한국표면공학회지 (Journal of the Korean institute of surface engineering)

  • 제57권4호
  • /
  • Pages.274-284
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  • 2024
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  • 1225-8024(pISSN)
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  • 2288-8403(eISSN)
한국표면공학회 (The Korean Institute of Surface Engineering)
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고전류밀도 전해도금 공정에서 PEG 첨가 효과

Effects of PEG addition as an additive for electroplating of Cu at high current density

  • 강병재 (전북대학교 금속공학과) ;
  • 윤준서 (전북대학교 금속공학과) ;
  • 박종재 (전북대학교 금속공학과) ;
  • 우태규 (전북대학교 유연인쇄전자전문대학원 및 로스알라모스연구소-전북대학교 한국공학연구소) ;
  • 박일송 (전북대학교 금속공학과)
  • Byeoung-Jae Kang (Department of Metallurgical Engineering, Jeonbuk National University) ;
  • Jun-Seo Yoon (Department of Metallurgical Engineering, Jeonbuk National University) ;
  • Jong-Jae Park (Department of Metallurgical Engineering, Jeonbuk National University) ;
  • Tae-Gyu Woo (Graduate School of Flexible and Printable Electronics and LANL-CBNU Engineering Institute Korea, Jeonbuk National University) ;
  • Il-Song Park (Department of Metallurgical Engineering, Jeonbuk National University)
  • 투고 : 2024.07.04
  • 심사 : 2024.07.23
  • 발행 : 2024.08.31
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초록

In this study, copper foil was electroplated under high current density conditions. We used Polyethylene Glycol (PEG), known for its thermal stability and low decomposition rate, as an inhibitor to form a stable and smooth copper layer on the titanium cathode. The electrolyte was composed of 50 g/L CuSO4 and 100 g/L H2SO4, MPSA as an accelerator, JGB as a leveler, and PEG as a suppressor, and HCl was added as chloride ions for improving plating efficiency. The copper foil electroplated in the electrolyte added PEG which induced to inhibit the growth of rough crystals. As a result, the surface roughness value was reduced, and a uniform surface was formed over a large area. Moreover, the addition of PEG led to priority growth to the (111) plane and the formation of polygonal crystals through horizontal and vertical growth of crystals onto the cathode. In addition, the grains became fine when more than 30 ppm of PEG was added. As the microcrystalline structure changed, mechanical and electrical properties were altered. With the addition of PEG, the tensile strength increased due to grain refinement, and the elongation was improved due to the uniform surface. However, as the amount of PEG added increased, the corrosion rate and resistivity increased due to grain refinement. Finally, it was possible to manufacture a copper foil with excellent electrical and mechanical properties and the best surface properties when electroplating was carried out under the condition of additives with Cl-20 ppm, MPSA 10 ppm, JGB 5 ppm, and PEG 10 ppm.

키워드

참고문헌

  1. M. Yokoi, S. Konishi, T. Hayashi, Adsorption behavior of polyoxyethyleneglycole on the copper surface in an acid copper-sulfate bath, Denki Kagaku, 52 (1984) 218-223.
  2. T.G. Woo, I.S. Park, Changes in electrical properties of copper-plated layer by organic additives on high current density, Korean Journal of Metals and Materials, 58 (2020) 41-48.
  3. T.G. Woo, J.J. Park, I.S. Park, Initial behavior of additives and mechanical properties of copper foils on high current density, Korean Journal of Metals and Materials, 59 (2021) 304-313.
  4. Y.H. Kim, J.W. Lim, G.Y. Park, O.T. Lim, Electric vehicle market and battery related technology research trends, The Korean Hydrogen and New Energy Society, 30 (2019) 362-368.
  5. T.G. Woo, M.H. Lee, K.W. Seol, Effect of gelatin and chloride ions on the mechanical properties and microstructural evolution of copper foil, Korean Journal of Metals and Materials, 56 (2018) 518-523.
  6. T.G. Woo, K.W. Seol, H.W. Lee, I.S. Park, D.J. Oh, O.J. Kwon, The effect of arabic gum and chloride ion on the nucleation and growth of copper during electrodeposition, Korean Journal of Metals and Materials, 44 (2006) 527-533.
  7. T.G. Woo, I.S. Park, Effects of JGB additives on the microstructures and electrical properties of electroplated copper foil, Korean Journal of Metals and Materials, 59 (2021) 404-411.
  8. A. Lee, M.J. Kim, S. Choe, J.J. Kim, High strength Cu foil without self-annealing prepared by 2M5S-PEG-SPS, The Korean Journal of Chemical Engineering, 36 (2019) 981-987.
  9. J.H. Moon, A study on the influence of the shape control factors for the characteristics of copper foil alloy, Thesis of MS, Ulsan University (2018).
  10. S.M. Kim, S.H. Jun, K.C. Jo, J.K. Ahn, Applications and technical trends of electroplating copper foil, In Proceedings of The Conference on Surface Engineering, (2015) 59.
  11. C.M. Park, U.H. Lee, H.J. Lee, Control of impurity concentrations in copper electrodeposits by using an organic additive, Korean Journal of Metals and Materials, 54 (2016) 469-474.
  12. S.S. Kim, Effects of organic additives on the elongation and hardness of copper electroplating in sulfuric acid bath, Thesis of MS, Inha University (2012).
  13. T.G. Woo, I.S. Park, Effect of potassium carbonate additives on the properties of copper foils electroplated at high current density, Korean Journal of Metals and Materials, 61 (2023) 347-354.
  14. T.P. Moffat, D. Wheeler, D. Josell, Electrodeposition of copper in the SPS-PEG-Cl additive system-I. kinetic measurements: Influence of SPS, Journal of the Electrochemical Society, 151 (2004) C262-C271.
  15. K.W. Lee, S.S. Rho, C.H. Choi, S.K. Kim, S.H. Son, H.K. Moon, D.H. Park, Organic additives effect affected on the property of electrodeposited copper foil, The Korean Institute of Electrical Engineers, 7 (2001) 1540.
  16. M. Tan, J.N. Harb, Additive behavior during copper electrodeposition in solutions containing Cl, PEG, and SPS, Journal of the Electrochemical Society, 150 (2003) C420-C425.
  17. F. Wafula, Y. Liu, L. Yin, S. Bliznakov, P. Borgesen, E.J. Cotts, N. Dimitrov, Impact of key deposition parameters on the voiding sporadically occurring in solder joints with electroplated copper, Journal of the Electrochemical Society, 157 (2010) D111-D118.
  18. J.H. Park, Correlation between equilibrium potential and electric current in copper clad laminate and spacial distribution of copper plating thickness, Thesis of MS, Chungnam National University (2016).
  19. J.S. Yoon, C.S. Park, S.Y. Hong, H.J. Lee, S.J. Lee, Y.D. Kim, Microstructural characteristics of electro-plated Cu films by DC and pulse systems, Korean Journal of Materials Research, 24 (2014) 105-110.
  20. E.E. Stansbury, R.A. Buchanan, Fundamentals of electrochemical corrosion, ASM International, Materials Park, OH, (2000) 127-181.
  21. S. Yoshimura, S. Yoshihara, T. Shirakashi, E. Sato, Preferred orientation and morphology of electrodeposited iron from iron(II) chloride solution, Electrochimica Acta, 39 (1994) 589-595.
  22. A. Ibanez, E. Fatas, Mechanical and structural properties of electrodeposited copper and their relation with the electrodeposition parameters, Surface and Coatings Technology, 191 (2005) 7-16.
  23. C.H. Yang, S.C. Lee, J.M. Wu, T.C. Lin, The properties of copper films deposited on polyimide by nitrogen and oxygen plasma pre-treatment, Applied Surface Science, 252 (2005) 1818-1825.
  24. H.S. Lee, H.S. Kim, C.M. Lee, Effects of plasma/RTA pretreatment on Cu electroplating, Korean Journal of Metals and Materials, 39 (2001) 920-926.
  25. H.S. Lee, D.K. Kwon, H.A. Park, C.M. Lee, Effects of post-deposition annealing on the copper films electrodeposited on the ECR plasma cleaned copper seed layer, Korean Journal of Materials Research, 13 (2003) 174-179.
  26. K.J. Park, J.Y. Kim, Tension tests of copper thin films, Transactions of the Korean Society of Mechanical Engineers, A, 41 (2017) 745-750
  27. B.N. Park, H.J. Kang, S.Y. Choi, Growth and annealing effect of Cu thin films using electroplating technique, Journal of the Institute of Electronics Engineers of Korea, 40 (2003) 1-8.
  28. T. Osaka, N. Yamachika, M. Yoshino, M. Hasegawa, Y. Negishi, Y. Okinaka, Effect of carbon content on the electrical resistivity of electrodeposited copper, Electrochemical and Solid-State Letters, 12 (2009) D15-D17.
  29. M.H. Kim, H.R. Cha, C.S. Choi, H.S. Kim, D.Y. Lee, Effects of gelatin additives on the microstructures and corrosion properties of electrodeposited Cu thin films, Korean Journal of Metals and Materials, 48 (2010) 757-764.
  30. K.D. Ralston, N. Birbilis, Effect of grain size on corrosion: a review, Corrosion, 66 (2010)