亚甲基二膦酸为配位体的无氰碱性镀铜  

Copper Electrodeposition from Non-Cyanide Alkaline Baths Containing Methylene Diphosphonic Acid as a Complexing Agent

作　　者：郑精武[1] 陆国英[1] 乔梁[1] 姜力强[1] 蒋梅燕[1] 

机构地区：[1]浙江工业大学化学工程与材料学院,杭州310032

出　　处：《物理化学学报》2011年第1期143-148,共6页Acta Physico-Chimica Sinica

基　　金：浙江省自然科学基金(Y406406)资助项目~~

摘　　要：提出一种以亚甲基二膦酸(MDPA,H4L)为主配位剂的无氰镀铜体系.采用pH电位滴定法分别测定MDPA的四级解离常数和MDPA-Cu(II)的稳定常数,并比较MDPA-Cu(II)和羟基乙叉二膦酸(HEDPA)-Cu(II)的循环伏安曲线和阴极极化曲线.结果表明:MDPA各级解离常数为,pK1=1.86,pK2=2.65,pK3=6.81,pK4=9.04;MDPA与Cu2+形成分级配合物的稳定常数为,pKML=10.65,pKML2=5.59,pKML3=2.50;随着pH升高,形成的配合物依次为,Cu(H3L)2、[Cu(H3L)(H2L)]-和[Cu(H2L)2]2-;当pH在7-10时,MDPA较HEDPA更易与Cu2+配位.当pH=9时,MDPA碱性镀铜体系阴极主要发生的是[Cu(H3L)(H2L)]-和[Cu(H2L)2]2-还原生成铜的过程;在10°C,MDPA体系的铜配位化合物还原生成铜的电位比HEDPA体系负移,扩散速度更快.A cyanide-free alkaline copper deposition bath was developed using methylene diphosphonic acid（MDPA,H4L） as a complexing agent for Cu2＋.The plating bath was investigated using potentiometric titrations,voltammetric curves,and polarization curves.The potentiometric titration gave dissociation constants for MDPA of：pK1=1.86,pK2=2.65,pK3=6.81,pK4=9.04,and the stability constants were：pKML=10.65,[pKML2=]5.59,[pKML3=]2.50.Three different complex species were present in the bath as the pH increases：Cu（H3L）2,[Cu（H3L）（H2L）]-,and [Cu（H2L）2]2-.MDPA was found to be more likely to form complex species with Cu2＋ than 1-hydroxyethylene-1,1-diphosphonic acid（HEDPA） from pH 7 to pH 10.At pH 9,[Cu（H3L）（H2L）]-and [Cu（H2L）2]2-were reduced to Cu at the cathode.Compared with the HEDPA system at 10 ℃ the peak potential shifted to more negative values and the rate of diffusion was faster.

关 键 词：无氰镀液 亚甲基二膦酸 铜电沉积 pH电位滴定 羟基乙叉二膦酸 

分 类 号：TQ153[化学工程—电化学工业]