Scanning Tunneling Microscopy I: General Principles and Applications to Clean and Absorbate-Covered Surfaces

287 Pages·1994·10.18 MB·English

by  R. Wiesendanger

Springer Series in
Surface Sciences
Editor: Robert Gomer
Springer Series in Surface Sciences
Editors: G. Ert!, R. Gomer and D. L. Mills Managing Editor: H. K. V Lotsch
Physisorption Kinetics 19 Desorption Induced by Electronic 'fransitions
By H. J. Kreuzer, Z. W. Gortel DIET IV
Editors: G. Betz, P. Varga
2 The Structure of Surfaces
Editors: M. A. Van Hove, S. Y. Tong 20 Scanning Tunneling Microscopy I
3 Dynamical Phenomena at Snrfaces, Interfaces General Principles and Applications to Clean
and Superlattices and Adsorbate-Covered Surfaces
Editors: F. Nizzoli, K.-H. Rieder, R. F. Willis Editors: H.-J. Giintherodt, R. Wiesendanger
2nd edition
4 Desorption Induced by Electronic 'fransitions,
DIET II 21 Surface Phonons
Editors: W. Brenig, D. Menzel Editors: W. Kress, F. W. de Wette
5 Chemistry and Physics of Solid Surfaces VI
22 Chemistry and Physics of Solid Surfaces VIII
Editors: R. Vanselow, R. Howe
Editors: R. Vanselow, R. Howe
6 Low-Energy Electron Diffraction
Experiment, Theory 23 Surface Analysis Methods in Materials Science
and Surface Structure Determination Editors: D. J. O'Connor, B. A. Sexton,
By M. A. Van Hove, W. H. Weinberg, C.-M. Chan R. St. C. Smart
7 Electronic Phenomena in Adsorption and Catalysis 24 The Structure of Surfaces III
By v: F. Kiselev, O. V. Krylov Editors: S. Y. Tong, M. A. Van Hove,
K. Takayanagi, X. D. Xie
8 Kinetics of Interface Reactions
Editors: M. Gruuze, H. J. Kreuzer
25 NEXAFS Spectroscopy
9 Adsorption and Catalysis on Trausition Metals By J. StOhr
and Their Oxides
By V. F. Kiselev, O. v: Krylov 26 Semiconductor Surfaces and Interfaces
ByW. Monch
10 Chemistry and Physics of Solid Surfaces VII
Editors: R. Vanselow, R. Howe 27 Helium Atom Scattering from Surfaces
Editor: E. Hulpke
11 The Structure of Surfaces II
Editors: J. F. van der Veen, M. A. Van Hove
28 Scanning Thnneling Microscopy II
12 Diffusion at Interfaces: Microscopic Concepts Further Applications
Editors: M. Grunze, H. J. Kreuzer, J. J. Weimer and Related Scanning Techniques
Editors: R. Wiesendanger, H.-J. Giintherodt
13 .Desorption Induced by Electrouic 'fransitions,
DIETll 29 Scanning Tunneling Microscopy III
Editors: R. H. Stulen, M. L. Knotek Theory of STM
and Related Scanning Probe Methods
14 Solvay Conference on Surface Science
Editors: R. Wiesendanger, H.-J. Giintherodt
Editor: F. W. de Wette
15 Surfaces and Interfaces of Solids 30 Concepts in Surface Physics
ByH. Liith *) By M. C. Desjonqueres, D. Spanjaard
16 Atomic and Electronic Structure of Surfaces 31 Desorption Induced by Electronic 'fransitions
Theoretical Foundations DIET V
By M. Lannoo, P. Friedel Editors: A. R. Burns, E. B. Stechel,
17 Adhesion and Friction D. R. Jennison
Editors: M. Grunze, H. J. Kreuzer
32 Scanning Tunneling Microscopy
18 Auger Spectroscopy and Electronic Structure and Related Techniques
Editors: G. Cubiotti, G. Mondio, K. Wandelt By Bai Chun-Li
H.-1. Giintherodt R. Wiesendanger (Eds.)
Scanning Tunneling
Microscopy I
General Principles and Applications
to Clean and Absorbate-Covered Surfaces
Second Edition
With Contributions by
D. Anselmetti R. J. Behm
P.J.M. van Bentum S. Chiang H.-J. Gtintherodt
R. J. Hamers H. J. Hug H. van Kempen Y Kuk
H. Rohrer R. Wiesendanger J. Wintterlin
With 172 Figures
Springer- Verlag
Berlin Heidelberg New York
London Paris Tokyo
Hong Kong Barcelona
Budapest
Professor Dr. Hans-Joachim Giintherodt
Department of Physics, University of Basel, Klingelbergstrasse 82,
CH-4056 Basel, Switzerland
Professor Dr. Roland Wiesendanger
Institute of Applied Physics, Uniyersitllt Hamburg, Jungiusstrasse 11,
0-20355 Hamburg, Germany
Series Editors
Professor Dr. Gerhard Ertl
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6,
0-14195 Berlin, Germany
Professor Robert Gomer, Ph.D.
The James Franck Institute, The University of Chicago, 5640 Ellis Avenue,
Chicago, IL 60637, USA
Professor Douglas L. Mills, Ph.D.
Department of Physics, University of California,
Irvine, CA 92717, USA
Managing Editor: Dr. Helmut K. V. Lotsch
Springer-Verlag, TIergartenstrasse 17,
0-69121 Heidelberg, Germany
ISBN-13:978-3-540-58415-5 e-ISBN-13:978-3-642-79255-7
DOl: 10.1007/978-3-642-79255-7
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Preface to the Second Edition
Since the first edition of "Scanning 'funneling Microscopy I" has been pub
lished, considerable progress has been made in the application of STM to the
various classes of materials treated in this volume, most notably in the field
of adsorbates and molecular systems. An update of the most recent develop
ments will be given in an additional Chapter 9.
The editors would like to thank all the contributors who have supplied up
dating material, and those who have provided us with suggestions for further
improvements. We also thank Springer-Verlag for the decision to publish this
second edition in paperback, thereby making this book affordable for an even
wider circle of readers.
Hamburg, July 1994 R. Wiesendanger
Preface to the First Edition
Since its invention in 1981 by G. Binnig, H. Rohrer and coworkers at the IBM
Zurich Research Laboratory, scanning tunneling microscopy (STM) has devel
oped into an invaluable surface analytical technique allowing the investigation
of real-space surface structures at the atomic level. The conceptual simplicity
of the STM technique is startling: bringing a sharp needle to within a few
Angstroms of the surface of a conducting sample and using the tunneling cur
rent, which flows on application of a bias voltage, to sense the atomic and elec
tronic surface structure with atomic resolution! Prior to 1981 considerable
scepticism existed as to the practicability of this approach.
In the past ten years the field of STM has grown rapidly and is still attract
ing researchers from various other fields. This fact is reflected by the ever in
creasing number of participants at STM conferences. STM's success is based
on it being a powerful local probe, capable of imaging, measuring and manip
ulating matter down to the atomic scale in almost any environment: in air, in
inert gas atmospheres, in liquids, in ultrahigh vacuum, and from low tempera
tures up to several hundred degrees centigrade. Due to its wide applicability,
STM has been adopted by many different scientific disciplines including solid
state physics, materials research, chemistry, biology, and metrology. The scope
VI Preface
has broadened even further since the development of related scanning tech
niques which are referred to as "SXM" techniques where "X" stands for any
kind of interaction between a sharp probe tip and a sample surface. The most
developed SXM technique - apart from STM - is scanning force microscopy
(SFM), invented in 1986 by G. Binnig, C.F. Quate and Ch. Gerber at Stanford
University. SFM also allows the study of surfaces of bulk insulators down to
the atomic level - a field where almost all conventional surface analytical
techniques have failed. The whole class of SXM techniques facilitates the study
of a wide range of nanometer-scale surface properties.
The present book is the first of two volumes devoted to STM and related
techniques. After an introduction to the field of STM (Chap. 1), H. Rohrer
gives his personal historical view of the birth of STM (Chap. 2). The applica
tions of STM covered by the first volume include metals (Chap. 3 by Y. Kuk
and Chap. 4 by J. Wintterlin and R. J. Behm), semiconductors (Chap. 5 by R. J.
Hamers), layered materials (Chap. 6 by R. Wiesendanger and D. Anselmetti),
molecular imaging (Chap. 7 by S. Chiang) and superconductors (Chap. 8 by
P. J. M. van Bentum and H. van Kempen). The second volume will include fur
ther applications of STM in fields such as electrochemistry, biology, and
nanometer-scale surface modifications. It will also include the description and
applications of related techniques. Finally we plan to present the detailed
theory of SXM techniques in a third volume.
Our first two volumes on STM and related techniques are intended for
researchers and scientists in the various disciplines including physics,
chemistry, biology and metrology, and also for graduate students. These two
volumes should be helpful to those who are active in the field of STM as well
as non-experts who have become interested in these novel techniques.
Therefore, it has been the aim to include many representative results together
with comprehensive lists of citations to help the reader to navigate through the
rapidly growing number of publications in the field of STM. Even under
graduate students or readers with little knowledge of the natural sciences
should find the two volumes on STM exciting, with their description of a
fascinating technique that allows us to visualize the beauty of nature on an
atomic scale and the richness of structures at the submicron level. This aspect
has surely played more than a chance role in stimulating the rapid development
of the STM field.
It is a pleasure for the editors to thank all the authors who have contributed
to the first two volumes on STM and related techniques. We also acknowledge
the pleasant collaboration with Springer-Verlag. Finally, we all thank the inven
tors of STM and its relatives and also the manufacturers of the instruments
for providing the foundation for the enormous development that has taken
place during the past ten years. It is the hope of the editors that these two
volumes on STM and related techniques will further stimulate both basic and
applied research in this exciting field.
Basel, October 1991 H.-J. Guntherodt
R. Wiesendanger
Contents
1. Introduction
By R Wiesendanger and H.-J. Guntherodt (With 5 Figures) 1
1.1 Historical Remarks on Electron Tunneling . . . . . . . . . . . . . . . 1
1.2 STM and Related Techniques .......... -. . . . . . . . . . . . . . . 4
1.2.1 Local Proximal Probes. . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2.2 Modes of Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3 Development of the Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.4 Prospects for the Future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
References .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2. The Rise of Local Probe Methods
By H. Rohrer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3. STM on Metals
By Y. Kuk (With 19 Figures). . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.1 Tunneling Tip . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2 Tunneling Spectroscopies ............................ 20
3.2.1 Current Versus Gap Distance. . . . . . . . . . . . . . . . . . . . . 20
3.2.2 Electronic Structure by dI/dV. . . . . . . . . . . . . . . . . . . . . 22
3.3 Examples on Metal Surfaces. . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.3.1 Surface Structures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.3.2 Dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.4 Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4. Adsorbate Covered Metal Surfaces and Reactions on Metal Surfaces
By J. Wintterlin and RJ. Behm (With 22 Figures). . . . . . . . . . . . . 39
4.1 Imaging of Adsorbates by STM ....................... 40
4.1.1 Representation ofIndividual Adsorbates . . . . . . . . . . . . 40
4.1.2 Resolution and Corrugation in Closed Adlayers ...... 47
4.1.3 Spectroscopy of Adsorbates . . . . . . . . . . . . . . . . . . . . . . 50
4.2 Processes at the Metal-Gas Interface . . . . . . . . . . . . . . . . . . . 54
4.2.1 Adsorption, Dissociation, Surface Diffusion. . . . . . . . . . 54
4.2.2 Formation of Ordered Adsorbate Layers. . . . . . . . . . . . 58
4.3 Structure Modifications of Metal Surfaces ............... 60
4.3.1 Adsorbate-Induced Reconstructive Transformations ... 60
4.3.2 Oxidation Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
VIII Contents
4.4 Epitaxial Growth of Metals on Metal Substrates . . . . . . . . . . 70
4.5 Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
References .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5. STM on Semiconductors
By R.J. Harners (With 29 Figures). . . . . . . . . . . . . . . . . . . . . . . . . 83
5.1 Experimental Technique .. . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
5.1.1 Topographic Imaging. . . . . . . . . . . . . . . . . . . . . . . . . . . 83
5.1.2 Tunneling Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . 85
5.2 Scanning Tunneling Microscopy/Spectroscopy on Surfaces .. 87
5.2.1 Clean Group IV Semiconductors. . . . . . . . . . . . . . . . . . 87
5.2.2 Clean Compound Semiconductor Surfaces. . . . . . . . . . . 106
5.2.3 Adsorbates and Overlayers on Semiconductors . . . . . . . 113
5.2.4 Chemical Reactions on Semiconductor Surfaces. . . . . . . 119
5.3 Other Tunneling Techniques Applied to Semiconductors . . . . 120
5.3.1 Surface Photovoltage . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
5.3.2 Tunneling-Induced Luminescence . . . . . . . . . . . . . . . . . 123
5.3.3 Potentiometry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
5.3.4 Ballistic Electron Emission Microscopy (BEEM) . . . . . . 125
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
6. STM on Layered Materials
By R. Wiesendanger and D. Anselrnetti (With 44 Figures) . . . . . . . 131
6.1 STM Studies of Graphite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
6.1.1 Site Asymmetry, Energy-Dependent Corrugation,
Tunneling Spectroscopy and Electronic Structure
of the Graphite Surface ......................... 133
6.1.2 Giant Corrugations, Tip-Sample Interaction
and Elastic Response of the Graphite Surface ........ 136
6.1.3 Anomalous STM Images. . . . . . . . . . . . . . . . . . . . . . . . 138
6.1.4 STM Imaging of Defects ............ , . . . . . . . . . . . . 140
6.1.5 STM Studies of Clusters on the Graphite Surface . . . . . 142
6.2 STM Studies of Graphite Intercalation Compounds. . . . . . . . 145
6.2.1 Donor Graphite Intercalation Compounds. . . . . . . . . . 149
6.2.2 Acceptor Graphite Intercalation Compounds. . . . . . . . 154
6.2.3 Interpretation and Comparison
with Theoretical Predictions ..................... 154
6.3 STM Studies of Transition Metal Dichalcogenides . . . . . . . . . 157
6.4 STM Studies of Charge Density Waves. . . . . . . . . . . . . . . . . . 161
6.4.1 Charge Density Waves
in Transition Metal Dichalcogenides . . . . . . . . . . . . . . . 161
6.4.2 Charge Density Wave Defects and Domains. . . . . . . . . 165
6.4.3 Charge Density Waves
in Quasi-One-Dimensional Systems. . . . . . . . . . . . . . . . 170
6.5 STM Studies of High-Tc Superconductors ............... 172
Contents IX
6.6 Concluding Comments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
7. Molecular Imaging by STM
By S. Chiang (With 19 Figures) . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
7.1 Introduction to STM of Molecules. . . . . . . . . . . . . . . . . . . . . 181
7.2 STM of Chemisorbed Molecules in Ultrahigh Vacuum. . . . . . 182
7.2.1 Coadsorbed Benzene and CO on Rh(111) . . . . . . . . . . . 182
7.2.2 Copper-Phthalocyanine on Cu(loo) and GaAs (110) . . . 186
7.2.3 Naphthalene on Pt(111) . . . . . . . . . . . . . . . . . . . . . . . . . 188
7.3 STM of Alkanes and Their Derivatives. . . . . . . . . . . . . . . . . . 191
7.3.1 Cadmium Arachidate
and Other Langmuir-Blodgett Films. . . . . . . . . . . . . . . 191
7.3.i n-Alkanes on Graphite . . . . . . . . . . . . . . . . . . . . . . . . . . 194
7.3.3 Alkylbenzenes on Graphite. . . . . . . . . . . . . . . . . . . . . . . 195
7.4 STM of Liquid Crystals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
7.4.1 Alkylcyanobiphenyls............................ 197
7.4.2 Other Liquid Crystals. . . . . . . . . . . . . . . . . . . . . . . . . . . 199
7.5 STM of Polymers .................................. 200
7.5.1 PODA, PMMA, and PMPS on Graphite. . . . . . . . . . . 200
7.5.2 Polyethylene on Graphite ....................... 202
7.6 Other Molecules. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
7.7 Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
8. STM on Superconductors
By P.J.M. van Bentum and H. van Kempen (With 21 Figures). . . . 207
8.1 Theory of Tunneling into Superconductors. . . . . . . . . . . . . . . 208
8.1.1 Coulomb Blockade. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
8.2 Low Temperature STM Spectroscopy
on Classical Superconductors . . . . . . . . . . . . . . . . . . . . . . . . . 215
8.3 Vortices. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
8.4 Organic Superconductors ............................ 220
8.5 STM Topography on High-T Superconductors. . . . . . . . . . . 221
c
8.5.1 Granularity and Growth Structures. . . . . . . . . . . . . . . . 221
8.5.2 Potentiometry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
8.5.3 Incommensurate Modulation. . . . . . . . . . . . . . . . . . . . . 224
8.6 STM Spectroscopy on High-Tc Superconductors . . . . . . . . . . 226
8.6.1 Normal State Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . 226
8.6.2 STM Spectroscopy of the Superconducting State. . . . . . 229
8.6.3 Energy Gap .................................. 230
8.7 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
Subject Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
X Contents
9. Recent Developments
By Y. Kuk, J. Wintterlin, R. J. Behm, S. Chiang,
H.-J. GUntherodt, H. J. Hug (With 13 Figures) ............... 243
9.1 STM on Metal Surfaces ............................... 243
9.2 Adsorption on Metal Surfaces ......................... 245
9.2.1 Dynamics of Surface Processes ................... 245
9.2.2 Adsorbate Structures ............................ 248
9.2.3 Adsorbate-Induced Reconstructions ............... 248
9.2.4 Phase 1tansitions ............................... 252
9.2.5 Metal-on-Metal Epitaxy .......................... 253
9.3 Molecular Imaging by STM ........................... 258
9.3.1 STM of Molecules on Metals in Ultrahigh Vacuum .. 258
9.3.2 Naphthalene, Azulene and Methylazulenes on Pt(l11) 259
9.3.3 Benzene on Pt(111) ............................. 262
9.3.4 Ethylene on Pt(111) ............................. 262
9.3.5 C on Au(111) and Cu(111) ...................... 265
60
9.3.6 Conclusions .................................... 267
9.4 STM on Superconductors ............................. 268
9.4.1 STM on Conventional Superconductors ............ 268
9.4.2 STM on High~ c Superconductors ................. 269
9.4.3 Scanning Probe Microscopy on High-Tc
Superconductors ................................ 269
References .............................................. 269
Subject Index 277