LAUSR

Processes of nucleation and growth largely determine the structure and properties of thin films obtained by electrodeposition on foreign substrates. Theoretical aspects of the initial stages of electrochemical phase formation under constant and variable overpotentials are considered in this work. Simulation of multiple nucleation with mixed (charge transfer, and diffusion) controlled growth was performed for three cases (cyclic voltammetry, potentiostatic electrodeposition, and galvanostatic electrodeposition). The influence of the bulk concentration of depositing ions and the exchange current density at the electrolyte/nucleus interface on cyclic voltammograms (CVs), transients of current and overpotential, as well as the number and size of non-interacting new-phase nuclei was analyzed. It is found that, under galvanostatic conditions, the number of nuclei decreases as the concentration of depositing ions increases due to a more rapid decrease in overpotential. The proposed model was applied to determine the diffusion coefficient, exchange current density, and transfer coefficient considering the experimental CV.