Zhang Jinyuan,Zhang Jie,Bai Zhongbo,et al.Effect of titanium sulfate and sodium tungstate composite additive on morphology and performance of electrolytic copper foil posttreatment?/html>[J].Plating & Finishing,2024,(5):101-109.[doi:10.3969/j.issn.1001-3849.2024.05.014]
硫酸钛-钨酸钠复合添加剂对电解铜箔后处理形貌及抗剥离强度的影响
- Title:
- Effect of titanium sulfate and sodium tungstate composite additive on morphology and performance of electrolytic copper foil posttreatment?/html>
- Keywords:
- electrolytic copper foil ; post-treatment ; additives ; micro-morphology ; anti-stripping properties ; electrochemical properties
- 分类号:
- TG147
- 文献标志码:
- A
- 摘要:
- 随着电子信息技术的高速发展，高端且精细的电子产品日益增多，对印制电路板（ PCB ）用电路板铜箔提出了更高的要求，要求铜箔兼有低粗糙度和高抗剥离强度。针对此问题，采用调控电解铜箔后处理添加剂含量的方法，研究了后处理添加剂对铜箔抗剥离强度的影响。采用预处理过的毛箔，在自制的方形电解槽中通直流电，用配制的不同粗化电解液进行微粗化试验。结果表明：硫酸钛浓度增高，铜箔表面瘤点状颗粒的成核趋势会增大。当浓度为 0.7 g/L 时，抑制晶粒成核，表面粗糙度先降低后升高。 0.3 g/L 的硫酸钛可以更好的促进成核，抑制晶粒生长，提高抗剥离强度。加入 0.05 g/L 钨酸钠和 0.3 g/L 硫酸钛时，深镀能力最优，其抗剥离性能最高可达到 0.7 N/mm 。与单纯的钨酸钠体系相比，铜箔的抗剥离强度提高了约 30.7% ，粗糙度提高了约 1.9% 。钨酸钠和硫酸钛复合会起到一定的深镀能力，随着钨酸钠的加入，铜箔的抗剥落强度提升，粗糙度呈现下降趋势。
- Abstract:
- ： With the rapid development of electronic information technology ， premium and fine electronic products are increasing ， which puts higher requirements on copper foil for printed circuit boards （ PCBs ）， requiring both low roughness and high peel strength. To address this issue ， a method involving the post-treatment of electrolytic copper foil with controlled additions of additives was used to study the impact of post-treatment additives on the peel strength of copper foils. In the study ， pretreated rough copper foil was used ， and a DC current was applied in a custom-made square electrolytic cell for micro- roughening tests using various roughening electrolytes. The results indicate that as the concentration of titanium sulfate increases ， the nucleation tendency of nodular particles on the copper foil surface increases. When the concentration is 0.7 g/L ， it inhibits grain nucleation ， causing surface roughness to initially decrease and then increase. An optimal concentration for promoting nucleation and inhibiting grain growth is found at 0.3 g/L of titanium sulfate. When 0.05 g/L of sodium tungstate and 0.3 g/L of titanium sulfate are added ， the deep plating capability is optimized ， and the peel strength of copper foil reaches a maximum of 0.7 N/mm. This represents a 30.7% improvement in peel strength compared to the sodium tungstate system alone ， and roughness increases by approximately 1.9%. In conclusion ， the combination of sodium tungstate and titanium sulfate does enhance the deep plating capability. The addition of sodium tungstate in the post-treatment process improves the peel strength of copper foils ， while roughness exhibits a decreasing trend.
参考文献/References:
[1] Wang X Y, Liu X F, Shi L X, et al. Characteristic and formation mechanism of matt surface of double-rolled copper foil[J]. Journal of Materials Processing Technology, 2015, 216: 463-471.
[2] Tae G W, lsong P, Kyeongwon S. Effect of additives on the elongation and surface properties of copper foils[J]. Electronic Materials Letters, 2013, 9(3): 341-345.
[3] 丁杰 . 高电流密度下电解铜箔添加剂的研究 [D]. 江西 : 南昌大学物理与材料学院 , 2022.
[4] 文雯 . 高频超薄载体铜箔制作及应用研究 [D]. 四川 : 电子科技大学材料与能源学院 , 2022.
[5] Yin X Q, Peng L J, Saif K, et al. Mechanical properties and microstructure of rolled and electrodeposited thin copper foil[J]. Rare Metals, 2016, 35(12): 909-914.
[6] 周文木 , 胡智宏 . 电解铜箔在印制电路板端的评估方法研究 [J]. 印制电路信息 , 2021, 29(12): 6-12.
[7] 刘耀 . 极薄载体铜箔制备及高抗剥离表面处理技术研究 [D]. 江西 : 江西理工大学稀土学院 , 2021.
[8] Dong Z C, Fei X Y, Gong B K, et al. Effects of deep cryogenic treatment on the microstructure and properties of rolled Cu foil[J]. Materials, 2021, 14(19): 5498.
[9] Zhao W C, Feng R, Wang X W, et al. Relationship between microstructure and etching performance of 12 mm thick rolled copper foil[J]. Journal of Materials Research and Technology, 2022(21): 1666-1681.
[10] Yu W Y, Lin C Y, Li Q Y, et al. A novel strategy to electrodeposit high-quality copper foils using composite additive and pulse superimposed on direct current[J]. Journal of Applied Electrochemistry, 2021, 51(3): 489-501.
[11] Cao Q D, Liang F, Lv J M, et al. Effects of pulse reverse electroforming parameters on the thickness uniformity of electroformed copper foil[J]. Transactions of the Institute of Metal Finishing, 2018, 96(2): 108-112.
[12] Zhao K, Wang Y W, Peng J P, et al. Electrochemical preparation of titanium and titanium-copper alloys with K 2 Ti 6 O 13 in KF-KCl melts[J]. Rare Metals, 2017, 36(6): 527-532.
[13] Liang X Y, Ren X F, He R, et al. Theoretical and experimental study of the influence of PEG and PEI on copper electrodeposition[J]. New Journal of Chemistry, 2021, 45(42): 19655-19659.
[14] 马秀玲 , 李永贞 , 姚恩东 , 等 . 不同厚度电解铜箔的组织与性能研究 [J]. 稀有金属材料与工程 , 2019, 48(9): 2905-2909.
[15] Cheng H Y, Tran D P, Tu K N, et al. Effect of deposition temperature on mechanical properties of nanotwinned Cu fabricated by rotary electroplating[J]. Materials Science and Engineering, 2021, 811: 141065.
[16] Getrouw M, Dutra A. The influence of some parameters on the surface roughness of thin coper foils using statistical analysis[J]. Journal of Applied Electrochemistry, 2001, 31(12): 1359-1366.
[17] Hiroaki K, Kazuo K, Yasuyuki O. Effect of titanium cathode surface condition on initial copper deposition during electrolytic fabrication of copper foil[J]. Journal of Chemical Engineering of Japan, 2010, 43(7): 612-617.
[18] Wang S P, Wei K X, Wei W, et al. Enhancing surface roughness and tensile strength of electrodeposited copper foils by composite additives[J]. Physica Status Solidi A-Applications and Materials Science, 2021, 219(5): 2100735.
[19] 宋言 , 朱若林 , 林毅 , 等 . N- 烯丙基硫脲在电解铜箔制备中的应用 [J]. 电镀与涂饰 , 2022, 41(3): 197-202.
[20] 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.
[21] 孙玥 , 刘玲玲 , 李鑫泉 , 等 . 添加剂对电解铜箔作用机理及作用效果的研究进展 [J]. 化工进展 , 2021, 40(11): 5861-5874.
[22] Tae G T, Ilsong P, Kyeongwon S. The effect of additives and current density on mechanical properties of cathode metal for secondary battery[J]. Electronic Materials Letters, 2013, 9(4): 535-539.
[23] Byoungyong I, Sunjung K, Soo-Hyun K. Influence of additives upon Cu thin film growth on atomic-layer-deposited Ru layer and trench-filling by direct electrodeposition[J]. Thin Solid Films, 2017(636): 251-256.
[24] James B M, Chukwudi A O, Obeng Y S, et al. The impact of organic additives on copper trench microstructure[J]. Journal of the Electrochemical Society, 2017, 164(9): 543-550.
[25] 樊小伟 . 超薄电解铜箔组织结构与力学性能调控及其表面处理技术研究 [D]. 江西 : 江西理工大学稀土学院 , 2021.
[26] 胡旭日 , 王海振 , 徐好强 , 等 . 无添加剂体系中电解铜箔的多步粗化 [J]. 电镀与涂饰 , 2015, 34(1): 20-24.
[27] 孙玉梅 . 退火工艺和粗化处理对压延银铜箔组织及性能的影响 [D]. 山东 : 山东理工大学材料科学与工程学院 , 2021.
[28] Im B, Kim S. Influence of additives on Cu thin films electrodeposited directly on Ti diffusion barrier in Cl - -free electrolytes for Cu interconnect[J]. Microelectronic Engineering, 2017(172): 8-12.
[29] Ryan R, Jha H, Dirk R, et al. Suppression of copper electrodeposition by PEG in methanesulfonic acid electrolytes[J]. Journal of the Electrochemical Society, 2019, 166(13): 551-558.
[30] 李如珍 , 张敏华 , 余英哲 . Cu 催化剂上酸碱中心的密度泛函理论研究 [J]. 计算机与应用化学 , 2012, 29(9): 1131-1134.
[31] Pavithra C L P, Sarada B V, Rajulapati K V, et al. Controllable crystallographic texture in copper foils exhibiting enhanced mechanical and electrical properties by pulse reverse electrodeposition[J]. Crystal Growth and Design, 2015, 15(9): 4448- 4458.
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备注/Memo
收稿日期： 2023-09-21 修回日期： 2024-01-05 作者简介： 张锦园（ 1999 — ），女，硕士， email ： 654781195@qq.com * 通信作者： 刘二勇， email ： liueryong@xust.edu.cn