Conformational engineering of co-sensitizers to retard back charge transfer for high-efficiency dye-sensitized solar cells

We demonstrate that the post-adsorption of small molecules (a phenothiazine-based dye) on the porphyrin-sensitized TiO₂ anode surface plays dual roles: (1) to greatly retard the back reaction between conduction-band electrons in TiO₂ and the oxidized species (I ₃^-) in the electrolyte and (2) to enhance the spectral response of solar cells. These two effects finally give rise to device efficiencies exceeding 10%, which are superior to those of individual dye-sensitized devices by either porphyrin (7.4%) or phenothiazine (8.2%) under the same conditions. Experimental analyses show that the incoming small molecules are adsorbed in the interstitial site of porphyrin dyes, forming densely surface packed molecules and thus impeding the I₃^- species from approaching the TiO₂ surface. Since a broad range of ruthenium-based dyes and porphyrin-based photosensitizers possess relatively large molecular volumes, this method is anticipated to be applicable for further improving the energy conversion efficiency of devices sensitized by these two classes of dyes.