臺灣博碩士論文加值系統

本研究中藉由熱裂解化學氣相沉積法的方式，以酒精蒸氣作為碳源，利用雙層觸媒系統以便成長出網絡狀單壁奈米碳管薄膜(SWCNT-networks)，並利用濕式蝕刻的方式將高透明度及高導電度的單壁奈米碳管網絡狀薄膜移除下來，並轉移到其他基材上以便繼續對它做還原與氧化的化學修飾(chemical modification)處理。
化學修飾處理主要著重於單壁奈米碳管薄膜經還原劑(聯胺)處理後，實驗結果發現，聯胺處理後碳管表面鍵結了許多NH2，此舉會引起單壁奈米碳管薄膜自發性的摻雜(doping)效應，進而導致單壁奈米碳管薄膜導電特性之改變，其改變機制將利用四點探針(Four-point Probe)、場發射電子顯微鏡(Field Emission Scanning Electron Microscope, FESEM)、拉曼光譜儀(Raman Spectroscopy)、X光光電子能譜儀(X-ray Photoemission Spectroscopy, XPS)、及紫外光光電電子能譜(Ultra-violet Photoelectron Spectroscopy, UPS)的量測，研究當單壁奈米碳管網絡狀薄膜在經還原與氧化處理後，對於其導電特性、整體結構、碳管表面化學鍵結結構以及價帶電子結構的改變行為做一整合性之探討。
文中亦將還原劑處理與一般常見之氧化劑(硫酸)處理後之碳管表面特性做一詳細之比較，並探討已氧化之單壁奈米碳管薄膜經再次聯胺處理後所引起之還原效應。

In this study, a simple thermal pyrolysis chemical vapor deposition technique which was used alcohol vapor as the carbon source was synthesized high purity single-walled carbon nanotube on silicon substrate by double-layered catalytic system, and this sample was used a lift-off technique with BOE solution subsequently. After those processes, the SWCNT-networks successfully were separated from the silicon substrate. The lifted-off SWCNT-networks which has excellent optical and electrical properties was transferred the suspended SWCNT-networks to various substrates, and proceeded with chemical modification of reduction and oxidation treatment.
Chemical modification focused primarily on the reducing agent (hydrazine) treatment in SWCNT-networks. As the results of this experiment showed, the surface of SWCNT-networks which were treated by hydrazine has bonded to their sidewalls using amino groups. This situation was induced a spontaneous charge transfer that was led to the doping effect, and the change of SWCNT-networks’ conductivity. The phenomenon of charge transfer was analyzed by the four-point probe systems, field emission scanning electron microscope, Raman spectroscopy, X-ray Photoemission spectroscopy, and Ultra-violet Photoelectron spectroscopy. Though those analyses was investigated the pristine and reacted SWCNT-networks properties of conductive characteristics, the sidewall structure, chemical bonding species and valence bond electronic structure. Those overall results provide a comprehensive exploration.
This paper was also compared the characteristics of hydrazine treatment with acid treatment. We have proposed the reduction effect by hydrazine treated pre-oxidized SWCNT-networks.

摘要 i
英文摘要 ii
致謝 iii
第一章 緒論 1
1-1 前言 1
1-2 奈米碳管之簡介與應用 1
第二章 理論背景與文獻回顧 4
2-1 單壁奈米碳管的基本性質 4
2-1-1 單壁奈米碳管的幾何結構 4
2-1-2 單壁奈米碳管的能帶結構 7
2-2 單壁奈米碳管的合成 8
2-3 單壁奈米碳管的拉曼光譜分析 13
2-4 單壁奈米碳管的化學修飾 16
2-5 研究動機與目的 17
第三章 儀器設備與實驗原理 20
3-1 電子槍蒸鍍系統(E-gun evaporation system) 20
3-2 高溫熱裂解化學氣相沉積系統 21
3-3 掃描式電子顯微鏡(Scanning Electron Microscopy, SEM) 21
3-4 微拉曼光譜儀 23
3-5 同步輻射光源(Synchrotron Radiation) 24
3-6 光電子發射能譜術(Photoemission Spectroscopy, PES) 25
3-6-1 超高真空系統(Ultra-high Vacuum System, UHV) 26
3-6-2 Ｘ光光電子發射能譜術(X-ray Photoelectron Spectroscopy, XPS) 27
3-6-3 紫外光光電電子能譜(Ultra-violet Photoelectron Spectroscopy, UPS) 29
3-7 四點探針量測儀 31
第四章 實驗方法與樣品量測 32
4-1實驗方法 32
4-2 單壁奈米碳管網絡薄膜的生長 33
4-2-1 基板的製備 33
4-2-2 以酒精催化式氣相沉積法合成單壁奈米碳管及薄膜 34
4-2-3 酒精催化式化學氣相沈積製程規劃及流程 35
4-2-4 酒精催化式化學氣相沈積之製程結果 36
4-2-5 半透明單壁奈米碳管網絡之導電薄膜 38
4-3 化學處理 40
4-4 XPS、UPS的量測 41
第五章 結果與討論 42
5-1 單壁奈米碳管網絡薄膜聯胺揮發蒸氣處理後之特性分析 42
5-1-1 導電性量測及其形貌變化 42
5-1-2 拉曼光譜表徵 47
5-1-3 奈米碳管薄膜表面之官能基鑑定 54
5-1-4 功函數變化 59
5-1-5 處理後穩定性觀察之結果 63
5-2 單壁奈米碳管網絡薄膜酸化處理後之特性分析 67
5-2-1 導電性量測及其形貌變化 67
5-2-2 拉曼光譜表徵 70
5-2-3 奈米碳管薄膜表面之官能基鑑定 72
5-2-4 功函數變化 76
5-3 單壁奈米碳管網絡薄膜聯胺處理與酸化處理之特性比較 80
5-4 單壁奈米碳管網絡薄膜聯胺處理後引起之還原效應 84
第六章 結論 89
參考文獻 90

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