Abstract
Copper deposition on Au(111) electrodes in aqueous sulfuric acid solution is an important model system which has been extensively studied. To improve the quality of electrodeposited films, additives, such as 3-Mercapto-1-propansulfonic acid (MPS) and chloride ions, are commonly employed in industrial plating bathes. Electrochemical scanning tunneling microscopy (EC-STM) and cyclic voltammetry (CV) were used to study the adsorption of MPS on Au(111) electrodes and the behavior of MPS desorption. STM images revealed an ordered (√21 毕 2√19) MPS adlayer at potentials >0.6V and a disordered phase at more cathodic potentials. Measurements revealed that MPS monolayer is stable in the electric double-layer at the potential between 0.11V to 0.8V. In Cu containing electrolytes, cathodic peak of Cu underpotential deposition (UPD), corresponding to (√3 毕 √3) transferred to (1 毕 1) is disappeared. In analog STM experiments, the MPS adlayer is (4 × √13) ordered structure in the position where no Cu deposition takes place. An additional amount of 1.4 mM chloride ions strongly affects the growth behavior of Cu UPD. Cu islands deposit in the region with the 库 phase. A two-dimensional growth of monoatomic height Cu islands forms the Cu UPD layer. Coalescence of the islands at the higher coverage results in a connected layer with fractal shape. Keywords: Self-assembly monolayer, scanning tunneling microscopy, electrochemical copper deposition
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