本研究將NiO與Li2CO3粉末混合燒結製備出 LixNi1-xO粉末，使用電子束蒸鍍法製備出LixNi1-xO電致色變薄膜，期望藉由Li2CO3的掺雜來改變NiO薄膜的結構及增加儲存電荷量，使得互補式電致色變元件(CECD)具有更佳的特性表現。
研究結果顯示，將NiO摻雜1 wt.%的Li2CO3 可以得到LixNi1-xO材料，藉由電子束蒸鍍法，最佳沉積條件為室溫下且氧氣壓力1×10-3 Torr、LixNi1-xO薄膜厚度約為530 nm。CECD的最佳電致色變特性為穿透率差(ΔT%)值為58.4%、光學密度(ΔOD)值為0.733、消耗電荷量(Q)值為8.02 mC/cm2、著色效率(η)值為91.3 cm2/C及比電容值為18.13 μF/cm2，相較於NiO薄膜所製成之CECD其著色效率(η)值74.6 cm2/C、比電容值14.68 μF/cm2，分別提升了22.3%與23.5%。顯示Li2CO3的摻雜能有效提升NiO薄膜的儲存電荷量，使得CECD的電致色變特性提升，且元件著色後靜置96h，著色態穿透率僅回升7.8%，顯示CECD有良好的記憶效應。

In this study, the LixNi1-xO powder was mixed and sintered by the NiO and Li2CO3 powders to produce the LixNi1-xO electrochromic film which was deposited by electron beam evaporation. Doping Li2CO3 not only can improve the NiO film structure but also increase the amount of charges stored, which makes the complementary electrochromic device (CECD) behave better.
Experimental results reveal that as the 1 wt.% of Li2CO3 was doped into NiO, the LixNi1-xO material was formed. The optimal deposition conditions of LixNi1-xO films were oxygen pressure of 1×10-3 Torr at room temperature (R.T.) by electron beam evaporation. The thicknesses of LixNi1-xO films were about 530 nm. The best characteristics of electrochromic CECD revealed a transmittance change (ΔT%) of 58.4%, an optical density (ΔOD) of 0.733, an intercalation charge (Q) of 8.02 mC/cm2, an coloration efficiency(η) of 91.3 cm2/C and a specific capacitance of 18.13 μF/cm2, which are, in turn, 22.3% and 23.5% increasing of the coloration efficiency (η = 74.6 cm2/C) and specific capacitance (14.68 μF/cm2) for the CECD made of NiO film. This results demonstrate that the doping of Li2CO3 can effectively improve the charges-storing amount of NiO film and CECD electrochromic characteristics. After 96h the ΔT of colored CECD is increased merely 7.8%, which shows that the CECD with LixNi1-xO film has a good memory effect.

中文審定書 .................................................................................................... i
英文審定書 ................................................................................................... ii
致謝 .............................................................................................................. iii
摘要 .............................................................................................................. iv
英文摘要 ....................................................................................................... v
總目錄 .......................................................................................................... vi
圖目錄 .......................................................................................................... xi
表目錄 ......................................................................................................... xv
第一章 前言................................................................................................. 1
1-1 概述 ............................................................................................. 1
1-2 文獻回顧 ..................................................................................... 3
1-2-1 NiO 薄膜 ............................................................................... 3
1-2-2 電致色變技術 ...................................................................... 4
1-3 研究動機 ..................................................................................... 7
第二章 理論................................................................................................. 8
2-1 變色材料簡介 ............................................................................. 8
2-2 電致色變材料與沈積方式 .......................................................... 9

2-3 電致色變元件結構 .................................................................... 13
2-3-1 陽楊極電致色變薄膜層 .................................................... 15
2-3-1-1 NiO 之結構 ...................................................................... 15
2-3-1-2 Li-Ni-O 之結構 ............................................................... 17
2-3-2 陰極電致色變薄膜層 ........................................................ 20
2-3-3 離子傳導層(電解質層) ..................................................... 23
2-4 電致色變機制 ........................................................................... 24
2-5 鍍膜技術 ................................................................................... 27
2-5-1 薄膜沉積 ............................................................................ 27
2-5-2 蒸鍍法 ................................................................................. 29
2-5-3 電子束的產生 ..................................................................... 30
2-5-4 電子束加速原理 ................................................................. 32
2-5-5 電子束蒸鍍法之優點 ......................................................... 32
2-6 光學性質 ................................................................................... 32
第三章 實驗............................................................................................... 34
3-1 薄膜之製備 ................................................................................ 35
3-1-1 透明導電基板之準備與清洗 .............................................. 35
3-1-2 NiO、Li 2 CO 3 、WO 3 材料之選用 ....................................... 36
3-1-3 NiO 摻雜 Li 2 CO 3 之粉末製備 ............................................. 37

3-1-4 NiO 與 Li-Ni-O 薄膜製備 ................................................... 38
3-1-5 NiO 與 Li-Ni-O 薄膜蒸鍍步驟 ........................................... 39
3-2 薄膜製程參數 ............................................................................ 42
3-2-1 NiO 與 Li-Ni-O 薄膜製程參數 .......................................... 42
3-2-2 WO 3 薄膜製程參數 ............................................................ 43
3-3 膠態電解質之製備 .................................................................... 44
3-4 電致色變元件製備 ..................................................................... 45
3-5 互補式電致色變元件製備 ......................................................... 47
3-6 薄膜性質分析 ............................................................................ 48
3-6-1 X 光繞射（X-ray diffraction, XRD） ................................ 48
3-6-2 場發射掃描式電子顯微鏡（Field emission scanning
electron microscope, FE-SEM）分析 ................................. 49
3-6-3 化學分析電子能譜儀 （ Electron Spectroscope for
Chemical Analysis, ESCA ）分析 ...................................... 49
3-7 元件特性量測與分析 ................................................................. 50
3-7-1 紫外-可見-紅外光譜儀(UV-Vis-NIR spectrometer)分析 .. 50
3-7-2 循環伏安(Cyclic voltammogram)以及階梯電壓量測分
析 ......................................................................................... 51
3-7-3 著色效率(Coloration efficiency, η)分析 ............................. 52

3-7-4 記憶效應 .............................................................................. 53
第四章 結果與討論 .................................................................................. 54
4-1 不同 Li 2 CO 3 摻雜量之薄膜與材料分析 .................................. 55
4-1-1 不同 Li 2 CO 3 摻雜量之粉末 XRD 分析 .............................. 55
4-1-2 不同 Li 2 CO 3 摻雜量之薄膜製程參數 ................................ 55
4-1-3 不同 Li 2 CO 3 摻雜量之薄膜 XRD 分析 .............................. 56
4-1-4 不同 Li 2 CO 3 摻雜量之薄膜 SEM 表面形貌 ..................... 57
4-1-5 不同 Li 2 CO 3 摻雜量之薄膜表面 ESCA 成份分析 ............ 58
4-1-6 不同 Li 2 CO 3 摻雜量之薄膜內部 ESCA 成份分析 ............ 59
4-1-7 不同 Li 2 CO 3 摻雜量之 ECD 循環伏安分析 ...................... 61
4-1-8 不同 Li 2 CO 3 摻雜量之 ECD 光學特性與著色效率分析 .. 62
4-1-9 不同 Li 2 CO 3 摻雜量之 ECD 比電容值分析 ..................... 63
4-2 不同氧氣壓力之 LiNiO 薄膜與元件分析 ................................ 64
4-2-1 不同氧氣壓力之 LiNiO 薄膜製程參數 ............................. 64
4-2-2 不同氧氣壓力之 LiNiO 薄膜 XRD 分析 ........................... 65
4-2-3 不同氧氣壓力之 LiNiO 薄膜 SEM 表面形貌 ................... 66
4-2-4 不同氧氣壓力之 LiNiO 薄膜內部 ESCA 成份分析 ......... 67
4-2-5 不同氧氣壓力之 ECD 循環伏安分析 ............................... 69
4-2-6 不同氧氣壓力之 ECD 光學特性與著色效率分析 ............ 70
4-2-7 不同氧氣壓力之 ECD 比電容值分析 ................................ 71
4-3 不同薄膜厚度之 LiNiO 薄膜與元件分析 ................................ 72
4-3-1 不同薄膜厚度之 LiNiO 薄膜製程參數 ............................. 72
4-3-2 不同薄膜厚度之 LiNiO 薄膜 SEM 剖面形貌 ................... 73
4-3-3 不同薄膜厚度之 ECD 循環伏安分析 ................................ 74
4-3-4 不同薄膜厚度之 ECD 光學特性與著色效率分析 ............ 75
4-3-5 不同薄膜厚度之 ECD 比電容值分析 ................................ 76
4-4 CECD 之特性探討 ..................................................................... 77
4-4-1 CECD 之循環伏安分析 ...................................................... 77
4-4-2 CECD 之光學特性與著色效率分析 .................................. 78
4-4-3 CECD 之比電容值分析 ...................................................... 79
4-5 CECD 記憶效應分析 ................................................................. 80
4-6 電致色變文獻比較表 ................................................................. 82
4-7 ECD 與 CECD 實際著褪色照片 ............................................... 82
第五章 結論............................................................................................... 84
參考文獻 ..................................................................................................... 87

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