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研究生： 古鎮豪
Ku, Chen-Hao
論文名稱： 以CCl4/H2於熱燈絲化學氣相沉積系統中 成長奈米鑽石薄膜之研究
Growth of Nanocrystalline Diamond Films by Hot Filament Chemical Vapor Deposition Using CCl4/H2 Gases
指導教授： 吳季珍
Wu, Jih-Jen
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2002
畢業學年度： 90
語文別： 中文
論文頁數： 119
中文關鍵詞： 低溫成長 、奈米鑽石 、熱燈絲 、四氯化碳 、表面粗糙度
外文關鍵詞： low temperature growth, carbon tetrachloride, surface roughness, nanocrystalline diamond, hot filament
相關次數： 點閱：144  下載：2 
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    • 摘要
    本論文乃利用CCl4/H2混合氣體作為反應物，以熱燈絲化學氣相沉積法沉積奈米鑽石薄膜。本研究之成長條件為熱燈絲溫度1900℃~2000℃，CCl4濃度([CCl4])為1.5%~3.5%，基板溫度(Ts)為530℃~730℃，基板距鎢絲距離(d)為4 mm~7 mm。本研究利用SEM分析薄膜之表面與截面型態，並由截面估算薄膜之厚度。薄膜之鍵結型態則以Raman光譜儀分析，而薄膜之結晶成分與微結構分別以XRD和TEM分析之，除此也以AFM分析薄膜之表面粗糙度。
    本研究結果顯示，在其他成長條件固定而分別以[CCl4]、Ts、及d為鍍膜變數時，隨[CCl4]或Ts提高，抑或是d值的降低，1小時成長之薄膜厚度有著先增加後下降繼而再增加的一般趨勢。而由進一步的鍵結及結構分析可知在厚度先增加的鍍膜條件範圍內成長的薄膜可分為鑽石薄膜(成長區域I)及奈米鑽石薄膜(成長區域II)兩區域，在厚度下降的鍍膜條件範圍內成長的亦為奈米鑽石薄膜(成長區域III)；而厚度繼而增加的範圍則為成長非晶形碳膜或石墨(成長區域IV)。當將鍍膜時間增長為獲得較厚之奈米鑽石薄膜時，則發現區域II成長的薄膜內，鑽石晶粒有隨厚度增加而增加之趨勢；即使在成長區域III的成長條件下，也必須在鍍膜變數達某一臨界值後沉積的奈米鑽石薄膜才能隨厚度增加時仍維持奈米級的晶粒大小。由AFM表面粗糙度之分顯示，在d=5 mm，基板溫度為610℃~730℃範圍內成長1 hr之奈米鑽石薄膜，薄膜之表面粗糙度皆小於30 nm(rms)，於2.0% CCl4，610℃的條件下甚至可成長出表面粗糙度約為6 nm之奈米鑽石薄膜。而根據XRD與TEM之分析也顯示，在此鍍膜條件範圍內，薄膜內鑽石之平均晶粒大小約介於10-30 nm之間。

    Abstract
    The growth characteristics of the nanodiamond films deposited using CCl4/H2 in a hot-filament chemical vapor deposition reactor were investigated in this study. Film growth was studied under the following conditions: filament temperature, concentration of CCl4 ([CCl4]), substrate temperature (Ts), distance between substrate and filament (d) in ranges 1900℃-2000℃, 1.5%-3.5%, 530℃-730℃ and 4 mm- 7 mm, respectively. Film thickness and surface morphology studies were conducted by scanning electron microscopy. The surface roughness of the diamond film was measured using atomic force microscopy. Raman spectroscopy and glancing incident angle X-ray diffraction were employed to evaluate the bonding and crystalline structures of the films, respectively. The microstructure of the diamond films was studied using transmission electron microscopy.
    The thickness of the film deposited for 1 hr first increased and decreased afterwards, then increased again when [CCl4] and Ts were increased and d was decreased, respectively. Bonding and structural analyses reveal that diamond films were synthesized in the first thickness increasing region (growth region I) and only amorphous carbon films or graphitic carbon films were obtained in the second thickness increasing region (growth region IV). Nanodiamond films were grown in the near maximum thickness region (growth region II) as well as in the thickness decreasing region (growth region III). As the growth times were elongated further, however, the grain sizes of the diamond films deposited in the growth region II were increased with film thickness. Thick nanodiamond films with uniform grain size over entire film were only successfully grown beyond a critical point in the growth region III. AFM analyses show that the nanodiamond films grown for 1 hr at substrate temperatures of 610℃-730℃ and a distance between substrate and filament of 5 mm possess typical rms surface roughness of 10-15 nm. An optimal rms surface roughness of 6 nm has been achieved. Furthermore, XRD and TEM analyses show that the average grain size in ranges 10-30 nm under these conditions.

    總目錄 中文摘要……………………………………………………I 英文摘要……………………………………………………II 誌謝…………………………………………………………IV 總目錄………………………………………………………V 圖目錄……………………………………………………VIII 表目錄……………………………………………………XIV 第一章 緒論………………………………………………1 1.1 前言……………………………………………1 1.1.1 鑽石薄膜………………………………………1 1.1.2 鑽石薄膜所面臨的瓶頸………………………5 1.1.3 奈米鑽石薄膜…………………………………6 1.2 研究動機與目的………………………………8 第二章 理論基礎與文獻回顧……………………………11 2.1 CVD法沉積鑽石薄膜…………………………………11 2.1.1 CVD法中鑽石之成核機制…………………………11 2.1.2 鑽石之成長機制…………………………………16 2.1.3 鑽石之表面結構與表面化學……………………22 2.1.3-1 氫原子與鑽石表面……………………………22 2.1.3-2 不同鑽石表面之成長模型……………………22 2.2 CVD法成長奈米鑽石薄膜……………………………28 2.2.1 前言………………………………………………28 2.2.2 提高CH4/H2比例成長奈米鑽石薄膜……………29 2.2.3 以CH4/Ar/H2成長奈米鑽石薄膜…………………29 2.2.3-1 以CH4/Ar/H2成長奈米鑽石薄膜之成長機構…33 2.2.3-2 以CH4/Ar/H2成長奈米鑽石薄膜之成核機構…35 第三章 實驗參數與研究方法……………………………42 3.1 實驗流程………………………………………………42 3.2 系統設計………………………………………………43 3.2.1 反應氣體輸送裝置…………………………………43 3.2.2 反應器………………………………………………43 3.2.3 真空及排氣裝置……………………………………44 3.3 實驗材料………………………………………………47 3.3.1 反應物………………………………………………47 3.3.2 基板材料……………………………………………47 3.4 基板前處理……………………………………………47 3.5 鎢絲之前處理…………………………………………48 3.6 實驗操作步驟…………………………………………48 3.7 分析與鑑定……………………………………………50 3.7.1 掃描式電子顯微鏡分析……………………………50 3.7.2 拉曼光譜分析………………………………………50 3.7.3 原子力顯微鏡………………………………………53 3.7.4 X光繞射分析儀……………………………………56 3.7.5 穿透式電子顯微鏡…………………………………56 第四章 結果與討論………………………………………57 4.1 鎢絲溫度效應…………………………………………57 4.2 CCl4濃度與基板溫度效應……………………………57 4.2.1 薄膜表面與截面型態之分析………………………59 4.2.2 薄膜結晶型態之分析………………………………59 4.2.3 薄膜鍵結型態之分析………………………………69 4.2.4 薄膜微結構之分析…………………………………72 4.2.5 薄膜表面粗糙度之分析……………………………73 4.3 鍍膜時間效應…………………………………………87 4.4 基板與鎢絲距離之效應………………………………91 4.5 討論……………………………………………………99 第五章 結論………………………………………………112 第六章 參考文獻…………………………………………114 作者簡介…………………………………………………119

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