臺灣博碩士論文加值系統

本篇研究分為兩個部分，第一部分使用2,7-雙(咔唑-9-基)-9,9-二甲苯基芴(2,7-bis(carbazol-9-yl)-9,9-ditolylfluorene，BCDF)為主體，以電化學聚合法聚合成P(BCDF)高分子薄膜，BCDF再分別與四種雙噻吩衍生物(2,2'-bithiophene (BTP)、3,3'-dibromo-2,2'-bithiophene (DBBT)、2-(2-thienyl)furan (TF)及cyclopentadithiophene ketone (CPDTK))以進料莫耳比例為1/1於ITO玻璃基板上進行電化學聚合，分別得到P(BCDF-co-BTP)、P(BCDF-co-DBBT)、P(BCDF-co-TF)以及P(BCDF-co-CPDTK) 四種高分子薄膜，使用電化學分析儀搭配紫外光-可見光光譜儀對高分子薄膜進行光電性質分析，分析內容包含穿透度變化、著色效率以及響應時間，從實驗結果得知，P(BCDF-co-BTP)於波長1000 nm處穿透度變化達到54.3%，著色效率為185.8 cm2 C-1，顏色變化從還原態的黃綠色轉變為氧化態的灰藍色。
將上述製備的五種高分子薄膜分別作為陽極材料，以poly(3,4-(2,2-dimethylpropylenedioxy)thiophene) (PProDOT-Me2)作為陰極材料，並使用膠態高分子電解質(PC-PMMA-LiClO4-ACN)作為陽極與陰極間的離子傳輸層，組裝成五種電致變色元件並對其進行光電性質測試，測試內容包含穿透度變化、著色效率、響應時間、光學記憶以及穩定度，經由測試結果得知P(BCDF-co-BTP)/PProDOT-Me2元件的性質最為優異，此元件於波長580 nm處時穿透度變化達到40.0%，著色效率為494.8 cm2 C-1，在光學記憶及穩定度上均有良好的表現。
第二部分使用2,7-雙(咔唑-9-基)-9,9-二辛基芴(2,7-bis(carbazol-9-yl)-9,9-dioctylfluorene，BCOF)為主體，以電化學聚合法聚合成P(BCOF)高分子薄膜，BCOF再分別與兩種雙噻吩衍生物(2,2'-bithiophene (BTP)及cyclopentadithiophene ketone (CPDTK))以不同進料莫耳比例為1/1及1/2在ITO玻璃基板上進行電化學聚合，分別得到P(BCOF-co-BTP)、P(BCOF-co-2BTP)、P(BCOF-co-CPDTK)及P(BCOF-co-2CPDTK) 四種高分子薄膜，並使用電化學分析儀搭配紫外光-可見光光譜儀對高分子薄膜進行光電性質分析，分析內容包含穿透度變化、著色效率以及響應時間，從實驗結果得知P(BCOF-co-BTP)於波長1000 nm處穿透度變化達到58.4%，著色效率為167.1 cm2 C-1，顏色變化從還原態的卡其色變為氧化態的灰藍色。
隨後將上述製備的五種高分子薄膜分別+作為陽極材料，以poly(3,4-ethylenedioxythiophene) (PEDOT)作為陰極材料，並使用膠態高分子電解質(PC-PMMA-LiClO4-ACN)作為陽極與陰極間的離子傳輸層，組裝成五種電致變色元件並對其進行光電性質測試，測試內容包含穿透度變化、著色效率、響應時間、光學記憶以及穩定度，測試結果得知P(BCOF-co-2BTP)/PEDOT元件的性質最為優異，此元件於波長640 nm處時穿透度變化達到39.7%，著色效率為449.2 cm2 C-1，在光學記憶及穩定度上均有良好的表現。

This study includes two parts. In first section, copolymers based on 2,7-bis(carbazol-9-yl)-9,9-ditolylfluorene (BCDF) and four dithiophene derivatives (2,2'-bithiophene (BTP), 3,3'-dibromo-2,2'-bithiophene (DBBT), 2-(2-thienyl)furan (TF) and cyclopentadithiophene ketone (CPDTK)) are successfully electrodeposited on ITO electrodes to obtain P(BCDF), P(BCDF-co-BTP), P(BCDF-co-DBBT), P(BCDF-co-TF) and P(BCDF-co-CPDTK) films, respectively. Spectroelectrochemical properties of copolymer films are investigated by UV–Vis spectroscopy and cyclic voltammetry (CV). P(BCDF-co-BTP) copolymer with BCOF/BTP =1/1 feed molar ratio shows high optical contrast and coloration efficiency which are measured as 54.3% and 185.8 cm2 C-1 at 1000 nm, respectively. Electrochromic devices (ECDs) are assembled using P(BCDF), P(BCDF-co-BTP), P(BCDF-co-DBBT), P(BCDF-co-TF) and P(BCDF-co-CPDTK) films as the anodic layers, poly(3,4-(2,2-dimethylpropylenedioxy)thiophene) (PProDOT-Me2) film as the cathodic layer and a PC-PMMA-LiClO4-ACN composite film as the electrochromic electrolyte. P(BCDF-co-BTP)/PProDOT-Me2 ECD shows two different colors (bright brown and purplish blue) when applied different potentials. P(BCDF-co-BTP)/PProDOT-Me2 ECD shows high optical contrast (40.0%) and coloration efficiency (494.8 cm2 C–1) at 580 nm. In addition, this ECD has satisfactory optical memory and long-term stability.
In second section, copolymers based on 2,7-bis(carbazol-9-yl)-9,9-dioctylfluorene (BCOF) and two dithiophene derivatives (2,2'-bithiophene (BTP) and cyclopentadithiophene ketone (CPDTK)) are successfully electrodeposited on ITO electrodes to obtain P(BCOF), P(BCOF-co-BTP), P(BCOF-co-2BTP), P(BCOF-co-CPDTK), and P(BCOF-co-2CPDTK) films, respectively. Spectroelectrochemical properties of copolymer films are investigated by UV–Vis spectroscopy and cyclic voltammetry (CV). P(BCOF-co-BTP) copolymer with BCOF/BTP =1/1 feed molar ratio shows high optical contrast and coloration efficiency which are measured as 58.4% and 167.1 cm2 C-1 at 1000 nm, respectively. Electrochromic devices (ECDs) are assembled using P(BCOF), P(BCOF-co-BTP), P(BCOF-co-2BTP), P(BCOF-co-CPDTK), and P(BCOF-co-2CPDTK) films as the anodic layers, poly(3,4-ethylenedioxythiophene) (PEDOT) film as the cathodic layer and a PC-PMMA-LiClO4-ACN composite film as the electrochromic electrolyte. P(BCOF-co-2BTP)/PEDOT ECD shows two different colors (light grey and purplish blue) when applied different potentials. P(BCOF-co-2BTP)/PEDOT ECD show high optical contrast (39.7%) and coloration efficiency (449.2 cm2 C–1) at 640 nm. In addition, this ECD has satisfactory optical memory and long-term stability.

摘要 i
Abstract iii
誌謝 v
目錄 vi
表目錄 ix
圖目錄 xi
第一章、緒論 1
1.1 前言 1
1.2 變色材料介紹及應用 2
1.3 電致變色簡介 4
1.3.1 電致變色材料發展 4
1.3.2 電致變色材料種類 5
1.3.3 電致變色元件結構介紹 7
1.3.4 電解質介紹 8
1.3.5 電致變色基本參數 8
1.4 文獻回顧 11
1.5 研究動機 23
第二章、BCDF分別與雙噻吩衍生物電合成共聚物並與PProDOT-Me2組成元件之電化學與光學性質探討 25
2.1 實驗內容 25
2.1.1 實驗架構 25
2.1.2 實驗藥品 26
2.1.3 實驗設備 26
2.1.4 ITO玻璃基板前處理 27
2.1.5 電化學實驗裝置 27
2.1.6 BCDF分別與四種雙噻吩衍生物電化學聚合反應示意圖 28
2.1.7 陽極材料在液態電解質環境下之光電性質之測試 30
2.1.8 PProDOT-Me2陰極材料製備 31
2.1.9 膠態電解質及電致變色元件製備 31
2.1.10 電致變色元件光電性質之測試 33
2.2 陽極高分子薄膜性質測試 34
2.2.1 BCDF、BTP、DBBT、TF以及CPDTK單體聚合起始電位 34
2.2.2 傅立葉紅外線光譜分析 36
2.2.3 電化學循環伏安法聚合分析 37
2.2.4 定電位法電聚合陽極薄膜 39
2.2.5 電化學特性分析 39
2.2.6 不同電位下之吸收光譜圖及顏色 43
2.2.7 不同電位下之CIE色座標(L*, a*, b*, x, y) 45
2.2.8 HOMO、LUMO及能階 47
2.2.9 操作電位範圍之穿透度變化及響應時間 48
2.2.10 電致變色參數整理及分析 51
2.3 電致變色元件性質測試 52
2.3.1 不同電位下之吸收光譜圖及顏色 52
2.3.2 不同電位下之CIE色座標(L*, a*, b*, x, y) 54
2.3.3 操作電位範圍之穿透度變化及響應時間 57
2.3.4 電致變色參數整理及分析 60
2.3.5 光學記憶分析 61
2.3.6 多圈循環伏安法穩定度測試 63
第三章、BCOF分別與雙噻吩衍生物合成共聚物並與PEDOT組成元件之電化學與光學性質探討 66
3.1 實驗內容 66
3.1.1 實驗架構 66
3.1.2 實驗藥品 67
3.1.3 實驗設備 67
3.1.4 ITO玻璃基板前處理 68
3.1.5 BCOF分別與雙噻吩衍生物電化學聚合反應示意圖 68
3.1.6 PEDOT陰極材料之製備 70
3.2 陽極高分子薄膜性質測試 70
3.2.1 BCOF、BTP以及CPDTK單體聚合起始電位 70
3.2.2 傅立葉紅外線光譜分析 72
3.2.3 電化學循環伏安法聚合分析 73
3.2.4 定電位法電聚合陽極薄膜 75
3.2.5 電化學特性分析 75
3.2.6 不同電位下之吸收光譜圖及顏色 79
3.2.7 不同電位下之CIE色座標(L*, a*, b*, x, y) 81
3.2.8 HOMO、LUMO以及能階 83
3.2.9 操作電位範圍之穿透度變化及響應時間 84
3.2.10 電致變色參數整理及分析 87
3.3 電致變色元件性質測試 88
3.3.1 不同電位下之吸收光譜圖及顏色 88
3.3.2 不同電位下之CIE色座標(L*, a*, b*, x, y) 90
3.3.3 操作電位範圍之穿透度變化及響應時間 93
3.3.4 電致變色參數整理及分析 96
3.3.5 光學記憶分析 97
3.3.6 多圈循環伏安法穩定度測試 99
第四章、結論 102
參考文獻 103

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