臺灣博碩士論文加值系統

本論文先以Stille coupling reaction合成小分子單體4,7-Bis(4-hexylthiophen-2-yl)benzo[c][1,2,5]thiadiazole(BHTBT)後，並藉由FeCl3氧化聚合法聚合出高分子Poly[4,7-Bis(3-hexyl-5-thiopheneyl)benzo-2,1,3-thiadiazole]（PBHTBT）。
透過1H-NMR及液相層析質譜儀LC-MS分析其結構和分子量，證明成功合出高純度小分子BHTBT；而聚合後的高分子PBHTBT經由1H-NMR圖譜鑑定其結構；經由AFM觀察高分子塗佈在ITO玻璃上的表面型態；經由TGA發現其具有良好的熱穩定性；在DSC分析中則觀察到有Tg點及Tm點，顯示PBHTBT為一結晶性材料；利用UV-Vis分析其吸收光譜；由循環伏安實驗量測高分子的化學能隙；並探討該高分子之熱性質、及光電性質。
最後，將PBHTBT製成有機太陽能電池，使用PBHTBT與PCBM依重量比例混合配成溶液，做為有機太陽能電池的主動層，藉此探討高分子PBHTBT對太陽能電池效率之影響。

The study is to synthesis Poly[4,7-Bis(3-hexyl-5-thiopheneyl)benzo-2,1,3-thiadiazole]（PBHTBT） by oxidation polymerization. First, we prepare BHTBT monomer by Stille coupling reaction, and then use FeCl3 as oxidant to polymerise BHTBT into PBHTBT.
The 1H-NMR spectrum and LC-MS spectrum show that the monomer has high purity. Also, the structure of PBHTBT was proved by 1H-NMR, and the surface appearance was observed by AFM. TGA results corroborate the good thermal stability. DSC analyses show that PBHTBT has Tg and Tm point, which mean PBHTBT is a crystalline material. The band gap was investigated by CV. The absorption spectra were analyzed via UV-Vis.
The application on solar cell of this polymer material was explored using this material as the active layer of solar cell.

目錄
摘要 I
ABSTRACT II
目錄 III
圖目錄 VII
圖目錄(SCHEME) X
表目錄 XI
第一章 序論 1
第二章 文獻回顧與理論介紹 3
2.1 共軛高分子 3
2.1-1 共軛高分子之簡介與導電機制 3
2.1-2 共軛高分子的能帶理論 5
2.2 STILLE COUPLING REACTION 7
2.3 聚(三-烷基噻吩)（P3AT）導電性高分子 9
2.3-1 P3AT相關合成方法 9
2.3-2 Oxidation Polymerization 17
2.4 太陽能電池 20
2.4-1 有機太陽能電池原理 20
2.4-2 有機太陽能電池特性分析 23
2.4-2-1 開路電壓(Open circuit voltage，Voc) 24
2.4-2-2 短路電流(Short circuit current，Isc) 24
2.4-2-3 填充因子(Fill Fator，FF) 25
2.4-2-4 光能轉換效率(Power Conversion Efficiency) 26
2.4-2-5 太陽能電池等效電路(Equivalent Circuit) 26
2.4-3 有機太陽能電池的形式 28
2.4-3-1 單層有機太陽能電池 28
2.4-3-2 異質接面雙層有機太陽能電池 28
2.4-3-3 整體摻混異質接面有機太陽能電池 29
2.4-3-4 無機奈米材料整體摻混型有機太陽能電池 30
2.4-3-5 染料敏化太陽能電池 (Dye sensitized solar cells) 30
2.5 研究動機 32
第三章 實驗內容與儀器分析 33
3.1 實驗藥品 33
3.2 實驗設備及分析儀器 36
3.3 儀器原理 38
3.3-1 核磁共振儀(Nuclear Magnetic Resonance Spectrometer, NMR) 38
3.3-2 凝膠滲透層析儀 (Gel Permeation Chromatography, GPC) 39
3.3-3 調幅式微差掃描熱分析儀 (Modulated Differential Scanning Calorimetry,MDSC) 41
3.3-4 熱重分析儀(Thermogravimetric Analyzer,TGA) 46
3.3-5 原子力顯微鏡(Atomic Force Microscope, AFM) 48
3.3-6 紫外光-可見外吸收光譜儀(UV/Vis spectroscopy, UV/Vis) 49
3.3-7 循環伏特安培儀(Cyclic Voltammeter , CV) 51
3.4 實驗步驟 52
3.4-1 3-Hexylthiophene之官能化 53
3.4-2 小分子PBHTBT之合成 54
3.4-3 高分子PBHTBT之合成 55
第四章 結果與討論 56
4.1 前言 56
4.2 小分子單體結構與性質分析 58
4.3 高分子PBHTBT結構分析 62
4.3-1 高分子PBHTBT之1H-NMR結構分析 62
4.3-2 高分子PBHTBT之GPC分析 64
4.3-3 高分子PBHTBT之AFM結構分析 65
4.3-4 高分子PBHTBT之溶解性分析 68
4.4 高分子PBHTBT熱性質分析 70
4.4-1 高分子PBHTBT之TGA熱性質分析 70
4.4-2 高分子PBHTBT之DSC熱性質分析 72
4.5 高分子PBHTBT之光學性質分析 74
4.6 高分子PBHTBT之電性分析 78
4.7 高分子PBHTBT與高分子複材之元件應用 82
第五章 結論 86
第六章 未來展望 88
參考文獻 90

 
圖目錄
圖2-1 Conjugated structure of 1,3-butene 4
圖2-2 常見的共軛導電高分子 4
圖2-3 Band structure of semiconductor 6
圖2-4 Outline of the catalytic cycle for the Stille coupling reaction. 8
圖2-5 聚三烷基噻吩(P3AT)之結構圖 9
圖2-6 不同Triad之結構配置 11
圖2-7 有機太陽能電池與有機電激發光顯示器[38] 20
圖2-8 有機太陽能電池能階示意圖 21
圖2-9 電極功函數影響有機質能帶示意圖 21
圖2-10 激子游離至界面藉由碰撞分離為自由電子與電洞[39] 22
圖2-11 太陽能電池特性曲線。(上)未照光情況，(下)照光情況[40] 23
圖2-12 光強度與短路電流成正比[41] 25
圖2-13 太陽能電池之等效電路 27
圖2-14 激子於有機材料與金屬電極接合處被蕭特基能障所分離 28
圖2-15 整體摻混異質接面有機太陽能電池結構 29
圖2-16 高分子中混合無機奈米顆粒 30
圖2-17 染料敏化太陽能電池的基本結構 31
圖2-18 以奈米線取代奈米顆粒製作染料敏化太陽能電池 31
圖3-1 真空系統構造圖 36
圖3-2 GPC層析管截面示意圖 40
圖3- 3 DSC加熱爐簡圖 42
圖3- 4 MDSC的加熱方式 44
圖3- 5 MDSC與DSC測量Cp之示意圖 45
圖3- 7 AFM結構示意圖 49
圖3-8 電子躍遷能量圖 50
圖3-9 簡單伏特安培儀裝置 51
圖4-1 小分子單體之1H-NMR圖譜 60
圖4-2 小分子單體之LC-MS圖譜 61
圖4-3 高分子PBHTBT之1H-NMR圖譜(三倍當量數的FeCl3、室溫下) 63
圖4-4 PBHTBT之AFM分析高度圖 67
圖4-5 PBHTBT之AFM分析高度圖(校正過後) 67
圖4-6 PBHTBT之AFM分析高度圖(數據分析) 68
圖4-7 P3HT與高分子PBHTBT之TGA分析 71
圖4-8 P3HT與高分子PBHTBT之 DSC分析圖(10℃/min, under N2) 73
圖4-9 高分子PBHTBT之UV-Vis圖﹝溶液態﹞ 76
圖4-10 高分子PBHTBT之UV-Vis圖﹝薄膜態﹞ 76
圖4-11 高分子P3HT之UV-Vis圖﹝溶液態﹞ 77
圖4-12 高分子P3HT之UV-Vis圖﹝薄膜態﹞ 77
圖4-13 高分子PBHTBT之CV圖形 81
圖4-14 高分子P3HT之CV圖形 81
圖4-15 太陽能元件製作程序 82
圖6-1 BHTBT-C60結構圖 88









 
圖目錄(Scheme)
Scheme 2-1 Synthesis of poly(3-alkylthiophene) by Elsenbaumer 10
Scheme 2-2 Synthesis of poly(3-alkylthiophene) by Sugimoto 10
Scheme 2-3 Synthesis regioregular poly(3-alkylthiophene) by McCullough method 12
Scheme 2-4 Synthesis regioregular poly(3-alkylthiophene) by Rieke Method 13
Scheme 2-5 Synthesis regioregular poly(3-alkylthiophene)by Iraqi method 14
Scheme 2-6 Regioselective synthesis of poly(3-octylthiophene) (POT) 14
Scheme 2-7 Synthesis regioregular poly(3-alkylthiophene) by metal catalysis method[33] 16
Scheme 2-8 Proposed Propagation Mechanism for the Regioselective Polymerization of POPT by FeCl3 via a Carbocation Mechanism 17
Scheme 2-9 The possible mechanism to produce regioregular polymers. 19
Scheme 3-1 Synthesis of PBHTBT 52
Scheme 6-1 Synthesis of BHTBT-C60 89

 
表目錄
表3-1 各種GPC分離管的適用範圍 40
表4-1 GPC量測高分子PBHTBT之整理表格 64
表4-2 高分子PBHTBT之溶解度測試表 68
表4-3 高分子PBHTBT之電化學性質 82

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