Influence of point defects on the performance of InVO₄ photoanodes

The properties of thin film InVO4 photoanodes for water splitting have been studied. Compact films of InVO4 were prepared by spray pyrolysis and are found to be stable between pH 3 and 11. Although the indirect bandgap is 3.2 eV, a modest amount of visible light absorption is observed. The origin of this absorption is attributed to the presence of deep donor states at ∼0.7 eV below the conduction band. These donor states presumably correspond to oxygen vacancies, which form as a result of small but unavoidable deviations of In:V from the ideal 1:1 stoichiometry during the wet-chemical synthesis process. Shallow donors are absent in this material, in contrast to what is normally observed for metal oxides. The deep donor model explains the much stronger visible light absorption of powders compared to thin films. The defect chemical reactions that lead to the formation of the deep donors are shown, and are supported by photoluminescence data.