Electrochemical nucleation and growth of copper on chromium-plated electrodes

Nucleation and growth of copper electrodeposited on chromium plated electrodes in copper sulfate electrolytes were examined, focusing on the influence of prior Cr plating conditions on the nucleation density and growth kinetics of the copper electrodeposits. The Cr-plated electrodes were made by electrodeposition of Cr on copper sheets for 2 to 60 s at 0.1 A cm−2 in CrO3 350 g L−1 + H2SO4 3.5 g L−1. Copper was then electrodeposited onto the Cr-plated electrode under potentiostatic conditions. Copper initially nucleated and grew according to a three-dimensional diffusion controlled progressive nucleation process, and later according to an instantaneous nucleation process. The period during which copper nucleation is controlled by the diffusion controlled progressive nucleation process decreases with increasing Cr plating time. The nucleation density of copper was extremely high on the 2 s Cr-plated electrode, producing an extremely fine and uniform electrodeposit. However, on the 4 s Cr-plated electrode, the nucleation density of copper significantly reduced to one hundredth of that on the 2 s Cr-plated electrode, and then decreased slightly with increasing Cr plating time (thickness of Cr layer). These results appear to be associated with the IR drop across the Cr layer, including the surface Cr oxide/hydroxide film (termed the cathode film), which significantly reduces the driving force for the electrodeposition of copper under potentiostatic plating conditions.