合成應用於溶液製程高分子太陽能電池的含苯並 [1,2-b:4,5-b’]二噻吩基共聚物

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研究生：	吳幼琦 Yu-Qi Wu
論文名稱：	合成應用於溶液製程高分子太陽能電池的含苯並 [1,2-b:4,5-b’]二噻吩基共聚物 Synthesis of Benzo[1,2-b:4,5-b']dithiophene-Based Copolymers for Solution Processed Polymer Solar Cells
指導教授：	吳春桂 Chun-Guey Wu
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
論文出版年：	2015
畢業學年度：	103
語文別：	中文
論文頁數：	151
中文關鍵詞：	高分子太陽能電池、P-型材料、塊材異質接面
外文關鍵詞：	Polymer solar cell, P-type semiconductors, Bulk Heterojunction
相關次數：	點閱：12 下載：0
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隨著科技的發展，石化燃料蘊藏量日益減少，尋找其他符合經濟效益的替代能源，是目前非常重要的議題。高分子太陽能電池(PSCs)因可以用塗佈或Roll-to-Roll方式製作，可大面積化以及可撓曲性，製程簡單、成本低廉，因而受到廣泛的注意，D-A (D = Donor; A = Acceptor)共聚物一般具有較高的光吸收係數，且其光電性質可藉由改變D或A的結構(或強度)而調整，常用於作為有機太陽能電池主動層中的P-型材料。本篇論文設計以((2-ethylhexyl)oxy) Benzo[1,2-b:4,5- b']-Dithiophene (BDT) Donor單元搭配(4-(hexyloxy)phenyl)-Quino- xaline (Q)或(4(hexyloxy)phenyl)Pyrido[3,4-b]pyrazine (P) Acceptor單元，並加入了Thiophene (T)或3-Hexylthiophene (RT)進行結構修飾，合成出可作為PSCs主動層P-型材料的六個共聚物，PBDTQ、PTBDTQ、PRTBDTQ、PBDTP、PTBDTP以及PRTBDTP，探討不同Acceptor單元與主鏈修飾對於共聚物光電性質的影響，並搭配N-型材料奈米碳球PC71BM混摻為主動層，組裝成高分子太陽能電池並測試元件光電表現，其中以PTBDTP作為主動層所組裝的反相太陽能電池具有最高光電轉換效率，為4.40%。

The gradually decrease in the fossil fuel reserves pushes the scientists to search for alternative cost-effective energy resources. Polymer solar cell (PSC) which can be fabricated by spin-coating or roll-to-roll processes is one of the potential further green energy resource due to some advantages such as light-weight, mechanical flexibility, simple processing, low cost, and large-area device can be fabricated by roll-to-roll method. D-A (D: Donor; A: Acceptor) copolymers which generally having high absorption coefficient and adjustable (by donor and acceptor units) optical properties, have been widely used as a P-type semiconductors in the active layer of PSCs. In this thesis we designed and synthesized six new D-A copolymers including PBDTQ、PTBDTQ、PRTBDTQ、PBDTP、PTBDTP and PRTBDTP. These copolymers were synthesized by stille coupling of ((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b']- dithiophene (BDT) donor unit with (4-(hexyloxy)phenyl)quinoxaline (Q) or (4(hexyloxy)phenyl)pyrido[3,4-b]pyrazine (P) acceptor unit. Furthermore, thiophene (T) or 3-hexylthiophene (RT) was also introdued in the main chain to adjust the optical property of the copolymers. The effects of the acceptor unit and side chain modifications on the optoelectronic properties of copolymers were investigated. The bulk heterojunction (BHJ) polymer solar cells based on these copolymers fabricated via solution process were also explored. When PC71BM was used as a N-type material, PTBDTP based inverted BHJ device has the maximum efficiency of 4.40%.

第1 章 緒論 1
1-1、 前言 1
1-2、 有機太陽能電池的發展歷史 2
1-3、 高分子太陽能電池的工作原理 9
1-4、 太陽能電池的光伏參數 11
1-5、 高分子太陽能電池相關文獻探討 14
1-6、 研究動機 25
第2 章 實驗部分 29
2-1、 實驗藥品 29
2-2、 共聚物與其中間產物的合成流程圖 33
2-2-1. (4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis(trimethylstannane) (Ditin-DiEH-BDT)之合成 33
2-2-2. ((4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis(thiophene-5,2-diyl))bis(trimethylstannane) (Ditin-DiT-DiEH-BDT)之合成 34
2-2-3. ((4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b']dithiophene-2,6-
diyl)bis(4-hexylthiophene-5,2-diyl))bis(trimethylstannane) (Ditin-DiRT-DiEH-BDT)之合成 35
2-2-4. 5,8-dibromo-2,3-bis(4-(hexyloxy)phenyl)quinoxaline (DiBr-DBQ)之合成 36
2-2-5. 5,8-dibromo-2,3-bis(4-(hexyloxy)phenyl)pyrido[3,4-b]pyrazine (DiBr-DBP)之合成 37
2-2-6. 共聚物之聚合反應─密閉式微波加熱 38
2-2-7. 共聚物之聚合反應─傳統加熱 39
2-3、 合成之反應物、中間體及最後所得共聚物之結構、命名與簡稱 41
2-4、 組裝BHJ 元件之相關材料 46
2-5、 合成步驟 47
2-5-1. Thiophene-3-carbonyl chloride 的合成 47
2-5-2. N,N-diethylthiophene-3-carboxamide 的合成 47
2-5-3. Benzo[1,2-b:4,5-b']dithiophene-4,8-dione 的合成 48
2-5-4. 4,8-Bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b']dithiophene的合成 49
2-5-5.(4,8-Bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis(trimethylstannane)的合成 51
2-5-6. 4,8-Bis((2-ethylhexyl)oxy)-2,6-di(thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene 的合成 52
2-5-7. ((4,8-Bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis(thiophene-5,2-diyl))bis(trimethylstannane)的合成 53
2-5-8. 4,8-Bis((2-ethylhexyl)oxy)-2,6-bis(3-hexylthiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene 的合成 54
2-5-9. ((4,8-Bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis(4-hexylthiophene-5,2-diyl))bis(trimethylstannane)的合成 55
2-5-10. 1,2-Bis(4-hydroxyphenyl)ethane-1,2-dione 的合成 56
2-5-11. 1,2-Bis(4-(hexyloxy)phenyl)ethane-1,2-dione 的合成 57
2-5-12. 4,7-Dibromobenzo[1,2,5]thiadiazole 的合成 58
2-5-13. 3,6-Dibromobenzene-1,2-diamine 的合成 59
2-5-14. 5,8-Dibromo-2,3-bis(4-(hexyloxy)phenyl)quinoxaline的合成 60
2-5-15. 2,5-Dibromopyridine-3,4-diamine 的合成 61
2-5-16. 5,8-Dibromo-2,3-bis(4-(hexyloxy)phenyl)pyrido[3,4-b]-pyrazine 的合成 62
2-5-17. Poly{4,8-bis(2’-ethylhexyloxy)-benzo[1,2-b:4,5-b’]dithio- phene-alt-2,3-bis[4-(hexyloxy)phenyl]quinoxaline}的合成─密閉式微波加熱 63
2-5-18. Poly{2,6-di-2-thienyl-4,8-bis(2’-ethylhexyloxy)-benzo[1,2-b:4,5-b’]dithiophene-alt-2,3-bis[4-(hexyloxy)phenyl]quinoxaline}的合成─密閉式微波加熱 64
2-5-19. Poly{2,6-bis(3-hexylthiophen-2-yl)-4,8-bis(2’-ethylhexyloxy)-benzo[1,2-b:4,5-b’]dithiophene-alt-2,3-bis[4-(hexyloxy)phenyl]quinox-aline}的合成─密閉式微波加熱 65
2-5-20. Poly{4,8-bis(2’-ethylhexyloxy)-benzo[1,2-b:4,5-b’]dithiophene-alt-2,3-bis[4-(hexyloxy)phenyl]quinoxaline}的合成─傳統加熱 66
2-5-21. Poly{2,6-di-2-thienyl-4,8-bis(2’-ethylhexyloxy)-benzo[1,2-b:4,5-b’]dithiophene-alt-2,3-bis[4-(hexyloxy)phenyl]quinoxaline}的合成─傳統加熱 68
2-5-22. Poly{2,6-bis(3-hexylthiophen-2-yl)-4,8-bis(2’-ethylhexyloxy)-benzo[1,2-b:4,5-b’]dithiophene-alt-2,3-bis[4-(hexyloxy)phenyl]quinoxaline}的合成─傳統加熱 69
2-5-23. Poly{4,8-bis(2’-ethylhexyloxy)-benzo[1,2-b:4,5-b’]dithiophene-alt-2,3-bis[4-(hexyloxy)phenyl]pyrido[3,4-b]pyrazine}的合成─傳統加熱 70
2-5-24. Poly{2,6-di-2-thienyl-4,8-bis(2’-ethylhexyloxy)-benzo[1,2-b:4,5-b’]dithiophene-alt-2,3-bis[4-(hexyloxy)phenyl]pyrido[3,4-b]pyrazine}的合成─傳統加熱 71
2-5-25. Poly{2,6-bis(3-hexylthiophen-2-yl)-4,8-bis(2’-ethylhexyloxy)-benzo[1,2-b:4,5-b’]dithiophene-alt-2,3-bis[4-(hexyloxy)phenyl]pyrido[3,4-b]pyrazine}的合成─傳統加熱 72
2-6、 共聚物純化方式 73
2-7、 儀器分析與樣品製備 74
2-7-1. 核磁共振光譜(Bruker 300 MHz Nuclear Magnetic Resonance Spectrometer, NMR) 74
2-7-2. 紫外光/可見光/近紅外光吸收光譜(HITACHI U-4100 Spectrophotometer) 75
2-7-3. 分子螢光光譜(HITACHI F-7000 Fluorescence Spectrophotometer) 76
2-7-4. 膠體滲透層析分析(HEWLETT PACKARD Series1100/Agilent 1100 Series, Gel Permeation Chromatography, GPC) 77
2-7-5. 熱重分析(TA Instruments TGA Q500) 79
2-7-6. 示差掃描熱分析(TA Instruments DSC Q2000) 79
2-7-7. 電化學循環伏安測試(AutoLab Potentiostat/Galvanostat PGSTAT30, CV) 80
2-7-8. 穿透式小角度X 光繞射分析(Rigaku-NANO-Viewer Diffractometer, GIXRD) 81
2-7-9. 塊材異質接面結構(BHJ)太陽能電池元件的組裝 82
2-7-10. 元件光伏參數的量測步驟 (Enlitech SS-F5-3A） 85
第3 章 結果與討論 86
3-1、 紫外光/可見光吸收光譜 86
3-2、 分子螢光光譜 91
3-3、 共聚物的分子量 93
3-4、 共聚物的熱分解溫度測定 97
3-5、 共聚物的玻璃轉換溫度測定 98
3-6、 電化學循環伏安測定共聚物的氧化還原電位 102
3-7、 共聚物所組裝的正相塊材異質接面結構(Regular Bulk Heterojunction, R-BHJ)太陽能電池元件的效率 106
3-8、 PTBDTQ 及PTBDTP 所組裝的反相塊材異質接面結構(Inverted Bulk Heterojunction, I-BHJ)太陽能電池元件的效率 109
第4 章 結論 116
參考文獻 117
附錄 121

                                

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