Investigation of the influence of coadsorbent dye upon the interfacial structure of dye-sensitized solar cells.

The interface between Ru(tcterpy)(NCS)3TBA2 [black dye (BD); tcterpy = 4,4',4"-tricarboxy-2,2':6',2"-terpyridine, NCS = thiocyanato, TBA = tetrabutylammonium cation] and nanocrystalline TiO2, as found in dye-sensitized solar cells, is investigated by soft-X-ray synchrotron radiation and compared with the adsorption structure of cis-Ru(Hdcbpy)2(NCS)2TBA2 (N719; dcbpy = 4,4/-dicarboxy-2,2'-bipyridine) on TiO2 to elucidate the relationship between the adsorption mode of BD and the photocurrent with and without coadsorbed indoline dye D131. The depth profile is charac-terized with X-ray photoelectron spectroscopy and S K-edge X-ray absorption fine structure using synchrotron radiation. Both datasets indicate that one of the isothiocyanate groups of BD interacts with TiO2 via its S atom when the dye is adsorbed from a single-component solution. In contrast, the interaction is slightly suppressed when D131 is coadsorbed, indicated by the fact that the pres-ence of D131 changes the adsorption mode of BD. Based upon these results, the number of BD dye molecules interacting with the substrate is shown to decrease by 10% when D131 is coadsorbed, and the dissociation is shown to be related to the short-circuit photocurrent in the 600-800 nm re-gion. The design of a procedure to promote the preferential adsorption of D131 therefore leads to an improvement of the short-circuit current and conversion efficiency. [ABSTRACT FROM AUTHOR]