Photochemical Charge Separation at Particle Interfaces: The n-BiVO₄–p-Silicon System

The charge transfer properties of interfaces are central to the function of photovoltaic and photoelectrochemical cells and photocatalysts. Here we employ surface photovoltage spectroscopy (SPS) to study photochemical charge transfer at a p-silicon/n-BiVO4 particle interface. Particle films of BiVO4 on an aluminum-doped p-silicon wafer were obtained by drop-coating particle suspensions followed by thermal annealing at 353 K. Photochemical charge separation of the films was probed as a function of layer thickness and illumination intensity, and in the presence of methanol as a sacrificial electron donor. Electron injection from the BiVO4 into the p-silicon is clearly observed to occur and to result in a maximum photovoltage of 150 mV for a 1650 nm thick film under 0.3 mW cm(-2) illumination at 3.5 eV. This establishes the BiVO4-p-Si interface as a tandem-like junction. Charge separation in the BiVO4 film is limited by light absorption and by slow electron transport to the Si interface, based on time-dependent SPS measurements. These problems need to be overcome in functional tandem devices for photoelectrochemical water oxidation.