Effect of Interfacial SiO(x) Defects on the Functional Properties of Si-Transition Metal Oxide Photoanodes for Water Splitting

[Image: see text] The transfer of photogenerated charges through interfaces in heterojunction photoanodes is a key process that controls the efficiency of solar water splitting. Considering Co(3)O(4)/SiO(x)/Si photoanodes prepared by physical vapor deposition as a representative case study, it is shown that defects normally present in the native SiO(x) layer dramatically affect the onset of the photocurrent. Electron paramagnetic resonance indicates that the signal of defects located in dangling bonds of trivalent Si atoms at the Si/SiO(x) interface vanishes upon vacuum annealing at 850 °C. Correspondingly, the photovoltage of the photoanode increases to ≈500 mV. Similar results are obtained for NiO/SiO(x)/Si photoanodes. Photoelectrochemical analysis and impedance spectroscopy (in solution and in the solid state) indicate how the defect annealing modifies the Co(3)O(4)/SiO(x)/Si junction. This work shows that defect annealing at the solid–solid interface in composite photoanodes strongly improves the efficiency of charge transfer through interfaces, which is the basis for effective solar-to-chemical energy conversion.