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Fundamentals of Semiconductor
Electrochemistry and
Photoelectrochemistry
Krishnan Rajeshwar
The University of Texas at Arlington, Arlington, Texas
Introduction and Scope ............................... 3
Electron Energy Levels in Semiconductors and Energy Band Model . 4
The Semiconductor–Electrolyte Interface at Equilibrium ........ 8
The Equilibration Process ............................. 8
The Depletion Layer ................................. 9
Mapping of the Semiconductor Band-edge Positions Relative to
Solution Redox Levels ................................ 11
Surface States and plications ................... 15
Charge Transfer Processes in the Dark .................... 16
Current-potential Behavior ............................ 16
Dark Processes Mediated by Surface States or by Space Charge Layer
bination .................................... 20
Rate-limiting Steps in Charge Transfer Processes in the Dark ..... 23
Light Absorption by the Semiconductor Electrode and Carrier
Collection ........................................ 25
Light Absorption and Carrier Generation ................... 25
Carrier Collection .................................. 25
Photocurrent-potential Behavior ......................... 29
Dynamics of Photoinduced Charge Transfer ................. 33
Hot Carrier Transfer ................................ 34
Multielectron Photoprocesses .......................... 34
Nanocrystalline Semiconductor Films and Size Quantization ..... 36
Introductory Remarks ............................... 36
The Nanocrystalline Film–Electrolyte Interface and Charge Storage
Behavior in the Dark ................................ 36
Photoexcitation and Carrier Collection: Steady State Behavior ..... 38
Photoexcitation and Carrier Collection: Dynamic Behavior ....... 40
Size Quantization ...............