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Effects of hydration on molecular junction transport

Nature Materials volume 5, pages 901–908 (2006)Cite this article

Abstract

The study of charge transport through increasingly complex small molecules will benefit from a detailed understanding of how contaminants from the environment affect molecular conduction. This should provide a clearer picture of the electronic characteristics of molecules by eliminating interference from adsorbed species. Here we use magnetically assembled microsphere junctions incorporating thiol monolayers to provide insight into changing electron transport characteristics resulting from exposure to air. Using this technique, current–voltage analysis and inelastic electron tunnelling spectroscopy (IETS) demonstrate that the primary interaction affecting molecular conduction is rapid hydration at the gold–sulphur contacts. We use IETS to present evidence for changing mechanisms of charge transport as a result of this interaction. The detrimental effects on molecular conduction discussed here are important for understanding electron transport through gold–thiol molecular junctions once exposed to atmospheric conditions.

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Figure 1: Effects of hydration on microsphere junction I(V) characteristics.
Figure 2: Temperature and a.c. modulation dependence of microsphere junction IETS.
Figure 3: IETS analysis of anhydrous and hydrated alkanethiol microsphere junctions.
Figure 4: IETS analysis of anhydrous and hydrated OPE microsphere junctions.
Figure 5: Comparison of low-energy region in anhydrous and hydrated OPE IET spectra.

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Acknowledgements

The authors are grateful to J. Kushmerick of the National Institute of Standards and Technology for helpful comments and density functional theory calculations and G. Malliaras of Cornell University for the fabrication of magnetic arrays. This work was supported by the Defense Advanced Research Projects Agency (DARPA), the Office of Naval Research (ONR), the Air Force Office of Scientific Research (AFOSR) and the National Science Foundation (NSF).

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Authors and Affiliations

  1. Research and Development Center, Science Applications International Corporation (SAIC), 9460 Innovation Drive, Manassas, Virginia, 20110, USA

    David P. Long, Jason L. Lazorcik, Brent A. Mantooth & Ranganathan Shashidhar

  2. Center for Bio/Molecular Science and Engineering (Code 6900), Naval Research Laboratory, Washington, District of Columbia, 20375, USA

    Martin H. Moore

  3. Department of Chemistry, Center for Nanofabrication and Molecular Self-Assembly, Northwestern University, Evanston, Illinois, 60208, USA

    Mark A. Ratner

  4. Department of Chemistry and Centre of Scientific Computing, University of Warwick, Gibbet Hill Rd, Coventry, CV4 7AL, UK

    Alessandro Troisi

  5. Department of Chemistry and Smalley Institute for Nanoscale Science and Technology, Rice University, MS 222, 6100 Main Street, Houston, Texas, 77005, USA

    Yuxing Yao, Jacob W. Ciszek & James M. Tour

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  1. David P. Long
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Contributions

D.P.L. is the inventor of the microsphere test bed and performed all surface preparations, device fabrications, environmental I(V) analysis, variable-temperature IETS and project planning. J.L.L. and B.A.M. performed environmental IETS. M.H.M., Y.Y., J.W.C. and J.M.T. performed organic synthesis of OPE molecules. M.A.R. and A.T. conducted theoretical modelling of IETS spectra. R.S. supplied funding support.

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Correspondence to David P. Long.

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Long, D., Lazorcik, J., Mantooth, B. et al. Effects of hydration on molecular junction transport. Nature Mater 5, 901–908 (2006). https://doi.org/10.1038/nmat1754

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