Dye-sensitized photocathodes: Efficient light-stimulated hole injection into p-GaP under depletion conditions

The steady-state photoelectrochemical responses of p-GaP photoelectrodes immersed in aqueous electrolytes and sensitized separately by six triphenylmethane dyes (rose bengal, rhodamine B, crystal violet, ethyl violet, fast green fcf, and brilliant green) have been analyzed. Impedance measurements indicated that these p-GaP(100) photoelectrodes operated under depletion conditions with an electric field of ∼8.5 × 10 ⁵ V cm ^-1 at the p-GaP/solution interface. The set of collected wavelength-dependent quantum yield responses were consistent with sensitization occurring specifically from adsorbed triphenylmethane dyes. At high concentrations of dissolved dye, the measured steady-state photocurrent- potential responses collected at sub-bandgap wavelengths suggested unexpectedly high (>0.1) net internal quantum yields for sensitized hole injection. Separate measurements performed with rose bengal adsorbed on p-GaP surfaces pretreated with (NH ₄) ₂S verified efficient sensitized hole injection. A modified version of wxAMPS, a finite-difference software package, was utilized to assess key operational features of the sensitized p-GaP photocathodes. The net analysis showed that the high internal quantum yield values inferred from the experimental data were most likely afforded by the internal electric field present within p-GaP, effectively sweeping injected holes away from the interface and minimizing their participation in deleterious pathways that could limit the net collection yield. These simulations defined effective threshold values for the charge carrier mobilities (≥10 ^-6 cm ² V ^-1 s ^-1 and ≥10 ^-1 cm ² V ^-1 s ^-1 at dopant densities of 10 ¹⁸ and 10 ¹³ cm ^-3, respectively), hole injection rate constants (≥10 ¹² s ^-1), and surface trap densities (10 ¹² cm ^-2) needed to attain efficient hole collection with the quality of p-GaP materials used here. The cumulative experimental and modeling data thus provide insight on design strategies for assembling new types of dye-sensitized photocathodes that operate under depletion conditions.