AbstractWe studied the initial stages of the electrodeposition of Pb in the presence of chlorine ions on Cu(100), using an oblique-incidence optical reflectivity difference (OIRD) technique. The OI-RD results reveal that immediately following the underpotential deposition (UPD) of the first Pb monolayer, two different types of bulk-phase films grow depending upon the magnitude of overpotential and cyclic voltammetry (CV) scan rate. At low overpotentials and/or slow scan rates, we propose that a bulk-phase Pb film grows on top of the UPD monolayer. At high overpotentials and/or fast scan rates, either a PbO, PbCl2, or a rough Pb bulk-phase layer grows on top of the UPD layer such that the reflectivity difference signal from such a film has an opposite sign.
