Photoinduced electron transfer from a terrylene dye to TiO2: Quantification of band edge shift effects

A terrylene chromophore exhibiting a high extinction coefficient has been developed as a sensitizer for photovoltaic applications. The photophysical and photochemical properties of the dye were analyzed both experimentally and theoretically. Terrylene-sensitized nanocrystalline TiO2 solar cells yielded good photocurrents providing more than 60% in external quantum efficiency. The photoinduced electron transfer from the dye to TiO2 was found to be very sensitive to conduction band edge shifts in TiO2 induced, either by changes in the composition of the redox electrolyte or by UV-illumination. This sensitivity was observed in quantum efficiencies for photocurrent generation of terrylene-sensitized solar cells and in photoinduced absorption experiments. The conduction band shifts were quantified using charge extraction methods. The observed sensitivity of the injection efficiency suggests that photoinduced electron transfer occurs from the relaxed excited state, possibly due to poor electronic coupling between TMIMA excited states and TiO2 conduction band states.