Abstract
The dominant interpretative framework within which semiconductor electrochemical studies have been carried out since the very earliest papers of Brattain and Garrett1 is that of the ideal metal/semiconductor interface. This framework has been tested most thoroughly for extrinsically doped semiconductors held at reverse bias, for which the majority carriers are attracted away from the interface toward the bulk of the semiconductor. The result is a layer, usually many hundreds of angstroms thick, which possesses an electrostatic charge owing to the uncompensated ionized extrinsic dopant sites and in which the potential distribution is described in terms of a classical Schottky barrier. Any change in applied potential is then postulated to be accommodated almost entirely within this space-charge layer, provided the semiconductor remains in reverse bias and the electrolyte has a concentration exceeding approximately 0.01 M. The central difference between this situation and that found in the more familiar electrochemistry of the metal/electrolyte interface is that the very high charge carrier density in the metal allows the buildup of a high uncompensated charge at the surface, ensuring that the change in applied potential is accommodated not within the metal, but in the electrolyte itself.
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Batchelor, R.A., Hamnett, A. (1992). Surface States on Semiconductors. In: Bockris, J.O., Conway, B.E., White, R.E. (eds) Modern Aspects of Electrochemistry. Modern Aspects of Electrochemistry, vol 22. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-3376-4_3
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