X-ray Photoelectron Spectroscopy

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.

"The book is a useful resource for those interested in the field, and will probably be found to be of particular value by instrumentation support professionals and nonspecialists." (Analytical and Bioanalytical Chemistry, 14 February 2013)"It is an excellent text and although a competent physicist might already have grasped the principles explained in this book, the multitude of XPS users I come across (PhD chemists, engineers and pharmacists) will find this a breath of fresh air." (Chemistry World, 1 September 2012)

• Foreword xiPreface xiiiAcknowledgments xvList of Constants xvii1 Introduction 11.1 Surface Analysis 11.2 XPSESCA for Surface Analysis 51.3 Historical Perspective 61.4 Physical Basis of XPS 71.5 Sensitivity and Specificity of XPS 101.6 Summary 112 Atoms, Ions, and Their Electronic Structure 132.1 Atoms, Ions, and Matter 132.1.1 Atomic Structure 142.1.2 Electronic Structure 152.1.2.1 Quantum Numbers 162.1.2.2 Stationary-State Notation 182.1.2.3 Stationary-State Transition Notation 202.1.2.4 Stationary States 212.1.2.5 Spin Orbit Splitting 232.2 Summary 253 XPS Instrumentation 273.1 Prerequisites of X-ray Photoelectron Spectroscopy (XPS) 273.1.1 Vacuum 283.1.1.1 Vacuum Systems 323.1.2 X-ray Sources 353.1.2.1 Standard Sources 373.1.2.2 Monochromated Sources 393.1.2.3 Gas Discharge Lamps 413.1.2.4 Synchrotron Sources 413.1.3 Electron Sources 423.1.3.1 Thermionic Sources 423.1.4 Ion Sources 433.1.4.1 EI Sources 433.1.5 Energy Analyzers 443.1.5.1 CMA 463.1.5.2 CHA 463.1.5.3 Modes of Operation 473.1.5.4 Energy Resolution 483.1.6 Detectors 493.1.6.1 EMs 503.1.7 Imaging 523.1.7.1 Serial Imaging 523.1.7.2 Parallel Imaging 543.1.7.3 Spatial Resolution 563.2 Summary 594 Data Collection and Quantification 614.1 Analysis Procedures 614.1.1 Sample Handling 624.1.2 Data Collection 644.1.3 Energy Referencing 654.1.4 Charge Compensation 694.1.5 X-ray and Electron-Induced Damage 714.2 Photoelectron Intensities 724.2.1 Photoelectron Cross Sections 744.2.2 The Analyzed Volume 754.2.2.1 Electron Path Lengths 764.2.2.2 Takeoff Angle 794.2.3 The Background Signal 804.2.4 Quantification 814.3 Information as a Function of Depth 834.3.1 Opening up the Third Dimension 844.3.1.1 AR-XPS and Energy-Resolved XPS 844.3.1.2 Sputter Depth Profiling 874.4 Summary 975 Spectral Interpretation 1015.1 Speciation 1015.1.1 Photoelectron Binding Energies 1025.1.1.1 The Z + 1 Approximation 1065.1.1.2 Initial State Effects 1075.1.1.3 Final State Effects 1185.1.1.4 The Auger Parameter 1335.1.1.5 Curve Fitting 1355.2 Summary 1386 Some Case Studies 1416.1 Overview 1416.1.1 Iodine Impregnation of Single-Walled Carbon Nanotube (SWNT) 1426.1.2 Analysis of Group IIA–IV Metal Oxides 1456.1.3 Analysis of Mixed Metal Oxides of Interest as SOFC Cathodes 1516.1.4 Analysis of YBCO and Related Oxides Carbonates 1566.2 Summary 163Appendices 167Appendix A Periodic Table of the Elements 169Appendix B Binding Energies (B.E.XPS OR B.E.XRF) Of the Elements 171B.1 1s-3s, 2p-3p, and 3d Values 171B.2 4s-5s, 4p-5p, and 4d Values 175Appendix C Some Quantum Mechanics Calculations of Interest 177Appendix D Some Statistical Distributions Of Interest 181D.1 Gaussian Distribution 182D.2 Poisson Distribution 182D.3 Lorentzian Distributions 183Appendix E Some Optical Properties Of Interest 185E.1 Chromatic Aberrations 186E.2 Spherical Aberrations 186E.3 Diffraction Limit 186Appendix F Some other Spectroscopic Spectrometric Techniques of Interest 189F.1 Photon Spectroscopies 191F.1.1 IR, RAIRS, ATR, and DRIFTS 191F.1.2 Raman, SERS, and TERS 192F.1.3 EDX and WDX 193F.1.4 XRF and TXRF 194F.2 Electron Spectroscopies 195F.2.1 UPS 195F.2.2 AES 195F.2.3 EELS, REELS, and HREELS 196F.3 Ion SpectroscopiesSpectrometries 196F.3.1 SIMS 196F.3.2 TAP 197F.3.3 Ion Scattering Methods 197Appendix G Some Microscopies of Interest 199G.1 SEM 200G.2 HIM 201G.3 TEM 201G.4 SPM (AFM AND STM)-Based Techniques 202Appendix H Some Reflectiondiffraction Techniques of Interest 205H.1 XRD 206H.2 GID 206H.3 XRR 207H.4 LEED 207H.5 RHEED 207Technique Abbreviations List 209Instrument-Based Abbreviations 213Glossary Of Terms 215Questions And Answers 221Xps Vendors 229References 233Index 237