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Single-nanowire photoelectrochemistry

Abstract

Photoelectrochemistry1,2,3 is one of several promising approaches4,5 for the realization of efficient solar-to-fuel conversion. Recent work has shown that photoelectrodes made of semiconductor nano-/microwire arrays can have better photoelectrochemical performance6,7,8 than their planar counterparts because of their unique properties, such as high surface area9,10,11. Although considerable research effort has focused on studying wire arrays, the inhomogeneity in the geometry, doping, defects and catalyst loading present in such arrays can obscure the link between these properties and the photoelectrochemical performance of the wires, and correlating performance with the specific properties of individual wires is difficult because of ensemble averaging. Here, we show that a single-nanowire-based photoelectrode platform can be used to reliably probe the current–voltage (I–V) characteristics of individual nanowires. We find that the photovoltage output of ensemble array samples can be limited by poorly performing individual wires, which highlights the importance of improving nanowire homogeneity within an array. Furthermore, the platform allows the flux of photogenerated electrons to be quantified as a function of the lengths and diameters of individual nanowires, and we find that the flux over the entire nanowire surface (7–30 electrons nm–2 s–1) is significantly reduced as compared with that of a planar analogue (1,200 electrons nm–2 s–1). Such characterization of the photogenerated carrier flux at the semiconductor/electrolyte interface is essential for designing nanowire photoelectrodes that match the activity of their loaded electrocatalysts.

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Figure 1: Single-nanowire photoelectrode for PEC measurements.
Figure 2: Schematic illustrations of the fabrication and measurement processes.
Figure 3: PEC performance of the single-silicon-nanowire devices.
Figure 4: Analysis of the flux of photogenerated electrons.

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References

  1. Bard, A. J. Photoelectrochemistry. Science 207, 139–144 (1980).

    Article  CAS  Google Scholar 

  2. Grätzel, M. Photoelectrochemical cells. Nature 414, 338–344 (2001).

    Article  Google Scholar 

  3. Walter, M. G. et al. Solar water splitting cells. Chem. Rev. 110, 6446–6473 (2010).

    Article  CAS  Google Scholar 

  4. Reece, S. Y. et al. Wireless solar water splitting using silicon-based semiconductors and earth-abundant catalysts. Science 334, 645–648 (2011).

    Article  CAS  Google Scholar 

  5. Wang, H. et al. Semiconductor heterojunction photocatalysts: design, construction, and photocatalytic performances. Chem. Soc. Rev. 43, 5234–5244 (2014).

    Article  CAS  Google Scholar 

  6. Hwang, Y. J., Boukai, A. & Yang, P. High density n-Si/n-TiO2 core/shell nanowire arrays with enhanced photoactivity. Nano Lett. 9, 410–415 (2009).

    Article  CAS  Google Scholar 

  7. Hwang, Y. J., Wu, C. H., Hahn, C., Jeong, H. E. & Yang, P. Si/InGaN core/shell hierarchical nanowire arrays and their photoelectrochemical properties. Nano Lett. 12, 1678–1682 (2012).

    Article  CAS  Google Scholar 

  8. Liu, R. et al. Silicon nanowires as photoelectrodes for carbon dioxide fixation. Angew. Chem. Int. Ed. 51, 6709–6712 (2012).

    Article  CAS  Google Scholar 

  9. Mayer, M. T., Lin, Y., Yuan, G. & Wang, D. Forming heterojunctions at the nanoscale for improved photoelectrochemical water splitting by semiconductor materials: case studies on hematite. Acc. Chem. Res. 46, 1558–1566 (2013).

    Article  CAS  Google Scholar 

  10. Wu, Y., Yan, H. & Yang, P. Semiconductor nanowire array: potential substrates for photocatalysis and photovoltaics. Top. Catal. 19, 197–202 (2002).

    Article  CAS  Google Scholar 

  11. Liu, C., Dasgupta, N. P. & Yang, P. Semiconductor nanowires for artificial photosynthesis. Chem. Mater. 26, 415–422 (2014).

    Article  CAS  Google Scholar 

  12. Cui, Y., Wei, Q., Park, H. & Lieber, C. M. Nanowire nanosensors for highly sensitive and selective detection of biological and chemical species. Science 293, 1289–1292 (2001).

    Article  CAS  Google Scholar 

  13. Yan, R. et al. Nanowire-based single-cell endoscopy. Nature Nanotech. 7, 191–196 (2012).

    Article  CAS  Google Scholar 

  14. Tian, B., Kempa, T. J. & Lieber, C. M. Single nanowire photovoltaics. Chem. Soc. Rev. 38, 16–24 (2009).

    Article  CAS  Google Scholar 

  15. Tang, J., Huo, Z., Brittman, S., Gao, H. & Yang, P. Solution-processed core–shell nanowires for efficient photovoltaic cells. Nature Nanotech. 6, 568–572 (2011).

    Article  CAS  Google Scholar 

  16. Hochbaum, A. I. et al. Enhanced thermoelectric performance of rough silicon nanowires. Nature 451, 163–167 (2008).

    Article  CAS  Google Scholar 

  17. Cox, J. T. & Zhang, B. Nanoelectrodes: recent advances and new directions. Annu. Rev. Anal. Chem. 5, 253–272 (2012).

    Article  CAS  Google Scholar 

  18. Boettcher, S. W. et al. Photoelectrochemical hydrogen evolution using Si microwire arrays. J. Am. Chem. Soc. 133, 1216–1219 (2011).

    Article  CAS  Google Scholar 

  19. Hou, Y. et al. Bioinspired molecular co-catalysts bonded to a silicon photocathode for solar hydrogen evolution. Nature Mater. 10, 434–438 (2011).

    Article  CAS  Google Scholar 

  20. Esposito, D. V., Levin, I., Moffat, T. P. & Talin, A. A. H2 evolution at Si-based metal–insulator–semiconductor photoelectrodes enhanced by inversion channel charge collection and H spillover. Nature Mater. 12, 562–568 (2013).

    Article  CAS  Google Scholar 

  21. Ji, L. et al. A silicon-based photocathode for water reduction with an epitaxial SrTiO3 protection layer and a nanostructured catalyst. Nature Nanotech. 10, 84–90 (2015).

    Article  CAS  Google Scholar 

  22. Gorostiza, P., Allongue, P., Díaz, R., Morante, J. R. & Sanz, F. Electrochemical characterization of the open-circuit deposition of platinum on silicon from fluoride solutions. J. Phys. Chem. B 107, 6454–6461 (2003).

    Article  CAS  Google Scholar 

  23. Hochbaum, A. I., Fan, R., He, R. & Yang, P. Controlled growth of Si nanowire arrays for device integration. Nano Lett. 5, 457–460 (2005).

    Article  CAS  Google Scholar 

  24. Allen, J. E. et al. High-resolution detection of Au catalyst atoms in Si nanowires. Nature Nanotech. 3, 168–173 (2008).

    Article  CAS  Google Scholar 

  25. Koren, E. et al. Direct measurement of individual deep traps in single silicon nanowires. Nano Lett. 11, 2499–2502 (2011).

    Article  CAS  Google Scholar 

  26. Barton, E. E., Rampulla, D. M. & Bocarsly, A. B. Selective solar-driven reduction of CO2 to methanol using a catalyzed p-GaP based photoelectrochemical cell. J. Am. Chem. Soc. 130, 6342–6344 (2008).

    Article  CAS  Google Scholar 

  27. Kumar, B., Smieja, J. M. & Kubiak, C. P. Photoreduction of CO2 on p-type silicon using Re(bipy-But)(CO)3Cl: photovoltages exceeding 600 mV for the selective reduction of CO2 to CO. J. Phys. Chem. C 114, 14220–14223 (2010).

    Article  CAS  Google Scholar 

  28. Benson, E. E., Kubiak, C. P., Sathrum, A. J. & Smieja, J. M. Electrocatalytic and homogeneous approaches to conversion of CO2 to liquid fuels. Chem. Soc. Rev. 38, 89–99 (2009).

    Article  CAS  Google Scholar 

  29. Appel, A. M. et al. Frontiers, opportunities, and challenges in biochemical and chemical catalysis of CO2 fixation. Chem. Rev. 113, 6621–6658 (2013).

    Article  CAS  Google Scholar 

  30. Hori, Y. et al. Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media. Electrochim. Acta 39, 1833–1839 (1994).

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, of the US Department of Energy (contract no. DE-AC02-05CH11231, Pchem). Y.S. is supported by graduate fellowship support from USTC-Suzhou Industrial Park. High-resolution transmission electron microscopy was performed at the National Center of Electron Microscopy (NCEM) in the Molecular Foundry at Lawrence Berkeley National Laboratory. The authors thank K. Sakimoto, J. Resasco, A. Wong, S. Eaton and J. Lim for discussions. The authors acknowledge the Marvell Nanofabrication Laboratory for use of their facilities.

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Authors and Affiliations

Authors

Contributions

Y.S., C.L. and P.Y. conceived and designed the experiments. Y.S., C.L., S.B. and J.T. fabricated the single-nanowire devices. Y.S. and C.L. performed the PEC measurements on single-nanowire devices. Y.S., C.L. and A.F. carried out the numerical calculation. Y.S. and Q.K. fabricated and characterized the nanowire array samples. N.K. carried out the high-resolution TEM imaging. Y.S., C.L. and P.Y. co-wrote the paper. All authors discussed the results and revised the manuscript.

Corresponding author

Correspondence to Peidong Yang.

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The authors declare no competing financial interests.

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Su, Y., Liu, C., Brittman, S. et al. Single-nanowire photoelectrochemistry. Nature Nanotech 11, 609–612 (2016). https://doi.org/10.1038/nnano.2016.30

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