Raman Spectroscopy and its Application in Nanostructures

Acknowledgements xiii

Part I Fundamentals of Raman Spectroscopy 1

1 Basic Knowledge of Raman Spectroscopy 3

1.1 Spectrum and Spectroscopy 3

1.2 Scattering and Raman Scattering 5

1.3 Fundamental Features of Raman Scattering Spectra 9

1.4 Discovery of the Raman Scattering Effects and Observation of the First Raman Spectrum 10

1.5 Historical Development of Raman Spectroscopy 13

References 16

2 Fundamental Theory of Light Scattering 19

2.1 Description of Scattering 20

2.2 Macroscopic Theory of Light Scattering 26

2.3 Microscopic Theory of Light Scattering 39

References 45

3 Experimental Foundation of Raman Spectroscopy 47

3.1 Generality of Raman Spectral Measurements 47

3.2 Experimental Apparatus 56

3.3 Main Performance Parameters of Raman Spectrometers 79

3.4 Experimental Measurements 83

3.5 Data Processing of Recorded Raman Spectra 88

3.6 A Typical Example of Vibration Raman Spectra - Raman Spectrum of CCl4 94

3.7 Interference Spectrometer and Fourier Transform Optics 97

References 104

4 Introduction to Modern Raman Spectroscopy I-New Raman Spectroscopic Branch Classified Based on Spectral Features 105

4.1 Non-visible Excited Raman Spectroscopy 106

4.2 Resonant Raman Spectroscopy (RRS) 106

4.3 High-Order/Multiple-Phonon Raman Spectroscopy (MPRS) 110

4.4 Raman Spectroscopy under Extreme Conditions 114

4.5 Polarized Raman Spectroscopy (PRS) 115

4.6 Time-Resolved (Transient) Raman Spectroscopy (TRRS) 116

4.7 Space-Resolved Micro-Raman Spectroscopy and Raman Microscopy 118

4.8 Surface-enhanced Raman Spectroscopy (SERS) 119

4.9 Near-Field Raman Spectroscopy (NFRS) 121

4.10 Tip-enhanced Raman Spectroscopy (TERS) 130

4.11 Non-linear and Coherent Raman Spectroscopy (NLRS) 136

4.12 Coherent Anti-Stokes Raman Scattering (CARS) 138

4.13 Stimulated Raman Scattering (SRS) 145

References 150

5 Introduction to Modern Raman Spectroscopy II-New Raman Spectroscopic Branch Classified Based on Applied Objects 153

5.1 Common Spectroscopic Basis Related to the Study and Application of Raman Spectroscopy 153

5.2 Chemistry Raman Spectroscopy 158

5.3 Condensed Matter Raman Spectroscopy 160

5.4 Biological and Medical Raman Spectroscopy 166

5.5 Geology and Mineralogy Raman Spectroscopy 175

5.6 Art and Archeology Raman Spectroscopy 177

5.7 Industry Raman Spectroscopy 178

5.8 Raman Spectroscopy in National Security and Judicature 181

References 182

Part II Study of Nanostructures by Raman Spectroscopy 185

6 General Knowledge of Nanostructures 187

6.1 Nanostructure, Characteristic Length, and Dimension 187

6.2 Nanomaterials 188

6.3 Properties of Nanostructures 190

6.4 Finite Size and Specific Surface 192

6.5 The Study of Nanostructure 196

References 197

7 Theoretical Fundamentals of Raman Scattering in Solids 199

7.1 General Knowledge of Lattice Dynamics 200

7.2 Microscopic Model of Lattice Dynamics 213

7.3 Macroscopic Model of Lattice Dynamics 222

7.4 Lattice Dynamics of Amorphous Matter 229

7.5 Raman Scattering Theories in Solids 230

References 246

8 Theoretical Fundamentals of Raman Scattering in Nanostructures 249

8.1 Superlattices 250

8.2 Nanostructure Materials 264

8.3 Micro-Crystal Models 283

8.4 Amorphous Feature and PDOS Expression of Nanostructure Raman Spectra 296

8.5 First-Principles/ab initio Calculation of Nanostructure Raman Spectra 298

References 306

9 Routine Raman Spectra of Nanostructures 309

9.1 Characteristic Raman Spectra of Semiconductor Superlattices 310

9.2 Characteristic Raman Spectra of Nanosilicon 318

9.3 Characteristic Raman Spectra of Nanocarbons 325

9.4 Characteristic Raman Spectra of Polar Nano-Semiconductors 337

9.5 Multiple-Phonon Raman Spectra 343

9.6 Anti-Stokes Raman Spectra 352

References 357

10 Raman Spectroscopy of Nanostructures with Exciting Laser Features 361

10.1 Raman Spectra with Changing of Exciting Light Wavelengths - Resonant Raman Spectra 361

10.2 Raman Spectra with Exciting Laser Polarization 373

10.3 Raman Spectra with Exciting Laser Intensity 378

References 392

11 Raman Spectra with Samples of Nanostructures 395

11.1 Effects of Sample Sizes on Raman Spectra of Nanostructures 395

11.2 Effects of Sample Shapes on Raman Spectra in Nanostructures 409

11.3 Effects of Sample Component and Micro-structure on Raman Spectra in Nanostructures 413

References 417

12 Electron-Phonon Interactions in Raman Spectroscopy of Nanostructures 419

12.1 Abnormal Raman Spectral Features in Nanostructures 419

12.2 Origin of No FSE on Phonons 420

12.3 FrEURohlich Interaction in Nanostructures 423

12.4 Theoretical Raman Spectra of Non-polar and Polar Nano-Semiconductors 424

12.5 Amorphous Feature of Nanocrystal Raman Spectra of No FSE on Phonons and the Breaking of Translation Symmetry in Nano-Semiconductors 426

References 428

Appendices 429

Appendix I Electromagnetic Waves and Lasers 429

I.1 Electromagnetic Wavelength 429

I.2 Laser Types 430

I.3 Laser Lines and Ionic/Atomic Lines of Gas Lasers used Commonly in Raman Spectroscopy 432

Appendix II Standard Spectral Lines 438

II.1 Spectral Lines of Mercury Lamp in Visible Range 438

II.2 Standard Lines of Neon Spectral Lamp 439

Appendix III Raman Tensors 442

III.1 Raman Tensors and Symmetric Attributes 442

III.2 Applications of Raman Tensors 447

Appendix IV Constitution, Polarity, and Symmetry Structure of Crystals 452

IV.1 Constitution, Polarity, and Crystal Structure of Crystals 452

IV.2 Syngony and its Basic Vector, Bravais Lattice, and Point Group Symmetry 455

Appendix V Brillouin Zones, Vibration Modes, and Raman Spectra of Typical Ordinary and Semiconducting Crystals 458

V.1 Brillouin Zones and Symmetrical Points of Cubic System 458

V.2 Vibrational Modes and their Symmetries of Several Crystals 460

V.3 Structures, Symmetries, and Raman Spectra of Several Semiconducting Crystals 461

Appendix VI Physical Parameters, Constants, and Units 466

VI.1 Periodic Table of the Elements 466

VI.2 Electronic Structure of Atoms 467

VI.3 Common Physical Constant and the Performance Parameters of Optical Glass 470

References 472

Index 473