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 Specificity 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 СНА .................................... 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 Profiling ................ 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 В BINDING ENERGIES (B.E.XPS OR B.E.XRF) OF THE
ELEMENTS ...................................................... 171
B.1 ls-3s, 2p-3p, and 3d Values ........................... 171
B.2 4s-5s, 4p-5p, and 4d Values ........................... 175
APPENDIX С 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.l.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 ТЕМ ................................................... 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
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