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    Sensitized Zinc–Cobalt–Oxide Spinel p-Type Photoelectrode
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    † ‡ †Renewable and Sustainable Energy Institute, and ‡Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0027, United States
    § National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States
    ∥ Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, United States
    *E-mail: [email protected]. Telephone: 303-384-6403. Mailing address: 027 UCB, Suite 208, Fleming Building Boulder, CO 80309-0027.
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2014, 118, 44, 25340–25349
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    https://doi.org/10.1021/jp508153j
    Published October 8, 2014
    Copyright © 2014 American Chemical Society
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    Abstract

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    Tandem dye-sensitized solar cells that use nickel oxide as a hole-transport layer have limited performance due to the poor transport properties of NiO; alternative p-type oxides with the correct band alignment, good hole mobility, and stability in corrosive electrolyte must be identified. In this paper, we present our study on the ternary oxide material (zinc–cobalt–oxide spinel) as a hole conductor in a sensitized architecture. Zinc substitution for cobalt in cobalt(II,III) oxide results in good p-type conductivity and a spinel crystal structure. The flatband potential of Zn–Co–O thin films was determined to be around 0.7 V vs NHE (pH 5) and varies slightly depending on the conducting substrate. The films were used as the hole-transport layer in a dye-sensitized solar cell, and the hole-injection current was generated upon sensitization by coumarin-343. The cells exhibited an IQE of >90% and an open-circuit voltage of around 260 mV. The increase in photon-to-electron conversion efficiency of Zn–Co–O over NiO was due to an increased diffusion length, lower recombination, and better transport within the semiconductor-electrolyte device. Although the films were assembled here as liquid electrolyte dye-sensitized photovoltaic devices, they are also applicable to dye-sensitized photoelectrochemical cells for solar fuels.

    Copyright © 2014 American Chemical Society

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    Supporting Information

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    IQE calculations, absorbance of the film and chromophore used in the experiment (Figure S1), crystallinity of a sputtered thin film (Figure S2), I–V curves of other devices (Figures S3 and S4), and details of the electrochemical impedance spectroscopy analysis. This material is available free of charge via the Internet at http://pubs.acs.org.

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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2014, 118, 44, 25340–25349
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jp508153j
    Published October 8, 2014
    Copyright © 2014 American Chemical Society
    Request reuse permissions

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