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A surface-anchored molecular four-level conductance switch based on single proton transfer

Nature Nanotechnology volume 7, pages 41–46 (2012)Cite this article

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Abstract

The development of a variety of nanoscale applications1,2 requires the fabrication and control of atomic3,4,5 or molecular switches6,7 that can be reversibly operated by light8, a short-range force9,10, electric current11,12 or other external stimuli13,14,15. For such molecules to be used as electronic components, they should be directly coupled to a metallic support and the switching unit should be easily connected to other molecular species without suppressing switching performance. Here, we show that a free-base tetraphenyl-porphyrin molecule, which is anchored to a silver surface, can function as a molecular conductance switch. The saddle-shaped molecule has two hydrogen atoms in its inner cavity that can be flipped between two states with different local conductance levels using the electron current through the tip of a scanning tunnelling microscope. Moreover, by deliberately removing one of the hydrogens, a four-level conductance switch can be created. The resulting device, which could be controllably integrated into the surrounding nanoscale environment, relies on the transfer of a single proton and therefore contains the smallest possible atomistic switching unit.

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Figure 1: Double proton transfer in 2H-TPP on Ag(111).
Figure 2: Sequential deprotonation of 2H-TPP on Ag(111).
Figure 3: Visualization of the four proton positions in 1H-TPP on Ag(111).
Figure 4: Current dependence of switching rate S for 2H-TPP and 1H-TPP recorded on an α-pyr position.
Figure 5: Voltage dependence of the switching rate S for 2H-TPP and 1H-TPP excited on an α-pyr position.

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Acknowledgements

The authors thank J. Repp for helpful suggestions concerning the data analysis. The work was supported by the ERC Advanced Grant MolArt (no. 247299), TUM-IAS and the Munich Center for Advanced Photonics (MAP). N.S. acknowledges a scholarship from DAAD. D.E. thanks the European Commission for support through the Marie Curie IntraEuropean Fellowship for Career Development FP7 programme.

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  1. Willi Auwärter and Knud Seufert: These authors contributed equally to this work

Authors and Affiliations

  1. Physik Department E20, Technische Universität München, D-85748, Garching, Germany

    Willi Auwärter, Knud Seufert, Felix Bischoff, David Ecija, Saranyan Vijayaraghavan, Sushobhan Joshi, Florian Klappenberger, Niveditha Samudrala & Johannes V. Barth

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  1. Willi Auwärter
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Contributions

K.S., W.A., F.B., D.E., S.V., S.J. and N.S. performed the STM experiments and analysed and interpreted the experimental data. F.K. supported the data analysis and contributed to the NEXAFS experiments. W.A., K.S. and J.V.B conceived the studies and co-wrote the paper.

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Correspondence to Willi Auwärter.

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Auwärter, W., Seufert, K., Bischoff, F. et al. A surface-anchored molecular four-level conductance switch based on single proton transfer. Nature Nanotech 7, 41–46 (2012). https://doi.org/10.1038/nnano.2011.211

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