Probing the Relative Photoinjection Yields of Monomer and Aggregated Dyes into ZnO Crystals

Cyanine dyes, often used in dye-sensitized solar cells (DSSCs), form a range of molecular species from monomers to large H and J aggregates in both solution and when adsorbed at a photoelectrode surface. To determine the relative capability of the different dye species to inject photoexcited electrons into a wideband gap oxide semiconductor, sensitization at a single-crystal zinc oxide surface was studied by simultaneous attenuated reflection (ATR) ultraviolet-visible (UV-vis) absorption and photocurrent spectroscopy measurements. ATR measurements enable identification of the dye species populating the surface with simultaneous photocurrent spectroscopy to identify the contribution of the various dye forms to photocurrent signal. We study the dye 2,2'-carboxymethylthiodicarbocyanine bromide that is particularly prone to aggregation both in solution and at the surface of sensitized oxide semiconductors.