以乙炔熱裂解式化學氣相沉積法成長奈米碳管製程之探討與研究

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研究生：	李家宏 Li , Chia-Hung
論文名稱：	以乙炔熱裂解式化學氣相沉積法成長奈米碳管製程之探討與研究
指導教授：	蔡春鴻 Tsai , Chuen-Hong
口試委員:
學位類別：	碩士 Master
系所名稱：	原子科學院 - 工程與系統科學系 Department of Engineering and System Science
論文出版年：	2005
畢業學年度：	93
語文別：	中文
論文頁數：	76
中文關鍵詞：	高溫爐、多層碳管、場發射
外文關鍵詞：	Thermal-CVD, Multiwall Carbon Nanotube, Field Emission
相關次數：	點閱：1 下載：0
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奈米碳管現在最熱門的應用之一，奈米碳管場發射顯示器(Carbon Nanotube Field Emission Display)，為了將奈米碳管優異的電子場發射特性應用在具有無限潛力的平面顯示器上，必須解決碳管成長於玻璃基板的材料基本問題。在本論文中，發展出一套臨場可定位的低溫奈米碳管製程，應用黃光微影製程將10 µm X 10 µm的圖案定位，成功以乙炔於熱裂解式化學氣相沉基法中，於550 ℃及500 ℃的玻璃基板上合成大面積臨場的奈米碳管。在穿透式電子顯微鏡(TEM)觀察之下，碳管結構上為中空結構，並無竹節狀結構的出現。場發射測試之下，550 ℃及500 ℃成長於玻璃基板上的碳管，每平方公分的電流密度達到數個至數十個毫米安培，經F – N 方程的計算，550 ℃碳管起始電壓為4.61 V / µm ， 500 ℃碳管起始電壓為6.15 V / µm。對550 ℃碳管作大面積場發射螢光實驗，當所加電壓由0 V 增加到700 V，螢光亮點有越來越多且越趨於均勻發光的趨勢，顯示在更大面積的應用上是可行的，此製程的發展對於碳管的應用開啟了新的一頁。

Carbon nanotube field emission display is one of the hot applications of carbon nanotube(CNT). For solving the package problem , we should directly grow well aligned-CNTs on the glass substrate.In large-area field emission display applications where high stress point glass substrate is used for vacuum-sealed packaging and low cost considerations, the CNTs synthesis temperature lower than the stress point of ~ 570℃ is required. In the thermal CVD processes, the catalyst passivation due to the slow carbon diffusion rate limiting and the consequent amorphous carbon formation on the catalyst surface was considered to be the main reason hampering carbon nanotube growth at the low temperature. The amount of amorphous carbon decreases apparently with the decrease of the process pressure for the low temperature growth of CNTs. In this approach, we report a successful synthesis of vertically aligned-MWNTs on Ni / Cr coated glass (PD200) substrate at 550 0C and 500 0C by low pressure (8 torr) thermal CVD with reasonably good field emission characteristics of ~ mA/cm2 emission current density.By the F-N equation analysis , the turn-on voltage is 4.61 V / µm at the 550℃ growing CNTs and 6.15 V / µm at the 550℃ growing CNTs. From the high resolution trasimission electronic microscopy (HRTEM) , we show the nearly hollow structure at our low pressure-temperature CNTs.We also repeat the parameter of growing CNTs on the 2 x 8 cm2 large glass substrate to prove this kind of CNTs can be the well emission source on the applications of field emission display.

摘要(中文)
摘要(英文)
第一章    前言與研究動機
1.1.    前言………………………………………………  1
1.2.    研究動機…………………………………………  2
1.3.    奈米碳管的發展歷程………………………      3
1.4.    奈米碳管的結構……………………………      5
1.5.    奈米碳管的應用前景及發展方向…………      6
1.6.    奈米碳管元件與應用………………………      7
1.6.1.    場效電晶體（Field-effect transistor）…… 8
1.6.2.    奈米導線（Nanowire）………………………    9
1.6.3.    強化複合材料……………………………………  9
1.6.4.    儲氫材料…………………………………………  9
1.6.5.    掃描探針………………………………………… 10
1.7.    參考文獻………………………………………… 10
第二章    文獻回顧
2.1. 奈米碳管製造方法………………………           13
2.1.1. 電弧法(Arc-discharge method)………………   13
2.1.2. 雷射蒸發法(Laser vaporization method)……  14
2.1.3. 化學氣相沉積法(Chemical vapor deposition method)…………………………………………………            14
2.1.3.1. 流動催化劑法(Floating catalyst)……………14
2.1.3.2. 熱裂解式化學氣相沉積法(Thermal chemical vaposr deposition )………………………………………        15
2.1.3.3. 電漿輔助化學氣相沉積法(Plasma enhanced chemical vaposr deposition)……………………………          15
2.2.成長機制…………………………………………      16
2.2.1.奈米碳管成長模型(Growth model)……………    16
2.2.1.1.頂部成長(Tip growth)………………………    16
2.2.1.2. 底部成長(Base growth)……………………    17
2.2.1.3. 完全成長(Fully growth)……………………   19
2.2.2.基板影響(Substrate effect )…………………… 19
2.2.3.催化金屬及其膜厚的影響(Catalyst effect and catalyst film effect) ……………………………………         22
2.2.4.氨氣的影響(NH3 effect)………………………    24
2.2.5.成長溫度影響(Select temperature effect)…… 28
2.2.6.壓力影響(pressure effect)……………………… 33
2.3.場發射理論概述…………………………………      35
2.4.拉曼光譜(Raman spectrum)………………………    37
第三章    實驗設備與步驟
             3.實驗內容………………………………… 39
             3.1.碳管製程設備………………………… 39
             3.2.實驗步驟……………………………… 40
               3.2.1.試片準備………………………… 40
               3.2.2.前處理及碳管成長……………… 42
               3.2.3.場發射量測設備………………… 44
第四章    結果與討論
             4.1.前處理影響…………………………… 47
             4.1.1.前處理時間控制及不同基板的影響 47
             4.1.2.結論………………………………… 53
             4.2.成長控制……………………………… 53
             4.2.1.爐管氣氛控制……………………… 55
             4.2.1.1.乙炔比例的影響………………… 55
             4.2.1.2.氨氣比例控制…………………… 57
             4.2.1.3.壓力控制………………………   58
             4.2.2.溫度影響…………………………… 61
             4.2.2.1.單一加熱溫度區間控制………… 61
             4.2.2.1.1.高溫碳管成長……… ………  61
             4.2.2.1.2. 550 ℃碳管成長……………  63
             4.2.2.1.3. 500 ℃碳管成長……………  63
             4.2.2.2.不同溫度區間控制……………… 64
             4.2.2.3.結論……………………………… 66
             4.3.場發射性質                       66
             4.3.1.550 ℃成長碳管…………………… 67
             4.3.2.500 ℃成長碳管…………………… 68
             4.4.場發射螢光實驗……………………   70
第五章    總結……………………………………………… 72
Reference…………………………………………………   73

                                

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