1 Light Microscopy 1
1.1 Optical Principles 1
1.1.1 Image Formation 1
1.1.2 Resolution 3
1.1.2.1 Effective Magnification 5
1.1.2.2 Brightness and Contrast 5
1.1.3 Depth of Field 6
1.1.4 Aberrations 7
1.2 Instrumentation 9
1.2.1 Illumination System 9
1.2.2 Objective Lens and Eyepiece 13
1.2.2.1 Steps for Optimum Resolution 15
1.2.2.2 Steps to Improve Depth of Field 15
1.3 Specimen Preparation 15
1.3.1 Sectioning 16
1.3.1.1 Cutting 16
1.3.1.2 Microtomy 17
1.3.2 Mounting 17
1.3.3 Grinding and Polishing 19
1.3.3.1 Grinding 19
1.3.3.2 Polishing 21
1.3.4 Etching 23
1.4 Imaging Modes 26
1.4.1 Bright-Field and Dark-Field Imaging 26
1.4.2 Phase-Contrast Microscopy 27
1.4.3 Polarized-Light Microscopy 30
1.4.4 Nomarski Microscopy 35
1.4.5 Fluorescence Microscopy 37
1.5 Confocal Microscopy 39
1.5.1 Working Principles 39
1.5.2 Three-Dimensional Images 41
References 45
Further Reading 45
2 X-Ray Diffraction Methods 47
2.1 X-Ray Radiation 47
2.1.1 Generation of X-Rays 47
2.1.2 X-Ray Absorption 50
2.2 Theoretical Background of Diffraction 52
2.2.1 Diffraction Geometry 52
2.2.1.1 Braggâs Law 52
2.2.1.2 Reciprocal Lattice 53
2.2.1.3 Ewald Sphere 55
2.2.2 Diffraction Intensity 58
2.2.2.1 Structure Extinction 60
2.3 X-Ray Diffractometry 62
2.3.1 Instrumentation 62
2.3.1.1 System Aberrations 64
2.3.2 Samples and Data Acquisition 65
2.3.2.1 Sample Preparation 65
2.3.2.2 Acquisition and Treatment of Diffraction Data 65
2.3.3 Distortions of Diffraction Spectra 67
2.3.3.1 Preferential Orientation 67
2.3.3.2 Crystallite Size 68
2.3.3.3 Residual Stress 69
2.3.4 Applications 70
2.3.4.1 Crystal-Phase Identification 70
2.3.4.2 Quantitative Measurement 72
2.4 Wide-Angle X-Ray Diffraction and Scattering 75
2.4.1 Wide-Angle Diffraction 76
2.4.2 Wide-Angle Scattering 79
References 82
Further Reading 82
3 Transmission Electron Microscopy 83
3.1 Instrumentation 83
3.1.1 Electron Sources 84
3.1.1.1 Thermionic Emission Gun 85
3.1.1.2 Field Emission Gun 86
3.1.2 Electromagnetic Lenses 87
3.1.3 Specimen Stage 89
3.2 Specimen Preparation 90
3.2.1 Prethinning 91
3.2.2 Final Thinning 91
3.2.2.1 Electrolytic Thinning 91
3.2.2.2 Ion Milling 92
3.2.2.3 Ultramicrotomy 93
3.3 Image Modes 94
3.3.1 Massâ"Density Contrast 95
3.3.2 Diffraction Contrast 96
3.3.3 Phase Contrast 101
3.3.3.1 Theoretical Aspects 102
3.3.3.2 Two-Beam and Multiple-Beam Imaging 105
3.4 Selected-Area Diffraction (SAD) 107
3.4.1 Selected-Area Diffraction Characteristics 107
3.4.2 Single-Crystal Diffraction 109
3.4.2.1 Indexing a Cubic Crystal Pattern 109
3.4.2.2 Identification of Crystal Phases 112
3.4.3 Multicrystal Diffraction 114
3.4.4 Kikuchi Lines 114
3.5 Images of Crystal Defects 117
3.5.1 Wedge Fringe 117
3.5.2 Bending Contours 120
3.5.3 Dislocations 122
References 126
Further Reading 126
4 Scanning Electron Microscopy 127
4.1 Instrumentation 127
4.1.1 Optical Arrangement 127
4.1.2 Signal Detection 129
4.1.2.1 Detector 130
4.1.3 Probe Size and Current 131
4.2 Contrast Formation 135
4.2.1 Electronâ"Specimen Interactions 135
4.2.2 Topographic Contrast 137
4.2.3 Compositional Contrast 139
4.3 Operational Variables 141
4.3.1 Working Distance and Aperture Size 141
4.3.2 Acceleration Voltage and Probe Current 144
4.3.3 Astigmatism 145
4.4 Specimen Preparation 145
4.4.1 Preparation for Topographic Examination 146
4.4.1.1 Charging and Its Prevention 147
4.4.2 Preparation for Microcomposition Examination 149
4.4.3 Dehydration 149
4.5 Electron Backscatter Diffraction 151
4.5.1 EBSD Pattern Formation 151
4.5.2 EBSD Indexing and Its Automation 153
4.5.3 Applications of EBSD 155
4.6 Environmental SEM 156
4.6.1 ESEM Working Principle 156
4.6.2 Applications 158
References 160
Further Reading 160
5 Scanning Probe Microscopy 163
5.1 Instrumentation 163
5.1.1 Probe and Scanner 165
5.1.2 Control and Vibration Isolation 165
5.2 Scanning Tunneling Microscopy 166
5.2.1 Tunneling Current 166
5.2.2 Probe Tips and Working Environments 167
5.2.3 Operational Modes 168
5.2.4 Typical Applications 169
5.3 Atomic Force Microscopy 170
5.3.1 Near-Field Forces 170
5.3.1.1 Short-Range Forces 171
5.3.1.2 van der Waals Forces 171
5.3.1.3 Electrostatic Forces 171
5.3.1.4 Capillary Forces 172
5.3.2 Force Sensors 172
5.3.3 Operational Modes 174
5.3.3.1 Static Contact Modes 176
5.3.3.2 Lateral Force Microscopy 177
5.3.3.3 Dynamic Operational Modes 177
5.3.4 Typical Applications 180
5.3.4.1 Static Mode 180
5.3.4.2 Dynamic Noncontact Mode 181
5.3.4.3 Tapping Mode 182
5.3.4.4 Force Modulation 183
5.4 Image Artifacts 183
5.4.1 Tip 183
5.4.2 Scanner 185
5.4.3 Vibration and Operation 187
References 189
Further Reading 189
6 X-Ray Spectroscopy for Elemental Analysis 191
6.1 Features of Characteristic X-Rays 191
6.1.1 Types of Characteristic X-Rays 193
6.1.1.1 Selection Rules 193
6.1.2 Comparison of K, L, and M Series 194
6.2 X-Ray Fluorescence Spectrometry 196
6.2.1 Wavelength Dispersive Spectroscopy 199
6.2.1.1 Analyzing Crystal 200
6.2.1.2 Wavelength Dispersive Spectra 201
6.2.2 Energy Dispersive Spectroscopy 203
6.2.2.1 Detector 203
6.2.2.2 Energy Dispersive Spectra 204
6.2.2.3 Advances in Energy Dispersive Spectroscopy 204
6.2.3 XRF Working Atmosphere and Sample Preparation 206
6.3 Energy Dispersive Spectroscopy in Electron Microscopes 207
6.3.1 Special Features 208
6.3.2 Scanning Modes 210
6.4 Qualitative and Quantitative Analysis 211
6.4.1 Qualitative Analysis 211
6.4.2 Quantitative Analysis 213
6.4.2.1 Quantitative Analysis by X-Ray Fluorescence 214
6.4.2.2 Fundamental Parameter Method 215
6.4.2.3 Quantitative Analysis in Electron Microscopy 216
References 219
Further Reading 219
7 Electron Spectroscopy for Surface Analysis 221
7.1 Basic Principles 221
7.1.1 X-Ray Photoelectron Spectroscopy 221
7.1.2 Auger Electron Spectroscopy 222
7.2 Instrumentation 225
7.2.1 Ultrahigh Vacuum System 225
7.2.2 Source Guns 227
7.2.2.1 X-Ray Gun 227
7.2.2.2 Electron Gun 228
7.2.2.3 Ion Gun 229
7.2.3 Electron Energy Analyzers 229
7.3 Characteristics of Electron Spectra 230
7.3.1 Photoelectron Spectra 230
7.3.2 Auger Electron Spectra 233
7.4 Qualitative and Quantitative Analysis 235
7.4.1 Qualitative Analysis 235
7.4.1.1 Peak Identification 239
7.4.1.2 Chemical Shifts 239
7.4.1.3 Problems with Insulating Materials 241
7.4.2 Quantitative Analysis 246
7.4.2.1 Peaks and Sensitivity Factors 246
7.4.3 Composition Depth Profiling 247
References 250
Further Reading 251
8 Secondary Ion Mass Spectrometry for Surface Analysis 253
8.1 Basic Principles 253
8.1.1 Secondary Ion Generation 254
8.1.2 Dynamic and Static SIMS 257
8.2 Instrumentation 258
8.2.1 Primary Ion System 258
8.2.1.1 Ion Sources 259
8.2.1.2 Wien Filter 262
8.2.2 Mass Analysis System 262
8.2.2.1 Magnetic Sector Analyzer 263
8.2.2.2 Quadrupole Mass Analyzer 264
8.2.2.3 Time-of-Flight Analyzer 264
8.3 Surface Structure Analysis 266
8.3.1 Experimental Aspects 266
8.3.1.1 Primary Ions 266
8.3.1.2 Flood Gun 266
8.3.1.3 Sample Handling 267
8.3.2 Spectrum Interpretation 268
8.3.2.1 Element Identification 269
8.4 SIMS Imaging 272
8.4.1 Generation of SIMS Images 274
8.4.2 Image Quality 275
8.5 SIMS Depth Profiling 275
8.5.1 Generation of Depth Profiles 276
8.5.2 Optimization of Depth Profiling 276
8.5.2.1 Primary Beam Energy 278
8.5.2.2 Incident Angle of Primary Beam 278
8.5.2.3 Analysis Area 279
References 282
9 Vibrational Spectroscopy for Molecular Analysis 283
9.1 Theoretical Background 283
9.1.1 Electromagnetic Radiation 283
9.1.2 Origin of Molecular Vibrations 285
9.1.3 Principles of Vibrational Spectroscopy 286
9.1.3.1 Infrared Absorption 286
9.1.3.2 Raman Scattering 287
9.1.4 Normal Mode of Molecular Vibrations 289
9.1.4.1 Number of Normal Vibration Modes 291
9.1.4.2 Classification of Normal Vibration Modes 291
9.1.5 Infrared and Raman Activity 292
9.1.5.1 Infrared Activity 293
9.1.5.2 Raman Activity 295
9.2 Fourier Transform Infrared Spectroscopy 297
9.2.1 Working Principles 298
9.2.2 Instrumentation 300
9.2.2.1 Infrared Light Source 300
9.2.2.2 Beamsplitter 300
9.2.2.3 Infrared Detector 301
9.2.2.4 Fourier Transform Infrared Spectra 302
9.2.3 Examination Techniques 304
9.2.3.1 Transmittance 304
9.2.3.2 Solid Sample Preparation 304
9.2.3.3 Liquid and Gas Sample Preparation 304
9.2.3.4 Reflectance 305
9.2.4 Fourier Transform Infrared Microspectroscopy 307
9.2.4.1 Instrumentation 307
9.2.4.2 Applications 309
9.3 Raman Microscopy 310
9.3.1 Instrumentation 310
9.3.1.1 Laser Source 311
9.3.1.2 Microscope System 311
9.3.1.3 Prefilters 312
9.3.1.4 Diffraction Grating 313
9.3.1.5 Detector 314
9.3.2 Fluorescence Problem 314
9.3.3 Raman Imaging 315
9.3.4 Applications 316
9.3.4.1 Phase Identification 317
9.3.4.2 Polymer Identification 319
9.3.4.3 Composition Determination 319
9.3.4.4 Determination of Residual Strain 321
9.3.4.5 Determination of Crystallographic Orientation 322
9.4 Interpretation of Vibrational Spectra 323
9.4.1 Qualitative Methods 323
9.4.1.1 Spectrum Comparison 323
9.4.1.2 Identifying Characteristic Bands 324
9.4.1.3 Band Intensities 327
9.4.2 Quantitative Methods 327
9.4.2.1 Quantitative Analysis of Infrared Spectra 327
9.4.2.2 Quantitative Analysis of Raman Spectra 330
References 331
Further Reading 332
10 Thermal Analysis 333
10.1 Common Characteristics 333
10.1.1 Thermal Events 333
10.1.1.1 Enthalpy Change 335
10.1.2 Instrumentation 335
10.1.3 Experimental Parameters 336
10.2 Differential Thermal Analysis and Differential Scanning Calorimetry 337
10.2.1 Working Principles 337
10.2.1.1 Differential Thermal Analysis 337
10.2.1.2 Differential Scanning Calorimetry 338
10.2.1.3 Temperature-Modulated Differential Scanning Calorimetry 340
10.2.2 Experimental Aspects 342
10.2.2.1 Sample Requirements 342
10.2.2.2 Baseline Determination 343
10.2.2.3 Effects of Scanning Rate 344
10.2.3 Measurement of Temperature and Enthalpy Change 345
10.2.3.1 Transition Temperatures 345
10.2.3.2 Measurement of Enthalpy Change 347
10.2.3.3 Calibration of Temperature and Enthalpy Change 348
10.2.4 Applications 348
10.2.4.1 Determination of Heat Capacity 348
10.2.4.2 Determination of Phase Transformation and Phase Diagrams 350
10.2.4.3 Applications to Polymers 351
10.3 Thermogravimetry 353
10.3.1 Instrumentation 354
10.3.2 Experimental Aspects 355
10.3.2.1 Samples 355
10.3.2.2 Atmosphere 356
10.3.2.3 Temperature Calibration 358
10.3.2.4 Heating Rate 359
10.3.3 Interpretation of Thermogravimetric Curves 360
10.3.3.1 Types of Curves 360
10.3.3.2 Temperature Determination 362
10.3.4 Applications 362
References 365
Further Reading 365
Index 367
