臺灣博碩士論文加值系統

　　本研究成功合成含吲哚(5-(2,5-di(thiophen-2-yl)pyrrolyl)-1-methylindole (DTPMI)、1-(2,5-di(thiophen-2-yl) pyrrol-1-yl) indole (DTPI))與硒吩(4-(2,5-di (thiophenyl)pyrrolyl)-N-(selenophen-ylmethylene)aniline (DTPSA))懸掛基之二噻吩一吡咯的電致變色材料，並使用電化學法聚合出PDTPMI、PDTPI及PDTPSA。亦合成出另一個新型陰極電致變色材料(2-(allyloxymethyl)-2,3-dihydrothieno [3,4-b][1,4]dioxine (EDOT-E))並將其以電化學法聚合出PEDOT-E，將PDTPMI、PDTPI、PDTPSA及PEDOT-E置於離子液體[EPI+][TFSI-]及組成三明治型式元件，探討其光學及電化學性質，包含光學對比、色彩變化、光譜電化學穩定性、著色效率與元件之長時間循環穩定性和光學記憶性質。藉由對高分子薄膜施加電壓，使得薄膜從中性態至氧化態，且具有可逆性的顏色變化，PDTPI具有褐色、淺灰色、紫灰色及灰色的可逆性顏色變化，在波長930 nm光學對比值能達到∆Tmax = 40.11%，材料光譜電化學穩定性也能達到90.91%，著色效率達到224.14 cm2/C，轉換時間也最迅速，著色時間與去色時間分別為0.98秒與1.32秒。PDTPI/PProDOT-Et2元件顯示多種顏色變化(淺灰色、灰色、紫灰色、紫藍色及深藍色)，在波長590 nm處之光學對比值能達到∆Tmax=48.39%，材料光譜電化學穩定性能達到98.91%，著色效率達到508.93 cm2/C，轉換時間也很迅速，著色時間與去色時間分別為0.92秒與0.91秒，電化學穩定性也能達到90.33%，而光學記
憶效果在著色態僅衰退1~2%。

　　In this study, indole (DTPMI and DTPI) and selenophene (DTPSA) pendants containing dithienylpyrroles are successfully synthesized. PDTPMI, PDTPI, and PDTPSA are prepared using DTPMI, DTPI, and DTPSA, respectively, by electrochemical polymerization method. A novel cathodically coloring material (2-(allyloxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine (EDOT-E)) is also synthesized, and its corresponding polymer (PEDOT-E) is prepared using electrochemical polymerization. The optical and electrochemical properties, such as optical contrast, color variations, spectroelectrochemical stability, coloration effiency of three anodically coloring materials (PDTPMI, PDTPI and PDTPSA) and a cathodically coloring material (PEDOT-E) in an ionic liquid solution, and long-term cycling stability and optical memory properties of their corresponding electrochromic devices (PDTPMI/PEDOT-E, PDTPI/PEDOT-E, and PDTPSA/PEDOT-E ECDs) are characterized. PDTPI film not only oxidized and reduced reversibly but also accompanied by obvious color change (brown, light gray, purple and gray). The maximum optical contrast (∆Tmax) of PDTPI film in an ionic liquid solution is 40.11% at 930 nm, and the maximum coloration efficiency (ηmax) of PDTPI film is 224.14 cm2/C. The τc and τb of PDTPI film in an ionic liquid solution are 0.98 and 1.32 s, respectively. PDTPI/PProDOT-Et2 ECD shows distinct color transition with five various colors (light gray, gray, purplish gray, purplish blue and dark blue). The maximum optical contrast (∆Tmax) of PDTPI/PProDOT-Et2 ECD is 48.38% at 590 nm, and maximum coloration efficiency (ηmax) of PDTPI/PProDOT-Et2 ECD is 508.93 cm2/C at 590 nm. The τc and τb of PDTPI/PProDOT-Et2 ECD are 0.92 and 0.91 s, respectively. PDTPI/PProDOT-Et2 ECD shows high electrochemical cycling stability
(90.33%) after 1000 cycles. PDTPI/PProDOT-Et2 ECD shows satisfactory optical memory effect, the variation of transmittance in coloring state is less than 2%.

目錄
摘要 i
Abstract ii
誌謝 iv
目錄 v
表目錄 vii
圖目錄 ix
第一章 緒論 1
1-1 前言 1
1-2 研究動機 2
1-3 電致色變簡介 3
1-4 電致變色的基本參數 3
1-5 電致色變的應用領域 6
第二章　文獻回顧 7
第三章 實驗部分 13
3-1 研究架構 13
3-2 實驗藥品 14
3-3 實驗儀器 15
3-4 實驗流程 16
3-4-1 管柱層析 16
3-4-2 電化學與光學性質測試 17
3-5 實驗合成 20
3-5-1 高分子單體合成 20
第四章　結果與討論 32
4-1 導電高分子之電化學聚合測試 32
4-1-1 導電高分子電鍍於ITO玻璃 32
4-1-2 起始電位 33
4-1-3 定電位聚合法 35
4-2 高分子薄膜分析 36
4-3 高分子薄膜於液態電解質下之光學性質測試 44
4-3-1 高分子薄膜之吸收光譜值變化圖 44
4-3-2 高分子薄膜之HOMO與LUMO整理 66
4-3-3 高分子薄膜之光學對比(穿透度變化) 67
4-3-4 高分子薄膜之轉換時間、穩定性以及著色效率 79
4-4 高分子薄膜於膠態電解質下之光電化學性質測試 86
4-4-1高分子薄膜於膠態電解質之吸收光譜值變化圖 86
4-4-2 高分子薄膜於膠態電解質之光學對比(穿透度變化) 111
4-4-3高分子薄膜於膠態電解質之轉換時間、穩定性以及著色效率 121
4-4-4 高分子薄膜於膠態電解質之多圈循環電化學穩定性 127
4-4-5 高分子薄膜於膠態電解質之光學記憶 136
第五章 結論 145
參考文獻 147

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