VALERI P. TOLSTOY, PhD, is Professor in the Department of Solid State Chemistry at St. Petersburg State University. IRINA V. CHERNYSHOVA, PhD, is Professor in the Physics Department at St. Petersburg State Technical University. VALERI A. SKRYSHEVSKY, PhD, is Professor in the Radiophysics Department at National Shevchenko University.

"…Wiley InterScience, the publisher of many state-of-the-art science books, has enlarged our understanding of infrared (IR) spectroscopy significantly with this book." (Journal of Metals Online, March 31, 2005) “...interesting  for the polymer community...due to the wide range of subjects...and also for the completeness...” (Polymer News, Vol. 28, No. 11)

• Preface xiiiAcronyms and Symbols xixIntroduction xxv1 Absorption and Reflection of Infrared Radiation by Ultrathin Films 11.1. Macroscopic Theory of Propagation of Electromagnetic Waves in Infinite Medium 21.2. Modeling Optical Properties of a Material 101.3. Classical Dispersion Models of Absorption 131.4. Propagation of IR Radiation through Planar Interface between Two Isotropic Media 241.4.1. Transparent Media 261.4.2. General Case 291.5. Reflection of Radiation at Planar Interface Covered by Single Layer 311.6. Transmission of Layer Located at Interface between Two Isotropic Semi-infinite Media 391.7. System of Plane–Parallel Layers: Matrix Method 431.8. Energy Absorption in Layered Media 491.8.1. External Reflection: Transparent Substrates 501.8.2. External Reflection: Metallic Substrates 521.8.3. ATR 551.9. Effective Medium Theory 601.10. Diffuse Reflection and Transmission 65Appendix 68References 702 Optimum Conditions for Recording Infrared Spectra of Ultrathin Films 792.1. IR Transmission Spectra Obtained in Polarized Radiation 792.2. IRRAS Spectra of Layers on Metallic Surfaces (“Metallic” IRRAS) 842.3. IRRAS of Layers on Semiconductors and Dielectrics 872.3.1. Transparent and Weakly Absorbing Substrates (“Transparent” IRRAS) 872.3.2. Absorbing Substrates 902.3.3. Buried Metal Layer Substrates (BML-IRRAS) 942.4. ATR Spectra 1002.5. IR Spectra of Layers Located at Interface 1022.5.1. Transmission 1022.5.2. Metallic IRRAS 1052.5.3. Transparent IRRAS 1102.5.4. ATR 1112.6. Choosing Appropriate IR Spectroscopic Method for Layer on Flat Surface 1182.7. Coatings on Powders, Fibers, and Matte Surfaces 1202.7.1. Transmission 1202.7.2. Diffuse Transmittance and Diffuse Reflectance 1222.7.3. ATR 1282.7.4. Comparison of IR Spectroscopic Methods for Studying Ultrathin Films on Powders 130References 1333 Interpretation of IR Spectra of Ultrathin Films 1403.1. Dependence of Transmission, ATR, and IRRAS Spectra of Ultrathin Films on Polarization (Berreman Effect) 1413.2. Theory of Berreman Effect 1463.2.1. Surface Modes 1473.2.2. Modes in Ultrathin Films 1513.2.3. Identification of Berreman Effect in IR Spectra of Ultrathin Films 1573.3. Optical Effect: Film Thickness, Angle of Incidence, and Immersion 1593.3.1. Effect in “Metallic” IRRAS 1593.3.2. Effect in “Transparent” IRRAS 1643.3.3. Effect in ATR Spectra 1673.3.4. Effect in Transmission Spectra 1693.4. Optical Effect: Band Shapes in IRRAS as Function of Optical Properties of Substrate 1713.5. Optical Property Gradients at Substrate–Layer Interface: Effect on Band Intensities in IRRAS 1753.6. Dipole–Dipole Coupling 1793.7. Specific Features in Potential-Difference IR Spectra of Electrode–Electrolyte Interfaces 1873.7.1. Absorption Due to Bulk Electrolyte 1893.7.2. (Re)organization of Electrolyte in DL 1903.7.3. DonationBackdonation of Electrons 2023.7.4. Stark Effect 2023.7.5. Bipolar Bands 2033.7.6. Effect of Coadsorption 2053.7.7. Electronic Absorption 2063.7.8. Optical Effects 2103.8. Interpretation of Dynamic IR Spectra: Two-Dimensional Correlation Analysis 2123.9. IR Spectra of Inhomogeneous Films and Films on Powders and Rough Surfaces. Surface Enhancement 2193.9.1. Manifestation of Particle Shape in IR Spectra 2203.9.2. Coated Particles 2233.9.3. Composite, Porous, and Discontinuous Films 2253.9.4. Interpretation of IR Surface-Enhanced Spectra 2323.9.5. Rough Surfaces 2413.10. Determination of Optical Constants of Isotropic Ultrathin Films: Experimental Errors in Reflectivity Measurements 2433.11. Determination of Molecular Packing and Orientation in Ultrathin Films: Anisotropic Optical Constants of Ultrathin Films 2523.11.1. Order–Disorder Transition 2533.11.2. Packing and Symmetry of Ultrathin Films 2573.11.3. Orientation 2663.11.4. Surface Selection Rule for Dielectrics 2803.11.5. Optimum Conditions for MO Studies 282References 2844 Equipment and Techniques 3074.1. Techniques for Recording IR Spectra of Ultrathin Films on Bulk Samples 3084.1.1. Transmission and Multiple Transmission 3084.1.2. IRRAS 3134.1.3. ATR 3174.1.4. DRIFTS 3274.2. Techniques for Ultrathin Films on Powders and Fibers 3284.2.1. Transmission 3294.2.2. Diffuse Transmission 3314.2.3. Diffuse Reflectance 3344.2.4. ATR 3424.3. High-Resolution FTIR Microspectroscopy of Thin Films 3434.3.1. Transmission 3454.3.2. IRRAS 3464.3.3. DRIFTS and DTIFTS 3474.3.4. ATR 3484.3.5. Spatial Resolution and Smallest Sampling Area 3504.3.6. Comparison of µ-FTIR Methods 3514.4. Mapping, Imaging, and Photon Scanning Tunneling Microscopy 3524.5. Temperature-and-Environment Programmed Chambers for In Situ Studies of Ultrathin Films on Bulk and Powdered Supports 3564.6. Technical Aspects of In Situ IR Spectroscopy of Ultrathin Films at Solid–Liquid and Solid–Solid Interfaces 3604.6.1. Transmission 3614.6.2. In Situ IRRAS 3634.6.3. ATR 3694.6.4. Measurement Protocols for SEC Experiments 3744.7. Polarization Modulation Spectroscopy 3764.8. IRRAS of Air–Water Interface 3814.9. Dynamic IR Spectroscopy 3834.9.1. Time Domain 3834.9.2. Frequency Domain: Potential-Modulation Spectroscopy 3874.10. Preparation of Substrates 3894.10.1. Cleaning of IREs 3894.10.2. Metal Electrode and SEIRA Surfaces 3914.10.3. BML Substrate 393References 3935 Infrared Spectroscopy of Thin Layers in Silicon Microelectronics 4165.1. Thermal SiO 2 Layers 4165.2. Low-Temperature SiO 2 Layers 4215.3. Ultrathin SiO 2 Layers 4275.4. Silicon Nitride, Oxynitride, and Carbon Nitride Layers 4345.5. Amorphous Hydrogenated Films 4395.5.1. a-Si:H Films 4395.5.2. a-SiGe:H 4445.5.3. a-SiC:H Films 4455.6. Films of Amorphous Carbon, Boron Nitride, and Boron Carbide 4465.6.1. Diamondlike Carbon 4465.6.2. Boron Nitride and Carbide Films 4485.7. Porous Silicon Layers 4505.8. Other Dielectric Layers Used in Microelectronics 4545.8.1. CaF 2 ,BaF 2 ,andSrF 2 Layers 4545.8.2. GeO 2 Film 4565.8.3. Metal Silicides 4575.8.4. Amorphous Ta 2 O 5 Films 4585.8.5. SrTiO 3 Film 4585.8.6. Metal Nitrides 4595.9. Multi- and Inhomogeneous Dielectric Layers: Layer-by-Layer Etching 460References 4656 Application of Infrared Spectroscopy to Analysis of Interfaces and Thin Dielectric Layers in Semiconductor Technology 4766.1. Ultrathin Oxide Layers in Silicon Schottky-Type Solar Cells 4766.2. Control of Thin Oxide Layers in Silicon MOS Devices 4816.2.1. CVD Oxide Layers in Al–SiO X –Si Devices 4826.2.2. Monitoring of Aluminum Corrosion Processes in Al–PSG Interface 4846.2.3. Determination of Metal Film and Oxide Layer Thicknesses in MOS Devices 4866.3. Modification of Oxides in Metal–Same-Metal Oxide–InP Devices 4886.4. Dielectric Layers in Sandwiched Semiconductor Structures 4926.4.1. Silicon-on-Insulator 4926.4.2. Polycrystalline Silicon–c-Si Interface 4936.4.3. SiO 2 Films in Bonded Si Wafers 4946.4.4. Quantum Wells 4956.5. IR Spectroscopy of Surface States at SiO 2 –Si Interface 4976.6. In Situ Infrared Characterization of Si and SiO 2 Surfaces 5026.6.1. Monitoring of CVD of SiO 2 5026.6.2. Cleaning and Etching of Si Surfaces 5046.6.3. Initial Stages of Oxidation of H-Terminated Si Surface 506References 5087 Ultrathin Films at Gas–Solid, Gas–Liquid, and Solid–Liquid Interfaces 5147.1. IR Spectroscopic Study of Adsorption from Gaseous Phase: Catalysis 5147.1.1. Adsorption on Powders 5157.1.2. Adsorption on Bulk Metals 5277.2. Native Oxides: Atmospheric Corrosion and Corrosion Inhibition 5327.3. Adsorption on Flat Surfaces of Dielectrics and Semiconductors 5427.4. Adsorption on Minerals: Comparison of Data Obtained In Situ and Ex Situ 5477.4.1. Characterization of Mineral Surface after Grinding: Adsorption of Inorganic Species 5477.4.2. Adsorption of Oleate on Calcium Minerals 5517.4.3. Structure of Adsorbed Films of Long-Chain Amines on Silicates 5547.4.4. Interaction of Xanthate with Sulfides 5617.5. Electrochemical Reactions at Semiconducting Electrodes: Comparison of Different In Situ Techniques 5707.5.1. Anodic Oxidation of Semiconductors 5717.5.2. Anodic Reactions at Sulfide Electrodes in Presence of Xanthate 5837.6. Static and Dynamic Studies of Metal Electrode–Electrolyte Interface: Structure of Double Layer 5957.7. Thin Polymer Films, Polymer Surfaces, and Polymer–Substrate Interface 6007.8. Interfacial Behavior of Biomolecules and Bacteria 6137.8.1. Adsorption of Proteins and Model Molecules at Different Interfaces 6147.8.2. Membranes 6247.8.3. Adsorption of Biofilms 626References 629Appendix 669References 687Index 691

VALERI P. TOLSTOY, PhD, is Professor in the Department of Solid State Chemistry at St. Petersburg State University. IRINA V. CHERNYSHOVA, PhD, is Professor in the Physics Department at St. Petersburg State Technical University. VALERI A. SKRYSHEVSKY, PhD, is Professor in the Radiophysics Department at National Shevchenko University.

"…Wiley InterScience, the publisher of many state-of-the-art science books, has enlarged our understanding of infrared (IR) spectroscopy significantly with this book." (Journal of Metals Online, March 31, 2005) “...interesting  for the polymer community...due to the wide range of subjects...and also for the completeness...” (Polymer News, Vol. 28, No. 11)

• Preface xiiiAcronyms and Symbols xixIntroduction xxv1 Absorption and Reflection of Infrared Radiation by Ultrathin Films 11.1. Macroscopic Theory of Propagation of Electromagnetic Waves in Infinite Medium 21.2. Modeling Optical Properties of a Material 101.3. Classical Dispersion Models of Absorption 131.4. Propagation of IR Radiation through Planar Interface between Two Isotropic Media 241.4.1. Transparent Media 261.4.2. General Case 291.5. Reflection of Radiation at Planar Interface Covered by Single Layer 311.6. Transmission of Layer Located at Interface between Two Isotropic Semi-infinite Media 391.7. System of Plane–Parallel Layers: Matrix Method 431.8. Energy Absorption in Layered Media 491.8.1. External Reflection: Transparent Substrates 501.8.2. External Reflection: Metallic Substrates 521.8.3. ATR 551.9. Effective Medium Theory 601.10. Diffuse Reflection and Transmission 65Appendix 68References 702 Optimum Conditions for Recording Infrared Spectra of Ultrathin Films 792.1. IR Transmission Spectra Obtained in Polarized Radiation 792.2. IRRAS Spectra of Layers on Metallic Surfaces (“Metallic” IRRAS) 842.3. IRRAS of Layers on Semiconductors and Dielectrics 872.3.1. Transparent and Weakly Absorbing Substrates (“Transparent” IRRAS) 872.3.2. Absorbing Substrates 902.3.3. Buried Metal Layer Substrates (BML-IRRAS) 942.4. ATR Spectra 1002.5. IR Spectra of Layers Located at Interface 1022.5.1. Transmission 1022.5.2. Metallic IRRAS 1052.5.3. Transparent IRRAS 1102.5.4. ATR 1112.6. Choosing Appropriate IR Spectroscopic Method for Layer on Flat Surface 1182.7. Coatings on Powders, Fibers, and Matte Surfaces 1202.7.1. Transmission 1202.7.2. Diffuse Transmittance and Diffuse Reflectance 1222.7.3. ATR 1282.7.4. Comparison of IR Spectroscopic Methods for Studying Ultrathin Films on Powders 130References 1333 Interpretation of IR Spectra of Ultrathin Films 1403.1. Dependence of Transmission, ATR, and IRRAS Spectra of Ultrathin Films on Polarization (Berreman Effect) 1413.2. Theory of Berreman Effect 1463.2.1. Surface Modes 1473.2.2. Modes in Ultrathin Films 1513.2.3. Identification of Berreman Effect in IR Spectra of Ultrathin Films 1573.3. Optical Effect: Film Thickness, Angle of Incidence, and Immersion 1593.3.1. Effect in “Metallic” IRRAS 1593.3.2. Effect in “Transparent” IRRAS 1643.3.3. Effect in ATR Spectra 1673.3.4. Effect in Transmission Spectra 1693.4. Optical Effect: Band Shapes in IRRAS as Function of Optical Properties of Substrate 1713.5. Optical Property Gradients at Substrate–Layer Interface: Effect on Band Intensities in IRRAS 1753.6. Dipole–Dipole Coupling 1793.7. Specific Features in Potential-Difference IR Spectra of Electrode–Electrolyte Interfaces 1873.7.1. Absorption Due to Bulk Electrolyte 1893.7.2. (Re)organization of Electrolyte in DL 1903.7.3. DonationBackdonation of Electrons 2023.7.4. Stark Effect 2023.7.5. Bipolar Bands 2033.7.6. Effect of Coadsorption 2053.7.7. Electronic Absorption 2063.7.8. Optical Effects 2103.8. Interpretation of Dynamic IR Spectra: Two-Dimensional Correlation Analysis 2123.9. IR Spectra of Inhomogeneous Films and Films on Powders and Rough Surfaces. Surface Enhancement 2193.9.1. Manifestation of Particle Shape in IR Spectra 2203.9.2. Coated Particles 2233.9.3. Composite, Porous, and Discontinuous Films 2253.9.4. Interpretation of IR Surface-Enhanced Spectra 2323.9.5. Rough Surfaces 2413.10. Determination of Optical Constants of Isotropic Ultrathin Films: Experimental Errors in Reflectivity Measurements 2433.11. Determination of Molecular Packing and Orientation in Ultrathin Films: Anisotropic Optical Constants of Ultrathin Films 2523.11.1. Order–Disorder Transition 2533.11.2. Packing and Symmetry of Ultrathin Films 2573.11.3. Orientation 2663.11.4. Surface Selection Rule for Dielectrics 2803.11.5. Optimum Conditions for MO Studies 282References 2844 Equipment and Techniques 3074.1. Techniques for Recording IR Spectra of Ultrathin Films on Bulk Samples 3084.1.1. Transmission and Multiple Transmission 3084.1.2. IRRAS 3134.1.3. ATR 3174.1.4. DRIFTS 3274.2. Techniques for Ultrathin Films on Powders and Fibers 3284.2.1. Transmission 3294.2.2. Diffuse Transmission 3314.2.3. Diffuse Reflectance 3344.2.4. ATR 3424.3. High-Resolution FTIR Microspectroscopy of Thin Films 3434.3.1. Transmission 3454.3.2. IRRAS 3464.3.3. DRIFTS and DTIFTS 3474.3.4. ATR 3484.3.5. Spatial Resolution and Smallest Sampling Area 3504.3.6. Comparison of µ-FTIR Methods 3514.4. Mapping, Imaging, and Photon Scanning Tunneling Microscopy 3524.5. Temperature-and-Environment Programmed Chambers for In Situ Studies of Ultrathin Films on Bulk and Powdered Supports 3564.6. Technical Aspects of In Situ IR Spectroscopy of Ultrathin Films at Solid–Liquid and Solid–Solid Interfaces 3604.6.1. Transmission 3614.6.2. In Situ IRRAS 3634.6.3. ATR 3694.6.4. Measurement Protocols for SEC Experiments 3744.7. Polarization Modulation Spectroscopy 3764.8. IRRAS of Air–Water Interface 3814.9. Dynamic IR Spectroscopy 3834.9.1. Time Domain 3834.9.2. Frequency Domain: Potential-Modulation Spectroscopy 3874.10. Preparation of Substrates 3894.10.1. Cleaning of IREs 3894.10.2. Metal Electrode and SEIRA Surfaces 3914.10.3. BML Substrate 393References 3935 Infrared Spectroscopy of Thin Layers in Silicon Microelectronics 4165.1. Thermal SiO 2 Layers 4165.2. Low-Temperature SiO 2 Layers 4215.3. Ultrathin SiO 2 Layers 4275.4. Silicon Nitride, Oxynitride, and Carbon Nitride Layers 4345.5. Amorphous Hydrogenated Films 4395.5.1. a-Si:H Films 4395.5.2. a-SiGe:H 4445.5.3. a-SiC:H Films 4455.6. Films of Amorphous Carbon, Boron Nitride, and Boron Carbide 4465.6.1. Diamondlike Carbon 4465.6.2. Boron Nitride and Carbide Films 4485.7. Porous Silicon Layers 4505.8. Other Dielectric Layers Used in Microelectronics 4545.8.1. CaF 2 ,BaF 2 ,andSrF 2 Layers 4545.8.2. GeO 2 Film 4565.8.3. Metal Silicides 4575.8.4. Amorphous Ta 2 O 5 Films 4585.8.5. SrTiO 3 Film 4585.8.6. Metal Nitrides 4595.9. Multi- and Inhomogeneous Dielectric Layers: Layer-by-Layer Etching 460References 4656 Application of Infrared Spectroscopy to Analysis of Interfaces and Thin Dielectric Layers in Semiconductor Technology 4766.1. Ultrathin Oxide Layers in Silicon Schottky-Type Solar Cells 4766.2. Control of Thin Oxide Layers in Silicon MOS Devices 4816.2.1. CVD Oxide Layers in Al–SiO X –Si Devices 4826.2.2. Monitoring of Aluminum Corrosion Processes in Al–PSG Interface 4846.2.3. Determination of Metal Film and Oxide Layer Thicknesses in MOS Devices 4866.3. Modification of Oxides in Metal–Same-Metal Oxide–InP Devices 4886.4. Dielectric Layers in Sandwiched Semiconductor Structures 4926.4.1. Silicon-on-Insulator 4926.4.2. Polycrystalline Silicon–c-Si Interface 4936.4.3. SiO 2 Films in Bonded Si Wafers 4946.4.4. Quantum Wells 4956.5. IR Spectroscopy of Surface States at SiO 2 –Si Interface 4976.6. In Situ Infrared Characterization of Si and SiO 2 Surfaces 5026.6.1. Monitoring of CVD of SiO 2 5026.6.2. Cleaning and Etching of Si Surfaces 5046.6.3. Initial Stages of Oxidation of H-Terminated Si Surface 506References 5087 Ultrathin Films at Gas–Solid, Gas–Liquid, and Solid–Liquid Interfaces 5147.1. IR Spectroscopic Study of Adsorption from Gaseous Phase: Catalysis 5147.1.1. Adsorption on Powders 5157.1.2. Adsorption on Bulk Metals 5277.2. Native Oxides: Atmospheric Corrosion and Corrosion Inhibition 5327.3. Adsorption on Flat Surfaces of Dielectrics and Semiconductors 5427.4. Adsorption on Minerals: Comparison of Data Obtained In Situ and Ex Situ 5477.4.1. Characterization of Mineral Surface after Grinding: Adsorption of Inorganic Species 5477.4.2. Adsorption of Oleate on Calcium Minerals 5517.4.3. Structure of Adsorbed Films of Long-Chain Amines on Silicates 5547.4.4. Interaction of Xanthate with Sulfides 5617.5. Electrochemical Reactions at Semiconducting Electrodes: Comparison of Different In Situ Techniques 5707.5.1. Anodic Oxidation of Semiconductors 5717.5.2. Anodic Reactions at Sulfide Electrodes in Presence of Xanthate 5837.6. Static and Dynamic Studies of Metal Electrode–Electrolyte Interface: Structure of Double Layer 5957.7. Thin Polymer Films, Polymer Surfaces, and Polymer–Substrate Interface 6007.8. Interfacial Behavior of Biomolecules and Bacteria 6137.8.1. Adsorption of Proteins and Model Molecules at Different Interfaces 6147.8.2. Membranes 6247.8.3. Adsorption of Biofilms 626References 629Appendix 669References 687Index 691

VALERI P. TOLSTOY, PhD, is Professor in the Department of Solid State Chemistry at St. Petersburg State University. IRINA V. CHERNYSHOVA, PhD, is Professor in the Physics Department at St. Petersburg State Technical University. VALERI A. SKRYSHEVSKY, PhD, is Professor in the Radiophysics Department at National Shevchenko University.

"…Wiley InterScience, the publisher of many state-of-the-art science books, has enlarged our understanding of infrared (IR) spectroscopy significantly with this book." (Journal of Metals Online, March 31, 2005) “...interesting  for the polymer community...due to the wide range of subjects...and also for the completeness...” (Polymer News, Vol. 28, No. 11)

• Preface xiiiAcronyms and Symbols xixIntroduction xxv1 Absorption and Reflection of Infrared Radiation by Ultrathin Films 11.1. Macroscopic Theory of Propagation of Electromagnetic Waves in Infinite Medium 21.2. Modeling Optical Properties of a Material 101.3. Classical Dispersion Models of Absorption 131.4. Propagation of IR Radiation through Planar Interface between Two Isotropic Media 241.4.1. Transparent Media 261.4.2. General Case 291.5. Reflection of Radiation at Planar Interface Covered by Single Layer 311.6. Transmission of Layer Located at Interface between Two Isotropic Semi-infinite Media 391.7. System of Plane–Parallel Layers: Matrix Method 431.8. Energy Absorption in Layered Media 491.8.1. External Reflection: Transparent Substrates 501.8.2. External Reflection: Metallic Substrates 521.8.3. ATR 551.9. Effective Medium Theory 601.10. Diffuse Reflection and Transmission 65Appendix 68References 702 Optimum Conditions for Recording Infrared Spectra of Ultrathin Films 792.1. IR Transmission Spectra Obtained in Polarized Radiation 792.2. IRRAS Spectra of Layers on Metallic Surfaces (“Metallic” IRRAS) 842.3. IRRAS of Layers on Semiconductors and Dielectrics 872.3.1. Transparent and Weakly Absorbing Substrates (“Transparent” IRRAS) 872.3.2. Absorbing Substrates 902.3.3. Buried Metal Layer Substrates (BML-IRRAS) 942.4. ATR Spectra 1002.5. IR Spectra of Layers Located at Interface 1022.5.1. Transmission 1022.5.2. Metallic IRRAS 1052.5.3. Transparent IRRAS 1102.5.4. ATR 1112.6. Choosing Appropriate IR Spectroscopic Method for Layer on Flat Surface 1182.7. Coatings on Powders, Fibers, and Matte Surfaces 1202.7.1. Transmission 1202.7.2. Diffuse Transmittance and Diffuse Reflectance 1222.7.3. ATR 1282.7.4. Comparison of IR Spectroscopic Methods for Studying Ultrathin Films on Powders 130References 1333 Interpretation of IR Spectra of Ultrathin Films 1403.1. Dependence of Transmission, ATR, and IRRAS Spectra of Ultrathin Films on Polarization (Berreman Effect) 1413.2. Theory of Berreman Effect 1463.2.1. Surface Modes 1473.2.2. Modes in Ultrathin Films 1513.2.3. Identification of Berreman Effect in IR Spectra of Ultrathin Films 1573.3. Optical Effect: Film Thickness, Angle of Incidence, and Immersion 1593.3.1. Effect in “Metallic” IRRAS 1593.3.2. Effect in “Transparent” IRRAS 1643.3.3. Effect in ATR Spectra 1673.3.4. Effect in Transmission Spectra 1693.4. Optical Effect: Band Shapes in IRRAS as Function of Optical Properties of Substrate 1713.5. Optical Property Gradients at Substrate–Layer Interface: Effect on Band Intensities in IRRAS 1753.6. Dipole–Dipole Coupling 1793.7. Specific Features in Potential-Difference IR Spectra of Electrode–Electrolyte Interfaces 1873.7.1. Absorption Due to Bulk Electrolyte 1893.7.2. (Re)organization of Electrolyte in DL 1903.7.3. DonationBackdonation of Electrons 2023.7.4. Stark Effect 2023.7.5. Bipolar Bands 2033.7.6. Effect of Coadsorption 2053.7.7. Electronic Absorption 2063.7.8. Optical Effects 2103.8. Interpretation of Dynamic IR Spectra: Two-Dimensional Correlation Analysis 2123.9. IR Spectra of Inhomogeneous Films and Films on Powders and Rough Surfaces. Surface Enhancement 2193.9.1. Manifestation of Particle Shape in IR Spectra 2203.9.2. Coated Particles 2233.9.3. Composite, Porous, and Discontinuous Films 2253.9.4. Interpretation of IR Surface-Enhanced Spectra 2323.9.5. Rough Surfaces 2413.10. Determination of Optical Constants of Isotropic Ultrathin Films: Experimental Errors in Reflectivity Measurements 2433.11. Determination of Molecular Packing and Orientation in Ultrathin Films: Anisotropic Optical Constants of Ultrathin Films 2523.11.1. Order–Disorder Transition 2533.11.2. Packing and Symmetry of Ultrathin Films 2573.11.3. Orientation 2663.11.4. Surface Selection Rule for Dielectrics 2803.11.5. Optimum Conditions for MO Studies 282References 2844 Equipment and Techniques 3074.1. Techniques for Recording IR Spectra of Ultrathin Films on Bulk Samples 3084.1.1. Transmission and Multiple Transmission 3084.1.2. IRRAS 3134.1.3. ATR 3174.1.4. DRIFTS 3274.2. Techniques for Ultrathin Films on Powders and Fibers 3284.2.1. Transmission 3294.2.2. Diffuse Transmission 3314.2.3. Diffuse Reflectance 3344.2.4. ATR 3424.3. High-Resolution FTIR Microspectroscopy of Thin Films 3434.3.1. Transmission 3454.3.2. IRRAS 3464.3.3. DRIFTS and DTIFTS 3474.3.4. ATR 3484.3.5. Spatial Resolution and Smallest Sampling Area 3504.3.6. Comparison of µ-FTIR Methods 3514.4. Mapping, Imaging, and Photon Scanning Tunneling Microscopy 3524.5. Temperature-and-Environment Programmed Chambers for In Situ Studies of Ultrathin Films on Bulk and Powdered Supports 3564.6. Technical Aspects of In Situ IR Spectroscopy of Ultrathin Films at Solid–Liquid and Solid–Solid Interfaces 3604.6.1. Transmission 3614.6.2. In Situ IRRAS 3634.6.3. ATR 3694.6.4. Measurement Protocols for SEC Experiments 3744.7. Polarization Modulation Spectroscopy 3764.8. IRRAS of Air–Water Interface 3814.9. Dynamic IR Spectroscopy 3834.9.1. Time Domain 3834.9.2. Frequency Domain: Potential-Modulation Spectroscopy 3874.10. Preparation of Substrates 3894.10.1. Cleaning of IREs 3894.10.2. Metal Electrode and SEIRA Surfaces 3914.10.3. BML Substrate 393References 3935 Infrared Spectroscopy of Thin Layers in Silicon Microelectronics 4165.1. Thermal SiO 2 Layers 4165.2. Low-Temperature SiO 2 Layers 4215.3. Ultrathin SiO 2 Layers 4275.4. Silicon Nitride, Oxynitride, and Carbon Nitride Layers 4345.5. Amorphous Hydrogenated Films 4395.5.1. a-Si:H Films 4395.5.2. a-SiGe:H 4445.5.3. a-SiC:H Films 4455.6. Films of Amorphous Carbon, Boron Nitride, and Boron Carbide 4465.6.1. Diamondlike Carbon 4465.6.2. Boron Nitride and Carbide Films 4485.7. Porous Silicon Layers 4505.8. Other Dielectric Layers Used in Microelectronics 4545.8.1. CaF 2 ,BaF 2 ,andSrF 2 Layers 4545.8.2. GeO 2 Film 4565.8.3. Metal Silicides 4575.8.4. Amorphous Ta 2 O 5 Films 4585.8.5. SrTiO 3 Film 4585.8.6. Metal Nitrides 4595.9. Multi- and Inhomogeneous Dielectric Layers: Layer-by-Layer Etching 460References 4656 Application of Infrared Spectroscopy to Analysis of Interfaces and Thin Dielectric Layers in Semiconductor Technology 4766.1. Ultrathin Oxide Layers in Silicon Schottky-Type Solar Cells 4766.2. Control of Thin Oxide Layers in Silicon MOS Devices 4816.2.1. CVD Oxide Layers in Al–SiO X –Si Devices 4826.2.2. Monitoring of Aluminum Corrosion Processes in Al–PSG Interface 4846.2.3. Determination of Metal Film and Oxide Layer Thicknesses in MOS Devices 4866.3. Modification of Oxides in Metal–Same-Metal Oxide–InP Devices 4886.4. Dielectric Layers in Sandwiched Semiconductor Structures 4926.4.1. Silicon-on-Insulator 4926.4.2. Polycrystalline Silicon–c-Si Interface 4936.4.3. SiO 2 Films in Bonded Si Wafers 4946.4.4. Quantum Wells 4956.5. IR Spectroscopy of Surface States at SiO 2 –Si Interface 4976.6. In Situ Infrared Characterization of Si and SiO 2 Surfaces 5026.6.1. Monitoring of CVD of SiO 2 5026.6.2. Cleaning and Etching of Si Surfaces 5046.6.3. Initial Stages of Oxidation of H-Terminated Si Surface 506References 5087 Ultrathin Films at Gas–Solid, Gas–Liquid, and Solid–Liquid Interfaces 5147.1. IR Spectroscopic Study of Adsorption from Gaseous Phase: Catalysis 5147.1.1. Adsorption on Powders 5157.1.2. Adsorption on Bulk Metals 5277.2. Native Oxides: Atmospheric Corrosion and Corrosion Inhibition 5327.3. Adsorption on Flat Surfaces of Dielectrics and Semiconductors 5427.4. Adsorption on Minerals: Comparison of Data Obtained In Situ and Ex Situ 5477.4.1. Characterization of Mineral Surface after Grinding: Adsorption of Inorganic Species 5477.4.2. Adsorption of Oleate on Calcium Minerals 5517.4.3. Structure of Adsorbed Films of Long-Chain Amines on Silicates 5547.4.4. Interaction of Xanthate with Sulfides 5617.5. Electrochemical Reactions at Semiconducting Electrodes: Comparison of Different In Situ Techniques 5707.5.1. Anodic Oxidation of Semiconductors 5717.5.2. Anodic Reactions at Sulfide Electrodes in Presence of Xanthate 5837.6. Static and Dynamic Studies of Metal Electrode–Electrolyte Interface: Structure of Double Layer 5957.7. Thin Polymer Films, Polymer Surfaces, and Polymer–Substrate Interface 6007.8. Interfacial Behavior of Biomolecules and Bacteria 6137.8.1. Adsorption of Proteins and Model Molecules at Different Interfaces 6147.8.2. Membranes 6247.8.3. Adsorption of Biofilms 626References 629Appendix 669References 687Index 691