Secondary Ion Mass Spectrometry An Introduction to Principles and Practices

Foreword xi

Preface xiii

Acknowledgments xvi

List of Constants xvii

1 Introduction 1

1.1 Matter and The Mass Spectrometer 1

1.2 Secondary Ion Mass Spectrometry 4

1.2.1 History 6

1.2.2 Physical Basis 8

1.2.2.1 Sensitivity and Detection Limits 9

1.2.3 Application Fields 12

1.3 Summary 18

SECTION I PRINCIPLES 21

2 Properties of Atoms, Ions, Molecules, and Solids 23

2.1 The Atom 23

2.1.1 Atomic Structure 23

2.1.1.1 Atomic Mass 25

2.1.1.2 Atomic Density 27

2.2 Electronic Structure of Atoms and Ions 27

2.2.1 Stationary States 28

2.2.1.1 Quantum Numbers 28

2.2.1.2 Spectroscopic and X-ray Notation 29

2.2.1.3 Ionization Potential and Electron Affinity 31

2.2.2 Bonding and the Resulting Properties of Solids 32

2.2.2.1 Bands and the Density of States 34

2.2.2.2 Work Function 35

2.2.2.3 Image Field 36

2.2.2.4 Electronic Excitation 36

2.3 Summary 42

3 Sputtering and Ion Formation 44

3.1 The Fundamentals of SIMS 44

3.1.1 Secondary Ion Generation 45

3.2 Sputtering 46

3.2.1 Sputtering by Ion Impact 47

3.2.1.1 Linear Cascade Model 50

3.2.1.2 Other Sputtering Models 54

3.2.1.3 Simulations 60

3.2.2 Sputter Rates and Sputter Yields 67

3.2.2.1 Sputter Yield Dependence on Primary Ion Conditions 69

3.2.2.2 Sputter Yield Dependence on Substrate 76

3.2.3 Sputter-induced damage 81

3.2.3.1 Recoil Implantation, Cascade Mixing, Diffusion, and Segregation 83

3.2.3.2 Substrate Amorphization and Re-crystallization 85

3.2.3.3 Surface Roughening and Surface Smoothing 86

3.3 Ionization/Neutralization 88

3.3.1 Ion–Solid Interactions 90

3.3.2 Secondary Ion Yields 93

3.3.2.1 Ionization Potential and Electron Affinity 95

3.3.2.2 Matrix Effects 97

3.3.2.3 Electronic Excitation 113

3.3.3 Models for Atomic Secondary Ions 121

3.3.3.1 LTE Formalism 123

3.3.3.2 Bond Breaking Model 124

3.3.3.3 Kinetic Emission Model 129

3.3.4 Models for Molecular Secondary Ions 130

3.3.4.1 Models for Molecular Ion Emission in SIMS 132

3.3.4.2 Models for Molecular Ion Emission in MALDI 135

3.4 Summary 138

SECTION II PRACTICES 145

4 Instrumentation Used in SIMS 147

4.1 The Science of Measurement 147

4.1.1 SIMS in its various forms 148

4.1.1.1 Static SIMS 148

4.1.1.2 Dynamic SIMS 149

4.1.1.3 Cluster Ion SIMS 150

4.2 Hardware 151

4.2.1 Vacuum 152

4.2.1.1 Vacuum and the Kinetic Theory of Gases 153

4.2.1.2 Pumping Systems 156

4.2.2 Primary Ion Columns 159

4.2.2.1 Ion Sources 161

4.2.3 Secondary Ion Columns 167

4.2.3.1 Mass Filters 170

4.2.3.2 Energy Filters 182

4.2.3.3 Detectors 184

4.3 Summary 191

5 Data Collection and Processing 195

5.1 The Art of Measurement 195

5.1.1 Data Formats and Definitions 196

5.1.1.1 Mass Spectra 197

5.1.1.2 Depth Profiling 201

5.1.1.3 Imaging 204

5.2 Sample Preparation and Handling 208

5.2.1 Preparation in the Materials Sciences 209

5.2.2 Preparation in the Earth Sciences 210

5.2.3 Preparation in the Biosciences 212

5.2.4 Sample Handling 213

5.3 Data Collection 215

5.3.1 Secondary Ion Mass, Energy, and Intensity Scales 216

5.3.1.1 Referencing the Mass, Energy, and Intensity Scales 216

5.3.1.2 Charge Buildup 218

5.3.1.3 Isobaric Interferences 221

5.3.2 Instrument Operation Modes 225

5.3.2.1 Primary Ion Beam Operation Modes 225

5.3.2.2 Secondary Ion Imaging Modes 231

5.3.2.3 The O2 Leak Methodology 233

5.3.2.4 Depth Profiling and Related Aspects 234

5.4 Data Processing 248

5.4.1 Spectral Identification 249

5.4.1.1 Atomic and Unfragmented Molecular Emissions 249

5.4.1.2 Heavily Fragmented Molecular Emissions 250

5.4.2 Quantification of the Depth Scale 251

5.4.2.1 Ex situ Methods 254

5.4.2.2 In situ Methods 256

5.4.3 Quantification of the Concentration Scale 259

5.4.3.1 The RSF Method 260

5.4.3.2 Fabrication of Reference Materials 265

5.5 Summary 268

Appendix A 273

A.1 Periodic Table of the Elements 273

A.2 Isotopic Masses, Natural Isotope Abundances, Atomic Weights, and Mass Densities of the Elements 273

A.3 1st and 2nd Ionization Potentials and Electron Affinities of the Elements 280

A.4 Work–Function Values of Elemental Solids 283

A.5 SIMS Detection Limits of Selected Elements 286

A.6 Charged Particle Beam Transport 288

A.6.1 Ion Beam Trajectories 288

A.6.1.1 Liouville’s Theorem 289

A.6.1.2 Phase Space Dynamics 289

A.6.1.3 Ray Tracing Methods 289

A.6.2 Optical Properties 290

A.6.2.1 Aberrations 290

A.6.2.2 Diffraction and the Diffraction Limit 292

A.7 Some Statistical Distributions of Interest 293

A.7.1 Gaussian Distribution 294

A.7.2 Poisson Distribution 294

A.7.3 Lorentzian Distributions 294

A.8 SIMS Instrument Designs 294

A.8.1 Physical Electronics 6600 295

A.8.2 ASI SHRIMP I, II, and IV 296

A.8.3 SHRIMP RG 297

A.8.4 Cameca IMS-1280 298

A.8.5 Cameca IMS 7f 299

A.8.6 Cameca nanoSIMS 50 300

A.8.7 Ion-Tof TOF-SIMS 5 302

A.8.8 Physical Electronics nano-SIMS 303

A.8.9 Ionoptika J105-3D Chemical Imager 303

A.8.10 Q-Star Chemical Imager 304

A.8.11 SIMS Instrument Capability Table 305

A.8.12 SIMS Instrument/Component Vendor List 308

A.9 Additional SIMS Methods of Interest 311

A.9.1 Matrix Transferable RSFs 312

A.9.2 The Infinite Velocity Method 313

A.9.3 Lattice Valency Model 314

A.9.4 PCOR-SIMSTM Method 315

A.10 Additional Spectroscopic/Spectrometric Techniques 316

A.10.1 Photon Spectroscopies 317

A.10.1.1 IR, RAIRS, ATR, and DRIFTS 317

A.10.1.2 Raman, SERS, and TERS 318

A.10.1.3 EDX, WDS, and LEXES 319

A.10.1.4 XRF and TXRF 320

A.10.1.5 VASE 320

A.10.2 Electron Spectroscopies 321

A.10.2.1 XPS and UPS 321

A.10.2.2 AES and SAM 321

A.10.2.3 EELS, REELS, and HREELS 322

A.10.3 Ion Spectroscopies/Spectrometries 322

A.10.3.1 GD-MS, GD-OES, and ICP-MS 322

A.10.3.2 MALDI and ESI-MS 323

A.10.3.3 SNMS and RIMS 324

A.10.3.4 APT 324

A.10.3.5 Ion Scattering Methods 325

A.10.3.6 ERD, NRA, NAA, and PIXE 326

A.11 Additional Microscopies 327

A.11.1 SEM 328

A.11.2 HIM 328

A.11.3 TEM 329

A.11.4 SPM (AFM and STM)-Based Techniques 329

A.12 Diffraction/Reflection Techniques of Interest 331

A.12.1 XRD and GID 332

A.12.2 GID 332

A.12.3 XRR 333

A.12.4 LEED 333

A.12.5 RHEED 333

A.12.6 Neutron Diffraction 333

Technique Acronym List 335

Abbreviations Commonly used in SIMS 338

Glossary of Terms 340

Questions and Answers 347

References 350

Index 359

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