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Tailoring Crystallographic Orientations to Substantially Enhance Charge Separation Efficiency in Anisotropic BiVO4 Photoanodes

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    Research Article

    Tailoring Crystallographic Orientations to Substantially Enhance Charge Separation Efficiency in Anisotropic BiVO4 Photoanodes
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    • Jaesun Song
      Jaesun Song
      School of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 61005, Republic of Korea
      More by Jaesun Song
    • Min Ji Seo
      Min Ji Seo
      School of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 61005, Republic of Korea
      More by Min Ji Seo
    • Tae Hyung Lee
      Tae Hyung Lee
      Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea
      More by Tae Hyung Lee
    • Yong-Ryun Jo
      Yong-Ryun Jo
      School of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 61005, Republic of Korea
      More by Yong-Ryun Jo
    • Jongmin Lee
      Jongmin Lee
      School of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 61005, Republic of Korea
      More by Jongmin Lee
    • Taemin Ludvic Kim
      Taemin Ludvic Kim
      Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea
      More by Taemin Ludvic Kim
    • So-Young Kim
      So-Young Kim
      School of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 61005, Republic of Korea
      More by So-Young Kim
    • Seung-Mo Kim
      Seung-Mo Kim
      School of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 61005, Republic of Korea
      More by Seung-Mo Kim
    • Sang Yun Jeong
      Sang Yun Jeong
      School of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 61005, Republic of Korea
      More by Sang Yun Jeong
    • Hyunji An
      Hyunji An
      School of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 61005, Republic of Korea
      More by Hyunji An
    • Seungkyu Kim
      Seungkyu Kim
      School of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 61005, Republic of Korea
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    • Byoung Hun Lee
      Byoung Hun Lee
      School of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 61005, Republic of Korea
      More by Byoung Hun Lee
      Orcidhttp://orcid.org/0000-0002-4540-7731
    • Donghwa Lee
      Donghwa Lee
      Department of Materials Science and Engineering, and Division of Advanced Materials Science, Pohang University of Science and Technology (POSTECH), Pohang 37673, Republic of Korea
      More by Donghwa Lee
      Orcidhttp://orcid.org/0000-0002-8956-3648
    • Ho Won Jang
      Ho Won Jang
      Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea
      More by Ho Won Jang
      Orcidhttp://orcid.org/0000-0002-6952-7359
    • Bong-Joong Kim
      Bong-Joong Kim
      School of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 61005, Republic of Korea
      More by Bong-Joong Kim
      Orcidhttp://orcid.org/0000-0002-5335-4342
    • Sanghan Lee*
      Sanghan Lee
      School of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 61005, Republic of Korea
      *E-mail: [email protected]
      More by Sanghan Lee
      Orcidhttp://orcid.org/0000-0002-5807-864X
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    ACS Catalysis

    Cite this: ACS Catal. 2018, 8, 7, 5952–5962
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    https://doi.org/10.1021/acscatal.8b00877
    Published May 22, 2018
    Copyright © 2018 American Chemical Society
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    Abstract

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    In photoelectrochemical (PEC) water splitting, BiVO4 is considered the most promising photoanode material among metal oxide semiconductors because of its relatively narrow optical bandgap and suitable band structure for water oxidation. Nevertheless, until now, the solar-to-hydrogen conversion efficiency of BiVO4 has shown significant limitations for commercialization because of its poor charge transport. Various strategies, including the formation of a heterojunction and doping of electron donors, have been implemented to enhance the charge transport efficiency; however, fundamental approaches are required for further enhancement. In this regard, we report the fundamental approach for BiVO4 thin film photoanodes by fabricating epitaxial oxide thin films with different crystallographic orientations for PEC water splitting. The crystalline anisotropy generally reveals distinct physical phenomena along different crystallographic orientations. In the same vein, in terms of the anisotropic properties of BiVO4, the electrical conductivity of BiVO4 is greater along the ab-plane than along the c-axis. Consequently, as the crystallographic orientation of the BiVO4 thin film changes from (001) to (010), the charge transport properties in the epitaxial BiVO4 thin film are significantly enhanced. Thus, at 1.23 VRHE, the photocurrent density of the epitaxial BiVO4 (010) thin film (2.29 mA cm–2) is much higher than that of the epitaxial BiVO4 (001) thin film (0.74 mA cm–2) because of significant enhancement in charge transport properties even for undoped BiVO4. These results strongly suggest that the growth of epitaxial BiVO4 thin films with specific crystallographic orientations has great potential to considerably improve the charge transport efficiency of photoanodes for solar water splitting.

    Copyright © 2018 American Chemical Society

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.8b00877.

    • Detailed information about DFT calculation, current–voltage curves, XRD reflection rocking curves, Raman spectra, XPS spectra, magnified SAED patterns, photocurrent density versus time curves, and conductive AFM images (PDF)

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    Cited By

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    This article is cited by 91 publications.

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    Cite this: ACS Catal. 2018, 8, 7, 5952–5962
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