Table Of Content20
Springer Series in Chemical Physics
Edited by Robert Gomer
_ _- J
~
Springer Series in Chemical Physics
Editors: V. I. Goldanskii R. Gomer F. P. Schafer J. P. Toennies
Volume I Atomic Spectra and Radiative Transitions By I. I. Sobelman
Volume 2 Surface Crystallography by LEED Theory, Computation
and Structural Results By M. A. Van Hove, S. Y. Tong
Volume 3 Advances in Laser Chemistry Editor: A. H. Zewail
Volume 4 Picosecond Phenomena Editors: C. V. Shank, E. P. Ippen, S. L. Shapiro
Volume 5 Laser Spectroscopy Basic Concepts and Instrumentation By W. Demtroder
Volume 6 Laser-Induced Processes in Molecules Physics and Chemistry
Editors: K. L. Kompa, S. D. Smith
Volume 7 Excitation of Atoms and Broadening of Spectral Lines
By I. I. Sobelman, L. A. Vainshtein, E. A. Yukov
Volume 8 Spin Exchange Principles and Applications in
Chemistry and Biology By Yu. N. Molin, K. M. Salikhov, K. I. Zamaraev
Volume 9 Secondary Ion Mass Spectrometry SIMS II Editors: A. Benninghoven,
C. A. Evans, Jr., R. A. Powell, R. Shimizu, H. A. Storms
Volume 10 Lasers and Chemical Change
By A. Ben-Shaul, Y. Haas, K. L. Kompa, R. D. Levine
Volume 11 Liquid Crystals of One-and Two-Dimensional Order
Editors: W. Helfrich, G. Heppke
Volume 12 Gasdynamic Laser By S. A. Losev
Volume 13 Atomic Many-Body Theory By I. Lindgren, J. Morrison
Volume 14 Picosecond Phenomena II Editors: R. Hochstrasser, W. Kaiser, C. V. Shank
Volume 15 Vibrational Spectroscopy of Adsorbates Editor: R. F. Willis
Volume 16 Spectroscopy of Molecular Excitons By V. L. Broude, E. I. Rashba, E. F. Sheka
Volume 17 Inelastic Particle-Surface Collisions Editors: E. Taglauer, W. Heiland
Volume 18 Modelling of Chemical Reaction Systems
Editors: K. H. Ebert, P. Deuflhard, W. Higer
Volume 19 Secondary Ion Mass Spectrometry SIMS III
Editors: A. Benninghoven, J. Giber, J. Laszlo, M. Riedel, H. W. Werner
Volume 20 Chemistry and Physics of Solid Surfaces IV
Editors: R. Vanselow, R. Howe
Volume 21 Dynamics of Gas-Surface Interaction
Editors: G. Benedek, U. Valbusa
Volume 22 Laser Photochemistry By V.S. Letokhov
Chemistry and Physics
of Solid Surfaces
IV
Editors: R.Vanselow and R. Howe
With 247 Figures
Springer-Verlag Berlin Heidelberg New York 1982
Professor RalfVanselow
Professor Russel Howe
Department of Chemistry and Laboratory for Surface Studies,
Thc University of Wisconsin-Milwaukee,
Milwaukee, WI 53201, USA
Series Editors
Professor Vitalii 1. Goldanskii Professor Dr. Fritz Peter Schafer
Institute of Chemical Physics Max-Planck-Institut fUr
Academy of Sciences Biophysikalische Chemie
Vorobyevskoye Chaussee 2-b D-3400 Gottingen-Nikolausberg
Moscow V-334, USSR Fed. Rep. of Germany
Professor Robert Gomer Professor Dr. J. Peter Toennies
The James Franck Institute Max-Planck-Institut fUr Stromungsforschung
The University of Chicago BottingerstraJ3e 6-8
5640 Ellis Avenue 0-3400 Gottingen
Chicago, IL 60637, USA Fed. Rep. of Germany
ISBN-13: 978-3-642-47499-6 e-ISBN-13: 978-3-642-47495-8
DOl: 10.1007/978-3-642-47495-8
Library of Congress Cataloging in Publication Data. Main entry under title: Chemistry and physics of
solid surfaces. At head oftitle, v.I: CRe. Vol. 4: editors, R. Vanselow and R. Howe. Heidelberg; New York:
Springer-Verlag. (Springer series in chemical physics; v. 20). Includes bibliographical references and
indexes. I. Surface chemistry. 2. Solid state chemistry. I. Vanselow, Ralf. II. Tong, S. Y. III. Howe,
R. (Russel), 1948-. IV. Chemical Rubber Company. V. Series: Springer series in chemical physics.
QD508.C48 541.3'453 77-25890
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Preface
At the International Summer Institute in Surface Science (ISISS), which is
held bienially on the Campus of the University of Wisconsin-Milwaukee,
invited speakers present tutorial review lectures during the course of one
week. The majority of the presentations deal with the gas-solid interface,
but now and then relevant reviews concerning liquid-solid or solid-solid
interfaces are included. The goal of ISISS was outlined in the first ISISS
publication:
"We recognize that the International Summer Institute in Surface Science
should foster mutual understanding and interaction among theorists and
experimentalists in the various areas of surface science. Progress can be
achieved only when we occasionally peek over the fence into neighboring
areas, not so much to amuse ourselves that the grass is greener on the other
side as to learn from their progress and, perhaps equally fruitfully, from
their limitations and setbacks. In addition, it is an important task in any
field of science to assess, take count of what is done and, what is more
important, to point in future directions."
Since the foundation of ISISS in 1973, the invited speakers - internation
ally recognized experts in their area of specialization - have been asked
to write review articles too. We wanted in this way to ensure that the
largest possible group of scientists could benefit from the special review
concept. The collected articles from past Institutes were published by the
CRC Press, Boca Raton, Florida, USA, under the following titles:
Surface Science: Recent Progress and Perspectives, Critical Reviews in
Solid-State Sciences 4, 124-559 (1974), and
Chemistry and Physics of Solid Surfaces, Vol. I (1976), Vol. II (1979),
Vol. III (1982).
It is not intended that anyone volume will offer a complete state-of-the
art report on the whole field of gas-solid interactions, an impossible task
given the rapidly expanding scope of the field. Instead, recent developments
VI
in selected areas are presented, providing up-to-date supplements to exis
ting textbooks on surface science. Each volume also contains an extensive
subject index, vital for the usefulness of a review series.
It has become a tradition to start each volume with a historical review.
Distinguished scientists such as P.H. Emmet, E.W. MUller, F.C. Tomkins, and
G.-M. Schwab have provided their services in the past. The authors of this
volume are led by William E. Spicer, who was recently named "Scientist of
the Year" by the journal "Industrial Research and Development."
It is no easy decision to change the publisher for an established book
series. Technical reasons, however, did not leave us any choice. We are con
vinced that the long experience of the Springer-Verlag and its expertise in
the area of surface science will ensure continuing success of "Chemistry
and Physics of Solid Surfaces." We hope that this fourth volume, with its
new format, will be as well received as its forerunners.
Finally, we would like to thank our faithful sponsors: The Air Force
Office of Scientific Resear.ch and the Office of Naval Research (Grant No.
NOOOI4-81-G-0059), as well as the College of Letters and Science and the
Graduate School at UvJt1.
Milwaukee, January 1982 R. Vanselow
R. Howe
Contents
7. Development of Photoemission as a Tool for Surface Science: 7900-7980
By W.E. Spicer (With 4 Figures) ................................... 1
1.1 I ntroducti on .................................................. 1
1.2 The Einstein Era: 1900-1930 ................................... 5
1.3 The Period of Misguided Quantum Mechanics: 1930-1945 ..... ..... 8
1.4 The Development of the Correct Fundamental Understanding of
the Photoemission Process: 1945-1960 .... ....... .......... ..... 10
1.5 The Development of Photoemission Spectroscopy: 1960-1970 . ..... 12
1.6 The Explosive Era in Which Photoemission Spectroscopy Was
Successfully Applied to the Study of Surfaces: 1970-1980 . ..... 15
1. 7 Conclusions................................................... 15
References ........................................................ 16
2. Auger Spectroscopy as a Probe of Valence Bonds and Bands
By D.E. Ramaker (With 19 Figures) ................................. 19
2.1 Introduction... .... ... ...................... ............. ..... 19
2.2 Lineshape Description - One-Electron Model.............. ...... 22
2.2.1 Atomic Auger Matrix Elements.. ........ .................. 24
2.2.2 Local or Mulliken Populations... ........ ............ .... 26
2.3 Localization.. ...... .... ........ ..... ...... ........... .... .... 28
2.4 Screeni ng ..................................................... 34
2.5 Outlook....................................................... 39
2.5. 1 ESDI PSD ................................................. 39
2.5.2 AES in the Gas Phase and Chemisorbed Systems .... ... ..... 41
2.5.3 AES in the Bulk and at Interfaces .. ........ ..... ........ 45
2.6 Summary ....................................................... 46
References ........................................................ 46
3. SIMS of Reactive Surfaces
By W.N. Delgass, L.L. Lauderback, and D.G. Taylor (Uith 16 Figures) 51
3.1 Introduction.................................................. 51
3.2 Single Crystal Metal Surfaces................................. 52
3.2.1 Characteristics of SIMS ............ ..................... 52
3.2.2 CO and 02 on Ru{OOn ................................... 55
3.2.3 Classicdl Dynamics Modelling...................... ...... 60
3.2.4 Structure from Angle Dependence.......... .... ........ ... 62
3.2.5 Reactive Intermediates.................................. 64
3.3 Molecular SIMS................................................ 66
3.3.1 SIMS of Molecular Solids................................ 66
3.3.2 Thiophene on Silver..................................... 68
3.3.3 Inorganic Complexes..................................... 69
VIII
3.4 Complex Surfaces.............................................. 69
3.4.1 Proximity.... ....................... .................... 69
3.4.2 Prospects for Catalysis............... .................. 71
3.5 Conclusions................................................... 73
References ........................................................ 74
4. Chemisorption Investigated by Ellipsometry
By G.A. Bootsma, L.J. Hanekamp, and O.L.J. Gijzeman
(With 18 Figures) ................................................. 77
4.1 Introduction.................................................. 77
4.2 Principles of Ellipsometry......... ......... .................. 78
4.3 (Sub)Monolayer Models......................................... 82
4.4 Clean Metal Surfaces.......................................... 86
4.5 Spectroscopic Ellipsometry of Overlayers ......... ............. 90
4.6 Kinetic Studies of Chemisorption..................... ......... 95
4.6.1 Coverage Cali brati on .................................... 95
4.6.2 Initial Stages of Oxidation.......... ................... 97
4.6.3 Reacti ons of Adsorbed Oxygen ............................ 101
References ........................................................ 104
5. The Implications for Surface Science of Doppler-Shift Laser
Fluorescence SRectroscopy
By D.M. Gruen, A.R. Krauss, M.J. Pellin, and R.B. Wright
(With 11 Figures) ................................................. 107
5.1 Introduction.................................................. 107
5.2 Charge Transfer Processes at Surfaces ......................... 109
5.3 Laser Fluorescence Spectroscopic Measurements of Fluxes and
Energy Distributions of Sputtered Particles ................... 113
References ........................................................ 121
6. Analytical Electron Microscopy in Surface Science
By J.A. Venables (With 9 Figures) ................................. 123
6.1 Introduction .................................................. 123
6.2 Analytical Electron Microscopy Techniques ..................... 125
6.3 Scanning Electron Microscopy of Surfaces ...................... 127
6.4 Surface Spectroscopies and Microscopy ......................... 132
6.4.1 Auger Electron Spectroscopy and Microscopy .............. 132
6.4.2 Secondary Electron Spectroscopy and Work Function
Imaging................................................. 135
6.4.3 Photoemission and Energy-Loss Spectroscopy .............. 136
6.5 Diffraction Techniques and Microscopy ......................... 138
6.5.1 Transmission Electron Diffraction and Microscopy ........ 138
6.5.2 RHEED and Refl ecti on Mi croscopy ......................... 140
6.5.3 LEED and Low-Energy Microscopy .......................... 142
References ........................................................ 143
7. He Diffraction as a Probe of Semiconductor Surface Structures
By M.J. Cardillo (With 15 Figures) ................................ 149
7.1 Introduction .................................................. 149
7.2 Si{lOO}: Disordered Dimer Array ............................... 151
7.2.1 Si{100} Periodicity..................................... 151
7.2.2 Diffraction Scans and Qualitative Features of the
Si{100} Surface......................................... 154
7.2.3 Specular Intensities .................................... 156
7.2.4 Structural Models for Si{100} ........................... 157
IX
7.3 Ga/\s {110} .................................................... 158
7.3.1 Diffraction Scans ....................................... 159
7.3.2 Specular Intensity Scans ................................ 160
7.3.3 Rigorous Calculation of Diffraction Intensities ......... 162
7.3.4 The Original of the He/GaAs Potential ................... 163
7.3.5 Computation of Rarified Charge Densities ................ 164
7.3.6 Summary ................................................. 165
7.4 Si{111} (7x7) ................................................. 165
7.4.1 Diffraction Scans ....................................... 166
7.4.2 Specular Intensity Interference ......................... 166
7.4.3 A Model of the Si{111} (7x7) ............................ 169
7.4.4 Summary ................................................. 171
References ........................................................ 172
8. Studies of Adsorption at Well-Ordered Electrode Surfaces Using
Low-Energy Electron Diffraction
By P.N. Ross, Jr. (With 19 Figures) ............................... 173
8.1 Introduction .................................................. 173
8.2 Thermodynamics of Electrodeposition ........................... 174
8.3 Experimenta 1 Methods .......................................... 177
8.4 Underpotential States of Hydrogen on Pt ....................... 180
8.4.1 Isotherms for Hydrogen on {1l1} and {l00} Pt ............ 181
8.4.2 Hydrogen at Stepped Surfaces ............................ 185
8.5 Underpotential States of Oxygen on Pt ......................... 188
8.6 Underpotential States of Metals on Metals ..................... 191
8.7 Relation of the Underpotential State to the Chemisorbed State
in Vacuum ..................................................... 194
References ........................................................ 200
9. Low-Energy Electron Diffraction Studies of Physically Adsorbed Films
By S.C. Fain, Jr. (~Iith 7 Figures) ................................ 203
9.1 Introduction .................................................. 203
9.2 Background .................................................... 203
9.3 LEED Instrument ............................................... 205
9.4 Krypton on Graphi te ........................................... 207
9. 5 Ar~on on Graphit~ ............................................. 210
9.5.1 Rotational Epitaxy of an Incommensurate Monolayer ....... 210
9.5.2 Thermodynamics of an Incommensurate Monolayer ........... 212
9.5.3 Overlayer-Substrate Spacing for an Incommensurate
Monolayer ............................................... 214
9.6 Nitrogen on Graphite .......................................... 214
9.7 Conclusions ................................................... 215
References ............................................... ,........ 216
70. Monte Carlo Simulations of Chemisorbed Overlayers
By L.D. Roelofs (With 15 Figures) ................................. 219
10.1 Introduction ................................................. 219
10.2 Motivation for Monte Carlo Simulation of Surface Systems ..... 220
10.2.1 Introduction to the Monte Carlo Method ................ 221
10.2.2 Results Obtainable via Monte Carlo .................... 223
10.2.3 Comparison to Other Methods for Treating Statistical
Systems ............................................... 225
10.3 Monte Carlo t1ethods for La tti ce Gases ........................ 227
10.3.1 Simulation Mode ....................................... 228
10.3.2 Microscopic Dynamics .................................. 229
10.3.3 Order of Transitions .................................. 230
x
10.4 Monto Carlo Simulation Results .............................. 232
10.4.1 Square Lattice Simulations ........................... 232
10.4.2 Rectangular Lattice Simulations ...................... 235
10.4.3 Triangular Lattice Simulations ....................... 237
10.4.4 Hexagonal Lattice Simulations ........................ 239
10.5 Summary and Discussion ...................................... 246
References ....................................................... 247
77. Critical Phenomena of Chemisorbed Over/ayers
By T.L. Einstein (With 8 Figures) ................................ 251
11.1 I ntroducti on ................................................ 251
11.2 Important Concepts .......................................... 252
11.2.1 Lattice Gas Model .................................... 252
11.2.2 Critical Exponents and Scaling Laws .................. 254
11.2.3 Corrections to Scaling ............................... 255
11.2.4 Crossover Phenomena [11.221 .......................... 256
11.2.5 Fisher Renormalization ............................... 258
11.3 Universality Classes for Atoms on a 2-d Lattice ............. 259
11.3.1 Order Parameters ..................................... 259
11.3.2 Universality Classes ................................. 259
11.3.3 Landau Theory for Adlayers ............................ 260
11.3.4 Catalogue of Transitions .............................. 262
11.3.5 Percolation .......................................... 266
11.4 LEED on Single Crystal Faces ................................ 266
11. 4.1 Measurement of Exponents ............................. 266
11.4.2 Surface Defects ...................................... 269
11.5 Case Study: O/Ni{lll} ....................................... 270
11.6 Conclusions and Exhortations ................................ 276
References ....................................................... 278
72. Structural Defects in Surfaces and Over/ayers
By M.G. Lagally (With 23 Figures) ................................ 281
12.1 Introduction ................................................ 281
12.2 The Effect of Defects on the Intensity Distribution in
Reci proca I Space ............................................ 283
12.3 Surface Defect Studies Using Low-Energy Electron Diffraction ·299
12.4 Surface Defect Studies by Alternative Diffraction Techniques .309
12.5 Summary ..................................................... 311
References ....................................................... 311
73. Some Theoretical Aspects of Metal Clusters, Surfaces, and
Chemisorption
By R.P. Messmer (With 10 Figures) ................................ 315
13.1 Intrinsic Properties of Metal Clusters ...................... 315
13.1.1 Cluster Density of States ............................ 317
13.1.2 Cluster Magnetism .................................... 321
13.2 The Interaction of CO with Cu Clusters ...................... 323
13.2.1 CugCO Calculations .................................... 329
13.2.2 Discussion of Core Level Spectra ..................... 335
References ....................................................... 339
74. The Inelastic Scattering of Low-Energy Electrons by Surface Excitations;
Basic Mechanisms
By D.L. Mills, and S.Y. Tong (With 5 Figures) .................... 341
14.1 Introduction ................................................ 341
14.2 Small-Angle Dipole Scattering '" ............................ 345
