臺灣博碩士論文加值系統

有機光敏化劑相較於一般Grätzel太陽能電池常用之釕金屬錯合物染料，有著無使用貴重金屬與高吸收係數之優點，並可經由多種有機結構的調變以增加光敏化劑的效能。一般有機小分子光敏化劑在設計上是在染料分子的一端接上具有推電子能力的取代基(如：含N、O的官能基)做為Donor，而在另一端接上具拉電子能力的取代基(如CN加上敏化劑所需具備的羧酸根)，稱之為Acceptor，在Donor與Acceptor中間置入可以傳遞電子的共軛結構(稱之為Spacer)，形成Donor-Spacer-Acceptor的結構。本研究是以具推電子能力的N-aryl Carbazole及Triphenylamine做為Donor，以雙噻吩環戊烷Cyclopentadithiophene (CPDT)做為Spacer，並在Donor與Spacer間分別引入了thiophene、bithiophene與octylthiophene來增加染料的共軛長度，所得光敏劑並組裝成染料敏化太陽能電池以測試光敏劑之結構與效能的關係，結果顯示以N-aryl Carbazole為Donor，bithiophene-CPDT 為Spacer之染料有最大的光電轉換效率 (1.78 %)，而影響有機染料之效能的因素很多，如吸收位置、HOMO與LUMO分佈的位置及分子中共軛片段的夾角，但與染料分子的吸收係數似乎沒有很大的關係。

The advantages of metal free sensitizers, compared to the Ru-based sensitizer in the Grätzel cell, are the high absorption coefficient and without using expensive metal. Furthermore, the structure of organic sensitizers can be widely modified to enhance the performance for solar cells. In general, the organic sensitizer contains a Donor group (such as Carbazole or Triphenylamine), a Spacer and Acceptor group (CN with COOH) to form so called Donor-Spacer-Acceptor type dyes. We synthesize a series organic dyes containing N-arylcarbazole or Triphenylamine as donor group and cyano arylic acid as a Acceptor, a low band gap CPDT moiety with thiophene, bithiophene, or octylthiophene, respectively as a Spacer. Dye-sensitize Solar Cells (DSCs) based on these dyes were fabricated and their performance was test to reveal the relationship between the structure of the dye and the performance of the DSC based on it. It was found that dye using N-aryl Carbazole as a Donor and CPDT-bithiophene as a Spacer has the highest conversion efficiency of 1.78%. Several parameters will affect the performance of dye for solar cell, such as ?max, distribution of HOMO and LUMO, and molecular dihedral angle. Nevertheless, it seems that the absorption coefficient of the dye did not have a significant effect on the conversion efficiency of the DSC based on it。

中文摘要....................................................................................................i英文摘要..................................................................................................ii
謝誌………………………………………………………………..…..iii
目錄………………………………………………………………..……iv
圖目錄………………………………………………………...……...…..x
表目錄…………………………………………………………..…......xii
附錄一…………………………………………………………..……xiii
附錄二…………………………………………………………..…........xv

壹、緒論...................................................................................................1
1-1、太陽能電池簡介..............................................................................1
1-2、太陽能電池的材料種類..................................................................3
1-3、染料敏化太陽能電池………..........................................................4
1-4、有機小分子染料光敏化劑…..........................................................6
1-5、研究動機........................................................................................15

貳、實驗部分..........................................................................................17
2-1、實驗藥品.........................................................................................17
2-2、實驗流程圖.....................................................................................21
2-2-1、Br-DMCPDT-al之合成路徑……...............................................21
2-2-2、染料分子W-1之合成路徑...........................................................22
2-2-3、染料分子W-2之合成路徑............................................................23
2-2-4、染料分子W-3之合成路徑...........................................................24
2-2-5、染料分子W-4之合成路徑............................................................25
2-2-6、染料分子W-5之合成路徑............................................................26
2-2-7、染料分子W-6之合成路徑.........................................................27
2-3、中間產物（單體）之結構、IUPAC全名與簡稱................................28
2-4、合成步驟..........................................................................................37
2-4-1、Di-thiophen-3-yl-methanol之合成.............................................37
2-4-2、Di-thiophen-3-yl-methanone之合成..........................................38
2-4-3、2,2-Di-thiophen-3-yl-[1,3]dioxolane之合成..............................38
2-4-4、2,2-Bis-(2-iodo-thiophen-3-yl)-[1,3]dioxolane之合成...............40
2-4-5、Cyclopenta[2,1-b;3,4-b´]dithiophen-4-dioxolane之合成......... 40
2-4-6、Cyclopenta[2,1-b;3,4-b'']dithiophen-4-one之合成.....................41
2-4-7、4H-Cyclopenta[2,1-b;3,4-b´]dithiophene之合成....................41
2-4-8、4,4-Dimethyl-4H-Cyclopenta[2,1-b;3,4-b´]dithiophene之合成.................................................................................................42
2-4-9、4,4-Dimethyl-4H-cyclopenta[2,1-b;3,4-b'']dithiophene-2- carbaldehyde之合成.................................................................43
2-4-10、6-Bromo-4,4-dioctyl-4H-cyclopenta[2,1-b;3,4-b'']
dithiophene-2-carbaldehyde(簡稱Br-DMCPDT-aldehyde)之合成..............................................................................................44
2-4-11、3,6-Di-tert-butyl-9H-carbazole(簡稱Ditertbutylcarbazole)之合成..............................................................................................45
2-4-12、3,6-di-tert-butyl-9-(thiophen-2-yl)-9H-Carbazole(簡稱TH-Ditertbutylcarbazole)之合成.............................................46
2-4-13、 3,6-di-tert-butyl-9-[5( trimethylstannanyl)thiophen-2-yl]-9H
-Carbazole(簡稱TMSn-TH-Ditertbutylcarbazole)之合成……........................................................................................47
2-4-14、3,6-di-tert-butyl-9-9H-carbazole-2-thiophen-4,4-dimethyl-2H- cyclopenta[2,1-b;3,4-b'']di-thiophene-2-carboxaldehyde (簡稱W-1-aldehyde)之合成...............................................................48
2-4-15、3,6-di-tert-butyl-9-9H-carbazole-2-thiophen-4,4-dimethyl-2H- cyclopenta[2,1-b;3,4-b'']di-thiophene -2-acrylicacid (簡稱W-1)之合成..............................................................................49
2-4-16、3,6-di-tert-butyl-9-[5-(thiophen-2-yl)thiophen-2-yl]-9H-
Carbazole(簡稱Ditertbutylcarbazole-DTH)之合成..................................................................................................50
2-4-17、3,6-di-tert-butyl-9-｛5-[5-(trimethylstannyl)thiophen-2-yl]thiophen- 2-yl｝-9H-Carbazole(簡稱TMSn-DTH-Ditertbutylcarbazole)之合成................................................................................................51
2-4-18、3,6-di-tert-butyl-9-[5-(thiophen-2-yl)thiophen-2-yl]-9H-
Carbazole-4,4-dimethyl-2H-cyclopenta[2,1-b;3,4-b'']di-thiophene-2-carbox-aldehyde (簡稱W-2-aldehyde)之合成............52
2-4-19、3,6-di-tert-butyl-9-[5-(thiophen-2-yl)thiophen-2-yl]-9H-
Carbazole-4,4-dimethyl-2H-cyclopenta[2,1-b;3,4-b'']di-thiophene-2-acrylicacid(簡稱W-2)之合成.........................................53
2-4-20、3-Octylthiophene(簡稱OTH)之合成.....................................54
2-4-21、2-Bromo-3-Octylthiophene(簡稱Br-OTH)之合成...............55
2-4-22、3,6-di-tert-butyl-9-(3-octylthiophen-2-yl)-9H-Carbazole(簡稱OTH-Ditertbutylcarbazole)之合成........................................56
2-4-23、3,6-di-tert-butyl-9-(5-(trimethylstannyl)-3-octylthiophen
-2-yl)-9H-Carbazole(簡稱TMSn-OTH-Ditertbutylcarbazole)之合成.......................................................................................57
2-4-24、3,6-di-tert-butyl-9-(3-octylthiophen-2-yl)-9H-Carbazole-4,4-
dimethyl-2H-cyclopenta[2,1-b;3,4-b'']di-thiophene-2-carboxaldehyde (簡稱W-3-aldehyde)之合成........................................58
2-4-25、3,6-di-tert-butyl-9-(3-octylthiophen-2-yl)-9H-Carbazole-4,4-
dimethyl-2H-cyclopenta[2,1-b;3,4-b'']di-thiophene-2-acrylicacid (簡稱W-3)之合成..............................................................59
2-4-26、N,N-diphenyl-4-(trimethylstannyl)benzenamine (簡稱TMSn-
TPA)之合成………………………………...............................60
2-4-27、N,N-diphenyl-4-(2-thienyl)benzenamine (簡稱TH-TPA)之合成……………………………………………………...............61
2-4-28、N,N-diphenyl-4-[ 5-(trimethylstannanyl)-2-thienyl]
benzenamine (簡稱TMSn-TH-TPA)之合成..........................62
2-4-29、5-[ 4-(diphenylamino)phenyl]-2-thiophen-4,4-dimethyl-2H-
cyclo- penta[2,1-b;3,4-b'']di-thiophene-2-carboxaldehyde (簡稱W-4-aldehyde)之合成...........................................................63
2-4-30、2-Cyano-{5-[ 4-(diphenylamino)phenyl]-2-thienyl]-4,4-
dimethyl-2H- cyclopenta[2,1-b;3,4-b'']di- thiophene-2-acrylicacid (簡稱W-4)之合成............................64
2-5、儀器分析及樣品製備.....................................................................66
2-5-1、Infrared Absorption Spectroscopy...........................................66
2-5-2、Ultraviolet/Visible and Near-Infrared Absorption Spectros- copy.............................................................................................66
2-5-3、Solution state Nuclear Magnetic Resonance Spectrometer…..67
2-5-4、Thermogravimetric Analyzer....................................................68
2-5-5、Electrochemical Measurement..................................................68
2-5-6、染料敏化太陽能電池元件的製作與效率測試………………...69

參、結果與討論.......................................................................................71
3-1、有機染料的合成………………………..........................................71
3-1-1、CPDT之合成................................................................................71
3-1-2、DMCPDT-aldehyde之合成.........................................................71
3-1-3、W-5、W-6之合成........................................................................71
3-2、有機染料之結構鑑定......................................................................74
3-2-1、有機染料之IR吸收光譜..............................................................74
3-2-2、有機染料之MASS質譜鑑定.......................................................75
3-2-3、有機染料之元素分析鑑定..........................................................78
3-3、有機染料之性質與元件效能探討..................................................79
3-3-1、有機染料之UV吸收光譜.............................................................79
3-3-2、有機染料之CV測試.....................................................................81
3-3-3、有機染料之熱穩定測試..............................................................85
3-3-4、有機染料之構型(conformation)及前置軌域(frontier orbitals)的理論計算..................................................................................86
3-3-5、由有機染料所組裝之DSC元件的性能......................................90
肆. 結論...................................................................................................94

伍. 參考文獻...........................................................................................95

附錄一、1H-NMR光譜…………………………………………………98

附錄二、13C-NMR光譜………………………………………………112



圖目錄
圖1-3-1: 染料敏化太陽能電池之光電轉換機制示意圖………............5
圖1-4-1: PPDCA染料結構式...................................................................7圖1-4-2: P5染料結構................................................................................7圖1-4-3: BIDC4染料結構式....................................................................7圖1-4-4: NKX-2311染料結構式..............................................................8
圖1-4-5: NKX-2677染料結構..................................................................8
圖1-4-6: NKX-2753染料結構式..............................................................9
圖1-4-7: NKX-2883染料結構..................................................................9
圖1-4-8: D102染料結構.........................................................................10
圖1-4-9: D149染料結構.........................................................................10
圖1-4-10: D205染料結構式...................................................................10
圖1-4-11: MK-2染料結構式..................................................................11
圖1-4-12: JK-2染料結構........................................................................12
圖1-4-13: TPAR4染料結構式.................................................................12
圖1-4-14: TA-ST-CA染料結構...............................................................13
圖1-4-15: JK-25染料結構.......................................................................13
圖1-4-16: dyeⅠ染料結構.......................................................................14
圖1-4-17: dyeⅡ染料結構式..................................................................14
圖1-4-18: S4染料結構...........................................................................15
圖2-5-5-1: 電化學測量裝置圖...............................................................69
圖3-1-3-1: W-5、W-6染料之IR吸收光譜..........................................72
圖3-1-3-2: W-5染料之NMR圖譜...............................................................73
圖3-1-3-3: W-6染料之NMR圖譜...........................................................73
圖3-2-1-1: W-1、W-2之IR吸收光譜……………………………….…74
圖3-2-1-2: W-3、W-4之IR吸收光譜……………………………...…..75
圖3-2-2-1: 染料分子W-1之質譜圖………………………….……….76
圖3-2-2-2: 染料分子W-2之質譜圖………………………….…….....76
圖3-2-2-3: 染料分子W-3之質譜圖......................................................77
圖3-2-2-4: 染料分子W-4之質譜圖譜....................................................77
圖3-3-1-1：W-1~W-4染料分子溶於THF之UV/Vis吸收光譜數據..........................................................................................81
圖3-3-2-1：染料分子W-1之CV圖譜.....................................................82
圖3-3-2-2：染料分子W-2之CV圖譜.....................................................82
圖3-3-2-3：染料分子W-3之CV圖譜.....................................................83
圖3-3-2-4：染料分子W-4之CV圖譜.....................................................83
圖3-3-2-6： TiO2與W-系列染料之能帶結構........................................84
圖3-3-3-1：W-系列染料之TGA圖………………..................................86
圖3-3-4-1：計算所得之W-1、W-2、W-3及W-4分子最穩定構型
............................................................................................87
圖3-3-4-3: W-1、W-2、W-3及W-4的Frontier Orbitals 分佈................89

表目錄
表2-1: 本研究所使用之藥品的純度與出處.........................................17
表2-3: 中間產物、目標產物之結構、全名、簡稱與分子量..................28
表3-2-3-1: W-Series Dyes之元素分析數據..........................................78
表3-3-1-2： W-系列染料分子溶於THF之吸收光譜數據...................81
表3-3-2-5: W-系列染料分子之氧化還原電位 (V vs Ag/Ag+).............84
表3-3-2-6： W-系列染料分子之HOMO及LUMO的位置與能隙大小........................................................................................85
表3-3-3-2：W-系列染料分子之5%重量損失溫度及最後殘餘物之重量........................................................................................86
表3-3-4-2：染料分子W-1~W-4之dihedral angle...................................88
表3-3-5-1: W-系列染料所組裝成DSC元件之效能............................91



附錄一
附圖一: 1H NMR spectrum of DTOH in CDCl3..................................98
附圖二: 1H NMR spectrum of DTketone in CDCl3...……………..…98
附圖三: 1H NMR spectrum of Dioxolane in CDCl3……….…..…..…99
附圖四: 1H NMR spectrum of DI-Dioxolane in CDCl3……..….....…99
附圖五: 1H NMR spectrum of CDT in CDCl3………………………100
附圖六: 1H NMR spectrum of CPDT in CDCl3………......................100
附圖七: 1H NMR spectrum of DMCPDT in CDCl3………………...101
附圖八: 1H NMR spectrum of DMCPDT-aldehyde in CDCl3…......101
附圖九: 1H NMR spectrum of Br-DMCPDT-aldehyde in CDCl3….102
附圖十: 1H NMR spectrum of Ditertbutylcarbazole in CDCl3….....102
附圖十一: 1H NMR spectrum of TH- Ditertbutylcarbazole in CDCl3……………………………………………………...103
附圖十二: 1H NMR spectrum of TMSn- TH- Ditertbutylcarbazole in CDCl3………...…………………………………..........103
附圖十三: 1H NMR spectrum of W-1-aldehyde in CDCl3…............104
附圖十四: 1H NMR spectrum of W-1 in DMSO-d6……...................104
附圖十五: 1H NMR spectrum of DTH- Ditertbutylcarbazole in CDCl3
……………………………………………………….…..…105
附圖十六: 1H NMR spectrum of TMSn- DTH- Ditertbutylcarbazole in CDCl3...............................................................................105
附圖十七: 1H NMR spectrum of W-2-aldehyde in CDCl3....................................................................................106
附圖十八: 1H NMR spectrum of W-2 in DMSO-d6...........................106
附圖十九: 1H NMR spectrum of Br-OTH in CDCl3..........................107
附圖二十: 1H NMR spectrum of OTH-Ditertbutylcarbazole in CDCl3...............................................................................107
附圖二十一: 1H NMR spectrum of TMSn-OTH-Ditertbutylcarbazole in CDCl3..........................................................................108
附圖二十二: 1H NMR spectrum of W-3-aldehyde in CDCl3...............................................................................108
附圖二十三: 1H NMR spectrum of W-3 in DMSO-d6.......................109
附圖二十四: 1H NMR spectrum of TMSn-TPA in CDCl3
……………………………………………………..……109
附圖二十五: 1H NMR spectrum of TH-TPA in CDCl3......................110
附圖二十六：1H NMR spectrum of TMSn-TH-TPA in CDCl3.........110
附圖二十七: 1H NMR spectrum of W-4-aldehyde in CDCl3.............111
附圖二十八: 1H NMR spectrum of W-4 in DMSO-d6………….…...111







附錄二
附圖二十九: 13C NMR spectrum of W-1 in DMSO-d6………….…..112
附圖三十: 13C NMR spectrum of W-2 in DMSO-d6…………….…..112
附圖三十一: 13C NMR spectrum of W-3 in CDCl3……..…………..113
附圖三十二: 13C NMR spectrum of W-4 in DMSO-d6………….…..113

1、http://www.cws.net.cn/Journal/Three_Gorges/200505/05.htm
2、E. Becquerel, "Mčmoire sur les effets électriques produits sous l''influence des rayons solaires", C. R. Acad. Sci. Paris, 1839, 9, 561.
3、“The History of PV” http://www.pvpower.com/pvhistory.html.
4、“The History of solar energy, http://www.californiasolarcenter.org/ history_pv.html.
5、http://documents.scribd.com/docs/1y6p4vvny7ftzzh1l5jo.txt
6、http://www.nsc.gov.tw/_newfiles/popular_science.asp?add_year=2005 & popsc_aid=68
7、http://www.e-tonsolar.com/edu.htm
8、B. O’Regan, M. Grätzel, Nature, 1991, 353, 737.
9、M. Grätzel, Nature, 2001, 414, 338.
10、http://www.materialsnet.com.tw/ePaperNewest.aspx?id=259
11、S. Ferrere, A. Zaban, B. A. Gregg, J. Phys. Chem. B 1997, 101, 4490.
12、S. Ferrere, B. A. Gregg, New J. Chem. 2002, 26, 1155.
13、Z.-S. Wang, F.-Y. Li, C.-H. Huang, Chem. Commun. 2000, 2063.
14、E. Stathatos, P. Lianos, Chem. Mater. 2001, 13, 3888.
15、Q.-H. Yao, F.-S. Meng, F.-Y. Li, H. Tian, C.-H. Huang, J. Mater. Chem. 2003, 13, 1048.
16、K. Hara, M. Kurashige, Y. Dan-oh, C. Kasada, A. Shinpo, S.Suga, K. Sayama, H. Arakcwa, New J. Chem. 2003, 27, 783.
17、Z.-S. Wang, K. Hara, Y. Dan-oh, C. Kasada, A. Shinpo, S. Suga, H.Arakawa, H. Sngihura, J. Phys. Chem. B 2005, 109, 3907.
18、Z.-S. Wang, Y. Cui, K. Hara, Y. Dan-oh, C. Kasada, A. Shinpo, Adv. Mater. 2007, 19, 1138.
19、T. Horiuchi, H. Miura S. Uchida, Chem. Commun. 2003, 3036.
20、T. Horiuchi, H. Miura, K. Sumioka, S. Uchida, J. Am. Chem. Soc. 2004, 126, 12218.
21、N. Koumura, Z.-S. Wang, S. Mori, M. Miyashita, E. Suzuki, K. Hara, J. Am. Chem. Soc. 2006, 128, 14256.
22、S. Kim, J. K. Lee, S. O. Kang, J. Ko, J.-H. Yum, S. Fantacci, F.De Angelis, D. Di Censo, Md. K. Nazeeruddin, M. Gratzel, J. Am. Chem. Soc. 2006 128,16701.
23、M. Liang, W. Xu, F. Cai, P. Chen, B. Peng, J. Chen, Z. Li, J. Phys. Chem. C.2007, 111, 4465.
24、S. Hwang, J. H. Lee, C. Park, H. Lee, C. Kim, C. Park, M.-H. Lee, W. Lee, J. Park, K. Kim, N.-G. Park, C. Kim ,Chem. Commun. 2007, 4887.
25、D. Kim, J. K. Lee, S. O. Kang, J. Ko, Tetrahedron, 2007, 63, 1913.
26、Y. Jin, J. Hua, W. Wu, X. Ma, F. Meng, Synthetic Metals 2008, 158, 64.
27、Z. Ning, Q. Zhang, W.Wu, H. Pei, B. Liu, H. Tian, J. Org. Chem. 2008, 73, 3791.
28、H. Choi, J. K. Lee, K. H. Song, K. Song, S. O. Kang, J. Ko, Tetrahedron, 2007, 63, 1553.