巯基吡啶异构体对电镀铜填盲孔的影响研究  

Study on the influence of pyrithione isomers on filling blind holes in electroplatedcopper

作　　者：陈洁 宗高亮 代禹涵 赵晓楠 肖宁[1] Chen Jie;Zong Gaoliang;Dai Yuhan;Zhao Xiaonan;Xiao Ning(School of Chemical Engineering,Beijing University of Chemical Technology,Beijing 100029,China;Shenzhen Banming Technology Co.,Ltd.,Shenzhen 518105,China)

机构地区：[1]北京化工大学化学工程学院,北京100029 [2]深圳市板明科技股份有限公司,广东深圳518105

出　　处：《电镀与精饰》2024年第9期1-9,共9页Plating & Finishing

基　　金：国家自然科学基金青年基金(21902010)。

摘　　要：本文以同分异构体2-巯基吡啶(2-MP)和4-巯基吡啶(4-MP)为研究对象,在对比其作为整平剂填充盲孔性能差异的基础上,阐述其分子构效关系。首先,通过哈林槽镀铜实验研究了2-MP与4-MP的填盲孔性能,结果表明,2-MP的填孔性能更佳,其填孔率可达82%。之后,通过量子化学计算,发现2-MP分子中S原子电子云密度低于4-MP,这说明2-MP更易吸附在铜表面。计时电位法测试结果表明:Cl^(-)可促进2-MP在铜表面的吸附,此外,2-MP与PEG之间的相互作用显著强于4-MP。最后,通过X射线光电子能谱(XPS)检测到了Cu-S键的存在,证明两种整平剂分子在铜表面均发生了化学吸附。然而,由于2-MP分子中的巯基S原子与N原子处于邻位,可以形成S-Cu^(2+)-N配合物,进而与Cl^(-)、PEG形成复杂且致密的抑制层,强烈抑制表面铜沉积,从而提高了其盲孔填孔率。The study focused on the isomers 2-mercaptopyridine(2-MP)and 4-mercaptopyridine(4-MP),comparing their performance as levelers in filling blind holes.Copper plating experiments in a Hull cell initially investigated the blind hole filling capabilities of 2-MP and 4-MP.The results indicated superior performance by 2-MP,achieving a filling rate of up to 82%.Quantum chemical calculations later revealed a lower electron cloud density of the sulfur atom in the 2-MP molecule than in 4-MP.This suggests a higher likelihood of 2-MP adsorbing onto the copper surface.Chronopotentiometric measurements showed that Cl^(-)can promote the adsorption of 2-MP on the copper surface.Furthermore,the interaction between 2-MP and PEG was significantly stronger than that of 4-MP.X-ray photoelectron spectroscopy(XPS)detected the existence of Cu-S bonds in the final stage,proving chemical adsorption of both levelers onto the copper surface.Nevertheless,the proximity of the mercapto S atom and N atom in the 2-MP molecule allows for the formation of a S-Cu^(2+)-N complex.This complex,in combination with Cl^(-)and PEG,creates a complex and dense inhibition layer.This layer strongly suppresses surface copper deposition,thereby enhancing the blind hole filling rate of 2-MP.

关 键 词：电镀铜 填充盲孔 整平剂 2-巯基吡啶 4-巯基吡啶 

分 类 号：TG176[金属学及工艺—金属表面处理]