臺灣博碩士論文加值系統

本論文主要是探討二維電子施體、電子受體交替共聚高分子的光電特性，我們藉由Stille偶合反應及Yammamoto偶合反應合成PHQT、PFQT、PFQT2、PFQT3四種高分子。利用在側鏈引入不同基團 (茀或4-己基苯基)觀察側鏈與主鏈之間的交互作用，還有改變主鏈上電子施體 (噻吩)所佔之比例，研究主鏈上共軛長度對高分子光學、電化學性質的影響：紫外-可見光吸收光譜分成兩個區域，一個在300 nm~400 nm為單體π→π*的吸收範圍；另一個在500 nm~700 nm間是高分子鏈上分子內電荷轉移 (intramoleculars charge transfer)所造成的吸收，高分子能帶隙大約在1.75 eV~1.90 eV之間，其最高佔有分子軌域 (highest occupied molecular orbital, 簡稱HOMO)能階值大約在-5.27 eV~-5.13 eV之間。此系列高分子擁有不錯的熱穩定性，其熱裂解溫度大約都在400 ℃上下；利用廣角X光繞射測量高分子鏈在不同溫度下(100)結晶面間的距離，約為2.5 nm，隨著溫度升高，此距離亦隨之增加至2.8 nm。綜合以上所述，此系列高分子具有應用在光電元件活性層的可能性。

Two-dimensional donor-acceptor (D-A) structured conducting polymers, PHQT, PFQT, PFQT2, PFQT3, were designed and synthesized by introducing electron-deficient quinoxaline (acceptor) as core with electron-rich alky-fluorene or 4-hexylbenzene as its side chain and thiophene/oligo-thiophene (donor) in the main chain. Benefited from the D-A structures, the polymers possess low bandgaps with energies of 1.79 eV, 1.85 eV, 1.89 eV, and 1.76 eV for PHQT, PFQT, PFQT2, PFQT3, respectively, and show a broad absorption band in the visible region: the shoter wavelength absorption peak at ca. 300 nm~400 nm attributed mainly to the conjugated side chains and the longer wavelength absorption peak (charge transfer CT peak) between 500 nm and 700 nm ascribed to the absorption of the conjugated D-A main chains. The polymers are electrochemically active in oxidation and the corresponding cyclic voltammetry (CV) measurements show that the HOMO level of the polymers is ca. -5.31 eV~ -5.13 eV which is significantly lower than that of the conventional and most studied conducting polymer of poly 3-hexyl thiophene (P3HT). Powder X-ray diffraction analysis confirms that monodispersed PFQT shows a crystalline order plane of (100). The TGA analysis reveals that the temperature at which all polymers degrades was higher than 400 ℃. In summary, these polymers show potential for use as an active material in optoelectronic devices.

目錄
目錄 I
中文摘要 II
英文摘要 III
圖目錄 IV
表目錄 VII
第一章 序論 1
1-1導電高分子 1
1-2太陽能光譜與大氣質量(air mass) 4
1-3 太陽能之優缺點 6
1-4 太陽能電池的發展與分類 7
1-5 有機太陽能電池的工作原理 8
1-6 太陽能元件的種類 13
1-7 太陽能電池的基礎知識 14
1-8分子設計：低能帶隙施體-受體共軛高分子 (low band gap donor-acceptor conjugated polymers) 17
第二章 結果與討論 22
2-1 分子合成策略 22
2-2 光學性質探討 32
2-3 電化學性質之探討 40
2-4熱化學性質之探討 45
2-5 高分子PFQT系列之廣角X光繞射 47
第三章 結論 48
第四章 實驗部分 49
4-1 實驗儀器和藥品 49
4-2 合成步驟 50
參考文獻 63
附錄 66

圖目錄
圖(1.1)1,3-丁二烯分子結構與軌域示意圖…………….………...……….1
圖(1.2)(a)β-胡蘿蔔素 (b)維他命A 結構式…………….………………..1
圖(1.3)共軛結構數目與能帶關係示意圖………………………..……….2
圖(1.4)合成聚乙炔(PA)之反應式………………………………….……..2
圖(1.5)能帶示意圖………………………………………………………...3
圖(1.6)導電高分子之結構圖……………………………………………...3
圖(1.7)不同溫度的普朗克黑體輻射分佈………………………..……….4
圖(1.8)太陽能光譜………………………………………………………...5
圖(1.9)大氣質量示意圖…………………………………………………...5
圖(1.10)太陽能電池按照材料之分類………………………………….…7
圖(1.11)p-n junction示意圖……………………………………………….8
圖(1.12)空乏區形成示意圖……………………………………………….9
圖(1.13)(a)p-n結光伏效應能帶結構圖......................................................9
(b)太陽能電池工作簡圖………………………………………..10
圖(1.14)有機太陽能電池光電轉換及損失流程圖……..…….……..…..10
圖(1.15)電荷分離示意圖……………………………….………………..11
圖(1.16)金屬與半導體界面的能階圖 (a)界面接觸前的能階 (b)Schottky (c)Ohmic contact……………………….…………………….….12
圖(1.17)有機薄膜太陽能電池元件結構示意圖……..………………….14
圖(1.18)理想太陽能電池等效電路圖………………..…………...……..14
圖(1.19)實際太陽能電池等效電路圖……………………..…………….15
圖(1.20)I-V曲線中Voc、Isc及FF示意圖………………………………16
圖(1.21)太陽輻照度、光子數目與波長對應圖……...………………….17
圖(1.22)電子施體與電子受體分子軌域交互作用圖………..………….18
圖(1.23)電子施體-受體交替低能帶隙高分子示意圖.………………….18
圖(1.24)(a)常見施體結構圖 (b)常見受體結構圖.………….…………..19
圖(1.25)二維的施體-受體共軛高分子………….…………….……...….20
圖(1.26)高分子PCQT及PThQx(diPh)………………………………..20
圖(1.27)目標高分子結構圖…………………………………...…………21
圖(2.1)高分子逆合成圖………………………………………………….22
圖(2.2)化合物11逆合成圖………………….………………………...…22
圖(2.3)化合物8、9逆合成圖……………….….………………………..23
圖(2.4)化合物4與5之逆合成圖………….……..……………………...23
圖(2.5)化合物1、2、3之合成圖………………………………………..24
圖(2.6)化合物4、5之合成圖…………………………………………….24
圖(2.7)化合物7之合成圖…………………………….………………….25
圖(2.8)化合物 8、9之合成圖……………………………………………25
圖(2.9)化合物10之合成圖………………………………………………26
圖(2.10)化合物11與三溴、四溴化合物副產物……………………...…26
圖(2.11)改良化合物11之合程圖……….……………………………….27
圖(2.12)化合物12之合成圖……………….…………………………….27
圖(2.13)高分子PHQT、PFQT、PFQT3之合成圖…………………...28
圖(2.14)噻吩氧化聚合示意圖…………………….……………………..28
圖(2.15)PFQT2氧化聚合失敗示意圖………….……………………….28
圖(2.16)高分子PFQT2之合成圖……………………………………….29
圖(2.17)(a)各高分子GPC ri圖...................................................................30
(b)各高分子GPC uv圖.................................................................30
(c)高分子PFQT系列 GPCri圖..................................................31
(d)高分子PFQT系列GPC uv圖..…………………....………...31
圖(2.18)化合物8、9、10、11之紫外-可見光吸收光譜………………….33
圖(2.19)化合物8、9、10、11之螢光放射光譜…………………………34
圖(2.20)化合物10在不同極性溶劑中的螢光放射光譜…….………….34
圖(2.21)化合物11在不同極性溶劑中的螢光放射光譜……….………35
圖(2.22)溶劑對螢光放射波長影響示意圖……………………..……….36
圖(2.23)高分子化合物PHQT、PFQT、PFQT2、PFQT3的溶液態紫外-可見光吸收光譜………..………………………….………….37
圖(2.24)化合物9、10與高分子PFQT、PFQT2、PFQT3的溶液態紫外-可見光吸收光譜…………………………..………………..38
圖(2.25)化合物8與高分子PHQT的溶液態紫外-可見光吸收光譜.…38
圖(2.26)不同分子量之高分子PFQT的溶液態紫外-可見光吸收光譜...................................................................................................39
圖(2.27)高分子UV吸收峰對應能量與重複單元數倒數關係圖……...40
圖(2.28)三電極測量裝置圖……………………………………………...40
圖(2.29)化合物8、9、10、11之循環伏安圖比較圖………………………42
圖(2.30)PHQT、PFQT、PFQT2、PFQT3之循環伏安圖比較圖……….44
圖(2.31)化合物10與PFQT、PFQT2、PFQT3循環伏安比較圖…….44
圖(2.32)化合物8與高分子PHQT循環伏安比較圖………………...…45
圖(2.33)(a)高分子PHQT、PFQT、PFQT2、PFQT3熱重分析比較圖 (b)高分子不同分子量PFQT系列熱重分析比較圖……………..46
圖(2.34)高分子PFQTc變溫廣角X光繞射圖……………………...…..47





表目錄
表(1.1)不同太陽入射角的大氣質量……………………………………...6
表(1.2)一些金屬的功函數……………………………………………….13
表(2.1)高分子化合物之分子量與分子量分佈….….…..….………...….29
表(2.2)化合物8、9、10、11之光譜性質………………………………….32
表(2.3)高分子化合物溶液態之紫外-可見光吸收光譜數據….……...…36
表(2.4)高分子PFQT系列溶液態之紫外-可見光吸收光譜數據…...…39
表(2.5)高分子PFQT系列UV吸收峰對應能量值及重複單元數據…..39
表(2.6)化合物8、9、10、11之氧化還原電位值……………………...…..42
表(2.7)高分子PHQT、PFQT、PFQT2、PFQT3溶液態氧化電位及其HOMO、LUMO能階……………………………………………..43
表(2.8)高分子化合物之熱分析數據……………………………....…….45

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