S. Roth, D. Carroll One-Dimensional Metals

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2 S. Roth, D. Carroll One-Dimensional Metals One-Dimensional Metals, Second Edition. Siegmar Roth, David Carroll Copyright 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN:

3 Related Titles from WILEY-VCH Ajayan, P., Schadler, L. S., Braun, P. V. Nanocomposite Science and Technology 2003 ISBN Caruso, F. Colloids and Colloid Assemblies 2004 ISBN Decher, G., Schlenoff, J. B. Multilayer Thin Films Sequential Assembly of Nanocomposite Materials 2003 ISBN Gómez-Romero, P., Sanchez, C. Köhler, M., Fritzsche, W. Nanotechnology An Introduction to Nanostructuring Techniques 2004 ISBN Komiyama, M., Takeuchi, T., Mukawa, T., Asanuma, H. Molecular Imprinting From Fundamentals to Applications 2003 ISBN Manners, I. Synthetic Metal-containing Polymers 2004 ISBN Functional Hybrid Materials 2004 ISBN

4 Siegmar Roth, David Carroll One-Dimensional Metals Conjugated Polymers Organic Crystals Carbon Nanotubes

5 Authors Dr. Siegmar Roth Max-Planck-Institut für Festkörperforschung Heisenbergstr Stuttgart Germany s.roth@fkf.mpg.de Prof. Dr. David Carroll Laboratory for Nanotechnology at Clemson Clemson University Clemson, SC USA dcarrol@clemson.edu Cartoons by Rolf D. Wuthe, Atelier Wuthe, Weinheim & This book was carefully produced. Nevertheless, authors and publisher do not warrant the information contained therein to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No. applied for British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. Bibliographic information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie, detailed bibliographic data is available in the Internet at < WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Printed on acid-free paper. All rights reserved (including those of translation in other languages). No part of this book may be reproduced in any form by photoprinting, microfilm, or any other means nor transmitted or translated into a machine language without written permission from the publisher. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Printed in the Federal Republic of Germany Composition Kühn & Weyh, Freiburg Printing betz-druck GmbH, Darmstadt Bookbinding Großbuchbinderei Schäffer GmbH & Co. KG, Grünstadt ISBN

6 V Biographies After studying physics at the University of Vienna, Siegmar Roth carried out his thesis work at the reactor center in Seibersdorf, Austria, and received his PhD at the Institute of Professor Erich Schmid. From 1968 to 1970 he worked at the Siemens Research Laboratories in Erlangen, Germany, on the solid-state physics of novel semiconductors. After a three-year stay at the High Flux Reactor of the Institute Laue Langevin and four years at the High-Field Magnet Laboratory, both in Grenoble, France, where his research centered on superconductors, he joined the Max-Planck-Institut für Festkörperforschung in Stuttgart, Germany. He is currently head of the Synthetic Nanostructures Group in von Klitzing s department. In addition, he is Senior Visiting Professor at the Shanghai Institute of Technical Physics of the Chinese Academy of Sciences, CEO of Sineurop Nanotech GmbH Stuttgart, and Scientific Advisor to Shanghai Yangtze Nanomaterials. David Carroll carried out his thesis work at Wesleyan University in Middletown, Connecticut, USA, receiving his PhD in At the University of Pennsylvania in Philadelphia, his postdoctoral work focused on the application of scanning probes to oxide surfaces. After this, he joined Prof. Rühle's group at the Max-Planck- Institut für Metallforschung in Stuttgart, Germany. For two years there, his work centered on the application of scanning probes to interface studies and supported nanostructures. From Stuttgart, he became an assistant professor at Clemson University, Clemson, South Carolina, USA. Professor Carroll now heads the Nanotechnology group at Wake Forest University in Winston-Salem, North Carolina.

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8 VII Table of Contents 1 Introduction Dimensionality Approaching One-dimensionality from Outside and Inside Dimensionality of Carbon Solids Three-dimensional Carbon: Diamond Two-dimensional Carbon: Graphite One-dimensional Carbon: Cumulene, Polycarbyne, Polyene Zero-dimensional Carbon: Fullerene What About Something in Between? Peculiarities of One-dimensional Systems 12 2 One-dimensional Substances A15 Compounds Krogmann Salts Alchemists Gold Bechgaard Salts and Other Charge-transfer Compounds Polysulfurnitride Phthalocyanines and Other Macrocycles Transition Metal Chalcogenides and Halides Conducting Polymers Halogen-bridged Mixed-valence Transition Metal Complexes Miscellaneous Poly-deckers Polycarbenes Isolated Nanowires Templates and Filler Pores Asymmetric Growth using Catalysts Nanotubes Inorganic Semiconductor Quantum Wires Metal Nanowires 48

9 VIII Table of Contents 3 One-dimensional Solid-State Physics Crystal Lattice and Translation Symmetry Classifying the Lattice Using a Coordinate System The One-dimensional Lattice Reciprocal Lattice, Reciprocal Space Describing Objects by Momentum and Energy Constructing the Reciprocal Lattice Application to One Dimension Electrons and Phonons in a Crystal, Dispersion Relations Crystal Vibrations and Phonons Phonons and Electrons are Different Nearly Free Electron Model, Energy Bands, Energy Gap, Density of States A Simple One-dimensional System 73 4 Electron Phonon Coupling, Peierls Transition 77 5 Conducting Polymers: Solitons and Polarons General Remarks on Conducting Polymers Conjugated Double Bonds Conjugational Defects Solitons Generation of Solitons Nondegenerate Ground State Polymers: Polarons Fractional Charges Soliton Lifetime Conducting Polymers: Conductivity General Remarks on Conductivity Measuring Conductivities Conductivity in One Dimension: Localization Conductivity and Solitons Experimental Data Hopping Conductivity Conductivity of Highly Conducting Polymers Superconductivity Basic Phenomena Measuring Superconductivity Applications of Superconductivity Superconductivity and Dimensionality Organic Superconductors One-dimensional Organic Superconductors Two-dimensional Organic Superconductors 167

10 Table of Contents IX Three-dimensional Organic Superconductors Future Prospects Charge Density Waves Introduction Coulomb Interaction, 4k F Charge Density Waves, Spin Peierls Waves, Spin Density Waves Phonon Dispersion Relation, Phase, and Amplitude Mode in Charge Density Wave Excitations Electronic Structure, Peierls Fröhlich Mechanism of Superconductivity Pinning, Commensurability, Solitons Field-induced Spin Density Waves and the Quantized Hall Effect Molecular-scale Electronics Miniaturization Information in Molecular Electronics Early and Radical Concepts Soliton Switching Molecular Rectifiers Molecular Shift Register Molecular Cellular Automata Carbon Nanotubes Molecular Materials for Electronics Introduction Switching Molecular Devices Photoabsorption Switching Rectifying Langmuir Blodgett Layers Organic Light-emitting Devices Fundamentals of OLEDs Materials for OLEDs Device Designs for OLEDs Solar Cells Organic Field-effect Transistors Applications Introduction Superconductivity and High Conductivity Electromagnetic Shielding Field Smoothening in Cables Capacitors Through-hole Electroplating Loudspeakers Antistatic Protective Bags 232

11 X Table of Contents 11.9 Other Electrostatic Dissipation Applications Conducting Polymers for Welding Plastics Polymer Batteries Electrochemical Polymer Actuators Electrochromic Displays and Smart Windows Electrochemical Sensors Gas Separating Membranes Corrosion Protection Holographic Storage and Holographic Computing Biocomputing Outlook Finally 245 Index 247

12 XI Preface and Acknowledgments This book originated from lectures on Physics in One Dimension given at the University of Karlsruhe in the 1980s. I am grateful to all the students who contributed by asking questions. Some of them later became PhD students in my research group in Stuttgart. The style and content of the book reflect the everyday research work of an interdisciplinary and international research group, where people of different background have to quickly catch up on basic concepts in order to meet on equal terms for discussions. The reader is expected to have some basic knowledge of science or engineering, for example, of physics, chemistry, biology, or materials science. To consolidate this knowledge you will have to consult textbooks on experimental physics, as well as on organic, inorganic, and physical chemistry. But the present book should help to forge links, and with these links the monographs recommended in the Appendix should be accessible. It should also be possible to follow international topical meetings. We hope that some of the aspects of the book are so interesting that they are attractive even to complete neophytes or to outsiders, and that some features will also appeal to the experienced researcher. My thanks are due to all the members of our team (Lidia Akselrod, Tarik Abou-Elazab, Teresa Anderson, Marko Burghard, Hugh Byrne, Claudius Fischer, Thomas Rabenau, Michael Schmelzer, Manfred Schmid, Andrea Stark-Hauser, Andreas Werner). Without constant discussions in the lab s coffee corner, the book would not have been possible. Particular thanks go to Andrea Stark-Hauser, who not only did all the typing but was also engaged in collecting references and figures. Manfred Schmid assisted in the preparation of technical drawings, and the cartoons were drawn by Günter Wilk. Teresa Anderson, Hugh Byrne, and Andreas Werner went through my first drafts and generated major inputs to the final phrasing of the text, which was ultimately polished by the experts at VCH-Verlag and with whom it was a pleasure to cooperate. The whole team has benefited from the cooperation within the Sonderforschungsbereich Molekulare Elektronik physikalische und chemische Grundlagen of the Deutsche Forschungsgemeinschaft, within the European BRJTE/EURAM Project HICOPOL (comprising groups in Stuttgart, Karlsruhe, Montpellier, Nantes, Strasbourg, and Graz), and within the European ESPRIT Network NEOME (Austria, Belgium, Denmark, England, France, Germany, Italy, The Netherlands, Sweden, and Switzerland). Siegmar Roth April 1995

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14 XIII Preface to the Second Edition About ten years have passed since the lectures in Karlsruhe on Physics in One Dimension and since the first edition of this book. When we were asked to work on an update for the second edition, we felt that many things had changed and were surprised that many parts were still valid! New are the Nobel Prizes to Curl, Smalley, and Kroto for the fullerenes in 1996 to Kohn and Pople in 1998 (see the soliton as a Pople Walmsley defect) and to Heeger, MacDiarmid, and Shirakawa in 2000 for conducting polymers. New are applications of conducting polymers, and in particular, the commercialization of several of these applications, and (almost) new are carbon nanotubes. In fact, these nanotubes are the new toys of the materials scientists, and like locust swarms, they crowd on every tiny bit of these carbon crumbs, producing a new wave in literature statistics (compare Figure 2-3). Since we are part of this swarm, we decided to devote several paragraphs and sections of the second edition of our book to nanotubes and to stress the relationships between conjugated polymers and carbon nanotubes. As was true for the first edition, this second edition would also not have been possible without the support and the many discussions among our teams in Stuttgart, Shanghai, Clemson, and Wake Forest. In particular, we are grateful to Ekkehard Palmer, who did most of the computer work for this edition and to the experts at Wiley-VCH in Weinheim. We enjoy working in this field, we enjoyed working on the book, and we hope that our readers will enjoy reading our modest oeuvre. David Carroll and Siegmar Roth October 2003