Optimizing the photocurrent efficiency of dye-sensitized solar cells through the controlled aggregation of chalcogenoxanthylium dyes on nanocrystalline titania films

Chalcogenoxanthylium dyes were characterized as sensitizers of nanocrystalline titania in dye-sensitized solar cells (DSSCs). Four series of dyes were characterized: 2,7-bis(dimethylamino)-9-(2-thienyl-5-carboxy)chalcogenoxanthylium dyes (I-E, where E = 0, S, Se); 2,7-bis(dimethylamino)-9-(3-thienyl-2-carboxy)chalcogenoxanthylium dyes (2-E, where E = S, Se); a 2,7-bis(dimethylamino)-9-(2-thienyl)selenoxanthylium dye (3-Se); 4-Se, a constrained analog of 1-Se. The orientation and aggregation state of the dyes were controlled by varying the position of the surface-attachment group relative to the xanthylium core. Series 1 dyes and 4-Se underwent H-aggregation on titania surfaces, whereas series 2 dyes adsorbed in amorphous monolayers. (3-Se did not adsorb appreciably to titania films, due to the lack of a tethering group.) The H-aggregated dyes exhibited broader absorption bands, increased light-harvesting efficiencies, and improved photoelectrochemical performance compared to the dyes which adsorbed in amorphous monolayers. The maximum incident photon-to-current efficiencies (IPCEs) of series I dyes ranged from 70% to 84%, whereas those of 2-S and 2-Se were 11% and 20%. Our findings reveal that the light-harvesting efficiency, IPCE, and absorbed photon-to-current efficiency (APCE) of DSSCs with organic dyes can be optimized by systematically varying the structure of the dyes and their orientation and aggregation state on the surface.