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Large negative differential conductance in single-molecule break junctions

Nature Nanotechnology volume 9, pages 830–834 (2014)Cite this article

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Abstract

Molecular electronics aims at exploiting the internal structure and electronic orbitals of molecules to construct functional building blocks1. To date, however, the overwhelming majority of experimentally realized single-molecule junctions can be described as single quantum dots, where transport is mainly determined by the alignment of the molecular orbital levels with respect to the Fermi energies of the electrodes2 and the electronic coupling with those electrodes3,4. Particularly appealing exceptions include molecules in which two moieties are twisted with respect to each other5,6 and molecules in which quantum interference effects are possible7,8. Here, we report the experimental observation of pronounced negative differential conductance in the current–voltage characteristics of a single molecule in break junctions. The molecule of interest consists of two conjugated arms, connected by a non-conjugated segment, resulting in two coupled sites. A voltage applied across the molecule pulls the energy of the sites apart, suppressing resonant transport through the molecule and causing the current to decrease. A generic theoretical model based on a two-site molecular orbital structure captures the experimental findings well, as confirmed by density functional theory with non-equilibrium Green's functions calculations that include the effect of the bias. Our results point towards a conductance mechanism mediated by the intrinsic molecular orbitals alignment of the molecule.

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Figure 1: Illustration of the experiment.
Figure 2: NDC effect: mechanical tunability and stability.
Figure 3: I–V breaking series on AH and AC.
Figure 4: Two-site model.

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Acknowledgements

This research was carried out with financial support from the Dutch Foundation for Fundamental Research on Matter (FOM), NWO/OCW, FP7-framework programme ELFOS, ERC grant no. 240299 and by an ERC advanced grant (Mols@Mols). The authors thank C. Verzijl for help with DFT calculations.

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Authors and Affiliations

  1. Kavli Institute of Nanoscience, Delft University of Technology, Lorentzweg 1, Delft, 2628 CJ, The Netherlands

    Mickael L. Perrin, Riccardo Frisenda, Max Koole, Johannes S. Seldenthuis, Jose A. Celis Gil, Joseph M. Thijssen, Diana Dulić & Herre S. J. van der Zant

  2. Stratingh Institute for Chemistry and Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, Groningen, 9747 AG, The Netherlands

    Hennie Valkenier & Jan C. Hummelen

  3. School of Chemistry, University of Bristol, Cantocks Close, Bristol, BS8 1TS, UK

    Hennie Valkenier

  4. Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, Delft, 2628 BL, The Netherlands

    Nicolas Renaud & Ferdinand C. Grozema

  5. Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Santiago de Chile, Chile

    Diana Dulić

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  1. Mickael L. Perrin
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Contributions

D.D. and H.v.d.Z. designed the project. M.P. fabricated the devices. H.V. and J.H. designed and provided the molecules. M.P. and M.K. performed the low-temperature I–V series without electrode fusion. M.P. and R.F. performed the low-temperature I–V breaking series. R.F. performed the room-temperature I–V breaking series. M.P., J.S., J.C.G. and J.T. performed the DFT + NEGF calculations. N.R. and F.G. performed the molecular dynamics simulations. M.P., J.S., J.T. and H.v.d.Z. wrote the manuscript. All authors contributed to the interpretation of the data and commented on the manuscript.

Corresponding author

Correspondence to Herre S. J. van der Zant.

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The authors declare no competing financial interests.

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Perrin, M., Frisenda, R., Koole, M. et al. Large negative differential conductance in single-molecule break junctions. Nature Nanotech 9, 830–834 (2014). https://doi.org/10.1038/nnano.2014.177

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