Theoretical study of charge recombination at the TiO2-electrolyte interface in dye sensitised solar cells

The charge recombination reaction from the semiconductor (TiO(2)) conduction band to electron accepting electrolytes (I(2), I(2)(-), I(3)(-)) in dye-sensitised solar cells is investigated theoretically. The non-adiabatic theory of electron transfer has been adapted to compute the charge transfer rate measured in different experimental settings (namely with and without external illumination). In both cases we are able to provide an atomic level description of the charge recombination to the electrolyte (CRE), which is in good agreement with the experimental data available. The model employs a detailed density-functional theory (DFT) description of the semiconductor-electrolyte interface and the internal reorganization energy. A continuum dielectric model is used to evaluate the external component of the reorganization energy due to the solvent degrees of freedom. The intrinsic limitations of DFT are kept to a minimum by taking two key energetic parameters (the conduction band edge and the reaction energy) from the experiments. The proposed methodology correctly reproduces (i) the ratio between CRE rate to iodine and triiodide in dark, (ii) the absolute CRE rate to triiodide in dark, and (iii) the absolute CRE rate to I(2)(-) under illumination.