Dye Dependent Regeneration Dynamics in Dye Sensitized Nanocrystalline Solar Cells: Evidence for the Formation of a Ruthenium Bipyridyl Cation/Iodide Intermediate

We report a transient absorption study of the kinetics of re-reduction of ruthenium bipyridyl dye cations adsorbed to nanocrystalline TiO2 films by iodide ions, employing a series of RuII(dcbpy)2X dyes, where dcpby ) 4,4′-dicarboxy-2,2′-bipyridyl and X ) (NCS)2, (CN)2, DTC (diethyldithiocarbamate), and Cl2. The data indicate that this re-reduction (or ‘regeneration’) reaction proceeds via a transient (dye+-iodide) intermediate complex formed by reaction of photogenerated dye cations with one iodide ion. The subsequent reaction of this complex with a second iodide ion, forming I2-, is shown to be the kinetically and thermodynamically limiting step in the overall regeneration reaction. The implications of this reaction scheme for the function of dye sensitized photoelectrochemical cells are discussed, considering in particular the high photovoltaic efficiencies obtained for such devices employing such ruthenium bipyridyl senstiser dyes in combination with iodide/tri-iodide based redox electrolytes.