JGB 첨가제에 의한 동박의 미세구조변화와 전기적 특성 = Effects of JGB Additives on the Microstructures and Electrical Properties of Electroplated Copper Foil

다국어 초록 (Multilingual Abstract)

Extremely thin film high quality copper foil is required to ensure high performance in electronics and slimness in secondary batteries. During the electroplating of copper foil, Janus Green B(JGB) and Collagen were introduced as additives to the electrolytes to study their effects. The structural and electrical properties of the electroplated copper foil were evaluated. When each additive was added individually, the potential was increased. Specifically, the potential of the group with 30 ppm added collagen was about 27% higher rather than the non-additive group. When Cl- ions and MPSA(3-mercapto-1-propane sulfonic acid) were added to the electrolytes without collagen and JGB, the surface roughness(Rz) increased by about 136% to 2.24 μm compared to the non-additive group. This was the highest value among all groups. However, a uniform layer with a surface roughness value below 0.3 μm was formed when less than 30 ppm and 10 ppm collagen and JGB were added, respectively, to the electrolyte. The direction of crystal growth with the JGB additives tended to go forward to the (220) direction, and the crystal size was reduced by 10~27% compared to the non-additive group. The addition of Collagen is necessary to reduce the difference in resistivity of the shiny layer and right matte layer. JGB additives were required to reduce the deviation in grain size. The results confirmed that the accelerators, inhibitors and leveler need to be properly added to form a copper plating layer with low surface roughness and to reduce differences in crystal texture of the shiny layer and right matte layer. Copper foil can be safely and uniformly deposited from electrolytes with JGB below 10 ppm and collagen below 30 ppm.

참고문헌 (Reference)

1 J. W. Gallaway, 156 : D287-, 2009

2 T. S. Kuan, 612 : D7-, 2000

3 J. Kelly, 159 : D563-, 2012

4 Q. Huang, 161 : D388-, 2014

5 I. S. Kang, 19 : 67-, 2012

6 C. H. Yang, 252 : 1818-, 2005

7 H. S. Lee, 39 : 920-, 2001

8 A. Gittis, 130 : 335-, 1985

9 S. Yoshimura, 39 : 589-, 1994

10 P. Stantke, 54 : 19-, 2002

11 Y. H. Jeong, Dong-A University 2016

12 S. K. Kim, 153 : C616-, 2006

13 Y. Cao, 148 : C466-, 2001

14 S. Choe, 160 : D3179-, 2013

15 S. W. Lee, Jeonbuk National University 2015

16 C. C. Hu, 176 : 75-, 2003

17 V. S Donepudi, 4 : C13-, 2001

18 Y. K. Lee, 54 : 40-, 2002

19 P. V. Brande, 52 : 1-, 1992

20 Z. Zhou, 28 : 461-, 1998

21 M. L. Sartorelli, 187 : 91-, 2001

22 J. J. Yang, 201 : 5574-, 2007

23 V. A. Vas’ko, 75 : 71-, 2004

24 S. K. Kim, 7 : C98-, 2004

25 S. K. Cho, 152 : C330-, 2005

26 김민호, "젤라틴 첨가에 의한 구리 박막의 미세구조 변화 및 부식 특성" 대한금속·재료학회 48 (48): 757-764, 2010

27 김민호, "젤라틴 첨가에 의한 구리 박막의 기계적 특성 변화" 대한금속·재료학회 48 (48): 884-892, 2010

28 우태규, "전해 동박의 표면 형상 및 기계적 물성에 미치는 SPS 첨가제 영향" 대한금속·재료학회 54 (54): 681-687, 2016

29 박채민, "유기첨가제에 의한 구리 도금층의 불순물 농도 제어" 대한금속·재료학회 54 (54): 469-474, 2016

30 이상훈, "스퍼터링 및 전기도금법으로 증착된 Cu 박막의 두께에 따른 어닝링 집합조직" 대한금속·재료학회 44 (44): 556-561, 2006

31 허석환, "반도체 배선용 구리 도금층의 미세조직 및 전기비저항 고찰" 대한금속·재료학회 52 (52): 943-948, 2014

32 김회철, "구리 전해 도금을 이용한 실리콘 관통 비아 채움 공정" 한국화학공학회 54 (54): 723-733, 2016

33 우태규, "고전류밀도에서의 첨가제 초기 거동 및 동박의 기계적 특성" 대한금속·재료학회 59 (59): 304-313, 2021

34 우태규, "고전류밀도에서 유기첨가제에 의한 구리 전착층의 전기적 특성 변화" 대한금속·재료학회 58 (58): 41-48, 2020

35 이민형, "Via-Filling 공정시 발생하는 첨가제 분해에 관한 연구" 한국표면공학회 46 (46): 153-157, 2013

36 진상훈, "Seed Step-Coverage Enhancement Process for a High-Aspect-Ratio Through-Silicon Via Using a Pyrophosphate Solution" 대한금속·재료학회 21 (21): 775-779, 2015

37 B. D. Cullity, "Elements of X-ray diffraction" Pearson Education 170-, 2001

38 김상현, "EMI 차페용 구리-니켈-스테인리스강 다층박막의 내식성" 대한금속·재료학회 43 (43): 538-543, 2005

39 이한승, "ECR plasma로 전처리된 Cu seed층 위에 전해도금 된 Cu막에 대한 Annealing의 효과" 한국재료학회 13 (13): 174-179, 2003