期刊
JOURNAL OF PHYSICAL CHEMISTRY C
卷 117, 期 10, 页码 4931-4936出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp311207x
关键词
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资金
- NSF [CHE-1214152, CHE-1042006]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1042006] Funding Source: National Science Foundation
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 similar to 25 mA cm(-2), MnOlSi 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 limited the fill factor and thus the solar energy-conversion efficiency of the photoelectrodes. Open-circuit photovoltages of 30 and 450 mV, respectively, were observed in contact with cobaltocene(+/0) or ferrocene(+/0) in CH3CN, indicating that the energetics of the MnO-coated Si surfaces were a function of the electrochemical potential of the contacting electrolyte solution.
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