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Thin (10 nm) films of manganese oxide have been deposited by atomic layer deposition (ALD) onto n-type silicon and onto degenerately doped p-type silicon. The photoelectrochemical properties of the resulting semiconductor/metal-oxide structures were evaluated in contact with aqueous 0.35 M K4Fe(CN)6–0.05 M K3Fe(CN)6, 1.0 M KOH(aq), as well as in contact with a series of nonaqueous one-electron, reversible, outer-sphere redox systems. Under simulated air mass (AM) 1.5 illumination in contact with 0.35 M K4Fe(CN)6–0.05 M K3Fe(CN)6(aq), MnO-coated n-Si photoanodes displayed open-circuit voltages of up to 550 mV and stable anodic currents for periods of hours at 0.0 V versus the solution potential. In contact with 1.0 M KOH(aq), at current densities of ∼25 mA cm–2, MnO|Si photoanodes under 100 mW cm–2 of simulated AM 1.5 illumination yielded stable oxygen evolution for 10–30 min. Variation in the thickness of the MnO films from 4 to 20 nm indicated the presence of a series resistance in the MnO film that limi...

Photoelectrochemical Behavior of n-type Si(100) Electrodes Coated with Thin Films of Manganese Oxide Grown by Atomic Layer Deposition