本研究首先利用4-疊氮苯胺鹽酸鹽對單壁奈米碳管進行表面改質，後續利用其管壁上的胺基與3-硝基苯胺進行共價接枝，最後使用二甲基亞碸、葡萄糖及氫氧化鉀於熱環境下將奈米碳管上之硝基還原為胺基。而表面改質是利用UV點光源之光化學反應，透過紫外光照射後，使4-疊氮苯胺鹽酸鹽之氮鍵斷鍵產生自由基，並藉由自由基與單壁奈米碳管表面進行反應，得到改質之單壁奈米碳管，再藉由其管壁上的胺基與3-硝基苯胺透過微波的方式進行共價接枝。而還原的目的是為了將共價接枝後奈米碳管上之拉電子基硝基轉為推電子基胺基，期望胺基之親水性質及推電子效應，使單壁奈米碳管具備高分散性及N型摻雜以利後續之各種應用。最後使用噴霧塗佈技術製作奈米碳管薄膜於玻璃基材上，並藉由觀察奈米碳管懸浮液之分散性、掃描式電子顯微鏡分析、元素分析、熱重分析、拉曼光譜分析、紅外光光譜分析、四點探針電性分析、載子霍爾係數量測等多種分析，用以證明我們成功製備穩定的N型單壁奈米碳管，並透過熱電量測系統，分析材料之熱電性質。不僅突破現今發展較為瓶頸之N型奈米碳管，也為能源應用跨出新的一步。

In this study, 4-azidoaniline hydrochloride was used to modify the surface of single-walled carbon nanotubes at first, and used the amine group of tube wall to covalently grafted 3-nitroaniline, and finally reduced the nitro group on carbon nanotubes to amine group under the hot environment by using dimethyl sulfoxide, glucose and potassium hydroxide. The surface modification was used the photochemical reaction of UV light source, the nitrogen bond of 4-azidoaniline hydrochloride would break to generate free radicals, which would react with single-walled carbon nanotubes. The surface is reacted to obtain the modified single-walled carbon nanotubes and used the amine group of tube wall to covalently grafted 3-nitroaniline via microwave. The purpose of reduction is to convert the electron-withdrawing effect of nitro group on carbon nanotubes after covalent grafting into electron-donating effect of amine group, which is expected that the hydrophilicity and the electron-donating effect of amine group will make the carbon nanotubes have high dispersibility and N-type effect for subsequent applications. Finally, spray coating technology was used to make the carbon nanotubes film on glass substrate, and by observing the dispersibility of carbon nanotubes suspension, scanning electron microscope analysis, elemental analysis, thermogravimetric analysis, Raman spectroscopy, Infrared spectroscopy analysis, four-point probe electrical analysis, carrier Hall coefficient measurement to prove that we successfully prepared stable N-type single-walled carbon nanotubes, and analyzed the thermoelectric properties of material via thermoelectric measurement system. Not only does it break through the current bottleneck of N-type carbon nanotubes, but also takes a new step for energy applications.

摘要 I
Abstract II
致謝 III
目錄 IV
表目錄 VII
圖目錄 VIII
一、緒論 1
1.1 前言 1
1.2 研究動機與目的 2
二、文獻回顧 4
2.1 奈米碳管簡介 4
2.2 奈米碳管結構 6
2.3 奈米碳管合成 8
2.4 奈米碳管電性 12
2.5 奈米碳管表面改質 16
2.5.1 共價改質法 17
2.5.2 非共價改質法 20
2.6 硝基化合物還原 21
2.7 奈米碳管P、N摻雜 24
2.8 奈米碳管N摻雜應用 25
2.9 熱電效應 29
2.9.1 Seebeck效應 29
2.9.2 Peltier效應 30
2.9.3 Thomson效應 31
三、儀器設備與操作原理 32
3.1 聚焦式微波反應儀 32
3.2 四點探針 33
3.3 掃描式電子顯微鏡 35
3.4 光譜儀器設備 37
3.4.1 紫外光-可見光-近紅外光光譜儀 38
3.4.2 傅立葉轉換紅外光光譜儀 40
3.5 共軛聚焦顯微拉曼光譜儀 41
3.6 載子霍爾係數量測系統 43
3.7 元素分析儀 45
3.8 熱重分析儀 45
3.9 熱電性質量測系統 46
3.9.1 Keithley 2400 Source Meter 46
3.9.2 程式溫度控制器 47
3.9.3 熱電量測平台組合 49
四、實驗內容 50
4.1 實驗藥品及儀器 50
4.2 實驗流程 50
4.2.1 單壁奈米碳管表面改質 51
4.2.2 共價接枝聚3-硝基苯胺 52
4.2.3 硝基還原為胺基 53
4.2.4 奈米碳管薄膜製備 54
五、結果與討論 55
5.1 共價改質奈米碳管之分散性 55
5.2 共價改質奈米碳管之掃描式電子顯微鏡分析 56
5.3 共價改質奈米碳管之元素分析 58
5.4 共價改質奈米碳管之熱重分析 58
5.5 共價改質奈米碳管之共軛聚焦顯微拉曼光譜分析 61
5.6 共價改質奈米碳管之傅立葉轉換紅外光光譜分析 63
5.7 共價改質奈米碳管薄膜之四點探針電性分析與載子霍爾係數量測 67
5.8 共價改質奈米碳管之熱電性質 70
六、結論 78
七、參考文獻 79

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