【作者】 吴伟刚； 杨防祖； 姚士冰； 陈秉彝； 郑雪清； 周绍民；

【Author】 Wei-Gang Wu,Fang-Zu Yang~*,Shi-Bing Yao,Bing-Yi Chen,Xue-Qing Zheng,Shao-Min Zhou (College of Chemistry and Chemical Engineering,State Key Laboratory of the Physical Chemistry of the Solid Surfaces,Xiamen University,Xiamen 361005)

【机构】 厦门大学化学化工学院固体表面物理化学国家重点实验室；

【摘要】 在研发的柠檬酸盐碱性无氰镀铜工艺基础上,应用线性扫描法和循环伏安法,研究了柠檬酸盐碱性镀铜电解液的阴极还原和阳极氧化过程,并探讨了在不同Cu²⁺浓度、温度及pH值下铜络合离子还原的电化学行为。结果表明,在阴极过程中,铜络合离子的还原近似于一步完成,其起波电位明显负于金属铜和铁的标准电极电位,可以满足在钢铁基体上直接镀铜的要求。在阳极过程中,沉积铜的溶出氧化按两步进行,Cu⁰→Cu⁺→Cu²⁺,但Cu⁺→Cu²⁺步骤进行得不完全。随着Cu²⁺浓度的增大、温度的升高、pH值的降低,铜络合离子的阴极极化程度减小,沉积电位正向偏移。铜络合离子阴极还原反应的交换电流密度i⁰=3.21×10^-7A/cm²,阴极传递系数=0.35;铜络合离子的扩散系数D=8.21×10^-6cm²/s;在-1.18 V～-1.30 V电位区间,表观活化能从30.50 kJ/mol降到13.16 kJ/mol.更多还原

【Abstract】 A new non - cyanide copper deposition bath was developed using citrate as main complexing agent and amine compound as assistant complexing agent.The electrochemical mechanism for the reduction of Cu²⁺ and the oxidation of copper deposits were studied by kinds of electrochemical methods,such as,sweep linear voltammetry（SLV）,cyclic voltammetry（CV）. Meanwhile,sweep linear voltammetry（SLV） was successfully applied to analyze the effects of temperature,Cu²⁺ concentration and pH value on cathodic polarization.The experimental results show that the Cu²⁺ probably gets two electrons in one step,while the oxidation of copper deposits is carried out in two steps,first the Cu⁰ to Cu+,and second the Cu + to Cu²⁺.Cu + can not be oxidized to Cu ²⁺ completely.The copper deposition potential shifts positively with the increasing of temperature and Cu ²⁺ concentration, and with the decreasing of pH value,respectively.The diffusion coefficient of copper ion is D = 8.21×10^-6 cm²/s and the transfer coefficient is = 0.35.The exchange current density is i⁰ =3.21×10^-7 A/cm².In the potential range from - 1.18 V to - 1.30 V,the apparent activation energy decreases from 30.50 KJ/mol to 13.16 KJ/mol.更多还原