類鑽碳（Diamond-like Carbon, DLC）膜具有許多的優異性質，諸如：高硬度、低摩擦係數、高化學穩性、絕緣性高等，在工業上有著重要的應用。本研究嘗試使用電沉積技術沉積DLC薄膜，與PVD及CVD技術比較，其具有低供應電壓、低溫、實驗步驟簡單、操作簡易、成本低廉等之優勢。其中使用SnO2覆蓋之ITO玻璃基板當作陰極，石膜薄板當作陽極，兩極間的供應電壓為2.1V~50V，電解液的主要成份為醋酸水溶液。透過製程上基板偏壓及電解液濃度等實驗條件的改變，來研究類鑽碳膜的性質。
研究結果顯示，當基板偏壓增加時，類鑽碳膜的沈積速率、硬度都呈現上升的趨勢，而表面粗糙度則呈現下降的趨勢，當電解液濃度增加時，同樣具有相似的現象。透過拉曼光譜的分析，顯示Dpeak和G peak分別位於1350cm-1和1580cm-1處，證明類鑽碳膜的存在。再由SEM和AFM之分析，分別觀察類鑽碳膜之表面結構，調整實驗參數藉以得到最佳品質之DLC薄膜。

The Diamond-like Carbon (DLC) films have numerous extraordinary advantages, such as high hardness, low friction factor, strong chemical stability, and high insulation properties for satisfying significant application in the industrial domain. In this study, DLC films are deposited by electrodeposition, which is different from the conventional technology of PVD and CVD. The methodology provides several advantages such as low voltage supply, low temperature electrodeposition, simple experimental steps and easy to operate, resulting in low costs. The experiment used ITO glass substrate covered with SnO2 as cathode, a thin graphite plate as anode, the voltage supply between the two poles is 2.1V ~ 50V, and the main components of electrolyte is the solution of acetic acid with deionized (DI) water. The property of Diamond-like Carbon films have been investigated to be associated with a variety of bias voltage, the concentration of acetic acid (electrolyte) during the process.
As a result, the deposition rate and hardness of Diamond-like Carbon films increase with the bias voltage. However, the surface roughness tends to decrease, and the same outcomes manifested when the concentration of electrolyte increased. For the analysis of Raman Spectrum, the D peak and G peak were at 1350cm-1 and 1580cm-1 individually, which demonstrated the existence of Diamond-like Carbon films. Finally, of analyzing the SEM and AFM photograph, the surface morphology of Diamond-like Carbon films are used to correlate the deposited parameters for obtaining the best quality of DLC films.

致謝.......................................................................................................... Ⅰ
中文摘要.................................................................................................. Ⅱ
英文摘要.................................................................................................. Ⅲ
目錄.......................................................................................................... Ⅳ
附圖目錄.................................................................................................. Ⅶ
附表目錄.................................................................................................. Ⅹ
第一章 緒論.............................................................................................. 1
1-1 前言.............................................................................................. 1
1-2 研究動機與目的.......................................................................... 4
1-3 論文架構...................................................................................... 5
第二章 理論基礎...................................................................................... 6
2-1 文獻回顧...................................................................................... 6
2-1-1 類鑽碳的起源.................................................................... 6
2-1-2 電沉積理論........................................................................ 7
2-1-3 電沉積技術........................................................................ 8
2-2 類鑚碳薄膜.................................................................................. 9
2-2-1 鑽石與石墨之結構........................................................... 9
2-2-2 類鑚碳的特性................................................................. 10
2-2-3 類鑚碳膜之種類............................................................. 11
2-3 類鑽碳薄膜的導電機制........................................................... 14
2-3-1 ⅤA 族元素的摻雜......................................................... 14
2-4 類鑽碳薄膜的成長機制........................................................... 14
第三章 樣品與實驗裝置........................................................................ 19
3-1 實驗流程.................................................................................... 19
3-2 實驗材料與儀器設備................................................................ 20
3-2-1 樣品的準備..................................................................... 20
3-2-2 實驗系統設備................................................................. 20
3-3 實驗操作流程............................................................................ 21
3-3-1 基板潔淨清洗................................................................. 21
3-3-2 電沉積之操作步驟......................................................... 22
3-4 分析與鑑定................................................................................ 23
3-4-1 表面型態觀察................................................................. 23
3-4-2 成長速率測定................................................................. 23
3-4-3 薄膜結構分析................................................................. 24
3-4-4 薄膜組成及鍵結型態分析............................................. 27
3-4-5 殘留應力測試................................................................. 27
3-4-6 硬度值測試..................................................................... 28
3-4-7 微結構分析..................................................................... 28
3-4-8 電性量測......................................................................... 29
第四章 量測結果與分析........................................................................ 31
4-1 鍍膜時之電流變化特性分析................................................... 31
4-1-1 偏壓之影響..................................................................... 31
4-1-2 電解液濃度之影響......................................................... 31
4-1-3 鍍膜電極間距之影響..................................................... 32
4-1-4 活化能之分析................................................................. 33
4-2 類鑽碳膜之成份與型態........................................................... 36
4-2-1 鍍膜的沉積速率............................................................. 36
4-2-2 鍍膜的元素成分與結構分析......................................... 38
4-2-3 類鑽碳膜的Raman 分析............................................... 38
4-2-4 類鑽碳膜的表面型態觀察............................................. 40
4-2-5 原子力顯微鏡分析鍍膜表面形態................................. 41
第五章 結論與未來展望........................................................................ 43
參考文獻.................................................................................................. 73

[1] J. Robertson, “Properties of diamond-like carbon”.Surface and Coating Technology 50(1992), pp185-203.
[2] A. Rengan, J. Narayan, C. Jahnke, S. Bedge, J.L. Park and Ming Li, “Characterics of diamond-like carbon films formed by hybrid laser-plasma ablation of graphite”, Materials Science and Engerring, B15(1992), pp15-24.
[3] Z.F. Li, Z.Y. Yang and R.F. Xiao, Appl. Phys. 63(1996)243.
[4] P. Vanden Brande, S. Lucas, R. Winand, A. Weymeersch and L. Renard, “Determination of the chemical and physical properties of hydrogenated carbon deposited produced by D.C. Technology, 68/69(1994), pp656-661.
[5] M. Matsuoka, K. Hoshino and K. Ono, J. Cac. Sci. Technol.,11(1993)2994.
[6] K. Kobayashi, K. Yamamoto, N. Mutsukura and Y. Machi,“ Sputtering characteristics of diamond and hydrogenated amorphous carbon films by R.F. plasma”, Thin Solid Films 185(1990), pp71-78.
[7] M.A. Tamor, C.H. Wu, R.O. Carter and N.E. Lindsay, Appl.Phys. Lett. 55(1989)1388.
[8] A. Raveh, J.E. Klenberg-Sapieha, L. Martinul and M.R. Wertheimer, J. Vac. Sci. Technol. 10(1992)1723.
[9] J. Won, A. Hatta, Tssaki and A. Hiraki, Appl. Phys. Lett. 69 (1996)4179.
[10] Y. C. Chan, X.S. Miao, X. M. He, and S. T. Lee, J. Elect. Materials, 27(1998)41.
[11] S.F. Yoon, H. Yang, Rusli, J. Ahn, and Q. Zhang, J. Elect. Materials, 27(1998)44.
[12] X. M. He, and S. T. Lee, I. Bello, A. C. Cheung, W. Z. Li, D. S. Chiu, Y. W. Lam, C. S. Lee, L. M. Leung, and X. T. Zhou, J. Mater. Res., No. 4, 14(1999)1617.
[13] A. Grill and B. Meyerson, in Synthetic Diamond: Emerging CVD Science and Technology, K. E. Spear and J. P. Dismukes, Eds., John Wiley & Sons, Inc., New York, 1994, p91.
[14] A. Grill, Surf. Coat. Technol. 507(1997)94.
[15] S. Aisenberg, R. Chabot, “Ion-Beam Deposition of Diamondlike Carbon”, Journal of Applied Physics, 42 (1971) pp.2953-2961.
[16] V. Kulikovsky, P. Bohac, F. Franc, A. Deineka, V. Vorlicek, L. Jastrabik, “Hardness, intrinsic stress, and structure of the a-C and a-C:H films prepared by magnetron sputtering”, Diamond and Related Materials, 10 ( 2001) pp.1076-1081.
[17] D.Y. Wang, C.L. Chang, “Influences of optical emission settings on wear performance of metal-doped diamond-like carbon films deposited by unbalanced magnetron sputtering”, Thin Solid Films, 392 (2000) pp.11-15.
[18] O. R. Monteiroa, I. G. Browna, “Tungsten-containing amorphous carbon Films deposited by pulsed vacuum arc”, Thin Solid Films, 342 (1999) pp.100-107.
[19] A. Kumar, H. L. Chan, J. S. Kapat, “Deposition an characterization of titanium carbide coatings using laser ablation method”, Applied Surface Science, 127-129 (1998) pp.549-552.
[20] Q. Juna, L. Jianbin, W. Shizhu, J. Wang, W. Li, “Mechanical and tribological properties of non-hydrogenated DLC films synthesized by IBAD”, Surface and Coatings Technology, 128-129 (2000) pp.324-328.
[21] P.P. Psyllaki, M. Jeandin, D.I. Pantelis, M. Allouard, “Pin-on-disk test of PE-CVD diamond-like carbon coatings on tool steel substrates”, Surface and Coatings Technology, 130 (2000) pp.297-303.
[22] M.K. Fung, K.H. Lai, C.Y. Chan, I. Bello, C.S. Lee, S.T. Lee, D.S. Mao, X. Wang, “Mechanical properties and corrosion studies of amorphous carbon on magnetic disks prepared by ECR plasma technique”, Thin Solid Films, 368 (2000) pp.208-210.
[23] Y. Namba, “Attempt to grow diamond phase carbon films from an organic solution”, Journal of Vacuum Science & Technology A, 10 (1992) pp.3368-3370.
[24] T. Suzuki, Y. Manita, T. Yamazaki, S. Wada, and T. Noma, “Deposition of carbon films by electrolysis of a water-ethylene glycol solution”, Journal of Materials Science, 30 (1995) pp.2067-2069.
[25] H Wang, MR Shen, ZY Ning, C Ye, CB Cao, HY Dang, “Deposition of diamond-like carbon films by electrolysis of methanol solution”, Applied Physics Letters, 69 (1996) pp.1074-1076.
[26] MC Tosin, AC Peterlevitz, GI Surdutovich, V Baranauskas, “Deposition of diamond and diamond-like carbon nuclei by electrolysis of alcohol solutions”, Applied Surface Science, 144-145 (1999) pp.260-264.
[27] D Guo, K Cai, L Li, Y Huang, Z Gui, H Zhu, “Electrodeposition of diamond-like amorphous carbon films on Si from N,N-dimethylformamide”, Chemical Physics Letters, 329 (2000) pp.346-350.
[28] H Wang, M Yoshimura “Electrodeposition of diamond-like carbon films in organic solvents using a thin wire anode”, Chemical Physics Letters, 348 (2001) pp.7-10.
[29] JT Jiu, LP Li, CB Cao, HS Zhu, “Deposition of diamond-like carbon films by using liquid phase electrodeposition technique and its electron emission properties”, Journal of Materials Science, 36 (2001) pp.5801-5804.
[30] RK Roy, B Deb, B Bhattacharjee, AK Pal, “Synthesis of diamond-like carbon film by novel electrodeposition route”, Thin Solid Films, 422 (2002) pp.92-97.
[31] D Guo, K Cai, LT Li, Y Huang, ZL Gui, “Evaluation of carbon films electrodeposited on different substrates from different organic solvents”, Applied Physics A, 74 (2002) pp.69-72.
[32] HS Zhu, JT Jiu, Q Fu, H Wang, CB Cao, “Aroused problems in the deposition of diamond-like carbon films by using the liquid phase electrodeposition technique”, Journal of Materials Science, 38 (2003) pp.141-145.
[33] S. Gupta, R.K. Roy, B. Deb, S. Kundu, A.K. Pal, “Low voltage electrodeposition of diamond-like carbon films”, Materials Letters, 57 (2003) pp.3479-3485.
[34] S Gupta, MP Chowdhury, AK Pal, S Gupta, MP Chowdhury, AK Pal, “Synthesis of DLC films by electrodeposition technique using formic acid as electrolyte”, Diamond & Related Materials, 13 (2004) pp.1680-1689.
[35] S Gupta, R.K. Roy, B. Deb, S. Kundu, K. Pal A, “Low voltage electrodeposition of diamond like carbon (DLC)”, Applied Surface
Science, 252 (2005) pp.296-302.
[36] W. D. Kingery, H. K. Bowen, and D. R. Uhlmann, Introduction to
Ceramics, Chapter 2, John Wiley & Sons, Canada, 1991
[37] 余樹楨，晶體之結構與性質，第十二章，渤海堂文化公司，台北台灣，1993
[38] J. Robertson, “The deposition mechanism of diamond-like a-C and a-C：H”, Diamond and Related Materials, 3 (1994) pp.361-368.
[39] J. Robertson, “Diamond-like amorphous carbon”, Materials Science and Engineering, R 37 (2002) pp.129-281.
[40] 宋健民，“碳的大千世界”，鑽石合成，全華書局，2000。
[41] J. Robertson, “structural models of a-C and a-C:H”, Diamond and Related Materials, 4 (1995) pp.297-301.
[42] B.B Pate, M.H. Hecht, C. Binns, “Photoemission and photon-stimulated ion desorption studies of diamond (111): hydrogen”, Journal of Vacuum Science Technology, 21 (1981) pp.364-367.
[43] A. Erdemir, I.B. Nilufer, O.L. Eryilmaz, M. Beschliesser, G.R. Fenske, “Friction and wear performance of diamond-like carbon films grown in various source gas plasmas”, Surface and Coatings Technology, 120-121(1999) pp.589-593.
[44] J. C. Angus and C. C. Hayman, “Low-Pressure, Metastable Growth of Diamond and ``Diamondlike' Phases”, Science, 241 (1998) pp.913-921.
[45] J. Roberson, “Properties of diamond-like carbon”, Surface and Technology, 50 (1992) pp.185-203.
[46] 錢國基，產業經濟第201卷，1998。
[47] C. D. Martino, F. Demichelis and A. Tagliaferro, “Determination of the sp3/sp2 Ratio in a-C:H Films by Infrared Spectrometry Analysis”, Diamond and Related Materials, 4 (1995) pp.1210-1215.
[48] V. S. Veerasamy, J. Yuan, G. A. J. Amaratunga, W. I. Milne, K. W. R.Gilkers, M. Weiler, and L. M. Brown, Phys. Rev. B 48, 8016 (1993)
[49] J. Robertson and C. A. Davis, Diamond Relat. Mater. 4, 441 (1995)
[50] S. R. P. Sliva and G. A. J. Amaratunga, Thin Solid Films 270, 194 (1995)
[51] S. R. P. Silva, J. Robertson, G. A. J. Amaratunga, B. Rafferty, L.M. Brown, J. Schwan, D. F. Franceschini, and G. M. Mariotto, J. Appl. Phys. 81, 2626 (1997)
[52] K. Ogata, J. F. D. Chubaci, and F. Fujimato, J. Appl. Phys. 76, 3791 (1994)
[53] N. V. Novikov, M. A. Voronkin, A. A. Smekhnov, N. I. Zaika, and A. P. Zakharchuk, Diamond Relat. Mater. 4, 3905 (1995)
[54] S. Kumar, K. S. A. Butcher, and T. L. Tonsley, J. Vac. Sci. Technol. A 14, 2687 (1996)
[55] H. Sjostrom, L. Hultman, J. E. Sundgren, S. V. Hainsworth, T. F. Page, and G. S. A. M. Theunissen, J. Vac. Sci. Technol. A 14, 56 (1996)
[56] A. Bousetta, M. Lu, A. Bensaoula, and A. Schultz, Appl. Phys. Lett. 65, 696 (1994)
[57] D. R. Mckenzie, D. A. Muller, and B. A. Pailthorpe, Phys. Rev. B 54, 144 (1996)
[58] J. G. Naeni, B. M. Way, J. R. Dahn, and J. C. Irwin, Phys. Rev. B 54, 144 (1996)
[59] J. H. Kaufman, S. Metin, and D. D. Saperstein, Phys. Rev. B 39, 13053 (1989)
[60] B. Kleinsorge, A. C. Ferrari, J. Robertson, and W. I. Milne, J. Appl. Phys. 88, 1149 (2000)
[61] S. Bhattacharyya, C. Vallee, C. Cardinaud, O. Chauvet, and G. Turban, J. Appl. Phys. 85, 2162 (1998)
[62] 巫金龍，類鑽碳薄膜成長MIS元件特性分析，國立中山大學，碩士論文，2006。
[63] 吳家偉，電子迴旋共振化學氣相沉積系統之製程參數對類鑽碳膜性質之影響，國立成功大學，碩士論文，2003。
[64] 許維勳，電沉積類鑽碳薄膜，國立中山大學，碩士論文，2007。
[65] 張振福，微波化學氣相沉積及磁控濺鍍成長類鑽石之研究，國立中山大學，博士論文，2002