Sn(MSA)_(2)电镀液体系表面活性剂性能优化的模拟研究  

Optimizing surfactants in Sn(MSA)_(2)-type electroplating solution:a molecular dynamics simulation study

作　　者：李吉辰 李腾 李宏飞[1] 许永姿 蔡珊珊 祝清省[4] 段晓征[1] 邢巍[5,6] Jichen Li;Teng Li;Hongfei Li;Yongzi Xu;Shanshan Cai;Qingsheng Zhu;Xiaozheng Duan;Wei Xing(State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China;Key Laboratory of Automobile Materials,Ministry of Education and College of Materials Science and Engineering,Jilin University,Changchun 130025,China;Research&Development Center,Yunnan Stannous Group(Holding)Co.,Ltd.,Kunming 650000,China;Shenyang National Laboratory for Materials Science,Institute of Metal Research,Chinese Academy of Sciences,Shenyang 110179,China;Laboratory of Advanced Power Sources,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China;State Key Laboratory of Electroanalytical Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China)

机构地区：[1]中国科学院长春应用化学研究所,高分子物理与化学国家重点实验室,长春130022 [2]吉林大学材料科学与工程学院,长春130025 [3]云南锡业集团(控股)有限责任公司研发中心,昆明650000 [4]中国科学院金属研究所,沈阳材料科学国家(联合)实验室,沈阳110179 [5]中国科学院长春应用化学研究所,先进化学电源实验室,长春130022 [6]中国科学院长春应用化学研究所,电分析化学国家重点实验室,长春130022

出　　处：《中国科学：化学》2023年第10期2089-2100,共12页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:22073094);云南省科学技术厅-云南锡业集团(控股)有限责任公司基础研究应用基础研究企业联合专项(编号:202101BC070001-007);吉林省科技发展计划(编号:20210402059GH)资助项目。

摘　　要：在本工作中,我们利用粗粒化分子动力学(MD)模拟方法,研究了两亲性表面活性剂构型及浓度对Sn(MSA)_(2)类电镀液体相溶液与铜基板周围电镀液微观结构的影响,从分子水平系统考察了主盐离子、表面活性剂与甲醛添加剂的分布和聚集情况,及其与铜基板的相互作用.研究表明,A_(4)B_(12)型表面活性剂的疏水链段(A4)协同效应较强,易在溶液中形成胶束,在基板上吸附能力有限;A_(2)B_(12)A_(2)疏水链较短,B_(6)A_(4)B_(6)疏水链居中,该两种表面活性剂在溶液中难以聚集,易充分吸附于基板之上;(AB_(3))_(4)型表面活性剂在体相溶液中充分分散,在基板上的吸附能力有限.A_(2)B_(12)A_(2)及B_(6)A_(4)B_(6)型表面活性剂的充分吸附,有助于金属离子及甲醛添加剂在基板表面的富集与覆盖,进而可能提升电镀效率.随着电镀液中表面活性剂浓度的升高,其在基板上的吸附逐渐饱和,金属离子和甲醛分子在表面的富集程度达到最大值.浓度继续升高,部分表面活性剂分散于溶液中,不利于金属离子及甲醛向基板表面传递.上述模拟结果证明,表面活性剂的构型及浓度优化可以有效提高电镀效率.本项研究有助于深入理解表面活性剂影响电镀液性质的微观机理.In this work,we use coarse-grained molecular dynamics simulations to study the effects of configurations and concentrations of amphiphilic surfactants on the microscopic structures of the bulk Sn(MSA)_(2)-type electroplating solution and the solution near the Cu substrate.We systematically explore the distribution and aggregation of main salt ions,surfactants,and formaldehyde additives at the molecular level,as well as their interactions with the substrate.Our simulations demonstrate that due to the strong cooperative effects of the connected A units,A_(4)B_(12)can form micelles in the solution,which limits their adsorptions on the substrate.By contrast,due to the disconnectivity of hydrophobic units in A_(2)B_(12)A_(2),and the intermediate location of the hydrophobic units in B_(6)A_(4)B_(6),these two types of surfactants can hardly aggregate in the solution,which facilitates their adsorption on the substrate.(AB_(3))_(4)are fully dispersed in the bulk solution,showing limited adsorption capacity on the substrate.The sufficient adsorption of A_(2)B_(12)A_(2)and B_(6)A_(4)B_(6)promotes the enrichment and coverage of ions and formaldehyde additives on the substrate and thereby might enhance the electroplating efficiency.With increasing the concentration of surfactants in the electroplating solution,their adsorption on the substrate gradually saturates,and the enrichment degree of metal ions and formaldehyde molecules on the surface reaches its maximum value.As the concentration further increases,partial surfactants disperse into the solution,which impedes the transfer of ions and formaldehyde toward the substrate surface.Our simulation results indicate that optimizing surfactant configurations and concentrations might effectively improve the electroplating efficiency.This study helps to deepen the understanding of the microscopic mechanisms for the effects of surfactants on the properties of electroplating solutions.

关 键 词：甲基磺酸 电镀液 表面活性剂 吸附 分子动力学模拟 

分 类 号：TQ153[化学工程—电化学工业]