Dye Sensitization of the Anatase (101) Crystal Surface by a Series of Dicarboxylated Thiacyanine Dyes

Dye sensitization of the single crystal anatase (101) surface was studied using a structurally similar series of dicarboxylated thiacyanine dyes that bind to the oxide surface through their carboxylate groups. An ultraviolet (UV) light treatment of the anatase (101) surfaces, immediately prior to dye adsorption, improved both the reproducibility of dye coverage and the incident photon-to-current efficiencies (IPCE) for sensitization. The UV treatment does not pit or roughen the anatase surface and results in high IPCEs of more than 1% in some cases and absorbed photon current efficiencies (APCE) from 5 to 100%. The photocurrent spectra showed features associated with surface-bound dye monomers and H-dimers that could be followed as a function of the dye surface coverage. Models for the surface structures of the adsorbed dye layers that are consistent with the measurements are presented, along with a discussion of adsorption isotherms.