On the influence of the nucleation overpotential on island growth in electrodeposition

Electrochemical deposition of a metal onto a foreign substrate usually occurs by an island growth mechanism. A key feature of island growth for a material M on a foreign substrate S is that the onset potential for deposition is shifted negative from the equilibrium potential for the metal ion couple. The nucleation overpotential, defined as η_n(M⁺/S) = |U_n(M⁺/S) − U_eq(M⁺/M)|, influences key aspects of deposition of a metal on a foreign substrate. Here we discuss how the nucleation overpotential influences the kinetics of island growth, the implications of the nucleation overpotential on island shape and orientation, and the consequences of the coupling between the island density (applied potential) and the island size at coalescence (grain size). We then discuss the kinetics of island growth in terms of the contributions to vertical and lateral growth. Finally, we present examples of experimental methods to manipulate the nucleation overpotential and overcome some of the limitations imposed by the nucleation overpotential.