Dr. van der Heide currently serves as the Group Lead of the Surface Analysis department at Samsung Austin, Texas which houses state-of-the-art XPS, AES, SIMS and AFM instrumentation. Former Assistant Professor, Chemistry Department, University of Houston, TX.

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