Cobalt Redox Mediators for Ruthenium-Based Dye-Sensitized Solar Cells: A Combined Impedance Spectroscopy and Near-IR Transmittance Study

Dye-sensitized solar cells with power conversion efficiencies of up to 6.5% have been fabricated using a cobalt trisbipyridyl redox mediator with the cis-diisothiocyanato-(2,2'-bipyridyl-4,4'-dicarboxylic acid)-(2,2'-bipyridyl-4,4'-dinonyl) ruthenium(II) (Z907) sensitizer. This represents a significant improvement in efficiency compared with previous reports using ruthenium sensitizers. In situ near-IR transmittance measurements in conjunction with electrochemical impedance spectroscopy have been used to explain the difference in performance between DSCs using Z907 and another benchmark sensitizer cis-diisothiocyanato-bis(2,2'-bipyridyl-4,4'-dicarboxylic acid) ruthenium(II) bis(tetrabutylammonium) (N719). It is found that the small-perturbation electron diffusion length (L-n) is significantly longer in Z907 cells compared with that in N719 cells, which can explain most of the difference in performance. It is also shown that the longer L-n in Z907 cells is caused by inhibited recombination, as opposed to faster transport, and possible reasons for this are discussed. Our methodological approach is especially useful for accurately determining L-n when it is shorter than the TiO2 layer thickness, where standard dynamic techniques start to become unreliable.