Effect of a coadsorbent on the performance of dye-sensitized TiO2 solar cells: shielding versus band-edge movement.

The mechanism by which the adsorbent chenodeoxycholate, cografted with a sensitizer onto TiO2 nanocrystals, alters the open-circuit photovoltage and short-circuit current of dye-sensitized solar cells was investigated. The influence of tetrabutylammonium chenodeoxycholate on dye loading was studied under a variety of conditions in which the TiO2 films were exposed to the sensitizing dye and coadsorbent. Photocurrent--voltage measurements combined with desorption studies revealed that adding chenodeoxycholate reduces the dye loading by as much as 60% while having a relatively small effect on the short-circuit photocurrent. Calculations along with measurements showed that even at low loading, enough dye is present to absorb a significant fraction of the incident light in the visible spectrum. In concurrence with the observations of others, we find evidence for weakly and strongly adsorbed forms of the dye resulting from either different binding conformations or aggregates. The most strongly adsorbed dyes are less susceptible to displacement by chenodeoxycholate than those that are weakly adsorbed. While having no observable effect on dye coverage, multiple exposures of a TiO2 film to a dye solution substantially increased the fraction of strongly adsorbed dye as judged by the resistance of the adsorbed dye to displacement by chenodeoxycholate. Measurements of the open-circuit voltage as a function of the photocharge density, determined by infrared transmittance, showed that chenodeoxycholate not only shifts the conduction band edge to negative potentials, but also significantly increases the rate of recombination. The net effect of adding chenodeoxycholate is, however, to improve the photovoltage.