Atomic layer-deposited tunnel oxide stabilizes silicon photoanodes for water oxidation

A leading approach for large-scale electrochemical energy production with minimal global-warming gas emission is to use a renewable source of electricity, such as solar energy, to oxidize water, providing the abundant source of electrons needed in fuel synthesis. We report corrosion-resistant, nanocomposite anodes for the oxidation of water required to produce renewable fuels. Silicon, an earth-abundant element and an efficient photovoltaic material, is protected by atomic layer deposition (ALD) of a highly uniform, 2nm thick layer of titanium dioxide (TiO2) and then coated with an optically transmitting layer of a known catalyst (3nm iridium). Photoelectrochemical water oxidation was observed to occur below the reversible potential whereas dark electrochemical water oxidationwas found to have low-to-moderate overpotentials at all pH values, resulting in an inferred photovoltage of similar to 550 mV. Water oxidation is sustained at these anodes for many hours in harsh pH and oxidative environments whereas comparable silicon anodes without the TiO2 coating quickly fail. The desirable electrochemical efficiency and corrosion resistance of these anodes is made possible by the low electron-tunnelling resistance (< 0.006 Omega cm(2) for p(+) -Si) and uniform thickness of atomic-layer deposited TiO2.