Effect of H2SeO3 on the early stages of nucleation and growth during Cu electrocrystallization in acidic medium on glassy carbon electrode

The early stages of Cu electrodeposition onto a GC electrode were investigated in 0.5 M H₂SO₄ + 0.01 M CuSO₄ solution without or with H₂SeO₃ when a molar concentration ratio [Cu(II)]/[Se(IV)] was 1.10⁴ to 2.10². The H₂SeO₃ solution in 0.5 M H₂SO₄ was also used. The electrochemical techniques such as cyclic voltammetry and chronoamperometry and structural investigation using ex situ AFM were applied to study the nucleation and growth of Cu onto a GC electrode. Chronoamperometric results were shown to follow an instantaneous 3D nucleation and diffusion-controlled growth model by Scharifker and Hills. The values of number of Cu nuclei N and average nuclei radius r _av were calculated. It was shown that, in the presence of H₂SeO₃ in amounts of 0.001 to 0.005 mM, N increases and r _av decreases. At higher concentrations of the additive, the changes of these parameters with the deposition potential E _dep were shown to be somewhat more complex. The dependences of N and r _av on the concentration of H₂SeO₃ in different regions of Cu overpotentials were also revealed.