Electrochemistry at Semiconductor and Oxidized Metal Electrodes

1. The Solid and the Solution.- 1.1. The Solid.- 1.1.1. Donors, Acceptors, and Traps.- 1.1.2. Energy Levels at the Surface.- 1.1.3. Conductance in Solids.- 1.2. The Solution.- 1.2.1. Introduction.- 1.2.2. The Electrode Fermi Energy as a Function of the Redox Couples in Solution.- 1.2.3. The Relation between the Hydrogen and the Vacuum Scales of Energy.- 1.2.4. Fluctuating Energy Levels in Solution.- 1.2.5. The Energy Levels Associated with Two-Equivalent Ions.- 1.2.6. Conductance in Liquids.- 2. The Solid/Liquid Interface.- 2.1. Surface Ions and Their Energy Levels.- 2.1.1. Adsorption.- 2.1.2. Surface States at the Solid/Liquid Interface.- 2.2. Double Layers at the Solid/Liquid Interface.- 2.2.1. General.- 2.2.2. The Gouy Layer.- 2.2.3. The Helmholtz Double Layer.- 2.2.4. The Space Charge Double Layer in the Semiconductor.- 2.3. Theoretical Predictions of the Energy Levels of Band Edges.- 2.4. The Band Model of the Solid/Solution Interface.- 3. Theory of Electron and Hole Transfer.- 3.1. Introduction.- 3.1.1. General.- 3.1.2. The Activation Energy in Electrode Reactions.- 3.2. Classical Model.- 3.3. The Energy Level Model of Charge Transfer.- 3.3.1. General.- 3.3.2. The Metal Electrode.- 3.3.3. The Semiconductor Electrode.- 3.4. Qualitative Description of Electrode Processes Using the Band Model.- 3.4.1. The Behavior of the Metal Electrode.- 3.4.2. The Behavior of the Semiconductor Electrode.- 3.4.3. The Transition between Semiconductor and Metallic Behavior.- 4. Measurement Techniques.- 4.1. Capacity Measurements.- 4.1.1. Introduction.- 4.1.2. Measurement Theory.- 4.1.3. Analysis.- 4.1.4. Complex Mott-Schottky Plots.- 4.1.5. Determination of Band Edges.- 4.2. Measurements of the Current/Voltage Characteristics.- 4.2.1. General Techniques Voltammetry.- 4.2.2. Rotating Electrodes.- 4.2.3. Illumination.- 4.3. Other Techniques.- 4.3.1. Techniques for Vs Measurement.- 4.3.2. Techniques to Determine Surface Species or Phases.- 4.3.3. Techniques to Study Electrode Reactions.- 5. The Properties of the Electrode and Their Effect on Electrochemical Measurements.- 5.1. The Behavior of the Perfect Crystal.- 5.1.1. The Helmholtz Double Layer: The Surface Charges on the Electrode.- 5.1.2. The Space Charge Region of the Perfect Crystal.- 5.2. The Behavior of Electrode Defects.- 5.2.1. Introduction.- 5.2.2. Deviations of Mott-Schottky Plots Due to Bulk Flaws.- 5.2.3. Current Flow Associated with Bulk Flaws.- 5.3. Observed Flat Band Potentials for Various Semiconductors.- 6. Observations of Charge Transfer at an Inert Semiconductor Electrode.- 6.1. Introduction.- 6.2. Majority Carrier Capture.- 6.2.1. Direct Carrier Transfer to Ions in Solution.- 6.2.2. Indirect Electron Transfer to Ions in Solution.- 6.3. Minority Carrier Capture.- 6.3.1. Minority Carrier Capture on Two-Equivalent Species: Radical Formation and Current Doubling.- 6.3.2. Minority Carrier Capture by One-Equivalent Ions.- 6.3.3. Photocatalysis.- 6.4. Intrinsic Surface States and Recombination Centers.- 6.4.1. Intrinsic Surface States as Carrier Transfer Centers.- 6.4.2. Intrinsic Surface States and Ions in Solution as Recombination Centers.- 6.5. Carrier Injection.- 6.5.1. Direct Electron and Hole Injection.- 6.5.2. Injection by Tunneling.- 6.5.3. Injection by Optically Excited Ions: Dye Injection.- 6.6. High-Current, High-Voltage Processes.- 6.6.1. Introduction.- 6.6.2. High Currents with Accumulation Layers.- 6.6.3. Tunneling and Breakdown on Non-Transition-Metal Semiconductors.- 6.6.4. Practical Electrodes.- 6.7. Analysis of Complicated Electrode Reactions using the Tools of Semiconductor Electrochemistry.- 6.7.1. The Photocatalytic Oxidation of Formic Acid.- 6.7.2. Analysis of the Energy Levels of Two-Equivalent Species.- 6.7.3. The Reduction of Iodine on CdS.- 7. Chemical Transformation in the Electrode Reaction.- 7.1. Introduction.- 7.2. Inner Sphere Changes during Redox Reactions at an Inert Electrode.- 7.3. Adsorption onto and Absorption into the Electrode.- 7.3.1. Adsorption of Water, Hydrogen, and Oxygen.- 7.3.2. Adsorption of Electrolyte Ions.- 7.3.3. Action of Deposited Species.- 7.3.4. Movement of Impurities and Defects into the Electrode.- 7.4. Corrosion.- 7.4.1. Introduction.- 7.4.2. Theory and Observations of Semiconductor Corrosion.- 7.4.3. Stabilizing Agents to Prevent Corrosion.- 8. Coated Electrodes.- 8.1. Introduction.- 8.1.1. The Band Model for Oxide Films.- 8.1.2. Thin Films.- 8.1.3. The Structure of Thick Films.- 8.2. Current Transport through Oxide Films.- 8.2.1. Thin Oxide Layers.- 8.2.2. Model of Electronic Conduction through Thick Coherent Layers.- 8.2.3. Semiconducting Oxide Layers on Metal Electrodes.- 8.2.4. Insulating Layers on Metal and Semiconductor Electrodes.- 8.3. Deposition of Reaction Products on Semiconductor Electrodes.- 9. Applications of Semiconductor Electrodes.- 9.1. Solar Energy Conversion.- 9.1.1. Introduction.- 9.1.2. Photovoltaic Cells.- 9.1.3. Conversion of Optical to Chemical Energy.- 9.1.4. Corrosion of PEC Cells.- 9.1.5. The Future Potential of PEC Solar Cells.- 9.2. Electrocatalysis on Semiconductors.- 9.2.1. General.- 9.2.2. Surface State Additives and Narrow Bands in Electrocatalysis.- 9.3. New Devices.- 9.4. Electropolishing of Semiconductors.- References.- References to Review Articles and Books.- Author Index.