The relationship between squaraine dye surface morphology and sensitization behavior on SnS2 electrodes

Bis(4-dimethylamino-2-dihydroxyphenyl)squaraine (1-1 OHSQ) dyes were deposited on van der Waals surfaces of SnS₂ single crystals by two methods, dipping in a dye solution and evaporation of dye solution. Dye morphologies and photosensitization properties on the same samples were studied with atomic force microscopy (AFM) and photoelectrochemical measurements. AFM experiments in air revealed two distinct morphologies of dye aggregates and photocurrent measurements on the same samples in aqueous electrolytes showed correspondingly different photocurrent spectra. Three-dimensional needle-shaped 1-1 OHSQ aggregates aligned along crystal directions and showed a broad excitation spectrum that extended into the near-IR region with a peak around 800 nm. In contrast, flat aggregates presumably consisting of monolayers of 1-1 OHSQ molecules, had a sensitization maximum around 680 nm. Both peaks were red-shifted from absorption peak of 1-1 OHSQ in bulk dichloromethane solution. Spectral differences between these dye aggregates are discussed in terms of intermolecular interactions.