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Charge Separation, Band-Bending, and Recombination in WO3 Photoanodes

  • Sacha Corby
    Sacha Corby
    Department of Chemistry and Centre for Plastic Electronics, Imperial College London, White City Campus, London W12 0BZ, United Kingdom
    More by Sacha Corby
  • Ernest Pastor
    Ernest Pastor
    Department of Chemistry and Centre for Plastic Electronics, Imperial College London, White City Campus, London W12 0BZ, United Kingdom
  • Yifan Dong
    Yifan Dong
    Department of Chemistry and Centre for Plastic Electronics, Imperial College London, White City Campus, London W12 0BZ, United Kingdom
    More by Yifan Dong
  • Xijia Zheng
    Xijia Zheng
    Department of Chemistry and Centre for Plastic Electronics, Imperial College London, White City Campus, London W12 0BZ, United Kingdom
    More by Xijia Zheng
  • Laia Francàs
    Laia Francàs
    Department of Chemistry and Centre for Plastic Electronics, Imperial College London, White City Campus, London W12 0BZ, United Kingdom
  • Michael Sachs
    Michael Sachs
    Department of Chemistry and Centre for Plastic Electronics, Imperial College London, White City Campus, London W12 0BZ, United Kingdom
  • Shababa Selim
    Shababa Selim
    Department of Chemistry and Centre for Plastic Electronics, Imperial College London, White City Campus, London W12 0BZ, United Kingdom
  • Andreas Kafizas
    Andreas Kafizas
    Department of Chemistry and Centre for Plastic Electronics, Imperial College London, White City Campus, London W12 0BZ, United Kingdom
    Grantham Institute for Climate Change, Imperial College London, South Kensington, London SW7 2AZ, United Kingdom
  • Artem A. Bakulin
    Artem A. Bakulin
    Department of Chemistry and Centre for Plastic Electronics, Imperial College London, White City Campus, London W12 0BZ, United Kingdom
  • , and 
  • James R. Durrant*
    James R. Durrant
    Department of Chemistry and Centre for Plastic Electronics, Imperial College London, White City Campus, London W12 0BZ, United Kingdom
    *E-mail: [email protected]
Cite this: J. Phys. Chem. Lett. 2019, 10, 18, 5395–5401
Publication Date (Web):August 16, 2019
https://doi.org/10.1021/acs.jpclett.9b01935
Copyright © 2019 American Chemical Society

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    Abstract

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    In metal oxide-based photoelectrochemical devices, the spatial separation of photogenerated electrons and holes is typically attributed to band-bending at the oxide/electrolyte interface. However, direct evidence of such band-bending impacting upon charge carrier lifetimes has been very limited to date. Herein we use ultrafast spectroscopy to track the rapid relaxation of holes in the space-charge layer and their recombination with trapped electrons in WO3 photoanodes. We observe that applied bias can significantly increase carrier lifetimes on all time scales from picoseconds to seconds and attribute this to enhanced band-bending correlated with changes in oxygen vacancy state occupancy. We show that analogous enhancements in carrier lifetimes can be obtained by changes in electrolyte composition, even in the absence of applied bias, highlighting routes to improve photoconversion yields/performance, through changes in band-bending. This study thus demonstrates the direct connection between carrier lifetime enhancement, increased band-bending, and oxygen vacancy defect state occupancy.

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    • Sample preparation, details of the experimental setup, and additional data on bias dependence of photogenerated electron kinetics (PDF)

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