臺灣博碩士論文加值系統

本實驗利用熱化學氣相沉積法來成長奈米碳管，主要的碳原子來源為甲烷，並以氬氣當載氣，將甲烷帶入爐管中反應，利用觸媒熱分解效應將甲烷分解成碳原子並成長出碳管。本研究中，我們針對催化劑厚度與成長溫度以及不同的催化劑三種因素對於所成長奈米碳管的的結構性質及場發射特性的影響來進行深入研究。
我們使用拉曼光譜及SEM來分析的奈米碳管的結構性質，而奈米碳管的場發射特性則是在高真空狀況下施加很大的電場所量測得到。從拉曼光譜及SEM的分析我們發現，當催化劑鎳膜成長厚度愈厚時，催化劑鎳膜在成核時期所形成鎳催化顆粒會愈大，造成碳管數量變少，而碳管的直徑卻會逐漸增大。當溫度較低時，所提供的熱能可能並不足以將原子填補至適當的結晶位置，所以在奈米碳管中會形成較多的結晶缺陷。而當溫度被提高時，碳原子的表面遷移速率增大，因此可以幫助碳管的成長，石墨結晶化程度也較好。而且從不同催化劑(Fe,Co,Ni)比較當中，以鎳膜成長的奈米碳管的性質最佳。
由F-N圖我們發現，鎳膜厚度增加的確會使功函數φ增大，場發射電流會因為所成長的碳管數量減少、碳管尖端電場增強效應減低、及碳管功函數增大三個因素同時作用而降低。這種場發射電流的改變不僅是因為所成長的碳管數量及直徑的改變所造成的，所成長碳管的結晶結構及功函數也會改變，造成電子發射難易程度的改變也是一個非常重要的因素。

In this work, thermal chemical vapor deposition was utilized to grow carbon nanotubes (CNTs). Silane was the main source for carbon, and argon was used as the carrier gas. CNTs were synthesized from carbon atoms obtained from catalytic thermal decomposition of silane. In this research, we study the effect of catalyst metal thickness and deposition temperature and different catalyst on structural properties and field emission characteristics of ocarbon nanotubes (CNTs) which were synthesized by thermal chemical vapor deposition of methane.
Raman spectroscopy and SEM were employed to study structural properties of CNTs, whereas field emission characteristics of CNTs were measured in high vacuum. From SEM and Raman spectroscopic studies, it is found that as catalyst nickel thickness gets thicker, the size of nickel balls formed in the nucleation period gets larger. Hence, the number of CNTs gets smaller, and the diameters of synthesized CNTs get larger. It is suspected that the supplied thermal energy at low temperature is not high enough to activate catalytic reaction to synthesize CNTs. At high temperature, thermal energy supplied has already cross the threshold for nucleation, and the diameter of CNT reach a saturation value. And CNTs were synthesized from tungsten layer is the best of different catalyst (Fe,Co,Ni).
From Fowler-Nordheim tunneling analysis, it was found that the increase in nickel thickness indeed increases the work function of CNT. Hence, we arrive at the conclusion that the decrease in the number of CNT, the decrease in the field enhancement factor, and the increase in the work function of CNT are three main factors that causes the decrease in the field emission current for larger nickel metal thickness. it is found that this change in field emission current is caused not only by the change in number and diameter of CNTs, but also by the change in crystalline structure and work function of CNTs. The increase in the work function of CNTs make it difficult for electrons to emit from CNTs which can play an important role in the emission current.

封面內頁
簽名頁
授權書．．．．．．．．．．．．．．．．．．．．．．．．．iii
中文摘要．．．．．．．．．．．．．．．．．．．．．．．．iv
英文摘要．．．．．．．．．．．．．．．．．．．．．．．．v
誌謝．．．．．．．．．．．．．．．．．．．．．．．．．．vii
目錄．．．．．．．．．．．．．．．．．．．．．．．．．．ix
圖目錄．．．．．．．．．．．．．．．．．．．．．．．．．xii
表目錄．．．．．．．．．．．．．．．．．．．．．．．．．xxi

第一章　緒論
1.1 奈米碳管的歷史與簡介．．．．．．．．．．．．．．． 2
1.2 奈米碳管的結構．．．．．．．．．．．．．．．．．． 7
1.3 奈米碳管的應用價值．．．．．．．．．．．．．．．． 9
第二章　理論與研究方法
2.1 電子場發射理論．．．．．．．．．．．．．．．．．． 12
2.1.1 奈米碳管作為場發射電子源．．．．．．．．．． 16
2.1.2 應用在場發射平面顯示器．．．．．．．．．．． 20
2.2 奈米碳管的成長機制．．．．．．．．．．．．．．．． 23
2.2.1 奈米碳管主要成長機制．．．．．．．．．．．． 23
2.2.2 催化劑在奈米碳管成長中扮演的角色．．．．．． 24
2.2.3 奈米碳管成長模式分類．．．．．．．．．．．． 29
2.3 奈米碳管的製程方法．．．．．．．．．．．．．．．． 31
第三章 實驗儀器與實驗步驟
3.1 實驗動機．．．．．．．．．．．．．．．．．．．．． 42
3.2 實驗流程方塊圖．．．．．．．．．．．．．．．．．． 43
3.3 實驗裝置與分析儀器．．．．．．．．．．．．．．．． 44
3.3.1 蒸鍍系統 & Thermal-CVD．．．．．．．．．．． 44
3.3.2 SEM&拉曼光譜量測&電性量測．．．．．．．．． 48
3.4 實驗方法與步驟．．．．．．．．．．．．．．．．．． 58
3.4.1 蒸鍍系統 & Thermal-CVD．．．．．．．．．．． 58
3.4.2 電性量測．．．．．．．．．．．．．．．．． 59
第四章 實驗結果與討論
4.1 鎳膜厚度對奈米碳管成長機制的研究與討論．．．．．． 61
4.1.1 SEM(掃瞄式電子顯微鏡)的分析．．．．．．．． 61
4.1.2 Raman(拉曼光譜)的分析．．．．．．．．．．．． 72
4.1.3 電子場發射的分析．．．．．．．．．．．．．． 77
4.2 不同催化劑(Fe,Co,Ni)對奈米碳管成長機制的研究與討論．．．．．．．．．．．．．．．．．．．．．．．．83
4.2.1 SEM(掃瞄式電子顯微鏡)的分析．．．．．．．．83
4.2.2 Raman(拉曼光譜)的分析．．．．．．．．．．．90
4.2.3 電子場發射的分析．．．．．．．．．．．．．． 93
4.3 成長溫度對奈米碳管成長機制的研究與討論．．．．．．97
4.3.1 SEM(掃瞄式電子顯微鏡)的分析．．．．．．．．97
4.3.2 Raman(拉曼光譜)的分析．．．．．．．．．．． 109
4.3.3 電子場發射的分析．．．．．．．．．．．．．． 114
第五章 結論．．．．．．．．．．．．．．．．．．．．．． 119

參考文獻．．．．．．．．．．．．．．．．．．．．．．．．122

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