FOREWORD xi
PREFACE xiii
ACKNOWLEDGMENTS xv
LIST OF CONSTANTS xvii
1 INTRODUCTION 1
1.1 Surface Analysis / 1
1.2 XPS/ESCA for Surface Analysis / 5
1.3 Historical Perspective / 6
1.4 Physical Basis of XPS / 7
1.5 Sensitivity and Specifi city of XPS / 10
1.6 Summary / 11
2 ATOMS, IONS, AND THEIR ELECTRONIC STRUCTURE 13
2.1 Atoms, Ions, and Matter / 13
2.1.1 Atomic Structure / 14
2.1.2 Electronic Structure / 15
2.1.2.1 Quantum Numbers / 16
2.1.2.2 Stationary-State Notation / 18
2.1.2.3 Stationary-State Transition Notation / 20
2.1.2.4 Stationary States / 21
2.1.2.5 Spin Orbit Splitting / 23
2.2 Summary / 25
3 XPS INSTRUMENTATION 27
3.1 Prerequisites of X-ray Photoelectron Spectroscopy (XPS) / 27
3.1.1 Vacuum / 28
3.1.1.1 Vacuum Systems / 32
3.1.2 X-ray Sources / 35
3.1.2.1 Standard Sources / 37
3.1.2.2 Monochromated Sources / 39
3.1.2.3 Gas Discharge Lamps / 41
3.1.2.4 Synchrotron Sources / 41
3.1.3 Electron Sources / 42
3.1.3.1 Thermionic Sources / 42
3.1.4 Ion Sources / 43
3.1.4.1 EI Sources / 43
3.1.5 Energy Analyzers / 44
3.1.5.1 CMA / 46
3.1.5.2 CHA / 46
3.1.5.3 Modes of Operation / 47
3.1.5.4 Energy Resolution / 48
3.1.6 Detectors / 49
3.1.6.1 EMs / 50
3.1.7 Imaging / 52
3.1.7.1 Serial Imaging / 52
3.1.7.2 Parallel Imaging / 54
3.1.7.3 Spatial Resolution / 56
3.2 Summary / 59
4 DATA COLLECTION AND QUANTIFICATION 61
4.1 Analysis Procedures / 61
4.1.1 Sample Handling / 62
4.1.2 Data Collection / 64
4.1.3 Energy Referencing / 65
4.1.4 Charge Compensation / 69
4.1.5 X-ray and Electron-Induced Damage / 71
4.2 Photoelectron Intensities / 72
4.2.1 Photoelectron Cross Sections / 74
4.2.2 The Analyzed Volume / 75
4.2.2.1 Electron Path Lengths / 76
4.2.2.2 Takeoff Angle / 79
4.2.3 The Background Signal / 80
4.2.4 Quantification / 81
4.3 Information as a Function of Depth / 83
4.3.1 Opening up the Third Dimension / 84
4.3.1.1 AR-XPS and Energy-Resolved XPS / 84
4.3.1.2 Sputter Depth Profi ling / 87
4.4 Summary / 97
5 SPECTRAL INTERPRETATION 101
5.1 Speciation / 101
5.1.1 Photoelectron Binding Energies / 102
5.1.1.1 The Z + 1 Approximation / 106
5.1.1.2 Initial State Effects / 107
5.1.1.3 Final State Effects / 118
5.1.1.4 The Auger Parameter / 133
5.1.1.5 Curve Fitting / 135
5.2 Summary / 138
6 SOME CASE STUDIES 141
6.1 Overview / 141
6.1.1 Iodine Impregnation of Single-Walled Carbon Nanotube (SWNT) / 142
6.1.2 Analysis of Group IIA–IV Metal Oxides / 145
6.1.3 Analysis of Mixed Metal Oxides of Interest as SOFC Cathodes / 151
6.1.4 Analysis of YBCO and Related Oxides/Carbonates / 156
6.2 Summary / 163
APPENDICES 167
APPENDIX A PERIODIC TABLE OF THE ELEMENTS 169
APPENDIX B BINDING ENERGIES (B.E.XPS OR B.E.XRF) OF THE ELEMENTS 171
B.1 1s-3s, 2p-3p, and 3d Values / 171
B.2 4s-5s, 4p-5p, and 4d Values / 175
APPENDIX C SOME QUANTUM MECHANICS CALCULATIONS OF INTEREST 177
APPENDIX D SOME STATISTICAL DISTRIBUTIONS OF INTEREST 181
D.1 Gaussian Distribution / 182
D.2 Poisson Distribution / 182
D.3 Lorentzian Distributions / 183
APPENDIX E SOME OPTICAL PROPERTIES OF INTEREST 185
E.1 Chromatic Aberrations / 186
E.2 Spherical Aberrations / 186
E.3 Diffraction Limit / 186
APPENDIX F SOME OTHER SPECTROSCOPIC/SPECTROMETRIC TECHNIQUES OF INTEREST 189
F.1 Photon Spectroscopies / 191
F.1.1 IR, RAIRS, ATR, and DRIFTS / 191
F.1.2 Raman, SERS, and TERS / 192
F.1.3 EDX and WDX / 193
F.1.4 XRF and TXRF / 194
F.2 Electron Spectroscopies / 195
F.2.1 UPS / 195
F.2.2 AES / 195
F.2.3 EELS, REELS, and HREELS / 196
F.3 Ion Spectroscopies/Spectrometries / 196
F.3.1 SIMS / 196
F.3.2 TAP / 197
F.3.3 Ion Scattering Methods / 197
APPENDIX G SOME MICROSCOPIES OF INTEREST 199
G.1 SEM / 200
G.2 HIM / 201
G.3 TEM / 201
G.4 SPM (AFM and STM)-Based Techniques / 202
APPENDIX H SOME REFLECTION/DIFFRACTION TECHNIQUES OF INTEREST 205
H.1 XRD / 206
H.2 GID / 206
H.3 XRR / 207
H.4 LEED / 207
H.5 RHEED / 207
TECHNIQUE ABBREVIATIONS LIST 209
INSTRUMENT-BASED ABBREVIATIONS 213
GLOSSARY OF TERMS 215
QUESTIONS AND ANSWERS 221
XPS VENDORS 229
REFERENCES 233
INDEX 237