Influence of the electrochemical environment on diffusion processes near step and island edges: Ag(111) and Ag(100)

The electrochemical cell provides a potentially powerful means of altering morphology and islanding phenomena on metallic surfaces. Diffusion and attachment processes on terraces and near step and island edges are known to profoundly affect island sizes, shapes and coarsening kinetics. Using the surface-embedded-atom-model (SEAM) for describing metallic surfaces in the electrolytic environment, we calculate the dependence of the activation energies for the aforementioned diffusion processes on the deposited surface charge for the Ag(lll)and Ag(100) surfaces in an electrolytic environment. While all these processes show some degree of dependence on the potential, the step-edge barrier and the edge diffusion processes are the most sensitive. Step-edge barriers increase (to over I eV) with large positive potential (0.85 V), while edge diffusion barriers monotonically decrease with positive surface charge on Ag(100) and Ag(lll). We assess the effect these diffusion barriers have on island size/shapes and coarsening dynamics and discuss the implications on electrochemical tuning of islanding phenomena.