A method for fabricating submicrometer-sized gold electrodes of conical or spherical geometry is described. By generating an electric arc between an etched gold microwire and a tungsten counter electrode, the very end of the gold microwire can be melted and given an overall spherical or conical shape a few hundred nanometers in size. The whole wire is subsequently insulated via the cathodic deposition of electrophoretic paint. By applying a high-voltage pulse to the microwire, the film covering its very end can then be selectively removed, thus exposing a submicrometer-sized electrode surface of predefined geometry. The selective exposure of the preformed end of the microwire is demonstrated by cyclic voltammetry, scanning electron microscopy, and metal electrodeposition experiments. The electrophoretic paint coating provides a low-capacitance, robust insulating film allowing exploration of a very wide potential window in aqueous solution. The submicrometer-sized electrodes can easily be turned into probes suitable for combined scanning electrochemical-atomic force microscopy by bending and flattening the gold microwire so that the tip is borne by a flexible enough arm. The good agreement between theoretical and experimental scanning electrochemical microscopy approach curves thus obtained confirms that only the very end of the tip, of predefined geometry, is exposed to the solution.

The combined atomic force-electrochemical microscopy (AFM-SECM) technique was used in aqueous solution to determine both the static and dynamical properties of nanometer-thick monolayers of poly(ethylene glycol) (PEG) chains end-grafted to a gold substrate surface. Approach of a microelectrode tip from a redox end-labeled PEG layer triggered a tip-to-substrate cycling motion of the chains' free ends as a result of the redox heads' oxidation at the tip and re-reduction at the substrate surface. As few as approximately 200 chains at a time could be addressed in such a way. Quantitative analysis of the data, in the light of a simple model of elastic bounded diffusion SECM positive feedback, gave access to the end-tethered polymer layer thickness and the end-to-end diffusion coefficient of the chains. The thickness of the grafted PEG layer was shown to increase with the chain surface coverage, while the end-to-end diffusion coefficient was found to be constant and close to the one predicted by Rouse dynamics. At close tip-substrate separation, slowing of the chains' motion, as a consequence of their vertical confinement within the tip-substrate gap, was observed and quantitatively modeled.