Binary Compound Formation upon Copper Dissolution: STM and SXPS Results

The initial stages of electrochemical oxidative CuI film formation on Cu(111), as studied by means of Cyclic Voltammetry (CV), in-situ Scanning Tunneling Microscopy (STM) and ex-situ Synchrotron X-ray Photoemission Spectroscopy (SXPS), indicate a significant acceleration of copper oxidation in the presence of iodide anions in the electrolyte. A surface confined supersaturation with mobile CuI monomers first leads to the formation of a 2D-CuI film via nucleation and growth of a Cu/I-bilayer on-top of a pre-adsorbed iodide monolayer. Structurally, this 2D-CuI film is closely related to the (111) plane of crystalline CuI (zinc blende type). Interestingly, this film causes no significant passivation of the copper surface. In an advanced stage of copper dissolution a transition from the 2D- to a 3D-CuI growth mode can be observed.