Adsorption and desorption behavior of organic additives during Cu electrodeposition using microfluidic devices and morphology estimation

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The adsorption and desorption behaviour of poly(ethylene glycol, PEG) during Cu electrodeposition was investigated with a microfluidic device and a flow cell type electrochemical quartz crystal microbalance. First, the current density (i) transition curves were measured by using the microfluidic device for rapid exchange from the base electrolyte to electrolytes with added Br- and different concentrations of PEG to determine the effective surface coverage ratio of the electrodes by PEG. Compared with Cl-, the most familiar additive for Cu electrodeposition, Br- produced a higher steady-state effective surface coverage ratio and lower PEG adsorption rate constant (ka). Finally, the amount of increase in the weight on the electrode by PEG in a Br-/PEG system was measured using an EQCM to calculate steady-state effective surface coverage ratio by delta(m). The results revealed that the different capability of PEG to suppress i in the presence of Cl- and Br- depends on the delta(m).