指導教授：楊吉水臺灣大學：化學研究所石育旻Shih, Yu-MinYu-MinShih2014-11-252018-07-102014-11-252018-07-102014http://ntur.lib.ntu.edu.tw//handle/246246/261326　　因為能源危機，以太陽能為替代能源的相關研究成為重要的課題，其中以聚噻吩及其衍生物具有寬的吸收光譜與高的導電能力，在聚合物太陽能電池的應用上具有相當的成果。近年來更發現，二維共軛的導電聚合物在載子移動率、導電能力與能隙等性質上均較一維共軛系統佳。在本研究中，我們將噻吩引入同時有鄰、間及對位二維共軛的異參茚并苯骨架，合成出一系列ITTn單體，並透過化學氧化聚合反應與Stille偶合聚合反應兩種方式將其製備成二維共軛聚合物PITTn與PITTnHT。此外，我們也合成對應的參茚并苯之聚合物PTT2HT，以與異參茚并苯聚合物做比較。 　　結果顯示，由於單體之溶解度與立體效應影響，PITTn與PITTnHT兩系列聚合物在聚合度上有明顯的差異。其中以化學氧化聚合反應所獲得之PITTn的聚合度最低，無法將單體去除，只能獲得單體與寡聚物之混合物。而以Stille偶合聚合反應獲得之PITTnHT系列聚合物，其在聚合度、能隙之表現均較PITTn系列較佳。在太陽能電池元件中，PITTnHT系列最好表現之效率為1.00%，PITTn系列則為1.66%，PITT2HT則為0.98%，PTT2HT則為0.51%。 　　透過PITT2HT與PTT2HT比較可知，在二維共軛聚合物太陽能電池中，一個材料之分子內電荷傳遞能力對太陽能電池之整體表現有重要影響；一個具有好的分子內電荷傳遞能力之材料在太陽能電池中，更可以透過增加分子間電荷傳遞之輔助，再適度提升其在元件之表現。Polythiophene (PTs) is an important class of conducting polymers for polymer solar cells (PSCs) owing to its broad absorption range and high electronic conductivity. Recently, we introduced oligothiophene unit to the ortho-, para-conjugated isotruxene core to form two-dimensional conjugated oligomers and polymers. The ITTn (n=1-4) oligomers that contain an isotruxene core and oligothiophene arms. Then oligomers ITTn were converted to the two-dimensional polymers. Two different polymerization methods have been tested and compared. One method is the direct oxidative polymerization of ITTn using FeCl3 as oxidant to form PITTn. The other method is through Stille coupling reaction for ITTn and 3-hexylthiophene (HT) to form PITTnHT. The results indicate that the degree of polymerization was controlled by the solubility and steric effect. Due to the similar solubility, the monomers can’t be removed from PITTn. PITTnHT have the lower band gap because of the higher degree of polymerization. When applied in PSCs, the PCE of PITTnHT/PCBM (1:2 % wt) is 1.00%, and that of the PITTn series reaches as PCE of 1.66%. The comparison of PITT2HT and PTT2HT indicates that intramolecular charge transportation plays an important factor in determining the performance of PSCs. A material of excellent intramolecular charge transportation can significantly enhance the performance of PSCs.謝誌.................................................................................................................................i 摘要................................................................................................................................ii Abstract........................................................................................................................ iii 目錄...............................................................................................................................iv 圖目錄..........................................................................................................................vii 表目錄........................................................................................................................ xiii 附圖目錄......................................................................................................................xv 第一章 序論................................................................................................................1 1-1 能源危機與替代能源.................................................................................1 1-2 有機太陽能電池(Organic Photovoltaics, OPVs) .....................................3 1-2-1 太陽能電池之專有名詞..................................................................4 1-2-2 有機太陽能電池結構......................................................................7 1-2-3 有機太陽能電池工作機制..............................................................9 1-3 主動層(Active layer) 材料.....................................................................12 1-3-1 電子受體(Acceptor).....................................................................12 1-3-2 電子予體(Donor) .........................................................................15 1-3-3 有機太陽能電池的結構形式........................................................16 1-4 主動層之形態學(Morphology) ..............................................................19 1-4-1 薄膜製備條件................................................................................21 1-4-2電子受體與電子予體.....................................................................22 1-4-3 退火處理(Annealing)...................................................................25 1-5 共軛聚合物(Conjugated Polymers)..........................................................29 1-5-1 一維共軛聚合物............................................................................29 1-5-2 聚噻吩(Polythiophene)與其衍生物............................................31 v 1-5-3 多維共軛聚合物............................................................................35 1-5-4 異參茚并苯(Isotruxene)及其衍生物...........................................38 1-6 研究動機...................................................................................................43 第二章結果與討論..................................................................................................47 2-1 化合物之合成...........................................................................................47 2-1-1 異參茚并苯之合成........................................................................47 2-1-2 合成策略........................................................................................47 2-1-3化合物ITXBr之合成討論.............................................................48 2-1-4 單體(ITTn及ITTnBr，n = 1-4)之合成討論..............................50 2-1-5 聚合物(PITTn及PITTnHT, n=1-4)之合成討論........................52 2-1-6 參茚并苯、TTn (n=1-2)與TTnBr (n=1-2)之合成討論...............55 2-2 單體(ITTn, n=1-4)光物理、電化學性質..............................................57 2-2-1 單體(ITTn, n=1-4)光物理性質....................................................57 2-2-2 單體ITTn (n = 1-4)電化學性質....................................................61 2-3 聚合物(PITTn、PITTnHT及PTT2HT，n = 1-4)分子量分布及光物理、電化學性質........................................................................................................64 2-3-1 聚合物(PITTn及PITTnHT，n = 1-4)分子量分布....................64 2-3-2 聚合物(PITTn、PITTnHT及PTT2HT，n = 1-4)光物理性質.69 2-3-3 聚合物(PITTnHT及PTT2HT，n = 1-4)電化學性質................73 2-4 化合物薄膜之性質...................................................................................77 2-4-1 單體ITTn (n = 1-4)薄膜之性質....................................................77 2-4-1 聚合物PITTnHT (n = 1-4)與PTT2HT薄膜之性質....................79 2-4-3 ITTn (n = 1-4)與PITTnHT (n = 1-4)薄膜之形態學......................81 2-5 有機太陽能電池製備及轉換效率...........................................................83 2-5-1 單體ITTn (n = 1-4)之太陽能電池元件效率................................83 vi 2-5-2 聚合物PITTnHT (n = 1-4)、PTT2HT與PITTn (n = 1-2)之太陽能電池元件效率...........................................................................................84 第三章結論..............................................................................................................87 第四章 實驗部份......................................................................................................88 4-1 實驗藥品...................................................................................................88 4-2 實驗儀器與方法.......................................................................................91 4-2-1 化合物結構的鑑定........................................................................91 4-2-2 溶劑純化系統(SPBT-103 of LC Technology Solutions Inc equipped with SP-505 column) .................................................................93 4-2-3 化合物光物理、電化學性質之量測............................................93 4-2-4 太陽能電池元件製備與測量........................................................96 4-3 實驗步驟...................................................................................................97 4-3-1 異參茚并苯之合成........................................................................97 4-3-2 化合物ITTn與ITTnBr之合成..................................................100 4-3-3 linker之合成.................................................................................105 4-3-4 化合物PITTn 之合成................................................................106 4-3-5 化合物PITTnHT 之合成..........................................................109 4-3-6 參茚并苯之合成..........................................................................111 4-3-7 化合物TTn與TTnBr之合成....................................................113 4-3-8 化合物PTT2HT之合成..............................................................115 參考文獻....................................................................................................................117 附圖............................................................................................................................12720729419 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