Reactive tunnel junctions in electrically driven plasmonic nanorod metamaterials


Non-equilibrium hot carriers formed near the interfaces of semiconductors or metals play a crucial role in chemical catalysis and optoelectronic processes. In addition to optical illumination, an efficient way to generate hot carriers is by excitation with tunnelling electrons. Here, we show that the generation of hot electrons makes the nanoscale tunnel junctions highly reactive and facilitates strongly confined chemical reactions that can, in turn, modulate the tunnelling processes. We designed a device containing an array of electrically driven plasmonic nanorods with up to 1011 tunnel junctions per square centimetre, which demonstrates hot-electron activation of oxidation and reduction reactions in the junctions, induced by the presence of O2 and H2 molecules, respectively. The kinetics of the reactions can be monitored in situ following the radiative decay of tunnelling-induced surface plasmons. This electrically driven plasmonic nanorod metamaterial platform can be useful for the development of nanoscale chemical and optoelectronic devices based on electron tunnelling.

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Fig. 1: Structural and optical properties of plasmonic nanorod metamaterials.
Fig. 2: Electrically driven nanorod metamaterial based on metal–air–metal tunnel junctions.
Fig. 3: Electrically driven nanorod metamaterial with reactive tunnel junctions.
Fig. 4: Electro-photo-chemistry in nanoscale tunnel junctions.


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This work has been funded in part by the Engineering and Physical Sciences Research Council (UK) and the European Research Council iPLASMM project (321268). A.V.Z. acknowledges support from the Royal Society and the Wolfson Foundation. The authors thank W. P. Wardley for helpful discussion.

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A.V.Z. and P.W. conceived the study. P.W. constructed the experiment, performed the measurement and analysed the data. M.E.N. and W.D. fabricated the plasmonic nanorod metamaterials. A.V.K. performed numerical simulations. All the authors discussed the results and co-wrote the paper.

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Correspondence to Pan Wang or Anatoly V. Zayats.

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Wang, P., Krasavin, A.V., Nasir, M.E. et al. Reactive tunnel junctions in electrically driven plasmonic nanorod metamaterials. Nature Nanotech 13, 159–164 (2018).

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