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Handbook of Infrared Spectroscopy of Ultrathin Films

Handbook of Infrared Spectroscopy of Ultrathin Films

Valeri P. Tolstoy, Irina Chernyshova, Valeri A. Skryshevsky

ISBN: 978-0-471-46183-8

Jul 2003

710 pages



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

Acronyms and Symbols.


1. Absorption and Reflection of Infrared Radiation by.Ultrathin Films.

1.1. Macroscopic Theory of Propagation of Electromagnetic.Waves in Infinite Medium.

1.2. Modeling Optical Properties of a Material.

1.3. Classical Dispersion Models of Absorption.

1.4. Propagation of IR Radiation through Planar Interface between Two Isotropic Media.

1.4.1. Transparent Media.

1.4.2. General Case.

1.5. Reflection of Radiation at Planar Interface Covered by Single Layer

1.6. Transmission of Layer Located at Interface between Two Isotropic Semi-infinite Media.

1.7. System of Plane–Parallel Layers: Matrix Method.

1.8. Energy Absorption in Layered Media.

1.8.1. External Reflection: Transparent Substrates.

1.8.2. External Reflection: Metallic Substrates.

1.8.3. ATR.

1.9. Effective Medium Theory.

1.10. Diffuse Reflection and Transmission.



2. Optimum Conditions for Recording Infrared Spectra of Ultrathin Films.

2.1. IR Transmission Spectra Obtained in Polarized Radiation.

2.2. IRRAS Spectra of Layers on Metallic Surfaces (“Metallic” IRRAS).

2.3. IRRAS of Layers on Semiconductors and Dielectrics.

2.3.1. Transparent and Weakly Absorbing Substrates (“Transparent” IRRAS).

2.3.2. Absorbing Substrates.

2.3.3. Buried Metal Layer Substrates (BML-IRRAS).

2.4. ATR Spectra.

2.5. IR Spectra of Layers Located at Interface.

2.5.1. Transmission.

2.5.2. Metallic IRRAS.

2.5.3. Transparent IRRAS.

2.5.4. ATR.

2.6. Choosing Appropriate IR Spectroscopic Method for Layer on Flat Surface.

2.7. Coatings on Powders, Fibers, and Matte Surfaces.

2.7.1. Transmission.

2.7.2. Diffuse Transmittance and Diffuse Reflectance.

2.7.3. ATR.

2.7.4. Comparison of IR Spectroscopic Methods for Studying Ultrathin Films on Powders.


3. Interpretation of IR Spectra of Ultrathin Films.

3.1. Dependence of Transmission, ATR, and IRRAS Spectra of Ultrathin Films on Polarization (Berreman Effect).

3.2. Theory of Berreman Effect.

3.2.1. Surface Modes.

3.2.2. Modes in Ultrathin Films.

3.2.3. Identification of Berreman Effect in IR Spectra of Ultrathin Films.

3.3. Optical Effect: Film Thickness, Angle of Incidence, and Immersion.

3.3.1. Effect in “Metallic” IRRAS.

3.3.2. Effect in “Transparent” IRRAS.

3.3.3. Effect in ATR Spectra.

3.3.4. Effect in Transmission Spectra.

3.4. Optical Effect: Band Shapes in IRRAS as Function of Optical Properties of Substrate.

3.5. Optical Property Gradients at Substrate–Layer Interface: Effect on Band Intensities in IRRAS.

3.6. Dipole–Dipole Coupling.

3.7. Specific Features in Potential-Difference IR Spectra of Electrode–Electrolyte Interfaces.

3.7.1. Absorption Due to Bulk Electrolyte.

3.7.2. (Re)organization of Electrolyte in DL.

3.7.3. Donation/Backdonation of Electrons.

3.7.4. Stark Effect.

3.7.5. Bipolar Bands.

3.7.6. Effect of Coadsorption.

3.7.7. Electronic Absorption.

3.7.8. Optical Effect.

3.8. Interpretation of Dynamic IR Spectra: Two-Dimensional Correlation Analysis.

3.9. IR Spectra of Inhomogeneous Films and Films on Powders and Rough Surfaces. Surface Enhancement.

3.9.1. Manifestation of Particle Shape in IR Spectra.

3.9.2. Coated Particles.

3.9.3. Composite, Porous, and Discontinuous Films.

3.9.4. Interpretation of IR Surface-Enhanced Spectra.

3.9.5. Rough Surfaces.

3.10. Determination of Optical Constants of Isotropic Ultrathin Films: Experimental Errors in Reflectivity.Measurements.

3.11. Determination of Molecular Packing and Orientation in Ultrathin Films: Anisotropic Optical Constants of Ultrathin Films.

3.11.1. Order–Disorder Transition.

3.11.2. Packing and Symmetry of Ultrathin Films.

3.11.3. Orientation.

3.11.4. Surface Selection Rule for Dielectrics.

3.11.5. Optimum Conditions for MO Studies.


4. Equipment and Techniques 307.

4.1. Techniques for Recording IR Spectra of Ultrathin Films on Bulk Samples.

4.1.1. Transmission and Multiple Transmission.

4.1.2. IRRAS.

4.1.3. ATR.

4.1.4. DRIFTS.

4.2. Techniques for Ultrathin Films on Powders and Fibers.

4.2.1. Transmission.

4.2.2. Diffuse Transmission.

4.2.3. Diffuse Reflectance.

4.2.4. ATR.

4.3. High-Resolution FTIR Microspectroscopy of Thin Films.

4.3.1. Transmission.

4.3.2. IRRAS.

4.3.3. DRIFTS and DTIFTS.

4.3.4. ATR.

4.3.5. Spatial Resolution and Smallest Sampling Area.

4.3.6. Comparison of µ-FTIR Methods.

4.4. Mapping, Imaging, and Photon Scanning Tunneling Microscopy.

4.5. Temperature-and-Environment Programmed Chambers for In Situ Studies of Ultrathin Films on Bulk and Powdered Supports.

4.6. Technical Aspects of In Situ IR Spectroscopy of Ultrathin Films at Solid–Liquid and Solid–Solid Interfaces.

4.6.1. Transmission.

4.6.2. In Situ IRRAS.

4.6.3. ATR.

4.6.4. Measurement Protocols for SEC Experiments.

4.7. Polarization Modulation Spectroscopy.

4.8. IRRAS of Air–Water Interface.

4.9. Dynamic IR Spectroscopy.

4.9.1. Time Domain.

4.9.2. Frequency Domain: Potential-Modulation Spectroscopy.

4.10. Preparation of Substrates.

4.10.1. Cleaning of IREs.

4.10.2. Metal Electrode and SEIRA Surfaces.

4.10.3. BML Substrate.


5. Infrared Spectroscopy of Thin Layers in Silicon Microelectronics.

5.1. Thermal SiO2 Layers.

5.2. Low-Temperature SiO2 Layers.

5.3. Ultrathin SiO2 Layers.

5.4. Silicon Nitride, Oxynitride, and Carbon Nitride Layers.

5.5. Amorphous Hydrogenated Films.

5.5.1. a-Si:H Films.

5.5.2. a-SiGe:H.

5.5.3. a-SiC:H Films.

5.6. Films of Amorphous Carbon, Boron Nitride, and Boron Carbide.

5.6.1. Diamondlike Carbon.

5.6.2. Boron Nitride and Carbide Films.

5.7. Porous Silicon Layers.

5.8. Other Dielectric Layers Used in Microelectronics.

5.8.1. CaF2, BaF2, and SrF2 Layers.

5.8.2. GeO2 Film.

5.8.3. Metal Silicides.

5.8.4. Amorphous Ta2O5 Films.

5.8.5. SrTiO3 Film.

5.8.6. Metal Nitrides.

5.9. Multi- and Inhomogeneous Dielectric Layers: Layer-by-Layer Etching.


6. Application of Infrared Spectroscopy to Analysis of Interfaces and Thin Dielectric Layers in Semiconductor Technology.

6.1. Ultrathin Oxide Layers in Silicon Schottky-Type Solar Cells.

6.2. Control of Thin Oxide Layers in Silicon MOS Devices.

6.2.1. CVD Oxide Layers in Al–SiOx –Si Devices.

6.2.2. Monitoring of Aluminum Corrosion Processes in Al–PSG Interface.

6.2.3. Determination of Metal Film and Oxide Layer Thicknesses in MOS Devices.

6.3. Modification of Oxides in Metal–Same-Metal Oxide–InP Devices.

6.4. Dielectric Layers in Sandwiched Semiconductor Structures.

6.4.1. Silicon-on-Insulator.

6.4.2. Polycrystalline Silicon–c-Si Interface.

6.4.3. SiO2 Films in Bonded Si Wafers.

6.4.4. Quantum Wells.

6.5. IR Spectroscopy of Surface States at SiO2 –Si Interface.

6.6. In Situ Infrared Characterization of Si and SiO2 Surfaces.

6.6.1. Monitoring of CVD of SiO2.

6.6.2. Cleaning and Etching of Si Surfaces.

6.6.3. Initial Stages of Oxidation of H-Terminated Si Surface.


7. Ultrathin Films at Gas–Solid, Gas–Liquid, and Solid–Liquid Interfaces.

7.1. IR Spectroscopic Study of Adsorption from Gaseous Phase: Catalysis.

7.1.1. Adsorption on Powders.

7.1.2. Adsorption on Bulk Metals.

7.2. Native Oxides: Atmospheric Corrosion and Corrosion Inhibition.

7.3. Adsorption on Flat Surfaces of Dielectrics and Semiconductors.

7.4. Adsorption on Minerals: Comparison of Data Obtained In Situ and Ex Situ.

7.4.1. Characterization of Mineral Surface after Grinding: Adsorption of Inorganic Species.

7.4.2. Adsorption of Oleate on Calcium Minerals.

7.4.3. Structure of Adsorbed Films of Long-Chain Amines on Silicates.

7.4.4. Interaction of Xanthate with Sulfides.

7.5. Electrochemical Reactions at Semiconducting Electrodes: Comparison of Different In Situ Techniques.

7.5.1. Anodic Oxidation of Semiconductors

7.5.2. Anodic Reactions at Sulfide Electrodes in Presence of Xanthate.

7.6. Static and Dynamic Studies of Metal Electrode–Electrolyte Interface: Structure of Double Layer.

7.7. Thin Polymer Films, Polymer Surfaces, and Polymer–Substrate Interface.

7.8. Interfacial Behavior of Biomolecules and Bacteria.

7.8.1. Adsorption of Proteins and Model Molecules at Different Interfaces.

7.8.2. Membranes.

7.8.3. Adsorption of Biofilms.





"…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)