Institute of Fundamental Technological Research

New semiconducting metal oxides of various compositions are of great interest for efficient solar water oxidation. In this report, Mo-doped SnO2 (Mo:SnO2) thin films deposited by reactive magnetron co-sputtering in the Ar and O2 gas environment are studied. The Sn to Mo ratio in the films can be controlled by changing the O2 partial pressure and the deposition power of the Sn and Mo targets. Increasing the Mo concentration in the film leads to the increase in the oxygen vacancy density, which limits the maximum achievable photocurrent density. The thin films exhibit a direct band gap of 2.7 eV, the maximum achievable photocurrent density of 0.6 mA cm^−2 at 0 VRHE and the onset potential of 0.14 VRHE. The incident photon to current transfer (IPCE) efficiency of 22% is shown at a 450 nm wavelength. The initial performance of the Mo:SnO2 thin films is evaluated for solar water oxidation.

Mo:SnO2, thin films, photoanode, photocurrent density, Sn/mo ratio, band gap

Semiconducting ternary metal oxide thin films exhibit a promising application for solarenergy conversion. However, the efficiency of the conversion is still limited by a band gapof a emiconductor, which determines an obtainable internal photovoltage for solar watersplitting. In this report the tunability of the tin tungstate band gap by O2 partial pressurecontrol in the magnetron co-sputtering process is shown. A deficiency in the Sn concentration increases the optical band gap of tin ungstate thin films. The optimum band gap of 1.7 eV for tin tungstate films is achieved for a Sn to W ratio at unity, which establishes thehighest photoelectrochemical activity. In particular, a maximum photocurrent density of 0.375 mA cm^2 at 1.23 VRHE and the lowest reported onset potential of -0.24 VRHE for SnWO4 thin films without any co-catalyst are achieved. Finally, we demonstrate that a Ni protection layer on the SnWO4 thin film enhances the photoelectrochemical stability, which isof paramount importance for application.

thin film, tin tungstate, reactive magnetron sputtering, photocurrent density, thickness band gap

There is an urgent need for new materials that can catalyze or drive the photoelectrochemical (PEC) conversion of solar energy into chemical energy, i.e. solar fuels. Copper bismuth oxide (CBO) is a promising photocathode material for the photochemical reduction of water. Here, we systematically control the stoichiometry of CBO thin films prepared by reactive, direct-current magnetron co-sputtering from metallic Bi and Cu targets. The intrinsic photophysical and PEC material properties are investigated and evaluated in order to determine the optimum composition for hydrogen formation. Changing the stoichiometry of the films reveals a dramatic change in the optical band gap and crystal structure of CBO. The largest photocurrent density was achieved for a copper-to-bismuth ion ratio of 0.53, close to the CuBi2O4 stoichiometry, which yielded Jph = − 0.48 mA cm^−2 at 0 VRHE (RHE = reversible hydrogen electrode). This is the highest value to date for the photochemical reduction of water with CuBi2O4 without an externally applied bias. The absorbed photon-to-current efficiency and the photostability of the films in neutral and alkaline electrolytes were also investigated.

CuBi2O4, copper bismuth oxide, water reduction, water splitting, photocathode, magnetron sputtering