臺灣博碩士論文加值系統

本文將以奈米碳管薄膜製作一氣體感測元件，利用奈米碳管的優良場發射特性及各種氣體各有其獨特的崩潰電壓，文中將針對奈米碳管在氧氣中的場致發射特性去做一探討。由於奈米碳管具有奈米尺度的管徑，極大的長寬比，穩定的化學性質及強韌的機械性質，因此，一直是極具有潛力的新興材料。由場致發射的量測中，發現奈米碳管具有非常優異的場發射特性，我們利用由熱化學氣相沉積法合成奈米碳管薄膜於矽基板上，將此奈米碳管薄膜用來在大氣底下，對個別氣體下以及針對氧氣的比例進行場發射量測。我們設計一奈米碳管氣體感測元件，分別通入純氮氣，純氧氣，進行電流對電壓的量測，再以氮氣為背景氣體，在量測腔體內通入不同比例濃度的氧氣，去分析電壓電流的曲線；由於利用奈米碳管的場發射來感測氣體，會有極佳的靈敏度，且藉由場發射電壓電流的曲線變化來感測氣體濃度，沒有吸附和去吸附的問題，也無可逆反應的考量，操作在極低的電壓，因此奈米碳管相當適合當作氣體感測元件。

In this thesis, we study on fine field emission characteristic of CNTs and make gas sensor with CNTs film. Various kinds of gas have unique breakdown voltage; we do a discussion to CNTs field emission characteristic in oxygen. Because CNTs has pipe diameter of nanometre-scale, great aspect ratio, steady chemical property and tough mechanical nature, so, it has been a new developing material extremely with potentiality all the time. While measurement of field emission, it’s found CNTs has very excellent characteristic of discharging. We synthesize CNTs film on Si-substrate by CVD, and use this CNTs film for examining to the discharging carried on of the proportion of oxygen to gas specifically under the atmosphere pressure. We design a CNTs gas sensor measurement, differentiate and enter pure nitrogen and pure oxygen, the quantity of carrying on voltage-current is examined. And then regard nitrogen as background gas, examine oxygen which enters the different proportions in chamber in quantity, and analyze I-V Curve; because make use of field emission of CNTs to detect the gas, there is extremely good sensitivity. And detect the proportions of gas with the I-V Curve change of discharging, there are not the questions of adsorption and desorption of gas, and it is not limited by consideration of reversibility, and operate it in the extremely low electric field.
So CNTs is quite suitable for regarding as gas sensor.

中文摘要 ----------------------------------------------------------------------------------- I
英文摘要 ----------------------------------------------------------------------------------- II
目錄 ----------------------------------------------------------------------------------------- IV
圖目錄 ------------------------------------------------------------------------------------- VII
第一章 序論
1-1 前言 ------------------------------------------------------------------------------ 1
1-2 章節介紹 ------------------------------------------------------------------------ 2
第二章 文獻回顧
2-1 奈米碳管的歷史與簡介 ------------------------------------------------------ 3
2-2 奈米碳管的結構 --------------------------------------------------------------- 4
2-3 奈米碳管的性質
2-3-1 熱傳導性質 --------------------------------------------------------------- 8
2-3-2 機械性質 ----------------------------------------------------------------- 9
2-3-3 電性 ----------------------------------------------------------------------- 9
2-3-4 場發射性質 --------------------------------------------------------------- 10
2-4 奈米碳管的成長機制
2-4-1 碳原子的擴散路徑 ----------------------------------------------------- 11
2-4-2 催化劑中碳原子的擴散驅動力 ------------------------------------- 12
2-4-3 成長起源 ---------------------------------------------------------------- 14
2-4-4 奈米碳管在觸媒表面成長機制的三步驟 -------------------------- 15
2-5 奈米碳管的製造方法
2-5-1 電弧放電法 (arc discharge method) --------------------------------- 15
2-5-2 雷射剝離法 (laser ablation method) --------------------------------- 16
2-5-3 化學氣相沉積法 (CVD, chemical vapor deposition) ------------- 16
2-5-4 電漿輔助化學氣相沉積法 (plasma-enhanced CVD) ------------- 17
2-5-5 其它方法製作奈米碳管 ---------------------------------------------- 18
2-6 CVD製程成長CNT的原理 ------------------------------------------------- 20
2-7 奈米碳管的應用
2-7-1 場發射顯示器 ------------------------------------------------------------ 23
2-7-2 場效電晶體 -------------------------------------------------------------- 24
2-7-3 強化複合材料 ------------------------------------------------------------ 25
2-7-4 儲氫材料 ---------------------------------------------------------------- 25
2-7-5 小而冷的X光源 ------------------------------------------------------- 26
第三章 奈米碳管於氣體之場發射
3-1 電子場發射理論
3-1-1 金屬的場發射理論 ----------------------------------------------------- 28
3-1-2 Fowler-Nordheim ----------------------------------------------------- 29
3-1-3 電子的場發射理論的適用性與限制 --------------------------------- 34
3-2 氣體放電
3-2-1 氣體放電 ----------------------------------------------------------------- 35
3-2-2 湯森放電理論 ------------------------------------------------------------ 41
3-3 各類型氣體感測器原理
3-3-1 觸媒燃料型氣體感測器 ----------------------------------------------- 43
3-3-2 場效電晶體型氣體感測器 --------------------------------------------- 43
3-3-3 金屬氧化物半導體氣體感測器 -------------------------------------- 44
3-3-4 質量型氣體感測器 ------------------------------------------------------ 44
3-3-5 光纖型氣體感測器 ------------------------------------------------------ 45
3-3-6 電化學式氣體感測器 --------------------------------------------------- 45
3-3-7 其他精密儀器 ------------------------------------------------------------ 46
第四章 實驗步驟與結果討論
4-1 實驗設計
4-1-1 陽極和陰極之選擇 ----------------------------------------------------- 47
4-1-2 實驗安排 ----------------------------------------------------------------- 50
4-2 奈米碳管置於氣體中量測
4-2-1 感測元件置於氮氣、氧氣、空氣中量測 --------------------------- 53
4-2-2 感測元件置於不同比例的氧氣中量測 ----------------------------- 55
4-2-3 感測元件對時間量測 --------------------------------------------------- 56
4-3 使用Spindle Type 驗證氣體感測
4-3-1 Spindle Type 元件結構 ------------------------------------------------- 59
4-3-2 Spindle Type 氣體感測 ------------------------------------------------- 60
4-4 使用短碳管於感測元件
4-4-1 實驗架構 ----------------------------------------------------------------- 65
4-4-2 加熱短碳管氣體感測器對時間量測 --------------------------------- 68
4-4-3 短奈米碳管對氧氣濃度作鑑別 -------------------------------------- 69
4-4-4 濕氣中對短奈米碳管場發射的影響 --------------------------------- 70
第五章 結論 ---------------------------------------------------------------------------- 72
參考文獻 ----------------------------------------------------------------------------------- 74


圖目錄 頁碼
圖2.1 碳的同素異形體 ---------------------------------------------------------------- 4
圖2.2 (a)石墨結構 (b)鑽石結構 ------------------------------------------------------- 6
圖2.3 (a)單壁奈米碳管 (b) 多壁奈米碳管構 -------------------------------------- 6
圖2.4 單層奈米碳管三種不同的結構 (a)椅狀armchair，(b)鋸齒狀 -------- 7
圖2.5 單層奈米碳管的分類方法 ----------------------------------------------------- 7
圖2.6 單層奈米碳管 ------------------------------------------------------------------- 8
圖2.7 單壁奈米碳管結構上參數的定義 ------------------------------------------ 8
圖2.8 碳經由觸媒擴散成長機構的示意圖 ---------------------------------------- 11
圖2.9 由觸媒表面擴散成長機構之示意圖 ---------------------------------------- 12
圖2.10 碳源在金屬催化劑顆粒中擴散的示意圖 -------------------------------- 13
圖2.11 (a)底部成長模式及(b)頂部成長模式之示意圖 -------------------------- 14
圖2.12 電弧放電法示意圖 ------------------------------------------------------------ 19
圖2.13 雷射激發法示意圖 ------------------------------------------------------------ 19
圖2.14 化學氣相沉積法原理示意圖 ------------------------------------------------ 20
圖2.15 化學氣相沈積法成長奈米碳管示意圖 ------------------------------------ 22
圖2.16 CNT-FED ------------------------------------------------------------------------ 26
圖2.17 顯微鏡 (AFM、STM) 掃描探針 ------------------------------------------- 27
圖2.18 以奈米碳管為主的場效電晶體 --------------------------------------------- 27
圖3.1(a) 未外加電場的能帶圖 ------------------------------------------------------- 28
圖3.1(b) 加強電場之下的能帶圖 --------------------------------------------------- 29
圖3.2 外加電場作用下固態金屬能階分佈 --------------------------------------- 34
圖4.1 陽極為鐵球之元件示意圖 ----------------------------------------------------- 47
圖4.2 陽極為直徑3mm銅柱之元件示意圖 --------------------------------------- 48
圖4.3 陽極為直徑6mm金屬圓柱之元件示意圖 -------------------------------- 49
圖4.4 自製實驗腔體-真空罐 --------------------------------------------------------- 51
圖4.5 自製金屬屏蔽環境 ------------------------------------------------------------ 51
圖4.6 奈米碳管感測元件結構示意圖 ---------------------------------------------- 52
圖4.7 奈米碳管薄膜FE-SEM圖 ----------------------------------------------------- 52
圖4.8 氮氣中奈米碳管的場發射電壓電流圖 ------------------------------------- 54
圖4.9 氧氣中奈米碳管的場發射電壓電流圖 ------------------------------------- 54
圖4.10 奈米碳管於各種氣體的場發射電壓電流圖 ------------------------------ 55
圖4.11 各種氧氣比例之奈米碳管場發射電壓電流圖 -------------------------- 56
圖4.12 奈米碳管薄膜電壓對時間量測曲線 ------------------------------------- 57
圖4.13奈米碳管薄膜電壓-電流曲線呈現電阻性 --------------------------------- 58
圖4.14 Spindle Type架構示意圖 ----------------------------------------------------- 59
圖4.15 Spindle Type之SEM圖 ------------------------------------------------------- 59
圖4.16 Spindle Type之SEM圖 ------------------------------------------------------- 60
圖4.17 Spindle Type於氮氣對時間量測 -------------------------------------------- 61
圖4.18 Spindle Type於氧氣對時間量測 -------------------------------------------- 61
圖4.19 Spindle Type於氮氣、氧氣對時間量測 ----------------------------------- 62
圖4.20 Spindle Type於空氣下電壓對電流關係圖 --------------------------------- 62
圖4.21 Spindle Type於氮氣下電壓對電流關係圖 --------------------------------- 63
圖4.22 Spindle Type於氧氣下電壓對電流關係圖 --------------------------------- 63
圖4.23 Spindle Type於氮、氧下電壓對電流關係圖 ------------------------------ 64
圖4.24 短奈米碳管之SEM圖 ------------------------------------------------------- 65
圖4.25 短奈米碳管製作感測元件架構圖 ------------------------------------------ 66
圖4.26 短奈米碳管製作感測元件圖 ------------------------------------------------ 66
圖4.27 水泥電阻 ----------------------------------------------------------------------- 67
圖4.28 短奈米碳管感測元件利用水泥電阻加熱圖 ------------------------------ 67
圖4.29 短奈米碳管加熱比較的I-V Curve ------------------------------------------ 68
圖4.30 不同氧濃度的I-V Curve ----------------------------------------------------- 69
圖4.31 實驗腔體中通入水氣 --------------------------------------------------------- 70
圖4.32 氮氣含水氣的短碳管I-V Curve -------------------------------------------- 71

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