The surface structure of Cu(100) modified by chloride and iodide has been studied in an electrochemical environment by means of in-situ scanning tunneling microscopy in combination with in-situ surface X-ray diffraction with a particular focus on adsorbate and potential dependent surface relaxation phenomena. For positive potentials close to the on-set of the copper dissolution reaction, the X-ray data disclose an extraordinarily large Cu-Cl bond length of 2.61 A for the c(2 x 2)-Cl phase. This finding points to a largely ionic character of the Cu-Cl interaction at the Cu(100) surface, with chloride particles likely to retain their full charge upon adsorption. Together with the positive surface charging at these high potentials, this ionic Cu-Cl bond drives the observed 2.2% outward relaxation between the first two copper layers. These results indicate that the bond between the first and the second copper layer is significantly weakened which appears as the crucial prerequisite for the high surface mobility of copper-chloride species under electrochemical annealing conditions at these high potentials. With 2.51 A the Cu-I bond is 4% shorter than the Cu-Cl bond implying that the nature of the Cu-I bond is mainly covalent. Accordingly, we observe a significant inward relaxation of the top Cu layers upon substituting chloride by iodide at the same electrode potential, which suggests that the iodide adsorption involves charge transfer from the halide to the copper substrate.

The initial stage of oxidative CuI film formation on Cu(111) has been studied in an electrochemical environment by means of cyclic voltammetry (CV), in situ scanning tunneling microscopy (STM) and ex situ synchrotron X-ray photoemission spectroscopy (SXPS). Cyclic voltammetric studies indicate a significant acceleration of copper oxidation in the presence of iodide. The reason for that is the iodide-mediated stabilization of cuprous species resulting in a downward shift of the onset potential for copper oxidation. Reactive sites for the copper oxidation followed by iodide complexation are exclusively defects such as substrate step edges. It is the surface-confined supersaturation of mobile CuI species that leads to the two-dimensional (2D) CuI film formation via nucleation and growth of a Cu/I bilayer on top of the preadsorbed iodide phase. In an advanced stage of copper oxidation, however, terraces are directly transformed into the 2D CuI film at the reactive boundary between metallic copper and the growing 2D CuI film. Structurally, this 2D CuI film is closely related to the (111) plane of crystalline CuI bulk (zinc blende type). There is no significant passivation of the copper surface against the oxidative dissolution reaction in the presence of the 2D CuI film. Copper dissolution in the presence of the 2D CuI film proceeds also via an inverse step flow mechanism involving the concerted receding of four atomic layers. A model of this process will be discussed on the basis of STM results. The transition from 2D to a three-dimensional (3D) CuI growth mode is observed for an advanced stage of copper oxidation.

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Charged organic adsorbates play an important role in a number of electrochemical reactions, e.g. as additives for metal plating relevant for device fabrication in the semiconductor industry. Fundamental investigations are mandatory in order to acquire profound knowledge of the structural and electronic properties of these layers parallel and perpendicular to the surface, and to finally achieve a deeper mechanistic understanding of the kinetics of involved charge transfer reactions taking place at these complex metal/organic/electrolyte interfaces. A key structural motif of these interfaces consists in 'paired' (inorganic)anion/(organic)cation layers that can have an enormous stability even during an ongoing charge transfer reaction. In this contribution we present and discuss a selected case study on the co-adsorption of halide anions and cationic organic molecules that exhibit a pronounced redox activity. It will be demonstrated that their phase behavior at the interface crucially depends on both their particular redox-state and the surface concentration of the halide counter ions. The subtle balance between adsorbate–adsorbate and adsorbate–substrate interaction of the poly-cationic organic layer can be carefully controlled by potential dependent anion adsorption and desorption processes through the organic layer. This process can be followed by in situ high-resolution scanning tunnelling microscopy, while additional information about the structural and chemical state of the respective phase is obtained from in situ X-ray diffraction and ex situ photoelectron spectroscopy.