化学镀锡中光亮剂PPS、咪唑和HD在Sn表面的吸附作用实验与模拟研究
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摘要
目的研究以丙烷磺酸吡啶嗡盐(PPS)、咪唑、己炔二醇(HD)为代表的三大类光亮剂,在化学镀锡过程中改善镀锡层表观形貌和影响镀速的作用机理。方法采用电化学阴极极化法,研究化学镀锡过程中光亮剂分子对镀锡液在沉锡过程中对沉锡峰电位变化的影响,运用Forcite模块中的COMPASS力场进行分子动力学计算,研究光亮剂分子在Sn层表面吸附过程的能量变化。结果阴极极化结果表明,光亮剂的加入会使沉锡峰电位负移,该过电位导致晶核水平增长速度大于垂直生长速度,从而起到整平作用,并在一定程度上抑制晶须的形成。分子动力学计算结果显示,PPS、咪唑、HD均有自发吸附到Sn层表面的趋势,且在Sn(111)面的吸附能分别为-445.338、-9.84、-22.651kcal/mol,表明三种光亮剂分子均易吸附在Sn层表面(吸附能数据越低,越容易吸附在锡层表面),从而在一定程度上抑制锡层的增长。结论光亮剂与Sn作用的吸附能,与其在化学镀过程中对Sn层表观形貌的改善和镀速减少有正相关作用。该研究为化学镀锡过程中光亮剂的选择提供了理论基础。
The work aims to study the effect mechanism of improving tin coating apparent morphology and influencing deposition rate by adding propane sulfonic acid pyridine salt(PPS), imidazole, 3-hexyne-2,5-diol(HD) as representatives of three types of brighteners during the process of electroless tin. The effect of brighteners on the peak potential change of tin deposition in tin plating bath was studied by electrochemical cathode polarization method. The molecular mechanics calculation method was carried out by COMPASS force field in Forcite model to explore the adsorption process of brighteners on the surface of Sn layer and. From the results of cathodic polarization, the addition of brightener could make the peak potential of tin deposition negatively shift. The over-potential caused the horizontal growth rate of nuclei to be greater than that of the vertical growth rate, thus leveling the Sn layer and inhibiting the formation of whiskers to a certain extent. Molecular dynamics calculation results demonstrated that PPS, imidazole and HD had a tendency to be spontaneously adsorbed to the surface of the Sn layer and the adsorption energy of PPS, imidazole and HD in the Sn(111) surface were-445.338 kcal/mol,-9.84 kcal/mol and-22.651 kcal/mol, respectively. The molecules of three brighteners were more likely to be adsorbed on the surface of the Sn layer, thereby inhibiting the growth of the Sn layer to some extent. The adsorption energy of brightener on Sn surface has a positive correlation with the improvement of Sn's apparent morphology and reduction of plating rate during electroless plating and provides some theoretical basis for the selection of brightener.
The work aims to study the effect mechanism of improving tin coating apparent morphology and influencing deposition rate by adding propane sulfonic acid pyridine salt(PPS), imidazole, 3-hexyne-2,5-diol(HD) as representatives of three types of brighteners during the process of electroless tin. The effect of brighteners on the peak potential change of tin deposition in tin plating bath was studied by electrochemical cathode polarization method. The molecular mechanics calculation method was carried out by COMPASS force field in Forcite model to explore the adsorption process of brighteners on the surface of Sn layer and. From the results of cathodic polarization, the addition of brightener could make the peak potential of tin deposition negatively shift. The over-potential caused the horizontal growth rate of nuclei to be greater than that of the vertical growth rate, thus leveling the Sn layer and inhibiting the formation of whiskers to a certain extent. Molecular dynamics calculation results demonstrated that PPS, imidazole and HD had a tendency to be spontaneously adsorbed to the surface of the Sn layer and the adsorption energy of PPS, imidazole and HD in the Sn(111) surface were-445.338 kcal/mol,-9.84 kcal/mol and-22.651 kcal/mol, respectively. The molecules of three brighteners were more likely to be adsorbed on the surface of the Sn layer, thereby inhibiting the growth of the Sn layer to some extent. The adsorption energy of brightener on Sn surface has a positive correlation with the improvement of Sn's apparent morphology and reduction of plating rate during electroless plating and provides some theoretical basis for the selection of brightener.
引文
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[2]王军丽,徐瑞东,郭忠诚,等.化学镀锡工艺条件的优化[J].电镀与环保,2002,22(5):13-16.WANG Jun-li,XU Rui-dong,GUO Zhong-cheng,et al.Optimization of the process conditions of electroless tin plating[J].Electroplating&pollution control,2002,22(5):13-16.
[3]孙武,李宁,苏晓霞,等.化学镀锡液中添加剂的影响研究[J].材料保护,2007,40(1):35-38.SUN Wu,LI Ning,SU Xiao-xia,et al.Study on the influence of additelectroless tin plating solution[J].Materials protection,2007,40(1):35-38.
[4]徐瑞东.酸性化学镀锡工艺及应用研究[D].昆明:昆明理工大学,2002.XU Rui-dong.Study on process and application of acid electroless tin plating[D].Kunming:Kunming University of Science and Technology,2002.
[5]张丽,张彦.化学镀的研究进展及发展趋势[J].表面技术,2017,46(12):104-109.ZHANG Li,ZHANG Yan.Research progress and development trend of chemical plating[J].Surface technology,2017,46(12):104-109.
[6]王帅,郭忠诚,陈步明,等.镀锡的研究进展[J].材料保护,2014,47(5):37-42.WANG Shuai,GUO Zhong-cheng,CHEN Bu-ming,et al.Research progress of tin plating[J].Material protection,2014,47(5):37-42.
[7]赵国鹏,樊江莉,温青.化学镀可焊性锡基合金的研究进展[J].电镀与涂饰,2001,20(1):46-49.ZHAO Guo-peng,FAN Jiang-li,WEN Qing.Progress of research on electroless plating of solderable tin alloy[J].Electroplating&finishing,2001,20(1):46-49.
[8]王钰蓉,曹小云,陈靓,等.温度对浸镀锡镀层的影响[J].常州大学学报(自然科学版),2015,27(1):32-36.WANG Yu-rong,CAO Xiao-yun,CHEN Liang,et al.Effect of plating temperature on immersion tin coating[J].Journal of Changzhou University(natural science edition),2015,27(1):32-36.
[9]ZHAO J,LI N,CUI G,et al.Study on immersion tin process by electrochemical methods and molecular orbital theory[J].Journal of the electrochemical society,2006,153(12):499-502.
[10]段富良,王梅.铜基上化学镀锡工艺分析[J].云南化工,2017,44(6):76-78.DUAN Fu-liang,WANG Mei.Process analysis of electroless tin plating on copper substrate[J].Yunnan chemical technology,2017,44(6):76-78.
[11]周栋,王瑀,丁毅,等.黄铜化学镀锡层性能的研究[J].电镀与环保,2016,36(2):25-27.ZHOU Dong,WANG Yu,DING Yi,et al.Study on properties of electroless tin coating on brass[J].Electroplating&pollution control,2016,36(2):25-27.
[12]李振城.硫酸亚锡在铜基上化学镀锡方法研究[J].当代化工研究,2015(5):70-71.LI Zhen-cheng.Tin sulfate in electroless tin plating on copper substrate method research[J].Chemical intermediate,2015(5):70-71.
[13]LOW C T J,WALSH F C.Electrode position of tin,copper and tin-copper alloys from a methane sulfonic acid electrolyte containing a perfluorinated cationic surfactant[J].Surface&coatings technology,2008,202(8):1339-1349.
[14]FENG Q,FENG S,YANG W B,et al.Study on process and application of electrodeposited non-bright tin coatings[C]//Proceedings of the 7th national conference on functional material and applications.Xi?an:Science Research Publishing,2010:2171-2178.
[15]LONG J M,ZHANG Z,GUO Z C,et al.Electrochemical study of the additive-effect on Sn electrodeposition in a methansulfonate acid electrolyte[J].Advanced materials research,2012,460:7-10.
[16]孙武.PCB上化学镀锡工艺的研究[D].哈尔滨:哈尔滨工业大学,2006.SUN Wu.The research of electroless tin plating on PCB[D].Harbin:Harbin Institute of Technology,2006.
[17]程骄.PCB上镀锡工艺研究及其电化学过程探讨[D].武汉:湖北工业大学,2010.CHENG Jiao.Study on tin-plating of PCB process and electrochemical behavior[D].Wuhan:Hubei University of Technology,2010.
[18]苏传港,苏燕旋,苏传猛,等.铜及铜合金的化学镀锡液:中国,CN101403112[P].2009-03-16.SU Chuan-gang,SU Yan-xuan,SU Chuan-meng,et al.Chemical plating of copper andcopperalloys:China,CN101403112[P].2009-03-16.
[19]周泽翔,程海斌,薛理辉,等.改善化学镀层结合力的方法及其检测手段[J].材料导报,2006,20(2):79-81.ZHOU Ze-xiang,CHENG Hai-bin,XUE Li-hui,et al.The method of improving and checking adhesion of coating electroless-plated[J].Materials review,2006,20(2):79-81.
[20]张景双.电镀溶液与镀层性能测试[M].北京:化学工业出版社,2003.ZHANG Jing-shuang.Electroplating solution and coating performance[M].Beijing:Chemical Industry Press,2003.
[21]廉兵杰,石泽民,徐慧,等.唑类缓蚀剂在铜表面的吸附机理[J].表面技术,2015,44(12):19-26.LIAO Bing-jie,SHI Ze-min,XU Hui,et al.Adsorption mechanism of azole corrosion inhibitors on Cu surface[J].Surface technology,2015,44(12):19-26.
[22]黄晓华,张相育,吉青,等.应用分子力学研究表面吸附能的可行性[J].计算机与应用化学,2007,24(3):375-379.HUANG Xiao-hua,ZHANG Xiang-yu,JI Qing,et al.Molecular mechanics(MM)study on the surface adsorption energy[J].Com applied chemistry,2007,24(3):375-379.
[23]丁运虎,周玉福,毛祖国,等.甲基磺酸亚光纯锡电镀添加剂的研究[J].材料保护,2006,39(3):4-7.DING Yun-hu,ZHOU Yu-fu,MAO Zu-Guo,et al.The study on the additive of the pure tin electroplating methyl sulfonate[J].Materials protection,2006,39(3):4-7.
[24]封勇.光亮酸性镀锡工艺综述[J].机电元件,2005,25(2):32-36.FENG Yong.An overview of bright acid tin plating process[J].Electromechanical components,2005,25(2):32-36.