Examining Ultramicroelectrodes for Scanning Electrochemical Microscopy by White Light Vertical Scanning Interferometry and Filling Recessed Tips by Electrodeposition of Gold

In this paper, we present a technique to rapidly and directly examine ultramicroelectrodes (UMEs) by white light vertical scanning interferometry (VSI). This technique is especially useful in obtaining topographic information with nanometer resolution without destruction or modification of the UME and in recognizing tips where the metal is recessed below the insulating sheath. Two gold UMEs, one with a metal radius a = 25 mu m and relative insulating sheath radius RG = 2 and the other with a = 5 mu m and RG = similar to 1.5, were examined, and the average depth of the gold recessions was determined to be 1.15 mu m and 910 nm, respectively. Electrodeposition of gold was performed to fill the recessed hole, and the depth was reduced to similar to 200 nm. With the electrodeposited gold electrode and a conventional microelectrode (a = 25 mu m) as a tip and substrate, respectively, a tip/substrate distance, d, of 600 nm was achieved allowing scanning electrochemical microscopy (SECM) in positive feedback mode at a close distance, which is useful for measuring fast kinetics.