Nucleation Overpotential and the Role of Nucleation Early and Late in a Deposition Cycle

Interest in monitoring nucleation overpotential in electrometallurgical processes dates back some 40 years or more. Conversely, remarkable progress has been made in recent years on describing in detail the processes involved in the formation of thin films by electrodeposition. The newer body of work underscores a need for greater clarity in speaking about the role of nucleation and in the acquisition and interpretation of nucleation overpotential measurements – the aim of this paper. In electrometallurgy, it is generally desirable to form deposits that remain smooth, compact, and relatively fine-grained while the deposit grows to a thickness on the order of 5-10 mm, about 100 times thicker than technological thin films. Hence, we distinguish two kinds of nucleation that can result in formation of new grains:- (1) initial nucleation (onto the substrate surface) of islands that coalesce into growing deposit, and (2) ongoing nucleation of new grains on the deposit surface long after the substrate has been covered and ceases to have a direct influence. Nucleation overpotential of the first type should be measured on an electrode surface truly representative of a real industrial substrate. The second type requires judicious choice of electrode material – an “ideal foreign substrate”. In general neither the industrial substrate nor native metal to be deposited is suitable for measurement of the second type of nucleation overpotential, because of interference by other processes. For the future, clear terminology is needed to distinguish these two types of nucleation potential. The second is the one for which the type of plot dubbed by Moats and Derrick as an “Adcock plot” and by us as a “Kerby-Adcock plot” was first conceived and correlated with relatively thick zinc electrodeposits. The data of Moats and Derrick showing trends for copper electrodeposition on stainless steel and on copper electrodes are interpreted within this framework.