Voltammetric Behavior of Gold Nanotrench Electrodes

We report the fabrication and electrochemical response of a gold nanoband electrode located at the bottom of a glass/epoxy nanotrench, hereafter referred to as a gold nanotrench electrode. Gold nanotrench electrodes of 12.5 and 40 nm in width with various depths from a few tens of nanometers to approximately 4 μm are fabricated and further characterized by cyclic voltammetry. The fabrication of a Au nanotrench electrode follows a simple electrochemical etching process in which a small AC signal is applied to an inlaid Au nanoband electrode submersed in a NaCl solution. The voltammetric behavior of a Au nanotrench electrode is characterized by a quasi-steady-state response at lower scan rates (e.g., <1 V/s for a 12.5-nm-wide electrode). We present an analytical expression for the quasi-steady-state diffusion-limited current of the nanotrench electrode based upon the analysis of the mass-transport resistance. Finite-element simulation of steady-state and transient voltammetric responses of the nanotrench electrodes provides additional insights for the analytical model. Peak-shaped transient voltammetric responses were observed at scan rates as low as 5 V/s for both inlaid and nanotrench electrodes. This result may suggest that the exposed area of the nanoband electrode is much greater than that expected from the fabrication of the inlaid bands. However, the extent to which this is seen is greatly decreased in the nanotrench electrode by a smoothing effect during etching. Our results confirm previous reports of excess overhanging metal and delamination crack contributing significantly to the shape and magnitude of the voltammetric response.