鑽石擁有傑出的材料特性，使得鑽石能在許多惡劣的環境下工作。本論文主要探討摻硼鑽石薄膜製作，提高摻硼薄膜的可見光穿透率並降低電阻率，使得應用在工業上有更多的發展空間。研究以氫氣、氬氣、甲烷以及氧氣為氣體源，硼酸三甲基酯為摻雜源，利用微波電漿輔助化學氣相沉積系統(MWCVD)，製作摻硼鑽石薄膜。沉積鑽石薄的的基板，以電漿輔助化學沉積系統(PECVD)成長類鑽碳(DLC)薄膜於矽基板上，作為成長鑽石的基板。研究先以不同硼酸三甲基酯載體氣體之流量、氬氣在製程氣體中比例改變、製程壓力變化，對摻硼鑽石薄膜可見光穿透率及電阻率的影響進行分析及探討，實驗最後再以偏壓輔助成長鑽石薄膜並加長沉積薄膜的時間，增加薄膜厚度。實驗的樣品經由N&K薄膜厚度分析儀、拉曼光譜儀、霍爾量測、van der pauw量測，分析鑽石薄膜厚度及薄膜光學特性、鑽石特性峰值、載子遷移率、載子濃度、薄膜電阻率。
實驗結果發現，以硼酸三甲基酯作為摻雜源，載體氣體流量越大表示反應氣體中所含硼原子濃度越高，可增加薄膜載子濃度並降低電阻率。增加製程壓力也會使載子濃度提高而增加薄膜對光的吸收率，降低光穿透率。改變氬氣在製程氣體比例增加可有效提高薄膜可見光穿透率。以類碳鑽膜作為成長鑽石的基板，可得到品質較好的鑽石薄膜，並利用偏壓機制及長時間的成長，使鑽石薄膜變厚，且成長速率穩定，約為0.37 μm/hr，成長三小時後薄膜電阻率為0.03Ω-cm，且厚度達微米時仍具有60%以上可見光穿透率。與文獻比較，具有相當低的薄膜電阻率及厚度，比起文獻的可見光穿透率30%~50%有更進一步的提高，成功做出摻硼的鑽石透明導電薄膜。

This thesis presents the fabrication of transparent conductive Boron-Doped CVD diamond (BDD) thin film with the appropriate processing parameters. The BDD shows the transmittance in the visible wavelength and good electrical conductivity. The depositing rate of Diamond films yields 0.37 μm per hour with Hydrogen, Argon, Methane and oxygen as gas sources, and B(OCH3)3 was used as the doping source. Microwave plasma chemical vapor deposition (MWCVD) was performed for the BDD deposition. Also, PECVD was applied to grow diamond-like Carbon (DLC) film on silicon as substrate. Through systematical experiments, the influence of carrier gas flow rates of B(OCH3)3, the variation of ratio of Argon, and growth pressure of BDD on the transmittance in the visible light and electrical conductivity has been studied. In addition, dc bias was applied to synthesize diamond films and extend long depositing time shows the stable growth rate of diamond films. The thickness of BDD films increases and acquired more than 60% optical transmittance. BDD samples were analyzed by Raman Spectroscopy for the diamond quality, N & K Analyzer for the film thickness and optical properties. Van Der Pauw I-V Measurement and Hall Measurement were analyzed p-type diamond films carrier mobility, carrier concentration, electrical resistivity.
By increasing Argon and applying negative dc bias can improve the growth rate and transmittance of diamond films. And the quality of diamond films could be improved by the coating of DLC on Si substrates. This work has achieved fabricating a transparent conducting BDD successfully.

目錄
中文摘要 ..................................……………………......... i
Abstract ...........................………………………............... ii
目錄.......................................……………………….…...... iii
表格目錄 .................................…………………….......... v
圖目錄...................................………………………......... vi
第一章 緒論 .................................…………………....... 1
1.1 前言……………………………………………………1
1.2 人工合成鑽石歷史回顧………………………………1
1.3 鑽石結構………………………………………………2
1.4 鑽石的特性及應用……………………………………2
1.5 鑽石薄膜製作方法……………………………………3
第二章 基本理論與文獻回顧……………………………5
2.1 鑽石薄膜光學及電性研究……………………………5
2.2 載子濃度與薄膜可見光穿透率關係…………………7
2.3 微波輔助化學氣相沉積………………………………8
2.4 鑽石薄膜成核與成長…………………………………8
2.5 摻硼鑽石薄膜…………………………………………9
第三章 研究方法與實驗步驟………………………….10
3.1 實驗方法及步驟……………………………………10
3.1.1 微波電漿輔助化學氣相沉積 ( MWCVD )系統…………………………………………………………10
3.1.2 基板前處理…………………………………………13
3.1.3 實驗操作步驟與實驗條件…………………………13
3.2 薄膜研究分析…………………………………………18
3.2.1 N&K薄膜厚度分析儀Van der Pauw……………18
3.2.2 Van der Pauw……………………………………18
3.2.3 室溫霍爾量測………………………………………22
3.2.4 拉曼光譜儀(Raman)………………………………24
第四章 實驗結果與討論…………………………………26
4.1 摻雜源改變載體氣體流量成長鑽石分析……………26
4.2 成長鑽石薄膜與製程壓力影響………………………29
4.3 成長鑽石薄膜對氬氣在製程氣體中的比例影響…………………………………………………………32
4.4偏壓輔助對成長鑽石薄膜影響………………………35
4.5鍍膜沉積時間對成長鑽石薄膜之分析………………41
4.5.1 無施加偏壓下增加鍍膜沉積時間…………………41
4.5.2 施加偏壓下增加鍍膜沉積時間……………………44
第五章 結論………………………………………………49
Reference………………………………………………50

[1]Y. Tzeng, M. Yoshikawa, M. Murakawa “,Applications of diamond films and related materials”, Materials & Design, 73, (1992) 60
[2] Takayuki Toyama，Yasuo Koide，Masanori Murakmi “,Field emission of polycrystalline diamond films grown by microwave-plasma chemical vapor deposition. I. Effects of surface morphology of diamond”. Diamond Relat. Mater. 11 (2002) 1897
[3] P.W.Bridgman “,Synthetic diamond”, Science American, 193, 5, (1955) 42
[4] W.G.Eversole “,Synthesis of Diamond”. U.S.Patent 3030187. 30, (1962) 188
[5] M. Aslam, I. Taher, A. Masood, M.A. Tamor and T.J.Potter, “Piezoresistivity in vapor-deposited diamond films” Appl. Phys. Lett, 60,(1992) 2923-2925.
[6] 陳偉斯 “,摻硼之化學氣相沉積鑽石的拉曼光譜分析”,國立中山大學碩士論文(2002)
[7] Jason Stotter, Jerzy Zak “,Optical and Electrochemical Properties of Optically Transparent, Boron-Doped Diamond Thin Films Deposited on Quartz”, Anal. Chem. 74, (2002) 5924-5930
[8] Min-Sheng You “,Low temperature growth of highly transparent nanocrystalline diamond films on quartz glass by hot filament chemical vapor deposition” Diamond & Related Mater 18 (2009) 155–159
54
[9] L. C. Chen, P. D. Kichambare “,Growth of highly transparent nanocrystalline diamond films and a spectroscopic study of the growth,” J. Appl Phys. 89 (2001) 753-759
[10] B. Chapman , Glow Discharge Process, John Wiley & Sons, N.Y. (1980)
[11] J.L. Vossen and W.Kern, Thin Film Processes, Acadmic Press, N.Y. (1978)
[12] Hong Xiao, “Introduction to Semiconductor Manufacturing Tehnology,” Prentice-Hall, N.Y. (2001)
[13]B.R. Stoner, G.H. Ma, S.D. Wolter, Y.C. Wang, R.F. Davis, J.T. Glass, Diamond Relat. Mater. 2(1993)142
[14]B.V. Derjaguin and D.V. Fedoseev, “Growth of Diamond and Graphite from Gas Phase”, Chap. 4 Nauka (1977)
[15] P.W.Bridgman “,Synthetic diamond”, Science American, 193, 5, (1955), 42
[16]施敏,半導體元件物理與製作技術,國立交通大學出版社,(2002),第二版
[17]潘明凱“,類鑽碳薄膜摻雜氮氣與氨氣性質探討”,國立中山大學碩士論文(2011)
[18] A.R. Forouhi and I.Bloomer “,Optical dispersion relations for amorphous semiconductors and amorphous dielectrics” Phys.Rev.B 34. (1986) 7018-7026.
[19] A.R. Forouhi and I.Bloomer “, Accurate and rapid determination of thickness n and k spectra, and resistivity of indium-tin-oxide films” J. Vac. Sci. Tech . A17, (1999) 55 1843 - 1847.
[20 ]Eugene Hecht “,Optics”Addison Wesley. (2002) 428-429.
[21] Yong Liu, Gang Xu, Chenlu Song, Wenjian Weng, Piyi Du, Gaorong “, Modification on Forouhi and Bloomer model for the optical properties of amorphous silicon thin films”, Elsevier, February (2007)
[22] C.X. Wang , G.W. Yang “,Highly oriented growth of n-type ZnO films on p-type
Single crystalline diamond films and fabrication of high-quality transparent ZnO/diamond heterojunction”, Carbon, 42, (2004) 317–321
[23] J.A.N. Goncalves, G.M. Sandonato, K. Iha “,Diamond Relat”, Mater. 11, (2002) 1578-1583.
[24] P. H. Lahr and W. G. Eversole, “Compression Isotherms of Argon, Krypton, and Xenon Through the Freezing Zone,” J. Chem. Eng. Data, 7, (1962) 42-47
[25] Chaochin Su and Jiing-Chyuan Lin, “Hydrogen Chemistrry on Diamond Surfaces,” 60, (2002) 449-456