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研究了电解液pH值对Cu和Ru电偶腐蚀的影响,并对其控制机理进行深入的研究。选取H_2O_2作为Cu和Ru电化学电解液中的氧化剂和腐蚀剂,选用HCl和KOH溶液作为pH调节剂,采用动电位扫描这种电化学技术,表征金属铜钌表面的电化学反应。实验结果表明:在pH值低于7时,Ru在电解液中逐渐生成不溶的RuO_2·2H_2O和RuO_3,Cu仅发生腐蚀反应。在Cu和Ru的电偶腐蚀中,Cu作为阳极而加速溶解,影响器件的可靠性。在pH值高于7时,Ru可生成可溶的过钌酸盐,Cu表面含有一层致密的氧化层。在Cu和Ru电偶腐蚀中,Ru作为阳极而加速溶解,Cu得到了保护。在pH值为9时,Cu和Ru的腐蚀电位差最小为5 mV,因此在弱碱性阻挡层抛光液中可减少Cu和Ru之间的腐蚀电位差,有效抑制Cu和Ru之间电偶腐蚀现象的产生。
The effect of pH value of electrolyte on the galvanic corrosion of Cu and Ru was studied, and the control mechanism was further studied. H_2O_2 was chosen as oxidant and etchant in Cu and Ru electrochemical electrolytes. HCl and KOH solutions were selected as pH modifiers. Electrochemical techniques such as potentiodynamic scanning were used to characterize the electrochemical reaction on the surface of copper-ruthenium metal. The experimental results show that at pH lower than 7, Ru gradually forms insoluble RuO 2 .2H 2 O and RuO 3 in the electrolyte, Cu only undergoes corrosion reaction. In the galvanic corrosion of Cu and Ru, Cu accelerates dissolution as an anode, affecting the reliability of the device. At pH above 7, Ru forms a soluble perruthenate and the Cu surface contains a dense oxide layer. In the galvanic corrosion of Cu and Ru, Ru acts as an anode to dissolve rapidly and Cu is protected. At a pH of 9, the potential difference between Cu and Ru is 5 mV, so the potential difference between Cu and Ru can be reduced in the weak alkaline barrier slurry to effectively suppress the potential difference between Cu and Ru Corrosion phenomenon.