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研究生： 林文楨
Lin, Wen-Chen
論文名稱： 不同成長時間對成長奈米碳管之影響與利用再活化的催化劑成長奈米碳管
Growth Kinetics of Carbon Nanotubes and The Re-Activation of Catalyst
指導教授： 丁志明
Ting, Jyh-Ming
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2008
畢業學年度： 96
語文別： 中文
論文頁數： 173
中文關鍵詞： 催化劑再活化 、階段性碳管 、奈米碳管 、成長時間
外文關鍵詞： Growth Time, Carbon Nanotubes, Step-Growth CNTs, Re-Activation of Catalyst
相關次數： 點閱：83  下載：2 
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    • 在前人的研究中指出，鋁-鐵-矽薄膜催化劑可以有效的在低溫下(370 ℃)以高成長速率合成準直性的奈米碳管。因為於催化劑薄膜下沉積一層鋁金屬薄膜可以有效的提供更具活性的成核位置，以助於奈米碳管的合成。因此本研究選用鐵-矽和鋁-鐵-矽薄膜催化劑來研究其不同的成長時間對奈米碳管之影響且利用再活化催化劑的處理生成階段性碳管。
    本研究主要採用前人最佳的Fe-Si薄膜參數，在固定厚度的Fe-Si薄膜催化劑下，沈積一層約0、2、4、8和10 nm的鋁層。實驗所使用的Al基層是以直流濺鍍法製備，而Fe-Si薄膜催化劑是由共濺鍍法(Co-sputtering)製備，並採用微波電漿輔助化學氣相沉積法(MPCVD)於低溫下成長奈米碳管且變化其成長的時間，另外改變其製程使催化劑得以再活化並獲得階段性碳管，碳管成長時所使用的反應氣體均為甲烷(碳源)及氫氣(載氣)的混合氣體。
    在以MPCVD成長碳管過程之中，先以氫氣電漿前處理使催化劑薄膜達到適合成長碳管的條件，再通入碳源並改變不同時間以提供奈米碳管的成長。發現使用Fe-Si薄膜催化劑，不論是否經過氫氣電漿前處理，其成長碳管的速度均低於使用Al/Fe-Si薄膜催化劑所生成碳管的成長速率。利用Fe-Si作為催化劑時其碳管最佳成長速率為2 μm/min；但若以Al/Fe-Si作為催化劑時其碳管最佳成長速率可達6 μm/min。
    經由不同成長時間可以探討碳管的成長歷程。在成長初期為一孕核期並無碳管生成，取而代之的是催化劑的碳化，且經由鋁層的添加可以使原催化劑層膨脹並趨向於棉花狀結構有助於碳源在內部擴散，故可有效的下降孕核期的時間。成長時間上升可使碳管長度增加，但至某成長時間後其碳管的長度下降，推估為催化劑已毒化，內部氫氣蝕刻造成碳管長度下降。
    本研究利用已毒化的催化劑接觸空氣後使催化劑再活化獲得階段性奈米碳管，分段式成長製程可分為兩段式、三段式和五段式成長製程，發現兩段式成長製程時碳管可達最快成長速度約21 μm/min，遠遠超過單段式成長速度，推估的原因可能為催化劑經過vent gas過程後，催化劑的氧化造成成長速度大幅上升的結果。且經過處理後碳管有不同製程下碳管與碳管間的連接點，可證明碳管遵循連續成長且由底部開始成長。並選用純鎳和純鐵觀察是否有階段性碳管的生成，且探討空氣中何種氣體導致催化劑再活化，最後探究碳管的場發特性。
    本研究中利用掃描式電子顯微鏡(SEM)觀察成長後碳管之形貌，穿透式電子顯微鏡(TEM)觀察階段性碳管接點和碳管結構，而拉曼(Raman)光譜加以觀察與分析碳管結構，最後以場發射量測(FED)設備量測連續式製程成長後碳管與階段式製程成長後碳管之場發特性。

    According to the previous report, we have achieved very fast growth rate of aligned carbon nanotubes (CNTs) at low temperature (370 ℃) using Al/Fe-Si thin film catalyst. Because of the introduction of an Al metal underlayer under the active catalyst layers appears to provide more active nucleation sites and its helpful for the synthesis of CNTs. Therefore we used Fe-Si and Al/Fe-Si thin film catalyst which had different thickness for growing CNTs with different growth time and different kind of experimental methods. We focused on the effect of different growth time prior to CNTs and the step-growth CNTs on re-activated catalyst.
    The Fe-Si thin film catalyst which fixed the thickness was prepared using dc magnetron co-sputter deposition and the Al underlayer which varied from 0 to 10 nm was deposited on the substrate using dc magnetron sputter deposition. Catalyst deposited substrates were then subjected to a MPCVD reactor for the growth of CNTs. We varied the growth time during the MPCVD process and changed the experimental method which made the catalyst re-activated for growing step-growth CNTs. The reaction gas used was methane along with hydrogen.
    In the process of CNT growth, the plasma pretreatment was necessary to make the thin film catalyst more active and could use to growth CNTs. It was found that the growth rate of CNTs which using Fe-Si thin film catalyst with or without plasma etching is lower than the CNTs which using Al/Fe-Si thin film catalyst. The maximum growth rate of CNTs which using Fe-Si thin film catalyst is 2 μm/min. And The maximum growth rate of CNTs which using Al/Fe-Si thin film catalyst is 6 μm/min.
    Due to different growth time, we could discuss with the CNTs growth kinetics. In the beginning of CNTs growth, it’s believe that there has a incubation time which had no CNTs growth up but the carburization of the catalyst is believed to take place. And the incubation time decreases with the thickness of the Al underlayer and the growth was also enhanced as a result of Al addition. This is attributed to the swelling of the etched catalyst, i.e., making the catalyst porous. Porous structure make carbon source diffuse more easily. After incubation time, the CNTs length increase due to growth time increase. And the maximum CNTs length is always fixed at a growth time, after this growth time, the CNTs length would get down due to the etched atmosphere inside the chamber. It’s believed that the catalyst is poisoned.
    In our research, we show an unprecedented re-growth of CNTs and step-growth CNTs due to the re-activation of catalyst which using vent gas process. The step-growth process could consist of two-steps, three-steps and five-steps procedure. Due to two-steps growth, the CNTs growth rate was reached to 21 μm/min due to the vent gas process. Amorphous Fe3O4 was formed during vent gas process, and found to enhance the growth rate of CNTs. Due to step-growth process, there has a interface line between different kind of experimental procedure. Owing to the interface line, it suggested that the growth of CNTs is continuous and growth from the base catalyst. This and the mechanism of such unprecedented growth are not clearly at the present time. It may be attributed to the re-oxidation of the catalyst due to the exposure to the air and the structural lessening or micro-cracking due to the sudden temperature drop from the growth temperature to the ambient temperature. Pure Fe and pure Ni catalyst was used in step-growth process. And also, we try to find out what kind of gas made the catalyst re-activated and the FED properties of CNTs.
    CNTs length and morphologic were analyzed using Hitachi S4100 and Philips XL-40FEG scanning electron microscopes (SEM). The interface line of CNTs and CNTs structure were analyzed using FEI Tecnai F20 G2 high transmission electron microscopes (HR-TEM) equipped with a field emission gun (FEG). Micro Raman spectrometer from Renishaw with He-Ne laser source with a wavelength of 633 nm was used to determine the quality of CNTs. Field emission properties was determined by FED equipment at the laboratory of micro-electric.

    摘 要 .................................................I Abstract ...............................................III 誌 謝 ................................................VI 目 錄 ..............................................VIII 表 目 錄 ...............................................XII 圖 目 錄 ..............................................XIII 第一章 緒論...........................................1 1-1 前言..................................................1 1-2 研究動機與目的........................................3 第二章 文獻回顧.......................................4 2-1 奈米碳管之結構與性質..................................4 2-1-1機械性質.......................................8 2-1-2電性質........................................11 2-1-3場發射特性....................................13 2-2 奈米碳管之成長機制與合成方法.........................15 2-2-1成長機制簡述..................................15 2-2-2合成方法簡述..................................20 2-3 催化劑準則...........................................34 2-3-1普遍使用的催化劑...................................34 2-3-2鐵-矽薄膜...........................................38 2-3-3鋁-鐵-矽薄膜........................................40 2-4階段性奈米碳管........................................42 2-5拉曼光譜簡介..........................................45 2-6場發射原理簡介........................................49 第三章 實驗.............................................54 3-1 實驗流程.............................................54 3-2 製程設備.............................................58 3-2-1磁控濺鍍系統..................................58 3-2-2微波電漿輔助化學氣相沉積系統..................60 3-3 實驗材料.............................................62 3-3-1基板材料......................................62 3-3-2反應氣體......................................62 3-3-3基材清潔......................................62 3-4 催化劑薄膜材料製備...................................62 3-5 MPCVD成長奈米碳管之步驟..............................63 3-6 TEM 觀察試片之製作步驟...............................68 3-7分析與鑑定............................................74 3-7-1表面型態觀察..................................74 3-7-2微結構分析....................................74 3-7-3微區拉曼光譜分析..............................74 3-7-4場發射特性分析................................75 第四章 結果與討論.......................................76 催化劑製備.........................................76 4-1催化劑薄膜在未經過或經過氫氣電漿前處理下成長奈米碳管比較.......................................................78  未經過氫氣電漿前處理下成長奈米碳管.................78  經過氫氣電漿前處理下成長奈米碳管...................81 4-2不同成長時間對於催化劑薄膜成長之碳管影響...........85  未經過氫氣電漿前處理下成長奈米碳管.................85  經過氫氣電漿前處理下成長奈米碳管...................92 4-3後期成長時間對奈米碳管成長之影響......................99 4-4不同成長製程對階段性奈米碳管成長之影響...............105  經過兩段式處理的碳管..............................105  經過三段式處理的碳管..............................110 經過五段式處理的碳管..............................116 4-5不同成長製程對階段性奈米碳管成長機制討論.............118  經過兩段式處理的碳管..............................121  經過三段式處理的碳管..............................123  經過五段式處理的碳管..............................130 4-6改變催化劑對於分段製程實驗的影響.....................132  以純鐵作為催化劑薄膜..............................132  以純鎳作為催化劑薄膜..............................136 4-7改變通入氣體對階段性碳管成長探討.....................140  經過兩段式處理的碳管..............................140  經過三段式處理的碳管..............................140 4-8 階段性奈米碳管成長機制探討.........................143 4-9奈米碳管的場發射特性探討.............................146  連續成長製程......................................146  經過一段式處理的碳管...........................146  分段成長製程......................................147  經過兩段式處理的碳管...........................147  經過三段式處理的碳管...........................148  連續成長製程和分段成長製程場發特性討論............149 第五章 結論.............................................154 第六章 未來工作.........................................158 參考文獻................................................159 作者簡介................................................173

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