Journal of Physical Chemistry B, Vol.110, No.42, 21050-21054, 2006
Crystal-face dependence and photoetching-induced increases of dye-sensitized photocurrents at single-crystal rutile TiO2 surfaces
Dye-sensitized photocurrents at (100)-, (001)-, and (110)- cut TiO2 rutile surfaces were increased by photoetching of TiO2, but the increasing ratio strongly depended on the cut crystal faces and the illumination intensity for the photoetching. For the (110)- cut surface, the photocurrent increase was moderately large and in proportion to the increase in the surface area of TiO2 induced by the photoetching, irrespective of the illumination intensity for the photoetching. On the other hand, the photocurrent increases for the (001)- and (100)-cut surfaces, especially that for the ( 001)- cut surface, were prominent and largely exceeded the increases in the surface area. The results were explained by taking into account the following factors: (1) The (001)- and (100)- cut surfaces were thermodynamically unstable in contrast to the (110)- cut surface and had thicker inactive surface layers ( or higher densities of surface defects), produced by surface reconstruction during heat treatment of TiO2 at 550 C in a hydrogen atmosphere for getting n-type semiconductivity. (2) Photoetching not only increased the surface area through formation of nanoholes and grooves at the surface but also effectively removed the thin inactive surface layers (or surface defects).