以往，液相電沈積的方式成長DLC薄膜總是在高的供應電壓下進行。本研究是利用電沈積的方法，在低的供應電壓下成長類鑽碳膜。其中使用SnO2覆蓋的ITO玻璃基板當作陰極，石墨薄板當作陽極。電解液的主要成份為醋酸水溶液，兩極間的供應電壓是2.1V。
使用傅式紅外光吸收譜(FTIR)，穿透式電子顯微照相(SEM)，拉曼光譜，去探討電沈積類鑽碳膜沈積物的結構。SEM顯示薄膜有一粗糙的表面，而且隨著時間和電壓的增加粗糙度就會增加。在拉曼光譜有兩個明顯的寬的特徵波峰在~1336(D-peak)和~1601cm-1(G-peak)的地方，分別代表失序的類石墨結構和石墨結構。當鍵結角發生扭曲或sp3含量提高時，G-peak 會造成偏移，同時D-peak 也會往低波數方向偏移。FTIR的吸收峰在~2956和~2917cm-1的地方，證實了具有sp3和sp2電子組態的碳原子存在於類鑽碳薄膜中。由上述的結果，證實使用電沈積的方法，在低電壓下可成長類鑽碳膜。

In the early years, DLC films was deposited at high voltage applied by electrochemical method. In this study, DLC film was deposited alternatively at low voltage applied using electrodeposition. The ITO glass substrate was used as the cathode, and graphite sheet was the anode. The electrolyte is a mixture of acetic acid with DI water. The applied voltage was mere 2.1 volt during the electrochemical process.
For investigating the structure of deposited films, the deposited DLC layers were characterized by Fourier transform infrared (FTIR), Scanning electron microscope (SEM) and Raman spectrometer. The SEM results show that the DLC films have a rough surface and their roughness increased with longer in deposition time as well as raise applied voltage. The Raman spectra shows distinct broad characteristic peaks at ~ 1336 cm-1 (D-peak) and ~ 1601 cm-1 (G-peak), which indicate the disordered graphite-like structure and the graphite structure, respectively. While the bond angles occur to bend or the increase the content of sp3 bonds in DLC film, both the G-peak and the D-peak shift to the lower wave numbers. Peaks at ~ 2956 and ~ 2917 cm-1 found in FTIR measurement were used to recognize the existence of sp3 and sp2 combined carbon atoms in the films. Based on above results, it could conclude that the DLC film could be prepared by electrodeposition under low applied voltage.

第一章 序 論 1
1-1前言 1
1-2 類鑽石碳膜之生成技術及其應用 3
1-3研究的目的 4
第二章理論基礎 6
2-1類鑽碳膜的文獻回顧 6
2-1-1 鑽石和石墨之組成 6
2-1-2類鑽碳膜的分類 7
2-1-3 類鑽碳膜的結構 9
2-2電鍍理論 11
2-2-1電解導電 11
2-2-2電阻和導電性 11
2-2-3電解質溶液 12
2-2-4電沈積 13
2-2-5 金屬電結晶動力學 14
2-2-6 沈積層應具有的主要性能 17
2-2-7 影響沈積層質量的因素 19
2-2-8 鍍件品質之標準 21
第三章 實驗 23
3-1實驗流程 23
3-2實驗的設備與材料 24
3-3實驗的條件 25
3-4實驗的變因： 26
3-5基材處理 26
3-6沈積層的分析與測試 27
3-7量測儀器的原理 28
3-7-1 拉曼測試 28
3-7-2 拉曼光譜學簡介 28
3-7-3 散射光種類 28
3-7-4 拉曼光譜的量子模型與實驗裝置 29
3-7-5 拉曼散射的古典波動模型 31
3-7-6 類鑽碳膜之拉曼光譜量測 34
3-8原子力顯微鏡[28] 39
第四章結果與討論 44
ITO玻璃基板成長DLC層之方法 44
4-1 物理氣相沈積（物理蒸鍍）（PVD） 45
4-1-1 蒸鍍(Evaporation) 46
4-1-2 濺鍍 46
4-1-2-(a) 直流濺鍍(DC sputtering) 48
4-1-2-(b) 射頻濺鍍(RF sputtering) 48
4-1-2-(c) 磁控濺鍍(Magnetron sputtering)[2][3][4][5] 49
4-1-3 射鍍電弧蒸鍍法(Arc Evaporation)[11-20] 52
4-2 化學氣相沈積（化學蒸鍍）（CVD） 54
4-2-1 大氣壓化學氣相沈積系統(APCVD)[29] 55
4-2-2 低壓化學氣相沈積系統(LPCVD)[30] 56
4-2-3 電漿輔助化學氣相沈積系統(PECVD)[31-44] 57
4-2-4 微波電子迴旋共振化學氣相沈積法(ECRCVD) 60
4-3 電沈積的方法 60
4-3-1 高壓電沈積ITO玻璃基板 60
4-3-2高壓電沈積aluminum基板 65
4-3-3 高壓電沈積Si玻璃基板 67
4-3-4 低電壓沈積SnO2覆蓋的玻璃基板 69
第五章 結論 75

第一章
[1] F.P. Bundy, H.T. Hall, H.M. Strong, and R.H. Wentorf, Nature 176, 51(1955)
[2]. Z. Ring and T.D. Mantei, J. Vac. Sci. Technol., A13 (1995) 1617.
[3]. Z. Ring and T.D. Mantei, Appl. Phys. Lett., 66 (1995) 3380.
[4]. C.R. Eddy, Jr., D.L. Youchison and B.D. Sartwell, Diamond Relat.Mater., 3 (1993) 105.
[5]. R.K. Singh, D. Gilbert, R. Tellshow, P. H. Holloway, R. Ochoa,
and J.H. Simmons, Appl. Phys. Lett., 61 (1992) 2863.
[6]. T. Yara, M. Yuasa, M. Shimizu and H. Makita, Jpn. J. Appl. Phys.,33 (1994) 4404.
[7]. M. Ihara, H. Maeno, K. Miyamoto and H. Komiyama, Diamond Relat.Mater., 1 (1992) 187.
[8]. S.H. Kim, Y.S. Park and S.K. Jung, J. Vac. Sci. Technol., A13(1995) 1619.
[9]. I. Watanabe, T. Matsushita and K. Sasahara, Jpn. J. Appl. Phys.,31 (1992) 1428.
[10]. W. Zhu, G. P. Kochanski, S. Jin and L. Seibles, Vacuum
MicroelectronicsConference., 35 (1995) 300.
[11]. P. Ruffieux, O. Groening, P. Groening, L.Diederich, O.Kuettel and L. Schlapbach, Electron Device, IEEE Transactions, 488(1997) 1295.
[12]. J. Robertson, Vacuum microelectronics Conference., 34 (1998) 162.
[13]. S. Aisenberg, and R. Chabot, J. Appl. Phys. 42 (1971) 2953.
[14]. J. Seth, M.I. Chaudhry and S.V. Babu, J. Vac. Sci. Technol.,10(1992) 3125.
[15]. G.F. Zhang and X. Zheng, Surf. Coatings. Technol., 82 (1996)
110.
[16]. Diamond Relat. Mater., 3 (1994) 732.
[17]. J. Robertson, Diamond Relat. Mater., 1 (1992) 397.
[18]. S. Aiesenberg and F.M. Kimock, Mater. Sci. Forum., 52 & 53 (1989)1.
[19]. I.R. McColl and T.L. Parker and A.A. Goruppa, Diamond Relat.
Mater., 3 (1993) 83.
[20]. K. Zolynski, P. Witkowski, A. Kaluzny, Z. Has, P.Niedzielski
and S. Mitura, J. Chem. Vapor Deposit., 4(1996) 232.
[21]. V.L. Arbuzov, A.B. Vladmirov, V.B. Vykhodets, A.E. Davletshin,S.HA. Plotnikov, I.Sh. Trakhtenberg, A.P.Rubshtein, S.D.Gorpinchenko and E.V. Kuzmina, Diamond. Relat. Mater., 3 (1994)775
[22]. J. Robertson, Surf.Coat.Technol., 50 (1992) 185.
[23] 陳豐彥，「電弧離子鍍膜製程參數對氮化鉻膜性質之影響」，工業材料145 期，民國88 年1 月，第167-171 頁。
[24] P.K.Bachmann and R.Messier， Emerging Technology
of Diamond Thin Film， C&EN， May15(1989)P24.
[25] K.E.Spear，Earth and Mineral Science，56(1987)pp53. 59.
[26]翁克偉,「陰極電弧沈積複層氮化鋁鈦薄膜界面性質之研究」，中
國材料科學學會87 年年會論文，第53-56 頁。
[27]張瑞發，「類鑽薄膜技術」，化工資訊，民國八十二年四月，68-77頁。
第二章
[1]. R. W. G. Wyckoff, Crystal Structures, Interscience, New York (1964).
[2]. J. C. Angus, F. A. Buck, M. Sunkara, T. F. Gorth, C. C. Hayman and R.Gat, MRS Bull, XIV, 10 （1989）.
[3]. B. T. Kelly, Physics of Graphite, Applied Science, London
(1981).
[4]Diamond-like Coatings”, JOM.APRILL , 1995, pp.16-19.W. D. Kingery, H. K. Bowen, and D. R. Uhlmann , Introduction to Ceramics, Chapter 2, John Wiley & Sons, Canada, 1991 林原誌，奈米壓痕儀之原理及操作簡介，2000，4 月。
[5]余樹貞，晶體之結構與性質，第十二章，渤海堂文化公司，台北台灣，1993 張瑞發, 化工資訊, 4 (1993) 68。
[6]G.H.Johnson，A.R.Badzian and M.W.Geis，Diamond and Diamond-
like Materials Synthesis，MRS，Pittsburgh，PA(1988)
[7]I.M.Buckley-Golder and A.T.Collins，Diamond Relat.Mater.，
1（1992）p1083.
[8]陳培麗，科儀新知，鑽石與類鑽薄膜簡介， 13，2（1991）pp82.91
[9] J.Robertson, Surf. Coat. Technol. 50, 185 (1992)
[10]張瑞發, 化工資訊, 4, 68 (1993)
[11]C. D. Martino, F. Demichelis, and A. Tagliaferro, Diamond Relat. Mater.4, 1210 (1995)
[12]. J. W. Zou, K. Schmidt, K. Reichelt, and B. Dischler, J. Appl. Phys., 67 (1990) 487.
[13]. J. C. Phillips, Phys. Rev. Lett., 51 (1979) 1355.
[14]. J. C. Angus, and F. Jansen, J. Vac. Sci. Technol., A6 (1988) 1778.
[15]. P. Reinke, W. Jacob and W. Moller,J. Appl. Phys., 74 (1993) 1354.
[16]. A. Grill, B. Meyerson, K. E. Spear, and J. P. Dismukes (Eds.),Synthetic Diamond：Emerging CVD Science and Technology,
Wiley, New York, 1994, p.121.
[17]. M. A. Tamor, and J. B. Wu, J. Appl. Phys., 67 (1990a) 1007.
[18]. C. F. Chen and S. H. Chen, Diamond Relat. Mater., 3 (1994) 443.
第三章
[1]. A. Smekal, Naturwiss.,Vol. 11, p.873
[2]. Z. C. Feng, A. A. Allerman, P. A. Barnes and S. Perkowitz, Appl. Phys. Lett., 60 (1992) 1848.
[3]. J. P. Estrera, P. D. Stevens, R. Glosser, W. M. Duncan, Y. C. Kao,Y. H.Liu and E. A. Beam, Appl. Phys. Lett., 61 (1992) 1927.
[4]. G. Lucovsky, M. H. Brodsky, M. F. Chen, R. J. Chicotka and A. T. Ward, Phys. Rev., B4 (1971) 1945.
[5]. K. Yano, and T. Katoda, J. Appl. Phys., 70 (1991) 7036.
[6]. D. P. Bour, J. R. Shealy, A. Ksendzov and Fred Pollak, J. Appl. Phys., 64 (1988) 6456.
[7]. J.W. Ager Ⅲ, S. Anders, and A. Anders, Appl. Phys. Lett., 66 (1995) 3444.
[8]. D. Beeman, J. Silverman, and R. Lynds, Phys. Rev. B30 (1984)
870.
[9]. A. Richter, H.J. Scheibe, and W. Pompe, J. Non-cryst. Solid.,
88 (1986) 131.
[10]. K. W. R. Gilkes, S. Prawer, and K.W. Nugent, J. Appl. Phys.,
87 (2000) 7283.
[11]. S. F. Yoon, H. Yang, A. Rusli, J. Ahn, and Q. Zhang, Diamond
Relat. Mater., 7 (1998) 70.
[12]. T. Sharda, T. Soga, T. Jimbo, and M. Umeno, Diamond Relat. Mater. 9 (2000) 1331.
[13]. S. F. Yoon, Rusli. J. Ahn, Q. Zhang, Y. S. Wu, and H. Yang,
Diamond Relat. Mater. 7 (1998) 1213.
[14]. M. Yoshikawa, Mater. Sci. Forum., 5253 (1989) 365.
[15]. D. Beeman, J. Silverman, R. Lynds, and M. R. Anderson, Phys.
Rev., B30 (1984) 870.
[16]. F. Tuinstra and J. L. Koenig, J. Chem. Phys., 53 (1970) 1126.
[17]. S. A. Solin Physica B 99 (1980) 443.
[18]. M. A. Tamor and W. C. Vassel, J. Appl. Phys., 76 (1994) 3823.
[19]. K. Capano, N. T. McDeutt, R. K. Singh and F. Qian, J. Vac. Sci. Technol., A14 (1996) 431.
[20]. D. S. Knight, and W. B. White, J. Mater. Res., 4 (1989) 385.
[21]. 何主亮，常挽瀾，陳育智，電漿化學氣相沉積氮化碳薄膜的微觀結構與機械性質，真空科技，第9 卷，第2 期，34-35，(1996)。
[22]. H. C. Tsai, D. B. Bogy, M. K. Kundmann, D. K. Veirs, M. R. Hilton and S. T. Mayer, J. Vac. Sci. Technol., A6 (1998) 2307.
[23]. A. K .Gangopadhyay, P. A . Willement, M. A. Tamor, and W. C. Vassel, Tribology International, 30 (1997) 9.
[24]. J. Schwan, S. Ulrich, V. Batori, H. Ehrhardt and S. R. P. Silva, J. Appl. Phys., 80 (1996) 440.
[25]. R. Vuppuladium, H. E. Jackson and R. L. C, J. Appl. Pphys.,
77 (1994) 2714.
[26]. A. C. Ferrari and J. Robertson, Phys. Rev., B 62 (2000) 11089.
[27]. F. Tuinstra, and J. L. Koening, J. Vhem. Phys., 53 (1970) 1126.
[28]. 阮彥凱. 製程參數對直流濺鍍複合電子迴旋共振系統沉積類鑽鍍膜之研究
第四章
[1]. J. –M. Ting, and H. Lee, Diamond Relat. Mater., 11 (2002)
1119–1123.
[2]. F. Jansen, M. Mackonkin, S. Kaplan and S. Hark, J. Vac. Sci.
Technol., A 3 (1985) 605.
[3]. N. Savvides. J. Appl. Phys., 55 (1984) 4232.
[4]. N.H. Cho, K.M. Krishnan, D.K. Vries, M.D. Rubin, C.B. Hopper,
B. Brushan and D.B. Bogy, J. Mater. Res., 5 (1990) 2543.
[5]. S.M. Rossnagel, M.A. Russak and J.J. Cuomo, J. Vac. Sci.
Technol., A 5 (1987), p. 2150.
[6]. 〝真空濺鍍薄膜〞，誠真有限公司
[7]. J. L. Vossen and W. Kern, “Thin Film Processes II”, Academic Press, New York (1991).
[8]. Rebert Parsons, “Thin Film Process II”, Chap. II-4, John L.Vossen and W. Kern.,Academic press. (1991).
[9]. F. Shinoki and A. Itoh, J. Appl. Phys., 46 (1975) 3381.
[10]. S. Berg. H. O. Blom, T. Larsson, and C. Nender, J. Vac. Sci.
Technol. A5 (1987) 202.
[11]. X. Shi, Y.Q. Tu and H.S. Tan, IEEE Trans. Plasma Sci., 24 (1996) 1309.
[12]. B.K. Tay, G.F. You, S.P. Lau and X. Shi. Surf. Coatings Technol.,133 (2000) 593.
[13]. M. Chhowalla, J. Robertson, C.W. Chen, S.R.P. Silva and G.A.J. Amaratunga, J. Appl. Phys., 81 (1997) 139.
[14]. X. Shi, D. Flynn, B.K. Tay, S. Prawer, K.W. Nugent, S.R.P. Silva, Y. Lifshitz and W.I. Milne. Philos, Mag, B 76 (1997) 351.
[15]. X. Shi, B.K. Tay and S.P. Lau, Int. J. Mod. Phys., 14 (2000)
154.
[16]. S. Anders, A. Anders, M.R. Dickinson, R.A. MacGill and I.G.
Brown, IEEE Trans. Plasma Sci., 25 (1997) 670.
[17]. A. Anders. Surf. Coatings Technol., 121 (1999) 319.
[18]. A. Anders and A.V. Kulkarni, Mater. Res. Soc. Symp. Proc., 675 (2001) W11.1.
[19]. M.C. Polo, J.L. Andujar, J. Robertson and W.I. Milne, Diamond Relat. Mater., 9 (2000) 663.
[20]. B.F. Coll, in: S.R.P. Silva, et al. (Eds.), Amorphous Carbon, Worid Scientific, Singapore, 1998.
[21]. John L.Vossen and Werner Rern， ” Thin Film Process II”，
Academic Press，(1991) 209.
[22]. A.E.Guile and B.Juttner ， IEEE Trans.On Plasma Science PS-8
(1980) 259.
[23]. N. Akita,, Y. Konishi, S. Ogura, M. Imamura, Y.H. Hu, and X. Shi, Diamond Relat. Mater.,10 (2001) 1017.
[24]. FRANC_OIS ROSSI Chaos, Solitons & Fractals, 10 (1999) 2019.
[25]. D. Kim, and S. Kim, Surf. Coatings Technol.,157 (2002) 66.
[26]. A. Stanishevsky, Diamond Relat. Mater., 8 (1999) 1246.
[27]. A. A. Voevodin, M. S. Donley, and J. S. Zabinski, Diamond Relat. Mater., 92 (1997) 42.
[28]. 莊達人，VLSI 製造技術，高立圖書有限公司，p183~185，87 年。
[29]. T. Otani, M. Hirata, Thin Solid Films, 442 (2003) 44.
[30]. M. Modream, M. Bercu, and C. Cobiaru, Thin solid Films, 383 (2001) 212.
[31]. L. Holland and S.M. Ohja, Thin Solid Films, 38 (1976) L17.
[32]. Y. Catherine, Diamond and diamond-like carbon thin films. NATOASI 266 (1991) 193.
[33]. Y. Catherine and C. Couderc, Thin Solid Films 144 (1986) 265.
[34]. A. Bubenzer, B. Dischler, G. Brandt and P. Koidl, J. Appl. Phys .,54 (1983) 4590.
[35]. C. Wild and P. Koidl, Appl. Phys. Lett ., 54 (1989) 505.
[36]. C. Wild and P. Koidl, J. Appl. Phys ., 69 (1991) 2909.
[37]. J.W. Zou, K. Reichelt, K. Schmidt and B. Dischler, J. Appl.
Phys ., 65 (1989) 3914.
[38]. J. W. Zou, K. Schmidt, K. Reichelt and D. Dischler, J. Appl.
Phys ., 67 (1989) 487.
[39]. M. A. Lieberman, A.J. Lichtenberg, Principles of Plasma
Discharges and Materials Processing, Wiley, NewYork, 1994.
[40]. L. Martinu, A. Raveh, D. Boutard, S. Houle and M. Wertheimer,
Diamond Relat. Mater., 2 (1993) 673.
[41]. M. Zarrabian, N. Fourches-Coulon and G. Turban, Appl. Phys.
Lett., 70 (1997), p. 2535.
[42]. X.M. He, S.T. Lee, L. Bello, A. Cheung and C.S. Lee. J. Mater.
Res., 14 (1999) 1055.
[43]. M. Weiler, S. Sattel, T. Giessen, K. Jung, H. Ehrhardt, V.S.
Veerasamy and J. Robertson, Phys. Rev., B 53 (1996) 1594.
[44]. M. Weiler, K. Lang, E. Li and J. Robertson, Appl. Phys. Lett., 72 (1998) 1314.
[45]. L. Martinu, A. Raveh, D. Boutard, S. Houle and M. Wertheimer,
Diamond Relat. Mater., 2 (1993) 673.
[46]. M. Zarrabian, N. Fourches-Coulon and G. Turban, Appl. Phys.
Lett., 70 (1997) 2535.
[47]. X.M. He, S.T. Lee, L. Bello, A. Cheung and C.S. Lee, J. Mater.
Res., 14 (1999) 1055.
[48]. S. Muhl, E. Camps, L. Escobar-Alarcon, O. Olea, M. Miki, and N. A. Morrison, Diamond Relat. Mater., 10 (2001) 915.
[49]. S. K. Patra and G. Mohan Rao, Vacuum, 74 (2004) 93.
[50]. E. Kamijo, T. Nakamura and Y. Tani, Nuclear Instruments and
Methods in Physics Research Section B: Beam Interactions with
Materials and Atoms, 121 (1997) 110.
[51]. Sheng-Rui Jian, Te-Hua Fang, and Der-San Chuu, Journal of
Non-Crystalline Solids, 333 (2004) 291.
[52]. K. Y. Li, Z. F. Zhou, C. Y. Chan, I. Bello, C. S. Lee, and S.T. Lee, Diamond Relat. Mater.,10 (2001) 1855.
[53]. S. F. Yoon, H. Yang, Rusli. J. Ahn and Q. Zhang, Vacuum 49 (1998) 67.
[54]. S. F. Yoon, H. Yang, Rusli. J. Ahn and Q. Zhang, Diamond Relat. Mater., 7 (1998) 70.
[55]. X. T. Zhou, S. T. Lee, I. Bello, A. C. Cheung, D. S. Chiu, Y.
W. Lam, C. S. Lee, K. M. Leung and X. M. He, Surf. Coatings
Technol.,123 (2000) 273.