Solvent-induced surface state passivation reduces recombination in semisquarylium dye-sensitized solar cells

The semisquarylium dye SY1T that is strongly bound to the surface of nanocrystalline TiO2 experiences very fast back-electron transfer of injected electrons to the SY1T cation, when the TiO2/SY1T interface is surrounded by ultrahigh vacuum. However, when located in methoxypropionitrile (MPN), which is frequently used as electrolyte solvent in dye-sensitized solar cells, the back-electron transfer is significantly retarded. Results are obtained both for picosecond and microsecond time scales using transient absorption spectroscopy. As solvent-induced interfacial energy level shifts can be excluded as possible cause, the role of TiO2 surface states in the beneficial retardation process is investigated. Highly surface sensitive synchrotron-induced photoelectron spectroscopy exhibits high densities of surface states on the pristine nanocrystalline TiO2 (nc-TiO2) surfaces. While SY1T dye-sensitization from a SY1T solution in tetrahydrofuran saturates about 30% of the surface states, the subsequent in-situ adsorption of MPN molecules at the TiO2/SY1T interface leads to further reduction by more than 50% of the remaining surface states. It is concluded that the saturation of TiO2 surface states hampers the otherwise efficient recombination of injected electrons with the SY1T dye cation. (C) 2014 AIP Publishing LLC.