Stochastic simulation of the early stages of kinetically limited electrodeposition

Kinetic Monte Carlo simulations are used to investigate nucleation and early stages of growth during metal electrodeposition at low overpotentials, where the kinetics of attachment of atoms to the electrode surface is rate-limiting. The surface diffusion energy barriers and deposition rate constants were varied to determine their effects on the deposition of metal onto a (111)-oriented facet of a face-centered cubic substrate material. The cluster density, average cluster size, and average cluster height were obtained from simulations. Over the range of parameters investigated here, the highest cluster densities were achieved when the metal-on-substrate surface diffusion rate was low relative to the metal-on-metal surface diffusion rate. It was found that the cluster density was highest after 0.3 equivalent monolayers had been deposited.