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研究生：	宋柏衡 Sung, Po-Heng
論文名稱：	熱蒸鍍法合成非摻雜及鉀摻雜立方三氧化鎢奈米線與其特性研究 Studies on the Synthesis and Properties of Undoped and Potassium-Doped Cubic Tungsten Trioxide Nanowires from Thermal Evaporation
指導教授：	呂國彰 Lu, Kuo-Chang
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：	2016
畢業學年度：	104
語文別：	中文
論文頁數：	94
中文關鍵詞：	立方三氧化鎢、奈米線、熱蒸鍍法、鉀摻雜、光致發光、場發射、光降解
外文關鍵詞：	cubic tungsten oxide, thermal evaporation, nanowires, photoluminescence, K doped
相關次數：	點閱：358 下載：0
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本論文首先利用純WO3粉當作前驅物，在相對高壓的環境下即能以改良的熱蒸鍍法，在薄片鎢基板上均勻且大量的合成稀有的立方三氧化鎢奈米線，並透過不同的架構配置及調整實驗參數來觀察其生長情況，例如試片及前驅物藥品位置、溫度、反應時間、氣流壓力等，後續再利用各種儀器對樣品進行分析，使用SEM觀察奈米線的外觀形貌，以XRD、EDX、XPS確認其晶相結構和組成成分比例，最後以TEM確認其晶格間距及缺陷的存在等基本性質。後續再針對形貌優良的立方三氧化鎢奈米線進行K的摻雜，透過此高溫擴散的摻雜製程除了可以改善奈米線的晶體結構、減少缺陷之外，對於奈米線PL發光及場發射性質也有明顯幫助。未摻雜及K摻雜之立方氧化鎢奈米線在PL的量測中均得到了相較於其他相更短的發光波段，分別位在360nm與410nm，而在場發射量測方面，未摻雜之奈米線起始電壓為13(V/um)而增強因子為1268，K摻雜之奈米線起始電壓大幅降低至5.5(V/um)而增強因子提升至1825，與多篇文獻相較具有更優異的場發特性，除了與奈米線的形貌、數量密度有關之外，也顯示K的摻雜對此一性質的提升也具有重大的貢獻。另外由於立方三氧化鎢奈米線較少被合成，故本實驗中也對其以及單斜的兩種相奈米線進行鐵電性質的觀測，透過量測電滯曲線來了解是否具有鐵電材料的特性，最後則是觀察不同溫度下合成之奈米線的光催化特性，透過觀測染料被降解的程度來探討與試片形貌及結構等關聯。本研究提供了經濟、簡單、可靠的立方三氧化鎢奈米線合成方法，並能夠透過改變實驗參數有效的控制其形貌，後續對其進行多種性質的量測，證明此材料具有相當多元應用的潛力。

We report an efficient and simple method to synthesize both the undoped and K-doped unique cubic tungsten trioxide nanowires through thermal evaporation of WO3 powders without catalyst. The thermal evaporation processing was conducted in a three zone horizontal tube furnace over temperatures ranging from 550to 850℃, where multiple substrates were placed at different temperature zones. The temperature of each zone was measured by a thermal couple. Processing parameters, including pressure, temperature, type of gas and flow rate, were varied and studied in terms of their influence on the morphology, aspect ratio and density of the nanowires. The morphologies of the products were observed with scanning electron microscopy. High resolution transmission electron microscopy, XPS and x-ray diffraction studies were conducted to further identify the chemical composition, crystal structure and growth direction of the nanostructures. Additionally, the growth mechanism has been proposed. Furthermore, we investigated the potassium doping effect on physical properties of the nanostructures. Since tungsten oxide has lots of interesting properties, including chromism, optical and field emission, the research at nanoscale here supports the development of promising potential applications for sensors, light-emitting diodes and field emitters.

摘要	III
Extended Abstract	IV
致謝	VIII
圖目錄	XII
第一章 前言	1
第二章 文獻回顧	3
2-1 奈米科技	3
2-2 奈米材料特性	3
2-2-1  量子尺寸效應	4
2-2-2  量子穿隧效應	5
2-2-3  庫倫堵塞效應	6
2-2-4  體表面積比效應	6
2-3 奈米材料特性	7
2-3-1  熱學性質	7
2-3-2  光學性質	7
2-3-3  磁學性質	7
2-3-4  電學性質	8
2-4 氧化鎢奈米線生長方法	8
2-4-1  熱蒸鍍法	8
2-4-2  水熱法	9
2-4-3  化學氣相沉積法	9
2-4-4  基材合成法	11
2-5氧化鎢基本性質及應用	13
2-5-1  變色性質	15
2-5-2  發光性質	15
2-5-3  場發射性質	17
2-5-4  鐵電性質	18
2-5-5  光催化性質	20
第三章 實驗方法	21
3-1 實驗大綱	21
3-2 實驗步驟	21
3-2-1  試片前處理	21
3-2-2  WO3奈米線成長參數	21
3-2-3  Mn摻雜實驗	25
3-2-4  K摻雜實驗	26
3-3 結構分析及特性性量測儀器	26
3-3-1  X光繞射分析儀	26
3-3-2  X光微區能量分析	27
3-3-3  X射線光電子能譜儀	28
3-3-4  掃描式電子顯微鏡	29
3-3-5  穿隧式電子顯微鏡	30
3-3-6  電滯曲線測量儀	32
3-3-7  場發射性質量測	32
3-3-8  光激發致螢光光譜儀	33
第四章 結果與討論	34
4-1 實驗架構討論	34
4-2 成長參數對奈米線形貌影響	38
4-2-1  反應溫度於奈米線的影響	38
4-2-2  氣體流量於形貌上影響	43
4-2-3  反應時間與線徑關係	47
4-2-4  壓力影響之生長關係	52
4-2-5 奈米線生長機制與結構分析	57
4-3 摻雜實驗	65
4-3-1  Mn摻雜實驗	65
4-3-2  K摻雜實驗	68
4-4 性質量測	73
4-4-1  PL量測	73
4-4-2  場發射量測	77
4-4-3  鐵電性質分析	83
4-4-4  光催化分析	84
第五章 結論	88
參考文獻	     90

                                    

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