臺灣博碩士論文加值系統

在本研究中，主要為利用Suzuki coupling聚合法合成一系列含有不同3,6-carbazole-based電子予體和2,1,3-benzothiadiazole-based電子接受體為主鏈的D-A或D-π-A聚芴高分子，這些高分子以核磁共振光譜(NMR)、元素分析(EA)、凝膠滲透層析(GPC)、紫外線可見光光譜(UV)和螢光光譜(PL)分析。我們探討不同電子予體分子結構對共軛高分子光電性質的影響和研究超分枝狀結構對於高分子發光行為的影響。我們所合成的高分子的重量平均分子量為0.34×104~5.09×104，分子量分佈為1.31~2.60，熱重量損失皆大於350 oC，而且溫度高達700 oC時，高分子仍有47.9 %的殘餘量，證明我們所合成的共軛高分子熱穩定性非常好。我們導入拉電子基2,1,3-benzothiadiazole結構於高分子主鏈中會造成破壞整體fluorene分子的共軛性，吸收波長有藍位移的現象。共軛高分子的UV-vis光譜，其薄膜態相較於溶液態皆有些微的紅位移現象產生，此原因推測為薄膜態時高分子容易堆疊，發生凝集效應所造成的紅位移。我們利用光學法計算能量間隙(energy bandgap)，D-A和D-π-A共軛型高分子其Eg約1.96~2.99 eV之間。將高分子與PCBM以1：1 (w/w)摻混做為主動層，在太陽光模擬器AM 1.5G的光照之下，以PFCBTT做為元件，得到最高的短路電流0.025 mA/cm2，開路電壓0.66 V，光電轉換效率0.38 %，在太陽光模擬器AM 1.5G的光照之下。

　　A series of well-defined D-A or D-π-A conjugated polyfluorenes, incorporating various 3,6-carbazole-based monomers as electron donor unit and 2,1,3-benzothiadiazole-based monomer as electron acceptor unit, were synthesized through Suzuki coupling polymerization and were further characterized by 1H-NMR, EA, gel permeation chromatography, UV-vis, and PL spectra. The structural effect of 3,6-carbazole-based units on optoelectronic properties and the effect of branched unit on photoluminescence spectra were investigated. Their weight-average molecular weights and polydispersity indices were in the range of 0.34 × 104 to 5.09 × 104 and 1.31~2.60, respectively. All synthesized polymers revealed highly thermally stable with decomposition temperatures (Td) greater than 350.0 oC and beyond 47.9 % weight loss occurred at 700.0 oC under nitrogen atmosphere.Optical properties, both in solution and film state, were investigated using absorption and photoluminescence (PL) spectra. The result suggests that the effective conjugation length of polymer chain is readily decreased by incorporation of 2,1,3-benzothiadiazole segment, leading to the formation of blue-shifts of absorption. The band gaps of D-A or D-π-A polymers calculated from the onset absorption in solution state are in the range of 1.96-2.99 eV. The bulk-heterojunction photovoltaic cell used PFCBTT polymer as the electron donor and PCBM as the electron acceptor when the weight ratio of PFCBTT/PCBM was 1/1 showed an energy conversion efficiency of 0.37 % with open-circuit voltage (Voc) of 0.66 V and short-circuit current density (Jsc) of 0.025 mA/cm2.

摘要 I
Abstract II
目錄 III
表目錄 VII
流程目錄 VIII
圖目錄 1
第一章　緒論 6
1-1　前言 6
1-2　太陽能電池簡介 6
1-3　太陽能電池種類概述 7
1-3-1　單結晶矽、非結晶矽、多結晶矽太陽能電池 8
1-3-1-1　單結晶矽太陽電池[4] 8
1-3-1-2　多結晶矽太陽電池 8
1-3-1-3　非結晶矽太陽電池 8
1-3-2　薄膜太陽能電池[5] 9
1-3-3　有機太陽能電池 9
1-3-4　各種太陽能電池的光電轉換效率 9
1-4　太陽光譜介紹 10
1-5　共軛高分子 13
1-6　研究動機與目的 13
第二章　原理與文獻回顧 15
2-1　有機共軛高分子介紹 15
2-2　操作原理[21] 16
2-3　高分子太陽能電池元件設計 18
2-3-1　雙層結構(bilayer devices) 18
2-3-2　塊狀異質接面(bulk heterojunction devices) 19
2-4　分子結構與能隙的關係[27] 20
2-5　低能隙高分子 21
2-5-1　設計原則 21
2-5-2　聯環系統 22
2-5-3　Donor–Acceptor共聚高分子系統 22
2-6　元件效率與I-V曲線定義 23
2-6-1　開路電壓(open circuit voltage, Voc) 25
2-6-2　短路電流(short circuit current) 26
2-6-3　外部量子效率(external quantum efficiency, EQE) 27
2-7　各種主鏈含2,1,3-benzothiadiazole(BT)的高分子材料 27
2-8　螢光原理 29
2-9　螢光能量轉移 31
第三章　實驗內容 33
3-1　實驗儀器與裝置 33
3-2　鑑定儀器 33
3-3　物性測量儀器 35
3-4　實驗藥品與材料 38
3-5　合成步驟 39
3-5-1　單體合成 39
3-5-2　高分子聚合 44
3-6　合成反應機制 53
3-6-1　Suzuki reaction 53
3-6-2　Stille reaction 54
3-7　循環伏安法 54
3-8　元件製作 56
3-8-1　ITO玻璃蝕刻與清洗 56
3-8-2　高分子發光膜的製作 56
3-8-3　陰極蒸鍍 57
3-8-4　元件測量 57
第四章　結果與討論 58
4-1　結構之鑑定 58
4-1-1　單體結構之鑑定 58
4-1-2　高分子結構之鑑定 62
4-2　熱性質分析 65
4-3　高分子光學性質分析 65
4-4　高分子電化學性質分析 72
4-5　太陽能元件性質 72
第五章　結論 104
參考文獻 106
自述 109

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