Vladimir G. Bordo and Horst-Gunter Rubahn Optics and Spectroscopy at Surfaces and Interfaces WILEY- VCH WILEY-VCH Verlag GmbH & Co. KGaA
Contents Preface IX 1 Introduction 1 2 Surfaces and Interfaces 5 2.1 Solid Surfaces 5 2.1.1 Surface Structure 6 2.1.1.1 Relaxation and Reconstruction 6 2.1.1.2 Surface Lattice and Superstructure 7 2.1.1.3 Surface Structure Notation 10 2.1.1.4 Reciprocal Lattice 22 2.1.2 Electronic Surface States 22 2.1.2.1 One-dimensional Problem 22 2.1.2.2 Nearly-free Electron Approximation 13 2.1.2.3 Tamm and Shockley States 16 2.1.2A Image States 18 2.1.2.5 Surface States of a 3D Crystal 19 2.1.2.6 Extrinsic Surface States 19 2.1.3 Surface Plasmons 29 2.1.4 Surface Phonons 22 2.1.5 Surface Roughness 25 2.2 Adsorption on Solid Surfaces 27 2.2.1 Physisorption 28 2.2.2 Chemisorption 31 2.2.3 Vibrational States of Adsorbates 33 2.2.3.1 Symmetry of Adsorption Sites 33 2.2.3.2 Vibrational Frequencies of Isolated Adsorbates 36 2.2.3.3 Coupled Vibrations of Overlayers 37 2.2.4 Relaxation of Adsorbate Excitations 39 Optics and Spectroscopy at Surfaces and Interfaces, Vladimir G. Bordo and Horst-Gunter Rubahn Copyright 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-40560-7
VI Contents 2.2.5 Adsorption and Desorption Kinetics 43 2.3 Liquid-Solid Interface 45 2.3.1 The Electric Double Layer 45 2.3.2 Linear-sweep and Cyclic Voltammetry 47 2.4 Gas-Solid Interface 48 2.4.1 Velocity Distribution Function 49 2.4.2 Scattering Kernel 50 2.4.3 Relaxation of Gas Excitation 52 3 Linear Optical Properties of Surfaces and Interfaces 57 3.1 Reflection and Refraction of Light 57 3.1.1 Fresnel Equations 57 3.1.2 Total Internal Reflection (TIR) 63 3.1.3 Account of a Transition Layer 64 3.1.3.1 Macroscopic layer 64 3.1.3.2 Microscopic layer 67 3.2 Nonlocal Optical Response 69 3.3 Surface Polaritons 73 3.3.1 Fundamental Properties 73 3.3.2 Surface Plasmon Polaritons 75 3.3.3 Surface Phonon Polaritons 76 3.3.4 Excitation of Surface Polaritons 77 3.3.5 Electromagnetic Field Enhancement 82 3.3.6 Localized Surface Polaritons 82 3.4 Scattering of Light at Rough Surfaces 85 4 Infrared Spectroscopy at Surfaces and Interfaces 93 4.1 Infrared Spectroscopic Ellipsometry (IRSE) 94 4.2 Infrared Reflection-Absorption Spectroscopy (IRAS) of Adsorbed Molecules 97 4.3 Infrared Surface Polariton Spectroscopy 200 4.3.1 Determination of Optical Constants of Crystals 202 4.3.2 Surface Electromagnetic Wave Spectroscopy of Overlayers 203 4.3.3 Correlation between Propagation Length and Surface Roughness 203 4.4 Time-resolved Infrared Spectroscopy 205 5 Linear Optical Techniques at Surfaces and Interfaces 111 5.1 Spectroscopic Ellipsometry (SE) 222 5.2 Reflection Difference Techniques 224 5.2.1 Surface Differential Reflectivity (SDR) 224 5.2.2 Reflection Anisotropy Spectroscopy (RAS) 226
Contents VII 5.3 Transmission Spectroscopy 227 5.4 Photoluminescence Spectroscopy 220 5.4.1 Fluorescence Spectroscopy of Adsorbed Atoms and Molecules 220 5.4.2 Photoluminescence Spectroscopy at Semiconductor Surfaces and Interfaces 222 5.5 Raman Spectroscopy 223 5.5.1 Raman Scattering 224 5.5.2 Surface-enhanced Raman Scattering (SERS) 226 5.6 Surface Plasmon Polariton Spectroscopy 228 5.6.1 Spectroscopy at Metal Surfaces and Interfaces 229 5.6.2 Spectroscopy at Electrochemical Interfaces 232 5.7 Electrochemical Optical Spectroscopy 235 6 Nonlinear Optical Techniques at Surfaces and Interfaces 139 6.1 Nonlinear Optical Response 239 6.2 Second Harmonic Generation 243 6.2.1 Determination of Coverages 244 6.2.2 Symmetries 250 6.2.3 Orientations and Chirality 252 6.2.4 Surface Magnetization 253 6.2.5 Spectroscopy 256 6.3 Sum Frequency Generation 258 6.4 Four-wave Mixing 260 6.5 Two-photon Fluorescence Spectroscopy of Adsorbed Atoms and Molecules 267 7 Optical Spectroscopy at a Gas-Solid Interface 173 7.1 Optical Response of a Gas Near a Solid 273 7.2 Selective Reflection Spectroscopy 2 79 7.2.1 Spectral Narrowing of Selective Reflection 279 7.2.2 Observation of Transient Effects 181 7.2.3 Manifestation of Atom-Surface Interactions 283 7.2.4 Selective Reflection in a Pump-Probe Scheme 285 7.3 Evanescent Wave Fluorescence Spectroscopy 287 7.3.1 One-photon Excitation 289 7.3.2 Two-photon Excitation 290 7.3.3 Temperature Dependence of Fluorescence Spectra 292 7.3.4 Excitation by Crossed Waves 295 8 Optical Microscopy 201 8.1 Optical Resolution and Simple Light Microscopes 202 8.2 Dark-field, Fluorescence and Confocal Microscopy 204
VIII Contents 8.2.1 Fluorescence and Phase Contrast Microscopy 205 8.2.2 Confocal Microscopy 207 8.3 Total Internal Reflection Microscopy (TIRM) 222 8.4 Brewster Angle Microscopy (BAM) 222 8.5 Phase Measurement Interference Microscopy (PMIM) 224 8.6 Second Harmonic Microscopy 216 9 Nano-optics and Local Spectroscopy 221 9.1 Scanning Near-field Optical Microscopy and Photon Scanning Tunneling Microscopy 222 9.2 Scanning Plasmon Near-field Microscopy (SPNM) 230 9.3 Near-field Optical Spectroscopy 232 9.3.1 Fluorescence Spectroscopy 232 9.3.2 Raman Spectroscopy 232 9.4 Near-field Nonlinear Optics 233 10 Solutions to Problems 237 Glossary 253 Bibliography 259 Index 269