Korean Journal of Materials Research (한국재료학회지)

Materials Research Society of Korea (한국재료학회)
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Influence of Reactivity of Reinforcing Nanoparticles with Aqueous Solution on Electroplating Copper Films

강화상 나노입자의 용액 반응성이 구리 도금 박막에 미치는 영향

  • Park, Jieun (Department of Cogno-mechatronics Engineering, Pusan National University) ;
  • Oh, Minju (Department of Cogno-mechatronics Engineering, Pusan National University) ;
  • Kim, Yiseul (Department of Advanced Circuit Interconnection, Pusan National University) ;
  • Lee, Dongyun (Department of Cogno-mechatronics Engineering, Pusan National University)
  • 박지은 (부산대학교 인지메카트로닉스공학과) ;
  • 오민주 (부산대학교 인지메카트로닉스공학과) ;
  • 김이슬 (부산대학교 차세대기판학과) ;
  • 이동윤 (부산대학교 인지메카트로닉스공학과)
  • Received : 2013.10.31
  • Accepted : 2013.11.18
  • Published : 2013.12.27
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Abstract

To understand how reactivity between reinforcing nanoparticles and aqueous solution affects electrodeposited Cu thin films, two types of commercialized cerium oxide (ceria, $CeO_2$) nanoparticles were used with copper sulfate electrolyte to form in-situ nanocomposite films. During this process, we observed variation in colors and pH of the electrolyte depending on the manufacturer. Ceria aqueous solution and nickel sulfate ($NiSO_4$) aqueous solutions were also used for comparison. We checked several parameters which could be key factors contributing to the changes, such as the oxidation number of Cu, chemical impurities of ceria nanoparticles, and so on. Oxidation number was checked by salt formation by chemical reaction between $CuSO_4$ solution and sodium hydroxide (NaOH) solution. We observed that the color changed when $H_2SO_4$ was added to the $CuSO_4$ solution. The same effect was obtained when $H_2SO_4$ was mixed with ceria solution; the color of ceria solution changed from white to yellow. However, the color of $NiSO_4$ solution did not show any significant changes. We did observe slight changes in the pH of the solutions in this study. We did not obtain firm evidence to explain the changes observed in this study, but changes in the color of the electrolyte might be caused by interaction of Cu ion and the by-product of ceria. The mechanical properties of the films were examined by nanoindentation, and reaction between ceria and electrolyte presumably affect the mechanical properties of electrodeposited copper films. We also examined their crystal structures and optical properties by X-ray diffraction (XRD) and UV-Vis spectroscopy.

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