Abstract
Photoelectrochemical (PEC) water splitting represents a promising route for renewable production of hydrogen, but trade-offs between photoelectrode stability and efficiency have greatly limited the performance of PEC devices. In this work, we employ a metal–insulator–semiconductor (MIS) photoelectrode architecture that allows for stable and efficient water splitting using narrow bandgap semiconductors. Substantial improvement in the performance of Si-based MIS photocathodes is demonstrated through a combination of a high-quality thermal SiO2 layer and the use of bilayer metal catalysts. Scanning probe techniques were used to simultaneously map the photovoltaic and catalytic properties of the MIS surface and reveal the spillover-assisted evolution of hydrogen off the SiO2 surface and lateral photovoltage driven minority carrier transport over distances that can exceed 2 cm. The latter finding is explained by the photo- and electrolyte-induced formation of an inversion channel immediately beneath the SiO2/Si interface. These findings have important implications for further development of MIS photoelectrodes and offer the possibility of highly efficient PEC water splitting.
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References
Chen, X. B., Shen, S. H., Guo, L. J. & Mao, S. S. Semiconductor-based photocatalytic hydrogen generation. Chem. Rev. 110, 6503–6570 (2010).
Walter, M. G. et al. Solar water splitting cells. Chem. Rev. 110, 6446–6473 (2010).
Turner, J. et al. Renewable hydrogen production. Int. J. Energy Res. 32, 379–407 (2008).
Munoz, A. G. & Lewerenz, H. J. Advances in photoelectrocatalysis with nanotopographical photoelectrodes. ChemPhysChem 11, 1603–1615 (2010).
Lewerenz, H. J. et al. Micro-and nanotopographies for photoelectrochemical energy conversion. II: Photoelectrocatalysis—classical and advanced systems. Electrochim. Acta 56, 10726–10736 (2011).
Chen, Y. W. et al. Atomic layer-deposited tunnel oxide stabilizes silicon photoanodes for water oxidation. Nature Mater. 10, 539–544 (2011).
Aharonshalom, E. & Heller, A. Efficient p-InP(RH-H alloy) and p-InP(RE-H alloy) hydrogen evolving photocathodes. J. Electrochem. Soc. 129, 2865–2866 (1982).
Heller, A. Hydrogen-evolving solar-cells. Science 223, 1141–1148 (1984).
Schulte, K. H. & Lewerenz, H. J. Combined photoelectrochemical conditioning and photoelectron spectroscopy analysis of InP photocathodes. I. The modification procedure. Electrochim. Acta 47, 2633–2638 (2002).
Lewerenz, H. J. et al. Photoelectrocatalysis: Principles, nanoemitter applications and routes to bio-inspired systems. Energy Environ. Sci. 3, 748–760 (2010).
Lee, M. H. et al. p-type InP nanopillar photocathodes for efficient solar-driven hydrogen production. Angew. Chem. Int. Ed. 51, 10760–10764 (2012).
Vesborg, P. C. K. & Jaramillo, T. F. Addressing the terawatt challenge: Scalability in the supply of chemical elements for renewable energy. RSC Adv. 2, 7933–7947 (2012).
Pourbaix, M. Atlas of Electrochemical Equilibria in Aqueous Solutions 2nd edn 458–463 (NACE, 1974).
Mur, P. et al. Ultra-thin oxides grown on silicon (100) by rapid thermal oxidation for CMOS and advanced devices. Appl. Surf. Sci. 175, 726–733 (2001).
Singh, R., Green, M. A. & Rajkanan, K. Review of conductor–insulator–semiconductor (CIS) solar-cells. Solar Cells 3, 95–148 (1981).
Connelly, D., Faulkner, C., Clifton, P. A. & Grupp, D. E. Fermi-level depinning for low-barrier Schottky source/drain transistors. Appl. Phys. Lett. 88, 012105 (2006).
Monch, W. On the alleviation of Fermi-level pinning by ultrathin insulator layers in Schottky contacts. J. Appl. Phys. 111, 073706 (2012).
Razouk, R. R. & Deal, B. E. Dependence of interface state density on silicon thermal-oxidation process variables. J. Electrochem. Soc. 126, 1573–1581 (1979).
Green, M. A. Effects of pinholes, oxide traps, and surface-states on MIS solar-cells. Appl. Phys. Lett. 33, 178–180 (1978).
Rhoderick, E. H. & Williams, R. H. Metal-Semiconductor Contacts AppendixA (Clarendon Press, 1988).
Bertoncello, P. Advances on scanning electrochemical microscopy (SECM) for energy. Energy Environ. Sci. 3, 1620–1633 (2010).
Lai, S. C. S., Macpherson, J. V. & Unwin, P. R. In situ scanning electrochemical probe microscopy for energy applications. Mater. Res. Soc. Bull. 37, 668–674 (2012).
Casillas, N., James, P. & Smyrl, W. H. A novel-approach to combine scanning electrochemical microscopy and scanning photoelectrochemical microscopy. J. Electrochem. Soc. 142, L16–L18 (1995).
Lee, J. W., Ye, H. C., Pan, S. L. & Bard, A. J. Screening of photocatalysts by scanning electrochemical microscopy. Anal. Chem. 80, 7445–7450 (2008).
Godfrey, R. B. & Green, M. A. 15-percent efficient silicon MIS solar-cell. Appl. Phys. Lett. 33, 637–639 (1978).
Wadhwa, P., Seol, G., Petterson, M. K., Guo, J. & Rinzler, A. G. Electrolyte-induced inversion layer Schottky junction solar cells. Nano Lett. 11, 2419–2423 (2011).
Tuner, J. A., Manassen, J. & Nozik, A. J. Photoelectrochemistry with pSi electrodes: Effects of inversion. 37, 488–491 (1980).
Morrison, S. R. Electrochemistry at Semiconductor and Oxidized Metal Electrodes (Plenum, 1980).
Conner, W. C. & Falconer, J. L. Spillover in heterogeneous catalysis. Chem. Rev. 95, 759–788 (1995).
Prins, R. Hydrogen spillover. Facts and fiction. Chem. Rev. 112, 2714–2738 (2012).
Tierney, H. L., Baber, A. E., Kitchin, J. R. & Sykes, E. C. H. Hydrogen dissociation and spillover on individual isolated palladium atoms. Phys. Rev. Lett. 103, 246102 (2009).
Eikerling, M., Meier, J. & Stimming, U. Hydrogen evolution at a single supported nanoparticle: A kinetic model. Z. Phys. Chem. 217, 395–414 (2003).
Su, L. & Wu, B. L. Investigation of surface diffusion and recombination reaction kinetics of H-adatoms in the process of the hydrogen evolution reaction (her) at Au electrodes. J. Electroanal. Chem. 565, 1–6 (2004).
Sata, S., Awad, M. I., El-Deab, M. S., Okajima, T. & Ohsaka, T. Hydrogen spillover phenomenon: Enhanced reversible hydrogen adsorption/desorption at Ta2O5-coated Pt electrode in acidic media. Electrochim. Acta 55, 3528–3536 (2010).
Roland, U., Braunschweig, T. & Roessner, F. On the nature of spilt-over hydrogen. J. Mol. Catal. A 127, 61–84 (1997).
Merte, L. R. et al. Water-mediated proton hopping on an iron oxide surface. Science 336, 889–893 (2012).
Roland, U., Salzer, R., Braunschweig, T., Roessner, F. & Winkler, H. Investigations of hydrogen spillover. 1. Electrical conductivity studies on titanium-dioxide. J. Chem. Soc. Faraday Trans. 91, 1091–1095 (1995).
Rocheleau, R. E. & Miller, E. L. Photoelectrochemical production of hydrogen: Engineering loss analysis. Int. J. Hydrogen Energy 22, 771–782 (1997).
Hydrogen, Fuel Cells and Infrastructure Technologies Program—Multi-Year Research, Development and Demonstration Plan. US Department of Energy Efficiency and Renewable Energy. Available from: http://www1.eere.energy.gov/hydrogenandfuelcells/mypp/ (2007).
Kern, W. & Puotinen, D. A. Cleaning solutions based on hydrogen peroxide for use in silicon semiconductor technology. RCA Rev. 31, 187–206 (1970).
Esposito, D. V. et al. A new photoelectrochemical test cell and its use for a combined two-electrode and three-electrode approach to cell testing. Rev. Sci. Instrum. 80, 125107 (2009).
Acknowledgements
We acknowledge the NIST Nanofab and its staff for support in sample fabrication, Sandra Claggett for assistance in TEM sample preparation, and the NIST glass shop (J. Anderson and A. Kirchhoff). D.V.E. acknowledges the National Research Council Research Associateship Programs for funding. A.A.T. was supported in part by the Science of Precision Multifunctional Nanostructures for Electrical Energy Storage (NEES), an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under award DESC0001160.
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D.V.E. synthesized samples and performed all measurements except TEM measurements. I.L. performed TEM measurements. D.V.E., T.P.M. and A.A.T. designed the experiments and prepared the manuscript.
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Esposito, D., Levin, I., Moffat, T. et al. H2 evolution at Si-based metal–insulator–semiconductor photoelectrodes enhanced by inversion channel charge collection and H spillover. Nature Mater 12, 562–568 (2013). https://doi.org/10.1038/nmat3626
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DOI: https://doi.org/10.1038/nmat3626
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