[1]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,(5):92-100.[doi:10.3969/j.issn.1001-3849.2024.05.013]
　Xu Xinying,Xiao Shucheng,Zhang Lulu,et al.Influence and mechanism of new leveler on through hole filling by copper electroplating[J].Plating & Finishing,2024,(5):92-100.[doi:10.3969/j.issn.1001-3849.2024.05.013]
点击复制

新型整平剂对电镀铜填通孔的影响及机制探究
()

《电镀与精饰》[ISSN:1001-3849/CN:12-1096/TG]

卷:
期数:
2024年5
页码:
92-100
栏目:
出版日期:
2024-05-15

文章信息/Info

Title:
Influence and mechanism of new leveler on through hole filling by copper electroplating
作者:
（北京化工大学 化学工程学院，北京 100029）
Author(s):
（School of Chemical Engineering， Beijing University of Chemical Technology，
Beijing 100029， China）
关键词:
通孔填充; 整平剂; 蝴蝶技术; 变电流计时电位法; 负微分电阻效应
Keywords:
through hole filling ;  leveler ;  butterfly technology ;  chronopotentiometry with current ramp ;  negative differential resistance effect
分类号:
TQ153.1
DOI:
10.3969/j.issn.1001-3849.2024.05.013
文献标志码:
A
摘要:
针对目前国内电子电镀专用化学品瓶颈问题，合成了一种由含氮杂环与含氧碳链组成的新型整平剂分子 SC-21 。通过哈林槽实验、循环伏安法 （ CV ）、计时电位法 （ CP & CPCR ）和电化学交流阻抗谱 （ EIS ）对比，研究了常见整平剂健那绿 （ JGB ） 、聚乙烯亚胺烷基盐 （ PN ） 与新型整平剂 SC-21 在电镀铜填充通孔过程中的作用差异。结果表明：以一定浓度 SC-21 为整平剂时可出现“蝴蝶填充”现象，进而实现对深径比 2 ∶ 1 通孔的无空洞填充；与 JGB 和 PN 相比，此浓度下的 SC-21 在较宽的电流密度范围内具有动态吸附行为，可产生“负微分电阻效应”，使得通孔内呈现与“蝴蝶填充”形状相匹配的沉铜速率梯度，最终实现对通孔的无空洞填充。
Abstract:
： To solve the bottlenecks of the specialized chemicals for electronic electroplating in domestic ， a new leveler named SC-21 was synthesized. It was consisted of a nitrogen-containing heterocycle and an oxygen-containing carbon chain. In this paper ， the different performances between the common leveler of Janus Green B （ JGB ）， polyethyleneimine alkyl salt （ PN ） and the new leveler SC-21 were studied by copper plating in haring cell ， cyclic voltammetry （ CV ）， chronopotentiometry （ CP & CPCR ）， and electrochemical impedance spectroscopy （ EIS ） . The results indicate that the copper deposition mode of “ butterfly filling ” can be achieved using a certain concentration of SC-21 as the leveler. Finally ， the through holes with the depth to ratio of 2 ∶ 1 can be completely filled without void. Compared with JGB and PN ， SC-21 at this concentration showed a dynamic adsorption behavior in a wide range of current density ， which resulted in the appearance of "negative differential resistance effect" （ NDR effect ） . The NDR effect can lead to the velocity gradients of copper deposition in the through hole ， which finally resulted in the void-free filling of through holes.

参考文献/References:



[1] 窦维平 . 利用电镀铜填充微米盲孔与通孔之应用 [J]. 复旦学报 ( 自然科学版 ), 2012, 51(2): 131-138.

[2] Dow W P, Li C C, Su Y C, et al. Microvia filling by copper electroplating using diazine black as a leveler[J]. Electrochimica Acta, 2009, 54(24): 5894-5901.

[3] 肖宁 , 李宁 , 谢金平 , 等 . 聚乙二醇与嵌段聚合物 L64 在超填孔镀铜中的行为 [J]. 电镀与涂饰 , 2012, 31(11): 15-19.

[4] 武锦辉 , 刘鑫宁 , 吴波 , 等 . 酸性镀铜整平剂的应用现状及展望 [J]. 电镀与精饰 , 2023, 45(4): 77-87.

[5] 程庆 , 李宁 , 潘钦敏 , 等 . 电解铜箔添加剂的研究进展及应用现状 [J]. 电镀与精饰 , 2022, 44(12): 69-79.

[6] Lin G Y, Yan J Y, Yen M Y, et al. Characterization of through-hole filling by copper electroplating using a tetrazolium salt inhibitor[J]. Journal of the Electrochemical Society, 2013, 160(12): D3028-D3034.

[7] Paul O, Edmond F, Nikolay D. Superconformal filling of high aspect ratio through glass vias (TGV) for interposer applications using TNBT and NTBC additives[J]. Journal of the Electrochemical Society, 2015, 162(9): D30-D32.

[8] Wang C, Zhang J Q, Yang P X, et al. Through-hole filling by copper electroplating using sodium thiazolinyl-dithiopropane sulfonate as the single additive[J]. International Journal of Electrochemical Science, 2012, 7(11): 10644-10651.

[9] Dow W P, Chen H H. A novel copper electroplating formula for laser‐drilled micro via and through hole filling [J]. Circuit World, 2004, 30(3): 33-36.

[10] 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, 44(11): 85-90.

[11] Dow W P, Chen H H, Yen M Y, et al. Through-hole filling by copper electroplating[J]. Journal of the Electro-chemical Society, 2008, 155(12): D750-D757.

[12] Bertocci U. Application of electrochemical theory to the behaviour of copper in cupric and cuprous solutions[J]. Electrochimica Acta, 1966, 11(9): 1261-1277.

[13] 何晓桐 , 谭伟 , 陈泳 , 等 . 苯基修饰含氮整平剂对高厚径比盲孔镀铜的影响 [J]. 电镀与涂饰 , 2022, 41(17): 1237-1244.

[14] 王旭 , 李振 , 冯龙龙 , 等 . 一种新型小分子电镀铜整平剂的模拟研究 [J]. 电镀与精饰 , 2023, 45(01): 80-84.

[15] 吴依彩 , 毛子杰 , 王翀 , 等 . 高端电子制造中电镀铜添加剂作用机制研究进展 [J]. 中国科学 : 化学 , 2021, 51(11): 1474-1488.

[16] Jovi? V D, Jovi? B M. Copper electrodeposition from a copper acid baths in the presence of PEG and NaCl[J]. Journal of the Serbian Chemical Society, 2001, 66(11-12): 935-952.

[17] Pasquale M A, Gassa L M, Arvia A J. Copper electrodeposition from an acidic plating bath containing accelerating and inhibiting organic additives[J]. Electrochimica Acta, 2008, 53(20): 5891-5904.

[18] Bozzini B, Mele C, D’urzo L, et al. An electrochemical and in situ SERS study of Cu electrodeposition from acidic sulphate solutions in the presence of 3-diethylamino-7-(4-dimethylaminophenylazo)-5-phenylphenazinium chloride (Janus Green B)[J]. Journal of Applied Electrochemistry, 2006, 36(9): 973-981.

[19] Li Y B, Wang W, Li Y L. Adsorption behavior and related mechanism of janus green b during copper via-filling process[J]. Journal of the Electrochemical Society, 2009, 156(4): D119-D124.

[20] Feng Z. V, Li X, Gewirth A A. Inhibition due to the interaction of polyethylene glycol, chloride, and copper in plating baths: a surface-enhanced Raman study[J]. Journal of Physical Chemistry B, 2003, 107(35): 9415-9423.

[21] Dow W P, Yen M Y, Chou C W, et al. Practical monitoring of filling performance in a copper plating bath[J]. Electrochemical and Solid-State Letters, 2006, 9(8): C134-C137.

[22] 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-C434.

[23] Mladenovi? I O, Bo?kovi? M V, Vuksanovi? M M, et al. Structural, mechanical and electrical characteristics of copper coatings obtained by various electrodeposition processes[J]. Electronics, 2022, 11(3): 443-443.

[24] Moffat T P, Josell D. Extreme bottom-up superfilling of through-silicon-vias by damascene processing: suppressor disruption, positive feedback and turing patterns[J]. Journal of the Electrochemical Society, 2012, 159(4): D208-D216.

[25] 王晓静 , 肖树城 , 肖宁 . 亚甲基紫对盲孔镀铜电化学行为和填孔效果的影响 [J]. 电镀与涂饰 , 2022, 41(3): 191-196.

相似文献/References:

[1]王 旭*,李 振,冯龙龙,等.一种新型小分子电镀铜整平剂的模拟研究[J].电镀与精饰,2023,(1):80.[doi:10.3969/j.issn.1001-3849.2023.01.012]
　Wang Xu*,Li Zhen,Feng Longlong,et al.Simulation study on a novel small molecular leveler for copper electroplating[J].Plating & Finishing,2023,(5):80.[doi:10.3969/j.issn.1001-3849.2023.01.012]
[2]武锦辉,刘鑫宁,吴波,等.酸性镀铜整平剂的应用现状及展望[J].电镀与精饰,2023,(4):77.[doi:10.3969/j.issn.1001-3849.2023.04.013]
　Wu Jinhui,Liu Xinning,Wu Bo,et al.Application status and prospect of acidic copper plating leveler[J].Plating & Finishing,2023,(5):77.[doi:10.3969/j.issn.1001-3849.2023.04.013]
[3]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,(5):1.[doi:doi: 10.3969/j.issn.1001-3849.2024.09.001]
[4]李仪婷,吴正旭,赵 鹏,等.doi: 10.3969/j.issn.1001-3849.2025.09.0174-苯基咪唑基季铵盐整平剂的合成及其在通孔镀铜中的应用[J].电镀与精饰,2025,(09):119.
　Li Yiting,Wu Zhengxu,Zhao Peng,et al.The synthesis of 4-phenylimidazolyl quaternary ammonium levelling agent and their application in through-hole plating[J].Plating & Finishing,2025,(5):119.

备注/Memo

备注/Memo:
收稿日期： 2023-10-07 修回日期： 2023-12-14 作者简介： 许昕莹（ 1997 —），女，硕士研究生， email ： 2021200172@mail.buct.edu.cn * 通信作者： 肖宁， email ： xiaoning@mail.buct.edu.cn 基金项目 ： 国家自然科学基金青年基金（ 21902010 ）?/html>
更新日期/Last Update: 2024-05-05