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72 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

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