酸性溶液中苯并三氮唑和3-巯基-1-丙烷磺酸钠在铜电极表面的电化学SERS研究

doi:10.13208/j.electrochem.210445

摘要/Abstract

摘要：

利用原位电化学表面增强拉曼光谱技术(EC-SERS)研究了酸性溶液中苯并三氮唑(BTAH)、 3-巯基-1-丙烷磺酸钠(MPS)及Cl^-在铜电极表面的竞争吸附行为。在较正电位区间, BTAH分子在铜电极表面的吸附主要是通过三唑环在铜电极表面形成[Cu(BTA)]_n聚合物膜; 随着电位负移, 聚合物膜逐渐转化为BTAH分子形式吸附在铜电极表面。而MPS主要是以巯基端吸附在铜电极表面, 其吸附方向的改变使得其在铜表面的拉曼信号呈现出先强后弱的趋势。Cl^-主要是以Cu-Cl的形式存在,占据电极表面的活性位点与MPS产生协同作用。当三者复配时是以BTAH在电极表面的强吸附性为主导,且随着电位的负移,BTAH的拉曼信号呈现出先增强再减弱的趋势,相较于BTAH的强吸附作用, MPS与Cl^-在电极表面的吸附强度较弱但依旧可以监测到两者参与竞争吸附的过程。

关键词: 苯并三氮唑, 3-巯基-1-丙烷磺酸钠, 表面增强拉曼光谱, 吸附

Abstract:

Since the development of acid copper plating technology, the role of additives is indispensable. In addition to the main salt copper sulfate and supporting electrolyte sulfuric acid, suppressors, accelerators, levelers and chlorine ions (Cl^-) are also required to be added into the plating solution. Appropriate additive system can have a significant impact on the coating or the plating solution, which can help improve the quality of the coating and increase the brightness of the coating. Through electrochemical measurement, vibrational spectroscopy, scanning probe microscopy, molecular dynamics simulation and other methods, researches have a deeper understanding in the adsorption configuration of some additives on the copper electrode surface and the changes in the electroplating process. Surface-enhanced Raman spectroscopy (SERS) is a powerful technique that yields vibrational information with ultra-high sensitivity. Enhancements of up to 10¹⁰ have been achieved in some systems, which provides sensitivity up to single molecule level. Therefore, SERS technique is one of the main methods to study the adsorption structure and mechanism of additives. In this paper, the competitive adsorption behaviors of benzotriazole (BTAH), 3-mercapto-1-propanesulfonate (MPS) and Cl^- in an acidic solution on the copper electrode were investigated by in-situ electrochemical surface-enhanced Raman spectroscopy (EC-SERS). It was found that in the positive potential range, the adsorption behavior of BTAH molecules was mainly through the formation of [Cu(BTA)]_n polymer film on the copper electrode surface by the triazole ring; with the negative shift of the potential, the polymer film was gradually transformed into the BTAH molecular. The MPS was mainly adsorbed on the copper electrode by the sulfhydryl end. Cl^- mainly existed in the form of Cu-Cl, and the active sites occupying the surface of the electrode had a synergistic effect with MPS. The electroplating process on the copper foil also verified the strong adsorption of BTAH, and the presence of small copper particles on the copper foil also confirmed that MPS and Cl^- have a synergistic effect, which promotes the local deposition of copper. As the only technical method that can realize nano-level electronic interconnection, electronic electroplating is the main direction of future research. Related additive basic research is also indispensable. In the process of copper electroplating, the interfacial competitive adsorption of additives and their mechanism of action need more in-depth study. It is hoped that this study will play an important guiding role in the development of electroplating additives and the improvement of electroplating technology in the future.

Key words: benzotriazole, 3-mercapto-1-propane sulfonate, surface enhanced Raman spectroscopy, adsorption

沈银飞, 陈艳丽, 王笙戌, 朱晔, 王文昌, 吴敏娴, 陈智栋. 酸性溶液中苯并三氮唑和3-巯基-1-丙烷磺酸钠在铜电极表面的电化学SERS研究[J]. 电化学（中英文）, 2022, 28(6): 2104451.

Yin-Fei Shen, Yan-Li Chen, Sheng-Xu Wang, Ye Zhu, Wen-Chang Wang, Min-Xian Wu, Zhi-Dong Chen. Electrochemical SERS study of Benzotriazole and 3-mercapto-1-propanesulfonate in Acidic Solution on Copper Electrode[J]. Journal of Electrochemistry, 2022, 28(6): 2104451.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.210445

https://electrochem.xmu.edu.cn/CN/Y2022/V28/I6/2104451

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