工程科学学报，第39卷，第9期：1380-1385,2017年9月 Chinese Journal of Engineering,Vol.39,No.9:1380-1385,September 2017 D0l:10.13374/j.issn2095-9389.2017.09.011;htp:/journals.ustb.edu.cn 聚二硫二丙烷磺酸钠在二元络合化学镀铜体系中的 作用 卢建红，焦汉东，焦树强四 北京科技大学钢铁冶金新技术国家重点实验室，北京100083 ☒通信作者，E-mail:sjiao@ustb.cdu.cm 摘要用电化学方法研究添加剂聚二硫二丙烷磺酸钠(SPS)对乙二胺四乙酸(EDTA)/四羟丙基乙二胺(THPED)二元络合 化学镀铜过程的影响，测量体系的混合电位-时间关系，加入SS后混合电位负移，负移过程较平缓，无突跃现象：采用线性扫 描伏安法研究体系，表明SS促进了阴阳两极的极化，但主要是影响甲醛氧化的阳极极化过程.SS也因此一定程度上提高 了过程的沉积速率.通过扫描电镜、能谱仪和X射线衍射仪对结构的分析，镀层铜纯净度较高，无氧化铜等夹杂，镀层细致平 滑，发现SPS有促进(200)晶面择优取向的作用. 关键词聚二硫二丙烷磺酸钠；化学镀铜：络合剂：混合电位；线性扫描伏安法；晶面择优取向 分类号TQ153.1 Effect of sodium 3,3'-dithiodipropane sulfonate in a dual-ligand electroless copper system LU Jian-hong,JIAO Han-dong,JIAO Shu-qiang State Key Laboratory of Advanced Metallurgy,University of Science and Technology Beijing,Beijing 100083,China Corresponding author,E-mail:sjiao@ustb.edu.en ABSTRACT The process of electroless copper plating in an EDTA/THPED dual-ligand system using sodium 3,3'-dithiodipropane sulfonate (SPS)as an additive was studied by the electrochemical method.The mixed potential of the system was measured as a func- tion of time,and results indicate that addition of SPS gradually shifts the mixed potential toward the negative direction without salta- tion.The dual-ligand electroless copper system was then tested by linear sweep voltammetry,and SPS is found to accelerate both ca- thodic and anodic polarization.The additive mainly influences the anodic polarization of the formaldehyde oxidation process and the rate of copper deposition is improved to a certain extent.The surface morphology and texture of the resulting plated copper were also analyzed by scanning electron microscope,energy dispersive spectrometer and X-ray diffraction,and a high-purity product without Cu2O inclusions is confirmed.Moreover,the X-ray diffraction results of the electroless copper layers show that addition of SPS favors the formation of the preferred orientation on the (200)lattice plane. KEY WORDS sodium 3,3'-dithiodipropane sulfonate;electroless copper;ligand;mixed potential;liner sweep voltammetry;pre- ferred orientation 1947年Narcus首先发表了第一篇化学镀铜的论 液的关键组分之一，二元或多元的络合体系兼有多功 文四，第一个商业化学镀铜则是Cahill在1957年提 能特性，可能比单一体系在镀速、稳定性及沉积结晶等 出).近些年来在科研工作者的努力下，化学镀铜无 方面有独特效能，也成为近来研究热点[3-). 论是机理研究、工艺及配方改进还是使用的拓展都取 聚二硫二丙烷磺酸钠(SPS)是一种含硫的阴离子 得了较大的进展，络合剂对化学镀铜有重要影响，是镀 表面活性剂，在电镀铜和化学镀铜溶液中常作为微量 收稿日期：2016-12-01工程科学学报,第 39 卷,第 9 期:1380鄄鄄1385,2017 年 9 月 Chinese Journal of Engineering, Vol. 39, No. 9: 1380鄄鄄1385, September 2017 DOI: 10. 13374 / j. issn2095鄄鄄9389. 2017. 09. 011; http: / / journals. ustb. edu. cn 聚二硫二丙烷磺酸钠在二元络合化学镀铜体系中的 作用 卢建红, 焦汉东, 焦树强苣 北京科技大学钢铁冶金新技术国家重点实验室, 北京 100083 苣通信作者, E鄄mail: sjiao@ ustb. edu. cn 摘 要 用电化学方法研究添加剂聚二硫二丙烷磺酸钠(SPS)对乙二胺四乙酸(EDTA) / 四羟丙基乙二胺(THPED)二元络合 化学镀铜过程的影响,测量体系的混合电位鄄鄄时间关系,加入 SPS 后混合电位负移,负移过程较平缓,无突跃现象;采用线性扫 描伏安法研究体系,表明 SPS 促进了阴阳两极的极化, 但主要是影响甲醛氧化的阳极极化过程. SPS 也因此一定程度上提高 了过程的沉积速率. 通过扫描电镜、能谱仪和 X 射线衍射仪对结构的分析,镀层铜纯净度较高,无氧化铜等夹杂,镀层细致平 滑,发现 SPS 有促进(200)晶面择优取向的作用. 关键词 聚二硫二丙烷磺酸钠; 化学镀铜; 络合剂; 混合电位; 线性扫描伏安法; 晶面择优取向 分类号 TQ153郾 1 Effect of sodium 3,3忆鄄dithiodipropane sulfonate in a dual鄄ligand electroless copper system LU Jian鄄hong, JIAO Han鄄dong, JIAO Shu鄄qiang 苣 State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China 苣Corresponding author, E鄄mail: sjiao@ ustb. edu. cn ABSTRACT The process of electroless copper plating in an EDTA/ THPED dual鄄ligand system using sodium 3,3忆鄄dithiodipropane sulfonate (SPS) as an additive was studied by the electrochemical method. The mixed potential of the system was measured as a func鄄 tion of time, and results indicate that addition of SPS gradually shifts the mixed potential toward the negative direction without salta鄄 tion. The dual鄄ligand electroless copper system was then tested by linear sweep voltammetry, and SPS is found to accelerate both ca鄄 thodic and anodic polarization. The additive mainly influences the anodic polarization of the formaldehyde oxidation process and the rate of copper deposition is improved to a certain extent. The surface morphology and texture of the resulting plated copper were also analyzed by scanning electron microscope, energy dispersive spectrometer and X鄄ray diffraction, and a high鄄purity product without Cu2O inclusions is confirmed. Moreover, the X鄄ray diffraction results of the electroless copper layers show that addition of SPS favors the formation of the preferred orientation on the (200) lattice plane. KEY WORDS sodium 3,3忆鄄dithiodipropane sulfonate; electroless copper; ligand; mixed potential; liner sweep voltammetry; pre鄄 ferred orientation 收稿日期: 2016鄄鄄12鄄鄄01 1947 年 Narcus 首先发表了第一篇化学镀铜的论 文[1] ,第一个商业化学镀铜则是 Cahill 在 1957 年提 出[2] . 近些年来在科研工作者的努力下,化学镀铜无 论是机理研究、工艺及配方改进还是使用的拓展都取 得了较大的进展,络合剂对化学镀铜有重要影响,是镀 液的关键组分之一,二元或多元的络合体系兼有多功 能特性,可能比单一体系在镀速、稳定性及沉积结晶等 方面有独特效能,也成为近来研究热点[3鄄鄄6] . 聚二硫二丙烷磺酸钠(SPS)是一种含硫的阴离子 表面活性剂,在电镀铜和化学镀铜溶液中常作为微量