Pulsed Electrodeposition of Two-Dimensional Ag Nanostructures on Au(111)

One-step pulsed potential electrodeposition of Ag on Au(111) in the underpotential deposition (UPD) region has been studied in 0.5 mM Ag2SO4 + 0.1 M H2SO4 aqueous electrolyte at various pulse durations from 0.2 to 500 ms. Evolution of the deposited Ag nanostructures was followed by in situ scanning tunneling microscopy (STM) and by measurement of the respective current transients. At short pulse durations a relatively high number density (4 × 1011 cm-2) of two-dimensional Ag clusters with a narrow size and distance distribution is observed. They exhibit a remarkably high stability characterized by a dissolution potential which lies about 200 mV more anodically than the typical potential of Ag−(1 × 1) monolayer dissolution. To elucidate the underlying nucleation and growth mechanism, two models have been considered: two-dimensional lattice incorporation and a newly developed coupled diffusion−adsorption model. The first one yields a qualitative description of the current transients, whereas the second one is in nearly quantitative agreement with the experimental data. In this model the transformation of a Ag−(3 × 3) into a Ag−(1 × 1) structure indicated in the cyclic voltammogram (peaks at 520 vs 20 mV) is taken into account.