Robust Au-Ag-Au bimetallic atom-scale junctions fabricated by self-limited Ag electrodeposition at Au nanogaps

Atom-scale junctions (ASJs) exhibit quantum conductance behavior and have potential both for fundamental studies of adsorbate-mediated conductance in mesoscopic conductors and as chemical sensors. Electrochemically fabricated ASJs, in particular, show the stability needed for molecular detection applications. However, achieving physically robust ASJs at high yield is a challenge because it is difficult to control the direction and kinetics of metal deposition. In this work, a novel electrochemical approach is reported, in which Au-Ag-Au bimetallic ASJs are reproducibly fabricated from an initially prepared Au nanogap by sequential overgrowth and self-limited thinning. Applying a potential across specially prepared Au nanoelectrodes in the presence of aqueous Ag(I) leads to preferential galvanic reactions resulting in the deposition of Ag and the formation of an atom-scale junction between the electrodes. An external resistor is added in series with the ASJ to control self-termination, and adjusting solution chemical potential (concentration) is used to mediate self-thinning of junctions. The result is long-lived, mechanically stable ASJs that, unlike previous constructions, are stable in flowing solution, as well as to changes in solution media. These bimetallic ASJs exhibit a number of behaviors characteristic of quantum structures, including long-lived fractional conductance states, that are interpreted to arise from two or more quantized ASJs in series.