Abstract
Assuming small-polaron model, an effective relation between the energy-band edge and the Fermi level is derived for the nondegenerate semiconductor. The new relation is distinct from the standard one based on rigid-ion model, and could be generally applied to electrochemistry to obtain valid band-edge positions from the measured flat-band potentials for small-polaron semiconductors. We reassign the band-edge position of small-polaronlike rutile TiO2. Essence of the new model and relation, e. g., in understanding photoinduced interfacial charge transfer, is demonstrated in the comparative studies of anatase and rutile TiO2 that are used in photocatalysis and dye-sensitized solar cells.
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