近年來電致變色玻璃已被廣泛的研究，在智能窗戶領域中具有優秀節能的應用實例。氧化釩(Vanadium Oxide)是個眾所皆知的變色材料，是綠色建築中非常具有前景的節能材料應用，然而此類型的材料在電致變色相關機制與微觀影響的研究已知甚少，因此本文採用溶膠凝膠法製備該薄膜。相較於其他材料，釩氧化物具有結構簡單與價格低廉的優點，且較於多彩。這種材料只需單層薄膜在玻璃上就足以有效改變玻璃光學性質。通過電子顯微鏡(SEM)、原子力顯微鏡(AFM)和X射線繞射(XRD)對薄膜進行厚度，表面形貌，晶體結構的量測。光學性質由UV-Vis分光光度計而得。電化學性能由循環伏安法(CV)、計時電流法(CA)測定。結果顯示，Ti-V2O5比V2O5顯示出較出色的著色率，可以歸因於局域原子結構的對稱性和電子結構的變化。原位吸收光譜即時觀測薄膜進行漂白與著色反應時的原子和電子結構變化，以便闡明其電致變色機制。本文還研究了對綠能窗戶應用至關重要的電致變色薄膜的化學反應穩定性。

 In recent years, electrochromic glass has been widely studied, and it has excellent energy-saving application in the field of smart windows. Vanadium oxide is a well-known electrochromic material. However, the research on the electrochromic mechanism and microscopic effects of this type of smart material is seldom known, this study uses sol-gel method to prepare the film. Vanadium oxide systems are simple, cheap, and exhibit different colors depend on its multiple oxidation states. A single layer of this material deposited on a glass is sufficient to change the optical property of the glass efficiently. The film thickness, surface morphology, crystal structure were confirmed by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD). Optical properties were obtained by UV-Vis spectrophotometer. Electrochemical properties were determined by cyclic voltammetry (CV) and chronoamperometry (CA). The results show that Ti-V2O5 has better coloring rate than V2O5, which can be attributed to the alternation of local atomic symmetry and electronic structures revealed by X-ray absorption spectroscopy. Moreover, in-situ XAS monitored the change of atomic and electronic structures during the bleaching-coloration to elucidate the electrochromic coloration mechanism of these films. The stability of the electrochromic film, which is critical for architectural window applications, is also investigated in this study.

目錄
第一章、緒論	1
1.1 前言	1
1.2 研究目的	4
第二章、文獻回顧及理論	5
2.1 電致變色(electrochromic)理論及文獻	5
2.2 奈米材料	7
2.3 溶膠凝膠法(sol-gel Process)	8
2.4 電致變色元件	10
2.5 五氧化二釩(V2O5)介紹	11
第三章、實驗步驟與方法	12
3.1實驗方式	12
3.2 五氧化二釩、鈦修飾五氧化二釩溶膠製備	13
3.3 ITO玻璃基板處理	14
3.4 薄膜生長	15
3.6 儀器介紹	16
第四章、實驗結果與討論	34
4.1 場發射掃描式電子顯微鏡 (SEM)分析	34
4.2 X光繞射儀 (XRD) 分析	39
4.3 電化學分析	42
4.4 紫外-可見光透射光譜(UV-vis)分析	45
4.5 Raman分析	50
4.5 X光吸收光譜(XAS) Soft X-ray分析	53
4.6 X光吸收光譜(XAS) hard X-ray分析	58
第五章、結論	62
參考資料	63

圖目錄 
圖1. 1  美國國能源資訊局（EIA）能源消耗分類[1]	2
圖1. 2  智能窗戶實際應用[12]	3
圖2. 1  常見過渡金屬氧化物的電致變色材料[17]	6
圖2. 2  溶膠凝膠過程[29]	9
圖2. 3  電致變色元件結構[30]	10
圖2. 4  五氧化二釩(V2O5) (a)晶體結構圖 (b)八面體示意圖	11
圖3. 1  五氧化二釩(V2O5)、鈦修飾五氧化二釩(Ti-V2O5)製備流程以及測量方式	13
圖3. 2  SEM內部結構圖[32]	17
圖3. 3  SEM儀器裝置	17
圖3. 4  AFM原理示意圖[33]	19
圖3. 5  AFM儀器圖	19
圖3. 6  UV-vis儀器裝置圖	21
圖3. 7  UV-vis 光路圖	21
圖3. 8  XRD 原理及儀器圖[34]	22
圖3. 9  Raman光譜儀原理[35]	23
圖3. 10  Raman光譜儀原理	24
圖3. 11  Raman光譜儀	24
圖3. 12  電化學分析儀裝置圖	25
圖3. 13  循環伏安法( Cyclic Voltammetry, CV )儀器電壓時間圖	26
圖3. 14  計時電流法( Chronoamperometry, CA ) 儀器電流時間圖	26
圖3. 15  同步輻射研究中心同步輻射光源的產生	28
圖3. 16  同步輻射研究中心	28
圖3. 17  X光吸收光譜實驗站示意圖	29
圖3. 18  儀器架設示意圖	29
圖3. 19  穿透式示意圖	30
圖3. 20  螢光式示意圖	30
圖3. 21  多重散射與單一散射示意圖	33
圖3. 22  X光吸收光譜XANES與EXAFS分界圖	33
圖4. 1  五氧化二釩 (V2O5) 薄膜、鈦修飾五氧化二釩薄膜 (Ti- V2O5)薄膜表面圖	35
圖4. 2  五氧化二釩 (V2O5) 薄膜、鈦修飾五氧化二釩薄膜 (Ti-V2O5)薄膜截面圖	35
圖4.3   (a)-(d) EDS 元素分析圖	37
圖4. 4  五氧化二釩 (V2O5) 薄膜、鈦修飾五氧化二釩薄膜 (Ti- V2O5)表面形貌圖	38
圖4. 5  五氧化二釩 (V2O5)、鈦修飾五氧化二釩薄膜 (Ti-V2O5) 5°-65°的XRD圖	40
圖4. 6  五氧化二釩 (V2O5)、鈦修飾五氧化二釩薄膜著色前 (Ti-V2O5) 5°-25°的XRD圖	40
圖4. 7  五氧化二釩 (V2O5)、鈦修飾五氧化二釩薄膜著色後 (Ti-V2O5) 5°-25°的XRD圖	41
圖4. 8  五氧化二釩 (V2O5)、鈦修飾五氧化二釩 (Ti-V2O5) CV比較圖(實線：第1圈，虛線 : 第300圈)	43
圖4. 9  300cycles 五氧化二釩 (V2O5)、鈦修飾五氧化二釩 (Ti-V2O5) CV圖	43
圖4. 10  五氧化二釩 (V2O5)、鈦修飾五氧化二釩 (Ti-V2O5)薄膜退色過程時間-電流關係圖	44
圖4. 11  五氧化二釩 (V2O5)、鈦修飾五氧化二釩 (Ti-V2O5)薄膜著色過程時間-電流關係圖	44
圖4. 12  五氧化二釩 (V2O5)、鈦修飾五氧化二釩 (Ti-V2O5)薄膜的樣品圖	46
圖4. 13  五氧化二釩 (V2O5)、鈦修飾五氧化二釩 (Ti-V2O5)不同電壓的可見-紫外光穿透率	46
圖4. 14  五氧化二釩 (V2O5)、鈦修飾五氧化二釩 (Ti-V2O5)波長600nm的可見-紫外光穿透率	47
圖4. 15  五氧化二釩 (V2O5)、鈦修飾五氧化二釩 (Ti-V2O5)薄膜原位(in-situ)穿透率與時間響應圖	48
圖4. 16  五氧化二釩 (V2O5)、鈦修飾五氧化二釩 (Ti-V2O5)漂白、著色效率圖	49
圖4. 17  五氧化二釩結構變化[38]	50
圖4. 18  (a)五氧化二釩(V2O5)結構變化、(b)不同結構之α、ε、δ、γ - LiV2O5[42]	51
圖4. 19  五氧化二釩 (V2O5)、鈦修飾五氧化二釩 (Ti-V2O5)Raman光譜圖	51
圖4. 20  不同偏壓下(1V、0.5V、0V、-0.5V、-1V) 五氧化二釩 (V2O5)、鈦修飾五氧化二釩 (Ti-V2O5)Raman光譜圖	52
圖4. 21  3d 軌域晶格場分裂[44]	53
圖4. 22  3d 軌道示意圖 [45]	54
圖4. 23  五氧化二釩 (V2O5)、鈦修飾五氧化二釩 (Ti-V2O5) (a) V L2,3-edge XANES 圖譜(b)O k-edge XANES 圖	55
圖4. 24  V2O5、Ti-V2O5 漂白與著色態V L2,3-edge的XANES光譜	56
圖4. 25  O K-edge(a)漂白態；(b)著色態 高斯擬合(Gaussian Fitting)圖	57
圖4. 26  a1/b1比值	57
圖4. 27  五氧化二釩 (V2O5)、鈦修飾五氧化二釩 (Ti-V2O5) (a)漂白態與 (b)著色態XANES圖	59
圖4. 28  五氧化二釩 (V2O5)、鈦修飾五氧化二釩 (Ti-V2O5) (a)漂白態與 (b)著色態前邊緣峰值	59
圖4. 29  氧化釩反曲點(Inflection point)與前緣峰(pre-edge peak)位置[48]	60
圖4. 30  氧化釩價數與吸收特徵位置關係圖[48]	60
圖4. 31  V K-edge 的前吸收邊緣位置計算漂白、著色價數分布圖	61

表目錄
表1. 1  變色機制原理特性比較	2
表2. 1  合成法奈米材料製備方式[24]	7
表3. 1  實驗參數	12
表3. 2  製備溶膠之藥品	14
表4. 1  薄膜粗糙度	38
表4. 2  著色前樣品(001)特徵峰位置與層間間距	41
表4. 3  著色後樣品(001)特徵峰位置與層間間距	41
表4. 4  電化學儀參數	43
表4. 5  電化學儀參數	44
表4. 6  薄膜穿透率變化	48
表4. 7  循環初期漂白、著色效率分析	49
表4. 8  循環末期漂白、著色效率分析	49
表4. 9  V K-edge 的前吸收邊緣位置與價態	61

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