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Electrochemical Study of the Effect of Additives on High Current Density Copper Electroplating

고전류밀도 구리도금에서 첨가제에 따른 전기화학적 특성변화 연구

  • Shim, Jin-Yong (Dept. of Materials Science and Engineering, Hongik University) ;
  • Moon, Yun-Sung (Process Development Team, LS-Nikko Copper Inc.) ;
  • Lee, Jae-Ho (Dept. of Materials Science and Engineering, Hongik University)
  • Received : 2011.06.10
  • Accepted : 2011.06.23
  • Published : 2011.08.31

Abstract

The maximum current density of copper electrorefining is 350 A/$m^2$ and the higher current density is required to promote the copper productivity. The 1000 A/$m^2$ high current density is possible when rotating disc electrode is employed to reduce diffusion thickness. The copper electroplating with 1000 A/$m^2$ is possible at 400 rpm. Thiourea and glue were used to improve the electrodeposition behaviors during copper electrorefining process. Potentiodynamic polarization tests were conducted to investigate the effects of additives on copper electrodeposition. Galvanostatic tests were also conducted at 1000 A/$m^2$. Copper were electroplated on cylindrical rotating electrodes to give the uniform flow on the electrode surface. The lowest surface roughness was obtained when 16 ppm thiourea was added to the electrolytes. The surface roughness was increased with glue concentration. The surface hardness was not influenced by addition of glue. The copper nuclei were getting smaller with thiourea concentration, however there is no glue effects on copper nucleation.

구리의 전해정련공정에서의 최대 전류밀도는 350 A/$m^2$ 이며 생산성의 증가를 위해선 고전류밀도가 필요하다. 회전전극(RDE)을 이용하면 구리의 표면 확산층의 두께조절이 가능하게 되며 안정적인 1000 A/$m^2$의 고전류밀도 구리 도 금이 가능하게 된다. 회전 속도 400rpm조건에서 안정적인 고전류밀도 구리 도금이 가능하였다. 구리 전해정련 과정 중 구리표면의 전착특성 향상을 위해 첨가제는 thiourea와 glue가 사용된다. 고전류밀도 조건에서 첨가제의 거동을 알아보기 위 해 구리가 전착되는 영역에서 첨가제의 농도에 따른 potentiodynamic polarization 실험을 하였고, 1000 A/$m^2$ 조건에서 정전류 실험을 하였다. 동일한 선속도를 인가하기 위해 원통형 회전전극을 이용해 구리도금을 하였고, 도금층의 표면조도 측정에서 thiourea가 16 ppm 들어갔을 때 가장 낮은 조도와 안정적인 취성특성을 나타내었다. 첨가되는 glue의 양이 증가할 수록 표면 조도는 증가하였고, 구리도금층의 경도는 큰 차이가 없었다. 결정립 미세화제로 사용되는 thiourea의 첨가량의 증가에 따라 구리의 핵 성장은 미세해졌고, glue 첨가량의 증가에 따라서는 핵 성장이 영향을 받지 않았다.

Keywords

References

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