구리전해도금에서 알킬아민의 영향 연구
Study on the Effect of Alkylamines on Cu Electroplating
2
조회
0
다운로드
2
인용
0
참고문헌
키워드
초록
본 연구에서는, 알킬아민이 구리전해도금에 미치는 영향을 cyclic voltammetry를 이용해 분석해보았다. 수용액상 용해도를 갖는 알킬아민을 도금액에 첨가할 경우, Cu2+의 환원반응이 억제되는 것을확인할 수 있었다. 다양한 알킬아민 중 1,12-diaminododecane에 대해 다양한 농도 및 도금액 조건에서 억제 효과를 관찰하였다. 1,12-diaminododecane은 산성 도금액상에서 protonation 되어, Cu2+ 의 착화제로써 작용하지 않았으며, 따라서 1,12-diaminododecane의 억제 효과는 Cu 표면상 흡착에의한 것임을 확인할 수 있었다. 1,12-diaminododecane는 (i) protonation에 의한 양이온화와 그에따른 Cu 표면상 기흡착한 음이온과의 정전기적 인력에 의한 흡착과 (ii) amine에 의한 Cu 표면상직접 흡착의 두가지 특성을 모두 가지고 있었다. 흡착한 1,12-diaminododecane은 도금 반응을 억제할 뿐만 아니라, 구리도금막 형성시 3차원적 성장과 표면 미세화를 야기하였다.
Abstract
In this study, the effect of alkylamine on copper electroplating was analyzed using cyclic voltammetry. When water-soluble alkylamines were added to the plating solution, the reduction reaction of Cu2+ was inhibited. The inhibition effect of 1,12-diaminododecane has been investigated at various concentrations and conditions of the plating solution. 1,12-diaminododecane was protonated in the acidic plating solution, and therefore, it did not act as a complexing agent for Cu2+. Accordingly, it was confirmed that the inhibiton effect of 1,12-diaminododecane was attributed to adsorption on the Cu surface. The adsorption of 1,12-diaminododecane exhibits two characteristics: (i) protonation and subsequent electrostatic attraction with anions pre-adsorbed on Cu surface, and (ii) direct adsorption on Cu surface via amine functional group. The adsorbed 1,12-diaminododecane caused three-dimensional growth and grain refining, as well as the inhibition effect, during Cu electroplating.
참고문헌 (16)
- 김재정, "전해 도금을 이용한 기가급 소자용 구리배선 공정", 전기화학회지, 10(2), pp.94~103 (2007), 한국전기화학회
- W. -P. Dow, "Influence of convection-dependent adsorption of additives on microvia filling by copper electroplating", J. Electrochem. Soc, 152, pp.C425~ (2005)
- T. Y. B. Leung, "Benzotriazole as an additive for copper electrodeposition influence of triazole ring substitution", J. Electrochem. Soc, 147, pp.3326~ (2000)
- S. K. Kim, "Electrodeposition of Cu in the PEI-PEG-Cl-SPS additive system", J. Electrochem. Soc, 153, pp.C616~ (2006)
- M. B. Gawande, "Cu and Cu-based nanoparticles: Synthesis and applications in catalysis", Chem. Rev, 116, pp.3722~ (2016)
- S. K. Kim, "Cationic surfactants for the control of overfill bumps in Cu superfilling", J. Electrochem. Soc, 153, pp.C826~ (2006)
- Y. E. Jo, "Revealing the inhibition effect of quaternary ammonium cations on Cu electrodeposition", J. Appl. Electrochem, 50, pp.245~ (2020)
- K. Shi, "Structural studies of electrochemically activated glassy carbon electrode: Effects of chloride anion on the redox responses of copper deposition", Electrochim. Acta, 52, pp.5907~ (2007)
- D. Grujicic, "Reaction and nucleation mechanisms of copper electrodeposition from ammoniacal solutions on vitreous carbon", Electrochim. Acta, 50, pp.4426~ (2005)
- A. Frank, "The decomposition of the sulfonate additive sulfopropyl sulfonate in acid copper electroplating chemistries", J. Electrochem. Soc, 150, pp.C244~ (2003)
- S. Aksu, "Electrochemistry of copper in aqueous ethylenediamine solutions", J. Electrochem. Soc, 149, pp.B340~ (2002)
- 신영민, "구리전해도금에서 양쪽이온성 계면활성제인 (Dodecyldimethylammonio)propanesulfonate의 영향 연구", 전기화학회지, 24(3), pp.35~41 (2021), 한국전기화학회
- C. Goletti, "Cu(110) surface in hydrochloric acid solution:Potential dependent chloride adsorption and surface restructuring", J. Phys. Chem. C, 119, pp.1782~ (2015)
- S. -H. Liu, "Selfassembled monolayer structures of hexadecylamine on Cu surfaces: density-functional theory", Phys. Chem. Chem. Phys, 18, pp.32753~ (2016)
- Z. Chen, "Adsorption of alkylamines on Cu surfaces: identifying ideal capping molecules using first-principles calculations", Nanoscale, 13, pp.18536~ (2021)
- O. M. Magnussen, "Magnussen, Ordered anion adlayers on metal electrode surfaces", Chem. Rev, 102, pp.679~ (2002)