表面活性剂<strong>PEG6000</strong>对二元络合体系化学沉积铜的影响

doi:10.11901/1005.3093.2019.060

材料研究学报

2019, Vol. 33

Issue (9): 666-672 DOI: 10.11901/1005.3093.2019.060

研究论文

本期目录 | 过刊浏览

表面活性剂PEG6000对二元络合体系化学沉积铜的影响

卢建红^1,²,邓小梅³,阎建辉³,涂继国¹,王明涌¹(

),焦树强¹(

)

1. 北京科技大学钢铁冶金新技术国家重点实验室北京 100083
2. 北京化工大学常州先进材料研究院常州 213164
3. 湖南理工学院化学化工学院岳阳 414006

Effect of PEG6000 on Electroless Copper in Dual-Ligands System

LU Jianhong^1,²,DENG Xiaomei³,YAN Jianhui³,TU Jiguo¹,WANG Mingyong¹(

),JIAO Shuqiang¹(

)

1. State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China
2. Changzhou Institutes of Advanced Materials, Beijing University of Chemical Technology, Changzhou 213164, China
3. School of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology, Yueyang 414006, China

引用本文:

卢建红, 邓小梅, 阎建辉, 涂继国, 王明涌, 焦树强. 表面活性剂PEG6000对二元络合体系化学沉积铜的影响[J]. 材料研究学报, 2019, 33(9): 666-672.
LU Jianhong, DENG Xiaomei, YAN Jianhui, TU Jiguo, WANG Mingyong, JIAO Shuqiang. Effect of PEG6000 on Electroless Copper in Dual-Ligands System[J]. Chinese Journal of Materials Research, 2019, 33(9): 666-672.

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摘要:

研究了表面活性剂聚乙二醇6000对乙二胺四乙酸(EDTA)/四羟丙基乙二胺(THPED)二元络合体系化学镀铜的过程和化学镀铜表面结构的影响。混合电位-时间测试结果表明，化学沉积过程分为三个区：诱发区、过渡区和稳定区。PEG6000使体系的混合电位负移趋势放缓，与表面活性剂在铜表面的吸附阻滞了对带电荷离子的吸附有关。线性扫描测试结果表明，阴极还原反应为控制步骤，PEG6000的吸附减缓了阴极还原反应，还原峰电流密度下降了约40%；铜化学沉积速率随着PEG6000浓度的提高呈线性下降趋势。SEM、EDS和XRD表征结果表明，化学镀铜的纯度较高，加入PEG6000使镀层呈现出明显的(220)晶面择优取向，且晶粒尺寸由77.7 nm减小到50.0 nm，有细化晶粒的作用。

关键词 ：材料表面与界面, 化学镀铜, 表面活性剂, 聚乙二醇6000, 混合电位, 晶面择优取向

Abstract：

The effect of surfactant polyethylene glycol (PEG) 6000 on the electroless copper plating process in a bath of dual-ligands ethylenediamine tetraacetic acid (EDTA)/tetrahydroxypropyl ethylenediamine (THPED) was investigated by electrochemical method. Mixed potential-time curves indicate that the overall process can be divided into three districts: induction, transitional and stable region. PEG6000 can slowdown the negative shifting of electrode potential, which related to the retardation of the adsorption of charged ions resulted from the surfactant adsorption on the copper electrode. Linear sweep voltammetry measurements show that cathodic reduction reaction is the controlling step for the plating process; PEG6000 could retard cathodic polarization, therewith, the peak value of cathodic reduction current decreased about 40%, so PEG6000 linearly reduced deposit speed. The copper layers prepared from the bath with PEG6000 are product of high-purity with a surface morphology of uniformly distributed fine particles, moreover, the addition of PEG6000 favored the formation of copper layer with (220) preferred orientation with refined grains of average size 50.0 nm, in comparison with 77.7 nm that from the bath without PEG6000 addition.

Key words： surface and interface in the materials electroless copper surfactant polyethylene glycol 6000 mixed potential preferred orientation

收稿日期: 2019-01-14

ZTFLH:

TQ153

基金资助:常州市科技计划(CJ20180014)

作者简介: 卢建红，男，1972年生，研究员

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https://www.cjmr.org/CN/10.11901/1005.3093.2019.060 或 https://www.cjmr.org/CN/Y2019/V33/I9/666

表1 化学镀铜溶液的组成

图1 PEG6000浓度不同时铜电极表面的混合电位-时间曲线

表2 不同PEG6000浓度的混合电位负移值

图2 PEG6000浓度对Cu(II)离子阴极还原的影响

表3 不同PEG6000添加剂浓度的阴极还原峰值

图3 PEG6000浓度对甲醛阳极氧化的影响

表4 PEG6000浓度不同的阳极氧化峰电流密度值

图4 PEG6000浓度对沉积速率的影响

图5 不同PEG6000浓度的化学沉积铜的SEM照片

图6 不同PEG6000浓度的化学沉积铜的EDS图

图7 不同PEG6000浓度化学镀铜沉积层的XRD谱图

表5 不同PEG6000浓度下铜镀层晶粒尺寸和特征衍射峰强度比

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