Reactive tunnel junctions in electrically-driven plasmonic nanorod metamaterials

Hot, nonequilibrium 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 which can in turn modulate the tunnelling processes. We designed a device containing an array of electrically-driven plasmonic nanorods with up to 10(11) tunnelling junctions per square centimeter, which demonstrates hot-electron activation of oxidation and reduction reactions in the junctions, induced by the presence of O(2) and H(2) 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.