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。
本文以銅觸媒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)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。

Boron-doped carbon nanotubes are predicted to behave as semiconductors over a large range of diameters and chiralities and might thus constitute a suitable class of material for nanoelectronics technology. Boron-doped CNTs were reported as by-products when BC2N nanotubes were prepared by an arc-discharge method. The potential doping of CNTs with different kinds of atoms might provide a mechanism for controlling their electronic properties. We have synthesized boron-doped carbon nanotubes (CNTs) directly on copper catalyst by decomposition of B(OCH3)3 in chemical vapor deposition method. The results were characterized and analyzed by scanning electron microscopy (SEM), Raman, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), solid-state NMR and TGA.

目錄
論文審定書.......................................................................................................................I
謝誌..................................................................................................................................II
中文摘要.........................................................................................................................III
英文摘要.........................................................................................................................IV
目錄 ................................................................................................................................V
圖目錄..........................................................................................................................VIII
表目錄.............................................................................................................................XI

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...........................................................................................................6
2-1 奈米碳管的結構與電子性質..........................................................................6
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..................................................................10
2-2奈米碳管氣相成長機制..................................................................................11
2-2-1 頂部與底部成長模式.............................................................................11
2-2-2碳原子擴散路徑......................................................................................12
2-2-3擴散驅動力..............................................................................................13
2-3製造奈米碳管主要的幾種製程.....................................................................13
2-3-1電弧放電法(Arc-discharge method)........................................................13
2-3-2雷射剝除法(Laser ablation).....................................................................14
2-3-3化學氣相沉積法(Chemical vapor deposition)........................................14
2-4含硼奈米碳管簡介.........................................................................................16
2-4-1含硼奈米碳管的發現..............................................................................16
2-4-2含硼奈米碳管的特性..............................................................................17
2-4-3含硼奈米管的製備方法..........................................................................17
2-4-4含硼奈米碳管的應用..............................................................................18
2-5銅觸媒生長奈米碳管的相關文獻 ...................................................................21
第三章 實驗方法...........................................................................................................26
3-1實驗樣品...........................................................................................................26
3-1-1實驗用氣體................................................................................................26
3-1-2實驗用藥品................................................................................................26
3-2實驗步驟...........................................................................................................26
3-3實驗裝置...........................................................................................................28
3-4分析方法...........................................................................................................29
3-4-1掃描式電子顯微鏡 (Scanning Electron Microscope，SEM)..................29
3-4-2穿透式電子顯微鏡 (Transmission Electron Microscope，TEM)...........29
3-4-3拉曼光譜儀 (Raman Spectrometer) .........................................................29
3-4-4熱重分析儀 (Thermogravimetric Analyzer，TGA).................................29
3-4-5射線光電子能譜儀(X-ray photoelectron spectrometer，XPS)................30
3-4-6高磁場固態核磁共振儀500MHz (Solid state Nuclear Magnetic
Resonance，S-NMR)................................................................................30
第四章 結果與討論.....................................................................................................31
4-1含硼前驅物的選擇.............................................................................................31
4-2反應溫度對於成長含硼奈米碳管的影響.........................................................32
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..............................................................32
4-2-3熱重損失分析..............................................................................................36
4-2-4 XPS分析......................................................................................................40
4-2-5固態NMR分析...........................................................................................41
4-2-6拉曼光譜分析..............................................................................................42
4-3前驅物濃度對於成長含硼奈米碳管的影響.....................................................44
4-3-1掃描式電子顯微鏡觀察..............................................................................44
4-3-2熱重損失分析..............................................................................................48
4-3-3拉曼光譜分析..............................................................................................51
4-3-4固態NMR分析...........................................................................................52
4-4載氣流速對於成長含硼奈米碳管的影響.........................................................54
4-4-1掃描式電子顯微鏡下之形貌觀察..............................................................54
4-4-2熱重損失分析..............................................................................................56
4-4-3拉曼光譜分析..............................................................................................60
4-4-4固態核磁共振儀分析..................................................................................60
4-5載氣類型對成長含硼奈米碳管的影響..............................................................64
第五章 結論....................................................................................................................69
參考資料..........................................................................................................................70

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