臺灣博碩士論文加值系統

本實驗以SEM、AFM、TEM研究無電鍍銅的成核與成長過程，無電鍍銅前處理採用置換活化與敏化活化兩種濕式活化法，使用的基材分別為Ta2N/SiO2/Si與TaN/SiO2/Si。
結果顯示，置換活化產生20-360 nm的Pd顆粒；無電鍍時，銅在具有催化能力的Pd顆粒上成核，而後靠銅的自我催化繼續成長銅膜。銅的成長初期是以約100-500 nm的島狀聚團分佈在基材上，每個聚團又是由很多形狀不規則約10-20 nm的小晶粒構成；隨著鍍著時間增加，銅聚團水平尺寸增加、合併相連，聚團之間的邊界逐漸模糊不可辨。繼續沉積則空隙部分逐漸填滿，銅由初期的島狀分佈歷經成核、成長、合併而彼此連接，消除銅顆粒間的邊界，逐漸形成平整的銅膜。晶粒的形狀也不再是以球形為主，而代之以多角形且有雙晶的晶粒；此現象是因為沉積過程中，鄰近的晶粒彼此競爭成長，導致晶粒成長，以降低表面能。
敏化活化法與置換活化法比較，敏化活化法形成的催化聚團較為細密均勻，可供後續無電鍍銅成長的成核點數量多，所以無電鍍銅可成長出連續而更為平整的銅膜。而置換活化法形成的催化位置粗大而稀疏，無電鍍銅成長慢，銅膜粗糙度也較大，但較利於觀察銅膜的成核與成長。

誌謝..........................................................................................................Ⅰ
摘要…………………………………………………………………..…Ⅱ
目錄……………………………………………………………………..Ⅲ
圖目錄………………………………………………………….……….Ⅵ
表目錄…………………………………………………………….…….Ⅹ
壹、前言…………………………………………………………………..1
貳、文獻回顧……………………………………………………………..3
2-1 擴散阻隔層…...……………………………….…………………….3
2-2 銅薄膜之沉積技術…...……………………………….…………….4
2-2-1 物理氣相沉積………………………………………………...4
2-2-2 化學氣相沉積………………………………………………...4
2-2-3 電鍍………………………………………………………...…5
2-2-4 無電鍍………………………………………………………...5
2-2-4-1 鈀錫膠體法……………………………………………8
2-2-4-2 敏化活化法…………………………………………...11
2-2-4-3 置換活化法…………………………………………...11
2-3 無電鍍銅之微結構及成長機制…………………………………...13
2-4 無電鍍銅溶液之組成與特性……………………………………...15
2-4-1 銅鹽………………………………………………………….15
2-4-2 錯化劑……………………………………………………….15
2-4-3 還原劑…………………………………………………….…16
2-4-4 安定劑……………………………………………………….18
2-4-5 pH調整劑……………………………………………………18
2-5 無電鍍銅之化學反應式…………………………………………...20
2-5-1 化學反應式[39]……………………………………………..20
2-5-2 無電鍍銅成長機制[32]……………………………………..20
2-6 研究目的…………………………………………………………...21
參、實驗步驟……………………………………………………………22
3-1 基材………………………………………………………………...22
3-2 置換活化法無電鍍銅……………………………………………22
3-3 敏化活化法無電鍍銅……………………………………………25
3-4 熱處理……………………………………………………………...25
3-5 無電鍍銅膜之微結構觀察………………………………………25
3-5-1 掃描式電子顯微鏡(SEM)分析…………………..……….25
3-5-2 原子力顯微鏡(AFM)分析…………………………….……25
3-5-3 穿透式電子顯微鏡(TEM)分析……………………………..28
肆、結果與討論…………………………………………………………29
4-1 擴散阻隔層………………………………………………………...29
4-1-1 拉塞福背向散射分析儀(Rutherford Backscattering Spectrometer, RBS)分析結果…………..………………….29
4-1-2 X光繞射分析結果……………………………………….….29
4-2 置換活化法無電鍍銅……………………………………………...32
4-2-1 置換活化處理…………………………………………….....32
4-2-2 置換活化法無電鍍銅……………………………………….33
4-2-2-1 SEM觀察……………………………………………...33
4-2-2-2 AFM分析……………………………………….…….38
4-2-2-3 TEM分析…………………………………………...…50
4-3 敏化活化法無電鍍銅……………………………………….……..63
4-3-1 敏化活化處理…………………………………………….…63
4-3-2 敏化活化法無電鍍銅晶種層及電鍍………………...……..68
伍、結論…………………………………………………………………71
陸、參考文獻……………………………………………………………73

1. R. A. Levy, M. L. Green, and P. K. Gallager, “Characterization of LPCVD Aluminum for VLSI Process,” J. Electrochem. Soc., 131 (1984) pp. 2175-2182.
2. 蔡明蒔, “半導體製程中銅電鍍技術之製程及設備,” 電子月刊, 4月號, (1999) pp. 155-160.
3. P. C. Andeicacos, C. Uaoh, J. O. Dukovic, J. Horkans, and H. Deligianni, “Damascene Copper Electro-Plating for Chip Interconnections,” IBM Journal of Research & Development, 42 (1998) pp. 567-570.
4. F. B. Kaufman and D. B. Thompson, “Chemical-Mechanical Polishing for Fabricating Patterned W Metal Feature as Chip Interconnects,” J. Electrochem. Soc., 138 (1991) pp.3460-3465.
5. Y. Morand, “Copper Metallization for Advanced IC: Requirements and Technological Solutions,” Microelectronic Engineering, 50 (2000) pp. 391-401.
6. A. Jain, A.V. Gelatos, T. T. Kodas, M. J. Hampden-Smith, R. Marsh, and C. J. Mogab, “Selective Chemical Vapor Deposition of Copper Using (hfac) Copper(I) Vinyltrimethylsilane in The Absence and Presence of Water,” Thin Solid Films, 262 (1995) pp. 52-59.
7. P. B. Ghate, “Metallization for Very-Large-Scale Integrated Icrcuits,” Thin Solid Films, 93 (1982) pp. 359-383.
8. X. Chen, G. G. Peterson, C. Goldberg, G. Nuesca, H. L. Frisch, B. Arkles, and J. Sullivan, “Low-Temperature Chemical Vapor Depoxition of Tantalum Nitride from Tantalum Pentabromide for Integrated Circuitry Copper Metallization Applications,” J. Mater. Res., 14 (1999) pp. 2043-2052.
9. S. Shibuki, H. Kanao, and T. Akahori, “Copper Film Formation Using Electron Cyclotron Resonance Plasma Sputtering and Reflow Method,” J. Vac. Sci. Technol. B, 15 (1997) pp. 60-65.
10. W. M. Kuschke, A. Kretschmann, R. M. Keller, R. P. Vinci, C. Kaufmann, and E. Arzt, “Textures of Thin Copper Films,” J. Mater. Res., 13 (1998) pp. 2962-2968.
11. J. H. Lee, K. J. Hwang, J. Y. Kim, C. G. Suk, and S. Y. Choi, “Effects of Hydrogen Plasma Pretreatment on Characteristics of Copper Film Deposited by Remote Plasma CVD Using (hfac)Cu(TMVS),” Thin Solid Films, 375 (2000) pp. 132-136.
12. P. J. Lin and M. C. Chen, Jpn. J. Appl. Phys., 38 (1999) pp. 4863.
13. R. Kröger, M. Eizenberg, D. Cong, N. Yoshida, L. Y. Chen, S. Ramaswami, and D. Carl, “Properties of Copper Films Prepared by Chemical Vapor Deposition for Advanced Metallization of Microelectronic Devices,” J. Electrochem. Soc., 146 (1999) pp. 3248-3254.
14. R. Kröger, M. Eizenberg, D. Cong, N. Yoshida, L. Y. Chen, and L. Chen, “Nucleation and Growth of CVD Cu Films,” Mat. Res. Soc. Symp. Proc. 564 (1999) pp. 237-241.
15. J. C. Hu, T. C. Chang, C. W. Wu, L. J. Chen, C. S. Hsiung, W. Y. Hsieh, W. Lur, and T. R. Yew, “Effects of a New Combination of Additives in Electroplating Solution on the Properties of Cu Films in ULSI Applications,” J. Vac. Sci. Technol. A, 18 (2000) pp. 1207-1210.
16. Y. Lantasov, R. Palmans, and K. Maex, “New Plating Bath for Electroless Copper Deposition on Sputtered Barrier Layers,” Microelect. Eng., 50 (2000) pp. 441-447.
17. A. Calusaru, Electrodeposition of Metal Powdwes, C. Laird, New York, (1979) pp. 122-343.
18. René Winand, “Electrodeposition of Metals and Alloys-New Results and Perspectives,” Electrochimica Acra, 39 (1994) pp. 1091-1105.
19. S. Nakahara, Y. Okinaka, “Microstructure and Ductility of Electroless Copper Deposits,” Acta metal., 31 (1983) pp. 713-724.
20. V. M. Dubin, Y. Shacham-Diamand, B. Zhao, P. K. Vasuder, and C. H. Ting, “Selective and Blanket Electroless Copper Deposition for Ultralarge Scale Integration,” J. Electrochem. Soc., 144 (1997) pp. 898-908.
21. M. J. Desilva and Y. S. Diamand, “A Novel Seed Layer Scheme to Protect Catalytic Surfaces for Electroless Deposition,” J. Electrochem. Soc., 143 (1996) pp. 3512-3516.
22. B. K. W. Baylis, A. Busuttil, N. E. Hedgecock, and M. Schlesinger, “Tin (Ⅳ) Chloride Solution as a Sensitizer in Photoselective Metal Deposition,” J. Electrochem. Soc., 123 (1976) pp. 348-351.
23. M. Froment, E. Queau, J. R. Martin, and G. Stremsdoerfer, “Structural and Analytical Characteristics of Adsorbed Pd-Sn Colloids,” J. Electrochem. Soc., 142 (1995) pp. 3373-3377.
24. H. H. Hsu, C. C. Hsie, M. H. Chen, S. J. Lin, and J. W. Yeh, “Displacement Activation of Tantalum Diffusion Barrier Layer for Electroless Copper Deposition,” J. Electrochem. Soc., 148 (2001) pp. C590-C598.
25. J. Kim, S. H. Wen, D. Y. Jung, R. W. Johnson, “Microstructure Evolution During Electroless Copper Deposition,” IBM J. Res. Develop., 28 (1984) pp. 697-710.
26. D. W. Parshley, M. J, Stowell, M. H. Jacobs, and T. J, Law, “The Growth and Structure of Gold and Silver Deposits Fromed by Evaporation Inside an Electron Microscope,” Phil. Mag. 4 (1964) pp. 127-158.
27. C. A. Neugebauer, Thin Film Technology, L, I, Maissel and R. Glang, Eds., McGraw-Hill Book Co., New York, (1970).
28. N. Feldstein and J. A. Weiner, “Surface Characterization of Sensitized and Activated Teflon,” J. Electrochem. Soc., 120 (1973) pp. 475-479.
29. Richard Sard, “The Nucleation, Growth, and Structure of Electroless Copper Deposits,” J. Electrochem. Soc., 117 (1970) pp. 864-870.
30. J. C. Patterson, C. Ni. Dheasuna, J. Barrett, T. R. Spalding, M. O’Reilly, X. Jiang, and G. M. Crean, “Electroless Copper Metallization of Titanium Nitride,” Appl. Surf. Sci., 91 (1995) pp. 124-128.
31. L. A. Nagahara, T. Ohmori, K. Hashimoto, and A. Fujishima, “Effects of HF Solution in the Electroless Deposition Process on Silicon Surface,” J. Vac. Sci. Technol. A, 11 (1993) pp. 763-767.
32. M. Schlesinger and M. Paunovic, Modern Electroplating, Fourth Edition, Wiley Interscience, New York, (2002) pp. 652-665.
33. J. Shu, B. P. A. Grandjean, and S. Kaliaguine, “Effect of Cu(OH)2 on Electroless Copper Plating,” Ind. Eng. Chem. Res., 36 (1997) pp. 1632-1636.
34. 方景禮, “電鍍添加劑總論,” 表面處理工業雜誌, 153期, 1995, pp. 137-167.
35. J. E. A. van den Meerakker, “On the Mechanism of Electroless Plating. Ⅱ. One Mechanism for Different Reductants,” J. Appl. Electrochem., 11 (1981) pp. 395-400.
36. J. E. A. van den Meerakker, “On the Mechanism of Electroless Plating. I. Oxidation of Formaldehyde at Different Electrode Surfaces,” J. Appl. Electrochem., 11 (1981) pp. 387-393.
37. 齊藤圈, “金屬表面技術,” 17期, 1966, pp.14-26.
38. M. Pounovic and R. Arndt, “The Effect of Some Additives on Electroless Copper Deposition,” J. Electrochem. Soc., 130 (1983) pp. 794-799.
39. R. M. Lukes, Plating, 51, (1964) pp. 1066-1073.
40. V. V. Svirdow, Byelorussian University, Minsk, Russia, “Electrolessly Deposited Diffusion Barriers for Microelectronics,” IBM J. Res. Develop., 42 (1998) pp. 607-620.
41. Kyung-Hoon Min, Kyu-Chang Chun, Ki-Bum Kim, “Comparative Study of Tantalum and Tantalum Nitrides (Ta2N and TaN) as a Diffusion Barrier for Cu Metallization,” J. Vac. Sci. Technol. B 14(5) (1996) pp. 3263-3269.
42. 蔡國強, “疊層阻障層鈦/氮化鈦及氮化鉭應用於銅金屬化及鋁金屬化之研究” 國立交通大學碩士論文, 1998年.
43. 鄧經緯, “濕式活化無電鍍銅技術在Ta(N)阻隔層上金屬化之研究,” 國立清華大學碩士論文, 2001年.
44. H. T. Ng, and S. F. Y. Li, “Sequential Observation of Electroless Copper Deposition via Noncontact Atomic Force Microscopy,” J. Electrochem. Soc., 145 (1998) pp. 3301-3307.
45. G. A. Jones and M. Aspland, “Some Aspects of the Growth and Structure of Electroless Deposited Films,” Physica status solidi (a) 11, (1972) pp. 637-644.
46. S. Nakahara, C. Y. Mak, and Y. Okinaka, “Effect of the Type of Substrates on the Ductility and Micreostructure of Electroless Copper Deposits,” J. Electrochem. Soc., 140 (1993) pp. 533-538.
47. S. Nakahara, Thin Solid Films, “Influence of Ion Implantation and Overlay Coatings on Various Physical Mechanical and Wear Properties of Stainless Steel, Titanium and Aluminium,” 64, (1970) pp. 191-203.
48. S. Nakahara, ibid., 64, 149 (1979).
49. J. Dumesic, J. A. Koutsky and T. W. Chapman, “The Rate of Electroless Copper Deposition by Formaldehyde Reduction,” J. Electrochem. Soc. 121 (1974) pp. 1405-1412.
50. 林志偉, “結合無電鍍銅與電鍍銅製備銅導線薄膜之研究,” 國立清華大學碩士論文, 2002年.
51. Hong-Hui Hsu, Ching-Wei Teng, Su-Jien Lin, and Jien-Wei Yeh, “Sn/Pd Catalyzation and Electroless Cu Deposition on TaN Diffusion Barrier Layers,” J. Electrochem. Soc. 149 (2002) pp. C143-C149.