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    Resonant Coupling between Molecular Vibrations and Localized Surface Plasmon Resonance of Faceted Metal Oxide Nanocrystals

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    Agrawal, Ankit; Singh, Ajay; Yazdi, Sadegh; Singh, Amita; Ong, Gary K.; More... Bustillo, Karen; Johns, Robert W.; Ringe, Emilie; Milliron, Delia J. Less...
    Date
    2017
    Abstract
    Doped metal oxides are plasmonic materials that boast both synthetic and postsynthetic spectral tunability. They have already enabled promising smart window and optoelectronic technologies and have been proposed for use in surface enhanced infrared absorption spectroscopy (SEIRA) and sensing applications. Herein, we report the first step toward realization of the former utilizing cubic F and Sn codoped In2O3 nanocrystals (NCs) to couple to the C–H vibration of surface-bound oleate ligands. Electron energy loss spectroscopy is used to map the strong near-field enhancement around these NCs that enables localized surface plasmon resonance (LSPR) coupling between adjacent nanocrystals and LSPR-molecular vibration coupling. Fourier transform infrared spectroscopy measurements and finite element simulations are applied to observe and explain the nature of the coupling phenomena, specifically addressing coupling in mesoscale assembled films. The Fano line shape signatures of LSPR-coupled molecular vibrations are rationalized with two-port temporal coupled mode theory. With this combined theoretical and experimental approach, we describe the influence of coupling strength and relative detuning between the molecular vibration and LSPR on the enhancement factor and further explain the basis of the observed Fano line shape by deconvoluting the combined response of the LSPR and molecular vibration in transmission, absorption and reflection. This study therefore illustrates various factors involved in determining the LSPR–LSPR and LSPR–molecular vibration coupling for metal oxide materials and provides a fundamental basis for the design of sensing or SEIRA substrates.
    Citation
    Agrawal, Ankit, Singh, Ajay, Yazdi, Sadegh, et al.. "Resonant Coupling between Molecular Vibrations and Localized Surface Plasmon Resonance of Faceted Metal Oxide Nanocrystals." Nano Letters, (2017) American Chemical Society: http://dx.doi.org/10.1021/acs.nanolett.7b00404.
    Published Version
    http://dx.doi.org/10.1021/acs.nanolett.7b00404
    Keyword
    EELS; Fano resonance; Infrared plasmon; metal oxide; SEIRA
    Type
    Journal article
    Publisher
    American Chemical Society
    Citable link to this page
    https://hdl.handle.net/1911/94054
    Rights
    This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
    Link to License
    http://pubs.acs.org.ezproxy.rice.edu/page/policy/authorchoice_termsofuse.html
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    • Chemistry Publications [705]
    • Faculty Publications [5504]
    • Materials Science and NanoEngineering Publications [404]

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    Managed by the Digital Scholarship Services at Fondren Library, Rice University
    Physical Address: 6100 Main Street, Houston, Texas 77005
    Mailing Address: MS-44, P.O.BOX 1892, Houston, Texas 77251-1892
    Site Map