The origin of slow electron injection rates for indoline dyes used in dye-sensitized solar cells

Abstract

This work highlights the direct impact of selecting acceptor moiety for organic dyes on the electron dynamics at faster time scales, in which overlooked photo-physical properties are present on semiconductor surfaces with specific acceptor moieties. Four top-performing dyes of indoline family (D131, D102, D149, and D205) sharing the same donor moiety, but through different acceptor groups, were selected and compared with respect of electron injection process, using ultrafast transient-infrared probe. The presence of rhodanine moiety at the acceptor unit in D102, D149 and D205, shows an additional slow electron injection process, of picosecond time-scale, on the low band-gap semiconductor, TiO2. This slow process is expected to be present due to a twisted intramolecular charge transfer/isomerized state of the excited dye prior to electron injection. This isomerized state reduces as well the detrimental electron recombination process rates, and results of high performance in solar cells based on these rhodanine dyes. Replacing the rhodanine moiety by a cyano-acrylic group in D131 dye shows faster electron injection and recombination processes, due to the lower dipole moment present in the excited state, hindering the formation of an isomerized state. These findings will aid to enhance the organic dyes design used in dye sensitized solar cells, in which designed photo-physical processes on semiconductor surfaces can increase the efficiencies of the solar cells.