Table Of Content72
Springer Series in Solid-State Sciences
Edited by Peter Fulde
Springer Series in Solid-State Sciences
Editors: M. Cardona P. Fulde K. von Klitzing H.-J. Queisser
Volumes 1-39 are listed on the back inside cover
40 Semiconductor Physics An Introduction 59 Dynamical Processes and
3rd Edition By K. Seeger Ordering on Solid Surfaces
41 The LMTO Method Editors: A Yoshimori and M. Tsukada
Muffin-Tin Orbitals and Electronic Structure 60 Excitonic Processes in Solids
By H. L. Skriver By M. Ueta, H. Kanzaki, K. Kobayashi,
Y. Toyozawa, and E. Hanamura
42 Crystal Optics with Spatial Dispersion,
and Excitons 61 Localization, Interaction, and
By V. M. Agranovich and V. L. Ginzburg Transport Phenomena
Editors: B. Kramer, G. Bergmann,
43 Resonant Nonlinear Interactions of
and Y. Bruynseraede
Light with Matter
By V. S. Butylkin, A E. Kaplan, 62 Theory of Heavy Fermions
Yu. G. Khronopulo, andE.1. Yakubovich and Valence Fluctuations
Editors: T. Kasuya and T. Saso
44 Elastic Media with Microstructure II
Three-Dimensional Models 63 Electronic Properties of
Polymers and Related Compounds
By I. A. Kunin
Editors: H. Kuzmany, M. Mehring, and S. Roth
45 Electronic Properties of Doped Semiconductors
64 Symmetries in Physics Group Theory
By B.1. Shklovskii and A L. Efros
Applied to Physical Problems
46 Topological Disorder in Condensed Matter By W. Ludwig and C. Falter
Editors: F. Yonezawa and T. Ninomiya
65 Phonons: Theory and Experiments II
47 Statics and Dynamics of Nonlinear Systems Experiments and Interpretation of
Editors: G. Benedek, H. Bilz, and R. Zeyher Experimental Results By P. Briiesch
48 Magnetic Phase Transitions 66 Phonons: Theory and Experiments III
Editors: M. Ausloos and R.J. Elliott Phenomena Related to Phonons
49 Organic Molecular Aggregates, Electronic By P. Briiesch
Excitation and Interaction Processes 67 Two-Dimensional Systems: Physics
Editors: P. Reineker, H. Haken, and H.C. Wolf and New Devices
Editors: G. Bauer, F. Kuchar, and H. Heinrich
50 Multiple Diffraction of X-Rays in Crystals
By Shih-Lin Chang 68 Phonon Scattering in Condensed Matter V
Editors: A.C. Anderson and J.P. Wolfe
51 Phonon Scattering in Condensed Matter
Editors: W. Eisenmenger, K. LaBmann, 69 Nonlinearity in Condensed Matter
and S. Dottinger Editors: AR. Bishop, D.K. Campbell,
P. Kumar and S. E. 1iullinger
52 Superconductivity in Magnetic and Exotic
70 From Hamiltonians to Phase Diagrams
Materials
The Electronic and Statistical-Mechanical
Editors: T. Matsubara and A. Kotani
Theory of sp-Bonded Metals and Alloys
53 Two-Dimensional Systems, Heterostructnres, By J. Hafner
and SuperJattices
71 High Magnetic Fields in Semiconductor Physics
Editors: G. Bauer, F. Kuchar, and H. Heinrich
Editor: G. Landwehr
54 Magnetic Excitations and Fluctuations
72 One-Dimensional Conductors
Editors: S. Lovesey, U. Balucani, F. Borsa,
By S. Kagoshima, H. Nagasawa,
and V. Tognetti
and T. Sambongi
55 The Theory of Magnetism II 73 Quantum Solid-State Physics
Thermodynamics and Statistical Mechanics Editors: S. V. Vonsovsky and M.1. Katsnelson
ByD.C. Mattis
74 Quantum Monte Carlo Methods in Equilibrium
56 Spin Fluctuations in Itinerant Electron and Nonequilibrium Systems
Magnetism By T. Moriya Editor: M. Suzuki
57 Polycrystalline Semiconductors, 75 Pseudo Potential for the Electronic Structure of
Physical Properties and Applications Semiconductors
Editor: G. Harbeke By M. L. Cohen and J. R. Chelikowsky
58 The Recursion Method and Its Applications 76 Electronic Properties of Conjugated Polymers
Editors: D. Pettifor and D. Weaire Editors: H. Kuzmany, M. Mehring, and S. Roth
S. Kagoshima H. Nagasawa
T. Sambongi
One-Dimensional
Conductors
With 161 Figures
Springer-Verlag Berlin Heidelberg New York
London Paris Tokyo
Professor Seiichi Kagoshima
Department of Pure and Applied Sciences, University of Tokyo
Komaba 3-8-1, Meguro, Tokyo 153, Japan
Professor Hiroshi N agasawa
Institute of Physics, Tsukuba University
Tennodai, Tsukuba, Ibaraki305,Japan
Professor Takashi Sambongi
Department of Physics, Hokkaido University
Kita-ku, Sapporo, Hokkaido 060, Japan
Series Editors:
Professor Dr., Dr. h. c. Manuel Cardona
Professor Dr., Dr. h. c. Peter Fulde
Professor Dr. Klaus von Klitzing
Professor Dr. Hans-Joachim Queisser
Max-Planck-Institut fUr Festk6rperforschung, Heisenbergstrasse 1
D-7000 Stuttgart 80, Fed. Rep. of Germany
Title of the original Japanese edition: Ichijigen denki dendotai
© Shokabo Publishing Co., Ltd., Tokyo 1982
ISBN-13:978-3-642-83181-2 e-ISBN-13:978-3-642-83179-9
DOl: 10.1007/978-3-642-83179-9
Library of Congress Cataloging-in-Publication Data. Kagosbirna, Seiichi, 1945- One-dimensional conduc
tors. (Springer series in solid-state sciences; 72) Translation of: Ichijigen denki dendotai. Bibliography: p.
Includes index. 1. One-dimensional conductors. I. Nagasawa, Hiroshi, 1936-. II. Sambongi, Takashi, 1937-.
III. Title. IV. Series. QC176.8.E4K3513 1987 530.4'1 87-26315
This work is subject to copyright. All rights are reserved, whether the whole or part of the material is
concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting,
reproduction on microfilms or in other ways, and storage in data banks. Duplication of this publication or
parts thereof is only permitted under the provisions of the German Copyright Law of September 9, 1965, in
its version of June 24, 1985, and a copyright fee must always be paid. Violations fall under the prosecution
act of the German Copyright Law.
© Springer-Verlag Berlin Heidelberg 1988
Softcover reprint of the hardcover 1st edition 1988
The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a
specific statement, that such names are exempt from the relevant protective laws and regulations and
therefore free for general use.
2153/3150-543210
Single-crystal growth of the organic one-dimensional conductor TTF-TCNQ by
the diffusion method. Single crystals grown are found in the bridge-tube. See
the text Sect. 3.1. (Photograph donated by Dr. Hiroyuki Anzai of Electrotechni
cal Laboratory)
Microscopic structure of a film
of the linear chain polymer
(CH)x observed by an electron
microscope. See the text Sect.
6.1. (Photograph donated by
Professor Hideki Shirakawa of
the University of Tsukuba)
-
X-ray diffuse scattering pattern
•
of TTF-TCNQ at 110 K. See the
text Sect. 3.4. (Photograph do
nated by Dr. Robert Comes of
Universite Paris-Sud)
Electron diffraction pattern of
NbSe3 below 140 K. See the text
Sect. 4.2. (Photograph donated
by Dr. Kitomi Tsutsumi of Iwate
University)
Preface
This volume deals with physical properties of electrically one-dimensional
conductors. It includes both a description of basic concepts and a review of
recent progress in research. One-dimensional conductors are those materials
in which an electric current flows easily in one specific crystal direction while
the resistivity is very high in transverse directions. It was about 1973 when
much attention began to be focussed on them and investigations started in
earnest. The research was stimulated by the successful growth of crystals
of the organic conductor TTF-TCNQ and of the inorganic conductor KCP.
New concepts, characteristic of one dimension, were established in the in
vestigations of their properties. Many new one-dimensional conductors were
also found and synthesized.
This field of research is attractive because of the discovery of new ma
terials, phenomena and concepts which have only recently found a place in
the framework of traditional solid-state physics and materials science. The
relation of this topic to the wider field of solid-state sciences is therefore
still uncertain. This situation is clearly reflected in the wide distribution of
the fields of specialization of researchers. Due to this, and also to the rapid
progress of research, no introductory book has been available which covers
most of the important fields of research on one-dimensional conductors.
The purposes of this volume are, first, to serve as an introduction to this
field for graduate and undergraduate students of physics and chemistry, and,
second, to provide a general survey of activities in this area for researchers
in various fields of solid-state physics and chemistry.
This volume is organized as follows: The opening chapter gives an over
all profile of one-dimensional conductors, and Chap. 2 deals with fundamen
tal properties of a one-dimensional electron system with the emphasis on
theoretical aspects. Some mathematical equations appear in this chapter
but most of them remain at the level of those found in conventional text
books on solid state physics. This chapter has the form of an exercise in
applying three-dimensional solid state physics to one-dimensional systems.
Subsequent chapters present experimental aspects of research into real one
dimensional conductors. The authors have tried to explain, as much as pos
sible, principles of measurements for students unfamiliar with practical ex
perimental research. Stress is laid upon typical one-dimensional conductors,
TTF-TCNQ, MX3, and KCP. Chapters 6 and 7 give a brief introduction
VII
to the properties of linear-chain polymers and a linear chain mercury com
pound which has a character slightly different from the others.
In the various sections of this volume, we have aimed to develop our
discussions following a unified way of presentation. Because of this, the pre
sentation of the investigations may not always be completely faithful to the
original. Moreover, because of space limitations, we have rather boldly omit
ted some of the problems that have less direct bearing on the main course
of the discussions. We also had to forego a description of many interesting
results of investigations. We trust that the original authors of those papers
and the readers of this volume will understand this necessity. The Japanese
edition on which this book is based was written at the suggestion of the
editors of the Shokabo Series in Materials Science, Professor Taira Suzuki,
Professor Sosin Chikazumi, and Professor Sadao Nakajima. On rewriting
the volume for the Springer Series in Solid-State Sciences, we revised the
content and updated each chapter in the light of recent developments in this
field. We were keenly aware of the need for an introductory book in this field
and would like to express our sincere thanks to those above and to Dr. H.
Lotsch and Dr. A.M. Lahee of Springer-Verlag for giving us this opportunity
and for their encouragement. We acknowledge also the following researchers
who kindly donated us glossy prints of their beautiful photographs shown
in the frontispiece: Dr. Hiroyuki Anzai of the Electrotechnical Laboratory,
Professor Hideki Shirakawa of the University of Tsukuba, Dr. Robert Comes
of Universite Paris-Sud and Dr. Kitomi Tsutsumi of Iwate University.
September 1987 The authors
VIII
Contents
1. What Are One-Dimensional Conductors? . . . . . . . . . . . . . . . . 1
2. Fundamental Properties of Electronic Systems
in One Dimension........................................... 4
2.1 The One-Dimensional Conduction Band and
the Peierls Instability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1.1 Conduction Electrons in a One-Dimensional Band.. 4
2.1. 2 The Peierls Instability and the Peierls Transition. . . 7
a) The Polarization Function. . . . . . . . . . . . . . . . . . . . . 7
b) The Peierls Transition. . . . . . . . . . . . . . . . . . . . . . . . . 12
2.1.3 Electron-Phonon Coupling and Kohn Anomalies... 15
a) Electron-Phonon Interactions. . . . . . . . . . . . . . . . . . 15
b) The Kohn Anomaly. . . . . . . . . . . . . . . . . . . . . . . . . . . 17
c) The Order Parameter of the Peierls Transition. 19
2.1.4 Nesting of the Fermi Surface. . . . . . . . . . . . . . . . . . . . . . . 20
2.2 Charge Density Waves. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2.1 Charge Density Waves and the Peierls-Frohlich
Mechanism. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2.2 Dynamics of Charge Density Waves. . . . . . . . . . . . . . . . 26
a) Phasons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
b) Motion of the Phase. . . . . . . . . . . . . . . . . . . . . . . . . . . 28
c) Pinning... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
d) Electrical Conduction Due to the Sliding
Motion of Charge Density Waves...... ....... . 31
e) Phase Solitons and Electrical Conductivity..... 32
2.3 Fluctuations and Three-Dimensionality............ ....... 35
2.3.1 Fluctuations in One Dimension. . . . . . . . . . . . . . . . . . . . 36
2.3.2 Fluctuations and the Pseudo-Gap. . . . . . . . . . . . . . . . . . 38
2.3.3 Three-Dimensionality and the Peierls 'fransition . . . 39
2.4 Roles of the Coulomb Interaction. . . . . . . . . . . . . . . . . . . . . . . . . 41
2.4.1 The Tight-Binding ModeL........ ........ ......... 41
2.4.2 Short-Range Coulomb Interactions. . . . . . . . . . . . . . . . . 43
2.4.3 Long-Range Coulomb Interactions........ ......... 45
2.4.4 Coulomb Interactions and Charge Density Waves. . 45
2.4.5 The Spin-Peierls Transition. . . . . . . . . . . . . . . . . . . . . . . . 46
IX
3. Properties of TTF-TCNQ and Its Family.. . . . . . . . . . . . . . . 48
3.1 Molecular Synthesis and Crystal Growth.................. 48
3.2 Electrical Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.2.1 The One-Dimensional Conduction Band and
the Electrical Conductivity. . . . . . . . . . . . . . . . . . . . . . . . 52
3.2.2 One-Dimensionality of the Metallic Property....... 57
3.2.3 High Frequency Conductivity. . . . . . . . . . . . . . . . . . . . . . 61
3.2.4 Nonlinear Conduction in the Insulating Phase...... 63
3.3 Magnetic Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.3.1 Spin Susceptibility. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.3.2 Spin Susceptibility of Each Kind of Molecular
Stack.............................................. 67
3.4 Behaviour ofthe CDW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.4.1 The 2kF CDW and the Kohn Anomaly. . . . . . . . . . . . 71
3.4.2 Interchain Interactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.4.3 Origins of the 4kF CDW. . . . . . . . . . . . . . . . . . . . . . . . . . . 80
3.4.4 Dynamics of Charge Density Waves. . . . . . . . . . . . . . . . 82
3.5 Characteristic Properties of Compounds Belonging to
the Family of TTF-TCNQ................................ 86
3.5.1 TSeF-TCNQ...................................... 87
3.5.2 HMTTF-TCNQ and TMTSF-TCNQ.............. 89
3.5.3 NMP-TCNQ...................................... 92
3.5.4 TMTSF-DMTCNQ................................ 94
3.6 Superconductivity in (TMTSFhX and Its Family. . . . . . . . . 96
3.6.1 Crystal Structure of (TMTSFhX . . . . . . . . . . . . . . . . . . 96
3.6.2 Electrical Properties. . . . . . . .. . . . . . . .. . . . . . . . . . . . . . . 97
3.6.3 Superconductivity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
3.6.4 Spin Density Waves. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
3.6.5 Orientational Ordering of Counter Anions X....... 103
3.6.6 Superconductivity in (BEDT-TTFhX............. 104
a) (BEDT-TTFhRe04.......................... 104
b) (BEDT-TTFhh.............................. 105
4. Properties of MX3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
4.1 Preparation and Crystal Structure. . . . .. . . . . . . . . . . . . . . . . . . 107
4.1.1 Preparation of Single Crystals. . . .. . . . . . . . . . . . . . . . . 107
4.1.2 Crystal Structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
4.2 Charge Density Waves in NbSe3 . . . . . . . . . . . . . . . . . . . . . . . . . . 111
4.2.1 Anomalies in the dc Conductivity and
the Periodic Lattice Distortion. . . . . . . . . . . . . . . . . . . . . 111
4.2.2 Conductivity Anisotropy, Hall Effect and
Thermoelectric Power............................. 118
x
