The time-dependent variation of effects of thiourea addition on Cu electrodeposition, and the electrochemical oxidation behavior of thiourea, were investigated by impedance measurements and cyclic voltammetry. In an aqueous sulfuric acid solution containing thiourea, an oxidation current of thiourea was observed at approximately 0.15–0.20 V on a Cu electrode and at approximately 0.7 V on a Pt electrode. The addition of thiourea or formamidine disulfide (FDS) decreased the charge transfer resistance of Cu deposition, thereby promoting Cu deposition. The FDS-added solution exhibited a lower charge transfer resistance than the thiourea-added solution. In the thiourea-containing solution, the charge transfer resistance further decreased with time from initial stage. Thereafter, it increased, and the additive effect gradually diminished. In the FDS-containing solution, the charge transfer resistance increased with time from the initial stage, and the additive effect gradually diminished. The loss of the additive effect occurred more rapidly under electrolysis conditions. This may be due to the acceleration of FDS decomposition induced by electrolysis. The enhancing effect of thiourea at initial stage is attributed to its conversion into FDS via electrochemical or chemical oxidation, which promotes the deposition reaction via a Cu[FDS]⁺ complex. In contrast, FDS may undergo hydrolysis, ultimately leading to the loss of its additive effect.
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