Search / Korean Journal of Chemical Engineering
Korean Chemical Engineering Research,
Vol.47, No.2, 141-149, 2009
구리 및 은 금속 배선을 위한 전기화학적 공정
Electrochemical Metallization Processes for Copper and Silver Metal Interconnection
초고속 연산용 CMOS(complementary Metal Oxide Semiconductor) 배선재료로 사용되고 있는 구리(Cu)가, 기가급 메모리 소자용 금속 배선 물질에도 사용이 시작되면서 구리 박막에 대한 재료 및 공정이 새로운 조명을 받고 있다. 반도체 금속 배선에 사용하는 수 nm 두께의 구리 박막의 형성에 전해도금(electrodeposition)과 무전해 도금(electroless deposition) 같은 전기화학적 방법을 이용하게 되어서 표면 처리, 전해액 조성과 같은 중요한 요소에 대한 최신 연구 동향을 요약하였다. 구리 박막에서 구리 배선을 제작하여야 하므로 새로운 패턴 기술인 상감기법이 도입되어, 구리도금과 상감기법과의 공정 일치성 관점에서 전해도금과 무전해 도금의 요소 기술에 대해 기술하였다. 구리보다 비저항이 낮아 차세대 소자용 배선에 있어서 적용이 예상되는 은(Ag)을 전기화학적 방법으로 금속 배선에 적용하는 최신 연구에 대하여도 소개하였다.
The Cu thin film material and process, which have been already used for metallization of CMOS(Complementary Metal Oxide Semiconductor), has been highlighted as the Cu metallization is introduced to the metallization process for giga - level memory devices. The recent progresses in the development of key elements in electrochemical processes like surface pretreatment or electrolyte composition are summarized in the paper, because the semiconductor metallization by electrochemical processes such as electrodeposition and electroless deposition controls the thickness of Cu film in a few nm scales. The technologies in electrodeposition and electroless deposition are described in the viewpoint of process compatibility between copper electrodeposition and damascene process, because a Cu metal line is fabricated from the Cu thin film. Silver metallization, which may be expected to be the next generation metallization material due to its lowest resistivity, is also introduced with its electrochemical fabrication methods.
[References]
  1. Ryan JG, Geffken RM, Poulin NR, Paraszczak JR, IBM J. Res. Dev., 39, 371, 1995
  2. Murarka SP, Hymes SW, Crit. Rev. Solid State, 20, 87, 1995
  3. Manepalli R, Stepniak F, Bidsturp-Allen SA, Kohl PA, IEEE Trans. Adv. Packag., 22, 4, 1999
  4. Alford TL, Zeng Y, Nguyen P, Chen L, Mayer JW, Microelectron. Eng., 55, 389, 2001
  5. Ahn EJ, Kim JJ, Electrochem. Solid State Lett., 7(10), C118, 2004
  6. Moffat TP, Baker B, Wheeler D, Bonevich JE, Edelstein M, Kelly DR, Gan L, Stafford GR, Chen PJ, Egelhoff WF, Josell D, J. Electrochem. Soc., 149(8), C423, 2002
  7. Datta M, Landolt D, Electrochim. Acta, 45(15-16), 2535, 2000
  8. Paunovic M, Schlesinger M, Fundamentals of Electrochemical Deposition, John Wiley & Sons Inc., New York, 1998
  9. Takahashi KM, Gross ME, J. Electrochem. Soc., 146(12), 4499, 1999
  10. Gomma GK, Mater. Chem. Phys., 56, 27, 1998
  11. Santos JR, Mattoso LHC, Motheo AJ, Electrochim. Acta, 43(3-4), 309, 1998
  12. Truman JE, Shreir LL, Corrosion: Metal/Environment, Vol. 1, Boston, 1976
  13. Farndon EE, Walsh FC, Campbell SA, J. Appl. Electrochem., 25(6), 574, 1995
  14. Sutter EMM, Ammeloot F, Pouet MJ, Fiaud C, Couffignal R, Corr. Sci., 41, 105, 1999
  15. Brusic V, Frisch MA, Eldridge BN, Novak FP, Kaufman FB, Rush BM, Frankel GS, J Electrochem. Soc., 138, 2253, 1991
  16. Kim YS, Kim SK, Kim JJ, Proceeding of VMIC conference, September, Santa Clara, 2001
  17. Kim JJ, Kim SK, Kim YS, J. Electroanal. Chem., 542, 61, 2003
  18. Kim SK, Kim JJ, Electrochem. Solid State Lett., 7(9), C98, 2004
  19. Frank A, Bard AJ, J. Electrochem. Soc., 150(4), C244, 2003
  20. Josell D, Baker B, Witt C, Wheeler D, Moffat TP, J. Electrochem. Soc., 149(12), C637, 2002
  21. Josell D, Wheeler D, Huber WH, Bonevich JE, Moffat TP, J. Electrochem. Soc., 148(12), C767, 2001
  22. Moffat TP, Wheeler D, Huber WH, Josell D, Electrochem. Solid State Lett., 4(4), C26, 2001
  23. Moffat TP, Wheeler D, Witt C, Josell D, Electrochem. Solid State Lett., 5(12), C110, 2002
  24. Josell D, Wheeler D, Huber WH, Moffat TP, Phys. Rev. Lett., 87, 016102, 2001
  25. West AC, Mayer S, Reid J, Electrochem. Solid State Lett., 4(7), C50, 2001
  26. Moffat TP, Wheeler D, Edelstein MD, Josell D, IBM J. Res. & Dev., 49, 19, 2005
  27. Josell D, Wheeler D, Moffat TP, Electrochem. Solid State Lett., 5(4), C49, 2002
  28. Dubin V, Hong K, Baxter N, “Electroplating Bath Composition,” US Patent, 6,491,806, 2002
  29. Bernards RF, Fisher G, Sonnenberg W, Cerwonka EJ, Fisher S, “Additive for Acid-copper Electroplating Baths to Increase Throwing Power,” US Patent, 5,051,154, 1991
  30. Tabakovic I, Riemer S, Inturi V, Jallen P, Thayer A, J. Electrochem. Soc., 147(1), 219, 2000
  31. Cho SK, Kim SK, Kim JJ, J. Electrochem. Soc., 152(5), C330, 2005
  32. Hau-Riege SP, Thompson CV, Appl. Phys. Lett., 76, 309, 2000
  33. Kim SK, Kim JJ, Electrochem. Solid-State Lett., C101, 2004
  34. Xia Y, Kim E, Mrksich M, Whitesides GM, Chem. Mater., 8, 601, 1996
  35. Xia Y, Zhao XM, Whitesides GM, Microelectron. Eng., 32, 255, 1996
  36. Cha SH, Kim SS, Cho SK, Kim JJ, Electrochem. Solid State Lett., 8(11), C170, 2005
  37. Cha SH, Kim SS, Cho SK, Kim JJ, Electrochem. Solid State Lett., 10(2), D22, 2007
  38. Ueno K, Ritzdorf T, Grace S, J. Appl. Phys., 86, 4930, 1999
  39. Hara T, Kamijima S, Shimura Y, Electrochem. Solid State Lett., 6(1), C8, 2003
  40. Kim JJ, Kim SK, Lee CH, Kim YS, J. Vac. Sci. Technol. B, 21(1), 33, 2003
  41. Webb E, Sukamto J, Andryushchenko T, Danek M, Klawuhn E, Rozbicki R, Alers G, Suwwan de Felipee T, Bhaskaran V, Frank A, Pfeifer K, Reid J, “Comparison of Options for Sub 0.10 Micron Generation Damascene Copper Feature Fill,” in Proceedings of the 18th VLSI Multilevel Interconnection Conference, September, Santa Clara, 2001
  42. Kim JJ, Kim SK, Kim YS, J. Electrochem. Soc., 151(1), C97, 2004
  43. Oskam G, Vereecken PM, Searson PC, J. Electrochem. Soc., 146(4), 1436, 1999
  44. Han H, Kim JJ, Yoon DY, J. Vac. Sci. Technol. A, 22(4), 1120, 2004
  45. Kim JJ, Kim SK, Kim YS, Jpn. J. Appl. Phys., Part 2, 42, L1080, 2003
  46. Chyan O, Arunagiri TN, Ponnuswamy T, J. Electrochem. Soc., 150(5), C347, 2003
  47. Josell D, Wheeler D, Witt C, Moffat TP, Electrochem. Solid State Lett., 6(10), C143, 2003
  48. Radisic A, Long JG, Hoffmann PM, Searson PC, J. Electrochem. Soc., 148(1), C41, 2001
  49. Graham L, Steinbruchel C, Duquette DJ, J. Electrochem. Soc., 149(8), C390, 2002
  50. Kim JJ, Cha SH, Jpn. J. Appl. Phys. Part 1, 40, 7151, 2001
  51. Cho SK, Kim SK, Han H, Kim JJ, Oh SM, J. Vac. Sci. Technol. B, 22(6), 2649, 2004
  52. Moffat TP, Walker M, Chen PJ, Bonevich JE, Egelhoff WF, Richter L, Witt C, Aaltonen T, Ritala M, Leskela M, Josell D, J. Electrochem. Soc., 153(1), C37, 2006
  53. Josell D, Witt C, Moffat TP, Electrochem. Solid State Lett., 9(2), C41, 2006
  54. Josell D, Bonevich JE, Moffat TP, Aaltonen T, Ritala M, Leskela M, Electrochem. Solid State Lett., 9(2), C48, 2006
  55. Baker BC, Witt C, Wheeler D, Josell D, Moffat TP, Electrochem. Solid State Lett., 6(5), C67, 2003
  56. Josell D, Burkhard C, Li Y, Cheng YW, Keller RR, Witt CA, Kelley DR, Bonevich JE, Baker BC, Moffat TP, J. Appl. Phys., 96, 759, 2004
  57. Baker BC, Freeman M, Melnick B, Wheeler D, Josell D, Moffat TP, J. Electrochem. Soc., 150(2), C61, 2003
  58. Cho SK, Lee JK, Kim SK, Kim JJ, Electrochem. Solid State Lett., 10(10), D116, 2007
  59. Koo HC, Ahn EJ, Kim JJ, J. Electrochem. Soc., 155(1), D10, 2008
  60. Koo HC, Cho SK, Lee CH, Kim SK, Kwon OJ, Kim JJ, J. Electroche. Soc., 155, D389, 2008
  61. Chang SY, Hsu CJ, Fang RH, Lin SJ, J. Electrochem. Soc., 150(9), C603, 2003
  62. Tseng WT, Lo CH, Lee SC, J. Electrochem. Soc., 148(5), C327, 2001
  63. Hsu HH, Teng CW, Lin SJ, Yeh JW, J. Electrochem. Soc., 149(3), C143, 2002
  64. Lee CH, Kim JJ, J. Vac. Sci. Technol. B, 23(2), 475, 2005
  65. Lee CH, Hwang S, Kim SC, Kim JJ, Electrochem. Solid State Lett., 9(10), C157, 2006
  66. Lee CH, Cha SH, Kim AR, Hong JH, Kim JJ, J. Electrochem. Soc., 154(3), D182, 2007
  67. Kim JJ, Cha SH, Lee YS, Jpn. J. Appl. Phys., 42, L953, 2003
  68. Lin JH, Hsieh WJ, Hsu JW, Liu XW, Chen US, Shih HC, J. Vac. Sci. Technol. B, 20(2), 561, 2002
  69. Hsu HH, Lin KH, Lin SJ, Yeh JW, J. Electrochem. Soc., 148(1), C47, 2001
  70. Shingubara S, Wang Z, Yaegashi O, Obata R, Sakaue H, Takahagi T, Tech. Dig. Int. Electron Devices Meet., 147, 2003
  71. Shingubara S, Wang ZL, Yaegashi O, Obata R, Sakaue H, Takahagi T, Electrochem. Solid State Lett., 7(6), C78, 2004
  72. Lee CH, Lee SC, Kim JJ, Electrochim. Acta, 50(16-17), 3563, 2005
  73. Lee CH, Lee SC, Kim JJ, Electrochem. Solid State Lett., 8(8), C110, 2005
  74. Lee CH, Cho SK, Kim JJ, Electrochem. Solid State Lett., 8(11), J27, 2005
  75. Lee CH, Kim AR, Kim SK, Koo HC, Cho SK, Kim JJ, Electrochem. Solid State Lett., 11(1), D18, 2008
  76. Norkus E, Vaskelis A, Jagminiene A, Tamasauskaite-Tamasiunaite L, J. Appl. Electrochem., 31(9), 1061, 2001
  77. Vaskelis A, Jagminiene A, Juskenas R, Matulionis E ,Norkus E, Surf. Coat. Technol., 82, 165, 1996
  78. Vaskelis A, Norkus E, Electrochim. Acta, 44(21-22), 3667, 1999
  79. Inberg A, Zhu L, Hirschberg G, Gladkikh A, Croitoru N, Shacham-Diamand Y, Gileadi E, J. Electrochem. Soc., 148(12), C784, 2001
  80. Inberg A, Shacham-Diamand Y, Rabinovich E, Golan G, Croitoru N, Thin Solid Films, 389(1-2), 213, 2001
  81. Shacham-Diamand Y, Inberg A, Sverdlov Y, Croitoru N, J. Electrochem. Soc., 147(9), 3345, 2000
  82. ten Kortenaar MV, de Goeij JJM, Kolar ZI, Frens G, Lusse PJ, Zuiddam MR, van der Drift E, J. Electrochem. Soc., 148(1), C28, 2001
  83. Cha SH, Koo HC, Kim JJ, J. Electrochem. Soc., 152(6), C388, 2005