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An electrodeposited inhomogeneous metal–insulator–semiconductor junction for efficient photoelectrochemical water oxidation

Nature Materials volume 14, pages 1150–1155 (2015)Cite this article

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Abstract

The photoelectrochemical splitting of water into hydrogen and oxygen requires a semiconductor to absorb light and generate electron–hole pairs, and a catalyst to enhance the kinetics of electron transfer between the semiconductor and solution. A crucial question is how this catalyst affects the band bending in the semiconductor, and, therefore, the photovoltage of the cell. We introduce a simple and inexpensive electrodeposition method to produce an efficient n-Si/SiOx/Co/CoOOH photoanode for the photoelectrochemical oxidation of water to oxygen. The photoanode functions as a solid-state, metal–insulator–semiconductor photovoltaic cell with spatially non-uniform barrier heights in series with a low overpotential water-splitting electrochemical cell. The barrier height is a function of the Co coverage; it increases from 0.74 eV for a thick, continuous film to 0.91 eV for a thin, inhomogeneous film that has not reached coalescence. The larger barrier height leads to a 360 mV photovoltage enhancement relative to a solid-state Schottky barrier.

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Figure 1: Characterization of photo-oxidized electrodeposited cobalt on (100) n-Si.
Figure 2: Photoelectrochemical performance of the n-Si/SiOx/Co/CoOOH photoanode.
Figure 3: Solid-state characterization of the electrodeposited n-Si/SiOx/Co junction.
Figure 4: Schematic of solid-state Schottky barrier and electrodeposited n-Si/SiOx/Co/CoOOH junctions.

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Acknowledgements

This material is based on work supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under Grant No. DE-FG02-08ER46518.

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Authors and Affiliations

  1. Department of Chemistry and Graduate Center for Materials Research, Missouri University of Science & Technology, Rolla, Missouri 65409-1170, USA

    James C. Hill, Alan T. Landers & Jay A. Switzer

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  1. James C. Hill
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  2. Alan T. Landers
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  3. Jay A. Switzer
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Contributions

J.C.H. and A.T.L. prepared the samples and performed all measurements. J.C.H. and J.A.S. wrote the manuscript. J.A.S. directed the research.

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Correspondence to Jay A. Switzer.

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The authors declare no competing financial interests.

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Hill, J., Landers, A. & Switzer, J. An electrodeposited inhomogeneous metal–insulator–semiconductor junction for efficient photoelectrochemical water oxidation. Nature Mater 14, 1150–1155 (2015). https://doi.org/10.1038/nmat4408

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