合成應用於高分子太陽能電池的含苯並[1,2-b:4,5-b′]二噻吩為骨架之D-π-A共聚物

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楊庭菽(Ting-Shu, Yang) 查詢紙本館藏

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合成應用於高分子太陽能電池的含苯並[1,2-b:4,5-b′]二噻吩為骨架之D-π-A共聚物

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摘要(中)

高分子太陽能電池中作為主動層的P型共軛高分子，其光電性質可藉由改變結構及分子量而調整。本研究利用8-bis(5-(2-ethylhexyl)
thiophen-2-yl)-2,6-di(thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene為Donor單元(D)，5,8-dibromo-2,3-bis(4-(hexyloxy)phenyl)pyrido[3,4-b]pyrazine為Acceptor單元(A)，合成出P11共聚物，並在D或A分別接上含有拉電子性的硫烷鏈或氟原子，合成出P12和P14共聚物，或同時接上硫烷鏈和氟原子的P15共聚物，並與本實驗室先前合成沒有thiophene bridge之P9和P10一起探討此六個共聚物的性質及光電表現。結果顯示含有thiophene bridge的P11和P12的共軛長度比P9和P10長，最大吸收波長往長波長移動，因此所組裝的元件有較高的Jsc值；含有拉電子性的氟原子之P15因其分子量最大，吸收係數高，形成主動層時結晶度良好，且與PC61BM形成彼此穿插且各自連續的網狀結構，組裝成元件有最高的Jsc值(11.70 mA/cm2)、FF值(0.53)及光電轉換效率為4.50%。另外，P2和P15共聚物分別可以藉由剛合成的Pd(PPh3)4為催化劑進行聚合反應，以及使用不同的混合溶劑(CHCl3/Hexane和THF/Hexane)進行索式萃取進而得到較高分子量的共聚物，組裝成元件時高分子量共聚物的元件效率(P2:1.67%, P15:4.31%)大於低分子量的元件效率(P2:0.91%, P15:2.43%)。

摘要(英)

The photovoltical performance of a P-type conjugated polymer can be tuned by changing the molecular structure and weight. In this study, 8-bis(5-ethylhexyl)thiophen-2-yl)-2,6-di(thiophen-2-yl)benzo[1,2-b:4,5-b′] dithiophene was used as a donor unit and bromo-2,3-bis(4-(hexyloxy) phenyl)pyrido[3,4-b]pyrazine was used as an acceptor to construct the copolymer P11. Furthermore, an electron-withdrawing alkylthio chain was attached on the donor to form P12, or adding electron-withdrawing fluorine atoms on the acceptor to prepare P14. P15 has alkylthio chain on the donor and fluorine on the acceptor. Combining these four new copolymers with P9 and P10 (without thiophenebridge) prepared in our lab before, the properties- photovoltical performance relationship were investigated. The results showed that the conjugation length of P11 and P12 which containing thiophene bridge was longer than P9 and P10, respectively therefore the corresponding solar cells have higher Jsc value. P15 has higher molecular weight, large absorption coefficient, good crystallinity and forms an interpenetrating bicontinuous network when blend with PC61BM. As a result, inverted cell based on P15 copolymer exhibits the highest Jsc value (11.70 mA/cm2), FF value (0.53) and conversion efficiency (4.50%) amongst the copolymers studied in this thesis. In addition, increasing the molecular weight of P2 by using the fresh prepared Pd(PPh3)4 as a catalyst, or by Soxhlet extraction of P15 with high polar solvent. We have proved the copolymers with higher molecular weight have the efficiency (P2:1.67%, P15:4.31%) higher than that of copolymers with lower molecular weight (P2:0.91%, P15:2.43%).

關鍵字(中)

★ 高分子太陽能電池
★ 含苯並二噻吩
★ 氟化
★ 硫烷鏈
★ 不同分子量的共聚物

關鍵字(英)

★ polymer solar cells
★ benzodithiophene
★ Fluorinated
★ alkylthio chain
★ different copolymers of molecular weight

論文目次

摘要 I
Abstract II
謝誌 IV
目錄 V
圖目錄 VIII
表目錄 XV
第一章緒論 1
1-1、前言 1
1-2、高分子太陽能電池元件的架構 2
1-3、反式高分子太陽能電池的工作機制 4
1-4、太陽能電池的光伏參數 6
1-5、高分子塊材異質接面(Bulk Heterojunction)太陽能電池 10
1-6、具有好的光伏表現之高分子特性 12
1-7、高分子太陽能電池相關文獻探討 13
1-8、研究動機 24
第二章實驗部分 27
2-1、實驗藥品 27
2-2、組裝反式BHJ元件之相關材料31
2-3、單元與共聚物單體之結構與簡稱 32
2-4、單體的合成 37
2-4-1. Donor 1單元的合成 37
2-4-2. Donor 2單元的合成 38
2-4-3. Donor 3單元的合成 42
2-4-4. Acceptor 1單元的合成 46
2-4-5. Acceptor 2單元的合成 47
2-4-6. Acceptor 3單元的合成 48
2-4-7. Pd(PPh3)4的合成 51
2-5、共聚物的合成 52
2-6、共聚物的純化方式 57
2-7、儀器分析與樣品製備 58
2-7-1. 核磁共振光譜 58
2-7-2. 紫外光/可見光/近紅外光吸收光譜 58
2-7-3. 膠體滲透層析分析 59
2-7-4. 熱重分析 61
2-7-5. 示差掃描熱分析 61
2-7-6. 電化學測試 62
2-7-7. X光繞射分析 63
2-7-8. 原子力顯微鏡 64
2-7-9. 塊材異質接面結構(BHJ)太陽能電池元件的組裝 65
2-7-10. 元件光伏參數的量測步驟 66
第三章結果與討論 68
3-1、共聚物的分子量 68
3-2、共聚物的熱分解溫度測定 70
3-3、共聚物的熱性質測定 72
3-4、共聚物的光學性質探討 74
3-5、共聚物的前置軌域能討 78
3-6、共聚物TD-DFT理論計算所得之分子構型及前置軌域分佈圖ㄙ82
3-7、以六個共聚物為吸光材料所組裝的反式高分子太陽能電池元件之光伏表現 89
3-7-1、共聚物的元件優化過程 89
3-7-2、共聚物組裝成元件優化所得的最高光伏表現探討 104
3-8、主動層膜的表面形貌分析 106
3-9、共聚物的結晶度探討 110
3-10、不同分子量的P2和P15共聚物之光伏性質 118
第四章結論 125
參考文獻 127
附錄 132
附錄1、NMR圖譜 132
附錄2、光電子光譜儀 146
附錄3、空間電荷限制電流 146
附錄4、P15-3RD元件的優化 148

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指導教授

吳春桂(Chun-Guey Wu)

審核日期

2017-8-16

推文