field of 1T. (b) Landau levels of graphite in a magnetic field of 25 T.
Only the lowest spin-split Landau levels of electron and hole bands cross the Fermi level. (a) Reproduced with permission
from Nakao (1976) Landau level structure and magnetic breakthrough in graphite. Journal of the Physical Society of Japan
40: 761. (b) Reprinted with permission from Iye Y, Tedrow PM, Timp G, et al. (1982) High-magnetic field electronic phase
transition in graphite observed by magnetoresistance anomaly. Physical Review B 25:5478. Copyright (1982) by the American
Physical Society.

The LLs are manifest as a series of peaks in the spectra
indicated by triangles. The observed spectra show
good agreement with the calculated ones with an
appropriate choice of the surface potential s , as
shown in Figure 14(b).
The advent of graphene has brought resurgence of
interest in graphite. The electronic properties of
graphite are now scrutinized under new light.
Luk’yanchuk and Kopelevich (2004, 2006) recently
made a new analysis of the SdH and dHvA oscilla-
tions in bulk graphite. Based on the values of residual
phase, they claim that the spectra indicate coexis-
tence of normal (massive) electrons and Dirac-like
(massless) holes. Schneider et al. (2009) made a simi-
lar but more precise experiment at 10 mK and
measured SdH oscillations up to N  90 quantum
numbers. They have shown that the data precisely fit
the prediction of the SWMcC model, so that there is
no ground for invoking massless Dirac fermions in
3D graphite.
For those electronic properties of graphite asso-
ciated with energy scale larger than the electron–
hole band overlap, j2 j  0:02eV, the Dirac-like
spectrum is obviously relevant so that interpretation
in such terms is possible, as discussed, for example, in
LL spectroscopy (Orlita et al., 2009) and photoemis-
sion spectroscopy (Gruneis et al., 2008). For low-
energy-scale properties such as transport, however,
the 3D nature of the graphite band is quite essential.
1.10.5.4 Magnetic-Field-Induced
Electronic Phase Transition
In magnetic fields higher than 7.4 T, both electrons
and holes are only in their lowest LLs, that is, the
system is in the extreme quantum limit. The magneto-
resistance traces in Figure 12 show distinct anomalies
in the high-field quantum limit regime. The abrupt
increase of resistance is indicative of a phase transition
to a new magnetic-field-induced electronic state. As
378 Electronic States and Transport Properties of Carbon Crystalline

(a)

4 B = 6T

5T

3 4T

dI/dV (nA/V) 3T

2T
2

0T

Kish graphite
T = 55 mK
0
(b) 30
φs = 17 meV
= 0 meV
dI/dV (nA/V)

20

10
Kish graphite
B=6T
T = 55 mK
0
−200 −100 0 100 200
V (mev)
Figure 14 (a) Tunneling spectrum of graphite in several magnetic fields obtained by a low-temperature scanning tunneling
microscope (LT-STM). (b) Comparison of the spectrum with the calculated local density of states curves for two different
values of surface potential s. Reprinted with permission from Matsui T, Kambara H, Niimi, Y, Tagami K, Tsukada M, and
Fukuyama H (2005) STS observation of Landau levels at graphite surfaces. Physical Review Letters 94: 226403. Copyright
(2005) by the American Physical Society.

seen in the figure, the onset magnetic field decreases
with decreasing temperature. Figure 15(a) shows the
phase boundary of the field-induced phase plotted
with T in a logarithmic scale versus 1/B. The data
points for the type A sample (crystals with lower
ionized impurity concentration) lie on a straight line,
which means that the phase boundary of the field-
induced phase can be empirically expressed as
Tc ðBÞ ¼ T  expb – B  =B c
for this field range.
The Landau subband structure in the quantum limit
regime is shown in Figure 13(b) for B ¼ 25 T (Iye et al.,
1982). In the quantum limit, the electronic motion in
along the c-axis (parallel to B). Yoshioka and
Fukuyama considered the possibility of Peierls-type
instability of such magnetic-field-induced 1D system
and proposed that the observed anomaly could be
attributed to occurrence of a charge-density-wave
instability (Yoshioka and Fukuyama, 1981; Sugihara,
1984; Takada and Goto, 1998). To be precise, two
charge density waves associated with two valleys
(along the H–K–H and H9–K9–H9 edges) occur out-
ð32Þ of-phase with each other to reduce the Hartree term of
the Coulomb interaction, so that a valley density wave
may be a better term for the proposed state. The critical
temperature given by Yoshioka and Fukuyama reads
   

the basal plane (perpendicular to B) is quenched so that cos2 12 ckF0" 1

Tc ¼ 4:53"F   exp – ð33Þ
the system is reduced to a narrow-band 1D system cos ckF 0" N0" ð"F Þũ
 Electronic States and Transport Properties of Carbon Crystalline 379

(a) 280 260 240 220 200 180 160 (b)

Kish graphite β′
2000 B || c-axis
α β1

β2
1000 α′
1.1 K
0

Resistance ρxx (a.u.)

500 1.7 K
Type A 0
Tc (mk)

2.2 K
0
Type B 3.2 K
200 0
4.2 K
0
100 8.0 K
0 10 K

50 0
4 5 6 0 10 20 30 40 50 60
1/B (×10–3 kG–1) Magnetic field (T)

(c)
10
α
8 α′
Temperature (K)

YF theory
6

0
20 30 40 50 60
Magnetic field (T)
Figure 15 (a) The phase boundary of the magnetic-field-induced phase (Iye, 1985). (b) Magnetoresistance traces up to 55 T
at different temperatures. (c) The phase boundary in a wider range of temperature and magnetic field, showing a re-entrant
behavior at higher magnetic fields. (c) Reprinted with permission from Yaguchi H and Singleton J (1998) Destruction of the
field-induced density-wave state in graphite by large magnetic fields. Physical Review Letters 81: 5193. Copyright (1998) by
the American Physical Society.

where N0" ð"F Þ is the Fermi-level density of states
of the lowest spin-up electron subband, and ũ is
a parameter representing the effective electron–
electron interaction strength. This is an analog
of a Bardeen-Cooper-Schrieffer (BCS) -type formula
for pairing instability, Tc  "F exp½ – ð1=N ð"F ÞV Þ
. temperature and magnetic field range. The dashed
Note that the empirical formula, Equation (31), reflects
the fact that N0" ð"F Þ_ B. The lower critical tempera-
ture for the type-B samples is attributed to the pair
breaking effect of ionized impurity (Iye et al., 1984; Iye,
1985). Studies of neutron-irradiated graphite also cor-
roborate this conclusion (Yaguchi et al., 1999).
Figure 15(b) shows magnetoresistance traces up to
55 T measured in a pulse magnet (Yaguchi and
Singleton, 1998). At the highest field, the resistance
comes back to the trace extrapolated from the low-
field region, indicating a reentrant behavior.
Figure 15(c) is a phase diagram over a wider
curve represents the prediction of Yoshioka–
Fukuyama theory, Equation (32). Thus, the valley-
density-wave phase exists only at temperatures
below 10 K. The disappearance of the density-
wave phase at higher field is naturally understood
since the ð0; " Þ subband relevant to the instability
becomes unoccupied.
380 Electronic States and Transport Properties of Carbon Crystalline
Application of hydrostatic pressure p modifies the
-band structure by changing the  2-parameter:
2 ðpÞ ¼ ð1 þ pÞ2 ð0Þ ð34Þ
with the coefficient   0:03. According to
Equation (32), the increased -band width affects
the transition temperature by changing both "F and
N0" ð"F Þ. The observed change of Tc with pressure is
found to agree with eq.(32) (Iye et al., 1990).
1.10.6 Concluding Remarks
In this sketchy overview of the crystalline carbon
materials, we have tried to convey the ever-fascinat-
ing variety of electronic transport properties that
unfolds in materials just consisting of carbon atoms.
As usually the case for this sort of review article,
there exists a huge volume of relevant literature so
that it is by no means possible to give credit to all
those who contributed to this field. The author apol-
ogizes for many omissions.
Carbon is indeed a fascinating element. Carbon
materials span all the dimensions: 3D (diamond),
quasi-2D (graphite), 2D (graphene), 1D (nanotube),
and 0D (fullerene). The honeycomb structure
with C–C double bond gives rise to delocalized
-electrons whose unique behavior is at the heart of
this field.
Back in the 1960s, semi-metal bismuth with its low
melting point and low carrier density was the mate-
rial of choice for electronic transport experiments.
Graphite was of much interest in the same context,
but research on graphite was sometimes hindered by
the difficulty in material preparation. The situation
was much improved when HOPG samples became
available. Around 1980, research on GICs flourished.
The discovery of fullerene in 1985 and that of nano-
tube in 1991 opened new frontiers. For the
development of nanotube research, popularization
of techniques facilities that enables to handle the
nanoscale materials played a great role. Now the
advent of graphene has opened yet another new
field of science and technology. What makes
graphene especially attractive is that it can be put
in an FET structure and various parameters can be
tuned. Under the guiding light of 2DEG physics and
technology developed in semiconductor heterostruc-
tures, graphene research is the most rapidly
developing field. (See Chapters 1.01, 1.02, 1.05, 1.06,
1.11 and 1.12).
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 1.11 Angle-Resolved Photoemission Spectroscopy of
Graphene, Graphite, and Related Compounds
T Sato and T Takahashi, Tohoku University, Sendai, Japan
ª 2011 Elsevier B.V. All rights reserved.

1.11.1 Introduction 383

1.11.2 Angle-Resolved Photoemission Spectroscopy 384
1.11.2.1 Basic Principle 384
1.11.2.2 Determination of Band Dispersions 385
1.11.2.2.1 Layered materials 385
1.11.2.2.2 Three-dimensional materials 386
1.11.2.3 Experimental Apparatus 387
1.11.3 Graphite 389
1.11.3.1 Band Structure 389
1.11.3.1.1 Fermi surface 393
1.11.3.2 Edge-Localized States 394
1.11.3.3 Many-Body Interactions 395
1.11.4 Graphite Intercalation Compounds 397
1.11.4.1 C8A (A ¼ K, Rb, Cs) 397
1.11.4.1.1 Band structure 398
1.11.4.1.2 Interlayer band 399
1.11.4.2 C6Ca 399
1.11.4.2.1 Band structure 400
1.11.4.2.2 Fermi surface 400
1.11.4.2.3 Superconducting gap 402
1.11.5 Graphene 403
1.11.5.1 Single-Layered Graphite: Dirac Fermion? 403
1.11.5.2 Comparison with Graphite 405
1.11.6 Concluding Remarks and Summary 407
References 407

1.11.1 Introduction Recently, single-layer graphite, named graphene,

Carbon-based nanomaterials, such as fullerenes and
carbon nanotubes, have attracted much attention
from both basic- and application-scientific point of
views. In an old textbook of solid-state physics, it is
stated that carbon takes only two solid-state forms,
diamond with the sp3 coordination and graphite
with the sp2 coordination. This famous and instruc-
tive phrase had to be faced with the appropriate
correction when fullerenes (C60), which involve
intermediate coordination of sp3 and sp2, were dis-
covered in the solid-state phase (Kroto et al., 1985).
Subsequent discovery of carbon nanotubes (Iijima,
1991) has further widened the concept of solid-state
carbon as well as opened a way to the industrial
application such as an electron emitter in displays.
has been a target of intensive theoretical and experi-
mental studies, since it is expected that graphene
would possess several superior physical properties
such as the high carrier mobility compared with
silicon due to the peculiar electronic structure
originating in the perfect two-dimensional elec-
tronic structure. The discovery of superconductivity
at an unexpectedly high temperature in a new
category of graphite intercalation compounds (GICs)
such as C6Ca (Weller et al., 2005) has revived the
attention to the intercalation to control the electronic
property and achieve a higher superconducting
transition temperature. Thus, the old famous phrase
in the textbook should be corrected as ‘‘Carbon
takes a variety of solid-state forms with a variety
of attractive properties.’’

383
384 Angle-Resolved Photoemission Spectroscopy

Angle-resolved photoemission spectroscopy In comparison with angle-integrated PES, which

(ARPES) is now regarded as one of the most essential
experimental techniques in solid-state physics.
However, the energy resolution of two decades ago
was at best about 0.3 eV, which enables only a rough
band mapping of valence band structure of the
crystal. It is well known that the physical and chemi-
cal properties of materials are governed mainly by
the electronic structure in a very narrow energy
region just at/around the Fermi level (EF). The
energy resolution at that time was not enough to
observe the many-body interactions in electrons,
which appear as quasi-particles produced at/around
EF. The discovery of high-temperature superconduc-
tors and the subsequent fierce race to observe the
superconducting gap have accelerated the improve-
ment of energy resolution, leading to the 1 meV
resolution at present, more than two orders better
than that of two decades ago. The superconducting
gap and its symmetry of high-temperature supercon-
ductors have been experimentally elucidated with
this ultrahigh-energy resolution.
In this chapter, we explain recent ARPES experi-
mental results on graphene, graphite, and GICs and
discuss the electronic structure that realizes the novel
properties observed in these materials.
1.11.2 Angle-Resolved
Photoemission Spectroscopy
1.11.2.1 Basic Principle
ARPES is the most sophisticated method among a
variety of photoemission spectroscopies, enabling us
to determine experimentally the electronic band
structure and Fermi surface of crystals. In ARPES
provides us the information only on the electronic
density of states (DOS), we need to measure much
more spectra in ARPES measurements, but instead
we obtain much more information on the electronic
structure as a function of momentum.
We show in Figure 2 the energy-conservation
diagram in an ARPES process.
1. An electron, which was at first located on the
occupied band (Ei), is excited to the otherwise empty
band (Ef) by a VUV photon with the energy of h!.
The energy conservation is as follows:
h! ¼ Ef – Ei ð1Þ
2. We assume that the excited state is the free-
electron state with the bottom of the energy disper-
sion at E0 with respect to the Fermi level (EF) in the
crystal. We define the momenta parallel and perpen-
dicular to the crystal surface of the photo-excited
electron in the crystal as kjj and k?, respectively.
Then, the energy of the electron in the excited state
in the crystal is described as follows:
Ef ¼ h2 ðkjj2 þ k?
2
Þ=2m – E0 ð2Þ
3. We define the kinetic energy of the photoelec-
tron emitted into vacuum as EK; then we have
Ef ¼ EK þW ð3Þ
where W is the work function of the sample (see
Figure 2).
4. On the other hand, the momenta parallel and
perpendicular to the crystal surface of the
Vacuum

experiments, as shown in Figure 1, we irradiate the Photoelectron

e–
crystal surface with vacuum ultraviolet (VUV) light, Ef
Energy

and measure the kinetic energy of photoelectrons

emitted from the crystal surface as a function EK photon
(h ω)
of two angles (: polar angle, : azimuthal angle).
Wave vector
Vacuum level
W
z Fermi level (EF)
e- Free-electron band (Energy zero)
hω Ei E0
Band
θ

Crystal surface
x y
Figure 2 Energy-conservation diagram of the
Figure 1 Schematic view of ARPES. photoemission process.
 Angle-Resolved Photoemission Spectroscopy 385

photoelectron emitted into the vacuum (outside the
crystal) are described as follows:
pffiffiffiffiffiffiffiffiffiffiffi
Kjj ¼
2mEK sin 
pffiffiffiffiffiffiffiffiffiffiffi
K? ¼ 2mEK cos 
where  is the polar angle of photoelectron as shown
in Figure 1.
5. When the photoelectron is emitted from the
crystal into the vacuum through the surface, the
momentum parallel to the surface is conserved
because the transverse symmetry parallel to the sur-
face is hold (Figure 3). This is the most important
assumption in ARPES:
kjj ¼ Kjj
Using Equations (1)–(6), we obtain the relationship
between the energy and the momentum of the initial
state in the crystal:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
hkjj ¼ 2mðEi þ h! – W Þsin 
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
hk? ¼ 2mððEi þ h! – W Þcos2  þ V0 Þ
where V0 is defined as the sum of E0 and W (V0 ¼ E0 þ W)
and is called the inner potential. By applying these
formulas to ARPES experimental results, we are able
to map out experimentally the relationship between the
initial-state energy (Ei) and the momentum (kjj and k?),
namely the band dispersions of electrons in the crystal.
1.11.2.2 Determination of Band
Dispersions
1.11.2.2.1 Layered materials
As described above, when we measure the polar
angle () and the kinetic energy (EK) of photoelec-
trons, we are able to map out the band dispersions (Ei)
zII
of electrons in a crystal as a function of the momen-
tum parallel to the surface (kjj). The schematic
diagram is shown in Figure 4. This method appears
ð4Þ
to be very powerful when the crystal under consid-
eration is a highly two-dimensional layered material.
ð5Þ
In this case, the energy dispersion perpendicular to
the layer is negligibly small and therefore the
obtained band dispersions as a function of kjj
represent the band structure of the material.
Figure 5 shows a set of ARPES spectra of layered
compound 1T-VSe2 and the experimental band dis-
persions obtained from these spectra (Terashima
et al., 2003). Several characteristic bands from Se 4p
and V 3d orbitals are clearly seen in the experi-
ð6Þ mental band structure. We also find that the V 3d
band reaches the Fermi level at midway between 
and M points in the Brillouin zone, producing a
metallic Fermi surface. The band structure calculation
is also shown for comparison in Figure 5. The good
agreement between the experiment and the calcula-
ð7Þ
tion indicates that ARPES is able to map out the band
structure of layered materials with high precision.
ð8Þ
The concept of Fermi surface is one of important
physical concepts based on which we discuss the
electronic properties of materials. By measuring
many ARPES spectra all over the Brillouin zone
and plotting the spectral intensity at the Fermi level
as a function of two-dimensional momentum (wave
vector), we are able to map out experimentally the
two-dimensional Fermi surface. Figure 6 shows an
example applied for 1T-VSe2, where the characte-
ristic two-dimensional cylindrical Fermi surface is
clearly mapped out by ARPES (Terashima et al.,
2003).
Energy band
θ0
EF
Photoelectron intensity

K θ1

θ θ θ2
KII
Energy

e– θ3
Crystal surface
k θ4 √2mEK
k = sinθ
h
θ5

kII
e– EF k0 k1 k2 k3 k4 k5
Binding energy Wave vector
Figure 3 Momentum parallel to the surface of
photoelectrons is conserved during the photoemission Figure 4 Schematic diagram to show how to determine
process. the E–k relation (band structure) by ARPES.
386 Angle-Resolved Photoemission Spectroscopy

1T-VSe2 EF V 3dz 2
M(L)
1 Se 4pz*

Binding energy (eV)

2

Intensity (a.u.)
Se 4px,y
3

4
Γ(A)
5

6
Γ M
7 6 5 4 3 2 1 EF A L
Binding energy (eV) Wave vector
Figure 5 Experimentally determined band structure of quasi-1D layered compound 1T-VSe2 (Terashima et al., 2003).

ky

Guideline of Fermi surface

M(L) K(H)

High
kx
Γ(A)
Intensity

Low

1T-VSe2
First Brillouin zone

Figure 6 Fermi surface of 1T-VSe2 determined by ARPES (Terashima et al., 2003).

1.11.2.2.2 Three-dimensional materials determine the three-dimensional band structure of

In the case of three-dimensional materials, the situa- three-dimensional materials in many cases, as
tion is complicated because electrons in the crystal explained in the following.
have a finite energy dispersion perpendicular to It is well known that the escape depth of photoe-
the measured crystal surface. When we change the lectrons is very short and comparable to a few atomic
polar angle () to change the momentum parallel layers from the surface. Electrons confined in this
to the surface (kjj) in ARPES experiments, the per- very thin layered space are expected to have the
pendicular counterpart (k?) is also simultaneously momentum substantially broadened perpendicular
altered according to Equation (8). However, in this to the layer (surface) because of the Heisenberg’s
case, we do not know explicitly the k? value because uncertainty principle (xp  h). In ARPES experi-
V0 is unknown. In other words, even when we fix the ments with VUV light of h! ¼ 20–40 eV, the escape
kjj value by setting the polar angle at a certain value, depth of photoelectrons is about 5 Å, meaning that
we are not able to know which point on the band the momentum (wave vector) perpendicular to the
structure perpendicular to the crystal surface we are surface has an ambiguity of about 0.2 Å1. Further,
actually seeing. Despite this difficulty, we can if there are no final-state bands corresponding to

Ef (see Figure 2), the escape depth becomes much
shorter (one-half to one-third) because the wave func-
tion of the photoelectrons outside the crystal becomes
an evanescent wave inside the crystal and cannot enter
deep inside the crystal. This situation enhances the
broadening of momentum perpendicular to the
surface, and finally a large portion of k? is simulta-
neously seen in ARPES measurements. In other
words, when we conduct ARPES measurements at a
certain polar angle (), the kjj component is uniquely
determined from Equation (7), while the k? compo-
nent is automatically integrated in all (or a large
portion of) Brillouin zone perpendicular to the crystal
surface because of the short escape depth of photo-
electrons. In general, the DOS is relatively larger on
the high-symmetry line in the Brillouin zone in com-
parison with other portions between high-symmetry
lines. When we integrate the DOS along k? at a fixed
kjj, the high-symmetry line produces a peak in the
ARPES spectrum. This means that the peak position
in the ARPES spectrum of three-dimensional mate-
rials traces the band dispersion on the high-symmetry
line in the Brillouin zone. This indicates that we can
compare the band dispersions obtained by ARPES for
three-dimensional materials with the band structure
calculated along the high-symmetry lines.
Figure 7 shows the band structure of LaSb deter-
mined by ARPES, compared with the band structure
calculation (Kumigashira et al., 1998). LaSb is a typi-
cal three-dimensional material with face-centered
cubic crystal structure. ARPES measurements were
X
z(001)
Γ X
W
X X
K
Σ
Δ W
2nd Brillouin zone
X Γ Δ X
X f
X
1st Brillouin zone
x(100)
Figure 7 Band structure of LaSb determined by ARPES (Kumigashira et al., 1998).
Angle-Resolved Photoemission Spectroscopy 387
done along the (010) direction at the (001) cleaved
surface. So, kjj and k? are defined along the (010) and
(001) directions, respectively. When we compare the
experimental band dispersions with the band struc-
ture calculated along several high-symmetry lines,
we find that the band dispersions along X and
XWX high-symmetry lines simultaneously appear
in the experimentally determined band structure.
This indicates that two different k? points are meas-
ured simultaneously at a fixed kjj due to the k?
integration effect. As shown above, the band structure
of three-dimensional materials can be determined by
ARPES in many cases.
1.11.2.3 Experimental Apparatus
Figure 8 shows a schematic diagram of a high-
resolution ARPES spectrometer. The apparatus
consists of mainly four parts: (1) a large electrostatic
hemispherical electron energy analyzer with the aver-
age diameter of about 40 cm; (2) a microwave-driven
discharging lamp to produce high-intensity VUV light;
(3) a sample preparation vacuum chamber where
samples are prepared by cleaving, sputtering, evapora-
tion, etc.; and (4) an ultrahigh vacuum analyzer
chamber where the sample is irradiated by VUV light
from the discharging lamp. In addition, the apparatus is
equipped with a liquid-helium cryostat to cool down
the sample, a sample transfer system, many vacuum
pumps, etc. We can use synchrotron radiation light to
excite photoelectrons.
e1 e3
EF
e2
h2 k
a
1.0 h1
Binding energy (eV)
c b j
i
2.0
d
g
y(010)
3.0
4.0
X W X
Γ X
388 Angle-Resolved Photoemission Spectroscopy

Hemispherical
electron analyzer

CCD
camera
Installation TMP
chamber
Main
He-flow chamber He discharge
cryostat lamp
Monochromator

Manipulator Cryostat
Sample
Preparation
chamber TMP
Radiation
shield

TSP Ion pump

Figure 8 High-resolution ARPES spectrometer.

The recent progress in the energy resolution in schematic diagram to explain how the energy and
ARPES experiments owes mainly to the improve- the polar angle of photoelectrons are measured
ment of electron energy analyzer. Figure 9 shows the with the hemispherical analyzer. By using the

Hemispherical analyzer

Slit E1 E2 E3 Energy
e θ1
gl
An MCP
θ2
Electron lens
Screen

Photoelectron

hω
CCD camera
θ1
θ2

Sample
Figure 9 Two-dimensional detection hemispherical electron analyzer.
 Angle-Resolved Photoemission Spectroscopy 389

15 K the temperature dependence of photoemission

25 K spectrum of gold (Au) in the vicinity of the Fermi
50 K
75 K level measured with the energy resolution of about
Au 100 K 1 meV. The spectrum shows a systematic tempera-
125 K
Intensity (a.u.)

150 K ture dependence with the common intersecting point

175 K at the Fermi level. This behavior is exactly the same
200 K
1 225 K as the temperature dependence of the Fermi–Dirac
f( ε) =
exp[(ε–EF) / kBT ] + 1 250 K (FD) distribution function. This state-of-the-art
280 K
f( EF) = 0.5 300 K experimental result indicates that high-resolution
320 K photoemission (ARPES) spectroscopy provide us
rich information with which we can discuss the
100 50 EF –50 –100 relationship between the electronic structure and
Binding energy (meV) the novel properties of materials such as
Figure 10 Temperature dependence of photoemission superconductivity.
spectrum of gold (Au) in the vicinity of EF.

two-dimensional detecting system with a multichan- 1.11.3 Graphite

nel plate (MCP) and a CCD camera, we are able to
measure simultaneously the energy and the polar
angle of photoelectrons as shown in Figure 9. This
two-dimensional detection system together with a
large size of hemispherical analyzer enables a rapid
and precise ARPES measurement to lead to the
ultrahigh-resolution measurement. Figure 10 shows
1.11.3.1 Band Structure
Carbon-based materials show a variety of interesting
properties owing to the dimensionality, structure,
and size. These materials have attracted much atten-
tion in both the basic science and the device
applications. As shown in Figure 11, the structural

Graphene ribbon

Graphene

Graphite

Nanotube

GIC
Figure 11 Crystal structures of graphene, graphite, and related materials.
390 Angle-Resolved Photoemission Spectroscopy

base of the sp2-hybridized carbon materials is
graphene, single-layered graphite, which is purely
two dimensional. As discussed later, this graphene
behaves as a zero-gap semiconductor where the
mass of carriers is regarded as zero (a Dirac fermion).
When the graphene stacks along the out-of-plane
direction, it becomes three-dimensional graphite.
In contrast to the zero-gap nature of graphene, gra-
phite is a semimetal with a small overlap of C 2p 
bands due to the finite interaction between graphene
sheets in the crystal. Various atoms or molecules can
be inserted between graphene sheets of graphite.
These compounds are called GICs and are usually
metallic and sometimes superconducting. It has been
theoretically predicted that by cutting the side of
graphite (graphite ribbon), anomalous electronic
states called edge-localized states appear in
the vicinity of EF (Fujita et al., 1996; Kobayashi,
1993; Nakada et al., 1996; Wakabayashi et al., 1999).
Moreover, carbon nanotube, created by smoothly
connecting both sides of graphene sheets, shows a
variety of interesting properties owing to its chirality.
The carbon nanotube would be technologically
useful for transistors, power fuel cells, displays,
and so on.
In all the carbon-based materials, the key to
understand the interesting physical properties
lies in the carbon 2p  and  orbitals whose atomic
wave functions are schematically shown in
Figure 12(a). The  orbital is elongated parallel to
the graphite plane while the  orbital perpendicular
to the plane. The band structure for high-symmetry
lines in the Brillouin zone derived from these orbitals
are shown in Figure 12(b). Because two carbon
atoms are included in the hexagonal unit cell in the
case of the AB stacking, we find two bonding
bands and four bonding bands below EF. The
corresponding antibonding counterparts are also
seen above EF ( and  bands). The bandwidth
along the momentum perpendicular to the plane
(kz) is very small compared to that for the in-plane,
reflecting the quasi-two-dimensional nature of
graphite. As one immediately notices from
Figure 12(b), both  and  bands cross EF at H or
K point and produce small hole and electron Fermi
surfaces. These small Fermi surfaces are responsible
for the electric conduction and hence the semimetal-
lic nature of graphite.
Figure 13 shows valence-band ARPES spectra of
kish graphite (artificially grown single-crystal

(a) (c) kz

Carbon atom

A
R Δ
π orbital L Q Γ
σ orbital S
ε
kx M P ∧
T
K

ky
(b)
Energy (Ry) Energy (eV)

0.0 σ* 0.0

–4.0
–0.4 π*
–8.0
–0.8 π
–12.0
σ
–1.2 –16.0

–20.0
–1.6
–24.0

κ ∧ Γ Σ M T KPH Q A R L S H

Figure 12 (a) Schematic view of the wave function of  and  orbitals. (b, c) Calculated band structure (Tatar and Rabii,
1982) and Brillouin zone of graphite.

Γ(A)
K(H)
(a) M(L)
Intensity (a.u.)
16 12 8 4
Binding energy (eV)
Figure 13 Valence-band ARPES spectra of graphite measured along two high-symmetry lines: (a) KM (AHL) and
(b) M (AL).
graphite) measured at 20 K along (a) KM (AHL)
and (b) M (AL) directions. We clearly find highly
dispersive bands along both directions. For example,
along the KM (AHL) direction (Figure 13(a)), one
band has the top of dispersion at the (A) point at
4 eV and disperses toward the higher binding energy
on approaching the K(H) point. This band has the
bottom at about 12 eV at the K(H) point and then
disperses back toward the lower binding energy on
approaching the M(L) point. We also find another
prominent peak located at about 8 eV at the (A)
point. This band rapidly approaches EF on moving
toward the K(H) point, and the spectrum shows a
clear Fermi-edge cutoff indicative of a tiny hole
pocket centered at the K(H) point. On the other
hand, along the M (AL) direction (Figure 13(b)),
the band does not cross EF but stays at 3 eV around
the M(L) point, indicative of the absence of Fermi
surface along this direction. These features are com-
monly observed in previous ARPES results
(Takahashi et al., 1985; Santoni et al., 1991). It is also
noted that we are able to observe separately the
electronic structure along the KM (AHL) and M
(AL) directions due to the single-crystal nature of
kish graphite, which is not possible with the highly
Angle-Resolved Photoemission Spectroscopy 391
Γ(A)
K(H)
(b) M(L)
M(L)
Intensity (a.u.)
K(H) M(L)
Γ(A)
Γ(A)
EF 16 12 8 4 EF
Binding energy (eV)
oriented pyrolytic graphite (HOPG). This suggests
that ARPES with a high-quality single crystal is
essential to establish the intrinsic electronic structure
of graphite.
To visualize more clearly the dispersive features
in ARPES spectra, we have mapped out the band
structure and show the result in Figure 14. The
experimental band structure was obtained by taking
the second derivative of ARPES spectra and plotting
the intensity by gradual shading as a function of wave
vector and binding energy. Bright areas correspond
to experimental bands. Figure 14 also shows the
first-principles band calculation of graphite (Tatar
and Rabii, 1982) using the Johnson and Dresselhaus
(1973) model (the JD model) with the AB stacking
sequence. It is clear that the experimental band
structure and the bulk band calculation show a
good agreement along both directions. However, we
also notice quantitative differences. For example, the
 band due to the C2p bonding states is located at
about 4 eV at the (A) point in both the experiment
and the calculation, while the dispersive feature from
the (A) point to the K(H) point shows a quantitative
deviation. The lower-lying branch of the  band
(2 band) along the  KM (AHL) direction is located
392 Angle-Resolved Photoemission Spectroscopy

(a) (b)
EF EF

4 4
Binding energy (eV)

Binding energy (eV)

8 8

High
12 12

16 16 Low
Γ K M Γ M
A H L A L
Wave vector Wave vector

Figure 14 Valence-band structure of graphite along two high-symmetry lines KM (AHL) and M (AL) determined by
ARPES, compared with the band-structure calculation (Tatar and Rabii, 1982).

at slightly higher binding energy in the experiment
than in the calculation. A similar trend is also seen in
the M (AL) direction. The  band is located at a
slightly higher binding energy in the experiment
than in the calculation at the (A) point, whereas
both perfectly coincide with each other near EF at the
K(H) point in the energy scale of Figure 14. The
finite deviation of the energy position of bands
between the experiment and the calculation may be
due to many-body effects and/or final-state effects
(Strocov et al., 2001; Heske et al., 1999).
While the ARPES technique determines the
occupied electronic states, the band structure in
the unoccupied side is also elucidated by the
angle-resolved inverse photoemission spectroscopy
(ARIPES) (Schäter et al., 1986; Ohsawa et al., 1987)
and angle-resolved secondary-electron emission
spectroscopy (ARSEES) (Maeda et al., 1988). In the
ARIPES, electrons are impinged into the sample sur-
face and emitted photons are detected. Figure 15(a)
shows ARIPES spectra of HOPG as a function of
polar angle. The ARIPES spectra show clear

(a) (b)
Graphite (HOPG)
ARIPES

69°
65° 20
Intensity (a.u)

60°
55°
50°
45°
40°
35°
10
30°
25°
20°
15° Ev
10°
5°
0° EF
0 5 10 15 20 25 K Γ M
Energy relative to EF

Figure 15 (a) Angle-resolved inverse photoemission spectra of graphite. (b) Comparison of ARIPES-derived unoccupied
band structure with the band calculation.

structures denoted by markers, whose energies and
intensities are very sensitive to the change of polar
angle. Figure 15(b) shows a comparison of experi-
mentally determined unoccupied band structure
with the band calculation (Tatar and Rabii, 1982).
An overall agreement between the ARIPES experi-
mental result and the calculation is found as in the
case of the occupied band structure, in both the 
and  bands. A similar result has been obtained by
comparison with a refined band calculation (Fretigny
et al., 1989). All these experimental results demon-
strate that the band-structure calculation serves as a
good starting point to discuss the electronic structure
of graphite.
1.11.3.1.1 Fermi surface
Since the graphite is a low-carrier semimetal, we
expect the presence of tiny Fermi surface(s). This
Fermi surface is successfully determined by the
high-resolution ARPES. Figure 16(a) displays the
ARPES intensity at EF of kish graphite plotted as
a function of two-dimensional wave vector. The
spectral weight is integrated within 10 meV with
respect to EF and the intensity is plotted by assum-
ing the hexagonal symmetry. The bright area
corresponds to the high intensity. Figure 16(b) is
(a)
1.0
ky (Å–1)
0.0
–1.0
–1.6
(b)
ky (Å–1)
–1.7
–1.8
–0.2
Figure 16 (a) Fermi surface of graphite determined by ARPES. (b) Expansion near the K(H) point.
Angle-Resolved Photoemission Spectroscopy 393
an expansion around the K(H) point. As clearly seen
in Figure 16(b), the spectral intensity at EF is
sharply peaked at the K(H) point, demonstrating
the existence of an extremely small Fermi surface
at the K(H) point. The volume of the observed small
hole-like Fermi surface can be estimated by the
following method. We first assume that the hole
pocket has an ellipsoidal shape elongated along
the kz (KH) axis with a circular cross section in the
kx–ky plane. The longer axis (2b) of the ellipsoid is
supposed to be just half of the unit cell along the kz
axis, namely the distance between the K and H
points, being 0.942 Å1, as predicted from the
band calculation (Charlier et al., 1991). We
determined the shorter axis (2a) of the ellipsoid as
0.034  0.004 Å1 by extrapolating the band disper-
sion near the K(H) point toward EF with a linear
function. The estimated volume (4a2b/3) of the
hole-like Fermi surface is 5.7  0.7  104 Å3,
which corresponds to the carrier number of
9.2  1.1  1018 cm3. This value is apparently
larger than the hole carrier number (2.0  1018)
estimated from the measurement of the Hall
coefficient (Brandt et al., 1988), possibly due to
the finite energy and momentum resolution in the
ARPES measurement.
kx (Å–1)
–1.0 0.0 1.0
M(L)
K(H)
Γ(A)
–0.1 0.0 0.1 0.2
kx (Å–1)
394 Angle-Resolved Photoemission Spectroscopy
1.11.3.2 Edge-Localized States
It has been theoretically suggested that a graphene
ribbon possesses a characteristic electronic state near
the Fermi level (EF) called the edge-localized state
(Fujita et al., 1996; Nakada et al., 1996; Kobayashi,
1993; Wakabayashi et al., 1999), which is not pre-
dicted from the bulk band calculation. This newly
created electronic state at the graphite edge has been
intensively discussed in relation to the magnetic and
transport properties. It has been theoretically pre-
dicted that the magnetic property of graphite
ribbon strongly depends on the structure of edge
(zigzag- or armchair-type) (Fujita et al., 1996;
Kobayashi, 1993; Nakada et al., 1996; Wakabayashi
et al., 1999), adsorbed atoms, and the stacking
sequence of graphite layers (Miyamoto et al., 1999).
Indeed, as shown in Figure 17, which plots the
calculated energy versus k relation of the  bands
for graphite ribbons parallel to the ribbon direction
(Nakada et al., 1996), we find almost nondispersive
bands in the close vicinity of EF in the case of ribbons
with zigzag edges (Figure 17(a)), while no such
feature is seen in the ribbon with armchair edges
(Figure 17(b)). It is also known that adsorption of
halogen atoms to graphite ribbon remarkably
changes the character of edge-localized states
(Kusakabe and Maruyama, 2003; Maruyama and
Kusakabe, 2004). Recent scanning tunneling
spectroscopy/microscopy studies reported a signa-
ture of the edge-localized states near EF in the DOS
(Matsui et al., 2005), whereas, until recently, there
(a) Zigzag ribbon (b) Armchair ribbon
1A 1A 2A 1B
1B
1
2B
2A
2B 2
3 4
N–1
N A
N N
NB NA N B
(c) (d)
–3 –3
0 0
E
3 3
–π 0 π –π 0 π
Figure 17 (a, b) Zigzag and armchair ribbons. (c, d)
Calculated energy dispersion for zigzag and armchair
ribbons.
have been no ARPES investigations reporting the
edge-localized states in the graphite surface.
By controlling the cleaving condition of kish
graphite under ultrahigh vacuum, anomalous feature
is sometimes observed in the ARPES spectra near the
K(H) point, which could be ascribable to the edge-
localized states. Figure 18 shows ARPES spectra
measured along the cut slightly away from the hole
pocket at the K(H) point as shown in the inset. We
first notice two prominent structures near EF around
kx ¼ 0 Å1. One of them, which is located closer to EF
and forms a sharper peak at about 80 meV, shows a
steep dispersion toward high binding energy with
gradual broadening on going to kx ¼ 0.1 Å1. This
band is assigned as the  band, as described pre-
viously. It is noted here that this  band does not
cross or touch EF because the measurement was done
in the cut slightly away from the hole pocket at the
K(H) point, as shown in the inset. In addition to the
 band, we find an anomalous feature (band) at about
130 meV around kx ¼ 0 Å1. In contrast to the bulk
 band, this band shows a peculiar energy dispersion
asymmetric with respect to kx ¼ 0 Å1; an almost
flat dispersion in the side of kx being positive, 0 to
0.05 Å1, and a slight upward dispersion toward EF
on the side of kx being negative of 0 to –0.10 Å1.
This asymmetric behavior might be due to the
kx (Å–1)
0.10
Intensity (a.u.)
1
2 Γ(A)
3
5 0.05
K(H)
M(L)
N–1
0.0
–0.05
–0.10
0.6 0.4 0.2 EF
Binding energy (eV)
Figure 18 Near-EF ARPES spectra of graphite showing
the edge-localized state. Inset shows the measured cut in
the Brillouin zone (red line near the K(H) point). Red arrows
indicate prominent structures around kx ¼ 0 Å1.

matrix-element effect in the photoelectron exciting
process because the polarization of incident light is
different between the two cases. We have measured
ARPES spectra for several cuts near the K(H) point
and found that this anomalous feature appears only
around the K(H) point.
In Figure 19, we plot the ARPES spectral inten-
sity as a function of binding energy and wave vector,
together with the projection of bulk band on the (001)
plane (dots) (McClure, 1957). As clearly seen in the
figure, the projection of the  band shows a good
agreement with the hole-like  band in the experi-
ment. The anomalous feature is observed well
outside the projection of the  band, indicating that
the dispersion along kz of the  band is not respon-
sible for the anomalous feature. The antibonding
electron-like  band ( band) might be the origin
of the anomalous feature. However, as seen in
Figure 19, the  band is situated well above EF in
this momentum region and cannot account for the
anomalous flat band below EF. The coupling of
electrons with a certain bosonic excitation as
observed in cuprate superconductors (Campuzano
et al., 1999; Lanzara et al., 2001; Sato et al., 2003)
cannot explain this observation. Because the band
produced by such an excitation should follow or
mimic the original hole-like dispersion (Norman
et al., 1997) with a considerable renormalization of
the bandwidth near EF. However, the observed
anomalous band shows an electron-like character in
contrast to the hole-like  band. The angle-
integrated-type background as the origin of the
EF
Binding energy (eV)
0.2
0.4
0.6
–0.10 –0.05 0.0 0.05
kx (Å–1)
Figure 19 ARPES-intensity plot near EF of graphite as a
function of wave vector and binding energy measured near
the K(H) point (see Figure 18), compared with the projection
of calculated bands (McClure, 1957).
Angle-Resolved Photoemission Spectroscopy 395
anomalous band is simply denied since such a back-
ground peak in ARPES spectrum would show no
dispersion, contrary to the small but finite energy
dispersion of the band. The edge-localized state pre-
dicted from the calculation for graphite ribbons
(Fujita et al., 1996; Nakada et al., 1996; Kobayashi,
1993; Wakabayashi et al., 1999) may account for the
observed anomalous band. According to the calcula-
tions, a zigzag edge of graphite ribbon possesses an
almost-flat band in the close vicinity of EF around the
K point, in good agreement with the present observa-
tion. We speculate that cleaved surface of kish
graphite contains similar zigzag edges at the steps.
In fact, a recent STS/STM study (Matsui et al., 2005)
reported the existence of zigzag steps and the resul-
tant edge-localized states on the graphite surface.
It is also revealed that the zigzag step affects the
electronic structure substantially away from the
step because the edge-localized state is observed on
the flat surface about 35 Å away from the step.
Probably this long-distance effect of the zigzag step
enables the observation of the edge-localized states
by ARPES, which probes the electronic structure
averaged over a wide area of the surface. The possi-
bility of dangling bonds are not ruled out to explain
the observed anomalous electronic states (Jensen and
Blase, 2004; Hahn and Kang, 1999). It has been theo-
retically suggested (Jensen and Blase, 2004) that the
character of the graphite surface is dramatically
affected by the presence of dangling bonds. These
dangling bonds are associated to undercoordinated
carbon atoms at the point or extended defects at the
step edges. According to the STM measurement by
Hahn and Kang (1999) such dangling bonds, which
are not passivated by adsorbates contribute to the
DOS near EF. We speculate that dangling atoms or
dimers at armchair or zigzag edges, which are not
passivated by the adsorbates, may be formed in the
present experiment where we cleave the sample in an
High
ultrahigh vacuum of 2  1011 Torr. In this case, the
observed anomalous feature near EF in the ARPES
experiment might be explained by the dangling-bond
scenario.
1.11.3.3 Many-Body Interactions
Low
0.10 ARPES is a strong experimental technique to deter-
mine the band structure of solids. By qualitatively
analyzing the energy dispersion and the energy
width of the peak in the ARPES spectrum, we are
able to obtain an insight into the many-body interac-
tions responsible for the anomalous physical
396 Angle-Resolved Photoemission Spectroscopy

properties. For instance, as shown in Figure 20(a),
when electrons are strongly coupled to some kind of
collective excitations or bosonic modes, a kink
appears in the energy dispersion near EF. The energy
scale of the kink basically reflects the characteristic
energy of the mode, and the effective mass of
the quasi-particle band is highly renormalized in
the vicinity of EF due to the interaction. The disper-
sion kink has been studied recently in various
materials, such as high-Tc cuprate superconductors
(Campuzano et al., 2004; Damascelli et al., 2003),
charge-density-wave materials (Valla et al., 2000;
Schäfer et al., 2003), and surface systems (Valla et al.,
1999; Hengsberger et al., 1999). As for the origin of
the mode, mainly phonons and magnetic excitations
were proposed so far.
By obtaining a flat clean surface with a negligible
contribution from the edge-localized states, we find
(a)
kF
EF
Mode
energy Kink With
a signature of the strong electron-mode coupling
in kish graphite (Sugawara et al., 2007). In
Figure 20(b), we plot ARPES spectra of kish
graphite near EF measured at 7 K along a cut that
includes the K(H) point (line at K(H) in the inset to
Figure 20(c)). Figure 20(c) shows the corresponding
intensity plot as a function of wave vector and
binding energy. We clearly identify in Figure 20(b)
a couple of hole-like bonding  bands separated by
0.6 eV, which disperse toward EF when approaching
the K(H) point. The splitting of  bands is created
by the AB stacking sequence of kish graphite as
seen in the band calculations (Tatar and Rabii,
1982; Charlier, 1991; McClure, 1957) (see also
Figure 12). An anomalously sharp quasi-particle
peak appears in the upper  band at a narrow angle
region centered at the K(H) point, while the peak
becomes significantly broad and does not show
prominent energy dependence when the position of
peak exceeds 0.2 eV. We also find a tiny peak
(b) slightly away from the K(H) point in the close
vicinity of EF, which shows a remarkable resem-
k
blance to the spectral line shape of the surface band
near EF in Be surface (Hengsberger et al., 1999). The
marked sharpening of the spectral line shape as well
Intensity (a.u)

interaction as the appearance of an additional peak indicates that

electrons are coupled to certain collective excita-
No interaction tions. It is noted that the observed quasi-particle
(bare band) peak in graphite is as sharp as the nodal quasi-particle
Energy

peak in hole-doped cuprates at the superconducting

state with the d-wave gap opening (Kaminski et al.,
2.5 2.0 1.5 1.0 0.5 EF
2000). Both cases can be explained by the similar
Binding energy (eV) phase space argument (Bena and Kivelson, 2005); in
F E D C BA graphite, the extremely small Fermi surface limits
(c)
the phase space available for the scattering, while in
EF
the d-wave superconductors, the scattering among
point nodes causes a similar effect and reduces the
0.5
Binding energy (eV)

scattering rate dramatically.

To elucidate quantitatively the character of
1.0
low-energy excitations, we fit ARPES spectrum by
High
two peaks corresponding to the upper and lower
1.5 K(H)
 bands. We simulate ARPES spectrum by two
M(L)
2.0
weakly asymmetric Lorentzian peaks together with
Γ(A) a broad background multiplied by the FD distribu-
tion function at 7 K, and they are convoluted with a
2.5 Low
–0.2 –0.1 0.0 0.1 Gaussian having an energy width of instrumental
kx (Å–1) resolution (4 meV). Figure 21 shows the result of
fitting for representative k points as denoted by
Figure 20 (a) Schematic diagram to explain the kink
arrows A–F in Figure 20(c). It is evident that
structure in the energy dispersion. (b) Ultrahigh-resolution
ARPES spectra near EF of graphite around the K(H) point the calculated spectral functions (solid curve) repro-
and (c) the corresponding ARPES-intensity plot as a duce satisfactorily the experimental data (open
function of wave vector and binding energy. circles) in whole energy region up to 2.5 eV. The

200
ImΣ (meV)
150
λ = 0.70 ± 0.08
100
50
Intensity (a.u.)
0 dence of |Im (!)|. The bulk three-dimensional
1.2 1.0 0.8 0.6 0.4 0.2
Binding energy (eV)
2.5 2.0 1.5 1.0
Binding energy (eV)
Figure 21 ARPES spectra near EF of graphite and their
numerical fittings. Inset shows the real and imaginary parts
of the self-energy of electrons in graphite.
inset in Figure 21 displays the imaginary part of the
self-energy |Im (!)|, which is equal to the quasi-
particle scattering rate and inversely proportional to
the quasi-particle lifetime, obtained by plotting the
half-width-at-half-maximum of the peak at the upper
 band. |Im (!)| shows a sudden drop below
0.18 eV, in accordance with the sharpening of the
quasi-particle peak. The sudden drop in |Im (!)|
is caused by the coupling between electrons and a
collective mode. In the inset to Figure 21, we also
plot the real part of the self-energy Re (!). We
defined Re (!) as the energy difference between
the obtained peak position of ARPES spectrum and
the linear bare band that passes through two points at
EF and 1.5 eV in the experimental dispersion
(see Figure 20(c)). As indicated by circles in the
inset to Figure 21, Re (!) shows a distinct
enhancement at the binding energy of 0.16 eV,
which indicates the mass renormalization of band.
The energy position of peak maximum in Re (!)
is close to the energy position of the sudden drop in
|Im (!)|. We also obtained Re (!) by Kramers–
Kronig transformation of Im (!) (triangles) and
Angle-Resolved Photoemission Spectroscopy 397
found a reasonable agreement with Re (!) deter-
100 mined from the fitting of energy distribution curve
80
(EDC), demonstrating that appearance of quasi-
particle peak and the renormalization of band
ReΣ (meV)
60 are directly connected to each other. To elucidate
40 the character of the mode quantitatively, we apply the
Debye model to reproduce the obtained self-energy on
20 an assumption of a linear scattering rate higher than
0 the Debye energy !D to account for the energy depen-
EF
model with !D ¼ 0.175 eV and the coupling constant
 ¼ 0.70  0.08 well reproduce the experimentally
obtained self-energy. The estimated !D is similar to
A
the known Debye energy of graphite (!D ¼ 0.2 eV)
(Kittel, 1953), suggesting that electrons are strongly
B coupled to phonons. It is remarked here that a
C
proper calculation would involve the actual phonon
dispersion into the Eliashberg coupling function
D
2F(!), but even the oversimplified analysis by
E using the Debye model reasonably reproduces the
obtained self-energy. We note that the estimated !D
F
value (0.175 eV) is similar to the highest phonon
0.5 EF energy at 0.2 eV determined from the tunneling
(Vitali et al., 2004) and the Raman scattering
(Kawashima and Katagiri, 1995) experiments.
According to the theoretical calculation of phonon
dispersion (Siebentritt et al., 1997), the highest
branch is attributed to the longitudinal optical
(LO) phonon which is essentially nondispersive at
0.2 eV around the zone center. Acoustic shear (SH)
phonon also produces a pronounced DOS at 0.18 eV.
Thus, the sudden drop in Im (!) could be
explained by the coupling of electrons with the SH
phonon and/or the LO phonon.
1.11.4 Graphite Intercalation
Compounds
1.11.4.1 C8A (A ¼ K, Rb, Cs)
GICs were first reported in 1840 (Schafhäl, 1840),
and the systematic study started in the early 1930s
(Dresselhaus and Dresselhaus, 2002). The intercala-
tion of atoms/molecules with host graphite changes
various physical properties. Among the most striking
properties are the superconductivity in the first-stage
alkali metal GIC C8K (Hannay et al., 1965; Koike
et al., 1978), first discovered in 1965 (Hannay et al.,
1965). The high conductivity of GICs originates
in the charge (electron or hole) transfer from the
intercalant to the graphite layer. Among all GICs,
alkali-metal GICs have been most intensively
398 Angle-Resolved Photoemission Spectroscopy

kz (a)
(a) (b) ∼
C8 K ΓΚ Ζ He I
C8K A Z
B
kx K Λ T
Σ ΓΔ
Y
ky

70°
65°

Intensity (a.u.)
Graphene layer K Y K Γ
kx 60°
Unit cell 1st layer α (K) (Γ)
2nd layer β Y 55°
3rd layer γ
Γ 50°
4th layer δ
5th layer α (M) 45°
ky 40°
35°
Figure 22 (a) Crystal structure and (b) Brillouin zone 30°
of C8K. 25°
20°
15°
10°
studied by ARPES, especially in the 1980s, in C6Li 5°
0°
(Eberhardt et al., 1980; McGovern et al., 1980), C8K
10 5 EF
(Takahashi et al., 1986), C8Rb (Eberhardt et al., 1980; Binding energy (eV)
(b)
McGovern et al., 1980), and C8Cs (Gunasekara
et al., 1987). The crystal structure and Brillouin EF
zone for C8K are shown in Figure 22. The graphite
Binding energy (eV)

and intercalant layers are arranged in the

AAA A
stacking sequence in C8K. As shown in
Figure 22(b), the modified two-dimensional
Brillouin zone for C8K occupies one-fourth of the
area of the whole Brillouin zone of graphite due to
the reconstruction of Brillouin zone by the periodic
potential from the alkali-metal ions.
1.11.4.1.1 Band structure
Figure 23(a) shows ARPES spectra of C8K meas-
ured along the KZ line (KM line of bulk
graphite) as a function of polar angle . We clearly
identify some characteristic features of the elec-
tronic states: (1) the unfolded  band, which is
located at about 9.5 eV in the normal-emission
spectrum, disperses remarkably toward the lower
binding energy on increasing , but it disperses back
again toward higher binding energy at   60 before
reaching EF; (2) the unfolded  band, which
abruptly appears at about 45 at EF, showing a
small but finite energy dispersion with the bottom at
1.0 eV; (3) the folded  bands, which appear at
4–7 eV in the spectra at   0–20 ; and (4) a non-
dispersive band at EF with the largest peak intensity at
 ¼ 0 with some additional features at  ¼ 25–30 . In
Figure 23(b), we plot energy positions of peaks and
shoulders in the ARPES spectra as a function of the
wave vector. We find the folding of energy bands of
5
10
∼ ∼ C K Γ
Γ Κ Y Κ 8 Y Γ YΓZ
M Κ (Graphite) Γ M Γ
Figure 23 (a) ARPES spectra of C8K and (b) the
experimentally determined band structure compared with
the band calculation (Ohno et al., 1979).
graphite into the Brillouin zone of the 2  2 super-
structure, as clearly seen between two K~ points.
This indicates that the surface region of the C8K
sample probed by ARPES has the same 2  2 super-
structure as in bulk. In Figure 23(b), we also plot
the bands calculated by Ohno, Nakao, and
Kamimura (the ONK model; Ohno et al., 1979) for
comparison. The experimentally obtained band
structure reasonably agrees with the band calcula-
tion, especially for the  and  bands. We find in
Figures 23(a) and 23(b) that the intensity of the
folded  bands is much weaker than that of the
unfolded ones like in C6Li (Eberhardt et al., 1980;
McGovern et al., 1980).
 Angle-Resolved Photoemission Spectroscopy
1.11.4.1.2 Interlayer band
As seen in Figure 23(b), some discrepancies are also
found between the ARPES experiment and the cal-
culation: (1) the so-called K 4s band (interlayer band)
in the calculation shows a nearly-free-electron-like
dispersion around the  point while we find only a
nondispersive band at EF in the ARPES experiment;
(2) the calculated highest energy level of the  band
at the  point is located at about 7 eV while it is
experimentally observed at about 6 eV. As for the
interlayer band, it has a large energy dispersion
along the interlayer direction (Z) as shown in
Figure 23(b). This interlayer dispersion may distort
the present ARPES spectra, causing a discrepancy
between the experiment and the calculation.
Although we do not find a clear signature for the
interlayer band, the present experimental data sug-
gest the existence of partially filled band around the
 point. This is derived from the following two
experimental facts. First, the experimentally
observed  band observed at the K~ point shows a
good agreement with that of the ONK model, which
predicts the presence of the interlayer band below EF
(Ohno et al., 1979), while the  band does not show
a good agreement with the model predicting
the absence of the interlayer band below EF
(DiVincenzo and Rabii, 1982). The size of electron
pocket in the experiment is similar to that in the
ONK model, which suggests an electron charge
transfer of 0.6e from potassium atoms (e is the unit
charge). In order to accommodate the remaining
electronic charge of about 0.4e, another band is neces-
sary somewhere below EF in the experimental band
structure. This extra band is supposed to be located
around the center of the Brillouin zone according to
the theoretical interpretations for C8K (Ohno et al.,
1979; DiVincenzo and Rabii, 1982). Second, the non-
dispersive feature observed at EF shows the largest
peak intensity at   0 , and when we increase the
polar angle, the peak intensity is again enhanced
around the  point in the next Brillouin zone. This
strongly suggests the existence of a band below EF
around the  point, which would likely be the inter-
layer band. It is noted that this interlayer band is
more clearly observed in C6Ca as we describe in
the next section.
1.11.4.2 C6Ca
The discovery of superconductivity in C6Yb and
C6Ca (Weller et al., 2005) in 2005 has revived a
considerable interest since their Tc values (6.5 and
399
11.5 K) are significantly higher than those of other
GICs. To determine its pairing symmetry, several
experimental results have been reported. Although
the isotropic s-wave superconducting order para-
meter within the conventional BCS theory has been
inferred from the thermodynamic (Sutherland et al.,
2007) and magnetic properties (Lamura et al., 2006),
substantial deviations and anomalies beyond the
conventional framework have also been suggested
by the tunneling spectroscopy (Bergeal et al., 2006;
Kurter et al., 2007) and the electron spin resonance
experiment (Muranyi et al., 2008), proposing the
strong-coupling superconductivity, the anisotropic
gap, and/or the multicomponent gaps. The discovery
of high-Tc GICs has also stimulated several theo-
retical proposals for the superconducting mechanism.
An earlier band calculation (Csanyi et al., 2005) has
proposed an unconventional pairing mechanism via
the interlayer band with intermediate bosons such as
low-energy acoustic plasmons (Csanyi et al., 2005)
and excitions (Allender et al., 1973). Pairing mechan-
ism by the resonating valence bond has also been
discussed (Black-Schaffer and Doniach, 2007).
Recent first-principles calculations (Boeri et al.,
2007; Calandra and Mauri, 2005; Mazin, 2005;
Mazin et al., 2007; Sanna et al., 2007) have suggested
that the electron coupling to the out-of-plane carbon
and intercalant phonons is responsible for achieving
higher Tc’s, while a clear demonstration to experi-
mentally distinguish various models has not yet been
made. This key issue as well as the discrepancies in
the nature of superconducting gap among experi-
ments request further precise investigations on the
momentum and Fermi-surface dependence of the
superconducting gap. However, such an experiment
had hardly been done because of the small super-
conducting gap as well as the lack of high-quality
single crystals.
Figure 24 shows (a) crystal structure and
(b) Brillouin zone of C6Ca. Since the Ca atom stacks
with the rhombohedral coordination with an
AAA sequence, the Brillouin zone of C6Ca is
different from that of C8A. The projected surface
Brillouin zone has a hexagonal shape but is rotated
by 30 with respect to the Brillouin zone of C8A
(Figure 22(b)).
C6Ca single crystals were usually grown by
the chemical vapor transport method (Weller et al.,
2005), while it is also produced by the alloy method
(Emery et al., 2005). The inset in Figure 25 shows a
picture of C6Ca single-crystal grown by the alloy
method by heating kish graphite mixed with molten
400 Angle-Resolved Photoemission Spectroscopy
(a)
: Ca
:C
Figure 24 (a) Crystal structure and (b) the Brillouin zone of C6Ca.
FC
0.0
Moment (e.m.u. cm–3)
–0.2
1 mm
–0.4
–0.6
–0.8
ZFC
H = 10 (Oe)
–1.0
6 8 10
Temperature (K)
Figure 25 The DC magnetic susceptibility of C6Ca. Inset
shows a picture of C6Ca single crystal used for ARPES
measurements.
lithium–calcium alloy at around 350  C for 6 days
under high vacuum. Figure 25 also shows the mag-
netic susceptibility of C6Ca single crystal as a
function of temperature for zero-field cooling
(ZFC) and field cooling at 10 Oe. The sharp drop
in the ZFC curve confirms that the crystal exhibits
the superconductivity with the onset Tc ¼ 11.5 K
with the superconducting volume fraction as high as
90%. While kish graphite is very easy to cleave
because of the weak van der Waals coupling among
graphite layers, C6Ca is harder to cleave due to more
three-dimensional-like bonding character.
1.11.4.2.1 Band structure
Figures 26(a) and 26(b) show ARPES spectra of
C6Ca measured at 15 K along K and M directions
of graphite Brillouin zone, respectively (Sugawara
et al., 2008). We clearly find highly dispersive features
(b)
Γ
M
K
L
X
T
Graphene layer 1st layer α χ
Unit cell 2nd layer β T
3rd layer γ X
4th layer α
in both directions, basically similar to those of kish
graphite (see Figure 13). We find a peak in the
vicinity of EF showing an electron-like energy dis-
persion around the K(H) point, which is not observed
in kish graphite. We also notice a small but finite
peak with the Fermi-edge cut off around the  point.
Tc = 11.5 K This behavior has not been recognized in kish
graphite.
Figure 27 shows the experimentally determined
valence-band structure of C6Ca along high-symmetry
lines. Although the overall band structure of
C6Ca looks to be similar to that of kish graphite
(Figure 14), it is noticed that the band structure of
12 14 C6Ca is shifted as a whole toward high binding energy
by 1.0–1.5 eV, indicating that electrons are certainly
doped into pristine graphite by Ca intercalation.
A small electron pocket that appears in the vicinity
of Fermi level (EF) at the K point in C6Ca is ascribed
to the  band, which is above EF in pristine graphite
and is shifted down below EF by the electron doping
(McChesney et al., 2007; Molodtsov et al., 2003;
Takahashi et al., 1986).
1.11.4.2.2 Fermi surface
Figure 28 shows the Fermi surface of C6Ca deter-
mined by plotting the ARPES-spectral intensity at EF
as a function of the two-dimensional wave vector.
The topology of the Fermi surface in C6Ca is dras-
tically different from that of graphite (Figure 16).
We find two different Fermi surfaces, a circular
Fermi surface at the  point and a triangular Fermi
surface at the K point, while only one tiny Fermi
surface is observed at the K(H) point in graphite
(Sugawara et al., 2006). The triangular Fermi surface
at the K point originates in the  band and is well
explained in terms of the simple rigid shift of the
chemical potential due to the electron doping (Tatar
 Angle-Resolved Photoemission Spectroscopy 401

(a) M(L) (b) M(L)

K(H) K(H)
M M
Γ(A) Γ(A)
K K

K(H)

Intensity (a.u.)
Intensity (a.u.)

M(L)

Γ(A)

Γ(A)

16 12 8 4 EF 16 12 8 4 EF
Binding energy (eV) Binding energy (eV)
Figure 26 Valence-band ARPES spectra of C6Ca measured along (a) the K and (b) M directions in the graphite Brillouin
zone (Sugawara et al., 2008).

C6Ca C6Ca
B′
EF
M
1 B
1.0 K
2 A
ky (Å–1)

0.0 M Γ A′
EF
Binding energy (eV)

K
High
–1.0
4

–1.0 0.0 1.0 Low

8
High kx (Å–1)

Figure 28 Fermi surface of C6Ca determined by ARPES.

12
of  band due to the superstructure of Ca interca-
lants, because the shape and size of Fermi surface
16 are distinctly different from those of the  Fermi
M K Γ M K Low surface. On the other hand, the band structure
Wave vector calculations (Boeri et al., 2007; Calandra and Mauri,
Figure 27 Band structure of C6Ca determined by ARPES. 2005; Mazin, 2005; Mazin et al., 2007; Sanna et al., 2007)
The top panel shows an expansion of the near-EF region. have predicted an additional band at the  point in
C6Ca (named the interlayer band), which has a sizable
and Rabii, 1982). In contrast, the small Fermi surface contribution from the intercalant states and produces a
observed at the  point is not explained by the small free-electron-like spherical Fermi surface at the
simple rigid shift of graphite bands or the folding  point. Considering a good agreement in the location
402 Angle-Resolved Photoemission Spectroscopy
and the shape, we assign the small Fermi surface
observed at the  point to the interlayer band
(Ohno et al., 1979) in C6Ca. In fact, the observed
circular Fermi surface is not ascribed to the calculated
two  Fermi surfaces in C6Ca, since one calculated
Fermi surface has a hexagonal shape and the other
is not centered at the  point (Sanna et al., 2007;
Mazin et al., 2007).
1.11.4.2.3 Superconducting gap
Figure 29 shows ARPES spectra near EF of C6Ca at
6 K measured at two representative Fermi vectors
(kF’s) on the circular Fermi surface at the  point
and the triangular Fermi surface at the K point,
respectively, as indicated by circles in Figure 28.
Note that the spectral intensity shows a sudden
drop at 80 meV on the circular Fermi surface
(point A) while a small but clear dip is observed at
170 meV in the spectrum measured on the triangu-
lar Fermi surface (point B). We find that the energy
position of dip does not vary in the momentum
region around the kF point. This is not explained
by the presence of another band located around the
dip energy, but is reminiscent of the strong many-
body effects observed in high-Tc cuprates
(Campuzano et al., 2004; Damascelli et al., 2003)
and Ba0.67K0.33BiO3 (Chainani et al., 2001). In fact,
as seen in Figure 29, the Eliashberg function 2F(!)
calculated for C6Ca (Calandra and Mauri, 2005)
C6Ca
Tc = 11.5 K
Intensity (a.u.)
1.0
C(xy)
α 2F(ω)
0.5
0.4 0.3 0.2 0.1
Binding energy (eV)
Figure 29 ARPES spectra near EF of C6Ca at 6 K
measured at points A and B (see Figure 28), compared to
the Elieshberg function 2F(!) (Calandra and Mauri, 2005).
shows dominant peaks at 50–75 and 160–180 meV
originating in the out-of-plane and the in-plane
vibrations of carbon atoms, respectively, in good
agreement with the anomalies observed in the
ARPES spectra. This suggests that electrons on the
circular Fermi surface at the  point are strongly
coupled to the out-of-plane vibrations while those
on the triangular Fermi surface at the K point are
coupled dominantly with the in-plane phonons.
This experimentally demonstrates that the interlayer
electrons strongly interact with the surrounding lat-
tice unlike in the free-electron picture, as predicted
from the first-principles calculations (Sanna et al.,
2007; Boeri et al., 2007). The reason why  electrons
at the K point are only weakly coupled to the out-of-
plane phonons may be the antisymmetry of the
wave function with respect to the graphene layer
(Calandra and Mauri, 2005). On the other hand, the
interlayer band forming the circular Fermi surface
at the  point is expected to be strongly coupled to
the out-of-plane phonons due to the symmetry
(Boeri et al., 2007). We note that a spectral dip
related to the coupling with the Ca vibrations is
not clearly observed in Figure 29, possibly because
the dip is broad (20–30 meV) compared to the Ca
phonon energy (15 meV).
Figure 30(a) shows ultrahigh-resolution ARPES
spectra near EF of C6Ca measured at two represent-
ative k points A and B as shown in Figure 28 at
temperatures below/above Tc (6 and 15 K). At point
A, the midpoint of the leading edge in the spectrum
at 6 K is shifted toward high binding energy by
approximately 0.8 meV with respect to EF while the
spectrum at 15 K has the midpoint at EF. This clearly
indicates the opening/closing of a superconducting
gap as a function of temperature. On the other hand,
at point B, the midpoint of the leading edge is located
at around EF even at 6 K, and the spectrum looks to
show a simple temperature dependence to obey the
A FD function, suggesting the absence or the very small
magnitude of the superconducting gap. This marked
C(z) difference is better illustrated in Figure 30(b) where
the spectra at 6 K at points A and B are directly
compared. To clarify the possible anisotropy of
Ca
(xy) B
the gap, we also plot the 6-K spectra measured at
points A9 and B9 on the same Fermi surfaces but on
different high-symmetry lines (Figure 28), since the
EF anisotropy, if it exists, should be largest between
points A and A9 (B and B9). As seen from
Figure 30(b), the leading edge at point A9 (B9)
almost coincides with that of points A (B). This
suggests that the anisotropy of superconducting gap
 Angle-Resolved Photoemission Spectroscopy 403

(a) (b)
C6Ca T=6K
Tc = 11.5 K A

Intensity (a.u.)

Intensity (a.u.)
A'
B
A B'
T=
6K ∆ = 1.8 meV
B Γ = 0.5 meV A
15 K

10 5 EF –5 10 5 EF –5
Binding energy (meV) Binding energy (meV)
Figure 30 (a) Superconducting gap of C6Ca measured at representative kF points A and B in Figure 28. (b) Top: direct
comparison of ARPES spectrum at T ¼ 6 K measured at four kF points in Fig. 28. Bottom: Numerical simulation of ARPES
spectrum at point A.

is very small in both circular and triangular Fermi 1.11.5 Graphene

surfaces, while the gap value is markedly different
between these two Fermi surfaces. To estimate the
size of superconducting gap, we numerically fit the
spectrum by using the Dynes function (Dynes et al.,
1978). The representative result for point A is dis-
played in Figure 30(b). The estimated gap size  at
6 K is 1.8  0.2 and 2.0  0.2 meV at points A and A9,
respectively. The reduced gap value of 2(0)/kBTc
by assuming the mean-field temperature dependence
is 4.1  0.5, indicating the intermediate- to strong-
coupling character. The first-principles calculation
(Sanna et al., 2007) has predicted a similar gap value.
On the other hand, at points B and B9, the estimated
superconducting gap size is 0.2  0.2 meV. These
results suggest the anisotropy of the superconducting
gap of 1 meV reported by the tunneling experiment
(Bergeal et al., 2006) is not explained in terms of the
anisotropy of interlayer Fermi surface at the  point,
but is actually influenced by a smaller superconduct-
ing gap of other Fermi surfaces, most likely the 
Fermi surface. The reported deviation of the specific
heat (Kim et al., 2006) from the single isotropic
1.11.5.1 Single-Layered Graphite: Dirac
Fermion?
Graphene has attracted much attention since it shows
various interesting physical properties such as
the massless Dirac-fermion-like behavior and the
unusual quantum Hall effect (Novoselov et al.,
2005). The recent success of spin injection at room
temperature (Ohishi et al., 2007; Tombros et al., 2007)
and the observation of bipolar supercurrent (Heersche
et al., 2007) suggest that graphene has a high potential
of application to spintronics devices. To reveal the
origin and the mechanism of these novel properties,
it is indispensable to elucidate the electronic structure
near the Fermi level (EF). As shown in Figure 31, it
has been theoretically predicted (Painter and Ellis,
20
Binding energy (eV)

s-wave behavior (Sanna et al., 2007; Mazin et al., σ∗ 10

2007) would also be explained by this Fermi surface
dependence of the superconducting gap. π∗
Present results demonstrate that the coupling of EF
π
electrons in the interlayer band with the out-of- σ
plane phonons is essential to realize the superconduc- –10
tivity in C6Ca, while the simple electron doping into
the  band of graphene layers may not lead to the
–20
superconductivity at such a high temperature. The
next challenge is to clarify the role of intercalant K Γ M K
(Ca) phonons which have been theoretically proposed Wave vector
to enhance the Tc value (Boeri et al., 2007; Calandra Figure 31 Schematic band structure of graphene
and Mauri, 2005; Mazin, 2005, 2007; Sanna et al., 2007). (Painter and Ellis, 1970).
404 Angle-Resolved Photoemission Spectroscopy
1970) that the  and  bands contact each other only
at K point of the Brillouin zone in graphene and the
energy at this contacting point is called the Dirac
energy (ED). It is obvious that ED is equal to EF in
pristine (undoped) graphene. To experimentally
investigate the electronic structure of graphene by
ARPES, a clean surface of graphene has to be pre-
pared under ultrahigh vacuum. There are several
methods to fabricate the graphene sample. First is
to peel off the bulk graphite many times known as a
micro cleaving (Novoselov et al., 2005). Second is to
evaporate/dissociate organic materials like ethylene
on a clean metal surfaces such as Ni(111) (Nagashima
et al., 1994a), TaC(111) (Nagashima et al., 1994b), and
Pt(111) (Fujita et al., 2005). Third is to segregate a
graphene sheet on SiC(0001) crystal surface by
heating the SiC crystal (Vanbommel et al., 1975).
First method has a difficulty in obtaining a large
surface area suitable for ARPES measurements. In
the second method, we expect a strong interaction
between the substrate and the graphene film, so that
near-EF energy bands of graphene are strongly
modulated by the hybridization by the energy
bands of the metallic substrate. The third method
seems useful for ARPES measurement because the
interaction between substrate and the graphene film
is much weaker than the second case, and a clean
surface with the large area (few mm2) is easily
obtained by controlling the annealing temperature
Graphene/SiC(0001)
(a)
Graphene (1 x 1)
6 3x6 3
Si (1 x 1)
(c) EF
π K
σ
Binding energy (eV)
12
16
Γ K
Wave vector
Figure 32 (a) LEED pattern of graphene grown on 6H-SiC(0001). (b) Valence-band ARPES spectra of graphene.
(c) Experimentally determined band structure compared with the band calculation of graphene.
and the temperature gradient on the surface. Here
we focus on the ARPES results of graphene film
prepared by the third method.
Graphene thin films were prepared by annealing
an n-type Si-rich 6H-SiC(0001) single crystal with
resistive heating in an ultrahigh vacuum of 1  1010
Torr (Bostwick et al., 2007; Zhou et al., 2007, 2008;
Rotenberg et al., 2008). By controlling the tempera-
ture and the heating time, it is possible to selectively
grow single-layer graphene and multilayer graphene
with more than 10 sheets (Kusunoki et al., 2000).
Graphene films are characterized by the low-energy
electron diffraction (LEED) and the energy position
of  and  bands observed by ARPES.
Figure 32(a) shows the LEED pattern of gra-
phene grown on 6H-SiC(0001) measured with
primary electron energy of 107 eV. The LEED
pattern of graphene on SiC(0001) consists of three
different spots: (1) the (1  1) spots from the bulk SiC
p p
substrate (SiC (1  1)); (2) the weak 6 3  6 3
spots which originate in the bulk SiC layer bonded
with the interface graphene layer (buffer layer);
and (iii) the C (1  1) spots due to the honeycomb
atomic pattern of graphene (Ni et al., 2008).
Figure 32(b) shows the valence-band ARPES
spectra of graphene measured along the KM direc-
tion. Several highly dispersive bands are clearly
observed, and the overall band dispersion is basically
similar to that of bulk graphite (see Figure 14(a)).
(b)
M
Intensity (a.u.)
Γ
16 12 8 4 EF
M
Binding energy (eV)

We find a single  band which rapidly disperses
toward EF on approaching the K point. Figure 32(c)
shows the ARPES-derived band structure of
graphene/SiC(0001) compared with the calculated
bands. The experimental band structure was obtained
by taking the second derivative of ARPES spectra and
plotting the intensity as a function of wave vector and
binding energy. As expected, the band structure of
graphene consists of the highly dispersive  and 
bands. The overall band structure is well reproduced
by the calculation, while some quantitative differences
are found in the energy position of the top of  band
and the bottom of  band at the  point.
1.11.5.2 Comparison with Graphite
Figure 33 shows the comparison of experimental
band structure between (a) graphene/SiC(0001) and
(b) graphite/SiC(0001). It is noted that the multilayer
graphene sample in this study shows the almost
identical band structure to that of bulk kish graphite
(Sugawara et al., 2006, 2007). Hence we refer to this
multilayer graphene as graphite in this section. As
clearly visible in Figure 33, the band structures of
graphene and graphite look very similar to each
other, consisting of the highly dispersive  and
 bands. The  band has the bottom of dispersion at
around 8–9 eV at the  point and the top at EF at the
K point, while the  band has the top at around
4–5 eV at  point and shows a strong downward
dispersion toward the K point. However, detailed
comparison reveals several quantitative differences.
(a) Graphene/SiC(0001)
EF
π π
σ σ
Binding energy (eV)
8 8
12
16
Γ K
Wave vector
Figure 33 Comparison of valence-band structure between (a) graphene/6H-SiC(0001) and (b) graphite/6H-SiC(0001).
Angle-Resolved Photoemission Spectroscopy 405
For example, the bottom of  band at  point in
graphene is shifted by about 0.7 eV toward the high
binding energy compared to that in graphite. As for the
 band, the top (bottom) of dispersion at the (K) point
in graphene is located at 0.5 eV higher (0.7 eV lower)
binding energy than that of graphite. These experi-
mental results indicate that the band width of both 
and  bands is larger in graphene than in graphite.
This quantitative difference in the band width may be
ascribed to the difference in the lattice constant.
Actually, the wave vector of the K point estimated
from the present ARPES results is slightly different
between graphene and graphite; 1.72  0.01 Å1 for
graphene and 1.70  0.01 Å1 for graphite. The
corresponding in-plane lattice vectors () are
2.44  0.01 and 2.46  0.01 Å, respectively, showing a
good agreement with the reported value (2.46 Å)
(Lukesh and Pauling, 1950) for the case of graphite.
The lattice contraction in graphene may be due to a
slight mismatch of the lattice constant between
graphite and SiC as observed by Raman spectroscopy
(Ni et al., 2008). In addition to the  and  bands, we find
a weakly dispersing band around 3–4 eV binding
energy in graphene, which is not predicted in the
band calculation (Painter and Ellis, 1970) and may be
p p
due to the 6 3  6 3 structure of the buffer layer
(Mattausch and Pankratov, 2007; Emtsev et al., 2008).
Figure 34 shows the plot of ARPES intensity
around the K point as a function of the wave vector
and the binding energy for (a) graphene and (b)
graphite. To remove the effect from the FD function,
the ARPES intensity is divided by the FD function
(b) Graphite/SiC(0001)
EF
4
Binding energy (eV)
K(H) M(L)
12
Γ(A)
16
M Γ(A) K(H) M(L)
Wave vector
406 Angle-Resolved Photoemission Spectroscopy
(a) Graphene/SiC(0001)
Binding energy (eV) EF
0.2
0.4 280 meV
0.6
0.8 kx =
0.0
1.0
–0.04 0.0 0.04 Intensity (a.u.)
kx (Å–1)
Figure 34 Comparison of near-EF band structure between (a) graphene/6H-SiC(0001) and (b) graphite/6H-SiC(0001),
together with the corresponding energy distribution curve at the K point.
convoluted with the Gaussian which reflects the
instrumental resolution. The corresponding ARPES
spectra at the K point are also shown for comparison.
It is remarked in Figure 34(a) that the Dirac energy
ED of graphene is not at EF, but is about 0.4 eV below
it, suggesting that the graphene sheet on SiC is doped
with electrons, as also evident from the appearance of
the  band at EF. It is speculated that electrons are
transferred from the n-type SiC substrate and/or the
buffer layer (Bostwick et al., 2007; Rotenberg et al.,
2008; Zhou et al., 2007; Zhou et al., 2008). On the other
hand, ED of graphite is at or very close to EF, as seen
in Figure 34(b). The band structure of graphite
grown on SiC shows a close resemblance to that of
bulk kish graphite (see Figure 14) (Sugawara et al.,
2007). The energy splitting of  band at the K point
due to the interlayer coupling between graphene
sheets is clearly observed and the energy interval is
almost identical to that of kish graphite. A sharp
quasi-particle peak appears at EF, and the Dirac
energy ED is at or very close to EF as in kish graphite.
These experimental results suggest that the graphite
sample grown on SiC in the present study consists of
a sufficiently large number of graphene sheets and
hardly suffers the charge-transfer effect from the
substrate (Zhou et al., 2007; Ohta et al., 2007). In
contrast, the graphene sheet grown on SiC substan-
tially suffers the charge-transfer effect as evident
from the large chemical potential shift as seen in
Figure 34(a). Further, very interestingly, there
seems to be an energy gap between the  and the
 bands in graphene on SiC, while no or a negligibly
small gap is seen in graphite. The size of energy gap
(b) Graphite/SiC(0001)
EF
Binding energy (eV)
0.2
0.4
High
0.6
0.8 kx =
Å–1 0.0Å–1
1.0
–0.04 0.0 0.04 Intensity (a.u.) Low
kx (Å–1)
in graphene estimated from the interval between the
two peaks in the ARPES spectrum is about 280 meV.
This band gap has also been observed (Zhou et al.,
2007, 2008) and discussed in terms of the sublattice-
symmetry breaking due to the graphene–substrate
interaction. On the other hand, it has also been
reported that there is no gap opening at ED and the
observed small anomaly of band dispersion around
ED is explained in terms of the electron–plasmon
coupling (Bostwick et al., 2007; Rotenberg et al.,
2008). The reason for this difference is unclear at
present, while it has also been discussed that the
quantitative value of the band gap may depend on
the sample preparation process (Zhou et al., 2008).
As for the origin of band gap in graphene observed
in the present ARPES study, it would be most likely
related to the interaction between the graphene sheet
and the SiC substrate. The band-gap size decreases
on increasing the number of layers (Zhou et al., 2007),
and finally vanishes in multilayer graphite (graphite)
as shown in Figure 34. As described above, the pre-
sent ARPES results have revealed that the lattice of
graphene grown on SiC(0001) slightly contracts
compared with that of bulk graphite, as evident
from the larger wave vector of the K point and the
resultant larger bandwidth of the  and  bands in
graphene. It is also noted that a graphene sheet grown
on TaC(111), which has a relatively large lattice
mismatch to the substrate, exhibits a substantially
large (1.3 eV) energy gap between the  and 
bands (Oshima and Nagashima, 1997). All these
experimental results suggest that the energy gap is
caused by the lattice strain due to the lattice
 Angle-Resolved Photoemission Spectroscopy
mismatch between the graphene sheet and the sub-
strate, and the gap gradually vanishes as the strain is
gradually released at the topmost layers of multilayer
graphene. This indicates that the effect from the
substrate should be taken into account when gra-
phene grown on a SiC crystal is investigated, and
also suggests that the magnitude of the band gap can
be controlled by tuning the lattice parameters of the
base substrate and resultant hybridization strength
between the graphene sheet and the substrate. We
note that it is important to grow a graphene film
free from the lattice mismatch/strain to investigate
the genuine Dirac-fermion-like behavior.
1.11.6 Concluding Remarks and
Summary
The recent remarkable improvement of the energy
and momentum resolutions in ARPES enables us to
determine experimentally the band structure and
the Fermi surface of various novel materials with
great accuracy. In fact, the Fermi surface and the
superconducting gap of high-temperature cuprate
superconductors have been precisely revealed by
ARPES. Further, electrons dressed with interactions,
namely quasi-particles, are directly observed by
high-resolution ARPES as a small anomaly (kink) in
the energy dispersion near EF and have been inten-
sively discussed in relation to the mechanism and the
origin of the novel properties such as the high-Tc
superconductivity. Theoretical calculations, such as
that of the band structure, are directly compared with
the experimental results from ARPES experiments to
examine the validity of the theory. Thus, ARPES is
now regarded as one of the essential experimental
techniques in solid-state physics and materials
science. On the other hand, the discovery and/or
the synthesis of new functional materials have been
successively achieved in recent years. In particular,
carbon-based new materials such as fullerenes and
carbon nanotubes have revived/stimulated the study
of the mother material (graphite) and produced
additional new functional carbon-based material,
grapheme, and high-Tc GICs.
In this chapter, we have reviewed high-resolution
ARPES studies of graphite, GICs, and graphene.
The high-resolution ARPES has revealed that this
simple sp2 material exhibits a variety of interesting
properties such as the interlayer state, the edge-localized
state, the Dirac-fermion, and the Fermi-surface-
dependent high-temperature superconductivity. In
407
particular, the direct ARPES observation of the inter-
layer state and its relationship to the superconductivity
in C6Ca has definitely resolved the long-standing
problem in the mechanism of superconductivity in
GICs. It is expected that high-resolution ARPES will
be applied to well-characterized single- or multilayer
graphene as well as well-fabricated graphene ribbons
to elucidate their novel electronic structures.
(See Chapters 1.02, 1.10, 1.12 and 2.05).
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 1.12 Theory of Superconductivity in Graphite Intercalation
Compounds
Y Takada, University of Tokyo, Kashiwa, Chiba, Japan
ª 2011 Elsevier B.V. All rights reserved.

1.12.1 Introduction 411

1.12.1.1 Crystal Structure 411
1.12.1.2 Superconductivity 411
1.12.1.3 Central Issues 412
1.12.1.4 Organization of This Chapter 413
1.12.2 First-Principles Calculation of Tc 413
1.12.2.1 Goal of the Problem 413
1.12.2.2 McMiland’s and Allen-Dynes’ Formulas for Tc 413
1.12.2.3 Coulomb Pseudopotential  413
1.12.2.4 Vertex Corrections and Dynamic Screening 414
1.12.2.5 Ideal Calculation Scheme 414
1.12.3 Calculation of Tc in the G0W0 Approximation 414
1.12.3.1 Formulation 414
1.12.3.2 Comments on the Formulation 415
1.12.3.3 Assessment: Application to SrTiO3 416
1.12.4 Density Functional Theory for Superconductors 416
1.12.4.1 Hohenberg–Kohn–Sham Theorem 416
1.12.4.2 Gap Equation 417
1.12.4.3 Applications 417
1.12.4.4 Basic Problems 418
1.12.5 Experiment on Superconductivity in GICs 418
1.12.6 Standard Model for Superconductivity in GICs 419
1.12.6.1 Characteristic Features of the System 419
1.12.6.2 Microscopic Model for Superconductivity 420
1.12.6.3 Calculation of Tc for Alkali-Doped GICs 421
1.12.7 Superconductivity in Alkaline-Earth GICs 421
1.12.7.1 CaC6 421
1.12.7.2 Other Alkaline-Earth GICs 422
1.12.8 Prediction of the Optimum Tc in GICs 422
1.12.9 Conclusion 423
References 423

Glossary
Allen-dynes formula In 1975, Allen and Dynes
modified the McMillan’s formula for Tc, producing a
rather large change in Tc for the electron–phonon
nondimensional coupling constant  larger than 2.
Coulomb pseudopotential A phenomenological
parameter to estimate the effect of the Coulomb
repulsion on the Cooper pairing by taking into
account both retardation and screening effects.
Density functional theory (DFT) A theory to
describe an interacting many-body system in terms
of its density distribution in three dimensions.
Eliashberg function In the phonon mechanism,
the phonon-mediated attractive interaction is
characterized by both the electron–phonon
coupling (!) and the phonon density of states F(!),
but in calculating Tc only their combination

410
 Theory of Superconductivity in Graphite Intercalation Compounds
(!)2F(!), which is called the Eliashberg function, is
important.
First-principles calculation A calculation is said
to be from first principles or ab initio if it starts
directly at the level of established laws of physics
which contain no fitting or phenomenological
parameters.
Graphite intercalation compounds
(GICs) Complex materials in which the graphite
layers remain largely intact, and the guest element
or molecule is inserted between the layers.
GW approximation In 1965, Hedin proposed an
approximation scheme to calculate the electron
self-energy in terms of the one-electron Green’s
function G and the effective electron–electron
interaction W without any vertex corrections. If the
same scheme is applied to superconductivity, it is
nothing but the Eliashberg theory for
superconductivity.
Isotope effect If Tc depends directly or indirectly
on the mass M of the ions building up the lattice, we
call the dependence the isotope effect. In the
standard Bardeen–Cooper–Schrieffer (BCS)
theory, Tc changes in proportion to M with the
isotope coefficient  ¼ 0.5.
McMillan’s formula In 1968, McMillan proposed a
simple formula for Tc in the phonon mechanism
composed of an average phonon energy !0, the
electron–phonon nondimensional coupling
constant , and the Coulomb pseudopotential ,
1.12.1 Introduction
1.12.1.1 Crystal Structure
For many decades, graphite intercalation compounds
(GICs) have been investigated from the viewpoint of
physics, chemistry, materials science, and engineer-
ing (or technological) applications (Fischer and
Thompson, 1978; Kamimura, 1987; Zabel and Solin,
1992; Dresselhaus and Dresselhaus, 2002). Among
various kinds of GICs, special attention has been
paid to the first-stage metal compounds, partly
because superconductivity is observed mostly in
this class of GICs, the chemical formula of which is
written as MCx, where M represents either an alkali
atom (such as Li, K, Rb, and Cs) or an alkaline-earth
atom (such as Ca, Sr, and Yb) and x is either 2, 6, or 8.
411
based on the numerical solution of the Eliashberg
equation for various systems.
Phonon mechanism If the Cooper pairs are
created by the attractive interaction induced by
virtual exchange of phonons between electrons,
the superconductivity is considered to be brought
about by the phonon mechanism.
Plasmon mechanism In the low-density electron
gas, plasmons can play a similar role to phonons in
superconductivity. We indicate this role as the
plasmon mechanism.
Spin-fluctuation mechanism In a system with
strong spin fluctuations at either long wavelengths
(related to a ferromagnetic instability) or short
wavelengths (related to an antiferromagnetic
instability), the fluctuations can play a role similar to
phonons in superconductivity. We indicate this role
as the spin-fluctuation mechanism.
Stage In a GIC, not every layer is necessarily
intercalated by guest elements or molecules. In the
so-called stage 1 GICs like KC8, graphite and
intercalated layers alternate, while in stage 2 GICs
such as KC24, two graphite layers with no guest
material in between alternate with an intercalated
layer. Similarly, we can define stage n with n > 2.
Vertex function A factor to describe the change in
the electron charge during scattering processes
due to the modification of the many-body wave
function. Its deviation from unity (or the bare
coupling) is called vertex corrections.
The crystal structure of MCx is shown in
Figure 1(a), in which the metal atom M occupies
the same spot in the framework of a honeycomb
lattice at every (x/2) layers of carbon atoms.
1.12.1.2 Superconductivity
The first discovery of superconductivity in GICs was
made in KC8 with the superconducting transition
temperature Tc of 0.15 K in 1965 (Hannay et al.,
1995). In pursuit of higher Tc, various GICs were
synthesized, mostly working with the alkali metals
and alkali-metal amalgams as intercalants, from the
late 1970s to the early 1990s (Alexander et al., 1980;
Belash et al., 1989; Belash et al., 1990; Dresselhaus
et al., 1989; Hannay et al., 1995; Iye and Tanuma,
412 Theory of Superconductivity in Graphite Intercalation Compounds
(a) (b)
101
d
Tc (K)
100
10–1
10–2
: M : C
Figure 1 (a) Crystal structure of MCx (x ¼ 2, 6, 8). The case of x ¼ 6 is illustrated here, in which the metal atoms, M’s, are
arranged in a rhombohedral structure with the  stacking sequence, implying that M occupies the same spot in the
framework of a graphene lattice at every three layers (or at the distance of 3d with d the distance between the adjacent
graphite layers). (b) Superconducting transition temperature Tc observed in the first-stage alkali- and alkaline-earth-
intercalated graphites plotted as a function of d.
1982; Koike et al., 1978; Kobayashi and Tsujikawa,
1979; Koike et al., 1980), but only a limited success
was achieved at that time; the highest attained Tc was
around 2–5 K in the last century. For example, it is
1.9 K in LiC2 (Belash et al., 1989).
A breakthrough occurred in 2005 when Tc went up
to 11.5 K in CaC6 (Weller et al., 2005; Emery et al.,
2005) (and even to 15.4 K under pressures up to
7.5 GPa (Gauzzi et al., 2007)). In other alkaline-earth
GICs, the values of Tc are 6.5 and 1.65 K for YbC6
(Weller et al., 2005) and SrC6 (Kim et al., 2006), respec-
tively, as indicated in Figure 1(b). Since then, very
intensive experimental studies have been made in
those and related compounds (Emery et al., 2005;
Kim et al., 2007, 2006; Kurter et al., 2007). Theoretical
studies have also been performed mainly by making
state-of-the-art first-principles calculations of the
electron–phonon coupling constant  to account for
the observed value of Tc for each individual super-
conductor (Mazin, 2005; Csanyi et al., 2005; Calandra
and Mauri, 2005; Sanna et al., 2007). Those experi-
mental/theoretical works have elucidated that,
although there are some anisotropic features in the
superconducting gap, the conventional phonon-driven
mechanism to bring about s-wave superconductivity
applies to those compounds. This picture of super-
conductivity is confirmed by, for example, the
observation of the Ca isotope effect with its exponent
 ¼ 0.50, the typical Bardeen–Cooper–Schrieffer
(BCS) value (Hinks et al., 2007).
CaC6
YbC6
LiC2 SrC6
KC8
RbC8 C5C8
4.0 4.5 5.0 5.5 6.0
d (Å)
1.12.1.3 Central Issues
In spite of all those efforts and the existence of such a
generally accepted picture, there remain several very
important and fundamental questions:
1. Can we understand the mechanism of supercon-
ductivity in both alkali GICs with Tc in the range
0.01–1.0 K and alkaline-earth GICs with Tc in the
range 1–10 K from a unified point of view? In
other words, is there any standard model for
superconductivity in GICs with Tc ranging over
three orders of magnitude?
2. What is the actual reason why Tc is enhanced so
abruptly (or by about a hundred times) by just
substituting K with Ca, the atomic mass of which
is almost the same as that of K? In terms of the
standard model, what are the key controlling phy-
sical parameters to bring about this huge
enhancement of Tc ? This change of Tc from
KC8 to CaC6 is probably the most important
issue in exploring superconductivity across the
entire family of GICs.
3. Is there any possibility to make a further enhance-
ment of Tc in GICs ? If possible, what is the
optimum value of Tc expected in the standard
model and what kind of atoms should be interca-
lated to realize the optimum Tc in actual GICs?
In order to provide reliable answers to the
above questions, it is indispensable to make a
 Theory of Superconductivity in Graphite Intercalation Compounds
first-principles calculation of Tc with sufficient accu-
racy and predictive power. Recently, such a
calculation has been completed by the present author,
and based on the calculation, some interesting predic-
tions have been proposed (Takada, 2009a; 2009b).
The present chapter not only reports some details of
this work on the superconducting mechanism in GICs
but also makes a brief summary of the current status
of the theories for first-principles calculations of Tc.
1.12.1.4 Organization of This Chapter
This chapter is organized as follows: In Sections
1.12.2–1.12.4, a critical review of the theories for
quantitative calculations of Tc is given. More speci-
fically, we make comments on the theories based on
the McMillan’s or the Allen-Dynes’ formula employ-
ing the concept of the Coulomb pseudopotential 
in Section 1.12.2. In Section 1.12.3 we explain the
theory on the level of the so-called G0W0 approxima-
tion, where Tc can be obtained without using , a
very important advantage. The same advantage can
be enjoyed in the density functional theory for super-
conductors, which will be addressed in Section 1.12.4.
In Sections 1.12.5–1.12.8, a review on superconduc-
tivity in GICs is given; starting with a summary of
the experimental works in Section 1.12.5, a standard
model for considering the mechanism of supercon-
ductivity in GICs is introduced in Section 1.12.6. In
Section 1.12.7, the calculated results of Tc are given
for the alkaline-earth GICs and they are compared
with the experimental results. The prediction of the
optimum Tc is given in Section 1.12.8. Finally in
Section 1.12.9, the conclusion of this chapter is
given, together with some perspectives on the
researches in this and related fields in the future.
1.12.2 First-Principles Calculation of Tc
1.12.2.1 Goal of the Problem
It would be one of the ultimate goals in the enterprise
of condensed matter theory to make a reliable pre-
diction of Tc only through the information on
constituent elements of a superconductor in consid-
eration. A less ambitious yet very important goal is to
make an accurate evaluation of Tc directly from a
microscopic (model) Hamiltonian pertinent to the
superconductor. If we could find the dependence of
Tc on the parameters specifying the model
Hamiltonian, we could obtain a deep insight into
the mechanism of superconductivity or the
413
competition between the attractive and the repulsive
interactions between electrons. Accumulation of such
information might pave the way to the synthesis of a
room-temperature superconductor, a big dream in
materials science. From this perspective, a continu-
ous effort has been made for a long time to develop a
good theory for first-principles calculations of Tc,
starting with a microscopic Hamiltonian.
1.12.2.2 McMiland’s and Allen-Dynes’
Formulas for Tc
In the phonon mechanism, for example, there has
been a rather successful framework for this purpose,
known as the McMillan’s formula (McMillan, 1968)
or its revised version (the Allen-Dynes’ formula)
(Allen and Dynes, 1975; Allen and Mitrović, 1982;
Carbotte, 1990), both of which are derived from the
Eliashberg theory of superconductivity (Eliashberg,
1960). In this framework, the task of a microscopic
calculation of Tc is reduced to the evaluation of the
so-called Eliashberg function 2F(!) from first prin-
ciples; the function 2F(!) enables us to obtain both
the electron–phonon coupling constant  and the
average phonon energy !0, through which we can
make a first-principles prediction of Tc by
additionally introducing a phenomenological
parameter  (the Coulomb pseudopotential (Morel
and Anderson, 1962)) in order to roughly estimate
the effect of the Coulomb repulsion between
electrons on Tc.
At present this framework is usually regarded as
the canonical one for making a first-principles predic-
tion of Tc. In fact, the superconducting mechanism of
many (so-called weakly correlated) superconductors is
believed to be clarified by using this framework,
whereby the key phonon modes to bring about super-
conductivity are identified. We can point out that
superconductivity in MgB2 with Tc ¼ 39 K is a good
recent example (Bohnen et al., 2001; Choi et al., 2002a;
2002b; Kong et al., 2001) to illustrate the power of this
framework. The case of CaC6 has also been investi-
gated along this line of theoretical studies (Mazin,
2005; Calandra and Mauri, 2005).
1.12.2.3 Coulomb Pseudopotential 
Nevertheless, this framework is not considered to be
very satisfactory, primarily because a phenomenolo-
gical parameter  is included in the theory.
Actually, it cannot be regarded as the method of
predicting Tc in the true sense of the word, if the
414 Theory of Superconductivity in Graphite Intercalation Compounds
parameter  is determined so as to reproduce the
observed Tc. Besides, as long as we employ  to avoid
a serious investigation of the effects of the Coulomb
repulsion on superconductivity, we cannot apply this
framework to strongly correlated superconductors.
Even in weakly or moderately correlated supercon-
ductors, this framework cannot tell anything about
superconductivity originating from the Coulomb
repulsion via charge and/or spin fluctuations (namely,
the electronic mechanism including the plasmon
mechanism (Takada, 1978, 1993a)). Furthermore, in
this framework, we cannot investigate the competition
or the coexistence (or even the mutual enhancement
due to the quantum-mechanical interference effect)
between the phonon and the electronic mechanisms.
The validity of the concept of  is closely con-
nected with that of the Eliashberg theory itself; the
theory is valid only when the Fermi energy of the
superconducting electronic system, EF, is very much
larger than !0. Under the condition of EF >> !0, the
dynamic response time for the phonon-mediated
attraction !01 is much shorter than that for the
Coulomb repulsion E–1 F , precluding any possible
interference effects between two interactions, so
that physically it is very reasonable to separate
them. After this separation, the Coulomb part
(which was not considered to play a positive role in
the Cooper-pair formation) has been simply treated
in terms of . Thus, for the purpose of searching for
some positive role of the Coulomb repulsion, the
concept of  is irrelevant from the outset.
1.12.2.4 Vertex Corrections and Dynamic
Screening
Incidentally, in some recently discovered supercon-
ductors in the phonon mechanism such as the alkali-
doped fullerenes with Tc ¼ 18–38 K (Gunnarsson,
1997; Hebard et al., 1991; Takada and Hotta, 1998;
Takabayashi et al., 2009), the condition of EF >> !0 is
violated, necessitating to include the vertex correc-
tions in calculating the phonon-mediated attractive
interaction (Takada, 1993b). Then, it is by no means
clear to treat the overall effect of various phonons in
terms of the sum of the contribution from each pho-
non, implying that the Eliashberg function 2F(!) is
not enough to properly describe the attraction because
of possible interference effects among virtually excited
phonons. As a consequence,  will not be simply the
sum of i, the contribution from the ith phonon, unless
i is small enough to validate the whole calculation in
lowest-order perturbation.
In the case of EF  !0, another complication
occurs in treating the screening effect of the conduc-
tion electrons. In the usual first-principles calculation
scheme, the static screening is assumed in calculating
2F(!), but it does not reflect the actual screening
process working during the formation of Cooper
pairs.
1.12.2.5 Ideal Calculation Scheme
In order to unambiguously solve this problem of
screening, we may imagine a following ideal calcula-
tion scheme for Tc: in the first step, we calculate the
microscopic dynamical electron–electron effective
interaction V in the whole momentum and energy
space. This V is assumed to contain both the
Coulomb repulsion and the phonon-mediated attrac-
tion on the same footing. Then in the second step, we
obtain Tc directly from this V by simultaneously
determining the gap function in the whole momen-
tum and energy space, reflecting the behavior of V. If
this scheme were developed, we could not only
calculate Tc from first principles without resort
to  but also correctly discuss the competition,
coexistence, and mutual enhancement between the
phonon and the electronic mechanisms.
1.12.3 Calculation of Tc in the G0W0
Approximation
1.12.3.1 Formulation
Although it is along the royal road in the project of
obtaining a reliable method for predicting Tc from first
principles, this ideal calculation scheme is extremely
difficult to achieve in actual situations, because all the
difficulties in the quantum-mechanical many-body
problem are associated with it. About three decades
ago, the present author, who was a graduate student at
that time, was struggling with developing such a
scheme without perceiving much of the difficulties
intrinsic to the many-body problem. After a year-
long struggle, he managed to propose a rather general
scheme to evaluate Tc directly from V without intro-
ducing the concept of  (Takada, 1978), though it
was still at the stage far from the ideal scheme.
In a broad sense, this scheme may be called an
approach from the weak-coupling limit, correspond-
ing to the G0W0 approximation or the one-shot GW
approximation in the terminology of the present-day
first-principles calculation community. In the same
terminology, by the way, the Eliashberg theory
 Theory of Superconductivity in Graphite Intercalation Compounds
corresponds to the GW approximation with respect to
the phonon-mediated attractive interaction between
electrons.
Let us explain this G0W0 scheme here (we employ
units in which h ¼ kB ¼ 1). For simplicity, imagine
the three-dimensional (3D) electron gas in which an
electron is specified by momentum p and spin . If
we write the electron annihilation operator by cp, we
can define the abnormal thermal Green’s function
F(p, i!p) at temperature T by
Z 1=T
F ðp; i!p Þ ¼ – dei!p  hT cp" ðÞc – p# i
0
with !p being the fermion Matsubara frequency. At
T ¼ Tc where the second-order phase transition
occurs, this function satisfies the following exact
gap equation:
F ðp; i!p Þ ¼ – Gðp;X ÞGð – p; – i!p Þ
i!pX
 Tc I˜ðp; p9; i!p ; i!p9 ÞF ðp9; i!p9 Þ
!p9 p9
where G(p, i!p) is the normal Green’s function and
˜ p9; i!p ; i!p9 Þ is the irreducible electron–electron
Iðp;
effective interaction.
Now, in the spirit of the G0W0 approximation, we
will replace G(p, i!p) by the bare one G0(p, i!p) X
(i!p  "p)1 in Equation (2), where "p(¼ p2/2m  )
is the bare one-electron dispersion relation with m
the band mass and  the chemical potential. We will
also consider the case in which Iðp; ˜ p9; i!p ; i!p9 Þ is
well approximated as a function of only the variables
(p  p9, i!p  i!p9) to write
˜ p9; i!p ; i!p9 Þ ¼ V ðp – p9; i!p – i!p9 Þ
Iðp;
just like the effective interaction in the random-
phase approximation (RPA), though we do not
intend to confine ourselves to the RPA at this
point. By substituting Equation (3) into Equation
(2) and making an analytic continuation on the !
plane to transform F(p, i!p) to the retarded function
FR(p, !) on the real-! axis, we get a gap equation
for FR(p, !). Then, by taking the imaginary parts in
both sides of the gap equation and integrating
over the ! variable, we finally obtain an equation
depending only on the momentum variable p.
Concretely, the equation can be cast into the
following BCS-type gap equation:
X p9 "p9
p ¼ – tanh Kp;p9
p9
2"p9 2Tc
415
where the gap function p and the pairing interac-
tion K 9p;p9 are, respectively, defined by
Z
  1
d!
p X 2"p  ImF R ðp; !Þ ð5Þ
0
and
Z    
1
2 "p  þ "p9 
Kp;p9 ¼ d     V ðp – p9; iÞ ð6Þ
0  þ ð"p  þ "p9 Þ2
2
By using Kp;p9 thus calculated, we can determine Tc
as an eigenvalue of Equation (4).
ð1Þ
1.12.3.2 Comments on the Formulation
Five comments are in order on this framework:
1. Based on Equations (4) and (6), we can obtain Tc
directly from the microscopic one-electron dis-
persion relation "p and the effective electron–
electron interaction V(q, i) with no need to
separate the phonon-mediated attraction from
ð2Þ the Coulomb repulsion.
2. In spite of the similarity of Equation (4) to the
BCS gap equation, artificial cutoffs involved in
constructing the BCS model are avoided in the
present scheme; natural cutoffs are automatically
introduced by the calculation of Kp;p9 defined in
Equation (6).
3. Except for the spin-singlet pairing, no assumption
is made on the dependence of the gap function on
angular valuables in deriving Equation (4), so that
this gap equation can treat any kind of anisotropy
in the gap function, indicating that it can be
applied to s-wave, d-wave, etc. and even their
ð3Þ mixture like (sþd)-wave superconductors.
4. As can be seen by its definition, the gap function
p in Equation (5) does not correspond to the
physical energy gap except in the weak-coupling
region. Similarly, Kp;p9 is not a physical entity.
Both quantities are introduced for the mathema-
tical convenience so as to make Tc invariant in
transforming Equation (2) into Equation (4). The
key point here is that we need not solve the full
gap equation (2) but a much simpler one (4) in
order to obtain Tc in Equation (2). Of course, if we
want to know the physical gap function rather
than p to compare with experiment, we need to
solve the full gap equation, Equation (2), with Tc
determined by Equation (4).
5. Historically, Cohen was the first to evaluate Tc in
ð4Þ degenerate semiconductors on the level of the
G0W0 approximation (Cohen, 1964; 1969).
416 Theory of Superconductivity in Graphite Intercalation Compounds

Unfortunately, the pairing interaction is not cor-
rectly derived in his theory, as explicitly pointed
out by the present author (Takada, 1980) who,
instead, has succeeded in obtaining the correct
pairing interaction (Takada, 1978) by consulting
the pertinent work of Kirzhnits et al. (1973).
1.12.3.3 Assessment: Application to SrTiO3
In order to assess the quality of this basic framework
of calculating Tc from first principles, we have
applied it to SrTiO3 and compared the results with
experiments (Takada, 1980). This material is an insu-
lator and exhibits ferroelectricity under a uniaxial
stress of about 1.6 kbar along the [100] direction,
but it turns into an n-type semiconductor by either
Nb doping or oxygen deficiency, whereby the con-
duction electrons are introduced in the 3d band of Ti
around the  point with the band mass of m  1.8me
(me: the mass of a free electron). At low temperatures,
superconductivity appears and the observed Tc
shows interesting features; Tc depends strongly on
the electron concentration n and it is optimized with
Tc  0.3 K at n  1020 cm3. Its dependence on the
pressure is unsual; Tc decreases rather rapidly with
hydrostatic pressures, but it increases with the [100]
uniaxial stress.
Taking these situations into account, we have
assumed that the superconductivity is brought about
by the polar-coupling phonons associated with the
stress-induced ferroelectric phase transition. Then
we have calculated the effective electron–electron
interaction V(q, i) in the RPA, in which the long-
range attraction induced by the virtual exchange of
polar-coupled phonons is included with the long-
range Coulomb repulsion on the same footing. By
substituting this V(q, i) into Equation (6), we have
obtained Tc directly from a microscopic model and
the results of Tc are in surprisingly good quantitative
agreement with experiment, as shown in Figure 2.
This success indicates that the present basic frame-
work including the adoption of the RPA is very useful
at least in the polar-coupled phonon mechanism.
1.12.4 Density Functional Theory for
Superconductors
1.12.4.1 Hohenberg–Kohn–Sham Theorem
Recently, much attention has been paid to an exten-
sion of the density functional theory (DFT) to treat
superconductivity, mainly because it provides
another scheme for first-principles calculations of

(a) 1.0 (b) 0.08

SrTiO3 0.04 Experiment
ΔTc (K)

0.5 : Experiment 0 : [100]

: [110]
–0.04 : H.P.
–0.08
n = 2.5 × 1019 cm–3
–0.12
Tc (K)

0.04
0.1
ΔTc (K)

0
–0.04
0.05
–0.08
–0.12 n = 6.3 × 10 cm
19 –3

30
m* = 1.8me : [100]
: [110]
ω t (cm–1)

0.01 20 : H.P.
0.05 0.1 0.5 1 5 10
n (1020 cm–3) 10

0 0.5 1.0 1.5 2.0

Stress (kbar)
Figure 2 (a) Electron density dependence of Tc in SrTiO3 and (b) pressure dependence of Tc (Takada, 1980). Both uniaxial
stress along either [100] or [110] direction and hydrostatic pressure (H.P.) are considered. The deviation of Tc, Tc, is plotted
as a function of stress in units of kbar. For comparison, corresponding experimental results are also shown, together with the
results of the transverse polar phonon energy !t in units of cm1.
 Theory of Superconductivity in Graphite Intercalation Compounds
Tc without resort to . We shall make a very brief
Fxc[n,]/
(r,r9) appear in
review of it in this section.
It is stated in the basic theorem in DFT that all the
physics of an interacting electron system is uniquely
determined, once its electronic density in the ground
state n(r) is specified. This Hohenberg–Kohn theo-
rem (Hohenberg and Kohn, 1964) implies that every
physical quantity including the exchange-correlation
energy Fxc may be considered as a unique functional
of n(r). The density n(r) itself can be determined by
solving the ground-state electronic density of the
corresponding noninteracting reference system that
is stipulated in terms of the Kohn–Sham (KS) equa-
tion (Kohn and Sham, 1965). The core quantity in the
KS equation is the exchange-correlation potential
Vxc(r), which is defined as the functional derivative
of Fxc[n(r)] with respect to n(r), namely,
Vxc(r) ¼
Fxc[n]/
n(r). It must be noted that Vxc(r) i ¼ –
as well as each one-electronic wave function at ith
level with its energy eigenvalue "i in the KS equation
have no physical relevance; they are merely intro-
duced for the mathematical convenience so as to
obtain the exact n(r) in connecting the noninteracting
reference system with the real many-electron system.
The Hohenberg–Kohn theorem can be applied to
the ordered ground state as well on the understand-
ing that the order parameter itself is regarded as a
functional of n(r). In providing some approximate
functional form for Fxc[n], however, it would be
more convenient to treat the order parameter as an
additional independent variable. For example, in
considering the system with some magnetic order,
we usually employ the spin-dependent scheme in
which the fundamental variable is not n(r) but the
spin-decomposed density n(r), leading to the spin-
polarized exchange-correlation energy functional
Fxc[n], based on which the spin-dependent KS
equation is formulated.
1.12.4.2 Gap Equation
Similarly, in treating the superconducting state in the
framework of DFT, it is better to construct the energy
functional by employing both n(r) and the electron-
pair density (r,r9)(X h"(r)#(r9)i) as basic vari-
ables, leading to the introduction of the exchange-
correlation energy functional Fxc[n(r), (r,r9)], where
a(r) is the electron annihilation operator (Oliveira
et al., 1988; Kurth et al., 1999). In accordance with this
addition of the order parameter as a fundamental
variable to DFT, not only the exchange-correlation
potential Vxc(r) but also the exchange-correlation pair
417
potential xc(r,r9) ¼ 
an extended KS equation, which is found to be writ-
ten in the form of the Bogoliubov-de Gennes
equation appearing in the usual theory for inhomo-
geneous superconductors (de Gennes, 1966). Just as is
the case with Vxc(r), xc(r,r9) has no direct physical
meaning, but in principle, if the exact form of Fxc[n,]
is known, the solution of the extended KS equation
gives us the exact result for (r,r9), containing all the
effects of the Coulomb repulsion including the one
usually treated phenomenologically through the con-
cept of . As a result, we can determine the exact Tc
by the calculation of the highest temperature below
which a nonzero solution for (r,r9) can be found.
In this formulation, we can write the fundamental
gap equation to determine Tc exactly as
X j "j
tanh Kij ð7Þ
2"j 2Tc
j
where i is the gap function for ith KS level. In just
the same way as its energy eigenvalue "i (which is
measured from the chemical potential), i is not the
quantity to be observed experimentally but just
introduced for the mathematical convenience so as
to obtain the exact Tc by solving this BCS-type
equation, Equation (7). Similarly, the pair interaction
Kij, defined as the second-functional derivative of
Fxc[n, ] with respect to  and , does not have
any direct physical meaning, either.
We note here the very impressive fact that the
final forms for the two gap equations, Equations (4)
and (7), are exactly the same, in spite of the fact that
they are derived from quite different foundations and
reasoning. We also note that because of this similar-
ity, we may judge that, as long as Kij is properly
chosen, the physics described by  is also included
in the framework of DFT for superconductors, at
least to the extent that it is included in the G0W0
scheme explained in Section 1.12.3.
1.12.4.3 Applications
In 2005, this DFT framework was extended to expli-
citly take care of the phonon-mediated attractive
interaction (Lüders et al., 2005) and it has been
applied to many superconductors (Sanna et al., 2007;
Marques et al., 2005; Floris et al., 2005, 2007; Profeta
et al., 2006; Sanna et al., 2006; Floris et al., 2007). In
order to perform these calculations for actual super-
conductors, it is necessary to provide a concrete form
418 Theory of Superconductivity in Graphite Intercalation Compounds
for Fxc[n, ]. In the judgment of the present author,
the presently available form for Fxc[n, ] contains the
information equivalent to that included in the
Eliashberg theory for the part of the phonon-
mediated attraction, indicating that no vertex correc-
tions are considered in this treatment, while for the
part of the Coulomb repulsion, it contains only very
crude physics; the screening effect is treated in the
Thomas–Fermi static-screening approximation,
which is nothing but the result of the RPA only in
the static and the long-wavelength limit, forgetting
the detailed dynamical nature of the screening effect.
Mainly for this reason, Tc in the present form of
Fxc[n, ] is not expected to be very accurate, even
though the calculated results for Tc seem to be in
good agreement with experiment.
1.12.4.4 Basic Problems
In relation to the above point, it would be appropriate
to give the following comment: in the calculations of
the normal-state properties in the local-density approx-
imation (LDA) and generalized gradient approximation
(GGA) (Perdew et al., 1997) to DFT, we usually antici-
pate that errors in the calculated results are of the order
of 1 and 0.3 eV for LDA and GGA, respectively. These
errors are much larger than those expected in the
calculation of quantum chemistry (0.05 eV). In DFT
for superconductors, calculations of Tc (which is of the
order of 0.001 eV in general) are done simultaneously
with those for the normal-state properties. This implies
that the errors anticipated for Tc would be very large
compared to Tc itself.
We should also point out that the present form for
Fxc[n, ] is not useful in the discussion of the electronic
mechanisms like the plasmon and the spin-fluctuation
ones, prompting us to improve on the approximate
form for Fxc[n, ]. In addition, there are several pro-
blems in the fundamental theory; for example, it is by
no means clear whether the second-functional deriva-
tive of Fxc[n, ] is a well-defined quantity, in just the
same way as we have already experienced in the
energy-gap problem (Perdew et al., 1997, 1983; Sham
and Schlüter, 1983) in semiconductors and insulators.
1.12.5 Experiment on
Superconductivity in GICs
From this section, let us get back to the review on
superconductivity in GICs. As briefly mentioned in
Section 1.12.1, the history of the researches on this
issue extends more than four decades. In 1965, the
first report of superconductivity was made for KC8,
RbC8, and CsC8 (Hannay et al., 1965) in which Tc was
not reliably determined; it depended very much on
samples. Subsequent works (Alexander et al., 1981;
Chaiken et al., 1990; Iye and Tanuma, 1982; Koike
et al., 1978, 1980; Kobayashi et al., 1979; Kobayashi
and Tsujikawa, 1981; Pendrys et al., 1981) confirmed
the occurrence of superconductivity in KC8 with
Tc ¼ 0.15 K, but superconductivity did not appear
in RbC8 and CsC8 when Tc was down to 0.09 and
0.06 K, respectively. Later works have found that Tc
is actually 26 mK for RbC8, but no superconductivity
is found in either LiC6 or the second- or higher-stage
alkali GICs, though the calculation of Tc based on
the McMillan’s formula (McMillan, 1968) predicted
an observable value of Tc even for KC24 (Kamimura
et al., 1980; Inoshita and Kamimura, 1981). It seems
that the usual first-principles calculation of 2F(!)
tends to provide an unrealistically large contribution
from the intralayer high-energy carbon oscillations
to . This unfavorable tendency in the calculation of
 seems to prevail even in CaC6 (Calandra and
Mauri, 2005).
The anisotropy of the critical magnetic field Hc2
was also a matter of interest, drawing attention of
both experimentalists (Chaiken et al., 1990;
Dresselhaus et al., 1989; Iye and Tanuma, 1982;
Koike et al., 1980; Roth et al., 1985) and theorists
(Jishi et al., 1991, 1992). Note that the gap function
p defined in Equation (4) has nothing to do with the
anisotropic behavior of Hc2, though in developing a
phenomenological theory (Jishi et al., 1991, 1992)
some critical comments were made on the results of
p (Takada, 1982) with the assumption that the
anisotropy in Hc2 should reflect on p.
In search of higher Tc, many attempts have
been made to synthesize new GIC superconductors
such as NaC2 (Tc ¼ 5K) (Belash et al., 1987), LiC2
(Tc ¼ 1.9K) (Belash et al., 1989), and alkali-metal
amalgams such as KHgC4 (Tc ¼ 0.73 K) and KHgC8
(Tc ¼ 1.90 K) (Alexander et al., 1980; Tanuma, 1981;
Koike and Tanuma, 1981; Pendrys et al., 1981;
Alexander et al., 1981; Iye and Tanuma, 1982), but
a larger enhancement of Tc was not achieved until
CaC6 was found in 2005 with Tc ¼ 11.5 K
(Weller et al., 2005). Subsequently, many works
have been done on alkaline-earth GIC superconduc-
tors (Emery et al., 2005; Hinks et al., 2007; Kadowaki
et al., 2007; Kim et al., 2006, 2007; Kurter et al., 2007;
Lamura et al., 2006; Sugawara et al., 2009;
Valla et al., 2009), but none ever succeeded in
 Theory of Superconductivity in Graphite Intercalation Compounds 419

synthesizing a new GIC with Tc larger than 15.4 K
which was observed in CaC6 under pressures (Gauzzi
et al., 2007). Thus, some new idea seems to be needed
to further enhance Tc. The present author hopes that
the suggestions given in Section 1.12.8 help experi-
mentalists synthesize a new GIC superconductor
with Tc much higher than 10 K.
1.12.6 Standard Model for
Superconductivity in GICs
1.12.6.1 Characteristic Features of the
System
Basically because GICs are not recognized as strongly
correlated systems, the usual ab initio self-consistent
band structure calculation is very useful in elucidating
the important features of the electronic structures of
GICs in the normal state. According to such calcula-
tions, it is found that there is no essential qualitative
difference between alkali and alkaline-earth GICs (see
Figure 3). The main common features among these
GICs may be summarized in the following way:
1. In MCx, each intercalant metal atom acts as a
donor and changes from a neutral atom M to an
ion MZþ with valence Z.
2. The valence electrons released from M will trans-
fer either to the graphite bands or to the 3D
band composed of the intercalant orbitals and the
graphite interlayer states (Posternak et al., 1984;
Halzwarth et al., 1984; Koma et al., 1986). We shall
define the factor f as the branching ratio between
these two kinds of bands. For example, Zf and
Z(1  f) electrons will go to the and the 3D
bands, respectively.
3. The electrons in the graphite bands are char-
acterized by the 2D motion with a linear
dispersion relation (known as a Dirac cone in the
case of graphene) on the graphite layer.
4. The dispersion relation of the graphite interlayer
band is very similar to that of the 3D free-electron
gas, folded into the Brillouin zone of the graphite
(Csanyi et al., 2005). Thus, its energy level is very
high above the Fermi level in the graphite,
because the amplitude of the wave function for
this band is small on the carbon atoms. In MCx, on
the other hand, the cation MZþ is located in the
interlayer position where the amplitude of the
wave functions is large, lowering the energy
level of the interlayer band below the Fermi
level. The dispersion of the interlayer band is
modified from that of the free-electron gas because

(a) (b)

3D band

EF

–1eV
KF3D
D
F2
K

2D band

KB
Z
(η, η, η,) (η, –η, 0) (η, η, 0) (η, 0, 0)
L Γ χ X Γ T KF3D Kz

Figure 3 (a) Band structure of CaC6 (Calandra and Mauri, 2005). (b) Fermi surface of KC8 (Wang et al., 1991). Both materials
are characterized by the common feature that the electronic system is composed of the 2D bands of graphite and the 3D
interlayer band.
420 Theory of Superconductivity in Graphite Intercalation Compounds

of the hybridization with the orbitals associated with (a)

M Z+ M Z+ M Z+
M, but generally it is well approximated by "p ¼ p2/
M > M Z+ + Ze– C–δ C–δ C–δ C–δ
2m  EF with an appropriate choice of the effective

>
band mass m and the Fermi energy EF. Here the f
2D π-electrons
d v M Z+
M Z+
M Z+ e–

value of m depends on M; in alkali GICs, the C–δ C–δ C–δ C–δ

>
e–
3D itinerant
hybridization occurs with s-orbitals, allowing us to 1–f electrons: m* M Z+
M Z+ M Z+

consider that m ¼ me, while in alkaline-earth GICs,

(δ = Zf /x)
the hybridization with d-orbitals contributes much,
leading to m  3me in both CaC6 and YbC6, as (b)
V V0 W0 Π2D, Π3D
revealed by the bandstructure calculation (Calandra
and Mauri, 2005; Mazin, 2005). = + + +
5. The value of f, which determines the branching
ratio Zf : Z(1  f ), can be obtained by the self- Figure 4 (a) Simplified model to represent MCx (x ¼ 2, 6, 8)
superconductors. We consider the attraction between the
consistent bandstructure calculation. In KC8, for 3D electrons in the interlayer band induced by polar-
example, it is known that f is around 0.6 (Ohno coupled charge fluctuations of the cation MZþ and the anion
et al., 1979). On the other hand, f is about 0.16 C
. (b) Diagrammatic representation of the equation in the
(Calandra and Mauri, 2005) in CaC6, making the RPA to calculate the effective electron–electron interaction
electron density n in the 3D band increase very V(pp9, i), which will be substituted in Equation (6) to
evaluate the kernel of the gap equation. Reproduced with
much. This increase in n is easily understood by the permission from Takada Y (2009) Unified model for
fact that the energy level of the interlayer band is superconductivity in graphite intercalation compounds:
much lower with Ca2þ than with Kþ. The concrete Prediction of optimum Tc and suggestion for its realization.
numbers for n are 3.5  1021 and 2.4  1022 cm3 Journal of the Physical Society of Japan 78(1): 013703:1–4.
for KC8 and CaC6, respectively, in which the dif-
ference in both d and x is also taken into account. a is the bond length between C atoms on the graphite
6. As inferred from experiments (Csanyi et al., 2005; layer (which is 1.419 Å). Note that with use of this nM,
Kamimura, 1987; Takada, 1982) and also from the the density n of the 3D electrons is given by
comparison of Tc calculated for each band (1  f )ZnM. There are also negatively charged carbon
(Takada, 1982), it has been concluded that only ions C
with the average charge of
X fZe/x.
the 3D interlayer band is responsible for super- Therefore, the 3D electrons will feel a large electric
conductivity. Note that LiC6 does not exhibit field of the polarization wave coming from oscillations
superconductivity because no carriers are present of MZþ and C
ions created by either out-of-phase
in the 3D interlayer band, although the properties optic or in-phase acoustic phonons.
of LiC6 are generally very similar to those of other We shall consider the coupling of those phonons
superconducting GICs in the normal state. with the 3D electrons in terms of the point-charge
model, allowing us to write the phonon-exchange
polar-coupled interaction W0(q,!) for the scattering
of the 3D electrons with momentum and energy
1.12.6.2 Microscopic Model for transfers of q and ! as
Superconductivity
!2p ð1 – f Þ2
With these common features in mind, we can think of W0 ðq; !Þ ¼ V0 ðqÞ
!2 – !LA ðqÞ2
a simple model for the GIC superconductors, which 2
 M þ f M=xM
2p ðM=M
!  CÞ
is schematically shown in Figure 4(a). Actually, þ V0 ðqÞ ð8Þ
exactly the same model was proposed in as early as !2  !LO ðqÞ2
1982 by the present author for describing supercon- p defined, respectively, as
with !p and !
ductivity in alkali GICs (Takada, 1982).
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
In order to give some idea about the mechanism to 4 e 2 Z2 nM 4 e 2 Z2 nM
induce an attraction between 3D electrons in this !p ¼ p ¼
and !  ð9Þ
MM þ xMC M
model, let us imagine how each conducting 3D elec-
tron sees the charge distribution of the system. First where MM and MC are, respectively, the atomic masses
of all, there are positively charged metallic Zþ 
of M and C, Mð¼ MM xMC =ðMM þ xMC ÞÞ is the
pffiffiffi 2ions M
with its density nM, given by nM ¼ 4=3 3a dx, where reduced mass of MCx, !LO(q) and !LA(q) are the
 Theory of Superconductivity in Graphite Intercalation Compounds
energies of LO- and LA-phonons, respectively, and
V0(q) is the bare Coulomb interaction 4 e2/q2. (The
subscript ‘0’ indicates that it is the bare interaction to be
screened by both 2D and 3D mobile electrons.)
Owing to the coupling with valence electrons,
both !LO(q) and !LA(q) depend on f, but the
f-dependence is not important, if we write the
phonon-mediated interaction in terms of the corre-
sponding transverse phonon energies, !TO(q) and
!TA(q). Thus, we specify the phonon energies in
terms of !TO(q) and !TA(q). In actual calculations,
we assume that !TO(q) ¼ !t(¼ constant) and
!TA(q) ¼ ctjqj, with !t of the order of 150 K and ct
of the order of 105 cm s1 for the oscillation perpen-
dicular to the graphite plane.
1.12.6.3 Calculation of Tc for Alkali-Doped
GICs
By combining this polar-phonon-mediated attrac-
tive interaction W0(q, !) with the bare Coulomb
interaction between electrons V0(q) on the same
footing and considering the polarization effects of
both 2D and 3D electrons, we faithfully calculate
V(q, !) the effective interaction between 3D elec-
trons in the RPA (see Figure 4(b)). The obtained
V(q, !) is put into the kernel, Equation (6), of the
gap equation (4) to obtain Tc from first principles.
The calculated results for Tc in alkali GICs are
plotted as a function of f in Figure 5 to find that
the overall magnitude of Tc is in the range of
0.1–0.01 K for f  0.5, which is in good agreement
LiC2 Z=1
1 KC8 m* = me
0.1 o
Experiment
Tc (K)
on KC8
0.01
0.001 RbC8
0.0001
CsC8
0.00001
0 0.2 0.4 0.6 0.8 1.0
f
Figure 5 Calculated results for Tc as a function of the
branching ratio f for alkali GIC superconductors in which
Z ¼ 1 and m ¼ me. Reproduced with permission from
Takada Y (2009) Unified model for superconductivity in
graphite intercalation compounds: Prediction of optimum Tc
and suggestion for its realization. Journal of the Physical
Society of Japan 78(1): 013703:1–4.
421
with experiment. Note that smaller values of Tc are
obtained for heavier alkali atoms because of the
smaller couplings as characterized by both !p and
p . This success indicates that the present simple
!
model applies well at least to alkali GIC
superconductors.
1.12.7 Superconductivity in Alkaline-
Earth GICs
1.12.7.1 CaC6
Now let us consider alkaline-earth GIC supercon-
ductors. We shall investigate them by adopting the
same simple model and by using exactly the same
calculation code developed in 1982 in order to see
whether the model and therefore the picture on the
mechanism of superconductivity successfully applied
to alkali GIC superconductors can also be relevant to
these newly synthesized superconductors or not
(Takada, 2009a; 2009b). The parameters specifying
the model will be changed in the following way, if
CaC6 is considered instead of KC8:
1. Because the valence Z changes from monovalence
to divalence, the attractive interaction W0, which
is in proportion to Z2, increases by 4 times.
2. The interlayer distance d decreases from 5.42 to
4.524 Å, so that the 3D electron density
n increases.
3. The factor f to determine the branching ratio
decreases from about 0.6 to 0.16.
4. The effective band mass for the 3D interlayer
band m increases from me to about 3me.
5. The atomic number of the ion A hardly changes
from 39.1 to 40.1.
Considering the changes in the parameters, we have
calculated Tc for CaC6 as a function of f. The results
are plotted in Figure 6, from which we can learn the
following points:
1. Overall, Tc becomes higher for smaller f. This can
be understood by the fact that the screening effect
due to the 2D electrons, which makes the polar-
coupled interaction weak, becomes smaller with
the decrease of f.
2. The enhancement of Tc by about one order is
brought about by doubling Z, if m is kept to be
the same value.
3. The enhancement of Tc by about one order is also
brought about by tripling m from me to 3me, if Z is
taken as Z ¼ 2.
422 Theory of Superconductivity in Graphite Intercalation Compounds
20
CaC6
Z=2
15
o Experiment on YbC6
Tc (K)
m* = 4me
10
Experiment
m* = 3me
5 o
m* = me
m* = 2me
0 0.2 0.4 0.6 0.8 1.0
f 0
Figure 6 Calculated Tc as a function of f for m in the  f
range of me–4me with other parameters suitably chosen for
CaC6. The experimental result is reproduced well, if we
choose m  3me. Reproduced with permission from
Takada Y (2009) Unified model for superconductivity in
graphite intercalation compounds: Prediction of optimum Tc
and suggestion for its realization. Journal of the Physical
Society of Japan 78(1): 013703:1–4.
Based on these observations, we can conclude that
the enhancement of Tc in CaC6 by about a hundred
times from that in KC8 is brought about by the combined
effects of doubling Z and tripling m. In this respect, the
value of m is very important. Appropriateness of m 
3me is confirmed not only from the bandstructure calcu-
lations (Mazin, 2005; Calandra and Mauri, 2005) but also
from the measurement of the electronic specific heat
(Kim et al., 2006) compared with the corresponding one
for KC8 (Mizutani et al., 1978).
1.12.7.2 Other Alkaline-Earth GICs
Similar calculations are done for other alkaline-earth
GIC superconductors as shown in Figure 7 in which
m is determined so as to reproduce EF supplied by
the bandstructure calculation. We see that very good
agreement is always obtained between theory and
experiment, implying that our simple model may be
regarded as the standard one for describing the
mechanism of superconductivity in GICs.
Here a note will be added to the case of YbC6; the
basic parameters such as Z, f, and m for YbC6 are about
the same as those for CaC6, according to the bandstruc-
ture calculation. The only big change can be seen in the
atomic mass; Yb (in which A ¼ 173.0) is much heavier
than that of Ca by about 4 times, indicating weaker
couplings between electrons and polar phonons as just
in the case of comparison between KC8 and CsC8. In
fact, Tc for YbC6 becomes about one-half of the corre-
sponding result for CaC6, which agrees well with
20
Experiment on CaC6 Z=2
(CaC6: under pressure)
CaC6: m* = 3.3me
15 o
CaC6: m* = 2.8me
o
Tc (K)
10
YbC6: m* = 3.0me
5
Experiment on SrC6
SrC6: m* = 1.5me
o
0.2 0.4 0.6 0.8 1.0
Figure 7 Calculated Tc as a function of f for alkaline-earth
GICs with m determined so as to reproduce EF provided by
the bandstructure calculation. Reproduced with permission
from Takada Y (2009) Unified model for superconductivity in
graphite intercalation compounds: Prediction of optimum Tc
and suggestion for its realization. Journal of the Physical
Society of Japan 78(1): 013703:1–4.
experiment. One way to understand this difference
is to regard it as an isotope effect with   0.5
(Mazin, 2005).
1.12.8 Prediction of the Optimum Tc
in GICs
As we have observed so far, our standard model could
have predicted Tc ¼ 11.5 K for CaC6 in 1982 and it is
judged that its predictive power is very high.
Incidentally, the author did not perform the calculation
of Tc for CaC6 at that time, partly because he did not
know of a possibility to synthesize such GICs, but mostly
because the calculation cost was extremely high in those
days; a rough estimate shows that the processing speed of
computers has increased by at least a million times in the
past three decades. This significant improvement in
computational environments is surely a boost to making
such first-principles calculations of Tc as reviewed in
Sections 1.12.3 and 1.12.4.
In any way, encouraged by this success in repro-
ducing Tc in alkaline-earth GICs, we have explored
the optimum Tc in the whole family of GICs by
widely changing various parameters involved in the
microscopic Hamiltonian. Examples of the calculated
results of Tc are shown in Figure 8(a) and 8(b), in
which f is fixed to zero, the optimum condition to
raise Tc, and d is tentatively taken as 4.0 Å. From this
exploration, we find that the most important para-
meter to enhance Tc is m. In particular, we need m
larger than at least 2me to obtain Tc over 10 K,
 Theory of Superconductivity in Graphite Intercalation Compounds
(a) (b)
100
f=0 Z=2
90
BC2(Z = 3) BeC2 f = 0
80
MgC2
70
60 BeC2(Z = 2)
Tc (K)
CaC6
50
YbC6
40
LiC2(Z = 1)
30
20 SrC6
10 BaC6
0 10 20 30 40 0 10 20 30 40 50
m*/ me m*/ me
Figure 8 Prediction of Tc as a function of m for various
GICs in pursuit of optimum Tc: (a) Z dependence for light-
atom intercalant and (b) dependence on intercalant atom.
We assume the fractional factor f ¼ 0. Reproduced with
permission from Takada Y (2009) Unified model for
superconductivity in graphite intercalation compounds:
Prediction of optimum Tc and suggestion for its realization.
Journal of the Physical Society of Japan 78(1): 013703:1–4.
irrespective of any choice of other parameters, and
Tc is optimized at m near 15me. The optimized Tc
depends rather strongly on the parameters to control
the polar-coupling strength such as Z and the atomic
mass A; if we choose a trivalent light atom such as
boron to make !t large, the optimum Tc is about
100 K, but the problem about the light atoms is that
m will never become heavy due to the absence of
either d- or f-electrons. Therefore, we do not expect
that Tc would become much larger than 10 K, even if
BeC2 or BC2 were synthesized. From this perspec-
tive, it will be much better to intercalate Ti or V,
rather than Be or B. Taking all these points into
account, we suggest synthesizing three-element
GICs providing a heavy 3D electron system by the
introduction of heavy atoms into a light-atom polar-
crystal environment.
1.12.9 Conclusion
In this chapter, by taking account of the common
features elucidated by both the bandstructure calcu-
lation and the various measurements on the normal-
state properties, we have constructed the standard
model pertinent for the description of the mechanism
of superconductivity in metal GICs and then made
first-principles calculations of Tc in the G0W0
423
scheme, directly from the microscopic Hamiltonian
representing the standard model. By suitably choosing
the parameters in the microscopic Hamiltonian, we
have found surprisingly good agreement between the-
ory and experiment for both alkali and alkaline-earth
GICs, in spite of the fact that Tc varies more than three
orders of magnitude. In this way, we have clarified that
superconductivity in metal GICs can be understood by
the picture that the 3D electrons in the interlayer band
supplied by the ionization of metals experience the
attractive interaction induced by the virtual exchange
of the polar-coupled phonons of the metal ions. We
have also predicted a further enhancement of Tc well
beyond 10 K, giving some suggestions to realize such
superconductors in the family of GICs.
By first principles we usually mean the calcula-
tions based on not the model but the first-principles
Hamiltonian. Thus, it might be considered as inap-
propriate to call the present G0W0 scheme first
principles, but it is not an easy task to specify the
key parameters to control Tc by just implementing
the calculations based on the first-principles
Hamiltonian. We can identify the importance of the
parameters, m and Z, only through the calculations
based on the model Hamiltonian, leading to a better
and unambiguous understanding of the mechanism of
superconductivity without probing too much into the
very details of each system which sometimes obscure
the essence in first-principles approaches. Besides,
because of the errors involved in the numerical cal-
culations of normal-state properties as mentioned in
Section 1.12.4, more accurate results of Tc will be
obtained by way of a suitable model Hamiltonian
rather than directly from the first-principles one.
As a project in the future, it would be important
to construct a more powerful scheme for the first-
principles calculation of Tc by combining the schemes
in Sections 1.12.3 and 1.12.4, based on which we may
make more detailed suggestions to synthesize GIC
superconductors with Tc much larger than 10 K.
(See Chapters 1.10 and 1.11).
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Bennemann KH and Ketterson JB (eds.) (2008)
Superconductivity I and II. Heidelberg:
Springer.
Emery N, Hérold C, Marêché J-F, and Lagrange P (2008)
Synthesis and superconducting properties of CaC6. Sci.
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Density Functional Theory. Heidelberg: Springer.
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Tinkham M (1996) Introduction to Superconductivity. Dover:
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