Kinetics of electrocrystallization of copper from an acid sulfate solution in the presence of N-methylpolyvinylpyridinemethylsulfate
Abstract
Purpose: In this work, kinetic patterns are established and the main parameters of heterogeneous nucleation and growth of a new phase during electrocrystallization of copper during cathodic deposition from an acid sulfate solution in the presence of N-methyl polyvinylpyridine-methyl sulfate of various molar masses are estimated. The polymer under study is quaternized polyvinylpyridine derivatives and is a promising organic additive for use in the technology of electrochemical void-free filling of through holes (through
silicon vias) of silicon wafers used in microelectronics in the manufacture of microcircuits.
Experimental: Using scanning electron microscopy, it was found that the use of N-methyl polyvinylpyridine-methyl sulfate additive leads to a noticeable decrease in the size of crystallites and blurring of grain boundaries, however, it can contribute to the localized formation of globular formations (if the molecular weight of the polymer is relatively small) or the formation of a layered structure (in the case of high-molecular derivatives). The introduction of a quaternized polymer into a copper plating solution significantly inhibits the electrodeposition process, which includes the stages of irreversible charge transfer and diffusion-controlled electrocrystallization.
Conclusions: It has been found that the activation process of heterogeneous nucleation sites in the presence of a polymer additive is instantaneous regardless of the molar mass. At the same time, as it increases, the density of active nucleation centers decreases significantly
Downloads
References
Wang F., Zeng P., Wang Y., Ren X., Xiao H., Zhu, W. High-speed and high-quality TSV filling with the direct ultrasonic agitation for copper electrodeposition. Microelectronic Engineering. 2017;180: 30–34. https://doi.org/10.1016/j.mee.2017.05.052
Beica R., Siblerud P., Erickson D. Advanced TSV copper electrodeposition for 3D interconnect applications. IMAPSource Proceedings 2010(DPC): 774–802. https://doi.org/10.4071/2010DPC-tp13
Chen X., Chen Z., Xiao L., … Zhang Z. Fabrication and electrical characterization of high aspect ratio through-ilicon vias with polyimide liner for 3D integration. Micromachines. 2022;13(7): 1147. https://doi.org/10.3390/mi13071147
Shen W.-W., Chen K.-N. Three-dimensional integrated circuit (3D IC) key technology: through-silicon via (TSV). Nanoscale Research Letters. 2017;12(1): 56. https://doi.org/10.1186/s11671-017-1831-4
Kondo K., Matsumoto T., Watanabe K. Role of additives for copper damascene electrodeposition: experimental study on inhibition and acceleration effects. Journal of The Electrochemical Society. 2004;151: C250. http://dx.doi.org/10.1149/1.1649235
Xiao H., He H., Ren X., Zeng P., Wang F. Numerical modeling and experimental verification of copper electrodeposition for through silicon via (TSV) with additives. Microelectronic Engineering. 2016;170: 54–58. https://doi.org/10.1016/j.mee.2016.12.030
Tsai T.-H., Huang J.-H. Electrochemical investigations for copper electrodeposition of through-silicon via. Microelectronic Engineering. 2011;88: 195–199. https://doi.org/10.1016/j.mee.2010.10.018
Jin Y., Sun M., Mu D., Ren X., Wang Q., Wen L. Investigation of PEG adsorption on copper in Cu2+-free solution by SERS and AFM. Electrochimica Acta. 2012;78: 459–465. https://doi.org/10.1016/j.electacta.2012.06.039
Kelly J., West A. Copper deposition in the presence of polyethylene glycol I. Quartz crystal microbalance study. Journal of The Electrochemical Society. 1998;145: 3472–3476. https://doi.org/10.1149/1.1838829
Dow W.-P., Chiu Y.-D., Yen M.-Y. Microvia filling by Cu electroplating over a Au seed layer modified by a disulfide. Journal of The Electrochemical Society. 2009;156: D155. https://doi.org/10.1149/1.3078407
Sun Q., Cao H., Ling H., Li M. Analysis of accelerator consumption in TSV copper electroplating. Proceedings - 2013 14th International Conference on Electronic Packaging Technology. 2013: 818–821. https://doi.org/10.1109/ICEPT.2013.6756589
Meng Y., Zhou M., Huang W., Min Y., Shen X., Xu Q. Benzyl-containing quaternary ammonium salt as a new leveler for microvia copper electroplating. Electrochimica Acta. 2022;429: 141013. https://doi.org/10.1016/j.electacta.2022.141013
Moffat T., Wheeler D., Kim S.-K., Josell D. Curvature enhanced adsorbate coverage mechanism for bottom-up superfilling and bump control in damascene processing. Electrochimica Acta. 2007;53: 145–154. https://doi.org/10.1016/j.electacta.2007.03.025
Jung M.-W., Kim K.-T., Koo Y.-S., Lee J.-H. The effects of levelers on electrodeposition of copper in TSV filling. Journal of the Microelectronics and Packaging Society. 2012;19. https://doi.org/10.6117/kmeps.2012.19.2.055
Kelly J., Tian Chunyan, West A. Leveling and microstructural effects of additives for copper electrodeposition. Journal of The Electrochemical Society. 1999;146: 2540-2545. https://doi.org/10.1149/1.1391968
Wang C., Zhang J., Yang P., An M. Electrochemical behaviors of Janus Green B in through-hole copper electroplating: An insight by experiment and density functional theory calculation using Safranine T as a comparison. Electrochimica Acta. 2013;92: 356–364. https://doi.org/10.1016/j.electacta.2013.01.064
Li J., Xu J., Wang X., Wei X., Lv J., Wang L. Novel 2,5-bis(6-(trimethylamonium)hexyl)-3,6-diaryl-1,4-iketopyrrolo[3,4-c] pyrrole pigments as levelers for efficient electroplating applications. Dyes and Pigments, 2020;186: 109064. https://doi.org/10.1016/j.dyepig.2020.109064
Yaqiang L., Ren P., Zhang Yu., … An M. Investigation of novel leveler Rhodamine B on copper superconformal electrodeposition of microvias by theoretical and experimental studies. Applied Surface Science. 2022;615: 156266. https://doi.org/10.1016/j.apsusc.2022.156266
Willey M. J., West A. C. SPS adsorption and desorptionduring copper electrodeposition and its impact on PEG adsorption. Journal of The Electrochemical Society. 2007;154(3): D156–D162. https://doi.org/10.1149/1.2431320
Zhou J., Reid J. D. Impact of leveler molecular weight and concentration on Damascene copper electroplating. ECS Transactions. 2007;2(6): 77–92. https://doi.org/10.1149/1.2408866
Jin S. H., Yoon Y., Jo Y., … Lee M. H.. The effects of polyvinylpyrrolidone molecular weight on defect-free filling of through-glass vias (TGVs). Journal of Industrial and Engineering Chemistry. 2021;96: 376–381. https://doi.org/10.1016/j.jiec.2021.01.046
Hatch J. J., Willey M. J., Gewirth A. A. Influence of aromatic functionality on quaternary ammonium levelers for Cu plating. Journal of The Electrochemical Society. 2011;158(6): D323–D329. https://doi.org/10.1149/1.3575636
Yuan B., Chen X., Zhao Y., Zhou W., Li X., Wang L. Unveiling the potential and mechanisms of 3,3’-bicarbazole-based quaternary ammonium salts as levelers. Electrochimica Acta. 2023;471: 143345. https://doi.org/10.1016/j.electacta.2023.143345
Li X., Yin X., Li J., … Wang L. Synthesis of coplanar quaternary ammonium salts with excellent electrochemical properties based on an anthraquinone skeleton and their application in copper plating. Electrochimica Acta. 2022;437: 141541. https://doi.org/10.1016/j.electacta.2022.141541
Jo Y. E., Yu D. Y., Cho S. K. Revealing the inhibition effect of quaternary ammonium cations on Cu electrodeposition. Journal of Applied Electrochemistry. 2020;50: 245–253. https://doi.org/10.1007/s10800-019-01381-4
Zou P., Li X., Chen X., Zhou W., Du K., Wang L. Synthesis and mechanism of quaternary ammonium salts based on porphyrin as high-performance copper levelers. Tetrahedron. 2024;159: 134011. https://doi.org/10.1016/j.tet.2024.134011
Garfias Garcia E., Romero-Romo M., María T., Ramírez-Silva, Palomar-Pardavé M. Overpotential nucleation and growth of copper onto polycrystalline and single crystal gold electrodes. International Journal of Electrochemical Science. 2012;7(4): 3102–3114. https://doi.org/10.1016/S1452-3981(23)13938-1
Sainsbury F. Stirling engine arrangement. Pat. US 3 682 939 A. Опубл. 08.08.1972.
Lyapkov A. V. Physicochemical methods for studying polymers: textbook* [Electronic resource] 2022. 152 p. Available at: https://www.researchgate.net/profile/Alex-Lyapkov/publication/360862354Fiziko-himiceskiemetodyis sledovaniapolimerov/links/628f641055273755ebb77b52/Fiziko-himiceskie-metody-issledovania-polimerov.pdf
Zhang Q., Yu X., Hua Y., Xue W. The effect of quaternary ammonium-based ionic liquids on copper electrodeposition from acidic sulfate electrolyte. Journal of Applied Electrochemistry. 2015;45: 79–86. https://doi.org/10.1007/s10800-014-0774-z
Scharifker B., Hills G. Theoretical and experimental studies of multiple nucleation. Electrochimica Acta. 1983;28(7): 879-889. https://doi.org/10.1016/0013-4686(83)85163-9
Wang F., Tian Y., Zhou K., … Yao W. Using a triblock copolymer as a single additive in high aspect ratio through silicon via (TSV) copper filling. Microelectronic Engineering. 2021;244-246: 111554. https://doi.org/10.1016/j.mee.2021.111554
Copyright (c) 2025 Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases
This work is licensed under a Creative Commons Attribution 4.0 International License.
