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研究生：	丁照緯 Ting, Chao-Wei
論文名稱：	無添加催化劑熱蒸鍍法合成單晶WO3-X奈米線與其物理性質之研究 Catalyst-Free Synthesis of Single-Crystalline WO3-x Nanowires via Thermal Evaporation and Their Physical Properties
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：	2018
畢業學年度：	106
語文別：	中文
論文頁數：	101
中文關鍵詞：	氧化鎢奈米線、熱蒸鍍法、氧空缺、電性量測、磁學性質、可見光光催化
外文關鍵詞：	WO3-x nanowires, thermal evaporation, oxygen vacancy, antiferromagnetic
相關次數：	點閱：69 下載：0
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本論文利用以晶粒成核長線配合高載流氣體的熱蒸鍍方法在相對高壓環境下以WO3粉末為前驅物在無鍍金的矽基板長出特殊的氧化鎢奈米線，並探討生長參數對其形貌與性質的影響，後續再利用各式儀器對樣品進行分析，先以XRD、TEM、XPS確認其晶相結構與組成比例，發現以此法長出之氧化鎢奈米線帶有大量的氧空缺是少見以五價鎢為主要鍵結形式的氧化鎢化合物其比例約為5:13，物理性質與常見的三氧化鎢有極大的不同，電性部分有較低的電阻率7.03 x 10-4 Ω ‧ cm，在可見光光降解上也極具應用潛力，且由缺陷誘發磁性產生與塊材氧化鎢之順磁性和三氧化鎢奈米線抗磁性特性不同的反鐵磁性，此外本實驗亦使用鎢基板討論不同成長溫度合成的氧化鎢奈米線結構與性質的差異，發現在較低溫生長的氧化鎢奈米線帶有許多剪力缺陷而高溫環境生長的氧化鎢奈米線有較佳的晶格排列，在電性方面高溫生長的奈米線有較優良的導電度8.77 x 10-3 Ω ‧ cm，但在可見光光降解的應用上低溫合成的氧化鎢奈米線效率較佳，由本實驗可知缺陷對氧化鎢奈米線之物性影響與其適合的應用面。

In our study, oxygen-vacancy-rich tungsten oxide nanowires were synthesized on Si via grain-by-grain thermal evaporation method without any catalyst; also, WO3-x nanowires were grown on W foil as comparison on their physical properties and growth mechanism. In the SEM cross-section images, we have clearly found that there is no thin film formation in the growth mechanism of tungsten oxide grown on Si. It shows that this process is a new grain-by-grain thermal evaporation method which nanowires grown from the previously deposited tiny nanoparticles. Surprisingly, the oxygen-vacancy-rich tungsten oxide nanowires grown on Si were found to have unusual W5+ dominated energy bond and the ratio of tungsten to oxygen was about 5:13 based on XPS analysis. TEM studies show that the lattice arrays of oxygen-vacancy-rich tungsten oxide nanowires grown on Si were crystalline, while those of WO3-x nanowires grown on W foil were improved in terms of crystallization with increase of growth temperature. We demonstrated this result with XRD analysis as well. For physical property measurements, the oxygen-vacancy-rich nanowire grown on Si had a very low resistivity of 7.03 x 10-4 Ω ‧ cm, while the resistivity of WO3-x nanowires grown on W decreased as the growth temperature rises. Additionally, we found that WO3-x nanowires exhibit different magnetic properties depending on the valence state of tungsten. Notably, the oxygen-vacancy-rich tungsten oxide nanowires grown on Si possessed special antiferromagnetic properties. For visible light photocatalytic applications, the WO3-x nanowires grown on W at the lowest temperature have the best degradation efficiency to methylene blue solution.

總目錄
摘要 …………………………………………………………….........……………………. I
Abstract ……………………………………………..…………………….…………….… II
致謝 ………………………………………………..………………………….………….XII 
總目錄 ……………………………………………..…………………………….………XIII
圖目錄 …………………………………………………….…………………………...XVI表目錄 ……………………………………………….………………………………. XX
第一章	前言 ………………………………………………………………………….. 1
第二章	文獻回顧 …………………………………………………………………….. 2
  2-1 奈米科技 …………………………………………………….……………………. 2
  2-2 奈米材料 ……………………………………………………….…………………. 3
  2-3 奈米材料特性 …………………………………………………….………………. 4
     2-3-1熱學性質 ………………………………………………………………….… 4
     2-3-2磁學性質 ………………………………………………………………….… 4
     2-3-3力學性質 ……………………………………………………………………. 5
     2-3-4電學性質 ……………………………………………………………………. 5
     2-3-5光學性質 ……………………………………………………………………. 5
  2-4 氧化鎢奈米線成長方法 ……………………………….…………………………. 6
     2-4-1熱蒸鍍法(Thermal Evaporation) ………………………………………….…. 6
     2-4-2水熱法( Hydrothermal Method ) ……………………………………….…. 8
     2-4-3化學氣相沉積法(Chemical Vapor Deposition ,CVD)……………………….. 8
     2-4-4脈衝雷射蒸鍍法 ( Pulsed Laser Deposition , PLD ) …...…………………. 10
     2-4-5模板法(Template method) ………...……………………………….……….. 10
   2-5 氧化鎢之基本特性和性質 …………………………………...………….…….. 11
     2-5-1發光性質 …………………………………………………………………... 13
     2-5-2光催化性質 ………………………………………………………………... 15
     2-5-3電致變色性質 ……………………………………………………………... 16
     2-5-4氣敏性質 …………………………………………………………………... 17
     2-5-5電性變化 …………………………………………………………………... 18
第三章	實驗方法與儀器 ………………………………....………………………… 20
   3-1實驗大綱 ………………………………………….........……………………….. 20
   3-2 實驗流程 ………………………………………………….........………………. 20
     3-2-1試片前處理 ………………………………….........………………………... 21
     3-2-2 藥品、試片放置 …………………………….........……………………….. 21
     3-2-3反應溫度 ………………………………………........……………………... 21
     3-2-4載流氣體與壓力 ……………………………………........…………..……. 22
     3-2-5升溫時間與反應時間 ………………………………………........……...… 22
     3-2-6 前驅物使用量 …………………………………………........…………….. 23
   3-3 結構分析及物理性質量測儀器 ……………………………….........…………. 24
     3-3-1 X光繞射分析儀 (X-Ray Diffractometer,XRD) ……………………........... 24       
     3-3-2掃描式電子顯微鏡(Scanning Electron Microscope,SEM ) ……………….. 26
     3-3-3 穿透式電子顯微鏡 (Transmission Electron Microscope , TEM ) .…..…... 27
     3-3-4 能量色散X射線光譜 ( Energy-dispersive X-ray Spectroscopy,EDS) …... 28
     3-3-5 微光激發螢光光譜儀(Photoluminescence,PL) ………………………….... 29
     3-3-6超導量子干涉儀(Superconducting Quantum Interference Device ,SQUID) .30
     3-3-7 X射線光電子能譜學(X-ray Photoelectron Spectroscopy, XPS) ………….. 31
     3-3-8四點探針(4-point probe ) …………………………………………………... 32
第四章	結果與討論 ……………………………………………………………...… 34
   4-1實驗架構設置 …………………………………………………………………. 34
   4-2成長參數對奈米線形貌之影響 ………………………………………………... 39
     4-2-1生長溫度對奈米線的影響 ………………………………………………... 39
     4-2-2 壓力對奈米線生長之影響 …...…………………………………………... 44
     4-2-3 反應時間對奈米線生長之影響 …...……………………………………... 47
     4-2-4載流氣體對奈米線生長之影響 …...………………………….…………... 50
     4-2-5 前驅物量對奈米線生長之影響 …...………………………….…...……... 54
   4-3生長機制比較 …...………………………….…...…………………………….... 57
   4-4氧化鎢奈米線之性質分析 …...……………………………………………….... 65
     4-4-1結構與缺陷分析 …...……………………………………….….…...……... 65
     4-4-2 氧化鎢奈米線XPS與PL分析 ………………………………………….. 72
     4-4-3氧化鎢奈米線電性量測 …………………………………………………... 81
     4-4-4氧化鎢奈米線可見光光降解 ……………………………………………... 90
     4-4-5氧化鎢奈米線磁性量測 …………………………………………………... 94
第五章	結論 ………………………………………………………………………… 98
參考文獻…………………………………………………………………..………………99

     
                                    

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