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Potential-Induced High-Conductance Transport Pathways through Single-Molecule Junctions

  • Parisa Yasini
    Parisa Yasini
    Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, United States
  • Sepideh Afsari
    Sepideh Afsari
    Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, United States
  • Haowei Peng
    Haowei Peng
    Department of Physics, Temple University, Philadelphia, Pennsylvania 19122, United States
    More by Haowei Peng
  • Piret Pikma
    Piret Pikma
    Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, United States
    More by Piret Pikma
  • John P. Perdew
    John P. Perdew
    Department of Chemistry  and  Department of Physics, Temple University, Philadelphia, Pennsylvania 19122, United States
  • , and 
  • Eric Borguet*
    Eric Borguet
    Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, United States
    *[email protected]
    More by Eric Borguet
Cite this: J. Am. Chem. Soc. 2019, 141, 25, 10109–10116
Publication Date (Web):June 17, 2019
https://doi.org/10.1021/jacs.9b05448
Copyright © 2019 American Chemical Society

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    Abstract

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    Employing single molecules as electronic circuit building blocks is one promising approach to electronic device miniaturization. We report single-molecule junction formation where the orientation of molecules can be controlled externally by the working electrode potential. The scanning tunneling microscopy break junction (STM-BJ) method is used to bridge tetrafluoroterephthalic acid (TFTPA) and terephthalic acid (TPA) molecules between the Au(111) electrode and the STM tip to measure the single-molecule conductance through the junction. When the Au(111) electrode is at negative potentials (with respect to the zero-charge potential), a highly ordered and flat-oriented superstructure forms, allowing for direct contact between the π system of the benzene ring of the molecules and the Au(111) electrode, leading to junction formation with no anchoring group involvement. Our first-principles nonequilibrium Green’s function (NEGF) computation shows a flat configuration yields a conductance that is 3 orders of magnitude larger than for a molecule vertically connected to the electrodes via anchoring groups. Conductances of 0.24 ± 0.04 and 0.22 ± 0.02 G0 are experimentally measured with the flat configurations of TFTPA and TPA, respectively. These values are at least 2 orders of magnitude higher than the experimental values previously reported for the conductance of TPA bridged through carboxylic acid anchoring groups (3.8 × 10–4–3.2 × 10–3 G0). In contrast, a positively charged surface triggers an order–disorder transition eliminating the high-conductance states, most likely because the formation of the flat-oriented junction is prevented. The dependence of TFTPA conductance on the electrode potential (electrode Fermi level) suggests a LUMO mediated transport mechanism. Calculation confirms the lack of an effect of the addition of an electron-withdrawing group are investigated.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.9b05448.

    • Chemicals and solutions, STM cell setup and sample preparation, electrochemical scanning tunneling microscopy imaging, electrochemical scanning tunneling microscopy break junction measurement, detailed analysis of STM images of TFTPA, sample rejected current–distance curves, single-molecule conductance vs sample bias, single molecule conductance vs sample potential, detailed analysis of STM images of TPA, single-molecule conductance control experiments, and computational details (PDF)

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    Cited By

    This article is cited by 16 publications.

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