Aqueous Electrodeposition of Ge Monolayers

The electrodeposition of germanium on Au(111) in aqueous solutions has been investigated by means of cyclic voltammetry, Auger electron spectroscopy, and in situ scanning tunneling microscopy (STM). The data yield a picture of germanium deposition, which starts with the formation of two well-ordered hydroxide phases, with 1/3 ML and 4/9 ML coverages upon initial reduction of the Ge(IV) species (probably H2GeO3 at pH 4.7). Those structures appear to result from a three-electron reduction to from surface-limited structures with (root 3 x root 3)R30 degrees or (3 x 3) unit Cells, respectively. Further reduction, probably in a two-electron process from the hydroxide structures, resulted in a germanium hydride structure, again surface-limited, with a coverage of close to 0.8 ML. The hydride structure is very flat, though with the periodic modulation characteristic of a Moire pattern. Longer deposition times and lower potentials resulted in increased coverage of Ge in some cases, but with apparently limited coverage as a function of pH. The maximum Ge coverage, about 4 M L, was observed using a pH 9.32 deposition solution. At potentials negative of the Moire pattern, about -850 mV versus Ag/AgCl, a corruption of the smooth Moire pattern Occurred. This roughening appears to mark the initial formation of a Au-Ge alloy, accounting for the observation of coverage in excess of that needed to form the Moire pattern at some pH values.