臺灣博碩士論文加值系統

本研究以Stille coupling reaction成功合成二種含二噻吩并噻咯-苯并呋咱分子衍生物給體-受體交錯型共軛高分子P1、P2，並當作活性層之電子給體材料。合成之P1、P2分別具有1.41 eV和1.38 eV的低能隙，分別具有300-1100 nm的寬吸收範圍。在鑑定方面透過FT-IR、1H NMR及13C NMR來做確認。而材料之光電特性可利用紫外-可見光光譜 (UV- Vis)及螢光光譜 (PL)以及循環伏安圖譜 (CV)來做研究。最後將合成之高分子材料製備成本體異質結太陽能電池元件，並探討不同混摻PCBM的比例及退火溫度對元件效率之影響。在P1:PCBM混摻比例為1:2及退火溫度為125℃時，以P1和PCBM為活性層之本體異質結太陽能電池有最佳的短路電流密度3.77mA/cm2，FF值37.1% 及光電轉換效率0.95％。在P2:PCBM混摻比例為1:2及退火溫度為150℃時，以P2和PCBM為活性層之本體異質結太陽能電池有最佳的元件表現，短路電流密度4.13mA/cm2，FF值38.5%及光電轉換效率1.22％。

We have sucessfully synthesized two donor-acceptor alternating conjugated polymers P1 and P2 containing dithienosilole and benzofurazan derivatives as the donor and acceptor units, respectively, for the donor materials of the active layer by Stille coupling reaction.
Both of them exhibited the intramolecular donor-acceptor characteristic and displayed a panchromatic absorption ranging from 300 to 1000 nm and P1 have an ideal bandgap of 1.41 eV, and P2 is 1.38 Ev. The structure of the polymers were confirmed by FT-IR, 1H NMR, and 13C NMR.
Optoelectronic properties of the polymer were investigated and observed by UV-vis, photoluminescence spectrum, and cyclic voltammogram. Finally we were application of both of the synthesized materials in the active layers of polymer bulk heterojunction photovoltaic (BHJ) solar cells and the measurements of power conversion efficiency in different weight ratios of the Polymer : PCBM blends and different annealing temperatures on the performance of polymer solar cells using the blend (Polymer : PCBM) as active layers. The bulk heterojunction polymer solar cell incorporating P1 and PCBM at a blend ratio of 1:2 and annealing temperature 125℃ exhibited the highest short-circuit current density of 3.77 mA/cm2 and a power conversion efficiency of 0.95%. The bulk heterojunction polymer solar cell incorporating P2 and PCBM at a blend ratio of 1:1 and annealing temperature 150℃ exhibited the highest short-circuit current density of 4.13 mA/cm2 and a power conversion efficiency of 1.22%.

目錄
謝誌 I
目錄 II
圖目錄 IX
表目錄 XIII
摘要 XV
ABSTRACT XVI
第一章 緒論 1
1.1 前言 1
1.2 有機光伏電池介紹 2
1.3高分子太陽能電池元件構造 3
1.4 高分子太陽能電池結構簡介 4
1.4.1 高分子太陽能電池結構種類 4
1.4.2 電洞傳輸層介紹 6
1.4.3 活性層介紹 7
1.5 太陽能電池工作原理 8
1.6 研究動機 9
第二章 理論基礎與文獻回顧 12
2.1 太陽能電池輸出特性 12
2.2 降低活性層材料之能隙 17
2.2.1常見給體-受體型共軛高分子之給體單元 19
2.2.2 常見給體-受體型共軛高分子之受體單元 21
2.2.3 含DTS給體結構特性 22
2.2.4 含BF受體結構特性 23
2.2.5 含矽或含氟之共軛高分子結構特性 23
2.3 高能量轉換效率太陽能電池元件製備條件探討 24
2.3.1 調整材料與PCBM的混摻比例及相容性 25
2.3.2 退火條件的影響 25
2.3.2.1 熱退火 25
2.3.2.2 溶劑退火 26
第三章 實驗 27
3.1 實驗目的與設計 27
3.1.1實驗流程 27
3.2 藥品與溶劑 28
3.3 溶劑前處理 32
3.4實驗儀器 32
3.4.1 一般儀器 32
3.4.2 分析儀器 32
3.5實驗合成步驟 36
3.5.1 受體單位A1單體之合成 40
3.5.1.1 4,7-Dibromobenzofurazan (1)的合成 40
3.5.1.2 4,7-Di(thiophen-2-yl)benzofurazan (2)的合成 41
3.5.1.3 4,7-Bis(5-bromothiophen-2-yl)benzofurazan (A1)的合成 42
3.5.2受體單位A2單體的合成 43
3.5.2.1 5,6-Difluorobenzo[c][1,2,5]oxadiazole 1-oxide (3)的合成 43
3.5.2.2 5,6-Difluorobenzo[c][1,2,5]oxadiazole (4)的合成 44
3.5.2.3 4,7-Dibromo-5,6-difluorobenzo[c][1,2,5]oxadiazole (5)的
合成 45
3.5.2.4 5,6-Difluoro-4,7-di(thiophen-2-yl)benzo [c][1,2,5]
oxadiazole (6)的合成 46
3.5.2.5 4,7-bis(5-bromothiophen-2-yl)-5,6-difluorobenzo [c]
[1,2,5]oxadiazole (A2)的合成 47
3.5.3 D1之給體單位的合成 48
3.5.3.1 3,3',5,5'-Tetrabromo-2,2'-bithiophene (7)的合成 48
3.5.3.2 3,3'-Dibromo-2,2'-bithiophene (8)的合成 49
3.5.3.3 4,4-Bis(2-ethylhexyl)-4H silolo[3,2-b:4,5-b']dithiophene
(9)的合成 50
3.5.3.4 4,4-Bis(2-ethylhexyl)-2,6-bis(trimethylstannyl)-4H-
silolo[3,2-b:4,5-b]dithiophene (D1)的合成 51
3.5.4高分子P1、P2的合成 52
3.5.4.1 高分子P1的合成 52
3.5.4.2 高分子P2的合成 53
3.6 元件製作 54
3.6.1 ITO玻璃基板之清洗與蝕刻 55
3.6.2 電洞傳輸層 55
3.6.3 活性層 56
3.6.4 金屬電極(Al/LiF) 56
第四章 結果與討論 57
4.1 高分子P1之結構鑑定、熱性質、表面型態及光電特性探討 57
4.1.1 高分子P1及其合成中間體、單體之1H NMR與13C NMR
光譜分析 57
4.1.2 高分子P1合成之中間體、單體FTIR光譜 58
4.1.3 單體A1、D1及高分子P1之溶解度測試 61
4.1.4 高分子P1之GPC鑑定 61
4.1.5 高分子P1之熱性質分析 62
4.1.6 高分子P1之螢光光譜特性分析 67
4.1.7 高分子P1之循環伏安計量分析 69
4.1.8 P1:PCBM之混摻比例對元件性質影響 71
4.1.8.1 P1：PCBM於不同混摻比例之UV-Vis光譜 72
4.1.8.2 P1：PCBM混摻比例對元件特性影響 73
4.1.9 退火溫度對P1:PCBM元件性質之影響 74
4.1.9.1 P1：PCBM於不同退火溫度下之UV-Vis光譜 75
4.1.9.2 P1：PCBM於不同退火溫度下之PL光譜 76
4.1.9.3 P1：PCBM於不同退火溫度下之AFM分析 77
4.1.9.4 P1：PCBM之退火溫度對元件特性影響 81
4.1.9.5 P1：PCBM之退火溫度對EQE特性影響 83
4.2高分子P2之結構鑑定、熱性質、表面型態及光電特性探討 84
4.2.1 高分子P2及其合成中間體、單體之1H NMR與13C NMR
光譜分析 84
4.2.2 高分子P2之合成中間體、單體FTIR光譜 84
4.2.3 單體A2及高分子P2之溶解度測試 86
4.2.4 高分子P2之GPC鑑定 86
4.2.5 高分子P2之熱性質分析 88
4.2.6 高分子P2之紫外/可見光光譜特性分析 89
4.2.7 高分子P2之螢光光譜特性分析 92
4.2.8 P2之循環伏安計量分析 94
4.2.9 P2之太陽能電池元件性質分析 97
4.2.9.1 P2：PCBM於不同混摻比例之UV-Vis光譜 97
4.2.9.2 P2：PCBM之混摻比例對元件特性影響 98
4.2.10 退火溫度對P2：PCBM元件性質之影響 100
4.2.10.1 P2：PCBM於不同退火溫度下之UV-Vis光譜 100
4.2.10.2 P2：PCBM於不同退火溫度下之PL光譜 101
4.2.10.3 P2：PCBM於不同退火溫度下之AFM分析 102
4.2.10.4 P2：PCBM之退火溫度對元件特性影響 106
4.2.10.5 P2：PCBM之退火溫度對EQE特性影響 108
4.3 以高分子P1、P2與P3HT分別為活性層給體材料之太陽能電
池元件性質比較 109
4.3.1高分子P1、P2之分子量及熱性質比較 110
4.3.2高分子P1、P2與P3HT 之紫外光-可見光吸收光譜比較 112
4.3.3高分子P1、P2與P3HT 之能階比較 113
4.3.4高分子P1、P2與P3HT分別之載子移動率性質比較 115
4.3.5高分子P1、P2與P3HT分別為活性層給體材料之元件能
量轉換效率及材料特性比較 116
第五章 結論 118
參考文獻 120
附錄 128

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