[1]王丹蕾,宋子豪,聂凯旋,等.doi: 10.3969/j.issn.1001-3849.2026.01.001聚合物整平剂用于浅孔超填充电镀的性能研究[J].电镀与精饰,2026,(01):1-7.
　WANG Danlei,SONG Zihao,NIE Kaixuan,et al.Performance study on using a polymeric leveler for copper electroplated superfilling of low aspect-ratio microvias[J].Plating & Finishing,2026,(01):1-7.
点击复制

doi: 10.3969/j.issn.1001-3849.2026.01.001聚合物整平剂用于浅孔超填充电镀的性能研究()

《电镀与精饰》[ISSN:1001-3849/CN:12-1096/TG]

卷:
期数:
2026年01
页码:
1-7
栏目:
出版日期:
2026-01-31

文章信息/Info

Title:
Performance study on using a polymeric leveler for copper electroplated superfilling of low aspect-ratio microvias
作者:
王丹蕾; 宋子豪; 聂凯旋; 李 哲; 孙 蓉
(中国科学院深圳先进技术研究院 深圳先进电子材料国际创新研究院,广东 深圳 518103)
Author(s):
WANG Danlei;  SONG Zihao;  NIE Kaixuan;  LI Zhe;  SUN Rong
(Shenzhen Institute of Advanced Electronic Materials, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518103, China)
关键词:
印制电路板; 电镀铜; 微孔超填充; 聚合物整平剂
Keywords:
printed-circuit boards;  copper electroplating;  microvia superfilling;  polymeric levelers
分类号:
TQ153.14
文献标志码:
A
摘要:
设计制备了一种新型二元共聚物型酸性硫酸电镀铜整平剂L。在酸铜基础镀液(VMS)中，添加2～4 mg/L聚二硫二丙烷磺酸钠(SPS)、200 mg/L聚乙二醇(PEG，MW10 000)和20～30 mg/L整平剂L，并以电流密度1.5～2.1 A/dm2电镀填充深径比1﹕2的印制电路板(PCB)微孔。结果表明：整平剂L及其配方技术可兼容可溶磷铜阳极和不溶铱钛阳极(添加10 g/L FeSO4?7H2O)工艺，表现出优异且稳定的填平能力。镀液具有宽泛的添加浓度和施镀电流控制窗口，镀层平整均匀、结构致密，无铜瘤或包芯等形貌缺陷，具有良好的抗拉强度、延展性和热冲击可靠性，能够满足包括高密度互连板、封装基板等在内高端PCB的应用需要。
Abstract:
A novel binary copolymer leveler L for acidic copper electroplating was designed and synthesized. In presence of 2~4 mg/L sodium 3,3’-dithiodipropane sulfonate (SPS), 200 mg/L polyethylene glycol (PEG, MW= 10000) and 20～30 mg/L leveler L in virgin makeup solution (VMS), this additive formular exhibited excellent superfilling of printed-circuit boards (PCB) microvias with aspect ratio of 1 ∶2, across a current density range of 1.5~2.1 A/dm2. The results show that leveler L based additive combination exhibit good compatibility with both phosphorus copper anode (soluble) and iridium-coated titanium anode (insoluble) processes (the latter with addition of 10 g/L FeSO4?7H2O), enable a consistently superior via fill capability. The electroplating bath allows wide control ranges for leveler concentrations and plating current densities and produces smooth and compact copper deposits free from any morphological defects such as nodulating or voiding. The electroplated copper materials also possess excellent tensile strength, ductility and thermal shock reliability, fulfilling the stringent requirements for advanced applications including high-density interconnect PCB and packaging substrates.

参考文献/References:

[1].HELTZEL S, CAUWE M, BENNETT J, et al. Advanced PCB technologies for space and their assessment using up-to-date standards[J]. CEAS Space Journal, 2023, 15(1): 89-100.
[2].廖小茹, 李真, 谭柏照, 等. 金属铜电沉积调控及其在芯片制造中的应用[J]. 中国科学: 化学, 2023, 53(10): 1989-2007.
[3].MOFFAT T P, BONEVICH J E, HUBER W H, et al. Superconformal electrodeposition of copper in 500-90 nm features[J]. Journal of the Electrochemical Society, 2000, 147(12): 4524.
[4].周苗淼, 张雨, 沈喜训, 等. 芯片电镀铜添加剂的研究进展[J]. 电镀与精饰, 2022, 44(2): 60-65.
[5].HAI N T M, HUYNH T T M, FLUEGEL A, et al. Competitive anion/anion interactions on copper surfaces relevant for damascene electroplating[J]. Electrochimica Acta, 2012, 70: 286-295.
[6].CHEN T C, TSAI Y L, HSU C F, et al. Effects of brighteners in a copper plating bath on throwing power and thermal reliability of plated through holes[J]. Electrochimica Acta, 2016, 212: 572-582.
[7].MAO Z J, WU Y C, MA X Y, et al. In situ wide-frequency surface-enhanced infrared absorption spectroscopy enables one to decipher the interfacial structure of a Cu plating additive[J]. Journal of Physical Chemistry Letters, 2022, 13(39): 9079-9084.
[8].TAN M, HARB J N. Additive Behavior during copper electrodeposition in solutions containing Cl??, PEG, and SPS[J]. Journal of the Electrochemical Society, 2003, 150(6): C420.
[9].BROEKMANN P, FLUEGEL A, EMNET C, et al. Classification of suppressor additives based on synergistic and antagonistic ensemble effects[J]. Electrochimica Acta, 2011, 56(13): 4724-4734.
[10].MROCZKA R, S?ODKOWSKA A, ?ADNIAK A, et al. Interaction of bis-(sodium-sulfopropyl)-disulfide and polyethylene glycol on the copper electrodeposited layer by time-of-flight secondary-ion mass spectrometry[J]. Molecules, 2023, 28(1): 433.
[11].杨彦章, 陈志华, 钟上彪, 等. PEG在电子电镀铜中的作用机制及应用[J]. 电镀与精饰, 2025, 47(3): 96-105.
[12].GALLAWAY J W, WEST A C. PEG, PPG, and their triblock copolymers as suppressors in copper electroplating[J]. Journal of the Electrochemical Society, 2008, 155(10): D632.
[13].HAI N T M, KR?MER K W, FLUEGEL A, et al. Beyond interfacial anion/cation pairing: The role of Cu(I) coordination chemistry in additive-controlled copper plating[J]. Electrochimica Acta, 2012, 83: 367-375.
[14].ZHENG L, HE W, ZHU K, et al. Investigation of poly (1-vinyl imidazole co 1, 4-butanediol diglycidyl ether) as a leveler for copper electroplating of through-hole[J]. Electrochimica Acta, 2018, 283: 560-567.
[15].LI Z, TAN B, LUO J, et al. Structural influence of nitrogen-containing groups on triphenylmethane-based levelers in super-conformal copper electroplating[J]. Electrochimica Acta, 2022, 401: 139445.
[16].LI Y, REN P, ZHANG Y, et al. The influence of leveler Brilliant Green on copper superconformal electroplating based on electrochemical and theoretical study[J]. Journal of Industrial and Engineering Chemistry, 2023, 118: 78-90.
[17].陈洁, 宗高亮, 代禹涵, 等. 巯基吡啶异构体对电镀铜填盲孔的影响研究[J]. 电镀与精饰, 2024, 46(9): 1-9.
[18].许昕莹, 肖树城, 张路路, 等. 新型整平剂对电镀铜填通孔的影响及机制探究[J]. 电镀与精饰, 2024, 46(5): 92-100.
[19].肖龙辉, 何为, 皮亦鸣, 等. 偶氮类染料添加剂在铜电沉积中的机理和应用研究[J]. 电镀与精饰, 2025, 47(3): 1-9, 33.
[20].HAI N T M, HUYNH T M T, FLUEGEL A, et al. Adsorption behavior of redox-active suppressor additives: Combined electrochemical and STM studies[J]. Electrochimica Acta, 2011, 56(21): 7361-7370.
[21].HAYASE M, NAGAO M. Copper deep via filling with selective accelerator deactivation by polyethyleneimine[J]. Journal of the Electrochemical Society, 2013, 160(12): D3216.
[22].DOW W P, HUANG H S, YEN M Y, et al. Roles of chloride ion in microvia filling by copper electrodeposition: II. Studies using EPR and galvanostatic measurements[J]. Journal of the Electrochemical Society, 2005, 152(2): C77.
[23].DOW W P, HUANG H S, YEN M Y, et al. Influence of convection-dependent adsorption of additives on microvia filling by copper electroplating[J]. Journal of the Electrochemical Society, 2005, 152(6): C425.
[24].DOW W P, YEN M Y, LIN W B, et al. Influence of molecular weight of polyethylene glycol on microvia filling by copper electroplating[J]. Journal of the Electrochemical Society, 2005, 152(11): C769.
[25].JIAO Y, LI Z, LIU X Q, et al. Computational and experimental study of a novel L-cysteine hydrochloride leveler for copper electroplated via fill in redistribution layers[C]//2023 24th International Conference on Electronic Packaging Technology (ICEPT), 2023: 1-5.
[26].JIN Y, SUN M, MU D, et al. Investigation of PEG adsorption on copper in Cu2+-free solution by SERS and AFM[J]. Electrochimica Acta, 2012, 78: 459-465.

相似文献/References:

[1]冀林仙*,王跃峰.多场耦合研究PCB电镀铜[J].电镀与精饰,2022,(11):18.[doi:10.3969/j.issn.1001-3849.2022.11.004]
　JI Linxian*,WANG Yuefeng.Research on Copper Electrodeposition of PCB Based on Multi-Physics Coupling[J].Plating & Finishing,2022,(01):18.[doi:10.3969/j.issn.1001-3849.2022.11.004]
[2]向 静,阮海波*,王 翀,等.添加剂竞争吸附机理研究及通孔电镀应用[J].电镀与精饰,2022,(11):85.[doi:10.3969/j.issn.1001-3849.2022.11.015]
　XIANG Jing,RUAN Haibo*,WANG Chong,et al.Study on Competitive Adsorption Mechanism of Additives and Its Application of Though Holes Plating[J].Plating & Finishing,2022,(01):85.[doi:10.3969/j.issn.1001-3849.2022.11.015]
[3]孙 鹏,沈喜训 *,马 祥,等.印制线路板的孔金属化技术的研究进展[J].电镀与精饰,2023,(12):89.[doi:doi ： 10.3969/j.issn.1001-3849.2023.12.013]
　Sun Peng,Shen Xixun,*,et al.Research progress in hole metallization technology for printed circuit boards[J].Plating & Finishing,2023,(01):89.[doi:doi ： 10.3969/j.issn.1001-3849.2023.12.013]
[4]郑家翀,何 为,陈先明,等.镀镍磷金属片表面处理对电镀铜生长状态影响的研究[J].电镀与精饰,2024,(1):84.[doi:10.3969/j.issn.1001-3849.2024.01.013]
　Zheng Jiachong,He Wei,Chen Xianming,et al.Effect of surface treatment on growth state of electroplating copper for nickel-phosphorus plated metal[J].Plating & Finishing,2024,(01):84.[doi:10.3969/j.issn.1001-3849.2024.01.013]
[5]刘颖*,邢希瑞,田栋,等.酸性一价铜电镀铜的工艺及能效分析[J].电镀与精饰,2024,(4):99.[doi:10.3969/j.issn.1001-3849.2024.04.014]
　Liu Ying*,Xing Xirui,Tian Dong,et al.Energy efficiency analysis of copper electroplating employing acidic cuprous solution[J].Plating & Finishing,2024,(01):99.[doi:10.3969/j.issn.1001-3849.2024.04.014]
[6]陈 洁,宗高亮,代禹涵,等.巯基吡啶异构体对电镀铜填盲孔的影响研究[J].电镀与精饰,2024,(9):1.[doi:doi: 10.3969/j.issn.1001-3849.2024.09.001]
　Chen Jie,Zong Gaoliang,Dai Yuhan,et al.Study on the influence of pyrithione isomers on filling blind holes in electroplated copper[J].Plating & Finishing,2024,(01):1.[doi:doi: 10.3969/j.issn.1001-3849.2024.09.001]
[7]性能影响研究.退火对TSV电镀铜膜层性能影响研究[J].电镀与精饰,2024,(10):42.
　Yu Xianxian*,Jiang Chuang,Zhang Cuicui.Effect of annealing on the properties of electroplated copper in TSV[J].Plating & Finishing,2024,(01):42.
[8]杨彦章,陈志华,钟上彪,等.doi: 10.3969/j.issn.1001-3849.2025.03.0014PEG在电子电镀铜中的作用机制及应用[J].电镀与精饰,2025,(03):96.
　Liu Binyun*,Zhan Dongping.The mechanism and application of PEG in electronic electroplating of copper Yang Yanzhang1,2, Chen Zhihua2, Zhong Shangbiao 2,Ye Shaoming3,[J].Plating & Finishing,2025,(01):96.
[9]方 正,韦相福,杨广柱,等.doi: 10.3969/j.issn.1001-3849.2025.03.015盲孔数值仿真电镀铜研究进展[J].电镀与精饰,2025,(03):106.
　Hu Xiaoqiang,Chen Dedeng.Advances in numerical simulation of copper electroplating in blind vias Fang Zheng1, Wei Xiangfu1,2, Yang Guangzhu1, Mao Xianchang1,3, Wei Song3*,[J].Plating & Finishing,2025,(01):106.
[10]高晓颖,王浩军,周雁文,等.doi: 10.3969/j.issn.1001-3849.2025.04.007HEDP体系无氰镀铜的工艺参数和性能研究[J].电镀与精饰,2025,(04):42.
　Gao Xiaoying,Wang Haojun*,Zhou Yanwen,et al.Research on process parameters and properties of non-cyanide copper plating in HEDP system[J].Plating & Finishing,2025,(01):42.

更新日期/Last Update: 2026-01-16