...1 1 Fundamentals of Semiconductor Electrochemistry and Photoelectrochemistry Krishnan Rajeshwar The University of Texas at Arlington, Arlington, Texas 1.1 1.2 1.3 1.3.1 1.3.2 1.3.3 1.3.4 1.4 1.4.1 1.4.2 1.4.3 1.5 1.5.1 1.5.2 1.5.3 1.5.4 1.5.5 1.6 1.7 1.7.1 1.7.2 1.7.3 1.7.4 1.7.5 Introduction and Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Electron Energy Levels in Semiconductors and Energy Band Model . The Semiconductor–Electrolyte Interface at Equilibrium . . . . . . . . The Equilibration Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The Depletion Layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Mapping of the Semiconductor Band-edge Positions Relative to Solution Redox Levels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Surface States and Other Complications . . . . . . . . . . . . . . . . . . . Charge Transfer Processes in the Dark . . . . . . . . . . . . . . . . . . . . Current-potential Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . Dark Processes Mediated by Surface States or by Space Charge Layer Recombination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Rate-limiting Steps in Charge Transfer Processes in the Dark . . . . . Light Absorption by the Semiconductor Electrode and Carrier Collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Light Absorption...
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