Formation and growth of oxide layers at platinum and gold nano- and microelectrodes

The construction and characterization of platinum and gold disk electrodes with minimum radii of 7 nm (platinum) and 500 nm (gold) is reported. The electrodes were prepared with a micropipet puller using a two step procedure and have been characterized using scanning electron microscopy, scanning electrochemical microscopy, high speed chronoamperometry, and cyclic voltammetry. The formation and growth of platinum and gold oxide layers, on the electrodes at time scales from microseconds to seconds, is reported. Significantly, the apparent microscopic area as determined by forming and subsequently reducing an oxide layer in acidic electrolyte using cyclic voltammetry depends dramatically on the scan rate. While conventional roughness factors between 1.8 and 3 are observed on average for scan rates above 5 V s(-1), the apparent roughness can exceed 30 for scan rates less than 0.5 V s(-1). Chronoamperometry, conducted on the microsecond to millisecond time scale, is used to probe the dynamics of monolayer and multilayer oxide formation as well as the reversibility of the oxide formation and removal. The latter study suggests that (at least for platinum) the growth of the oxide layer proceeds with a lower constant rate after an oxide monolayer is formed.