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研究生： 莫堯安
Yao-An Mo
論文名稱： 各種催化劑對奈米碳管成長機制及動力學之研究
The effect of catalysts(iron, cobalt and nickel) on the mechanism and kinetics of carbon nanotube growth by thermal CVD method.
指導教授： 蔡春鴻 教授
Dr.Chuen-Horng Tsai
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： 111
中文關鍵詞： 奈米碳管 、成長機制 、成長動力學 、催化劑
外文關鍵詞： carbon nanotube, mechanism, kinetics, thermal CVD method
相關次數： 點閱：2  下載：0 
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    • 　　　雖然多層奈米碳管已經被人們發現超過十年了，但是其成長的機制和動力學也大多是由電腦模擬、理論推導及成長結束後的穿透式電子顯微鏡(TEM)影像來預測，拜定點即時電子顯微鏡in-situ TEM的技術之賜，可以對奈米碳管成長有更多的了解，但是顯微鏡所無法察覺的部分仍是缺憾，有些學者開始利用成長動力學來推測成長碳管時的成長速率限制步驟(rate controlling limiting)，在第一章以舉出許多先進所得到的結果，但是沒有發現提出有實驗為基礎適用於各催化劑探討奈米碳管由成核到去活化的成長機制及動力學研究，因此，基於這個理由，利用三種催化劑在相同成長參數、製程下，不同的溫度成長奈米碳管，作出隨成長時間的增加奈米碳管長度的變化，利用掃描式電子顯微鏡量得不同時間和催化劑所成長的奈米碳長度，製作出成長曲線，利用這個曲線的趨勢、或是配合動力學的數學模式，將可能的動力學和機制釐清；在此之前，必須找到各催化劑的製成窗口(可以成長出奈米碳管的參數範圍)，才能訂定成長曲線所使用的製程參數，所以我將這個工作做完整一些，作成資料庫的形式，使得日後要是使用同一套成長機台的人有參考依據，也經由這個步驟，能更為了解催化劑在成長碳管所扮演的角色。

    The kinetics of multi-walled carbon nanotubes (MWCNTs) growth reported so far were mostly based on simulation or deriving the activation energy of one kind of catalyst assuming steady growth. Whether the growth mechanism of MWCNT growth on different catalyst metals can fall into the same mechanism, and whether the nucleation and growth kinetics share the same kinetic controlling mechanism need to be clarified. In this study, we synthesized MWCNTs over different catalysts (iron, cobalt and nickel) deposited by e-gun evaporation and measured the length of MWCNTs varying with time. It was found that there consisted three stages of MWCNTs formation: (1) Nucleation stage by observing the shape transformation of catalyst particles in the initial stage and also by extrapolating the change of length with time to derive the nucleation period. (2) Steady growth stage from which the activation energy of the controlling step could be derived by Arrhenius plot. (3) Growth saturation period, which was caused by amorphous carbon formation. After intensive observations of the relation between the sizes and shapes of the catalyst nanoparticles and the growth rates of MWCNTs at different temperatures over different catalyst metals, it was concluded that the catalyst shape transformation at nucleation stage was important for the growth on nickel and cobalt, but not on iron. As to the steady growth rate, it was found that MWCNTs growth followed the same growth mechanism in all temperature range for iron and cobalt, whereas for nickel there observed a transition of growth mechanism at temperature of ~840oC. There were also observed different growth saturation behaviors on different catalyst metals, which will be discussed in this paper as well.

    第一章　　緒論............................................1 1-1奈米碳管的合成.....................................1 1-2奈米碳管的可能成長機制.............................8 1-3奈米碳管的成長動力學..............................16 1-4催化劑對奈米碳管的成長的影響......................21 1-5尺寸效應對材料熔點下降的影響......................27 參考文獻.................................................38 第二章　　研究目的及方法.................................39 2-1 研究目的.........................................40 2-2 研究方法.........................................41 參考文獻.................................................42 第三章　　實驗設備及製程.................................43 3-1 催化劑的製備.....................................43 3-2 前處理及碳管成長.................................45 3-2-1 機台簡介...................................45 3-2-2 製程方式...................................45 3-3 檢測機台.........................................47 參考文獻.................................................51 第四章　　結果與討論.....................................52 4-1 碳管成長的可能機制及對力學研究：碳管成長的三步驟..52 4-1-1反應器系統的研究............................54 4-1-2 控制奈米碳管叢成長高度的碳管直徑...........63 4-1-3 成核的可能機制及控制步驟...................67 4-1-4 穩態成長的可能機制及控制步驟...............74 4-1-5 成長減慢到催化劑去活化的可能機制及控制步驟.77 4-1-6碳供給路徑..................................84 4-1-7 結論.......................................85 4-2 比較各催化劑對成長奈米碳管的影響.................85 4-2-1 各催化劑成長奈米碳管的形貌、結構及特色.....86 4-2-2 各催化劑前處理的結果及對奈米碳管成長的影響.92 4-2-3 製程溫度對各催化劑成長奈米碳管的影響.......98 4-2-4 成長氣體比例對各催化劑成長奈米碳管的影響..103 4-2-5 成長環境變動對各催化劑成長奈米碳管的影響..105 參考文獻................................................107 第五章　　總結與未來展望................................108 5-1 總結............................................108 5-2 未來展望.......................................109 5-2-1建立對奈米碳管成長的資料庫................109 5-2-2密度控制對場發射的應用....................109 參考文獻...............................................111

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