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Received February 6, 2009
Accepted February 27, 2009
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구리 및 은 금속 배선을 위한 전기화학적 공정
Electrochemical Metallization Processes for Copper and Silver Metal Interconnection
인천대학교 기계공학과, 402-749 인천시 남구 인천대길 319 1서울대학교 화학생물공학부, 151-742 서울시 관악구 신림동 산 56-1
Department of Mechanical Engineering, University of Incheon, 319 Incheondaegil, Nam-gu, Incheon 402-749, Korea 1School of Chemical and Biological Engineering, Seoul National University, San 56-1, Sillim-dong, Kwanak-gu, Seoul 151-742, Korea
jjkimm@snu.ac.kr
Korean Chemical Engineering Research, April 2009, 47(2), 141-149(9), NONE Epub 6 May 2009
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Abstract
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_x000D_
material due to its lowest resistivity, is also introduced with its electrochemical fabrication methods.
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Alford TL, Zeng Y, Nguyen P, Chen L, Mayer JW, Microelectron. Eng., 55, 389 (2001)
Ahn EJ, Kim JJ, Electrochem. Solid State Lett., 7(10), C118 (2004)
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)
Datta M, Landolt D, Electrochim. Acta, 45(15-16), 2535 (2000)
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Gomma GK, Mater. Chem. Phys., 56, 27 (1998)
Santos JR, Mattoso LHC, Motheo AJ, Electrochim. Acta, 43(3-4), 309 (1998)
Truman JE, Shreir LL, Corrosion: Metal/Environment, Vol. 1, Boston (1976)
Farndon EE, Walsh FC, Campbell SA, J. Appl. Electrochem., 25(6), 574 (1995)
Sutter EMM, Ammeloot F, Pouet MJ, Fiaud C, Couffignal R, Corr. Sci., 41, 105 (1999)
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Kim YS, Kim SK, Kim JJ, Proceeding of VMIC conference, September, Santa Clara (2001)
Kim JJ, Kim SK, Kim YS, J. Electroanal. Chem., 542, 61 (2003)
Kim SK, Kim JJ, Electrochem. Solid State Lett., 7(9), C98 (2004)
Frank A, Bard AJ, J. Electrochem. Soc., 150(4), C244 (2003)
Josell D, Baker B, Witt C, Wheeler D, Moffat TP, J. Electrochem. Soc., 149(12), C637 (2002)
Josell D, Wheeler D, Huber WH, Bonevich JE, Moffat TP, J. Electrochem. Soc., 148(12), C767 (2001)
Moffat TP, Wheeler D, Huber WH, Josell D, Electrochem. Solid State Lett., 4(4), C26 (2001)
Moffat TP, Wheeler D, Witt C, Josell D, Electrochem. Solid State Lett., 5(12), C110 (2002)
Josell D, Wheeler D, Huber WH, Moffat TP, Phys. Rev. Lett., 87, 016102 (2001)
West AC, Mayer S, Reid J, Electrochem. Solid State Lett., 4(7), C50 (2001)
Moffat TP, Wheeler D, Edelstein MD, Josell D, IBM J. Res. & Dev., 49, 19 (2005)
Josell D, Wheeler D, Moffat TP, Electrochem. Solid State Lett., 5(4), C49 (2002)
Dubin V, Hong K, Baxter N, “Electroplating Bath Composition,” US Patent, 6,491,806 (2002)
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)
Tabakovic I, Riemer S, Inturi V, Jallen P, Thayer A, J. Electrochem. Soc., 147(1), 219 (2000)
Cho SK, Kim SK, Kim JJ, J. Electrochem. Soc., 152(5), C330 (2005)
Hau-Riege SP, Thompson CV, Appl. Phys. Lett., 76, 309 (2000)
Kim SK, Kim JJ, Electrochem. Solid-State Lett., C101 (2004)
Xia Y, Kim E, Mrksich M, Whitesides GM, Chem. Mater., 8, 601 (1996)
Xia Y, Zhao XM, Whitesides GM, Microelectron. Eng., 32, 255 (1996)
Cha SH, Kim SS, Cho SK, Kim JJ, Electrochem. Solid State Lett., 8(11), C170 (2005)
Cha SH, Kim SS, Cho SK, Kim JJ, Electrochem. Solid State Lett., 10(2), D22 (2007)
Ueno K, Ritzdorf T, Grace S, J. Appl. Phys., 86, 4930 (1999)
Hara T, Kamijima S, Shimura Y, Electrochem. Solid State Lett., 6(1), C8 (2003)
Kim JJ, Kim SK, Lee CH, Kim YS, J. Vac. Sci. Technol. B, 21(1), 33 (2003)
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)
Kim JJ, Kim SK, Kim YS, J. Electrochem. Soc., 151(1), C97 (2004)
Oskam G, Vereecken PM, Searson PC, J. Electrochem. Soc., 146(4), 1436 (1999)
Han H, Kim JJ, Yoon DY, J. Vac. Sci. Technol. A, 22(4), 1120 (2004)
Kim JJ, Kim SK, Kim YS, Jpn. J. Appl. Phys., Part 2, 42, L1080 (2003)
Chyan O, Arunagiri TN, Ponnuswamy T, J. Electrochem. Soc., 150(5), C347 (2003)
Josell D, Wheeler D, Witt C, Moffat TP, Electrochem. Solid State Lett., 6(10), C143 (2003)
Radisic A, Long JG, Hoffmann PM, Searson PC, J. Electrochem. Soc., 148(1), C41 (2001)
Graham L, Steinbruchel C, Duquette DJ, J. Electrochem. Soc., 149(8), C390 (2002)
Kim JJ, Cha SH, Jpn. J. Appl. Phys. Part 1, 40, 7151 (2001)
Cho SK, Kim SK, Han H, Kim JJ, Oh SM, J. Vac. Sci. Technol. B, 22(6), 2649 (2004)
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)
Josell D, Witt C, Moffat TP, Electrochem. Solid State Lett., 9(2), C41 (2006)
Josell D, Bonevich JE, Moffat TP, Aaltonen T, Ritala M, Leskela M, Electrochem. Solid State Lett., 9(2), C48 (2006)
Baker BC, Witt C, Wheeler D, Josell D, Moffat TP, Electrochem. Solid State Lett., 6(5), C67 (2003)
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)
Baker BC, Freeman M, Melnick B, Wheeler D, Josell D, Moffat TP, J. Electrochem. Soc., 150(2), C61 (2003)
Cho SK, Lee JK, Kim SK, Kim JJ, Electrochem. Solid State Lett., 10(10), D116 (2007)
Koo HC, Ahn EJ, Kim JJ, J. Electrochem. Soc., 155(1), D10 (2008)
Koo HC, Cho SK, Lee CH, Kim SK, Kwon OJ, Kim JJ, J. Electroche. Soc., 155, D389 (2008)
Chang SY, Hsu CJ, Fang RH, Lin SJ, J. Electrochem. Soc., 150(9), C603 (2003)
Tseng WT, Lo CH, Lee SC, J. Electrochem. Soc., 148(5), C327 (2001)
Hsu HH, Teng CW, Lin SJ, Yeh JW, J. Electrochem. Soc., 149(3), C143 (2002)
Lee CH, Kim JJ, J. Vac. Sci. Technol. B, 23(2), 475 (2005)
Lee CH, Hwang S, Kim SC, Kim JJ, Electrochem. Solid State Lett., 9(10), C157 (2006)
Lee CH, Cha SH, Kim AR, Hong JH, Kim JJ, J. Electrochem. Soc., 154(3), D182 (2007)
Kim JJ, Cha SH, Lee YS, Jpn. J. Appl. Phys., 42, L953 (2003)
Lin JH, Hsieh WJ, Hsu JW, Liu XW, Chen US, Shih HC, J. Vac. Sci. Technol. B, 20(2), 561 (2002)
Hsu HH, Lin KH, Lin SJ, Yeh JW, J. Electrochem. Soc., 148(1), C47 (2001)
Shingubara S, Wang Z, Yaegashi O, Obata R, Sakaue H, Takahagi T, Tech. Dig. Int. Electron Devices Meet., 147 (2003)
Shingubara S, Wang ZL, Yaegashi O, Obata R, Sakaue H, Takahagi T, Electrochem. Solid State Lett., 7(6), C78 (2004)
Lee CH, Lee SC, Kim JJ, Electrochim. Acta, 50(16-17), 3563 (2005)
Lee CH, Lee SC, Kim JJ, Electrochem. Solid State Lett., 8(8), C110 (2005)
Lee CH, Cho SK, Kim JJ, Electrochem. Solid State Lett., 8(11), J27 (2005)
Lee CH, Kim AR, Kim SK, Koo HC, Cho SK, Kim JJ, Electrochem. Solid State Lett., 11(1), D18 (2008)
Norkus E, Vaskelis A, Jagminiene A, Tamasauskaite-Tamasiunaite L, J. Appl. Electrochem., 31(9), 1061 (2001)
Vaskelis A, Jagminiene A, Juskenas R, Matulionis E ,Norkus E, Surf. Coat. Technol., 82, 165 (1996)
Vaskelis A, Norkus E, Electrochim. Acta, 44(21-22), 3667 (1999)
Inberg A, Zhu L, Hirschberg G, Gladkikh A, Croitoru N, Shacham-Diamand Y, Gileadi E, J. Electrochem. Soc., 148(12), C784 (2001)
Inberg A, Shacham-Diamand Y, Rabinovich E, Golan G, Croitoru N, Thin Solid Films, 389(1-2), 213 (2001)
Shacham-Diamand Y, Inberg A, Sverdlov Y, Croitoru N, J. Electrochem. Soc., 147(9), 3345 (2000)
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)
Cha SH, Koo HC, Kim JJ, J. Electrochem. Soc., 152(6), C388 (2005)
