Effect of PEG and its compound additives on post-treatment of electrolytic copper foils

doi:10.16085/j.issn.1000-6613.2023-0999

Abstract

Abstract:

In order to improve the peel strength of electrolytic copper foil after roughening treatment, the additive PEG and the composite additive of PEG and sodium tungstate were selected to electroplate the 12μm electrolytic copper foil. SEM, roughness detection, electrochemical analysis, XRD analysis, anti-peeling strength and conductivity test were used to analyze the effect of additives on the surface morphology and properties of copper foil and the mechanism of additives. With the addition of PEG to the basic plating solution, the surface morphology of the post-treated copper foil gradually changed from coarse dendrites to short granular grains, and the roughness of the post-treated copper foil showed an upward trend. When the concentration of PEG was 0.09g/L, compared with the plating liquid system without additives, the anti-peeling strength of the post-treatment copper foil was increased by 103%, and the roughness was increased. The addition of PEG played a dual role in promoting copper nucleation and inhibiting deposition. After the composite additive of PEG and sodium tungstate was added to the basic plating solution, the peel strength of the copper foil was about 21.35% higher than that of the single PEG system and the roughness was reduced by about 20.34% when the PEG concentration was 0.005g/L. Because the composite additive inhibited the deposition and nucleation of copper ions and promoted the deposition of (200) crystal plane, the grain deposition on the surface of copper foil was uniform, but the grain was coarse. The addition of PEG alone can greatly improve the peel strength of copper foil with improvement of the roughness. The composite additive of PEG and sodium tungstate further improved the peel strength and decreased the roughness decreases, and thus the deep plating ability was greatly improved.

Key words: electrolysis, copper foil, surface deposition, electrochemistry, peel resistance, roughness, nucleation

摘要：

为提高电解铜箔在粗化处理后的抗剥离强度。选择添加剂聚乙二醇-8000（PEG-8000）及PEG和钨酸钠的复合添加剂对12μm电解铜箔进行电镀处理，采用扫描电子显微镜（SEM）、粗糙度检测、电化学分析、X射线衍射分析（XRD）、抗剥离强度及导电性测试来分析添加剂对铜箔表面形貌、性能及添加剂的作用机理分析。随着PEG加入基础镀液，后处理铜箔表面形貌从粗大的树枝晶逐渐转变为短小的粒状晶粒，后处理铜箔粗糙度呈上升趋势。当PEG浓度为0.09g/L时，相较不含添加剂的镀液体系，后处理铜箔抗剥离强度提升达103%，粗糙度升高，PEG的加入会起到促进铜形核和抑制沉积的双重作用。PEG和钨酸钠的复合添加剂加入基础镀液后，当PEG浓度为0.005g/L时，铜箔的抗剥离强度较单一PEG体系提升约21.35%，粗糙度降低约20.34%，由于复合添加剂抑制了铜离子的沉积和形核，并促进了(200)晶面的沉积，铜箔表面晶粒沉积均匀，但晶粒粗大化。PEG单独加入可以大幅提升铜箔的抗剥离强度，且提高粗糙度，PEG和钨酸钠的复合添加剂抗剥离强度进一步提升，且粗糙度下降，深镀能力大幅提升。

关键词: 电解, 铜箔, 表面沉积, 电化学, 抗剥离, 粗糙度, 成核

CLC Number:

TG146.1

ZHANG Jie, BAI Zhongbo, FENG Baoxin, PENG Xiaolin, REN Weiwei, ZHANG Jingli, LIU Eryong. Effect of PEG and its compound additives on post-treatment of electrolytic copper foils[J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 374-381.

张杰, 白忠波, 冯宝鑫, 彭肖林, 任伟伟, 张菁丽, 刘二勇. PEG及其复合添加剂对电解铜箔后处理的影响[J]. 化工进展, 2023, 42(S1): 374-381.

Figures/Tables 15

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试剂名称	纯度
生箔	12μm
CuSO₄·5H₂O	AR
H₂SO₄	AR
CH₃CH₂OH	AR
Na₂WO₄	纯度≥99.5%
PEG-8000	纯度≥98%
H₂O	去离子水

试剂名称	纯度
生箔	12μm
CuSO₄·5H₂O	AR
H₂SO₄	AR
CH₃CH₂OH	AR
Na₂WO₄	纯度≥99.5%
PEG-8000	纯度≥98%
H₂O	去离子水

PEG/g·L^-1	TC₍₁₁₁₎	TC₍₂₀₀₎	TC₍₂₂₀₎
0	30.212	10.895	58.893
0.05	30.628	10.130	59.242
0.07	31.128	9.805	59.067
0.09	32.469	9.959	57.571
0.11	31.149	9.753	58.754

PEG/g·L^-1	TC₍₁₁₁₎	TC₍₂₀₀₎	TC₍₂₂₀₎
0	30.212	10.895	58.893
0.05	30.628	10.130	59.242
0.07	31.128	9.805	59.067
0.09	32.469	9.959	57.571
0.11	31.149	9.753	58.754

PEG/g·L^-1	TC₍₁₁₁₎	TC₍₂₀₀₎	TC₍₂₂₀₎
0	27.345	11.343	61.312
0.001	29.091	8.589	62.696
0.005	28.951	9.924	61.125
0.01	29.894	10.118	59.988
0.015	28.616	10.445	60.938