三苯甲烷类染料整平剂用于再布线层高速电镀铜的形貌调控机制研究

doi:10.61558/2993-074X.3591

电化学（中英文） ›› 2026, Vol. 32 ›› Issue (2): 2509091. doi: 10.61558/2993-074X.3591

• 论文 • 上一篇

三苯甲烷类染料整平剂用于再布线层高速电镀铜的形貌调控机制研究

宋子豪^a^,^b, 王伟斌^a^,^c, 柳晓辉^d^,^e, 韩晓敏^d^,^e, 周毅^f, 黄蕊^f, 姜艳霞^f, 李哲^a^,^*(), 刘晓伟^a^,^*(), 肖梅玲^d^,^e^,^*(), 廖洪钢^f^,^*(), 徐维林^d^,^e, 孙蓉^a

^a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 518055
^b中国科学技术大学纳米科学技术学院，江苏苏州 215123
^c南方科技大学工学院，广东深圳 518055
^d中国科学院长春应用化学研究所，电分析化学国家重点实验室，吉林长春 130022
^e中国科学技术大学应用化学与工程学院，安徽合肥 230026
^f厦门大学化学化工学院，表界面化学全国重点实验室，福建厦门 361005

收稿日期:2025-09-09 接受日期:2025-10-28 发布日期:2025-10-28 出版日期:2026-02-28

Triphenylmethane-Derived Levelers for High-Speed Redistribution Layer Copper Electroplating of Tailored Surface Morphologies

Zi-Hao Song^a^,^b, Wei-Bin Wang^a^,^c, Xiao-Hui Liu^d^,^e, Xiao-Min Han^d^,^e, Yi Zhou^f, Rui Huang^f, Yan-Xia Jiang^f, Zhe Li^a^,^*(), Xiao-Wei Liu^a^,^*(), Mei-Ling Xiao^d^,^e^,^*(), Hong-Gang Liao^f^,^*(), Wei-Lin Xu^d^,^e, Rong Sun^a

^aShenzhen Institute of Advanced Electronic Materials, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen, 518055, China
^bNano Science and Technology Institute, University of Science and Technology of China, Suzhou, 215123, China
^cCollege of Engineering, Southern University of Science and Technology, Shenzhen, 518055, China
^dState Key Laboratory of Electroanalytic Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China
^eSchool of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, 230026, China
^fState Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China

Received:2025-09-09 Accepted:2025-10-28 Online:2025-10-28 Published:2026-02-28
Contact: Zhe Li, E-mail: zhe.li@siat.ac.cn (Z. Li); Xiao-Wei Liu, xw.liu@siat.ac.cn (X. Liu); Mei-Ling Xiao, E-mail: mlxiao@ciac.ac.cn (M. Xiao); Hong-Gang Liao, E-mail: hgliao@xmu.edu.cn (H.-G. Liao)
About author:First author contact:^# Zi-Hao Song and Wei-bin Wang have contributed equally to this work.

摘要/Abstract

摘要：

再布线层由多层的介电材料和电镀铜材料构成，是晶圆级先进封装中用于重新布局芯片表面引脚的基本结构。作为电解液中最关键的化学成分，电镀铜添加剂正在快速发展迭代，以满足工业界对高速沉积和细线宽、窄线距的应用需求。然而，探究电镀添加剂的分子结构与电镀铜材料性能之间复杂的构效关系仍然是一项重要挑战。本研究对比考察了一组三苯甲烷类染料分子结晶紫和甲基绿作为整平剂在高速再布线层电镀中的应用效果和作用机制。结果表明，甲基绿相比结晶紫分子在仅增加一个季铵化的端基的条件下，即可显著增强分子的电化学极化并实现镀层形貌平整。结合量子化学计算、电化学原位光谱及微观结构分析表征，我们发现甲基绿具有更强的静电吸附、更高的表面覆盖以及明显的多添加剂协同，从而实现对电镀铜线路形貌的精确调平。本研究阐明了三苯甲烷衍生物整平剂体系的吸附机制及筛选依据，并提出了适用于高速电镀铜应用的添加剂备选结构。

关键词: 再布线层, 电镀整平剂, 理论计算, 电化学原位红外光谱, 微观结构表征

Abstract:

Redistribution Layer (RDL), composed of layered dielectrics and electroplated copper materials, is a basic structure to rearrange numerous I/O pads on the chip surface in wafer-level advanced packaging. As the key chemicals in electrolyte baths, electroplating additives have undergone continuous development to meet the industrial needs for high-speed and fine-line/fine-pitch applications. Meanwhile, the intricate relationships between additive chemical structures and electroplated copper properties are yet to be well understood. In this work, a pair of triphenylmethane-based dye molecules, i.e., gentian violet (GV) and methyl green (MG), was comparatively investigated as levelers for high-speed RDL copper electroplating. Compared to GV, significantly stronger electrochemical polarization and tunable deposit morphology can be achieved by MG with just one extra quaternized amine terminal. Combining quantum chemical computations, in situ spectroelectrochemical analyses, and microstructural characterization, it is found that MG possesses enhanced electrostatic adsorption, surface coverage and multi-additive synergies, enabling tailored copper trace morphology. This study elaborates the adsorption mechanism and screening criteria of triphenylmethane-derived levelers, and presents a candidate additive structure for high-speed copper electroplating.

Key words: Redistribution layer, Copper electroplating leveler, Theoretical computation, In situ spectroelectrochemical analysis, Microstructural characterization

宋子豪, 王伟斌, 柳晓辉, 韩晓敏, 周毅, 黄蕊, 姜艳霞, 李哲, 刘晓伟, 肖梅玲, 廖洪钢, 徐维林, 孙蓉. 三苯甲烷类染料整平剂用于再布线层高速电镀铜的形貌调控机制研究[J]. 电化学（中英文）, 2026, 32(2): 2509091.

Zi-Hao Song, Wei-Bin Wang, Xiao-Hui Liu, Xiao-Min Han, Yi Zhou, Rui Huang, Yan-Xia Jiang, Zhe Li, Xiao-Wei Liu, Mei-Ling Xiao, Hong-Gang Liao, Wei-Lin Xu, Rong Sun. Triphenylmethane-Derived Levelers for High-Speed Redistribution Layer Copper Electroplating of Tailored Surface Morphologies[J]. Journal of Electrochemistry, 2026, 32(2): 2509091.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.61558/2993-074X.3591

https://electrochem.xmu.edu.cn/CN/Y2026/V32/I2/2509091

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参考文献 40

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Leveler	No.	Concentration (mg·L^-1)	Current Density (ASD)	Electroplated Copper (Line width 20 μm)
Leveler	No.	Concentration (mg·L^-1)	Current Density (ASD)	TIR%	Sa (μm)
GV	a1	2	2	15.4	0.10
	a2	6	2	19.9	0,16
	a3	10	2	-10.8	0.16
	b1	2	5	15.0	0.23
	b2	6	5	4.5	0.40
	b3	10	5	9.0	0.10
MG	c1	2	2	3.6	0.12
	c2	6	2	3.6	0.12
	c3	10	2	-1.9	0.09
	d1	2	5	2.0	0.08
	d2	6	5	-1.6	0.14
	d3	10	5	-1.9	0.08

Leveler	E_ad (kcal·mol^-1)
Leveler	0 ps	400 ps	500 ps
GV	-23.16	-106.21	-98.23
MG	-39.28	-102.62	-109.35

三苯甲烷类染料整平剂用于再布线层高速电镀铜的形貌调控机制研究

Triphenylmethane-Derived Levelers for High-Speed Redistribution Layer Copper Electroplating of Tailored Surface Morphologies

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