臺灣博碩士論文加值系統

本研究中以咔唑并噻吩熔合之七環分子 (dithienocyclopentacarbazole, DTC) 為主體，並在末端修飾上含有腈基之缺電子基團2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile (IC)，設計出新的受體材料，另外在不同末端及側鏈上做不同的修飾，合成出四個新的非富勒烯受體。本研究第一部份討論不同側鏈的影響，設計並合成出首兩個非富勒烯受體：側鏈為烷苯基之 DTC(4Ph)-IC 及側鏈為烷基之 DTC(4R)-IC，第二部份則是在末端 IC 上接上氟原子，設計並合成出另外兩個非富勒烯受體：DTC(4Ph)-4FIC 及 DTC(4R)-4FIC。
我們分別鑑定及分析了四個材料之熱性質、光學性質及電化學性質，同時也利用理論計算來模擬出分子之最佳構型。四個非富勒烯受體皆擁有良好的熱穩定性，DTC(4Ph)-IC 為非晶性，DTC(4Ph)-4FIC、DTC(4R)-IC及DTC(4R)-4FIC則有較明顯的結晶性，在光學性質上，這些非富勒烯受體皆在 500-800 nm 有吸收帶且擁有高消光係數，另外藉由修飾上末端的 IC 基團來降低其 LUMO 能階，使其從予體性質轉換為受體性質。最後將此四個新的非富勒烯受體搭配適合的予體 J71 並做太陽能電池元件測試，得到最高的光電轉換效率 10.89%、開路電壓 0.82 V、短路電流 18.92 mA cm-2、填充因子 70.22%。

In this study, a heptacyclic carbazoled-based dithienocyclopentacarbazole (DTC) structure was formylated to couple with two 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile (IC) moieties, forming a series of new non-fullerene acceptors. Four new non-fullerene acceptors (NFAs) were synthesized by utilizing different functional groups on either end groups or side chains. The side-chain engineering was used to design the first two NFAs, DTC(4Ph)-IC and DTC(4R)-IC which contain four alkylphenyl side chains and four alkyl side chains on the DTC unit respectively. The fluorination approach was used to design the other two NFAs, DTC(4Ph)-4FIC and DTC(4R)-4FIC which contain four fluorine atoms on the IC units.
The thermal, optical and electrochemical properties of four NFAs were characterized respectively. We also used DFT calculations to calculate the optimized geometries of molecular structure. These four NFAs are all thermally stable. Notably, DTC(4Ph)-IC shows amorphous character while DTC(4Ph)-4FIC, DTC(4R)-IC and DTC(4R)-4FIC have higher crystallinity. For optical properties, all NFAs exhibit broad absorption in the range from 500 to 800 nm with high extinction coefficients. Moreover, IC units can downshift the LUMO levels, which gives sutible energy levels to be acceptors. Furthermore, devices based on these acceptors were fabricated by employing narrow-bandgap polymer J71 as the donor because of its compatible energy alignments and complimentary absorption. Overall, the device gave the best performance of 10.89% with a Voc of 0.82 V, a Jsc of 18.92 mA cm-2, and an FF of 70.22%.

摘要 I
Abstract III
謝誌 V
目錄 VI
合成目錄 IX
圖目錄 X
表目錄 XII
附圖目錄 XIII
第一章 緒論 1
1.1 前言 1
1.2 太陽能電池介紹與現況 1
1.3 有機薄膜太陽能電池工作原理 3
1.4 有機薄膜太陽能電池參數 5
1.5 元件演進 8
1.5.1 主動層形態演進 9
1.5.2 元件結構演進 12
1.6 有機薄膜太陽能電池主動層介紹 14
1.7 非富勒烯材料發展 19
1.8 研究動機 26
第二章 實驗部分 28
2.1 試藥 28
2.2 量測儀器 28
2.2.1 核磁共振光譜儀 (Nuclear Magnetic Resonance，NMR) 28
2.2.2 熱重分析儀 (Thermal Gravimetric Analyzer，TGA) 28
2.2.3 微差掃描卡計 (Differential Scanning Calorimeter，DSC) 29
2.2.4 紫外線與可見光光譜儀 (UV-Vis Spectrophotometer) 29
2.2.5 循環伏安計量儀 (Cyclic Voltammetry，CV) 30
2.2.6 臨界入射廣角X射線散射儀 (Grazing Incidence Wide-Angle X-ray Scattering，GIWAXS) 30
2.3 有機薄膜太陽能電池元件製程 31
2.4 合成部份 32
第三章 結果與討論 41
3.1 DTC 系列分子之合成與鑑定 41
3.1.1 熱性質分析 42
3.1.2 光學性質分析 45
3.1.3 電化學分析 48
3.1.4 理論計算 50
3.1.5 元件表現 53
3.1.6 Grazing Incidence Wide-Angle X-ray Scattering 57
第四章 結論 60
第五章 參考文獻 62
第六章 附圖 68

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