臺灣博碩士論文加值系統

欲製作商業用之可靠元件，須瞭解元件之動靜態特性。電致色變材料近年快速的發展，對應其元件產品的特性亦須獲得對等的重視，因此全固態元件是電致色變材料通往應用之路，又如元件之變色特性，如響應時間、驅動電壓、光學密度差等決定了商品化成功與否的關鍵。所以本研究利用直流及直流脈衝濺鍍(Sputtering)方式製備電致色變氧化鎢薄膜，利用不同的製程參數，探討製備之氧化鎢薄膜電致色變特性與耐久使用性能，而其電化學性質量測時所使用之電解質溶液為0.1M LiClO4。
本研究在不同的電漿電源與操作參數下，實驗結果顯示當直流及脈衝直流濺鍍時通入氬氣/氧氣流量為60:42sccm與氫氣分別為4sccm、3sccm時，有較佳的穿透調節率變化量(△OD在可見光區接近1.818、1.816)，氧化鎢薄膜厚度越厚，則光學穿透調節率亦越大，而過高的外加電位會對電致色變薄膜結構造成破壞，使穿透調節率明顯下降，且充入的陽離子電荷量會隨著鍍膜功率增加或薄膜堆積密度增加而減少。在拉曼(Raman)光譜中，脈衝直流再加入氫氣時，六價(W6+)峰值面積變強，但在五價(W5+)及四價(W4+)有缺陷；而相較之下直流則沒有出現缺陷。而在交流阻抗分析(AC Impedance)中，再加入最佳參數氫氣下，脈衝直流的阻值比直流來的高，故氧化鎢在直流濺鍍下比脈衝直流來的佳。

The rapid development of electrochromic materials has draw much attention to the evaluation of the performance of its devices. To understand the dynamic performance is necessary for the sake of making a reliable electrochromic device in commercial purpose, which in term mostly is all-solid-state electrochromic devices. The key to the success of these products reflects strongly on various electrochromic performance of such a device. These include response time, memory effect, transmittance, optical density change and color-bleach cyclic lifetime. In this study, the tungsten oxide thin film with high coloration efficiency and durability was prepared by direct current (DC) and pulsed direct current (pulsed DC) sputtering system with different hydrogen conditions. The 0.1M LiClO4 solution was used as an electrolyte in the measurement of electrochemistry.
As the results, the tungsten oxide film have better optical density change when the gas flow ratio Ar:O2 was 60:42 sccm and hydrogen was 4sccm、3sccm entering the direct current (DC) and pulsed direct current (pulsed DC) sputtering system. As the thickness of film increased, the optical density change was increased. The film was defeated by a higher applied voltage. In the Raman spectra, when adding hydrogen into pulsed DC, the peak area of W6+ becomes stronger, but there is flaw appeared in W5+ and W4+ compared with DC which is not existed flaw. To the AC impedance, when adding hydrogen with the optimized parameters, the resistance value of pulsed DC is higher than DC, so there is a better performance in DC sputtering than pulsed DC to tungsten oxide.

中文摘要 i
ABSTRACT ii
誌謝 iii
目錄 iv
表目錄 vi
圖目錄 vii
第一章 緒論 1
1-1 前言 1
1-2 研究動機與目的 4
1-3 文獻回顧 5
1-4 論文結構 7
第二章 基本理論 8
2-1電致變色性質 8
2-2電致色變元件 11
2-3電致色變機制 14
2-3-1 非晶氧化鎢的電致色變機制 14
2-3-2 結晶氧化鎢的電致色變機制 16
2-4 氧化鎢的結構 18
2-5 電漿的產生 18
2-6 反應濺鍍 22
2-7 薄膜形成機制 23
2-8 薄膜微觀結構 26
2-9 薄膜製備方法介紹 28
2-9-1 物理氣相沉積法（Physical vaporb deposition，PVD） 28
2-9-2 電子槍蒸鍍 28
2-9-3 離子束濺鍍 31
2-9-4 磁控濺鍍 33
2-10 交流阻抗分析 35
2-10-1交流阻抗分析原理 35
2-10-2交流阻抗分析在電致色變之應用 35
2-10-3建構電致色變鍍膜之等效電路 37
第三章 實驗設備及方法 39
3-1 實驗流程圖 39
3-2 實驗材料 39
3-2-1 導電層ITO薄膜 39
3-2-2 接觸(Contact)層Ti薄膜 40
3-2-3 上下電極層Ag薄膜 40
3-2-3 電致變色層WO3薄膜 41
3-3 基材的前處理 41
3-4 實驗設備 42
3-5 氧化鎢薄膜之製備 43
3-6 量測及分析工具 44
3-6-1 表面輪廓儀( α-step 膜厚量測) 44
3-6-2 反射式光譜儀( Film Tek 2000 ) 44
3-6-3 可見光-近紅外線光光譜儀(UV-VIS-IR) 45
3-6-4 拉曼散射光譜儀(Raman scattering spectrum) 45
3-6-5 交流阻抗分析儀(AC Impedance) 46
3-6-6 掃瞄式電子顯微鏡(Scanning Electron Microscopy; SEM) 46
3-6-7 X-射線繞射儀(X-ray diffratometer；XRD) 47
3-6-8 循環伏安儀(Cyclic Voltammetry) 48
3-7 電致色變元件之製作條件 50
3-7-1直流磁控濺鍍參數 50
3-7-2脈衝直流磁控濺鍍參數 50
3-8 電解質之調製條件 51
第四章 結果與討論 52
4-1 沉積速率分析 52
4-2 反射式光譜儀分析 54
4-3 拉曼(Raman)散射光譜之分析 56
4-4 光譜儀(UV-VIS-IR)分析 60
4-5 著色與退色穿透變化率分析(ΔT) 74
4-6 著退色效率分析(Coloration Efficiency) 75
4-7 循環伏安分析(Cyclic Voltammetry) 78
4-8 薄膜壽命分析(Life time) 79
4-8 薄膜交流阻抗值分析(AC Impedance) 85
4-9 掃瞄式電子顯微鏡分析(Scanning Electron Microscopy; SEM) 88
第五章 結論與未來展望 90
5-1 結論 90
5-2 未來展望 91
參 考 文 獻 92

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