博碩士論文 109223063 詳細資訊




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姓名 劉欣宜(Hsin-Yi Liu)  查詢紙本館藏   畢業系所 化學學系
論文名稱 噻吩並吡咯酮二聚體與雙噻吩並吡咯之有機光電材料開發
(Development of Thienoisoindigo (TII) and Dithienopyrrole (DTP) Derivatives of Organic Optoelectronic Applications)
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摘要(中) 本論文研究主要分為有機光伏打電池 (Organic Photovoltaic, OPV) 與有機薄膜電晶體 (Organic Thin Film Transistor, OTFT) 的材料開發。
有機光伏打電池 (OPV) 的部分,本研究成功開發出兩個系列之非富勒烯 (Nonfullerene acceptor, NFA) 材料,第一個系列以噻吩並吡咯酮二聚體 (Thienoisoindigo, TII) 為核心,先接上環戊烷二噻吩 (Cyclopentadithiophene, CDT) 作為 -spacer,再外接四種不同拉電子單元,開發出 IN-CDT-TII (1)、INCl-CDT-TII (2)、INBr-CDT-TII (3)、DCV-CDT-TII (4) 等四個有機分子。第二個系列則是以雙噻吩並吡咯 (Dithienopyrrole, DTP) 為核心,接上 CDT 後,再外接四種不同拉電子單元,製備出 IN-CDT-DTP (5)、INCl-CDT-DTP (6)、INBr-CDT-DTP (7)、DCV-CDT-DTP (8) 等四個材料。經由末端茚酮引入氯、溴等鹵素進行前置軌域能階之調控。此八種新開發之 NFA 材料未來將應用於 OPV,也會測試其作為添加劑應用於鈣鈦礦太陽能電池 (Perovskite solar cell, PSC)。
ii
本研究亦同時以具苯基烷氧鏈之 DTPP 為核心,開發可進行溶液製程之醌型 DTPPQ-16 (9) 與 DCV-DTPP-16 (10) 有機薄膜電晶體材料,目前正進行其作為 n-type OTFT 元件之測試。
這些新材料的電化學及光學性能 (HOMO/LUMO 與 Eg) 已藉由 DPV 及 UV-Vis 測定,材料之熱穩定性已透過 TGA 及 DSC 檢測,這些新開發的有機光電材料正進行其相關之元件測試。
摘要(英) Two series of new small molecules were synthesized and characterized for the applications in organic thin-film transistors (OTFTs), organic photovoltaic cells (OPVs), and perovskite solar cells (PSCs).
N-substituted highly planar thienoisoindigo (TII) and dithienopyrrole (DTP) building blocks were used as central units and coupled with cyclopentadithiophene (CDT) to develop new conjugated cores CDT-TII and CDT-DTP, respectively. Further, these conjugated cores were end-capped with various electron-withdrawing groups, such as dicyanomethylene indanone (IN), dichlorodicyanomethylene indanone (INCl), dibromodicyanomethylene indanone (INBr) and dicyanovinyl (DCV), via Knoevenagel condensation, yielding target compounds, IN-CDT-TII (1), INCl-CDT-TII (2), INBr-CDT-TII (3), DCV-CDT-TII (4), IN-CDT-DTP (5), INCl-CDT-DTP (6), INBr-CDT-DTP (7), and DCV-CDT-DTP (8), respectively. In addition to the application in OPV, these newly developed non-fullerene acceptors could also be used as passivating agents in PSCs based on our recent studies.
For the OTFT materials development, DTPP-based quinoidal DTPPQ-16 (9) and DCV end-capped DCV-DTPP-16 (10) were synthesized for comparative study. The optical and electrochemical properties of these newly developed compounds were characterized by UV-vis spectroscopy and DPV. Chemical structures were characterized by 1H NMR, 13C NMR and mass spectrometry. Thermal properties were investigated by DSC and TGA. At present, optoelectronic devices based on these new organic semiconductors and non-fullerene acceptors are under optimization.
關鍵字(中) ★ 有機光伏打電池
★ 非富勒烯受體
★ 有機薄膜電晶體
★ 有機場效電晶體
★ 有機半導體
關鍵字(英) ★ Organic photovoltaic solar cell
★ Non-fullerene acceptor
★ Organic thin film transistor
★ Organic field effect transistor
★ Organic semiconductor
論文目次 摘 要 I
ABSTRACT III
謝 誌 IV
目錄 V
LIST OF FIGURES XI
LIST OF SCHEMES XIII
LIST OF TABLES XVI
附錄目錄 XVII
第一章 緒論 1
1-1 有機太陽能電池之前言 2
1-2 有機太陽能電池的發展 3
1-2-1 矽晶太陽能電池 6
1-2-2 無機化合物半導體太陽能電池 6
1-2-3 有機太陽能電池 7
1-3 有機光伏打電池之元件結構 8
1-3-1 雙層式異質接面 (Bilayer heterojunction) 9
1-3-2 總體異質接面 (Bulk heterojunction, BHJ) 10
1-3-3 串聯結構 10
1-4 有機光伏打電池之運作原理 11
1-4-1 光激發 (Optical absorption) 12
1-4-2 激子擴散與分離 (Exciton diffusion and dissociation) 12
1-4-3 電荷傳輸 (Charge transfer) 13
1-4-4 電荷收集 (Charge collection) 13
1-5 有機光伏打電池參數介紹 13
1-5-1 J-V 曲線 15
1-5-2 短路電流 (Short circuit current, JSC) 15
1-5-3 開路電壓 (Open circuit voltage, VOC) 16
1-5-4 外部量子效率 (Eternal quantum efficiency, EQE) 16
1-5-5 填充因子 (Fill factor, FF) 17
1-5-6 能量轉換效率 (Power conversion efficiency, PCE) 17
1-6 富勒烯與非富勒烯受體 18
1-6-1非富勒烯稠環電子受體 19
1-7 有機光伏打電池材料 20
1-7-1 P-type 有機光伏打材料 21
1-7-2 N-type 有機光伏打材料 24
1-8 有機薄膜電晶體之前言 29
1-9 有機薄膜電晶體結構 30
1-9-1 基板 (Substrate) 31
1-9-2 絕緣層 (Insulator) 31
1-9-3 有機半導體層 (Organic Semiconductor) 32
1-9-4 閘極 (Gate)、源極 (Source)、汲極 (Drain) 32
1-10 有機薄膜電晶體之元件結構 32
1-11 有機薄膜電晶體之工作原理 33
1-12 有機薄膜電晶體之應用 34
1-13 有機薄膜電晶體傳導機制 36
1-14 有機薄膜電晶體材料排列方式 37
1-14-1 分子結晶度 37
1-14-2 有機半導體分子排列模式 38
1-15 有機薄膜的製備方式 39
1-15-1 氣相沉積 40
1-15-2 液相沉積 41
1-16 有機薄膜電晶體材料 44
1-16-1 P-type 有機薄膜電晶體材料 44
1-16-2 N-type 有機薄膜電晶體材料 47
1-16-3 Ambipolar 有機薄膜電晶體材料 49
1-17 鈣鈦礦太陽能電池簡介 50
1-17-1 基本構造 52
1-17-2 工作原理 54
1-17-3 添加劑 (Additives) 54
1-18 研究動機與目的 58
1-18-1 有機光伏打電池材料 58
1-18-2 有機薄膜電晶體材料 62
第二章 實驗部份 64
2-1 化合物名稱對照表 65
2-2 實驗藥品 68
2-2-1 實驗所用之化學藥品 68
2-2-2 實驗所用之溶劑除水方式 71
2-3 實驗儀器 71
2-3-1 核磁共振光譜儀 (Nuclear Magnetic Resonance, NMR);Bruker AVANCE 300 / 500 MHz 71
2-3-2 高解析質譜儀 (High Resolution Mass Spectrometer, HRMS);ATS-00670, Bruker, New ultrafleXtremeTM, Bremen, D.E. 72
2-3-3 紫外光 / 可見光吸收光譜 (Ultraviolet / Visible Spectro -Photometer);HITACHI U-3900 、U-4100型 72
2-3-4 示差熱掃描卡計 (Differential Scanning Calorimeter, DSC);METTLER TOLEDO DSC 1 / DSC 3 73
2-3-5 電化學裝置 (Electrochemical Analyzer / Work- station);HCH Instrumentent Model 621C 73
2-4 合成步驟 74
2-4-1 2,3-Dibromothiophene (11) 之合成 74
2-4-2 Bis(4-((2-ethylhexyl)oxy)phenyl)methanone (12) 之合成 74
2-4-3 7-(Bromomethyl)pentadecane (13) 之合成 75
2-4-4 2-(3-Oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile (14, IN) 之合成 76
2-4-5 2-(5,6-Dichloro-3-oxo-2,3-dihydro-1H-inden-1- ylidene)malononitrile (15, INCl) 之合成 77
2-4-6 2-(5,6-Dibromo-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (17, INBr) 之合成 78
2-4-7 3-Bromo-2,2′-bithiophene (18) 之合成 80
2-4-8 [2,2′-Bithiophen]-3-ylbis(4-((2-ethylhexyl)oxy)phenyl)methanol (19, CDT-OH) 之合成 81
2-4-9 (4,4-Bis(4-((2-ethylhexyl)oxy)phenyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophen-2-yl)trimethylstannane (21) 之合成 82
2-4-10 Tert-butyl-5,6-dioxo-5,6-dihydro-4H-thieno[3,2-b]pyrrole-4-carboxylate (23, TP-Boc) 之合成 83
2-4-11 (E)-[6,6′-bithieno[3,2-b]pyrrolylidene]-5,5′(4H,4′H)-dione (25, TII-H) 之合成 85
2-4-12 (E)-2,2′-dibromo-4,4′-bis(2-hexyldecyl)-[6,6′-bithieno[3,2-b]pyrrolylidene]-5,5′(4H,4′H)-dione (27) 之合成 87
2-4-13 (E)-2,2′-bis(4,4-bis(4-((2-ethylhexyl)oxy)phenyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophen-2-yl)-4,4′-bis(2-hexyldecyl)-[6,6′-bithieno[3,2-b]pyrrolylidene]-5,5′(4H,4′H)-dione (28, CDT-TII) 之合成 89
2-4-14 (E)-6,6′-(4,4′-bis(2-hexyldecyl)-5,5′-dioxo-4,4′,5,5′-tetrahydro-[6,6′-bithieno[3,2-b]pyrrolylidene]-2,2′-diyl)bis(4,4-bis(4-((2-ethylhexyl)oxy)phenyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2-carbaldehyde) (29) 之合成 90
2-4-15 IN-CDT-TII (1) 之合成 92
2-4-16 INCl-CDT-TII (2) 之合成 93
2-4-17 INBr-CDT-TII (3) 之合成 94
2-4-18 DCV-CDT-TII (4) 之合成 96
2-4-19 3,3′-Dibromo-2,2′-bithiophene (30) 之合成 97
2-4-20 4-((2-hexyldecyl)oxy)aniline (32) 之合成 98
2-4-21 2,6-dibromo-4-(4-((2-hexyldecyl)oxy)phenyl)-4H-dithieno[3,2-b:2′,3′-d]pyrrole (34) 之合成 99
2-4-22 2,6-bis(4,4-bis(4-((2-ethylhexyl)oxy)phenyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophen-2-yl)-4-(4-((2-hexyldecyl)oxy)phenyl)-4H-dithieno[3,2-b:2′,3′-d]pyrrole (35, CDT-DTP) 之合成 101
2-4-23 6,6′-(4-(4-((2-hexyldecyl)oxy)phenyl)-4H-dithieno[3,2-b:2′,3′-d]pyrrole-2,6-diyl)bis(4,4-bis(4-((2-ethylhexyl)oxy)phenyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2-carbaldehyde) (36) 之合成 102
2-4-24 IN-CDT-DTP (5) 之合成 104
2-4-25 INCl-CDT-DTP (6) 之合成 105
2-4-26 INBr-CDT-DTP (7) 之合成 107
2-4-27 DCV-CDT-DTP (8) 之合成 108
2-4-28 DTPPQ-16 (9) 之合成 109
2-4-29 DCV-DTPP-16 (10) 之合成 110
第三章 結果與討論 113
3-1 有機半導體材料之光學性質探討 114
3-1-1 有機光伏打電池電池材料 (OPV) 114
3-1-2 有機薄膜電晶體材料 (OTFT) 117
3-2 有機半導體材料之電化學性質探討 118
3-2-1 有機光伏打電池電池材料 (OPV) 119
3-2-2 有機薄膜電晶體材料 (OTFT) 121
3-3 有機半導體材料之熱穩定性分析 123
3-3-1 有機光伏打電池電池材料 (OPV) 123
3-3-2 有機薄膜電晶體材料 (OTFT) 124
第四章 結論 127
參考資料 130
附 錄 139
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指導教授 陳銘洲(Ming-Chou Chen) 審核日期 2022-7-28
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