The initial stages of Sn and Sn-Cu electrodeposition from Sn-citrate and Sn-Cu-citrate solutions on Pt were studied using both current-controlled and potential-controlled electrochemical techniques. For both Sn-citrate and Sn-Cu-citrate solutions, when the current density is controlled to lower than 15 mA/cm(2), potentials remain almost constant which is appropriate to plate dense and uniform films. When the current density is controlled to between 25 and 35 mA/cm(2), potentials drop quickly initially, followed by a gradual increase to a constant value. When current density is controlled to higher than 50 mA/cm(2), potential oscillation happens, and significant hydrogen evolution prevents the formation of dense and continuous Sn and Sn-Cu films. A constant transition time constant indicates a diffusion-controlled process. The diffusion coefficient calculated from the Sand equation is about 3.8 x 10(-6) cm(2)/s for the Sn-citrate solution and 4.1 X 10(-6) cm(2)/s for the Sn-Cu-citrate solution. The morphology of both Sn and Sn-Cu deposits plated under different potentials was examined by atomic force microscopy (AFM) and the distribution of each element were analyzed using Auger imaging. Analysis of both the electrochemical results at -0.72, -1.1 and -1.5 V and AFM images for both Sn and Sn-Cu deposits at -1.1 and -1.5 V suggested progressive nucleation controlled by diffusion for both Sn and Sn-Cu electrodeposition. Tin reacted with Pt to form PtSn4, and co-deposited with Cu to form Cu6Sn5 during nucleation, with more Sn forming at higher applied potentials. (C) 2009 Elsevier Ltd. All rights reserved.