Semiconductor Electrochemistry -- Contents -- Preface to the Second Edition -- Preface -- 1 Principles of Semiconductor Physics -- 1.1 Crystal Structure -- 1.2 Energy Levels in Solids -- 1.3 Optical Properties -- 1.4 Density of States and Carrier Concentrations -- 1.4.1 Intrinsic Semiconductors -- 1.4.2 Doped Semiconductors -- 1.5 Carrier Transport Phenomena -- 1.6 Excitation and Recombination of Charge Carriers -- 1.7 Fermi Levels under Nonequilibrium Conditions -- 2 Semiconductor Surfaces and Solid-Solid Junctions -- 2.1 Metal and Semiconductor Surfaces in a Vacuum -- 2.2 Metal-Semiconductor Contacts (Schottky Junctions) -- 2.2.1 Barrier Heights -- 2.2.2 Majority Carrier Transfer Processes -- 2.2.3 Minority Carrier Transfer Processes -- 2.3 p-n Junctions -- 2.4 Ohmic Contacts -- 2.5 Photovoltages and Photocurrents -- 2.6 Surface Recombination -- 3 Electrochemical Systems -- 3.1 Electrolytes -- 3.1.1 Ion Transport in Solutions -- 3.1.2 Interaction between Ions and Solvent -- 3.2 Potentials and Thermodynamics of Electrochemical Cells -- 3.2.1 Chemical and Electrochemical Potentials -- 3.2.2 Cell Voltages -- 3.2.3 Reference Potentials -- 3.2.4 Standard Potential and Fermi Level of Redox Systems -- 4 Experimental Techniques -- 4.1 Electrode Preparation -- 4.2 Current-Voltage Measurements -- 4.2.1 Voltametry -- 4.2.2 Photocurrent Measurements -- 4.2.3 Rotating Ring Disk Electrodes -- 4.2.4 Scanning Electrochemical Microscopy (SECM) -- 4.3 Measurements of Surface Recombination and Minority Carrier Injection -- 4.4 Impedance Measurements -- 4.4.1 Basic Rules and Techniques -- 4.4.2 Evaluation of Impedance Spectra -- 4.4.3 Intensity Modulated Photocurrent Spectroscopy (IMPS) -- 4.5 Surface Conductivity Measurement -- 4.6 Flash Photolysis Investigations -- 4.7 Surface Science Techniques -- 4.7.1 Spectroscopic Methods.

4.7.2 In situ Surface Microscopy (STM and AFM) -- 5 Solid-Liquid Interface -- 5.1 Structure of the Interface and Adsorption -- 5.2 Charge and Potential Distribution at the Interface -- 5.2.1 The Helmholtz Double Layer -- 5.2.2 Gouy Layer in the Electrolyte -- 5.2.3 Space Charge Layer in the Semiconductor -- 5.2.4 Charge Distribution in Surface States -- 5.3 Analysis of the Potential Distribution -- 5.3.1 Germanium Electrodes -- 5.3.2 Silicon Electrodes -- 5.3.3 Compound Semiconductor Electrodes -- 5.3.4 Flatband Potential and Position of Energy Bands at the Interface -- 5.3.5 Unpinning of Energy Bands during Illumination -- 5.4 Modification of Semiconductor Surfaces -- 6 Electron Transfer Theories -- 6.1 The Theory of Marcus -- 6.1.1 Electron Transfer in Homogeneous Solutions -- 6.1.2 The Reorganization Energy -- 6.1.3 Adiabatic and Nonadiabatic Reactions -- 6.1.4 Electron Transfer Processes at Electrodes -- 6.2 The Gerischer Model -- 6.2.1 Energy States in Solution -- 6.2.2 Electron Transfer -- 6.3 Quantum Mechanical Treatments of Electron Transfer Processes -- 6.3.1 Introductory Comments -- 6.3.2 Nonadiabatic Reactions -- 6.3.3 Adiabatic Reactions -- 6.4 The Problem of Deriving Rate Constants -- 6.5 Comparison of Theories -- 7 Charge Transfer Processes at the Semiconductor-Liquid Interface -- 7.1 Charge Transfer Processes at Metal Electrodes -- 7.1.1 Kinetics of Electron Transfer at the Metal-Liquid Interface -- 7.1.2 Diffusion-controlled Processes -- 7.1.3 Investigations of Redox Reactions by Linear Sweep Voltametry -- 7.1.4 Criteria for Reversible and Irreversible Reactions -- 7.2 Qualitative Description of Current-Potential Curves at Semiconductor Electrodes -- 7.3 One-step Redox Reactions -- 7.3.1 The Energetics of Charge Transfer Processes -- 7.3.2 Quantitative Derivation of Current-Potential Curves -- 7.3.3 Light-Induced Processes.

7.3.4 Majority Carrier Reactions -- 7.3.5 Minority Carrier Reactions -- 7.3.6 Electron Transfer in the "Inverted Region" -- 7.4 The Quasi-Fermi-Level Concept -- 7.4.1 Basic Model -- 7.4.2 Application of the Concept to Photocurrents -- 7.4.3 Consequences for the Relation between Impedance and IMPS Spectra -- 7.4.4 Quasi-Fermi-Level Positions under High-Level Injections -- 7.5 Determination of the Reorganization Energy -- 7.6 Two-step Redox Processes -- 7.7 Photoluminescence and Electroluminescence -- 7.7.1 Kinetic Studies by Photoluminescence Measurement -- 7.7.2 Electroluminescence Induced by Minority Carrier Injection -- 7.8 Hot Carrier Processes -- 7.9 Catalysis of Electrode Reactions -- 8 Electrochemical Decomposition of Semiconductors -- 8.1 Anodic Dissolution Reactions -- 8.1.1 Germanium -- 8.1.2 Silicon -- 8.1.3 Compound Semiconductors -- 8.2 Cathodic Decomposition -- 8.3 Dissolution under Open Circuit Conditions -- 8.4 Energetics and Thermodynamics of Corrosion -- 8.5 Competition between Redox Reaction and Anodic Dissolution -- 8.6 Formation of Porous Semiconductor Surfaces -- 9 Photoreactions at Semiconductor Particles -- 9.1 Quantum Size Effects -- 9.1.1 Quantum Dots -- 9.1.2 Single Crystalline Quantum Films and Superlattices -- 9.1.3 Size Quantized Nanocrystalline Films -- 9.2 Charge Transfer Processes at Semiconductor Particles -- 9.2.1 Reactions in Suspensions and Colloidal Solutions -- 9.2.2 Photoelectron Emission -- 9.2.3 Comparison between Reactions at Semiconductor Particles and at Compact Electrodes -- 9.2.4 The Role of Surface Chemistry -- 9.2.5 Enhanced Redox Chemistry in Quantized Colloids -- 9.2.6 Reaction Routes at Small and Big Particles -- 9.2.7 Sandwich Formation between Different Particles and between Particle and Electrode -- 9.3 Charge Transfer Processes at Quantum Well Electrodes (MQW, SQW).

9.4 Photoelectrochemical Reactions at Nanocrystalline Semiconductor Layers -- 9.4.1 Impact Ionization and Carrier Multiplication -- 9.4.2 Hot Carrier Cooling and Exciton Multiplication in Quantum Dots -- 9.4.3 Multiple Exciton Collection in a Sensitized Photovoltaic System -- 10 Electron Transfer Processes between Excited Molecules and Semiconductor Electrodes -- 10.1 Energy Levels of Excited Molecules -- 10.2 Reactions at Semiconductor Electrodes -- 10.2.1 Spectra of Sensitized Photocurrents -- 10.2.2 Dye Molecules Adsorbed on the Electrode and in Solution -- 10.2.3 Potential Dependence of Sensitization Currents -- 10.2.4 Sensitization Processes at Semiconductor Surfaces Modified by Dye Monolayers -- 10.2.5 Quantum Efficiencies, Regeneration, and Supersensitization -- 10.2.6 Kinetics of Electron Transfer between Dye and Semiconductor Electrode -- 10.2.7 Sensitization Processes at Nanocrystalline Semiconductor Electrodes -- 10.3 Comparison with Reactions at Metal Electrodes -- 10.4 Production of Excited Molecules by Electron Transfer -- 11 Applications -- 11.1 Photoelectrochemical Solar Energy Conversion -- 11.1.1 Electrochemical Photovoltaic Cells -- 11.1.2 Photoelectrolysis -- 11.1.3 Photoreduction of CO2 -- 11.2 Photocatalytic Processes -- 11.2.1 Photodegradation of Pollutants -- 11.2.2 Photocatalytic Reactions -- 11.2.3 Light-Induced Chemical Reactions -- 11.3 Etching of Semiconductors -- 11.4 Light-Induced Metal Deposition -- Appendices -- A.1 List of Major Symbols -- A.2 Physical Constants -- A.3 Lattice Parameters of Semiconductors -- A.4 Properties of Important Semiconductors -- A.5 Effective Density of States and Intrinsic Carrier Densities -- A.6 Major Redox Systems and Corresponding Standard Potentials -- A.6.1 Aqueous Solutions -- A.6.2 In Acetonitrile (vs Ag/AgCl) -- A.7 Potentials of Reference Electrodes -- References -- Index.