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A Method for Application of Ammonium-based Pretreatment Solution in Preparation of Copper Flakes Coated by Electroless Ag Plating

구리 플레이크의 무전해 은도금에서 암모늄계 구리 전처리 용액의 적용법

  • Kim, Ji Hwan (Department of Materials Science & Engineering, Seoul National University of Science & Technology) ;
  • Lee, Jong-Hyun (Department of Materials Science & Engineering, Seoul National University of Science & Technology)
  • 김지환 (서울과학기술대학교 신소재공학과) ;
  • 이종현 (서울과학기술대학교 신소재공학과)
  • Received : 2015.12.01
  • Accepted : 2015.12.24
  • Published : 2015.12.30

Abstract

In order to prepare a low-cost conductive filler material possessing improved anti-oxidation property, Ag-coated Cu flakes were fabricated and the effects of an applying method of ammonium-based pretreatment solution on the Cu flakes were analyzed. The pretreatment solution was used to remove the surface oxide layer on Cu flake. During a single-stage pretreatment process, hole-shaped defects were formed on the flake surface during the pretreatment after 2 min, and the number and size increased in proportion to the pretreatment time. In the case that Ag plating solution was injected in the pretreatment solution after the pretreatment for 2 min, the defects were also formed during Ag plating. In contrast, the defects tremendous decreased in the case that the pretreatment solution was removed after the first pretreatment for 2 min and the Ag plating proceeded after the second pretratment using a low concentration pretreatment solution. As the final result, the 15 wt% Ag-coated Cu flake sample which was fabricated using the single-stage pretreatment oxidized at $166^{\circ}C$, but the sample fabricated by the double-stage pretreatment oxidized at $224^{\circ}C$, indicating definitely improved anti-oxidation property.

내산화 특성을 가지는 저가격 도전성 필러 소재로의 적용을 위해 Ag 코팅 Cu 플레이크의 제조를 수행하면서 Cu 플레이크 표면의 산화층 제거를 위한 암모니아수 기반 전처리 용액의 적용법에 따른 영향을 분석해 보았다. 1회 전처리법 적용 시 전처리 시간이 2분을 초과하면서 플레이크 표면에서 홀 형태의 결함들이 생성되었으며, 유지시간에 비례하면서 그 개수와 크기가 점차 증가하였다. 또한 2분간의 전처리 후 Ag 도금 용액을 투입한 결과 도금 반응 중에 결함 발생이 다시 진행되어 플레이크 입자의 손상을 막을 수 없었다. 이에 비해 2분간의 1차 전처리 후 전처리 용액을 제거하고 저농도의 전처리 용액을 투입하여 2차 전처리를 실시하면서 Ag 도금 용액을 투입한 공정법에서는 상기 결함의 발생 빈도를 크게 줄일 수 있었다. 그 결과 1회 전처리법으로 제조된 15 wt% Ag 코팅 Cu 시료의 경우 약 $166^{\circ}C$의 온도부터 산화가 시작되었지만, 2회 전처리법으로 제조된 시료는 약 $224^{\circ}C$에서 산화가 시작되어 월등히 향상된 내산화 특성을 나타내었다.

Keywords

References

  1. J.-S. Park, J.-H. Hwang, J.-G. Kim, Y.-H. Kim, H.-D. Park and S.-G. Kang, "Properties of Ag Thick Films Fabricated by Using Low Temperature Curable Ag Pastes", Kor. J. Mater. Res., 13(1), 18 (2003). https://doi.org/10.3740/MRSK.2003.13.1.018
  2. H. S. Kim, J. C. Choi, B. O. Rhee and S. C. Choi, "Preparation and Characterization of Bi Based Frit for Ag Electrode in PDP Application", J. Microelectron. Packag. Soc., 10(4), 47 (2003).
  3. J.-K. Lee, S.-H. Park and G.-S. Yang, "Effect of Sintering Aid and Glass-Frit on the Densification and Resistivity of Silver Paste", Kor. J. Mater. Res., 18(5), 283 (2008). https://doi.org/10.3740/MRSK.2008.18.5.283
  4. L. Tongxiang, G. Wenli, Y. Yinghui and T. Chunhe, "Electroless Plating of Silver on Graphite Powders and the Study of Its Conductive Adhesive", Int. J. Adh. Adh. 28(1-2), 55 (2008). https://doi.org/10.1016/j.ijadhadh.2007.03.006
  5. S. Wu, "Preparation of Fine Copper Powder Uusing Ascorbic Acid as Reducing Agent and Its Aapplication in MLCC", Mater. Lett., 61(4-5), 1125 (2007). https://doi.org/10.1016/j.matlet.2006.06.068
  6. X. Xu, X. Luo, H. Zhuang, W. Li and B. Zhang, "Electroless Silver Coating on Fine Copper Powder and Its Effects on Oxidation Resistance", Mater. Lett., 57(24-25), 3987 (2003). https://doi.org/10.1016/S0167-577X(03)00252-0
  7. D. S. Jung, H. M. Lee, Y. C. Kang and S. B. Park, "Air-stable Silver-coated Copper Particles of Sub-micrometer Size', J. Colloid Interface Sci., 364(2), 574 (2011). https://doi.org/10.1016/j.jcis.2011.08.033
  8. J. Zhao, D. M. Zhang and J. Zhao, "Fabrication of Cu-Ag Core-Shell Bimetallic Superfine Ppowders by Eco-friendly Reagents and Structures Characterization", J. Solid State Chem., 184(9), 2339 (2011). https://doi.org/10.1016/j.jssc.2011.06.032
  9. H. T. Hai, J. G. Ahn, D. J. Kim, J. R. Lee, H. S. Chung and C. O. Kim, "Developing Process for Coating Copper Particles with Silver by Electroless Plating Method", Surf. Coat. Technol., 201(6), 3788 (2006). https://doi.org/10.1016/j.surfcoat.2006.03.025
  10. R. Zhang, W. Lin, K. Lawrence and C. P. Wong, "Highly Reliable, Low Cost, Isotropically Conductive Adhesives Filled with Ag-coated Cu Flakes for Electronic Packaging Applications", Int. J. Adh. Adh. 30(6), 403 (2010). https://doi.org/10.1016/j.ijadhadh.2010.01.004
  11. Y. Peng, C. Yang, K. Chen, S. R. Popuri, C.-H. Lee and B.- S. Tang, "Study on Synthesis of Ultrafine Cu-Ag Core-Shell Powders with High Electrical Conductivity", Appl. Surf. Sci., 263(15), 38 (2012). https://doi.org/10.1016/j.apsusc.2012.08.066
  12. G. Kim, K.-M. Jung, J.-T. Moon and J.-H. Lee, "Electrical Resistivity and Thermal Conductivity of Paste Containing Ag-coated Cu Flake Filler", J. Microelectron. Packag. Soc., 21(4), 51 (2014). https://doi.org/10.6117/kmeps.2014.21.4.051
  13. J. H. Kim and J.-H. Lee, "Effects of Pretreatment and Ag Coating Processes Conditions on the Properties of Ag-Coated Cu Flakes", J. Mater. Res., 24(11), 617 (2014).
  14. Y. Wei, S. Chen, Y. Lin, Z. Yang and L. Liu, "Cu-Ag Core- Shell Nanowires for Electronic Skin with a Petal Molded Microstructure", J. Mater. Chem. C, 3(37), 9594 (2015). https://doi.org/10.1039/C5TC01723H
  15. J. H. Kim, Y. H. Cho and J.-H. Lee, "Fabrication of a Ultrathin Ag Film on a Thin Cu Film by Low-Temperature Immersion Plating in an Grycol-Based Solution", J. Microelectron. Packag. Soc., 21(2), 79 (2014). https://doi.org/10.6117/kmeps.2014.21.2.079
  16. D. W. Shoesmith, S. Sunder, M. G. Bailey, G. J. Wallace and F. W. Stanchell, "Anodic Oxidation of Copper in Alkaline Solutions: Part IV. Nature of the Passivating Film", J. Electroanal. Chem., 143(1-2), 153 (1983). https://doi.org/10.1016/S0022-0728(83)80261-7
  17. G.-L. Song, R. Mishra and Z. Xu, "Crystallographic Orientation and Electrochemical Activity of AZ31 Mg Alloy", Electrochem Comm., 12(8), 1009 (2010). https://doi.org/10.1016/j.elecom.2010.05.011
  18. A. Muzikansky, P. Nanikashvili, J. Grinblat and D. Zitoun, "Ag Dewetting in Cu@Ag Monodisperse Core-Shell Nanoparticles", J. Phys. Chem. C, 117(6), 3093 (2013). https://doi.org/10.1021/jp3109545
  19. C.-H. Tsai, S.-Y. Chen, J.-M. Song, I.-G. Chen and H.-Y. Lee, "Thermal Stability of Cu@Ag Core-Shell Nanoparticles", Corros. Sci., 74(Sep), 123 (2013). https://doi.org/10.1016/j.corsci.2013.04.032
  20. S.-S. Chee and J.-H. Lee, "Preparation and Oxidation Behavior of Ag-coated Cu Nanoparticles Less Than 20 nm in Size", J. Mater. Chem. C, 2(27), 5372 (2014). https://doi.org/10.1039/c4tc00509k