偶氮类染料添加剂在铜电沉积中的机理和应用研究  

Investigation of the mechanism and application of azo dye additives in copper electrodeposition

作　　者：肖龙辉 何为 皮亦鸣 王城 何科翰 黎钦源 曾红 田玲 王悦聪 黄云钟 陈苑明 Xiao Longhui;He Wei;Pi Yiming;Wang Cheng;He Kehan;Li Qinyuan;Zeng Hong;Tian Ling;Wang Yuecong;Huang Yunzhong;Chen Yuaming(School of Materials and Energy,University of Electronic Science and Technology of China,Chengdu 610054,China;School of Science,Xichang University,Xichang 615013,China;Institute of Electronic and Information Engineering of UESTC in Guangdong,Dongguan 523808,China;Delton Technology(Guangzhou)Co.,Ltd,Guangzhou 510735,China;Sichuan Heentai Semiconductor Co.,Ltd,Suining 629019,China)

机构地区：[1]电子科技大学材料与能源学院,四川成都610054 [2]西昌学院理学院,四川西昌615013 [3]电子科技大学广东电子信息工程研究院,广东东莞523808 [4]广州广合科技股份有限公司,广东广州510735 [5]四川和恩泰半导体有限公司,四川遂宁629019

出　　处：《电镀与精饰》2025年第3期1-9,33,共10页Plating & Finishing

基　　金：中国科学院STS计划-黄埔专项(STS-HP-202309);四川省科技项目(2022SNZY002)。

摘　　要：铜电沉积是高密度互连印制电路中实现电气连接的主要方式,电沉积铜层质量直接影响到层间互连和信号传输稳定性。有机添加剂在金属电沉积过程中能够通过特征官能团在电极表面电流密度较高区域的吸附作用调控阴极表面的电流分布,提高镀液的均镀能力和微观整平能力。在铜电沉积过程中,偶氮类化合物中与苯环相连的氮-氮双键被认为是发挥调控作用的关键基团,因此采用直接黄86、灿烂黄和活性嫩黄3G-P三种偶氮类染料作为电沉积铜添加剂。采用电化学和量子化学方法探究了3种添加剂的化学性质及其在铜电沉积过程中的作用机制,通过哈林槽实验研究了3种偶氮类染料添加剂对金属铜镀层的影响,分析了3种添加剂对通孔电沉积效果,并通过电镀通孔的均匀性评估了添加剂作用下镀液的均镀能力(Throwing Power,TP),实现厚径比为10:1通孔的TP值达92.03%。Copper electrodeposition is the primary method for achieving electrical connections in high-density interconnect(HDI)printed circuit boards,and the quality of the electrodeposited copper layer directly impacts interlayer interconnection and signal transmission stability.Organic additives can regulate the current distribution on the cathode surface through the adsorption of characteristic functional groups in regions with higher current densities during metal electrodeposition,thereby enhancing the leveling and micro-smoothing capabilities of the plating solution.In copper electrodeposition,the nitrogen-nitrogen double bond linked to the benzene ring in azo compounds is considered a crucial functional group that exerts regulatory effects.Consequently,three azo dyes,namely Direct Yellow 86,Brilliant Yellow,and Cibacron Brilliant Yellow 3G-P,were selected as additives for copper electrodeposition.Electrochemical tests and quantum chemical methods were employed to investigate the chemical properties of these three additives and their mechanisms of action during copper electrodeposition.Hull cell experiments were conducted to study the effects of these azo dye additives on the copper metal coating.Furthermore,the impact of the three additives on the plating of through-holes during copper electrodeposition was analyzed,and the uniformity of plated through-holes was used to evaluate the throwing power(TP)of the plating solution under the influence of different additives.As a result,a TP value of 92.03%was achieved for through-holes with an aspect ratio of 10:1.

关 键 词：铜电沉积 通孔 偶氮类染料添加剂 均镀能力 

分 类 号：TQ153.1[化学工程—电化学工业]