共軛高分子及共軛高分子/金屬氧化物奈米複合材料之電變色特性的探討

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呂明怡(Ming-I Lu) 查詢紙本館藏

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論文名稱

共軛高分子及共軛高分子/金屬氧化物奈米複合材料之電變色特性的探討
(The Electrochromic Properties of Conjugated Polymers and Their Metal Oxide Nanocomposites)

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摘要(中)

電變色元件因可應用於聰明窗戶、防眩光後視鏡、及顯示器等而受到矚目，傳統電變色材料皆以無機物為主，雖然無機材料具有較高的環境及電化學穩定性，但加工不易，顏色變化不多，而有機電變色材料具有較好的溶劑加工性、撓曲性、低能量損耗及短應答時間等優點而受到重視。本研究中以4,4-Dioctyl-cyclopenta[2,1-b;3,4-b’]dithiophene (DOCPDT) 為主架構，將DOCPDT iazthiole (PS)、Octylthiophene (OT)、carbazol (Cz)進行對接，合成出有機可溶的PDOCPDT衍生共聚物，包含紅色的PDOCPDT-OT (Poly[4,4-dioctyl-cyclopentadithiophene-alt-3-octyl- thiophene])和DOCPDT-DOT (Poly[4,4-dioctyl-cyclopentadithiophene-alt-bis-2,5-(3-octylthiophene)
、綠色的PDOCPDT-PS (Poly [4,4-dioctylCyclopenta-di-thiophene-alt-4,7-(piazthiole)])和藍色的PDOCPDT (Poly[4,4-Dioctylcyclopenta[2,1-b; 3,4-b’]-dithiophene]) 三原色之陰極著色材料及淡黃色的PDOCPDT-Cz (Poly-[4,4-dioctyl-Cyclopentadithiophene-alt-4,7-(piazthiole)])陽極著色材料，這些有機可溶共聚物具有低的驅動電位、快的應答時間、良好的電化學和環境穩定性及高的著色效率等特性。另外，為增加材料的效能本研究利用在PDOCPDT中，加入無機奈米粒子合成奈米複合材料，藉由材料的複合來擷取兩者的優點，當PDOCPDT加入有機可溶之TiO2後，可明顯的增加高分子的著色及去著效率，在此TiO2扮演著類似分散劑及電荷暫存區的角色。最後將所合成之陰極著色高分子搭配V2O5離子儲存層、或高分子陽極著色材料組裝成電變色元件，這些
元件皆具有低的驅動電位，而兩極皆為高分子材料的元件之著色及去著色效率皆會高於使用V2O5離子儲存層做為陽極的元件，以PDOCPDT/ PDOCPDT-Cz元件具有最高的光學對比與光學密度及最快的應答時間。

摘要(英)

Electrochromic materials will change their optical properties (color or transmittance) upon applying dc voltages. Electrochromic devices have been developed for the application as smart windows and anti-glare rear view mirrors, due to their various merits such as multicolor, high contrast, optical memory, and no visual dependence on viewing angle. In this proposal, we synthesize a series of new soluble electrochromic copolymers containing 4,4-Dioctylcyclopenta[2,1-b; 3,4-b’]dithiophene (DOCPDT) unit. Including Red colored Poly[4,4-dioctyl-cyclopentadithiophene-alt-3-octyl-thiophene] (PDOCPDT-OT)
and Poly [4,4-dioctyl-Cyclopentadithiophene-alt-bis-2,5-(3-octyl-thiophene)] (PDOCPDT-DOT)、Green colored Poly [4,4-dioctylCyclopentadithiophene-alt-4,7-(piazthiole)] (PDOCPDT-PS) and Blue colored Poly[4,4-Dioctylcyclopenta[
2,1-b;3,4-b’]dithiophene] (PDOCPDT) as cathodic electrochromic materials and pale-yellow colored Poly [4,4-dioctyl- Cyclopentadithiophene-alt-4,7-(piazthiole)] (PDOCPDT-Cz) as an anodic electrochromic material. All
polymers have low operation voltage, fast response time, good chemical and environmental stability as well as high optical contrast and coloration efficiency.Furthermore, in order to enhance the electrochromic performances of polymer,TiO2 nano-wires were added into PDOCPDT to form inorganic/polymer nano-hybrid material. The coloration efficiency of the nanocomposite increased significantly without sacrifying other properties. The function of the nanowire is to disperse the aggregated polymer chains, it may be the temporary electron storage centers, electrons can be transferred reversibly between PDOCPDT and
TiO2 nano-wires. Finally, the electrochromic devices based on these new polymers/copolymers were fabricated by using cathodic polymer combines with anodic polymer or V2O5 ion storage anode. All devices have a low operation voltage and dual polymer (PDOCPDT/ PDOCPDT-Cz) device has the highest optical contrast of 50% and the shortest response time of 0.5 second.

關鍵字(中)

★ 共軛高分子
★ 電變色材料

關鍵字(英)

★ electrochromic material
★ conjugated polymer

論文目次

目錄
中文摘要……………………………………….................. I
英文摘要……………………………………….................. II
謝誌................................................... III
目錄…………………………………………….................. IV
圖目錄………………………………………………............. VII
表目錄..………………………………………………........... XI
第一章緒論………………………………….................. 1
1-1 前言……………………………………..................... 1
1-2 電變色材料的基本特性…………………………............. 1
1-3 電致色變材料……………………………………………....... 4
1-4 控制變色分子顏色的方法………………………………......12
1-5 提升電變色特性的方法…………………………………......16
1-6 研究目的…………………………………………………..... 21
第二章實驗部分……………………………………………...... 23
2-1 研究範圍及架構…………………………………………..... 23
2-2 實驗藥品…………………………………………........... 25
2-3 PDOPCDT 共軛高分子衍生物合成之實驗流程圖……....... 29
2-3-1 4,4-Dioctyl-cyclopenta[2,1-b;3,4-b’]dithiophene(DOCPDT)之合成……..................................... 29
2-3-2 Poly(4H-Cyclopenta[2,1-b;3,4-b']dithiophene) (PDOCPDT-OP)之合成……………………….................... 29
2-3-3 以Stille coupling 的方式合成Poly[4,4-dioctyl-Cyclo-pentadithiophenealt-3-octyl-thiophene] (PDOCPDT-OT-S), oly[4,4-dioctyl-Cyclopenta-di-thiophene-alt-4,7-(piazthiole)] (PDOCPDT-PS), Poly[4,4-dioctyl-Cyclo-pentadithiophene-alt-3,6-(9H-carbazol)(PDOCPDT-Cz) 及Poly[4,4-dioctyl-Cyclopenta-di-thiophene-alt-3,6-(9-metyl-9H-carbazol)] (PDOCPDT -N-MeCz-S)共聚物之合成路徑.................... 30
2-3-4 以oxidation polymerization 合成poly[4,4-dioctyl-cyclopentadithiophene-alt-bis(3-octyl-thiophene)] (PDOCPDT-DOT-OP)及以Yamamoto coupling reaction 合成poly[4,4-dioctyl-cyclopentadithiophene-alt- bis(3-octyl-thiophene)] (PDOCPDT-DOT-Y)之合成路徑…………....................... 31
2-4 中間產物及目標產物之結構命名及簡稱………………...... 32
2-5 Poly(4H-Cyclopenta[2,1-b;3,4-b']dithiophene)s 之合成步驟……...... ............................................35
2-6 有機可溶之奈米金屬氧化物及金屬的製備…………….......49
2-7 複合物的製備……………………………………………...... 51
2-8 離子儲存層及陽極著色電極的製備……………………...... 52
2-9 電變色元件的組裝………………………………………...... 54
2-10 使用儀器及樣品的製備………………………………....... 54
第三章結果與討論……………………………………………..... 63
3-1 Poly(cyclopenta-dithiophene) (PCPDT)衍生物的電變色分析…….................................................. 63
3-2 Poly(4,4-Dioctyl-cyclopenta[2,1-b;3,4-b’]dithiophene) (PDOCPDT)衍生共聚物的合成與電變色性質探討…............. 79
3-2-1 Poly[4,4-dioctyl-Cyclopentadithiophene)-alt-4,7-(piazthiole)](PDOCPDT-PS)之電變色特性………............. 79
3-2-2 Poly[4,4-dioctyl-Cyclopentadithiophene)-alt-3,6-(9H-carbazol)](PDOCPDT-Cz)之電變色特性………................ 91
3-2-3 Poly(4,4-dioctyl-cyclopentadithiophene-alt-3-octyl-thiophene)(PDOCPDT-OT)之電變色特性…………............. 100
3-2-4 Poly(4,4-Dioctyl-cyclopenta[2,1-b;3,4-b’]di- thiophene)(PDOCPDT)衍生物之電變色特性總整理............ 107
3-2-5 不同合成途徑之PDOCPDT-OT 系列的電變色特性和物性的探討 .....................................................109
3-3 PDOCPDT/有機可溶之金屬氧化物之電變色分析……....... 122
3-3-1 有機可溶之奈米無機物及高分子複合膜特性鑑定…......122
3-3-2 PDOCPDT/有機可溶之TiO2複合材料之電化學及光學特性..126
3-3-3 有機可溶之TiO2 在高分子複合膜中的功能………...... 134
3-4 共軛高分子電變色元件的特性分析……………………..... 138
3-4-1 V2O5 離子儲存層的特性……………………………...... 138
3-4-2 PDOCPDT/V2O5元件之電變色特性…………………....... 141
3-4-3 PDOCPDT/PDOCPDT-Cz 元件之電變色特性………........ 143
3-4-4 PDOCPDT/PDOCPDT-DOT 元件之電變色特性……......... 148
3-4-5 PDOCPDT-DOT/V2O5 元件之電變色特性…………........ 152
3-4-6 PDOCPDT-DOT/PDOCPDT-Cz 元件之電變色特性.......... 156
3-4-7 PDOCPDT-PS/PDOCPDT-Cz 元件之電變色特性…......... 160
3-4-8 PDOCPDT 衍生物/PDOCPDT-Cz 元件之電變色特性總比較. 165
第四章結論…………….................................. 167
參考文獻............................................... 172
附錄.................................................. 178

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指導教授

吳春桂(Chun-Guey Wu)

審核日期

2008-12-24

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