臺灣博碩士論文加值系統

　　本實驗使用非平衡磁控濺鍍系統披覆含氫及含兩種金屬類鑽碳鍍層，針對此類鑽碳膜的製程、微結構、磨潤性質及應用，作一系列分析研究。將以石墨靶(純度99.99%)靶材作為主要碳源。實驗將分為三階段進行：變化試件夾持器(holder)的轉速、添加不同流量的甲烷氣氛及改變兩種金屬元素含量。藉由往復式磨耗試驗機(SRV)探討在何種參數下具有最佳的磨秏性質，並利用SRV做鍍層耐磨耗特性之研究。並探討經高溫處理後磨潤特性及機械性質變化。以掃描式電子顯微鏡(SEM)與能譜儀(EDS)對鍍層斷面及磨耗面進行分析，為避免底材效應的產生將利用奈米壓痕試驗機(nano-indentation)測試鍍層之奈米硬度。而後將以拉曼光譜儀(Raman Spectroscopy)觀察各鍍層結構的sp³/sp²鍵結比例變化及G、D波峰偏移的位置來比對磨耗試驗下的結果，最後將求得之最佳參數值實際應用於車削工具與印刷電路板之高速微鑽針上。經由以上的檢測分析將可得到類鑽碳鍍層最適當的碳氫含量及金屬含量在各種磨潤特性之最佳參數配對，並提高類鑽碳膜在工業上之實用價值。

　　The main purpose of this projest is to study the process, microstructure, tribological properties and application of diamond-like carbon coating with hydrogen and two kind of metal element by close-field unbalanced magnetron sputtering system. The main carbon source use graphite target. The experiment have three sections：The variety of substrate holder, adding the different methane flow rate and changing two metal element content. We confer in what kind of parameter had the best tribological performance and use SRV to study the resistant abrasion of films. The films cross-section and wear surface analysis be used by SEM and EDS, the nanohardness of films use nano-indentation tester in order to avoid substrate effect occur. Then we will be use Raman Spectroscopy observed the variety of sp³/sp² bond proportion of films structure and G、D position peak position deflection to compare the result of resistance wear test. Finally, we would obtain the best parameter for apply cutting tool and high speed PCB drilling needle. By test analysis would get the appropriate carbon hydrogenation content and metal element content of diamond-like carbon in all the tribological characteristic of the best parameter match and promote the DLC practice application in the industry.

授權書……………………………………………………….……….I
考試合格證明書……………………………………………….………. II
中文摘要……………………………………………………….………III
英文摘要…………………………………………………………..……IV
致謝……………………………………………………………….……V
總目錄………………………………………………………………..... VI
表目錄……………………………………………………………..... ⅩII
圖目錄……………………………………………………………… ⅩIII
第一章 緒論……………………………………………………………1
1-1前言…………………………………………………………..1
1-2研究動機…………………………………………….……….2
第二章 理論基礎與文獻回顧…………………………………………3
2-1類鑽碳之結構性質………………………………............……3
2-2氫原子對於類鑽碳結構之影響…………………………………4
2-3含氫類鑽碳與非含氫類鑽碳之差異性……………………....5
2-4改善類鑽碳鍍層之方式…………………………...…8
2- 5類鑽碳膜在拉曼光譜所顯現之特性……………………….10
第三章 實驗方法與內容……………………………………………..12
3-1實驗目的…………………………………………….……….12
3-2實驗流程……………………………………………………..12
3-3濺鍍參數與鍍層設定……………………………….……….13
3-4實驗內容………………………………….………………….14
3-4-1鍍層微結構分析………………………………..…....14
3-4-2鍍層成份分析………………………………………..….15
3-4-3硬度實驗……………………………………….………..15
3-4-4電阻率實驗……………………………………...………16
3-4-5附著性實驗………………………………………..…….16
3-4-6磨耗實驗………………………………………..……….17
3-4-7耐熱實驗…………………………………………..…….17
3-4-8鑽削實驗…………………………………………..…….18
3-4-9車削實驗…………………………………………..…….19
3-5實驗所需設備………………………………………………..19
第四章 實驗結果與討論………………………………………….….22
4-1鍍層基本性質……………………………….……………….22
4-2第一階段實驗過程(變化底材轉速)………………...………22
4-2-1鍍層結晶構造、拉曼分析………………………………22
4-2-2底材轉速對微硬度的影響………………………..…….23
4-2-3底材轉速對膜厚、成分的影響………………..……….23
4-2-4底材轉速對附著性的影響………………………..…….24
4-2-5第一階段鍍層磨耗試驗…………………………..…….24
4-3第二階段實驗過程(變化甲烷流量)…………………..……25
4-3-1鍍層結晶構造、拉曼分析………………………….…..25
4-3-2氣體流量對微硬度之影響………………………….…..27
4-3-3氣體流量對膜厚、成分的影響…………………….…..27
4-3-4氣體流量對附著性的影響………………………….…..28
4-3-5第二階段鍍層磨耗試驗…………………………….…..28
4-4第三階段實驗過程(變化金屬含量)…………………….….29
4-4-1鍍層結晶構造、拉曼分析……….…………………..…30
4-4-2金屬成份含量對微硬度之影響……………...…………30
4-4-3金屬成份含量對膜厚、成分的影響…………..……….31
4-4-4金屬成份含量對附著性的影響………………….……..31
4-4-5第三階段鍍層SRV試驗………………………….……..32
4-5各階段鍍層鍍層電阻率……………………………………..33
4-6鍍層磨耗壽命………………………………………………..33
4-7熱穩定性能…………………………………………………..34
4-8車削磨耗實驗…………………………………………..……35
4-9鑽削磨耗實驗………………………………………………..35
第五章 結論…………………………………………………….…….36
5-1實驗結論…………………………………………….……….37
5-2實驗心得與改善方法……………………………..…………38
第六章 參考文獻……………………………………………………..39
附錄……………………………………..……………………………..101

1. M.Schlatter, Diamond Relat.Mater. 11 (2002) 1781-1787.
2. M.Neuhaeuser, H.Hilgers, P. Joeris, R. White, J. Windeln, Diamond Relat. Mater.9 (2000) 1500-1505.
3. R. Hauert, Diamond Relat. Mater. 12 (2003) 583-589.
4. M.-S. Hwang, E.-T. Kim, C. Lee, Diamond Relat. Mater. 10 (2001) 2063-2068.
5. C. Prado, S.J. Wilkins, F. Marken, R.G.. Compton, Electroanalysis 14 (2002) 262.
6. A. Matthews, S.S. Eskildsen, Diamond Relat. Mater. 3 (1994) 902-908.
7. J. Robertson, Mater. Sci. Eng. R, 37 (2002) 129-281.
8. L.G. Jacobsohn, R. Prioli, F.L. Freirejr, G. Mariotto, M.M.Lacerda, Y.W. Chung,Diamond Relat. Mater. 9 (2000) 680.
9. R.F. Huang, C.Y. Chan, C.H. Lee, J. Gong, K.H. Lai, C.S. Lee, K.Y. Li, L.S. Wen, C. Sun, Diamond Relat. Mater. 10 (2001) 1850.
10. M. Maharizi, N. Croitoru, A. Seidman, J. Non-Cryst. Solids. 289 (2001) 221.
11. P. Merel, M. Tabbal, M.Chaker, S. Moisa, J. Margot, Appl. Surf. Sci. 136 (1998) 105.
12. S.J.Harris, A.M. Weiner, W.-J. Meng, Wear. 211 (1997) 208.
13. A.K. Gangopadhyay, P.A. Wolermet, M.A. Tamor, W.C. Wassell, Tribol. Int. 30 (1997) 9.
14. D. Schneider, C.F. Meyer, H. Mai, B. Schoneich, H. Ziegele, H.J. Scheibe, Y. Lifshitz, Diamond Relat. Mater.7 (1998) 973.
15. Y.S. Zou, W. Wang, G.H. Song, H. Du, J. Gong, R.F. Huang, L.S. Wen, Mater. Lett. 58 (2004) 3271-3275.
16. T.C.S. Vandevelde, K. Vandierendonck, M. Van Stappen et al., Surf. Coat.
Technol. 113 (1999) 80-85.
17. Prog. Solid State Chem. 21 (2002) 199.
18. J.Robertson, Mater. Sci. Eng., R Rep. 37 (2002) 129.
19. M. Ishihara, M. Suzuki, T. Watanabe, T. Nakamura, A. Tanaka, Y. Koga, Surf.Coat. Technol. 200 (2005) 620-624.
20. S. Neuville, A. Matthews, MRS Bull. 22 (9) (1997) 22.
21. John Robertson, Diamond Relat. Mater. 12 (2003) 79-84.
22. S. Yang，D. Camino，A.H.S. Jones ，D.G. Teer, Surf. Coat. Technol. 124 (2000) 110-116.
23. J. Roberston, Mater. Sci. Eng., R Rep. 37 (2002) 129.
24. A.C. Ferrari, A. Libassi, B.K. Tanner, V. Stolojan, J. Yuan, L.M. Brown, S.E. Rodil, B. Kleinsorge, J. Robertson, Phys. Rev., B 62 (2000) 11089.
25. A.C. Ferrari, J. Robertson, M.G. Beghi, C.E. Bottani, R. Ferulano, R. Pastorelli, Appl. Phys. Lett. 75. 75 (1999) 1893.
26. N.A. Morrison, S.E. Rodil, A.C. Ferrari, J. Roberston, W.I. Milne, Thin Solid Films. 337 (1999) 71.
27. A. Erdemir, I.B. Nilufer, O.L. Eryilmaz, M. Beschliesser, G.R. Fenske, Surf. Coat. Technol. 120-121 (1999) 589-593.
28. A.K. Gangopadhyay, P.A. Wolermet, M.A. Tamor, W.C. Wassell, Tribol. Int. 30 (1997) 9.
29. C. Donnet, A.Grill, Surf. Coat. Technol. 54-55 (1997) 456.
30. Y. Liu，A. Erdemir，E. Meletis, Surf Coat. Technol. 86-87 (1996) 564.
31. A. Erdemir，C. Bindal，J.Pagan，P. Wilbur, Surf. Coat. Technol. 76-77 (1995) 559-563.
32. A.A. Voevodin, A.W. Phelps, J.s. Zabinski, M.S. Donley, Diamond Relat. Mater. 5 (1996) 1264.
33. R. Gilmore, R. Hauert, Thin Solid Films. 398-399 (2001) 199.
34. M. Pancielejko，W. Precht，A. Czyzniewski, Vaccum, 53 (1999) 57-60.
35. E.I. Melets，A. Erdemire. G.R. Fenske, Surf. Coat. Technol. 73 (1995) 39.
36. H. Ronkainen，S. Varjus，J. Koskinen, Tribological, 11 (4) (1992) 133-141.
37.A. Erdemir，F.A. Nichols，X.Z. Pan，R. Wei，P. Wilbur, Diamond Relat. Mater. 3 (1994) 119.
38. C. Donnet，A. Grill, Surf Coat. Technol. 94-95 (1997) 456-462.
39. T.L. Huu，H. Zaidi，D. Paulmier, Wear. 181-183(1995)766-770.
40. J.C. Sanchez-Lopez，C. Donnet，J. Fontaine，et al., Diamond Relat. Mater. 9 (2000) 638-642.
41. B. Marchon，M.R. Khan，N. Heiman，P. Pereira, IEEE Transactions on Magnetics, 26 (5) (1990) 2670.
42. D.S. Kim，T.E. Fischer，B. Gallois, Surf. Coat. Technol. 49 (1991) 537.
43. A. Erdemir, F.A. Nichols, X.Z. Pan, R. Wei, P. Wilbur, Diamond Relat. Mater. 3 (1994) 119.
44. N. Savvides, B. Windows, J. Vac. Sci. Technol. 82 (1996)
45. B.K. Tay, D. Sheeja, S.P. Lau, X. Shi, B.C. Seet, Y.C. Yeo, Surf. Coat. Technol. 108 (1998) 72.
46. Y. Lifishitz, Diamond Relat, Mater. 8 (1999) 1659.
47. B. Marchon，M.R. Khan，N. Heiman，P. Pereira, IEEE Transactions on Magnetics, 26 (5) (1990) 2670.
48. J. Deng, M. Braun, Diamond Relat. Mater. 5 (1996) 478-482.
49. D.R. McKenzie，Y. Yin，N.A. Marks，et al., Diamond Relat. Mater. 3 (1994) 353.
50. A.H. Deutchman, R.J. Partyka, Adv. Mater. Proc. 6 (1989) 29-33.
51. H. Dimigen, H. Hubsch, R. Memming, Apply. Phys. Lett. 50 (16) (1987) 1056.
52. D. Sheeja, B.K. Tay, K.W. Leong, C.H. Lee, Diamond Relat Mater. 11 (2002)1643-1647.
53. V. Fox，A. Jones，N.M. Renevier，D.G. Teer, Surf. Coat. Technol. 125 (2000)347-353.
54. C. Corbella, M. Vives, A. Pinyol, E. Bertran, C. Canal, M.C. Polo, J.L. Andujar, Surf. Coat. Technol. 177-178 (2004) 409-414.
55. A. Grill, B. Meyerson, V. Patel, J. Mater. Res. 3 (1988) 214.
56 .Y.L. Su，W.H. Kao, J. Mater. Engine. Perfor. 9 (2000) 38-50.
57. H. Dimigen，C.P. Klages, Surf. Coat. Technol. 49 (1991) 543.
58. Q.F. Huang, S.F. Yoon, Rusli, H. Yang, B. Gan, K. Chew, J. Ahn, J. Appl. Phys. 7 (2000) 4191.
59. H. Dimigen，C.P. Klages, Surf. Coat. Technol. 49 (1991) 543.
60. Y.L. Su, W.H. Kao, Wear, 236 (1999) 221-234
61. K. Bewilogua，H. Dimigen, Surf. Coat. Technol. 61 (1993) 144.
62. L. Feng, J. Tang, Mater. Sci. Enginer. A257 (1998) 240-249.
63. H. Holleck，M. Lahres，P. Woll, Surf. Coat. Technol. 41 (1990) 179.
64. M. Benlahsen, V. Branger, J. Henocque, F. Badawi, K. Zellama,
Diamond Relat. Mater. 7 (1998) 769-773.
65. B. Bhushan, B.K. Gupta, Handbook of Tribology, 2nd edition, Mcgraw-Hill, New York, 1997
66. K-L. C, E. Felix, Mater. Sci. Eng. A278 (2000) 162-169.
67. A.A. Voevodin，R. Bantle，A. Matthews, Wear, 185 (1995) 151-157.
68. A. Matthews，A. Leyland，et al., Surf. Coat. Technol. 100-101 (1998) 1-6.
69. J. Bulir, M. Novotny, M. Jelinek, T. Kocourek, V. Studnicka, Surf. Coat. Technol. 200 (2005) 708-711.
70. V.V. Lyubimov，A.A. Voevodin，S.E. Spassky，et al. Thin Solid Films, 207 (1992) 117.
71. K.Tay, X. Shi, H.S. Yang, Z.Sun, Surf. Coat. Technol. 105(1998) 155.
72. M.J. Paterson, K.G. Orrman-Rossiter, Diamond Relat. Mater. 2(1993) 1439.
73. C. Chilung, W. Dayung, Diamond Relat. Mater. 10 (2001) 1528-1534.
74. C. Corbella, M. Vives, A. Pinyol, E. Bertran, C. Canal, M.C. Polo, J.L. Andujar, Surf. Coat. Technol. 177-178 (2004) 409-414.
75. M. Miyanaga, K. Oda, A. Ikegaya, in: W.M. Kriven, H.T. Lin(Eds.), The American Ceramic Society, vol. 24(3), 2003, p. 567.
76. Chien-Min Sung, Ming-Fong Tai, Int.J.Refract. Metals Hard Mater.15 (1997) 237–256.
77. R. Krawietz, B. Kampfe, E. Auerswald, M. Brucher, Cryst. Res. Technol. 40, No. 1/2, 143-148 (2005).
78. C. Fauteux, J. Pegna, Apply. Phys. A 78, 883-888 (2004).
79. K. Dietr, Semi. Mater. Device charter. Chapter 1 2-5 (1990).
80. T. Arai, H. Fujita, M. Watanable, Thin Solid Films. 154 (1987) 391.
81. S. J. Bull, Surf. Coat. Technol. 50 (1991) 25-32.
82. P. Villiger, C. Sprecher, J.A. Peter, Surf. Coat. Technol. 116-119 (1999) 585-590.
83. J. Robertson, Diamond Relat. Mater. 14 (2005) 942-948.
84. A.V. Stanishevsky, L.Yu. Khriachtchev, Diamond Relat. Mater. 5 (1996) 1355-1358.
85. A.C. Ferrari, Diamond Relat. Mater. 11 (2002) 1053-1061.
86.唐自標, ”金屬熱處理學 ”,六合出版社, 中華民國87年3月, pp.128。
87. S. Zhang, X.T. Zeng, H. Xie, P. Hing, Surf. Coat. Technol. 123 (2000) 256-260.