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: 3-527-30749-4
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Siegmar Roth, David Carroll

One-Dimensional Metals

Conjugated Polymers
Organic Crystals
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authors and publisher do not warrant the information
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 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 f
r
Festkrperforschung in Stuttgart, Germany.
He is currently head of the Synthetic Nanostruc-
tures 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, receiv-
ing his PhD in 1993. 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. R
hle's group at the Max-Planck-
Institut f
r Metallforschung in Stuttgart, Germany.
For two years there, his work centered on the applica-
tion of scanning probes to interface studies and sup-
ported 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.
 VII

Table of Contents

1 Introduction 1
1.1 Dimensionality 1
1.2 Approaching One-dimensionality from Outside and Inside 2
1.3 Dimensionality of Carbon Solids 7
1.3.1 Three-dimensional Carbon: Diamond 7
1.3.2 Two-dimensional Carbon: Graphite 8
1.3.3 One-dimensional Carbon: Cumulene, Polycarbyne, Polyene 9
1.3.4 Zero-dimensional Carbon: Fullerene 10
1.3.5 What About Something in Between? 12
1.4 Peculiarities of One-dimensional Systems 12

2 One-dimensional Substances 19
2.1 A15 Compounds 22
2.2 Krogmann Salts 26
2.3 Alchemists’ Gold 28
2.4 Bechgaard Salts and Other Charge-transfer Compounds 30
2.5 Polysulfurnitride 33
2.6 Phthalocyanines and Other Macrocycles 34
2.7 Transition Metal Chalcogenides and Halides 36
2.8 Conducting Polymers 38
2.9 Halogen-bridged Mixed-valence Transition Metal Complexes 41
2.10 Miscellaneous 42
2.10.1 Poly-deckers 42
2.10.2 Polycarbenes 43
2.11 Isolated Nanowires 43
2.11.1 Templates and Filler Pores 44
2.11.2 Asymmetric Growth using Catalysts 45
2.11.3 Nanotubes 46
2.11.4 Inorganic Semiconductor Quantum Wires 47
2.11.5 Metal Nanowires 48
VIII Table of Contents

3 One-dimensional Solid-State Physics 53

3.1 Crystal Lattice and Translation Symmetry 54
3.1.1 Classifying the Lattice 54
3.1.2 Using a Coordinate System 56
3.1.3 The One-dimensional Lattice 58
3.2 Reciprocal Lattice, Reciprocal Space 60
3.2.1 Describing Objects by Momentum and Energy 60
3.2.2 Constructing the Reciprocal Lattice 61
3.2.3 Application to One Dimension 61
3.3 Electrons and Phonons in a Crystal, Dispersion Relations 63
3.3.1 Crystal Vibrations and Phonons 64
3.3.2 Phonons and Electrons are Different 67
3.3.3 Nearly Free Electron Model, Energy Bands, Energy Gap,
Density of States 68
3.4 A Simple One-dimensional System 73

4 Electron–Phonon Coupling, Peierls Transition 77

5 Conducting Polymers: Solitons and Polarons 85

5.1 General Remarks on Conducting Polymers 85
5.2 Conjugated Double Bonds 86
5.3 Conjugational Defects 89
5.4 Solitons 92
5.5 Generation of Solitons 100
5.6 Nondegenerate Ground State Polymers: Polarons 103
5.7 Fractional Charges 106
5.8 Soliton Lifetime 108

6 Conducting Polymers: Conductivity 113

6.1 General Remarks on Conductivity 113
6.2 Measuring Conductivities 118
6.3 Conductivity in One Dimension: Localization 126
6.4 Conductivity and Solitons 129
6.5 Experimental Data 133
6.6 Hopping Conductivity 139
6.7 Conductivity of Highly Conducting Polymers 145

7 Superconductivity 153
7.1 Basic Phenomena 153
7.2 Measuring Superconductivity 159
7.3 Applications of Superconductivity 161
7.4 Superconductivity and Dimensionality 162
7.5 Organic Superconductors 163
7.5.1 One-dimensional Organic Superconductors 164
7.5.2 Two-dimensional Organic Superconductors 167
 Table of Contents IX

7.5.3 Three-dimensional Organic Superconductors 168

7.6 Future Prospects 170

8 Charge Density Waves 177

8.1 Introduction 177
8.2 Coulomb Interaction, 4kF Charge Density Waves, Spin Peierls Waves,
Spin Density Waves 178
8.3 Phonon Dispersion Relation, Phase, and Amplitude Mode in
Charge Density Wave Excitations 181
8.4 Electronic Structure, Peierls–Fr
hlich Mechanism of
Superconductivity 183
8.5 Pinning, Commensurability, Solitons 184
8.6 Field-induced Spin Density Waves and the Quantized Hall Effect 188

9 Molecular-scale Electronics 193

9.1 Miniaturization 193
9.2 Information in Molecular Electronics 196
9.3 Early and Radical Concepts 197
9.3.1 Soliton Switching 197
9.3.2 Molecular Rectifiers 200
9.3.3 Molecular Shift Register 201
9.3.4 Molecular Cellular Automata 203
9.4 Carbon Nanotubes 204

10 Molecular Materials for Electronics 211

10.1 Introduction 211
10.2 Switching Molecular Devices 212
10.2.1 Photoabsorption Switching 212
10.2.2 Rectifying Langmuir–Blodgett Layers 215
10.3 Organic Light-emitting Devices 216
10.3.1 Fundamentals of OLEDs 218
10.3.2 Materials for OLEDs 219
10.3.3 Device Designs for OLEDs 220
10.4 Solar Cells 220
10.5 Organic Field-effect Transistors 223

11 Applications 227
11.1 Introduction 227
11.2 Superconductivity and High Conductivity 227
11.3 Electromagnetic Shielding 227
11.4 Field Smoothening in Cables 228
11.5 Capacitors 229
11.6 Through-hole Electroplating 230
11.7 Loudspeakers 231
11.8 Antistatic Protective Bags 232
X Table of Contents

11.9 Other Electrostatic Dissipation Applications 233

11.10 Conducting Polymers for Welding Plastics 234
11.11 Polymer Batteries 235
11.12 Electrochemical Polymer Actuators 236
11.13 Electrochromic Displays and Smart Windows 237
11.14 Electrochemical Sensors 237
11.15 Gas Separating Membranes 238
11.16 Corrosion Protection 239
11.17 Holographic Storage and Holographic Computing 239
11.18 Biocomputing 240
11.19 Outlook 242

12 Finally 245

Index 247
 XI

Preface and Acknowledgments

This book originated from lectures on “Physics in One Dimension” given at the Univer-
sity 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 interdisci-
plinary 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 meet-
ings. 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 prep-
aration of technical drawings, and the cartoons were drawn by G
nter Wilk. Teresa
Anderson, Hugh Byrne, and Andreas Werner went through my first drafts and generat-
ed 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 Sonderforschungsber-
eich “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, Den-
mark, England, France, Germany, Italy, The Netherlands, Sweden, and Switzerland).

Siegmar Roth April 1995

 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 ap-
plications of conducting polymers, and in particular, the commercialization of sever-
al of these applications, and (almost) new are carbon nanotubes. In fact, these nano-
tubes 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 Stutt-
gart, Shanghai, Clemson, and Wake Forest. In particular, we are grateful to Ekke-
hard 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