Chen Jie,Zong Gaoliang,Dai Yuhan,et al.Study on the influence of pyrithione isomers on filling blind holes in electroplated copper[J].Plating & Finishing,2024,(9):1-9.[doi:doi: 10.3969/j.issn.1001-3849.2024.09.001]
巯基吡啶异构体对电镀铜填盲孔的影响研究
- Title:
- Study on the influence of pyrithione isomers on filling blind holes in electroplated copper
- Keywords:
- copper electroplating; filling blind holes; levelers; 2-mercaptopyridine; 4-mercaptopyridin
- 分类号:
- TG176
- 文献标志码:
- A
- 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-Cu2+-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。
- Abstract:
- 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.
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