新型噻吩環戊烷有機染料於染料敏化太陽能電池之應用

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姓名

鍾旻峯(Min-Fong Jhong) 查詢紙本館藏

畢業系所

化學學系

論文名稱

新型噻吩環戊烷有機染料於染料敏化太陽能電池之應用
(Novel Organic Dyes Incorporating Low-Band-Gap CPDT Unit for Dye-Sensitized Solar Cells)

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★ 含雙噻吩環戊烷之電變色高分子的研究	★ 含噻吩衍生物非對稱方酸染料應用於染料敏化太陽能電池
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★ 合成新穎輔助配位基於無硫氰酸釕金屬光敏劑在染料敏化太陽能電池上的應用	★ Design and Synthesis of Ruthenium Dyes for High Open-circuit Voltage Dye-sensitized Solar Cells

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摘要(中)

染料敏化太陽能電池 (DSCs)中的染料為有機分子時，相較於一般Grätzel太陽能電池常用之金屬錯合物染料，有著高吸收係數及無需使用貴重金屬元素的好處。本研究以雙噻吩環戊烷 (CPDT，cyclopentadithiophene)出發，將CPDT單體策略性接上酯基，再利用Stille coupling或氧化聚合的方式分別合成共聚物F-P1 ester、F-P2 ester及高分子F-P3 ester，隨後將酯基酸化成羧酸以便和二氧化鈦奈米粒子行自組裝作用。此外我們也會將CPDT衍生物策略性的引入有機小分子染料的結構中，將CPDT作為染料電子acceptor與作電子donor之Triphenylamine coupling合成出F-O3，同時使用其他較高能隙結構的Fluorene及Bithiophene取代CPDT，合成出染料F-O1及F-O2，並探討不同結構之染料組成元件後的效能差異，以做為設計DSCs之新結構有機光敏化染料的參考。

摘要(英)

Organic dye, compared to the Ruthenium-based photo-sensitizer in the Grätzel cell, has the advantages of high absorbance coefficient and without using expensive metal. We synthesize a series of polymer and organic dyes containing a low band gap moiety CPDT. The polymer dyes F-P1、F-P2 and F-P3 were prepared by Stille coupling or oxidative polymerization and identified with 1H-NMR. CPDT was also used as acceptor in the preparation of the “donor-acceptor” typed metal free dyes, such as F-O3. Furthermore, other conjugated moieties such as fluorene and bithiophene were also used instead of CPDT to synthesize small molecule F-O1 and F-O2 dyes for comparison. The polymers and small molecular organic dyes were used to assemble the DSC cells and the performance of the cells was measured. The properties related cell performance was interpreted. The strategy for high efficiency organic dye was also proposed.

關鍵字(中)

★ 有機小分子染料光敏化劑
★ 有機高分子染料光敏化劑
★ 染料敏化太陽能電池

關鍵字(英)

★ aggregation
★ dihedral angle
★ recombination
★ froniter orbitals
★ parent peak
★ polymer dyes
★ metal-free organic dyes
★ metal to ligand charge transfer

論文目次

目錄
中文摘要....................................................................................................i英文摘要..................................................................................................ii
謝誌………………………………………………………………..…..iii
目錄………………………………………………………………..……iv
圖目錄………………………………………………………...…...……ix
表目錄……………………………………………………………...….xii
附錄………………………………………………………………..…xiii
壹、緒論...................................................................................................1
1-1、前言..................................................................................................1
1-2、染料敏化太陽能電池......................................................................4
1-3、釕金屬錯合物染料光敏化劑..........................................................6
1-4、染料敏化太陽能電池的結構........................................................10
1-5、有機小分子染料光敏化劑............................................................13
1-6、有機高分子染料光敏化劑............................................................21
1-7、研究動機........................................................................................24
貳、實驗部分..........................................................................................26
2-1、實驗藥品.........................................................................................26
2-2、實驗流程圖.....................................................................................32
2-2-1、CPDT單體之合成路徑.................................................................32
2-2-2、共聚物F-P1和F-P2之合成路徑..................................................33
2-2-3、高分子F-P3之合成路徑...............................................................34
2-2-4、有機小分子F-O1、F-O2和F-O3之合成路徑..............................35
2-3、中間產物（單體）之結構、IUPAC全名與簡稱................................36
2-4、合成步驟..........................................................................................41
2-4-1、Di-thiophen-3-yl-methanol之合成............................................41
2-4-2、Di-thiophen-3-yl-methanone之合成.........................................42
2-4-3、2,2-Di-thiophen-3-yl-[1,3]dioxolane之合成.............................43
2-4-4、2,2-Bis-(2-iodo-thiophen-3-yl)-[1,3]dioxolane之合成..............44
2-4-5、Cyclopenta[2,1-b;3,4-b´]dithiophen-4-dioxolane之合成.........45
2-4-6、Cyclopenta[2,1-b;3,4-b']dithiophen-4-one之合成....................45
2-4-7、Cyclopenta[2,1-b;3,4-b´]dithiophene-4-(biscarboxy methyl) methylidene之合成....................................................................46
2-4-8、2-(2,6-Dibromo-cyclopenta[2,1-b;3,4-b']dithiophen-4-
ylidene)malonic acid dimethyl ester之合成............................47
2-4-9、4H-Cyclopenta[2,1-b;3,4-b´]dithiophene之合成......................48
2-4-10、4,4-Dioctyl-4H-cyclopenta[2,1-b;3,4-b']dithiophene之合成
...................................................................................................49
2-4-11、4,4-Dioctyl-2,6-bis-trimethylstannanyl-4H-cyclopenta[2,1-
b;3, 4-b']dithiophene之合成..................................................50
2-4-12、Copolymer F-P1 ester之合成...................................................50
2-4-13、Copolymer F-P1之合成...........................................................51
2-4-14、4,4-Dimethyl-4H-cyclopenta[2,1-b;3,4-b']dithiophene之合成
...................................................................................................52
2-4-15、4,4-Dimethyl-2,6-bis-trimethylstannanyl-4H-cyclopenta [2,1-b; 3,4-b']dithiophene之合成.........................................................53
2-4-16、Copolymer F-P2 ester之合成...................................................54
2-4-17、Copolymer F-P2之合成...........................................................55
2-4-18、(4-Methoxycarbonylmethyl-4H-cyclopenta[2,1-b;3,4-b'] dithiophen-4-yl)-acetic acid methyl ester之合成.................56
2-4-19、Polymer F-P3 ester之合成.......................................................57
2-4-20、Polymer F-P3之合成................................................................57
2-4-21、9,9-Dimethyl-9H-fluorene之合成.............................................58
2-4-22、2,7-Dibromo-9,9-dimethyl-9H-fluorene之合成.....................59
2-4-23、7-Bromo-9,9-dimethyl-9H-fluorene-2-carbaldehyde之合成
...................................................................................................60
2-4-24、(2,3-Dihydro-thieno[3,4-b][1,4]dioxin-5-yl)-trimethyl-sta- nnane之合成............................................................................61
2-4-25、[4-(2,3-Dihydro-thieno[3,4-b][1,4]dioxin-5-yl)-phenyl] diphen- ylamine之合成.........................................................................62
2-4-26、Diphenyl-[4-(7-trimethylstannanyl-2,3-dihydro-thieno- [3,4-b][1,4]dioxin-5-yl)-phenyl]-amine之合成......................63
2-4-27、7-[7-(4-Diphenylamino-phenyl)-2,3-dihydro-thieno[3,4-b]
[1,4]dioxin-5-yl]-9,9-dimethyl-9H-fluorene-2-carbaldehyde之合成.......................................................................................63
2-4-28、2-Cyano-3-{7-[7-(4-diphenylamino-phenyl)-2,3-dihydrothie- no[3,4-b][1,4]dioxin-5-yl]-9,9-dimethyl-9H-fluoren-2-yl}-acrylic acid之合成........................................................................64
2-4-29、[2,2']Bithiophenyl-5-carbaldehyde之合成.............................65
2-4-30、5'-Bromo-[2,2']bithiophenyl-5-carbaldehyde之合成............66
2-4-31、5'-[7-(4-Diphenylamino-phenyl)-2,3-dihydro-thieno[3,4-b]-
[1,4]dioxin-5-yl]-[2,2']bithiophenyl-5-carbaldehyde之合成
...................................................................................................67
2-4-32、2-Cyano-3-{5'-[7-(4-diphenylamino-phenyl)-2,3-dihydro-
thie-no[3,4-b][1,4]dioxin-5-yl]-[2,2']bithiophenyl-5-yl}-acrylic acid之合成............................................................................68
2-4-33、4,4-Dioctyl-4H-cyclopenta[2,1-b;3,4-b']dithiophene-2- carbaldehyde之合成................................................................69
2-4-34、6-Bromo-4,4-dioctyl-4H-cyclopenta[2,1-b;3,4-b']-
dithiophene-2-carbaldehyde之合成......................................70
2-4-35、6-[7-(4-Diphenylamino-phenyl)-2,3-dihydro-thieno
[3,4-b]-[1,4]dioxin-5-yl]-4,4-dioctyl-4H-cyclopenta[2,1-b;3,4-b']di- thiophene-2-carbaldehyde之合成...............................71
2-4-36、2-Cyano-3-{6-[7-(4-diphenylamino-phenyl)-2,3-
dihydrothieno[3,4-b][1,4]dioxin-5-yl]-4,4-dioctyl-4H-cyclopenta[2,1-b;3,4-b']dithiophen-2-yl}-acrylic acid之合成..........72
2-5、儀器分析及樣品製備.....................................................................73
2-5-1、Infrared Absorption Spectroscopy............................................73
2-5-2、Ultraviolet/Visible and Near-Infrared Absorption Spectros- copy.............................................................................................74
2-5-3、Solution state Nuclear Magnetic Resonance Spectrometer....75
2-5-4、Gel Permeation Chromatography.............................................76
2-5-5、Thermogravimetric Analyzer.....................................................77
2-5-6、Electrochemical Measurement..................................................78
參、結果與討論.......................................................................................79
3-1、合成中間產物及目標產物遭遇之困難...........................................79
3-1-1、CPDT之合成困難.......................................................................79
3-1-2、Copolymer之合成困難...............................................................79
3-2、染料單體與高分子之性質..............................................................80
3-2-1、高分子之IR吸收光譜鑑定..........................................................80
3-2-2、高分子之UV/Vis吸收光譜鑑定..................................................82
3-3、高分子之性質與元件效能探討......................................................86
3-3-1、高分子之UV吸收光譜性質探討.................................................86
3-4、有機小分子染料之性質..................................................................94
3-4-1、有機小分子之IR吸收光譜鑑定..................................................94
3-4-2、有機小分子之MASS質譜鑑定....................................................95
3-4-3、有機小分子之元素分析鑑定.......................................................96
3-4-4、有機小分子之熱穩定測試..........................................................97
3-5、有機小分子之性質與元件效能探討...............................................98
3-5-1、有機小分子之UV吸收光譜性質探討..........................................98
3-5-2、有機小分子之CV測試..................................................................99
3-5-3、有機小分子染料之DSC元件的性能探討.................................101
3-5-4、理論計算有機小分子之構型(conformation)及前置軌域(frontier orbitals)...................................................................103
3-5-5、吸附上染料之TiO2電極之穿透式UV/Vis吸收光譜測試........106
肆、結論.................................................................................................107
伍、參考文獻........................................................................................108
陸、附錄................................................................................................112

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指導教授

吳春桂(Chun-Guey Wu)

審核日期

2007-7-18

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