Surface Science

Advanced Texts in Physics

This program of advanced texts covers a broad spectrum of topics which are of
current and emerging interest in physics. Each book provides a comprehensive and
yet accessible introduction to a field at the forefront of modern research. As such,
these texts are intended for senior undergraduate and graduate students at the MS
and PhD level; however, research scientists seeking an introduction to particular
areas of physics will also benefit from the titles in this collection.

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Springer-Verlag Berlin Heidelberg GmbH
[Link] V. G. Lifshits A. A. Saranin
A.V. Zotov M. Katayama

Surface Science
An Introduction

With 372 Figures and 16 Tables

, Springer
Professor K. Oura Professor V.G. Lifshits
Professor M. Katayama Professor A.A. Saranin
Department of Electronic Engineering Institute of Automation
Faculty of Engineering and Control Processes
Osaka University 5 Radio Street
Suita, Yamada -oka 2-1 690041 Vladivostok
Osaka 565-0871 Japan Russia

Professor A.V. Zotov

Vladivostok State University
of Economics and Service
690600 Vladivostok
Russia

Library of Congress Cataloging-in-Publication Data: Surface science: an introduction! aura ... let al.l.
p. cm. - (Advanced texts in physics, ISSN 1439-2674) Includes bibliographical references and index.
1. Surfaces (Physics) I. aura, K. (Kenjiro), 1941- II. Series. QC
173.4.S94S96425 2003 530.4'27-dc21 2003042812

ISSN 1439-2674
ISBN 978-3-642-05606-2 ISBN 978-3-662-05179-5 (eBook)
DOI 10.1007/978-3-662-05179-5

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Preface

Surface Science - An Introduction is designed as a textbook for undergrad-

uate and graduate students in engineering and physical sciences who want
to get a general overview of surface science. It also provides necessary back-
ground information for researchers just starting out in the field. The book
covers all the most important aspects of modern surface science with all sub-
jects being presented in a concise and clear form accessible to a beginner.
It includes:
• Experimental background on ultra-high-vacuum technology;
• An overview of the most widely used analytical techniques;
• The basics of two-dimensional crystallography;
• Information on atomic structure of well-defined clean and adsorbate-
covered crystal surfaces;
• Consideration of a variety of surface phenomena and properties;
• Application of surface science to thin film growth and nanostructure for-
mation.
The whole is rounded off with:
• Numerous vivid examples from classical and very recent original works;
• Problems and practice exercises which aim to develop a deeper awareness
of the subject;
• Principal references for further reading.

Osaka and Vladivostok K. Oura

January 2003 V. G. Lifshits
A.A. Saranin
A. V. Zotov
M. Katayama
Contents

1. Introduction.............................................. 1

2. Basics of Two-Dimensional Crystallography. . . . . . . .. .. .. .. 3

2.1 Two-Dimensional Lattices. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.1 Lattice, Basis, and Crystal Structure (3D Case) ... . . . 3
2.1.2 Concept of a 2D Lattice. . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.3 2D Bravais Lattices. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2 Miller Indices for Crystal Planes. . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2.1 Definition of Miller Indices ........................ 6
2.2.2 Low-Miller-Index Planes of Some Important Crystals. 8
2.2.3 High-Miller-Index Stepped Surfaces. . . . . . . . . . . . . . . . . 8
2.3 Indices of Directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 11
2.4 Notation for Surface Structures .......................... 11
2.4.1 Matrix Notation. . . .. . . .. . . . . . ... . . . . . . . . . .. ... . .. 11
2.4.2 Wood's Notation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 12
2.4.3 Some Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 13
2.5 2D Reciprocal Lattice. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 14
2.6 Brillouin Zone ......................................... 16
Problems .................................................. 17
Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 18

3. Experimental Background ............................. , .. 19

3.1 Why Ultra-High Vacuum? . . . . . . . . . . . .. . .. . . . . . . . .. . . .. .. 19
3.2 Vacuum Concepts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 20
3.3 Ultra-High-Vacuum Technology. . . .. . ... . . . . . . . . . . . . .. ... 23
3.3.1 UHV Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 23
3.3.2 UHV Pumping System. . . . . . . . . . . . . . . . . . . . . . . . . . .. 24
3.3.3 UHV Hardware .................... . . . . . . . . . . . . .. 32
3.4 Preparation of Atomically Clean Surfaces. . . . . . . . . . . . . . . . .. 35
3.4.1 Cleavage........................................ 35
3.4.2 Heating......................................... 37
3.4.3 Chemical Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 37
3.4.4 Ion Sputtering and Annealing. . . . . . . . . . . . . . . . . . . . .. 37
3.5 UHV Deposition Technology. . . . . . . . . .. . . . . . . . . . . . . . . . . .. 38
VIII Contents

3.5.1 Deposition Concepts. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 38

3.5.2 Deposition Sources ............................... 39
3.5.3 Deposition Monitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 43
3.5.4 Exposure to Gases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 44
Problems .................................................. 45
Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 46

4. Surface Analysis I. Diffraction Methods .................. 47

4.1 Low-Energy Electron Diffraction (LEED) . . . . . . . . . . . . . . . . .. 47
4.1.1 Ewald Construction in LEED Conditions. . . . . . . . . . .. 47
4.1.2 LEED Experimental Set-Up. . . . . . . . . . . . . . . . . . . . . .. 49
4.1.3 Interpretation of a LEED Pattern. . . . . . . . . . . . . . . . .. 51
4.2 Reflection High-Energy Electron Diffraction (RHEED) ...... 59
4.2.1 Ewald Construction in RHEED Conditions. . . . . . . . .. 59
4.2.2 RHEED Set-Up. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 60
4.2.3 RHEED Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 61
4.3 Grazing Incidence X-Ray Diffraction (GIXRD) . . . . . . . . . . . .. 66
4.3.1 Refraction of X-Rays at Grazing Incidence. . . . . . . . . .. 66
4.3.2 Ewald Construction in GIXRD Conditions
and Basics of the Kinematic Approximation. . . . . . . .. 67
4.3.3 GIXRD Experimental Set-Up. . . . . . . . . . . . . . . . . . . . .. 69
4.3.4 Structural Analysis by GIXRD . . . . . . . . . . . . . . . . . . . .. 69
4.4 Other Diffraction Techniques. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 73
4.4.1 Transmission Electron Diffraction (TED) . . . . . . . . . . .. 73
4.4.2 Atom Scattering ................................. 73
4.4.3 Photoelectron Diffraction (PED)
and Auger Electron Diffraction (AED) . . . . . . . . . . . . .. 74
Problems .................................................. 74
Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 75

5. Surface Analysis II. Electron Spectroscopy Methods. . . . .. 77

5.1 General Remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 77
5.1.1 Surface Specificity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 77
5.1.2 Spectrum of Secondary Electrons. . . . . . . . . . . . . . . . . .. 77
5.1.3 Electron Energy Analyzers ........................ 78
5.2 Auger Electron Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 82
5.2.1 Physical Principles ............................... 82
5.2.2 AES Experimental Set-Up. . . . . . . . . . . . . . . . . . . . . . . .. 84
5.2.3 AES Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 86
5.3 Electron Energy Loss Spectroscopy ... . . . . . . . . . . . . . . . . . . .. 89
5.3.1 Core Level Electron Energy Loss Spectroscopy. . . . . .. 90
5.3.2 Electron Energy Loss Spectroscopy. . . . . . . . . . . . . . . .. 92
5.3.3 High-Resolution Electron Energy Loss Spectroscopy .. 95
5.4 Photoelectron Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 98
5.4.1 Photoelectric Effect. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 98
 Contents IX

5.4.2 PES Experimental Set-Up. . . . . .. . . . . . . . . . . . . . . . . .. 99

5.4.3 PES Analysis .................................... 101
Problems .................................................. 107
Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 108

6. Surface Analysis III. Probing Surfaces with Ions .......... 109

6.1 General Principles ...................................... 109
6.1.1 Classical Binary Collisions ......................... 109
6.1.2 Scattering Cross-Section ........................... 113
6.1.3 Shadowing and Blocking .......................... 114
6.1.4 Channeling ...................................... 117
6.1.5 Sputtering ....................................... 118
6.1.6 Ion-Induced Electronic Processes ................... 120
6.2 Low-Energy Ion Scattering Spectroscopy .................. 123
6.2.1 General Remarks: Merits and Problems ............. 123
6.2.2 Alkali Ion Scattering and Time-of-Flight Techniques .. 124
6.2.3 Quantitative Structural Analysis
in Impact-Collision Geometry ...................... 126
6.3 Rutherford Backscattering
and Medium-Energy Ion Scattering Spectroscopy ........... 129
6.3.1 General Remarks ................................. 129
6.3.2 Surface Peak ..................................... 131
6.3.3 Thin Film Analysis ............................... 136
6.4 Elastic Recoil Detection Analysis ......................... 137
6.5 Secondary Ion Mass Spectroscopy ........................ 138
Problems .................................................. 142
Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 143

7. Surface Analysis IV. Microscopy .......................... 145

7.1 Field Emission Microscopy ............................... 145
7.2 Field Ion Microscopy .................................... 147
7.3 Transmission Electron Microscopy ........................ 149
7.4 Reflection Electron Microscopy ........................... 152
7.5 Low-Energy Electron Microscopy ......................... 154
7.6 Scanning Electron Microscopy ............................ 156
7.7 Scanning Tunneling Microscopy .......................... 159
7.8 Atomic Force Microscopy ................................ 164
Problems .................................................. 168
Further Reading ............................................ 168

8. Atomic Structure of Clean Surfaces ....................... 171

8.1 Relaxation and Reconstruction ........................... 171
8.2 Relaxed Surfaces of Metals .............................. 173
8.2.1 Al(l1O) ......................................... 173
8.2.2 Fe(211) ......................................... 174
X Contents

8.3 Reconstructed Surfaces of Metals ......................... 176

8.3.1 Pt(100) ......................................... 176
8.3.2 Pt(llO) ......................................... 178
8.3.3 W(100) ......................................... 178
8.4 Graphite Surface ....................................... 179
8.5 Surfaces of Elemental Semiconductors ..................... 180
8.5.1 Si(100) .......................................... 181
8.5.2 Si(lll) .......................................... 183
8.5.3 Ge(l11) ......................................... 187
8.6 Surfaces of II 1-V Compound Semiconductors ............... 188
8.6.1 GaAs(llO) ...................................... 188
8.6.2 GaAs(lll) and GaAs(III) ........................ 189
Problems .................................................. 192
Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 194

9. Atomic Structure of Surfaces with Adsorbates ............ 195

9.1 Surface Phases
in Submonolayer Adsorbate/Substrate Systems ............. 195
9.2 Surface Phase Composition .............................. 196
9.2.1 Coverage of Adsorbate ............................ 197
9.2.2 Coverage of Substrate Atoms ...................... 199
9.2.3 Experimental Determination of Composition ......... 200
9.3 Formation Phase Diagram ............................... 205
9.4 Metal Surfaces with Adsorbates .......................... 210
9.4.1 Family of v'3x v'3 Structures
on (111) fcc Metal Surfaces ........................ 210
9.4.2 Ni(1l0)2x I-CO . ................................. 213
9.4.3 nx1 Structures in Pb/Cu(llO), Bi/Cu(llO),
Li/Cu(llO), and S/Ni(llO) Systems ................ 214
9.5 Semiconductor Surfaces with Adsorbates .................. 217
9.5.1 Family of v'3xv'3 Structures on Si(lll) and Ge(lll) .217
9.5.2 2x1, lxI, and 3x1 Phases in the H/Si(100) System .. 224
Problems .................................................. 226
Further Reading ............................................ 227

10. Structural Defects at Surfaces ............................ 229

10.1 General Consideration Using the TSK Model .............. 229
10.1.1 Point Defects .................................... 229
10.1.2 Steps, Singular and Vicinal Surfaces, Facets ......... 232
10.2 Selected Realistic Examples .............................. 237
10.2.1 Adatoms ........................................ 237
10.2.2 Vacancies ....................................... 239
10.2.3 Anti-Site Defects ................................. 243
10.2.4 Dislocations ..................................... 245
10.2.5 Domain Boundaries ............................... 247
 Contents XI

10.2.6 Steps ........................................... 252

10.2.7 Facetting ........................................ 257
Problems .................................................. 260
Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260

11. Electronic Structure of Surfaces .......................... 261

11.1 Basics of Density Functional Theory ...................... 261
11.2 Jellium Model. ......................................... 263
11.3 Surface States .......................................... 266
11.4 Electronic Structure of Selected Surfaces .................. 272
11.4.1 Si(111)2x1 ...................................... 272
11.4.2 Si(111)7x7 ...................................... 273
11.4.3 Si(111)lx1-As ................................... 275
11.4.4 Si(111)v'3xv'3-In ................................ 277
11.5 Surface Conductivity .................................... 277
11.6 Work Function ......................................... 282
11.6.1 Work Function of Metals .......................... 282
11.6.2 Work Function of Semiconductors .................. 286
11.6.3 Work Function Measurements ...................... 286
Problems .................................................. 293
Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293

12. Elementary Processes at Surfaces I.

Adsorption and Desorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
12.1 Adsorption Kinetics .................................... 295
12.1.1 Coverage Dependence ............................. 296
12.1.2 Temperature Dependence .......................... 301
12.1.3 Angular and Kinetic Energy Dependence ............ 305
12.2 Thermal Desorption .................................... 305
12.2.1 Desorption Kinetics ............................... 305
12.2.2 Thermal Desorption Spectroscopy .................. 308
12.3 Adsorption Isotherms ................................... 315
12.4 Non-Thermal Desorption ................................ 319
Problems .................................................. 322
Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323

13. Elementary Processes at Surfaces II. Surface Diffusion .... 325

13.1 Basic Equations ........................................ 325
13.1.1 Random-Walk Motion ............................ 325
13.1.2 Fick's Laws ...................................... 327
13.2 Tracer and Chemical Diffusion ........................... 330
13.3 Intrinsic and Mass Transfer Diffusion ..................... 331
13.4 Anisotropy of Surface Diffusion ........................... 333
13.5 Atomistic Mechanisms of Surface Diffusion ................ 335
13.5.1 Hopping Mechanism .............................. 336
XII Contents

13.5.2 Atomic Exchange Mechanism ...................... 338

13.5.3 Tunneling Mechanism ............................. 338
13.5.4 Vacancy Mechanism .............................. 340
13.6 Surface Diffusion of Clusters ............................. 341
13.7 Surface Diffusion and Phase Formation .................... 345
13.8 Surface Electromigration ................................ 348
13.9 Experimental Study of Surface Diffusion ................... 349
13.9.1 Direct Observation of Diffusing Atoms .............. 349
13.9.2 Profile Evolution Method .......................... 350
13.9.3 Capillarity Techniques ............................ 353
13.9.4 Island Growth Technique .......................... 354
Problems .................................................. 356
Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356

14. Growth of Thin Films .................................... 357

14.1 Growth Modes ......................................... 357
14.2 Nucleation and Growth of Islands ........................ 359
14.2.1 Island Number Density ............................ 359
14.2.2 Island Shape ..................................... 365
14.2.3 Island Size Distribution ........................... 368
14.2.4 Vacancy Islands .................................. 374
14.3 Kinetic Effects in Homoepitaxial Growth .................. 374
14.4 Strain Effects in Heteroepitaxy ........................... 377
14.5 Thin Film Growth Techniques ........................... 379
14.5.1 Molecular Beam Epitaxy .......................... 379
14.5.2 Solid Phase Epitaxy .............................. 381
14.5.3 Chemical Beam Epitaxy ........................... 382
14.6 Surfactant-Mediated Growth ............................. 383
Problems .................................................. 386
Further Reading ............................................ 387

15. Atomic Manipulations

and Nanostructure Formation . ........................... 389
15.1 Nano-Size and Low-Dimensional Objects .................. 389
15.2 Atomic Manipulation with STM .......................... 393
15.2.1 Lateral Atomic Displacement ...................... 394
15.2.2 Atom Extraction ................................. 399
15.2.3 Atom Deposition ................................. 403
15.3 Self-Organization of Nanostructures ....................... 404
15.4 Fullerenes and Carbon Nanotubes ........................ 408
Further Reading ............................................ 415

References . ................................................... 417

Index ......................................................... 433