Electron donor-acceptor distance dependence of the dynamics of light-induced interfacial charge transfer in the dye-sensitization of nanocrystalline oxide semiconductors

The effect of electronic and nuclear factors on the dynamics of dye-to-semiconductor electron transfer was studied employing RuII(terpy)(NCS)3 sensitizers grafted onto transparent films made of titanium dioxide nanoparticles. Various approaches were strived to understand the dependence of the kinetics of charge injection and recombination processes upon the distance separating the dye molecules and the redox active surface. A series of bridged sensitizers containing p- phenylene spacers of various lengths and phosphonic anchoring groups were adsorbed onto TiO2 films. The kinetics of interfacial charge transfer was recorded by use of time-resolved spectroscopy in the fs-ps domain. The electron injection process was found to be biphasic with a clear exponential distance dependence of the fast kinetic component. The slower part of the kinetics was essentially unaffected by the length of the spacer bridge and was attributed to sensitizer molecules that are weakly bound to the surface with no direct contact of the anchoring group with the semiconductor. In a second approach, the kinetics of both forward- and back-electron transfer across a layer of insulating Al2O3 deposited onto TiO2 nanocrystalline particles was investigated. Efficient charge injection was observed over distances up to 3 nm.