特殊整平剂甲基橙在通孔电镀铜的应用

doi:10.13208/j.electrochem.2213003

电化学（中英文） ›› 2022, Vol. 28 ›› Issue (7): 2213003. doi: 10.13208/j.electrochem.2213003

所属专题： “电子电镀和腐蚀”专题文章

特殊整平剂甲基橙在通孔电镀铜的应用

徐佳莹¹, 王守绪¹^,², 苏元章¹, 杜永杰³, 齐国栋⁴, 何为¹^,², 周国云¹, 张伟华², 唐耀², 罗毓瑶², 陈苑明¹^,²^,^*()

1.电子科技大学材料与能源学院,四川成都 611731
2.珠海方正科技高密电子有限公司&珠海方正科技多层电路板有限公司,广东珠海 519175
3.珠海市能动科技光学产业有限公司,广东珠海 519050
4.珠海杰赛科技有限公司,广东珠海 519175

收稿日期:2022-03-04 修回日期:2022-04-10 出版日期:2022-07-28 发布日期:2022-05-24
通讯作者: 陈苑明 E-mail:ymchen@uestc.edu.cn

Investigation of Through-Hole Copper Electroplating with Methyl Orange as A Special Leveler

Jia-Ying Xu¹, Shou-Xu Wang¹^,², Yuan-Zhang Su¹, Yong-Jie Du³, Guo-Dong Qi⁴, Wei He¹^,², Guo-Yun Zhou¹, Wei-Hua Zhang², Yao Tang², Yu-Yao Luo², Yuan-Ming Chen¹^,²^,^*()

1. School of Materials and Energy, University of Electronic Science and Technology of China, Chengdu 611731, Sichuan, China
2. Zhuhai Founder Sci-Tech High-density Electronics Co., Ltd and Zhuhai Founder Sci-Tech Multilayer Circuit Board Co., Ltd., Zhuhai 519175, Guangdong, China
3. Zhuhai Dynamic Technology Optical Industry Co., Ltd, Zhuhai 519050, Guangdong, China
4. GCI Science & Technology（Zhuhai）Co., Ltd, Zhuhai 519175, Guangdong, China

Received:2022-03-04 Revised:2022-04-10 Published:2022-07-28 Online:2022-05-24
Contact: Yuan-Ming Chen E-mail:ymchen@uestc.edu.cn

摘要/Abstract

摘要：

甲基橙具有两种基团,可以同时起到加速和抑制作用,可作为特殊的整平剂应用与通孔电镀铜实验中。通过分子动力学模拟和量子化学计算来表征甲基橙在通孔电镀铜中的作用,结果表明甲基橙可以很好地吸附在阴极表面并抑制铜的电沉积。通过恒电流测试和循环伏安测试结果显示, 甲基橙由于同时具有磺酸基的去极化和其分子结构部分的极化作用, 形成协同分子内对铜加速还原和阻碍传质的竞争效应, 所以几乎不影响电位。在板厚孔径为10:1的通孔电镀铜实验中, 仅以甲基橙和环氧乙烷和环氧丙烷嵌段共聚物作为添加剂, TP值可达到92.34%。

关键词: 电镀铜, 通孔, 添加剂, 甲基橙

Abstract:

Methyl Orange (MO) with two kinds of functional groups can act as both an accelerator and an inhibitor, which has been used as a special leveler to simplify the electroplating additive system in the through-hole (TH) copper electroplating experiments. In this work, the role of MO in TH electroplating is characterized by molecular dynamics simulations and quantum chemical calculations. It is suggested that MO can spontaneously flatten the copper surface and be well adsorbed on the cathode surface, which inhibit the copper electrodeposition on the cathode. Electrochemical behavior of MO was evaluated by galvanostatic measurements (GM) and cyclic voltammetry (CV) to confirm that MO hardly affects the potential due to its duel functions of depolarizing and polarizing effects from the molecular structure of sulfonic acid group and other groups to achieve the internal Cu²⁺ reduction acceleration and mass transfer inhibition. Throw power value of TH with the aspect ratio of 10:1 could reach 92.34% from the base plating solution bath with the additions of only EO/PO and MO. The study of MO could provide new ideas for the development of electroplating additive system.

Key words: copper electroplating, through-hole, additive, methyl orange

徐佳莹, 王守绪, 苏元章, 杜永杰, 齐国栋, 何为, 周国云, 张伟华, 唐耀, 罗毓瑶, 陈苑明. 特殊整平剂甲基橙在通孔电镀铜的应用[J]. 电化学（中英文）, 2022, 28(7): 2213003.

Jia-Ying Xu, Shou-Xu Wang, Yuan-Zhang Su, Yong-Jie Du, Guo-Dong Qi, Wei He, Guo-Yun Zhou, Wei-Hua Zhang, Yao Tang, Yu-Yao Luo, Yuan-Ming Chen. Investigation of Through-Hole Copper Electroplating with Methyl Orange as A Special Leveler[J]. Journal of Electrochemistry, 2022, 28(7): 2213003.

图/表 7

参考文献 15

[1]	Wang C, Zhang J Q, Yang P X, Zhang B Q, An M Z. Through-hole copper electroplating using nitrotetrazolium blue chloride as a leveler[J]. J. Electrochem. Soc., 2013, 160(3): D85-D88. doi: 10.1149/2.035303jes URL
[2]	Wang C, Zhang J Q, Yang P X, An M Z. Electrochemical behaviors of Janus Green B in through-hole copper electroplating: An insight by experiment and density functional theory calculation using Safranine T as a comparison[J]. Electrochim. Acta, 2013, 92: 356-364. doi: 10.1016/j.electacta.2013.01.064 URL
[3]	Ding X C, Peng D M, Chen Z X, Cheng J. Effect of novel leveling agent TS-L on electrodeposition of copper[J]. Ele-ctroplating&Finishing, 2016, 35(11): 556-559.
[4]	Zheng L. Investigation on electrochemical performance and tuning property of the organic-additive-system for copper electrodeposition[D]. Chengdu: University of Electronic Science and Technology of China, 2020.
[5]	Zhang Y H, An M Z, Yang P X, Zhang J Q. Recent advances in electroplating of though-hole copper interconnection[J]. Electrocatalysis, 2021, 12(6): 619-627. doi: 10.1007/s12678-021-00687-2 URL
[6]	Li Y B, Wang W, Li Y L. Adsorption behavior and related mechanism of Janus Green B during copper via-filling process[J]. J. Electrochem. Soc., 2009, 156(4): D119-D124. doi: 10.1149/1.3071603 URL
[7]	Tao Z H, Liu G T, Li Y X, Su H. Electrochemical and analytical study of electroplating additive in copper plating solution for microvia filling[J]. Circuit World, 2019, 45(3): 124-131. doi: 10.1108/CW-07-2018-0052 URL
[8]	Zheng L, He W, Zhu K, Wang C, Wang S X, Hong Y, Chen Y M, Zhou G Y, Miao H, Zhou J Q. Investigation of poly (1-vinyl imidazole co 1, 4-butanediol diglycidyl ether) as a leveler for copper electroplating of through-hole[J]. Electrochim. Acta, 2018, 283: 560-567. doi: 10.1016/j.electacta.2018.06.132 URL
[9]	Xiang J. Mechanism and application of copper eletrodeposition for the interconnection structures in package substrate[D]. Chengdu: University of Electronic Science and Technology of China, 2018.
[10]	Chen B A, Wang A Y, Wu S Y, Wang L M. Polyquaternium-2: A New levelling agent for copper electroplating from acidic sulphate bath[J]. Electrochemistry, 2016, 84(6): 414-419. doi: 10.5796/electrochemistry.84.414 URL
[11]	Wang C, Peng C, Xiang J, Chen Y M, He W, Su X H, Luo Y Y. Research and application of copper electroplating in interconnection of printed circuit board[J]. J. Electrochem., 2021, 27(3): 257-268.
[12]	Lai Z Q. Research and application of high speed copper electroplating for the interconnection micro-holes of pri-nted circuit board[D]. Chengdu: University of Electronic Science and Technology of China, 2020.
[13]	Liu C W, Tsao J C, Tsai M S, Wang Y L. Effects of wetting ability of plating electrolyte on Cu seed layer for electroplated copper film[J]. J. Vac. Sci. Technol. A, 2004, 22(6): 2315-2320. doi: 10.1116/1.1795831 URL
[14]	Wang C. Study on molecular simulation and mechanism of the additives used for through-hole copper electroplating on PCB[D]. Harbin: Harbin Institute of Technology, 2013.
[15]	Wang Y F, Hong Y, Zhou G Y, Wang X H, Song J H, He W, Gao Z P, Zhang W H, Sun R, Sun Y K, Ai K H, Li Q H. Mechanism of a catalytic silver(I)-complex: assisted electroless deposition of inductance coil on poly(ethylene terephthalate) film[J]. J. Mater. Sci.-Mater. Electron., 2020, 31(11): 8165-8173. doi: 10.1007/s10854-020-03289-8 URL

特殊整平剂甲基橙在通孔电镀铜的应用

Investigation of Through-Hole Copper Electroplating with Methyl Orange as A Special Leveler

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 15

相关文章 15

Metrics

[1]	翟悦晖, 彭逸霄, 洪延, 陈苑明, 周国云, 何为, 王朋举, 陈先明, 王翀. 铜互连电镀中有机添加剂的合成与分析[J]. 电化学（中英文）, 2023, 29(8): 2208111-.
[2]	张修庆, 唐帅, 付永柱. 锂硫电池电解液功能性添加剂研究进展[J]. 电化学（中英文）, 2023, 29(4): 2217005-.
[3]	孙云娜, 吴永进, 谢东东, 蔡涵, 王艳, 丁桂甫. 硅通孔内铜电沉积填充机理研究进展[J]. 电化学（中英文）, 2022, 28(7): 2213001-.
[4]	谭柏照, 梁剑伦, 赖子亮, 罗继业. 高均匀性的铜柱凸块电镀[J]. 电化学（中英文）, 2022, 28(7): 2213004-.
[5]	杨森, 王文昌, 张然, 秦水平, 吴敏娴, 光崎尚利, 陈智栋. 醇硫基丙烷磺酸钠对电解高性能锂电铜箔的影响[J]. 电化学（中英文）, 2022, 28(6): 2104501-.
[6]	杨凯, 陈际达, 陈世金, 许伟廉, 郭茂桂, 廖金超, 吴熷坤. 高深径比通孔脉冲电镀添加剂及电镀参数的优化[J]. 电化学（中英文）, 2022, 28(6): 2104491-.
[7]	缪桦, 李明瑞, 邹文中, 周国云, 王守绪, 叶晓菁, 朱凯. Sn-Ag-Cu三元合金焊料电沉积中添加剂的影响研究[J]. 电化学（中英文）, 2022, 28(6): 2104411-.
[8]	纪执敬, 凌惠琴, 吴培林, 余瑞益, 于大全, 李明. 玻璃通孔三维互连镀铜填充技术发展现状[J]. 电化学（中英文）, 2022, 28(6): 2104461-.
[9]	张远航, 安茂忠, 杨培霞, 张锦秋. 数值模拟方法在周期换向脉冲电镀通孔中的应用[J]. 电化学（中英文）, 2022, 28(6): 2104511-.
[10]	战充波, 张润佳, 付旭, 孙海静, 周欣, 王保杰, 孙杰. 氯离子对ChCl-Urea低共熔溶剂中银电沉积的电化学行为影响[J]. 电化学（中英文）, 2022, 28(5): 2111151-.
[11]	谢茂玲, 王钧, 胡晨吉, 郑磊, 孔华彬, 沈炎宾, 陈宏伟, 陈立桅. 基于非亲核电解液构建稳定的镁离子电池[J]. 电化学（中英文）, 2022, 28(3): 2108561-.
[12]	黄波, 张新胜, 钮东方, 胡硕真. 对称季铵碱的烷基链长度对草酸电还原反应的影响[J]. 电化学（中英文）, 2021, 27(5): 529-539.
[13]	张彪, 帅毅, 王玉, 杨纳川, 陈康华. 碳酸酯类电解液中Mg(NO₃)₂添加剂抑制锂枝晶生长的研究[J]. 电化学（中英文）, 2021, 27(4): 423-428.
[14]	王赵云, 金磊, 杨家强, 李威青, 詹东平, 杨防祖, 孙世刚. 高密度互连印制电路板孔金属化研究和进展[J]. 电化学（中英文）, 2021, 27(3): 316-331.
[15]	王翀, 彭川, 向静, 陈苑明, 何为, 苏新虹, 罗毓瑶. 印制电路中电镀铜技术研究及应用[J]. 电化学（中英文）, 2021, 27(3): 257-268.