臺灣博碩士論文加值系統

在乾式離子蝕刻機反應真空腔所使用的基材為鋁合金6061，經硫酸陽極處理之後封孔而成。長時間處於蝕刻電漿的氣氛下，對鋁基材與氧化鋁膜產生破壞。本實驗是使用SEM和EPMA分析。結果顯示在乾式離子蝕刻機真空腔所使用鋁陽極處理膜的主要破壞基本原因是含氟、氯元素的電漿氣氛與位於鋁陽極處理膜下方點缺陷基地裡的鋁基材反應而形成AlF3或是AlCl3。這些點缺陷基地是在陽極處理層上的瑕疵是由析出物和空孔造成的，如:Mg、Si。由於每個析出物的不同的膨脹係數造成裂隙。或是不同的陽極處理製程技術在氧化鋁膜生成時會造成體積的收縮形成裂隙，電漿氣氛很容易透過此裂隙造成損壞。此外鋁合金6061中因氟氣份下的電漿轟擊使得上述這些點缺陷成為高能態基地。這些點缺陷，如: Mg、Si會與氟分別形成MgF2和SiF4。在陽極處理膜下形成的MgF2層為一安定的化合物，對氧化鋁有一定的保護作用。MgF2層的形成完全依靠Mg在鋁合金6061中的擴散到氧化鋁界面的速度和分佈量的多寡來決定。但MgF2層一旦形成，會在MgF2層下形成鎂的空乏區，同時氟原子會與基板的Al反應形成AlF3。另外SiF4具揮發性對氧化鋁膜有推擠作用，結果在陽極處理膜中造成應力最後導致在陽極處理膜中細分數層造成破壞。另外若反應真空腔暴露在大氣之下，與氯電漿氣氛反應而形成的AlCl3，會與空氣中的水分子結合形成HCl，產生循環式的腐蝕。

目錄
第一章 前言…………………………………………………………………...1
第二章 重要資料及文獻回顧………………………………………………...3
2-1多孔性鋁陽極處理膜………………………………………………….3
2-2鋁陽極處理膜之機構………………………………………………….3
2-2.1孔核形成…………………………………………………………4
2-2.2穩態成長…………………………………………………………6
2-2.3規則排列的氧化鋁孔洞…………………………………………7
2-2.4鋁陽極處理的條件………………………………………………8
2-3鋁陽極處理之類別…………………………………………………...10
2-4鋁陽極處理之封孔程序……………………………………………...12
2-5電漿簡介……………………………………………………………...14
2-5.1電漿原理………………………………………………………..14
2-5.2 DC電漿電位……………………………………………………18
2-5.3 AC電漿電位……………………………………………………21
2-6電漿的應用…………………………………………………………...26
2-7電漿損壞……………………………………………………………...28
2-7.1離子轟擊………………………………………………………..28
2-7.2電漿表面交互作用……………………………………………..29
2-7.3離子和電子所誘發的化學反應………………………………..30
2-7.4電漿誘發的損壞………………………………………………..30
第三章 實驗流程及破損分析……………………………………………….31
3-1實驗流程簡圖………………………………………………………...31
3-2實驗步驟……………………………………………………………...32
3-3分析儀器及其量測原理……………………………………………...32
3-3.1電子探測光顯微分析（EPMA）………………………………...32
3-3.2場發射電子顯微鏡（FEG-SEM）……………………………….34
3-3.3 X光繞射(XRD)………………………………………………...36
3-4真空腔機室內殼……………………………………………………...37
3-5試片表面SEM觀察…………………………………………………..39
3-6試片截面SEM觀察…………………………………………………..44
3-7 EPMA之定量及定性分析…………………………………………...49
3-8 EPMA x-ray mappings之top-view…………………………………..50
3-9 EPMA x-ray mappings之cross-section………………………………62
3-10 X-ray的繞射分析…………………………………………………...76
第四章 加速模擬電漿損壞試驗…………………………………………….78
4-1實驗目的……………………………………………………………...78
4-2實驗步驟……………………………………………………………...78
4-2.1實驗流程圖……………………………………………………..79
4-3加速模擬電漿系統…………………………………………………...80
4-4結果與討論…………………………………………………………...82
4-4.1表面分析………………………………………………………..82
4-4.2 EPMA元素分析………………………………………………..87
第五章 數據分析與討論…………………………………………………….90
5-1結果討論……………………………………………………………...90
5-2鋁合金陽極處理破損機制圖示……………………………………...93
5-2.1氧化鋁膜本身的缺陷…………………………………………..93
5-2.2陽極處理膜Si之析出物………………………………………..95
5-2.3陽極處理膜Mg之析出物………………………………………96
5-2.4循環性的腐蝕…………………………………………………..97
第六章 結論………………………………………………………………….99
參考文獻……………………………………………………………………...100

1. 尤光先，民國86年，鋁的陽極處理技術，徐氏基金會。
2. 小久保定次郎，民國71年，鋁的表面處理，復漢出版社。
3. 永田伊佐也，民國74年，鋁箔乾式電解電容器，日本蓄電器工業株式會社。
4. 莊達人，民國86年，VLSI製造技術，高立圖書有限公司。
5. Srihari Ponnekanti, Laxman Murugesh, and Eric Hanson. J. Vac. Sci. Technol. A 14(3), May/Jun 1996 .
6. X. Atkinson, Surf. Finishing, 528 July (1983).
7. J. N. Panitz and M. Carr, Sandia National Laboratory Report (1992).
8. H. I. Ono and N. Masuko, J. Electrochem. Soc. 138, 3705 (1991).
9. C. Lea and C. Molinari, J. Mater. Sci. 19, 2336 (1984).
10. G.E. Thompson. Thin Solid Films 297 (1997) 192-201.
11. Hideki Masuda and Fumio Hasegwa. J. Electrochem. Soc. Vol. 144, No. 5, May 1997.
12. See, for example, P. M. Asbeck, M.-C. F. Chang, K. C. Wang, and D. L. Miller, in introduction to Semiconductor Technology: GaAs and Related Compounds, edited by C. T. Wang(Wiley-Interscience, New York, 1990),Chap. 4.
13. K. Honjo, Solid-State Electron. 38, 1569 (1995).
14. P. M. Asbeck, Solid-State Electron 38, 1691 (1995).
15. S. Tanaka, H. Hayama, A. Furukawa. T. Baba, M. Muzuta. and H. Honjo. Electron. Lett. 26. 1439 (1990).
16. H. F.Chau, W. Liu, and E. A. Beam Ⅲ. Proceedings of the 7th International Conference on InP and Related Materials (IEEE. New York, 1995).
17. E. A. Beam Ⅲ, B. Brar, T. P. E. Broekaert, H. F. Chan. W. Liu. and A. C. Seabaugh, Mater. Res. Soc. Symp. Proc. 421, 3 (1996).
18. T. R. Fullowan, S. J. Pearton, R. F. Kopf, and R. P. Smith, J. Vac. Sci. Technol. B9, 1445 (1991).
19. M. Hafizi and W. E. Stanchina, in InP HBTs: Growth, Processing, and Applications, edited by B. Jalai and S. J. Pearton (Artech House, Boston, 1994), Chap. 5.
20. S. Thomas Ⅲ, K. K. Ko, and S. W. Pang , J. Vac. Sci. Technol. A 13, 894 (1995).
21. High Density Plasma Sources, edited by O. A. Popov (Noyes, Park Ridge, NJ, 1996).
22. C. R. Abernathy, Mater. Sci. Eng. R. Rep. 14, 203 (1995).
23. F. Ren, C. R. Abernathy, S. J. Pearton, T. R. Fullowan, J. R.Lothian, P. Wisk, Y. K. Chen, W. S. Hobson, and P. R. Smith, Electron. Lett. 27, 2391 (1991).
24. S. J. Peatron, Mater. Sci. Eng. R. Rep. 4, 313 (1990).
25. E. L. Hu, C.—H. Chen, and D. L. Green, J. Vac. Sci. Techenol. B 14, 3632 (1996).
26. S. Murad, M. Rahman, N. Johnson, S. Thomas, S. P. Beaumont, and C. D. W. Wilkinson, J. Vac. Sci. Technol. B 14, 3658 (1996).
27. See, for example, G. A. Prinz, in Ultra-Magnetic StructureⅡ, edited by B. Heinrich and J. A. C. Bland (Springer, Berlin, 1994).
28. M. J. Vasile and C. J. Mogab J. Vac Sci Technol A 4, 1841 (1986).
29. K. Kinoshita K. Yamada, and H. Matutera, IEEE Trans. Magn. 27, 4888 (1991).
30. R. A. Morgan, Plasma Etching in Semiconductor Fabrications (Elsevier, Amsterdam, 1985).
31. D. S. Fischl and D. W. Hess, J. Vac. Sci. Technol. B 6, 1577 (1988).
32. M. Balooch, D. S. Fischl, D. R. Olander, and W. J. Siekhaus, J. Electrochem. Soc. 135, 2090 (1998).
33. H. Gokan and S. Eho. J. Vac. Sci. Technol. 18, 23 (1981).
34. See, for example, Physics Today April 1995, edited by G. A. Prinz and K. Hathaway.
35. S. J. Pearton , T. Nakano, and R. A. Gottscho, J. Appl. Phys. 69, 4206 (1991).
36. R. J. Davis and E. D. Wolf, Vac. Sci. Technol. B 8, 1798 (1990).
37. M. A. Lieberman and A. J. Lichtenburg, Principles of Plasma Discharge and Materials Processing (Wiley, New York, 1994).
38. R. J. Shul, M. L. Lovejoy, D. L. Hetherington, D. J. Rieger, J. F. Klem, and M. R. Melloch, J. Vac. Sci. Technol. B 13, 27 (1995).
39. G. S. Oehrlem, Y. Zheng, D. Vender, and O. Joubert, J. Vac. Sci. Technol. A 12, 323 (1994).
40. J. W. Lee, J. Hong, and S. J. Pearton, Appl. Phys. Lett. 68, 847 (1996).
41. M. Vernon, T. R. Hayes, and V. M. Donnelly, J. Vac. Sci. Technol. B 10, 3499 (1992).
42. D. G. Lishan and E. L. Hu, Appl. Phys. Lett. 56, 1667 (1990).
43. C. Youtsey, R. Grundbacher, R. Pannepucci, I. Adesida, and C. Caneau, J. Vac. Sci. Technol. B 12, 3317 (1994).
44. D. A. Danner, M. Dalvie, and D. W. Hess, J. Electrochem. Soc. 134, 669 (1987).
45. J. Mau, J. Vac. Sci. Technol. B 6, 652 (1987).
46. M. Bhatnager, and B. J. Baliga, IEEE Trans. Electron Device Lett. ED-40, 645 (1993).
47. J. R. Flemish, Proceedings of the Symposium on Wide Band Gap Semiconductors and Device, edited by F. Ren (Electrochemical Society, Pennington, NJ, 1995), Vol. 10, pp. 231-235.
48. J. S. Shor, R. A. Weber, L. G. Provost, D. Goldstein, and A. D. Kurtz, J. Electrochem. Soc. 141, 579 (1994).
49. N. Lundberg and M. Ostling, Solid State Electron. 38. 2023 (1995).
50. J. A. Powell, D. J. Larkin, L. G. Matus, W. J. Choyke, J. L. Bradshaw, L. Hendersson, M. Yoganthan, J. Yang, and P. Pirouz, J. Appl. Phys. 76, 1363 (1994).
51. H. Morkoc, S. Strite, G. B. Bao, M. E. Lin, B. Sverdlov, and M. Burns J. Appl. Phys. 76 1363 (1994).
52. Y. Wang, W. Xie, J. A.Cooper, Jr., M. R. Melloch, and J. W. Palmour, Technical Digest of International Conference on SiC and Related Materials, Kyoto, Japan, Sept. 1995, pp. 591-592.
53. S. Tanaka, R. S. Kern, and R. F. Davis, Appl. Phys. Lett. 66, 37 (1995)
54. A. J. Steckl, P. H. Yih, Appl. Phys. Lett. 60, 1966 (1992).
55. P. H. Yih, A. J. Steckl, J. Electrochem. Soc. 140, 1813 (1993).
56. J. W. Palmour, R. F. Davis, T. M. Wallett, and K. B. Bhasin, J. Vac. Sci. Technol. A 4, 590 (1986).
57. J. B. Casady, E. D. Luckowski, M. Bozack, D. Sheridan, R. W. Johnson, and J. R. Williams, Technical Digest of International Conference on SiC and Related Materials, Kyoto, Japan, Sept. 1995, pp. 382-383.
58. J. R. Flemish, K. Xie, and J. H. Zhao, Appl. Phys. Lett. 64, 2315 (1994).
59. J. R. Flemish, K. Xie, W. Buchwald, L. Casas, J. H. Zhao, G. McLane, and M. Dubey, Mater. Res. Soc. Symp. Proc. 339, 145 (1994).
60. S. J. Pearton, J. W. Lee, J. D. MacKenzie, C. R. Abernathy, and R. J. Shul, Appl. Phys. Lett. 67, 2329 (1995).
61. J. W. Lee, S. J. Pearton, C. R. Abernathy, W. S. Hobson, and F. Ren, Appl. Phys. Lett. 67, 3129 (1995).
62. S. J. Pearton, Mater. Sci. Rep. 4, 313 (1990).
63. N. Tsuya, T. Tokushima, M. Shiraki, IEEE TRANSACTIONS ON MAGNETICS, VOL. MAG-22, No. 5, September 1986, p1140.
64. S. Iwasaki, Y. Nakamura & K. Ouchi, IEEE TRANSACTIONS ON MAGNETICS, VOL. MAG-15, No. 6, November 1979, p1456.
65. M. Shiraki, Y. Wakui, T. Tokushima, and N. Tsuya, IEEE TRANSACTIONS ON MAGNETICS, VOL. MAG-21, No 15, September 1985, p1465.
66. G. E. Thompson, Nature Vol.272, 30 March 1978,433.
67. L. Young, Anodic Oxide Films, Academic Press New York, 1971.
68. J. P. S. Pringle, J. Electrochem. Soc. 119, 1972, p482.
69. G. E. Thompson, J. Appl. Electrochem. 15, 1985, p781.
70. G. E. Thompson, Thin Solid Films, 297, 1997, p192.
71. Y. Xu, Ph.D. Thesis, University of Manchester, 1983.
72. Hideki Masuda and Fumio Hasegwa, J. Electronchem. Soc, Vol. 144, No.5, May. 1997, L127.
73. L. Zhang, H. S. Cho, J. Materials Science Letters, 17, 1998, p291.
74. H. Masuda, K. Fukuda, Science 268, 1995, p1466.
75. O. Jessensky, F. Muller, U. Gosele, Applied Physics Letter, Vol. 72, No.10 1998, p1173.
76. A. A. Mazhar, F. El-Taib Heakal, Kh.M. Awad, Thin Solid Film, 192, 1990, p193.
77. S. Ping Lee, Nucl. Sci. J, Vol.15, p235-244, Dec. 1978.
78. R. C. Furneaux, W. R. Rigby & A. P. Davidson, Nature Vol. 337, 12, January 1989.
79. J. L. Vossen and W. Kern, Thin Film Process, PartⅡ, Academic Press, 1978.
80. E. Nasser, Fundamentals of Gaseous Ionization and Plasma Electronics, Wiely Interscience,1971.
81. K. Kohler, et al., J. Applied Physics, Vol. 57, 1985, p59.
82. H. S. Butler and G. S. Kino, Physics Fluids, Vo. 6, 1963, p1346.