孙海静,杨帅,丁明玉,孙杰.ChCl-OxA低共熔溶剂中铜的电沉积行为研究[J].表面技术,2021,50(11):313-320.
SUN Hai-jing,YANG Shuai,DING Ming-yu,SUN Jie.Electrochemical Behavior of Copper Electroplating Progress in ChCl-OxA Eutectic Solvent[J].Surface Technology,2021,50(11):313-320
ChCl-OxA低共熔溶剂中铜的电沉积行为研究
Electrochemical Behavior of Copper Electroplating Progress in ChCl-OxA Eutectic Solvent
投稿时间:2020-05-29  修订日期:2020-08-21
DOI:10.16490/j.cnki.issn.1001-3660.2021.11.033
中文关键词:  低共熔溶剂  草酸    电沉积  电化学行为  形核机制
英文关键词:deep eutectic solvent  oxalic acid  copper  electrodeposition  electrochemical behavior  nucleation mechanism
基金项目:辽宁省教育厅青年科技人才“育苗”项目(LG201928)
作者单位
孙海静 沈阳理工大学 环境与化学工程学院,沈阳 110159 
杨帅 沈阳理工大学 环境与化学工程学院,沈阳 110159 
丁明玉 沈阳理工大学 环境与化学工程学院,沈阳 110159 
孙杰 沈阳理工大学 环境与化学工程学院,沈阳 110159 
AuthorInstitution
SUN Hai-jing School of Environmental and Chemical Engineering, Shenyang Ligong University, Shenyang 110159, China 
YANG Shuai School of Environmental and Chemical Engineering, Shenyang Ligong University, Shenyang 110159, China 
DING Ming-yu School of Environmental and Chemical Engineering, Shenyang Ligong University, Shenyang 110159, China 
SUN Jie School of Environmental and Chemical Engineering, Shenyang Ligong University, Shenyang 110159, China 
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中文摘要:
      目的 研究铜在氯化胆碱-草酸(ChCl-OxA)低共熔溶剂中的电化学行为、电结晶机理及电沉积历程。方法 采用循环伏安法(CV)和计时电流法(CA)研究了铜在ChCl-OxA低共熔溶剂中的电化学行为和不同电位阶跃下的电结晶机理。采用扫描电子显微镜(SEM)和X-射线衍射技术(XRD)对铜镀层的微观形貌和物相组成进行了表征。结果 ChCl-OxA低共熔溶剂的电化学稳定窗口为2.10 V。铜离子经过两个连续的电化学步骤还原为金属铜,两个还原峰电位(vs. Ag)分别为0.686 V(Cu2+/Cu+)和0.365 V(Cu+/Cu0),还原电位均位于正电位区,说明铜离子具有强还原性。不同扫描速度下的CV曲线表明,两个还原峰电位Ep均随扫描速度v的增加而呈现负移的趋势,符合不可逆电极反应的特征。对Ip和v1/2之间的关系进行了线性拟合,发现Ip与v1/2之间均为线性关系,故可认为该体系中Cu(Ⅱ)的两步还原反应均是受扩散控制的,进一步计算出扩散系数DCu(Ⅱ)、DCu(Ⅰ)分别为7.27×10–9、5.70×10–9 cm2/s。在–0.60~–0.68 V下测定CA曲线,通过拟合CA曲线和理论曲线对比发现,Cu(Ⅱ)在ChCl-OxA体系中的电结晶过程符合Scharifker-Hill三维瞬时形核模型。SEM结果表明,不同沉积时间下的铜晶粒具有不同形态,如球形、短棒状等,可获得均匀、致密的铜镀层。XRD结果表明,镀层由面心立方结构(FCC)的单质铜组成,最优结晶面为(111)。结论 Cu(Ⅱ)在ChCl-OxA低共熔溶剂中的电沉积过程为受扩散控制的不可逆电极过程,且形核机制为三维瞬时形核。在该体系中可得到均匀、细致的铜镀层,且铜镀层平均晶粒尺寸为45.34 nm。
英文摘要:
      The work aims to study the electrochemical behavior, electro-crystallization mechanism and electrodeposition process of copper in the Choline Chloride-Oxalic Acid (ChCl-OxA) eutectic solvent system. The electrochemical behavior of copper in the ChCl-OxA eutectic solvent system was studied by cyclic voltammetry (CV). The electro-crystallization mechanism of copper at different potential steps was investigated by chronoamperometry (CA). The micro-morphology and phase composition of copper coatings were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The electrochemical stability window of the ChCl-OxA eutectic solvent was 2.10 V. The copper ion was reduced to copper after two successive electrochemical steps, and the two reduction peak potentials (vs. Ag) were respectively 0.686 V (Cu2+/Cu+) and 0.365 V (Cu+/Cu0). The reduction potentials were all located in the positive potential region, indicating that the copper ion had strong reducibility. The cyclic voltammetry curves of different scanning velocities showed that Eptrended to shift to negative value when the scanning velocities were increasing, which conforms to the characteristics of irreversible reactions. Therefore, it could be judged that Cu(Ⅱ) in the ChCl-OxA eutectic solvent was the process of irreversible reactions. The relationship between Ipand v1/2 was linearly fitted, and it was found that the relationship between Ipand v1/2 was linear. Therefore, the two reduction reactions of copper ions were controlled by diffusion. After calculation, the diffusion coefficient of DCu(Ⅱ), DCu(Ⅰ)were 7.27×10–9cm2/sand 5.70×10–9cm2/s. The third oxidation peak was found in the oxidation process, which was speculated to be the oxidation process of chloride ion (at a higher concentration). The chronoamperometry measured at –0.60~ –0.68 V showed that the electro-crystallization process of Cu(Ⅱ) in the ChCl-OxA system was found to conform to the Scharifker-Hill three- dimensional nucleation model through the comparison between the chronoelectric curve and the theoretical curve. The results for micro-morphologies showed that different micro-morphologies could be formed, such as spherical shape, short bar shape, and square shape. Uniform and fine copper coatings could be obtained in the ChCl-OxA system. The results for phase composition showed that copper coating consisted of Face-Centered Cubic (FCC) phase and the optimal crystal surface was (111). The electrodepositing process of copper(Ⅱ) in the ChCl-OxA eutectic solvent is an irreversible electrochemical process controlled by diffusion, and the nucleation mechanism is the three-dimensional instantaneous nucleation. The fine and uniform nanocrystalline copper coating with an average particle size of 45.34 nm can be obtained.
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