印制电路中电镀铜技术研究及应用

doi:10.13208/j.electrochem.201255

电化学（中英文） ›› 2021, Vol. 27 ›› Issue (3): 257-268. doi: 10.13208/j.electrochem.201255

所属专题： “电子电镀和腐蚀”专题文章

印制电路中电镀铜技术研究及应用

王翀¹^,^*(), 彭川¹, 向静¹^,², 陈苑明¹^,³, 何为¹^,³^,^*(), 苏新虹³, 罗毓瑶³

1.材料与能源学院,电子科技大学,四川成都 610054
2.重庆市高校新型储能器件及应用工程研究中心,重庆文理学院,重庆 402160
3.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

收稿日期:2021-03-01 修回日期:2021-03-24 出版日期:2021-06-28 发布日期:2021-04-22
通讯作者: 王翀,何为 E-mail:wangchong@uestc.edu.cn;heweiz@uestc.edu.cn
基金资助:
国家自然科学基金项目(61974020);珠海市引进创新团队项目(ZH0405190005PWC)

Research and Application of Copper Electroplating in Interconnection of Printed Circuit Board

Chong Wang¹^,^*(), Chuan Peng¹, Jing Xiang¹^,², Yuan-Ming Chen¹^,³, Wei He¹^,³^,^*(), Xin-Hong Su³, Yu-Yao Luo³

1. School of Materials and Energy, University of Electronic Science and technology of China, Chengdu 610054, Sichuan, China
2. Engineering Research Center of New Energy Storage Devices and Application, Chongqing University of Art and Science, Chongqing 402160, China
3. Zhuhai Founder Tech. Hi-Density Electronic Co., Ltd. & Zhuhai Founder Tech. Multilayer Circuit Board Co., Ltd, Zhuhai 519175, Guangdong, China

Received:2021-03-01 Revised:2021-03-24 Published:2021-06-28 Online:2021-04-22
Contact: Chong Wang,Wei He E-mail:wangchong@uestc.edu.cn;heweiz@uestc.edu.cn

摘要/Abstract

摘要：

电镀铜技术是制造印制电路板、封装载板等电子互连器件的核心技术。本文介绍了印制电路中电镀铜技术及其发展概况,主要总结了电子科技大学印制电路与印制电子团队在印制电路电镀铜技术基础研究和产业化应用等方面的工作。首先,以三次电流分布理论为基础,采用多物理场耦合方法构建阴极表面轮廓线随时间变化的镀层生长过程模型。该模型描述了铜沉积与微纳孔结构、添加剂特性、输入电流、对流强度等相关影响因素的函数关系。通过引入添加剂相关函数,该模型能够较好应用到整平剂筛选和性能评价、电镀铜需求和镀液配方匹配、电镀参数优化等技术开发和应用领域。然后,介绍了添加剂竞争吸附过程的电化学研究以及利用传质调控添加剂局域浓度实现快速微盲孔、微沟槽填充的工业技术。之后,介绍了氮杂环低聚物系列整平剂结构-电化学构效关系研究和应用。最后展示了氧化还原型添加剂的开发情况,并对印制电路中电镀铜技术的研究和应用发展进行了预测。

关键词: 电镀铜, 印制电路板, 超级填孔, 多物理场耦合, 有机添加剂, 竞争吸附

Abstract:

Copper electroplating is the key technology for manufacturing of integrated circuit, packaging substrate, printed circuit board, and other electronic interconnection components. However, the electrochemistry and mechanism of deposition growth have not been fully elucidated, and the development of additives and bath maintenance are inseparable from a large number of experiments. This article reviews recent fundamental research and application progress in copper electroplating for printed circuit board industry, and these works are mainly dedicated by the research group of Printed Circuit and Printed Electronics from University of Electronic Science and Technology of China. First of all, a brief history of copper plating in printed circuit board is given. Then, modeling and simulation studies are introduced. A multi-physics coupling model is built on the basis of an electroplating bath, and an additive related parameter is introduced into the model to connect the convection intensity and the voltammetric response of the electrolyte. Base on tertiary current distribution, a relational model with the growth process of cathode surface related to micro-scale hole structure, plating current, convection intensity, additives etc., is obtained. Some applications using the above model are presented successively. By simplifying this model, a fast electrochemical evaluation method is developed to screen leveler candidates. Two dependent indicators, polarization overpotential of leveler injection (Δη) and deposition potential difference with low and high convection (ΔEr), are introduced, and the chemical having both high Δη and Δ Er may be an appropriate leveler. Fix the parameters of plating conditions and set TP as the index, the additive related parameter, size and structure of micro-scale hole are varied. It is feasible for a specific copper electroplating application couple to an appropriate additives’ pack. Then, a multi-physics modeling helping to optimize plating parameters of fine circuit pattern plating to meet the requirement of high thickness uniformity over the whole board has been demonstrated. Secondly, the mechanism of competitive adsorption of the organic additives has been discussed from the electrochemical results. The adsorption amount of the accelerator is independent of solution convection, but it shows dependency on the suppressor, and the adsorption strength of the accelerator is weaker than that of the suppressor. From that, a fast via-filling process is developed. Molecules of accelerator are selectively replaced from board surface but remained on via bottom by a mass-transport controlled pre-dip step of oxidant or suppressor, and the plating time of via filling is significantly shortened. Thirdly, the structure-electrochemistry relationship of series nitrogen heterocyclic oligomers is studied, and applications of the levelers and redox additive are discussed. Finally, a prospect on the research and application of copper electroplating has been made.

Key words: copper electroplating, electronic interconnection, super-filling, multi-physics coupling, organic additives, competitive adsorption

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.

Chong Wang, Chuan Peng, Jing Xiang, Yuan-Ming Chen, Wei He, Xin-Hong Su, Yu-Yao Luo. Research and Application of Copper Electroplating in Interconnection of Printed Circuit Board[J]. Journal of Electrochemistry, 2021, 27(3): 257-268.

图/表 13

图1

表1

图2

图3

图4

图5

图6

图7

图8

图9

图10

图11

图12

参考文献 30

[1]	Wang C (王翀). Priciple and application of copper electro-deposition[M]//He W(何为), Wang S X(王守绪). Advanced technology of printed circuit and printed electronics (volume 2)(印制电路与印制电子先进技术(下册)). Bejing: Science Press, 2016: 25-61.
[2]	Dou W P (窦维平). Appliactions of microvia and through-hole filling by copper electroplating[J]. J. Fudan Univ. (Nat. Sci.)(复旦学报(自然科学版)), 2012, 51(2): 131-138+259-260.
[3]	Bai R S (白蓉生). The past, present and future of electroplating copper (Part.1)[J]. Printed Circuit Info.(印制电路资讯), 2003, 6: 7-16.
[4]	Bai R S (白蓉生). The past, present and future of electroplating copper (Part.2)[J]. Printed Circuit Info.(印制电路资讯), 2004, 1: 5-12.
[5]	Zhu K (朱凯). Investigation and application of metal deposition for the electrical interconnection structure of electronic components[D]. University of Electronic Science and Technology(电子科技大学), 2019.
[6]	Bowerman B, Bellemar R. Making sense of plating chem-istries[J]. PCB007 Mag., 2020, 11: 22-28.
[7]	West A C. Theory of filling of high-aspect ratio trenches and vias in presence of additives[J]. J. Electrochem. Soc., 2000, 147(1): 227-232. doi: 10.1149/1.1393179 URL
[8]	Xiao N, Li D Y, Cui G F, Li N, Li Q, Wu G. Adsorption behavior of triblock copolymer suppressors during the copper electrodeposition[J]. Electrochim. Acta, 2014, 116: 284-291. doi: 10.1016/j.electacta.2013.11.056 URL
[9]	Schultz Z D, Feng Z V, Biggin M E, Gewirth A A. Vibrational spectroscopic and mass spectrometric studies of the interaction of bis(3-sulfopropyl)-disulfide with Cu surfaces[J]. J. Electrochem. Soc., 2015, 153(2): 209-212.
[10]	Wiener F, Morlein F, Ma-Rlein F, Moerlein F. Galvanic plating device for galvanic metal deposition on printed circuit foils, has substrate guiding element which is in conjunction with surface of covering plate of galvanic plating module: American, WO2017071908-A1[P]. 2016-9-30.
[11]	Kanakarajan K. Polyimide based adhesive material useful in dielectric layer comprises polyimide base polymer with specific glass transition temperature and thermal expansion coefficient, and micro fiber reinforcing agent: American, US2007231568-A1[P]. 2016-3-31.
[12]	Moffat T P, Wheeler D, Josell D. Electrodeposition of copper in the SPS-PEG-Cl additive system-I. Kinetic measurements: Influence of SPS[J]. J. Electrochem. Soc., 2004, 151(4): C262-C271. doi: 10.1149/1.1651530 URL
[13]	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
[14]	Dow W P, Huang H S, Yen M Y, Huang H C. Influence of convection-dependent adsorption of additives on microvia filling by copper electroplating[J]. J. Electrochem. Soc., 2005, 152(6): C425-C434. doi: 10.1149/1.1901670 URL
[15]	Ji L X, Wang C, Wang S X, Zhu K, He W, Xiao D J. Multi-physics coupling aid uniformity improvement in pattern plating[J]. Circuit World, 2016, 42(2): 69-76. doi: 10.1108/CW-05-2015-0023 URL
[16]	Ji L X, Wang S X, Wang C, Chen G Q, Chen Y M, He W, Tan Z. Improved uniformity of conformal through-hole copper electrodeposition by revision of plating cell configuration[J]. J. Electrochem Soc., 2015, 162(12): D575-D583. doi: 10.1149/2.0761512jes URL
[17]	Ji L X, Wang C, Wang S X, He W, Xiao D J. An electrochemical model for prediction of microvia filling process[J]. Trans. Inst. of Metal Finis., 2016, 94(1): 49-56. doi: 10.1080/00202967.2015.1124638 URL
[18]	Paunovic M, Schlesinger M. Fundamentals of electrochemical deposition, 2nd edition[M]. New Jersey: John Wiley & Sons Inc, 2006: 249-270.
[19]	Ji L X (冀林仙). Investigation of copper electrodeposition for printed-circuit interconnection based on multiphysics coupling method[D]. University of Electronic Science and Technology(电子科技大学), 2016.
[20]	Xiang J, Wang S X, Li J, He W, Wang C, Chen Y M, Zhang H W, Hua M, Zhou J Q, Jin X F. Electrochemical factors of levelers on plating uniformity of through-holes: simulation and experiments[J]. J. Electrochem. Soc., 2018, 165(9): E359-E365. doi: 10.1149/2.0331809jes URL
[21]	Zheng L (郑莉). Investigation on electrochemical performance and tuning property of the organic-additive-system for copper electrodeposition[D]. University of Electronic Science and Technology(电子科技大学), 2020.
[22]	Xiang J (向静). Mechanism and application of copper electrodeposition for the interconnection structures in package substrate[D]. University of Electronic Science and Technology of China(电子科技大学), 2018.
[23]	Lai Z Q, Wang S X, Wang C, Hong Y, Chen Y M, Zhang H W, Zhou G Y, He W, Ai K H, Peng Y Q. Computational analysis and experimental evidence of two typical levelers for acid copper electroplating[J]. Electrochim. Acta, 2018, 273: 318-326. doi: 10.1016/j.electacta.2018.04.062 URL
[24]	Xiang J, Chen Y M, Wang S X, Wang C, He W, Zhang H W. Improvement of plating uniformity for copper patterns of ic substrate with multi-physics coupling simulation[J]. Circuit World, 2018, 44(3): 150-160. doi: 10.1108/CW-12-2017-0078 URL
[25]	Zhu K, Wang C, Wang S X, Chen Y M, Zhou G Y, Hong Y, He W, Zhou J Q, Miao H, Wen Z S. Communication-localized accelerator pre-adsorption to speed up copper electroplating microvia filling[J]. J. Electrochem. Soc., 2019, 166(10): D467-D469. doi: 10.1149/2.0041912jes URL
[26]	Zhu K, Wang C, Wang J Z, Hong Y, Chen Y M, He W, Zhou J Q, Miao H, Chen Q G. Convection-dependent competitive adsorption between SPS and EO/PO on copper surface for accelerating trench filling[J]. J. Electrochem. Soc., 2019, 166(4): D93-D98. doi: 10.1149/2.0491904jes URL
[27]	Brunner H, Kohlmann L, Witczak A, Mann O. New imidazoyl urea polymer comprising polymeric building block used in metal or metal alloy plating bath used for depositing metal or metal alloy onto substrate e.G. Printed circuit boards: American, WO2017036816-A1[P]. 2016-8-19.
[28]	Kanakarajan K. Polyimide adhesive composition for, e.G. Chip on lead package, contains polyimide base polymer synthesized by contacting aromatic dianhydride with diamine component comprising aliphatic diamine and aromatic diamine: American, US2006068211-A1[P]. 2006-3-30.
[29]	Chen G Q (陈国琴). Behavior research on copper electrodeposition in solution threading through hole for PCB[D]. University of Electronic Science and Technology(电子科技大学), 2016.
[30]	Baron D T, Lamprecht S, Massey R. Method for manufacturing of e.G. Conductor line used in printed circuit board, involves filling openings with filling material selected from group consisting of metals, metal alloys and optically transparent materials: American, WO2016180944-A1[P]. 2016-5-12.

Component	Chemical	Effect	Concentration
Main salt	CuSO₄	Providing Cu²⁺	50 ~ 250 g·L^-1
Electrolyte	H₂SO₄	Improving conductivity and maintain acidity	30 ~ 250 g·L^-1
Halide ion	Cl^-,Br^-,I^-	The electronic bridge of Cu²⁺ reduction	30 ~ 80 mg·L^-1
Accelerator	SPS,MPS et al	Depolarization and brightening	0.3 ~ 10 mg·L^-1
suppressor	PEG,EO/PO et al	polarization, grain refiner	100 ~ 2000 mg·L^-1
Leveler	N-containing organic compounds	Improving TP of the bath	1 ~ 100 mg·L^-1

印制电路中电镀铜技术研究及应用

Research and Application of Copper Electroplating in Interconnection of Printed Circuit Board

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 30

相关文章 6

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]	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-.
[3]	邹浩斌, 谭超力, 熊伟, 席道林, 刘彬云. 酸性镀铜添加剂开发及应用技术[J]. 电化学（中英文）, 2022, 28(6): 2104531-.
[4]	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.
[5]	殷列, 王增林, . 不同分子量PEG的铜电镀液对电化学沉积铜行为的研究[J]. 电化学（中英文）, 2008, 14(4): 431-435.
[6]	成银梅;蔡兰坤;宋强;. 镀锡电解液中有机添加剂的电化学氧化[J]. 电化学（中英文）, 2005, 11(4): 450-452.