WANG Yu,LIU Liyun,DU Rongbin*,et al.Effects of Additives MPS， DDAC and Cl- on the Copper Foil[J].Plating & Finishing,2021,(5):1-9.[doi:10.3969/j.issn.1001-3849.2021.05.001]
添加剂MPS、DDAC、Cl-对铜箔电沉积的影响
- Title:
- Effects of Additives MPS， DDAC and Cl- on the Copper Foil
- Keywords:
- electrodeposition polarization nucleation density preferential orientation microscopic morphology
- 文献标志码:
- A
- 摘要:
- 本文针对添加剂对铜电沉积机理的影响进行了研究，并采用控制变量法研究了MPS、DDAC、Cl-对铜箔电沉积的影响，以探索MPS与DDAC对铜箔晶体择优和微观形貌的协同影响作用。结果表明，在基础镀铜液确定的条件下，MPS单独存在可以增大阴极极化和成核数密度，减小Cu2+扩散系数；DDAC可以增大阴极极化，其浓度与Cu2+扩散系数呈负相关，与成核数密度呈正相关；Cl-本身对阴极极化作用并不明显，但会改变铜电结晶过程的成核方式。MPS、DDAC和Cl-协同作用时，随着MPS浓度增加，扩散系数和成核数密度最终趋于一定值，MPS浓度达到10 mg/L后只有（220）晶面择优，此时镀层平整性最优。
- Abstract:
- In this paper, the effect of additives on copper electrodeposition mechanism was studied, and the influence of MPS, DDAC, Cl- on copper foil electrodeposition was studied by using the control variable method, so as to explore the synergistic effect of MPS and DDAC on the crystal preference and micro morphology of copper foil. The results show that under the condition that the basic copper plating bath is determined, the presence of MPS alone can increase the cathodic polarization and nucleation number density, and reduce the diffusion coefficient of Cu2+ DDAC can increase the cathodic polarization, and its concentration has a negative correlation with the diffusion coefficient of Cu2+ and a positive correlation with the nucleation number density Cl- itself has no obvious effect on the cathodic polarization, but will change the nucleation mode of copper during the process of electrocrystallization. When MPS, DDAC and Cl- work together, as the MPS concentration increases, the diffusion coefficient and nucleation number density eventually tend to a certain value. When the MPS concentration reaches 10 mg/L, only （220） crystal face is preferred, and the coating has the best flatness.
参考文献/References:
[1] 袁孚胜. 中国电解铜箔市场现状及发展趋势[J]. 有色冶金设计与研究, 2019, 40(5): 19-22.
Yuan F S. Status and development trend of Chinas electrolytic copper foil market[J]. Design and Research of Nonferrous Metallurgy, 2019, 40 (5): 19-22 (in Chinese).
[2] Yen M H, Liu J H, Song J M, et al. Electrochemical corrosion properties of commercial ultra-thin copper foils[J]. Journal of Electronic Materials, 2017, 46(8): 5150-5157.
[3] Lawler J, Koratkar N, Garofalo J, et al. Analysis of deposition methods for lithium-ion battery anodes using reduced graphene oxide slurries on copper foil[J]. Journal of manufacturing science and engineering: Transactions of the ASME, 2018, 140(9): 1-9.
[4] Seakr R. Microstructure and crystallographic characteristics of nanocrystalline copper prepared from acetate solutions by electrodeposition technique[J]. Transactions of Nonferrous Metals Society of China, 2017, 27: 1423-1430.
[5] Popvo K I, Djokic S S, Nikolic N D, et al. Morphology of electrochemically and chemically deposited metals[M]. New York: Springer, 2016.
[6] Sekar R. Synergistic effect of additives on electrodeposition of copper from cyanide-free electrolytes and its structural and morphological characteristics[J]. Transactions of Nonferrous Metals Society of China, 2017, 27: 1665-1676.
[7] Yuan L, Ding Z Y, Liu S J, et al. Effects of additives on zinc electrodeposition from alkaline zincate solution[J]. Transactions of Nonferrous Metals Society of China, 2017, 27: 1656-1664.
[8] Chang T R, Jin Y, Wen L, et al. Synergistic effects of gelatin and convection on copper foil electrodeposition[J]. Electrochimica Acta, 2016, 211: 245-254.
[9] Tomoyuki F, Keiichiro T, Yasuhiro N, et al. Influence of thickness on tensile property of copper foil[J]. Key Engineering Materials, 2018, 4700(1548): 19-24.
[10] Sunghee Y, Morton S, Cefet al. Rotating ring-disk electrode studies of copper electrodeposition effect of chloride ion and organic additives[J]. Plating and Surface Finishing, 1994, 81(12): 65.
[11] 安茂忠. 电镀理论与技术[M]. 哈尔滨: 哈尔滨工业大学出版社, 2004.
[12] Kim J J, Kim S K, Yong S K. Catalytic behavior of 3-mercapto-1-propane sulfonic acid on cu electrodeposition and its effect on cu film properties for CMOS device metallization[J]. Journal of Electroanalytical Chemistry, 2003, 542(1): 61-66.
[13] Gu M, Zhong Q. Influence of MPS concentration on copper electrocrystallisation from acidic sulphate electrolyte with MPS additive systems[J]. Transactions of the Institute of Metal Finishing, 2014, 89(4): 187-193.
[14] Gu M, Zhong Q. Effect of 3-mercapto-1-propane sulfonate sodium salt composite additive on electrodeposition of copper[J]. Material Protection, 2011, 44(4): 11-14.
[15] Chiu Y D, Dow W P, Krug K, et al. Adsorption and desorption of Bis-(3-sulfopropyl) disulfide during Cu electrodeposition and stripping at Au electrodes[J]. Langmuir, 2012, 28(40): 14476-14487.
[16] 三井金属矿业株式会社. 电解铜箔的制造方法、该制造方法得到的电解铜箔、使用该电解铜箔得到的表面处理铜箔以及使用该电解铜箔或该表面处理铜箔得到的覆铜层压板[P]. 中国, CN101297067 A, 2008-10-29.
[17] Pasquale M A, Gassa L M, Arvia A J. Copper electrodeposition from an acidic plating bath containing accelerating and inhibiting organic additives[J]. Electrochim Acta, 2008, 53: 5891-5904.
[18] Tan M, Guymon C G, Wheeler D R. The Role of SPS, MPSA and chloride in additive systems for copper electrodeposition[J]. Journal of The Electrochemical Society, 2007, 154: 78-81.
[19] Wang C, Zhou G Y, Wang S X, et al. A comparison of typical additives for copper electroplating based on theoretical computation[J]. Computational Materials Science, 2018, 147: 95-102.
[20] Vereecken P M, Binstesd R A, Deligianni H, et al. The chemistry of additives in damascene copper plating[J]. IBM Journal of Research and Development, 2005, 49(1): 3-18.
[21] Scharifker B, Hills G. Theoretical and experimental studies of multiple nucleation[J]. Electrochimica Acta, 1983, 28(7): 879-889.
[22] Ren P, Dai N, Deng H Y, et al. Growth kinetics and microstructures of Cu nanofilms on Mo substrate by electrodeposition[J]. Journal of The Electrochemical Society, 2015, 162(1): 9-14.
[23] Fabricus G, Kontturi K, Sundholm G. Influence of thiourea on the nucleation of copper from acid sulphate solutions[J]. Electrochimica Acta, 1994, 39: 2353-2357.
[24] Zhao Y, Deng F X, Hu L F, et al. Electrochemical deposition of copper on single-crystal gallium nitride (0001) electrode: Nucleation and growth mechanism[J]. Electrochimica Acta, 2014, 130: 537-542.
[25] 钟琴. 添加剂MPS、PEG、Cl-对铜电沉积的影响研究[D]. 重庆大学, 2010.
[26] 周绍民. 金属电沉积原理与研究方法[M]. 上海: 上海科技出版社, 1987: 254.
相似文献/References:
[1]张冰怡,张莎莎*,姚正军,等.电沉积Ni-W纳米晶镀层制备与显微硬度研究[J].电镀与精饰,2019,(8):20.[doi:10.3969/j.issn.1001-3849.2019.08.005]
ZHANG Bingyi,ZHANG Shasha*,YAO Zhengjun,et al.Preparation and Microhardness of Electrodeposited Ni-W Nanocrystalline Coatings[J].Plating & Finishing,2019,(5):20.[doi:10.3969/j.issn.1001-3849.2019.08.005]
[2]雷同鑫,鞠 辉,张长科,等.电镀Ni-W-P合金在钻杆接头上的应用[J].电镀与精饰,2019,(10):38.[doi:10.3969/j.issn.1001-3849.2019.10.009]
LEI Tongxin,JU Hui,ZHANG Changke,et al.Application of Ni-W-P Alloy Prepared by Electroplating to Tool Joints[J].Plating & Finishing,2019,(5):38.[doi:10.3969/j.issn.1001-3849.2019.10.009]
[3]李晓峰*,孟 芳,董会超,等.电沉积法制备掺铋金属锌及其性能表征[J].电镀与精饰,2020,(1):12.[doi:10.3969/j.issn.1001-3849.2020.01.003]
LI Xiaofeng*,MENG Fang,DONG Huichao,et al.Electrodeposited Preparation of Bi-Doped Metal Zinc and Its Performance Characterization[J].Plating & Finishing,2020,(5):12.[doi:10.3969/j.issn.1001-3849.2020.01.003]
[4]张永霞,王 玫,方 华*,等.Co3O4/碳纳米管复合膜的超级电容器性能[J].电镀与精饰,2020,(2):1.[doi:10.3969/j.issn.1001-3849.2020.02.001]
ZHANG Yongxia,WANG Mei,FANG Hua*,et al.Co3O4/Carbon Nanotube Composite Film for Supercapacitor and Its Performances[J].Plating & Finishing,2020,(5):1.[doi:10.3969/j.issn.1001-3849.2020.02.001]
[5]侯珂珂,陈新华,张万强,等.电沉积法制备仿生超疏水滤网及其油水分离性能[J].电镀与精饰,2020,(4):1.[doi:10.3969/j.issn.1001-3849.2020.04.0010]
HOU Keke,CHEN Xinhua,ZHANG Wanqiang,et al.Preparation of Biomimetic Superhydrophobic Filter Screen by Electrodeposition and the Oil-Water Separation Performance[J].Plating & Finishing,2020,(5):1.[doi:10.3969/j.issn.1001-3849.2020.04.0010]
[6]肖成龙,梁世雍,于兆勤*.可控阵列微柱超疏水表面实验研究[J].电镀与精饰,2020,(7):27.[doi:10.3969/j.issn.1001-3849.2020.07.0060]
XIAO Chenglong,LIANG Shiyong,YU Zhaoqin*.Experimental Study on Superhydrophobic Surface of Controllable Array Microcolumns[J].Plating & Finishing,2020,(5):27.[doi:10.3969/j.issn.1001-3849.2020.07.0060]
[7]徐 超,王淼宇,周建波,等.电沉积Ni-Mo-Fe-La合金析氢电极的工艺研究[J].电镀与精饰,2020,(8):7.[doi:10.3969/j.issn.1001-3849.2020.08.0020]
XU Chao,WANG Miaoyu,ZHOU Jianbo,et al.Study on Electrodeposition Process of Ni-Mo-Fe-La Alloy Hydrogen Evolution Electrode[J].Plating & Finishing,2020,(5):7.[doi:10.3969/j.issn.1001-3849.2020.08.0020]
[8]高 辉,刘伟杰*.2A12铝合金电沉积Ni-Co-MoS2复合镀层的耐磨性能研究[J].电镀与精饰,2020,(10):1.[doi:10.3969/j.issn.1001-3849.2020.10.0010]
GAO Hui,LIU Weijie*.Research on Wear Resistance of Ni-Co-MoS2 Composite Coating Electrodeposited on 2A12 Aluminium Alloy[J].Plating & Finishing,2020,(5):1.[doi:10.3969/j.issn.1001-3849.2020.10.0010]
[9]杨惠良*.硫酸盐镀液中紫铜电沉积Ni-Co/WC复合镀层的工艺条件优化[J].电镀与精饰,2021,(6):30.[doi:10.3969/j.issn.1001-3849.2021.06.007]
YANG Huiliang*.Optimization of Process Conditions for Electrodeposition of Ni-Co/WC Composite Coatings on Red Copper from Sulfate Bath[J].Plating & Finishing,2021,(5):30.[doi:10.3969/j.issn.1001-3849.2021.06.007]
[10]孟香茗,宋振兴*,卜路霞,等.电沉积法制备纳米线阵列的研究进展[J].电镀与精饰,2021,(6):35.[doi:10.3969/j.issn.1001-3849.2021.06.008]
MENG Xiangming,SONG Zhenxing*,BU Luxia,et al.Research Progress of Producing Nanowire Arrays by Electrodeposition[J].Plating & Finishing,2021,(5):35.[doi:10.3969/j.issn.1001-3849.2021.06.008]
备注/Memo
收稿日期： 2020-07-27；修回日期： 2020-09-05
作者简介： 王羽，男，硕士研究生，Email：117110480@qq.com
通信作者： 杜荣斌，Email：durb@aqnu.edu.cn
基金项目： 安徽省科技重大专项(18030901069)，安徽省高校学科（专业）拔尖人才学术资助项目(gxbjZD202075)