Atomic layer deposited TiO <sub/>2</sub> -IrO <sub/>x</sub> alloys enable corrosion resistant water oxidation on silicon at high photovoltage.

摘要： We synthesized by atomic layer deposition (ALD) TiO2-IrOx alloys that enable high photovoltages and catalyze water oxidation on silicon metal-insulator-semiconductor (MIS) photoanodes. The ratio of TiO2 to IrOx was precisely controlled by varying the number of ALD cycles for each precursor. Silicon with a 2 nm surface SiO2 layer was coated with TiO2-IrOx alloys ranging in composition from 18-35% iridium relative to the sum of titanium and iridium concentrations. IrOx catalyzed oxygen evolution and imparted a high work function to the TiO2-IrOx alloys, enabling photovoltages during water oxidation that exceeded 600 mV. TiO2 imparted stability and inhibited corrosion of the underlying silicon light absorber. After annealing in forming gas (5% H2 / 95% N2), TiO2-IrOx alloys were stable for 12 hours of continuous water oxidation in 1 M H2SO4. Key properties of the MIS junction affecting electrochemical operation were also extracted by electrochemical impedance spectroscopy. This work demonstrates that alloying by ALD is a promising approach for designing corrosion resistant Schottky contacts with optimized electronic and materials properties for catalyzed, solar driven water oxidation.