Electroless Plating of Co-Alloy Thin Films using Alkali-Free Chemicals

Alkali 물질이 포함되지 않은 화학물질을 이용한 Co 합금박막의 무전해도금

  • Kim, Tae Ho (Department of Chemical Engineering, Division of Energy Systems Research, Ajou University) ;
  • Yun, Hyeong Jin (Department of Chemical Engineering, Division of Energy Systems Research, Ajou University) ;
  • Kim, Chang-Koo (Department of Chemical Engineering, Division of Energy Systems Research, Ajou University)
  • 김태호 (아주대학교 에너지시스템학부 화학공학전공) ;
  • 윤형진 (아주대학교 에너지시스템학부 화학공학전공) ;
  • 김창구 (아주대학교 에너지시스템학부 화학공학전공)
  • Received : 2007.06.13
  • Accepted : 2007.07.06
  • Published : 2007.12.31

Abstract

Electroless plating of Co-alloy thin films as capping layers for Cu interconnection has been investigated using alkali-free precursors such as $(NH_4)_2Co(SO_4)_2{\cdot}6H_2O$, $(NH_4)_2WO_4$, $(NH_4)H_2PO_4$, etc. The characteristics of the Co-alloy thin films were discussed by analyses of the effects of pH, Co-precursor concentration, and deposition temperature on the thickness and surface morphology of the films. The thickness of the Co-alloy thin films increased with increasing pH, Co-precursor concentration, and deposition temperature, similarly to the results of electroless plating of Co-alloy thin films using alkali-containing chemicals. The SEM images of the surface of the Co-alloy thin films showed that the proper ranges of pH and deposition temperature were 8.5~9.5 and $75{\sim}85^{\circ}C$, respectively. This work found a feasibility that Co-alloy thin films as capping layers for Cu interconnection could be electroless plated using alkali-free chemicals.

Alkali 물질이 포함되지 않은 $(NH_4)_2Co(SO_4)_2{\cdot}6H_2O$, $(NH_4)_2WO_4$, $(NH_4)H_2PO_4$ 등의 전구체를 사용하여 구리배선의 보호막 제조를 위한 Co 합금박막의 무전해도금을 수행하였다. pH, Co 전구체 농도, 증착온도 등의 공정변수들의 변화에 대한 Co 합금박막의 두께와 표면형상을 살펴봄으로써 이들 공정변수가 alkali 물질이 포함되지 않은 화학물질로 무전해도금된 Co 합금박막의 특성에 끼치는 영향을 살펴보았다. pH, Co 전구체 농도, 증착온도가 증가할수록 Co 합금 박막의 두께가 증가하였고 이는 alkali 물질이 포함된 Co 합금박막의 무전해도금 결과와 비슷하다. SEM(scanning electron microscopy)을 이용한 Co 합금박막의 표면형상 관측 결과, 본 연구에서 사용된 공정조건에서 Co 합금박막의 무전해도금을 위한 적절한 pH와 온도의 범위가 각각 8.5~9.5와 $75{\sim}85^{\circ}C$임을 얻었다. 본 연구를 통하여 alkali 물질이 포함되지 않은 화학물질을 이용한 무전해도금으로 구리배선의 보호막 제조용 Co 합금박막의 증착이 가능함을 확인하였다.

Keywords

Acknowledgement

Supported by : 한국과학재단

References

  1. Mitchell, B. S., An Introduction to Materials Engineering and Science for Chemical and Materials Engineers, John Wiley & Sons, Inc., New York, NY(2004)
  2. Shacham-Diamand, Y., Sverdlov, Y. and Petrov, N., 'Electroless Deposition of Thin-Film Cobalt-Tungsten-Phosphorus Layers Using Tungsten Phosphoric Acid for ULSI and MEMS Applications,' J. Electrochem. Soc., 148(3), C162-C167(2001) https://doi.org/10.1149/1.1346605
  3. Wang, S. Q., 'Barriers against Copper Diffusion into Silicon and Drift through Silicon Dioxide,' MRS Bull., 19(8), 30-40(1994)
  4. Gao, W., Gong, H., He, J., Thomas, A., Chan. L. and Li, S., 'Oxidation Behavior of Cu Thin Films on Si Wafer at 175-400,' Materials Letters, 51(1), 78-84(2001) https://doi.org/10.1016/S0167-577X(01)00268-3
  5. Paunovic, M. and Schlesinger, M., Fundamentals of Electrochemical Deposition, John Wiley & Sons, Inc., New York, NY(1988)
  6. Petrov, N., Sverdlov, Y. and Shacham-Diamand, Y., 'Electrochemical Study of the Electroless Deposition of CoP and CoWP Alloys,' J. Electrochem. Soc., 149(4), C187-C194(2002)
  7. Einati, H., Bogush, V., Sverdlov, Y., Rosenberg, Y. and Shacham-Diamand Y., 'The Effect of Tungsten and Boron on the Cu Barrier and Oxidation Properties of Thin Electroless Cobalt-Tungsten-Boron Films,' Microelec. Eng., 82, 623-628(2005) https://doi.org/10.1016/j.mee.2005.07.082
  8. Shacham-Diamand, Y. and Lopatin, S., 'Integrated Electroless Metallization for ULSI', Electrochim. Acta, 44(21-22), 3639-3649(1999) https://doi.org/10.1016/S0013-4686(99)00067-5
  9. Huang Y. and Cui F., 'Effect of Complexing Agent on the Morphology and Microstructure of Electroless Deposited Ni-P Alloy,' Surface & Coatings Technology, 201, 5416-5418(2007) https://doi.org/10.1016/j.surfcoat.2006.07.189
  10. Liu, W., Chen, W., Tsai, T., Hsieh, S. and Chang S., 'Effect of Nickel on the Initial Growth Behavior of Electroless Ni-Co-P Alloy on Silicon Substrate', Appl. Surf. Sci., 253(8), 3843-3848(2007) https://doi.org/10.1016/j.apsusc.2006.08.017
  11. Wolf, S. and Tauber, R. N., Silicon Processing for the VLSI Era Volume 1-Process Technology, 2nd ed., Lattice Press, Sunset Beach, CA(2000)
  12. Chang, S. Y., Wan, C. C., Wang, Y. Y., Shih, C. H., Tsai, M. H., Shue, S. L., Yu, C. H. and Liang, M. S., 'Characterization of Pd-Free Electroless Co-Based Cap Selectively Deposited on Cu Surface via Borane-Based Reducing Agent,' Thin Solid Films, 515(3), 1107-1111(2006) https://doi.org/10.1016/j.tsf.2006.07.044
  13. Sverdlov, Y. and Shacham-Diamand, Y., 'Electroless Deposition of Co(W) Thin Films,' Microelec. Eng., 70, 512-518(2003) https://doi.org/10.1016/S0167-9317(03)00459-3
  14. Gambino, J., Wynne, J., Gill, J., Mongeon, S., Meatyard, D., Lee B., Bamnolker, H., Hall, L., Li, N., Hernandez, M., Little, P., Hamed, M., Ivanov, I. and Gan, C. L., 'Self-aligned Metal Capping Layers for Copper Interconnects Using Electroless Plating,' Microelec. Eng., 83, 2059-2067(2006) https://doi.org/10.1016/j.mee.2006.09.008
  15. Cotton, F. A., Wilkinson, G. and Gaus, P. L., Advanced Inorganic Chemistry: A Comprehensive Text, 4th ed., John Wiley, John Wiley & Sons, Inc., New York, NY(1980)
  16. Antonelli, S. B., Allen, T. L., Johnson, D. C. and Dubin, V. M., 'Crystallization Behavior of Ni-P Alloy Films on Co and Cu Seed Layers,' J. Electrochem. Soc., 152(9), J120-J124(2005) https://doi.org/10.1149/1.1997175