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基本説明
The first compilation of longitudinal frequencies of different substances. Covers new approaches, such as Surface Enhanced IR spectroscopy (SEIR), time-resolved FTIR spectroscopy, and more.
Full Description
Because of the rapid increase in commercially available Fourier transform infrared spectrometers and computers over the past ten years, it has now become feasible to use IR spectrometry to characterize very thin films at extended interfaces. At the same time, interest in thin films has grown tremendously because of applications in microelectronics, sensors, catalysis, and nanotechnology. The Handbook of Infrared Spectroscopy of Ultrathin Films provides a practical guide to experimental methods, up-to-date theory, and considerable reference data, critical for scientists who want to measure and interpret IR spectra of ultrathin films. This authoritative volume also: Offers information needed to effectively apply IR spectroscopy to the analysis and evaluation of thin and ultrathin films on flat and rough surfaces and on powders at solid-gaseous, solid-liquid, liquid-gaseous, liquid-liquid, and solid-solid interfaces.
* Provides full discussion of theory underlying techniques
* Describes experimental methods in detail, including optimum conditions for recording spectra and the interpretation of spectra
* Gives detailed information on equipment, accessories, and techniques
* Provides IR spectroscopic data tables as appendixes, including the first compilation of published data on longitudinal frequencies of different substances
* Covers new approaches, such as Surface Enhanced IR spectroscopy (SEIR), time-resolved FTIR spectroscopy, high-resolution microspectroscopy and using synchotron radiation
Contents
Preface xiii
Acronyms and Symbols xix
Introduction xxv
1 Absorption and Reflection of Infrared Radiation by Ultrathin Films 1
1.1. Macroscopic Theory of Propagation of Electromagnetic Waves in Infinite Medium 2
1.2. Modeling Optical Properties of a Material 10
1.3. Classical Dispersion Models of Absorption 13
1.4. Propagation of IR Radiation through Planar Interface between Two Isotropic Media 24
1.4.1. Transparent Media 26
1.4.2. General Case 29
1.5. Reflection of Radiation at Planar Interface Covered by Single Layer 31
1.6. Transmission of Layer Located at Interface between Two Isotropic Semi-infinite Media 39
1.7. System of Plane-Parallel Layers: Matrix Method 43
1.8. Energy Absorption in Layered Media 49
1.8.1. External Reflection: Transparent Substrates 50
1.8.2. External Reflection: Metallic Substrates 52
1.8.3. ATR 55
1.9. Effective Medium Theory 60
1.10. Diffuse Reflection and Transmission 65
Appendix 68
References 70
2 Optimum Conditions for Recording Infrared Spectra of Ultrathin Films 79
2.1. IR Transmission Spectra Obtained in Polarized Radiation 79
2.2. IRRAS Spectra of Layers on Metallic Surfaces ("Metallic" IRRAS) 84
2.3. IRRAS of Layers on Semiconductors and Dielectrics 87
2.3.1. Transparent and Weakly Absorbing Substrates ("Transparent" IRRAS) 87
2.3.2. Absorbing Substrates 90
2.3.3. Buried Metal Layer Substrates (BML-IRRAS) 94
2.4. ATR Spectra 100
2.5. IR Spectra of Layers Located at Interface 102
2.5.1. Transmission 102
2.5.2. Metallic IRRAS 105
2.5.3. Transparent IRRAS 110
2.5.4. ATR 111
2.6. Choosing Appropriate IR Spectroscopic Method for Layer on Flat Surface 118
2.7. Coatings on Powders, Fibers, and Matte Surfaces 120
2.7.1. Transmission 120
2.7.2. Diffuse Transmittance and Diffuse Reflectance 122
2.7.3. ATR 128
2.7.4. Comparison of IR Spectroscopic Methods for Studying Ultrathin Films on Powders 130
References 133
3 Interpretation of IR Spectra of Ultrathin Films 140
3.1. Dependence of Transmission, ATR, and IRRAS Spectra of Ultrathin Films on Polarization (Berreman Effect) 141
3.2. Theory of Berreman Effect 146
3.2.1. Surface Modes 147
3.2.2. Modes in Ultrathin Films 151
3.2.3. Identification of Berreman Effect in IR Spectra of Ultrathin Films 157
3.3. Optical Effect: Film Thickness, Angle of Incidence, and Immersion 159
3.3.1. Effect in "Metallic" IRRAS 159
3.3.2. Effect in "Transparent" IRRAS 164
3.3.3. Effect in ATR Spectra 167
3.3.4. Effect in Transmission Spectra 169
3.4. Optical Effect: Band Shapes in IRRAS as Function of Optical Properties of Substrate 171
3.5. Optical Property Gradients at Substrate-Layer Interface: Effect on Band Intensities in IRRAS 175
3.6. Dipole-Dipole Coupling 179
3.7. Specific Features in Potential-Difference IR Spectra of Electrode-Electrolyte Interfaces 187
3.7.1. Absorption Due to Bulk Electrolyte 189
3.7.2. (Re)organization of Electrolyte in DL 190
3.7.3. DonationBackdonation of Electrons 202
3.7.4. Stark Effect 202
3.7.5. Bipolar Bands 203
3.7.6. Effect of Coadsorption 205
3.7.7. Electronic Absorption 206
3.7.8. Optical Effects 210
3.8. Interpretation of Dynamic IR Spectra: Two-Dimensional Correlation Analysis 212
3.9. IR Spectra of Inhomogeneous Films and Films on Powders and Rough Surfaces. Surface Enhancement 219
3.9.1. Manifestation of Particle Shape in IR Spectra 220
3.9.2. Coated Particles 223
3.9.3. Composite, Porous, and Discontinuous Films 225
3.9.4. Interpretation of IR Surface-Enhanced Spectra 232
3.9.5. Rough Surfaces 241
3.10. Determination of Optical Constants of Isotropic Ultrathin Films: Experimental Errors in Reflectivity Measurements 243
3.11. Determination of Molecular Packing and Orientation in Ultrathin Films: Anisotropic Optical Constants of Ultrathin Films 252
3.11.1. Order-Disorder Transition 253
3.11.2. Packing and Symmetry of Ultrathin Films 257
3.11.3. Orientation 266
3.11.4. Surface Selection Rule for Dielectrics 280
3.11.5. Optimum Conditions for MO Studies 282
References 284
4 Equipment and Techniques 307
4.1. Techniques for Recording IR Spectra of Ultrathin Films on Bulk Samples 308
4.1.1. Transmission and Multiple Transmission 308
4.1.2. IRRAS 313
4.1.3. ATR 317
4.1.4. DRIFTS 327
4.2. Techniques for Ultrathin Films on Powders and Fibers 328
4.2.1. Transmission 329
4.2.2. Diffuse Transmission 331
4.2.3. Diffuse Reflectance 334
4.2.4. ATR 342
4.3. High-Resolution FTIR Microspectroscopy of Thin Films 343
4.3.1. Transmission 345
4.3.2. IRRAS 346
4.3.3. DRIFTS and DTIFTS 347
4.3.4. ATR 348
4.3.5. Spatial Resolution and Smallest Sampling Area 350
4.3.6. Comparison of µ-FTIR Methods 351
4.4. Mapping, Imaging, and Photon Scanning Tunneling Microscopy 352
4.5. Temperature-and-Environment Programmed Chambers for In Situ Studies of Ultrathin Films on Bulk and Powdered Supports 356
4.6. Technical Aspects of In Situ IR Spectroscopy of Ultrathin Films at Solid-Liquid and Solid-Solid Interfaces 360
4.6.1. Transmission 361
4.6.2. In Situ IRRAS 363
4.6.3. ATR 369
4.6.4. Measurement Protocols for SEC Experiments 374
4.7. Polarization Modulation Spectroscopy 376
4.8. IRRAS of Air-Water Interface 381
4.9. Dynamic IR Spectroscopy 383
4.9.1. Time Domain 383
4.9.2. Frequency Domain: Potential-Modulation Spectroscopy 387
4.10. Preparation of Substrates 389
4.10.1. Cleaning of IREs 389
4.10.2. Metal Electrode and SEIRA Surfaces 391
4.10.3. BML Substrate 393
References 393
5 Infrared Spectroscopy of Thin Layers in Silicon Microelectronics 416
5.1. Thermal SiO 2 Layers 416
5.2. Low-Temperature SiO 2 Layers 421
5.3. Ultrathin SiO 2 Layers 427
5.4. Silicon Nitride, Oxynitride, and Carbon Nitride Layers 434
5.5. Amorphous Hydrogenated Films 439
5.5.1. a-Si:H Films 439
5.5.2. a-SiGe:H 444
5.5.3. a-SiC:H Films 445
5.6. Films of Amorphous Carbon, Boron Nitride, and Boron Carbide 446
5.6.1. Diamondlike Carbon 446
5.6.2. Boron Nitride and Carbide Films 448
5.7. Porous Silicon Layers 450
5.8. Other Dielectric Layers Used in Microelectronics 454
5.8.1. CaF 2 ,BaF 2 ,andSrF 2 Layers 454
5.8.2. GeO 2 Film 456
5.8.3. Metal Silicides 457
5.8.4. Amorphous Ta 2 O 5 Films 458
5.8.5. SrTiO 3 Film 458
5.8.6. Metal Nitrides 459
5.9. Multi- and Inhomogeneous Dielectric Layers: Layer-by-Layer Etching 460
References 465
6 Application of Infrared Spectroscopy to Analysis of Interfaces and Thin Dielectric Layers in Semiconductor Technology 476
6.1. Ultrathin Oxide Layers in Silicon Schottky-Type Solar Cells 476
6.2. Control of Thin Oxide Layers in Silicon MOS Devices 481
6.2.1. CVD Oxide Layers in Al-SiO X -Si Devices 482
6.2.2. Monitoring of Aluminum Corrosion Processes in Al-PSG Interface 484
6.2.3. Determination of Metal Film and Oxide Layer Thicknesses in MOS Devices 486
6.3. Modification of Oxides in Metal-Same-Metal Oxide-InP Devices 488
6.4. Dielectric Layers in Sandwiched Semiconductor Structures 492
6.4.1. Silicon-on-Insulator 492
6.4.2. Polycrystalline Silicon-c-Si Interface 493
6.4.3. SiO 2 Films in Bonded Si Wafers 494
6.4.4. Quantum Wells 495
6.5. IR Spectroscopy of Surface States at SiO 2 -Si Interface 497
6.6. In Situ Infrared Characterization of Si and SiO 2 Surfaces 502
6.6.1. Monitoring of CVD of SiO 2 502
6.6.2. Cleaning and Etching of Si Surfaces 504
6.6.3. Initial Stages of Oxidation of H-Terminated Si Surface 506
References 508
7 Ultrathin Films at Gas-Solid, Gas-Liquid, and Solid-Liquid Interfaces 514
7.1. IR Spectroscopic Study of Adsorption from Gaseous Phase: Catalysis 514
7.1.1. Adsorption on Powders 515
7.1.2. Adsorption on Bulk Metals 527
7.2. Native Oxides: Atmospheric Corrosion and Corrosion Inhibition 532
7.3. Adsorption on Flat Surfaces of Dielectrics and Semiconductors 542
7.4. Adsorption on Minerals: Comparison of Data Obtained In Situ and Ex Situ 547
7.4.1. Characterization of Mineral Surface after Grinding: Adsorption of Inorganic Species 547
7.4.2. Adsorption of Oleate on Calcium Minerals 551
7.4.3. Structure of Adsorbed Films of Long-Chain Amines on Silicates 554
7.4.4. Interaction of Xanthate with Sulfides 561
7.5. Electrochemical Reactions at Semiconducting Electrodes: Comparison of Different In Situ Techniques 570
7.5.1. Anodic Oxidation of Semiconductors 571
7.5.2. Anodic Reactions at Sulfide Electrodes in Presence of Xanthate 583
7.6. Static and Dynamic Studies of Metal Electrode-Electrolyte Interface: Structure of Double Layer 595
7.7. Thin Polymer Films, Polymer Surfaces, and Polymer-Substrate Interface 600
7.8. Interfacial Behavior of Biomolecules and Bacteria 613
7.8.1. Adsorption of Proteins and Model Molecules at Different Interfaces 614
7.8.2. Membranes 624
7.8.3. Adsorption of Biofilms 626
References 629
Appendix 669
References 687
Index 691
