含硼奈米碳管(Boron doped carbon nanotube, B-CNTs)為新穎之奈米材料，其結構相似於碳管，同樣有著優異的機械性能，且具有更高的高溫抗氧化能力。不同於奈米碳管由於複雜的手性問題導致的性質不可控性，含硼奈米碳管的電子結構主要依賴於它的化學組成，與其幾何手性無關，在理論計算中顯示，其能隙之大小主要決定於其原子化學組成，藉由合成硼碳奈米管時在製程參數的調控下，改變其原子組成比例，可調變硼碳奈米管之能隙。對於應用發展於光電元件亦或是場效電晶體等奈米電子元件之製作極具潛力。在目前有關於含硼奈米碳管的研究中，所使用的觸媒皆以溶碳度較高的金屬為主，常見的有鐵、鈷、鎳或是這些金屬的合金，尚無文獻提到是否可利用低溶碳度的觸媒成長含硼奈米碳管，如金、銀、銅等金屬。
本文以Cu/γ-Al2O3作為催化劑，B(OCH3)3為反應源氣體，採用化學氣相沉積法(Chemical Vapor Deposition method)合成含硼奈米碳管(B-doped CNTs)。所得的含硼奈米碳管為多壁奈米碳管(Multiwall Carbon Nanotube, MWCNT)，具有中空竹節狀、封閉的結構。此外藉由一系列不同反應溫度/載氣流速/前驅物濃度實驗過程中，尋找合成含硼奈米碳管之最佳成長條件，並藉助拉曼光譜儀(Raman)、掃描式電子顯微鏡(SEM)、穿透式電子顯微鏡(TEM) 、熱重分析儀(TGA) 、感應耦合電漿質譜儀(ICP-MS)、X-射線光電子能譜儀(XPS)等儀器討論各變因下產物的形貌、結構、生長量、含硼量之差異。

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目錄

摘要...................................................................................................................................I
目錄 ................................................................................................................................II
圖目錄..............................................................................................................................V
表目錄.........................................................................................................................VIII

第一章 緒論.....................................................................................................................1
1-1. 前言...................................................................................................................1
1-2. 研究動機...........................................................................................................2
1-3. 實驗目的...........................................................................................................3
第二章 文獻回顧.............................................................................................................7
2-1 奈米碳管的結構與電子性質............................................................................8
2-1-1單壁奈米碳管之結構與電性....................................................................7
2-1-2多壁奈米碳管之結構與電性..................................................................11
2-2奈米碳管氣相成長機制...................................................................................12
2-2-1 頂部與底部成長模式.............................................................................12
2-2-2碳原子擴散路徑......................................................................................13
2-2-3擴散驅動力..............................................................................................14
2-3製造奈米碳管主要的幾種製程........................................................................15
2-3-1電弧放電法(Arc-discharge method).........................................................15
2-3-2雷射剝除法(Laser ablation).....................................................................16
2-3-3化學氣相沉積法(Chemical vapor deposition)........................................16
2-4含硼奈米碳管簡介...........................................................................................18
2-4-1含硼奈米碳管的發現..............................................................................18
2-4-2含硼奈米碳管的特性..............................................................................18
2-4-3含硼奈米管的製備方法..........................................................................19
2-4-4含硼奈米碳管的應用..............................................................................20
2-5銅觸媒生長奈米碳管的相關文獻 .................................................................24
第三章 實驗方法...........................................................................................................30
3-1實驗樣品...........................................................................................................30
3-1-1實驗用氣體................................................................................................30
3-1-2實驗用藥品................................................................................................30
3-2實驗步驟...........................................................................................................30
3-3實驗裝置...........................................................................................................32
3-4分析方法...........................................................................................................33
3-4-1掃描式電子顯微鏡 (Scanning Electron Microscope，SEM)................33
3-4-2穿透式電子顯微鏡 (Transmission Electron Microscope，TEM).........33
3-4-3拉曼光譜儀 (Raman Spectrometer) .........................................................33
3-4-4熱重分析儀 (Thermogravimetric Analyzer，TGA).................................34
3-4-5射線光電子能譜儀(X-ray photoelectron spectrometer，XPS)................34
3-4-6感應耦合電漿質譜儀(ICP-MS)................................................................34
第四章 結果與討論......................................................................................................35
4-1含硼前驅物的選擇..............................................................................................35
4-2反應溫度對於成長含硼奈米碳管的影響.........................................................36
4-2-1掃描式電子顯微鏡下之形貌觀察..............................................................32
4-2-2穿透式電子顯微鏡下之形貌觀察..............................................................39
4-2-3熱重損失分析..............................................................................................43
4-2-4拉曼光譜分析…..........................................................................................48
4-2-5 X-射線光電子能譜儀(XPS)分析...............................................................51
4-2-6感應耦合電漿質譜儀(ICP-MS)分析.........................................................52
4-3前驅物濃度對於成長含硼奈米碳管的影響.....................................................53
4-3-1掃描式電子顯微鏡觀察..............................................................................53
4-3-2熱重損失分析..............................................................................................59
4-3-3拉曼光譜分析................................................................................................64
4-4反應時間對於成長含硼奈米碳管的影響.........................................................67
4-4-1掃描式電子顯微鏡下之形貌觀察..............................................................67
4-4-2熱重損失分析..............................................................................................72
4-4-3拉曼光譜分析..............................................................................................76
4-5碳管的生長機制.................................................................................................79
第五章 結論....................................................................................................................82
參考資料..........................................................................................................................83


圖目錄

圖1-1 奈米碳管TEM影像圖...........................................................................................4
圖1-2 (a)奈米碳管(b)氣相成長碳纖維.............................................................................5
圖1-3 碳的各種結構.........................................................................................................6
圖1-4 以Cu/γ-Al2O3為催化劑，生長出的奈米碳管之SEM圖...................................6
圖2-1 單晶石墨之晶體結構，六圓環以ABAB….順序堆積........................................8
圖2-2 (a)廿面體C60，(b)球狀C70之結構示意圖............................................................8
圖2-3 二維石墨平面向量表示奈米碳管結構.................................................................9
圖2-4 graphene sheet 之平面結構.....................................................................................9
圖2-5單層奈米碳管之結構與電性..................................................................................10
圖2-6 多層碳管之結構，(a)Russian doll，(b)Swiss doll...............................................11
圖2-7底部與頂部生長模式示意圖..................................................................................13
圖2-8觸媒體擴散示意圖..................................................................................................13
圖2-9觸媒表面擴散示意圖..............................................................................................14
圖2-10電弧放電法設備圖................................................................................................17
圖2-11雷射剝除法設備圖................................................................................................17
圖2-12化學氣相沉積法設備圖........................................................................................17
圖2-13含硼奈米碳管示意圖............................................................................................19
圖2-14 化學氣相沉積法製備含硼奈米碳管設備圖.......................................................20
圖2-15硼酸甲醇水溶液為碳源製備的含硼奈米碳管....................................................21
圖2-16不同硼含量奈米碳管其電阻率與溫度的關係圖................................................22
圖2-17含氮奈米碳管儲氫能力優於一般碳管................................................................23
圖2-18含硼奈米碳管儲氫能力與一般碳管及PBC比較圖...........................................23
圖2-19含硼奈米碳管與一般奈米碳管組成的太陽能電池的電流電壓特性比較......24
圖2-20利用電弧放電法在氫氣(500torr)環境下生長奈米碳管之穿透式電子顯微鏡圖..........................................................................................................................................26
圖2-21微波電漿輔助化學氣相沉積法之實驗裝置圖...................................................26
圖2-22利用微波電漿輔助化學氣相沉積法所製備的奈米碳管穿透式顯微鏡圖.....27
圖2-23鈷、鎳、鐵與碳的相圖.......................................................................................28
圖2-24銅與碳的相圖.......................................................................................................28
圖2-25超酸結構示意圖...................................................................................................29
圖2-26超酸環境下碳氫化合物裂解機制.......................................................................29
圖3-1實驗流程圖.............................................................................................................31
圖3-2實驗裝置圖.............................................................................................................32
圖4-1不同反應溫度下所製備之奈米碳管之掃描式電子顯微鏡圖............................38
圖4-2 載氣流速50ml/min，注射速率200μl/hr之奈米碳管穿透式電子顯微鏡圖...41
圖4-3碳管頂端包覆金屬的能量散佈分析圖.................................................................42
圖4-4 HRTEM含硼碳管層間距之計算結果..................................................................42
圖4-5高解析穿透式電子顯微鏡下觀察到的奈米碳管石墨層排列及觸媒顆粒.......43
圖4-6不同反應溫度下所得到的產物的熱重損失圖.....................................................43
圖4-7 實驗反應後經氧化處理的石英管比較圖............................................................45
圖4-8不同反應溫度產物的DTG圖..............................................................................48
圖4-9，不同反應溫度的拉曼光譜圖..............................................................................51
圖4-10以5% CuSO4/Al2O3為催化劑，B(OCH3)3注射速率200μl/hr，He流速60ml/min，反應溫度900℃下產物的B(1s)XPS能譜.......................................................................52
圖4-11不同前驅物注射速率條件下的SEM圖.............................................................59
圖4-12不同B(OCH3)3注射速率所製備產物之熱重分析圖.........................................60
圖4-13不同B(OCH3)3注射速率的DTG圖………………………………………….61
圖4-14不同B(OCH3)3注射速率的拉曼光譜圖.............................................................66
圖4-15不同反應時間條件下的SEM圖.........................................................................71
圖4-16不同反應時間下所得到的產物的熱重損失圖...................................................72
圖4-17不同反應時間的DTG圖.....................................................................................76
圖4-18不同反應時間的拉曼光譜圖...............................................................................78
圖4-19觸媒輔助奈米碳管生長機制圖...........................................................................79
圖4-20本實驗碳管的生長機制圖...................................................................................81

表目錄

表4-1不同反應溫度下所得到的產物的積碳量.............................................................44
表4-2不同碳結構的起然溫度…………………………………………………….......46
表4-3不同反應溫度下所成長的含硼碳管的IG/ID值………………………...……...49
表4-4不同B(OCH3)3注射速率的條件下所製備的產物之積碳量比較……...……..60
表4-5不同B(OCH3)3注射速率下所成長的含硼碳管的IG/ID值…………...……….64
表4-6不同反應時間(min)下所製備的產物之積碳量比較………………....…….......73
表4-7不同反應時間下所成長的含硼碳管的ID/IG值………………………..………76

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54. W. KOWBEL,* Y. HUANG, and H. Tsou Department of Mechanical Engineering, Auburn University, Auburn, AL 36849, U.S.A.