Kinetics of cathodic deposition of copper from an acid sulfate solution in the presence of organic disulfides
DOI:
https://doi.org/10.17308/kcmf.2026.28/13559Keywords:
Copper, Cathodic deposition, Organic disulfides, Kinetics, Voltammetry, Chronopotentiometry, Phase formationAbstract
Objectives: In this work, we established the kinetic patterns and evaluated the main parameters of heterogeneous nucleation and growth of a new phase during the electrocrystallization of copper during cathode deposition from an acid sulfate solution in the presence of organic disulfides (disodium salts of 3,3′-dithiodipropanedisulfonic acid, 4,4′-dithiodibenzene disulfonic acid and 3,3’-dithiodi(4-aminobenzene) sulfonic acids). The additives under study contain a disulfide group (-S-S-), which is characteristic of accelerators of the copper cathode deposition process in the implementation of electrochemical void-free filling of through holes (through silicon vias) of silicon wafers used in microelectronics in the manufacture of microcircuits.
Experimental: Electrodeposition of copper coatings was carried out from aqueous sulfate solutions of copper plating in galvanostatic mode. Using scanning electron microscopy, it was found that in the presence of all the studied organic disulfides, copper crystallites with clearer edges are formed in the acid sulfate electrolyte of copper plating than in solutions without additives. The presence of aromatic groups in the structure of the accelerator molecule increases the size of the crystallites of the galvanic copper deposit, and the additional introduction of terminal amino groups into the disulfide structure, on the contrary, leads to a decrease in the size of the crystallites. The latter can be explained by the bifunctional nature of 3,3′-dithiodi(4-aminobenzene)sulfonic acid, capable of exhibiting both an accelerating and leveling effect due to the presence of a disulfide group and an amino group in the structure, respectively. The kinetics of cathodic deposition of copper coatings was studied using transient electrochemical methods of voltammetry, chronopotentiometry, and chronoammetry. In the presence of the studied additives, the overvoltage of copper electrodeposition decreases, while the kinetics of the process does not change: the charge transfer stage proceeds irreversibly, the activation of nucleation sites is progressive, and the growth of a new phase is controlled by the diffusion of copper ions from the solution to the cathode surface.
Conclusions: The functionalization of aliphatic disulfide by the introduction of aromatic and amino groups does not lead to significant changes in the parameters of heterogeneous nucleation and the growth of a new phase during cathodic deposition of copper from an acid sulfate solution. However, the rate of electrocrystallization increases with the transition from aliphatic disulfide (disodium salt of3,3′-dithiodipropanedisulfonic acid) to disodium salt of 3,3’-dithiodi(4-aminobenzene)sulfonic acid, which contains both aromatic groups and amino groups in its structure
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References
1. Lau J. Overview and outlook of through-silicon via (TSV) and 3D integrations. Microelectronics International. 2011; 28( 2): 8–22. https://doi.org/10.1108/13565361111127304
2. Morrow P. R., Park C. M., Ramanathan S., Kobrinsky M. J., Harmes M. Three-dimensional wafer stacking via Cu-Cu bonding integrated with 65-nm strained-Si/low-k CMOS technology. IEEE Electron Device Letters. 2006;27(5): 335–337. https://doi.org/10.1109/led.2006.873424
3. 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
4. Josell D., Moffat T. Superconformal copper deposition in through silicon vias by suppression-breakdown. Journal of the Electrochemical Society. 2018;165(2): 23–30. https://doi.org/10.1149/2.0061802jes
5. Burkett S. L., Jordan M. B., Schmitt R. P., Menk L. A., Hollowell A. E. Tutorial on forming through-silicon vias. Journal of Vacuum Science & Technology A. 2020;38(3): 31202. https://doi.org/10.1116/6.0000026
6. Gavrilov S. A., Belov A. N. Electrochemical processes in micro- and nanoelectronics technology: textbook. manual 2nd ed*. Moscow: RIOR: INFRA-M Publ.; 2019. 240 p. Available at: https://library.atu.edu.kz/flgl/48784.pdf
7. 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: 250. https://doi.org/10.1149/1.1649235
8. Chan P.-F., Chiu Y.-D., Dow W.-P., Krug K., Lee Y.-L., Yau S. Use of 3,3-thiobis(1-propanesulfonate) to accelerate microvia filling by copper electroplating. Journal of the Electrochemical Society. 2013;160(12): 3271–3277. https://doi.org/10.1149/2.047312jes
9. Wang F., Zhou K., Zhang Q., … Feng W. Effect of molecular weight and concentration of polyethylene glycol on through‑silicon via filling by copper. Microelectronic Engineering. 2019;215: 111003. https://doi.org/10.1016/j.mee.2019.111003
10. Aleshina V. Kh., Grigoryan N. S., Asnis N. A., Abrashov A. A., Fadeeva V. A., Chudnova T.A. Effect of organic additives on copper electrodeposition in the manufacture of printed boards. International Journal of Corrosion and Scale Inhibition. 2023;12(1): 126–144. https://doi.org/10.17675/2305-6894-2023-12-1-7
11. 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: 155. https://doi.org/10.1149/1.3117562
12. Sun Q., Cao H., Ling H., Li M. Analysis of accelerator consumption in TSV copper electroplating. In: Proceedings –2013 14th International Conference on Electronic Packaging Technology. 2013: 818–821. https://doi.org/10.1109/ICEPT.2013.6756589
13. Chrzanowska A., Mroczka R., Florek M. Effect of interaction between dodecyltrimethylammonium chloride (DTAC) and bis(3-sulphopropyl) disulphide (SPS) on the morphology of electrodeposited copper. Electrochimica Acta. 2013; 106: 49–62. https://doi.org/10.1016/j.electacta.2013.05.061
14. Wang F., Le Y. Bis-(3-sulfopropyl) disulfide acceleration of copper electrodeposition via molecular dynamics and quantum chemical calculations. International Journal of Electrochemical Science. 2020;15(6): 4931–4943. https://doi.org/10.20964/2020.06.11
15. Arnold M., Emnet C., Fluegel A., … Broekmann P. Alternative pathway of SPS action: impact on electrochemistry and additive action. ECS Meeting Abstracts. 2010;2(34): 2036–2036. https://doi.org/10.1149/MA2010-02/34/2036
16. Garcia-Cardona E., Wong E. H., Barkey D. P. NMR spectral studies of interactions between the accelerants SPS and MPS and copper chlorides. Journal of the Electrochemical Society. 2011; 158(3): 143–148. https://doi.org/10.1149/1.3529937
17. Schmitt K. G., Schmidt R., Gaida J., Gewirth A. A. Chain length variation to probe the mechanism of accelerator additives in copper electrodeposition. Physical Chemistry Chemical Physics. 2019;21(30):16838−16847. https://doi.org/10.1039/c9cp00839j
18. Pasquale M.A., Gassa L.M., Arvia A.J. Copper electrodeposition from an acidic plating bath containing accelerating and inhibiting organic additives. Electrochimica Acta. 2008;53(20): 5891–5904. https://doi.org/10.1016/j.electacta.2008.03.073
19. Guo L., Li S., He Z., … Yang G. Electroplated copper additives for advanced packaging: a review. ACS Omega. 2024;9(19): 20637–20647. https://doi.org/10.1021/acsomega.4c01707
20. Jin S., Kim S.-M. Jo Y., Lee W. Y., Lee S.-Y., Lee M.-H. Unraveling adsorption behaviors of levelers for bottom-up copper filling in through-silicon-via. Electronic Materials Letters. 2022;18(1): 583–591. https://doi.org/10.1007/s13391-022-00364-6
21. Dow W.-P., Li C.-C., Su Y.-C., … Hsu S. Microvia filling by copper electroplating using diazine black as leveler. Electrochimica Acta. 2009;54(2): 5894-5901. https://doi.org/10.1016/j.electacta.2009.05.053
22. Wang C., Zhang J., Yang P., An М. 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
23. Wu H., Wang Y., Li Z., Zhu W. Investigations of the electrochemical performance and filling effects of additives on electroplating process of TSV. Scientific Reports. 2020;10(1): 9204. https://doi.org/10.1038/s41598-020-66191-7
24. Sun J.-J., Kondo K., Okamura T. Oh S., … Takahashi K. High-aspect-ratio copper via filling used for threedimensional chip stacking. Journal of the Electrochemical Society. 2003;150(6). https://doi.org/10.1149/1.1572154
25. Tang J., Zhang Y., Zhang X., Guo J. D., Shang J. K. Copper bottom-up filling for through silicon via (TSV) using single JGB additive. ECS Electrochemistry Letters. 2015;4(9): 28–30. https://doi.org/10.1149/2.0101509eel
26. Wang F., Le Y. Experiment and simulation of single inhibitor SH110 for void-free TSV copper filling. Scientific Reports. 2021;11(1). https://doi.org/10.1038/s41598-021-91318-9
27. Wang C., Zhang J., Yang P., Zhang B., An M. Throughhole copper electroplating using nitrotetrazolium blue chloride as a leveler. Journal of the Electrochemical Society. 2013;160(3): 85–88. https://doi.org/10.1149/2.035303jes
28. Chen T.-C., Tsai Y.-L., Hsu C.-F., Dow W.-P., Hashimoto Y. Effects of brighteners in a copper plating bath on throwing power and thermal reliability of plated through holes. Electrochimica Acta. 2016;212: 572–582. https://doi.org/10.1016/j.electacta.2016.07.007
29. Le Y., Fu-liang W. Void free TSV copper filling using single additive 3-(1-pyridinio)-1 propanesulfonate (PPS). In: 2020 3rd International Conference on Advanced Electronic Materials, Computers and Software Engineering (AEMCSE). 2020: 636–640. https://doi.org/10.1109/AEMCSE50948.2020.00139
30. Kozaderov O., Sotskaya N., Yudenkova L., Buylov N., Ilina E. Electrocrystallization and morphology of copper coatings in the presence of organic additives. Coatings. 2023;13(11): 1896. https://doi.org/10.3390/coatings13111896
31. Ilina E. A., Kozaderov O. A., Sotskaya N. V., Vandyshev D. Y., Polikarchuk V. A., Shikhaliev K. S. Kinetics of copper electrocrystallization from an acid sulfate solution in the presence of N-methyl polyvinylpyridine-methyl sulfate. Condensed Matter and Interphases. 2025;27(3): 368–379. https://doi.org/10.17308/kcmf.2025.27/13013
32. 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
33. 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
34. 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
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