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    Redox-active monolayers in mesoporous silicon

    Access Status
    Fulltext not available
    Authors
    Ciampi, S.
    Guan, B.
    Darwish, Nadim
    Reece, P.
    Gooding, J.
    Date
    2012
    Type
    Journal Article
    
    Metadata
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    Citation
    Ciampi, S. and Guan, B. and Darwish, N. and Reece, P. and Gooding, J. 2012. Redox-active monolayers in mesoporous silicon. Journal of Physical Chemistry C. 116 (30): pp. 16080-16088.
    Source Title
    Journal of Physical Chemistry C
    DOI
    10.1021/jp303980x
    ISSN
    1932-7447
    School
    Nanochemistry Research Institute
    URI
    http://hdl.handle.net/20.500.11937/39356
    Collection
    • Curtin Research Publications
    Abstract

    Herein, redox reactions at chemically derivatized porous silicon (PSi) films are investigated. Passivation of the PSi matrix, by replacing metastable Si-H termini with nonpolar Si-C=C-R linkages, allows the electrochemical PSi device to operate in aqueous environments under oxidizing conditions (i.e., electron hole accumulation regime). Cu(I)-catalyzed alkyne-azide cycloaddition reactions are used to anchor ferrocene derivatives and probe electrochemical reactions at the exceedingly large surface area-to-volume ratio of mesoporous PSi. The forward-biased p-type PSi/electrolyte interface retains a quasi-metallic behavior throughout its entire contour, and it does so for prolonged times even when the electrode is poised at potentials at which a bare silicon electrode would rapidly oxidize. The interfacial capacitance of the PSi matrix is, however, unexpectedly low. An explanation is proposed where PSi morphology and the semiconductor space-charge layer capacitance play a significant role in determining the charging properties of the electrode. These results are important for the application of porous semiconductor electrodes in sensing, electrocatalytic, and energy-conversion devices.

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