臺灣博碩士論文加值系統

本次研究為合成新型含薰草素基團之有機染料並研究其光學性質，同時使染料應用在有機染料敏化太陽能電池上。

新型含薰草素基團之有機染料重要的步驟如schemeΙ所示，由2-胺基-5-溴-苯硫(3) 3,3,3-三乙氧丙酸乙酯(5)在溶劑acetic acid 及 T HF下進行縮合反應得(6-溴-苯駢-2-基)-乙酸乙酯(6)，接續著8-羥基-1,1,7,7-三甲基-2,3,6,7-四氫-1H,5H,必啶[3,2,1-ij]喹林-9-梭醛(9) 進行縮合反應得9-(6-溴-苯駢-2-基)-1,1,6,6-四甲基-2,3,5,6-四氫-1H,4H-11-氧-3a-吖-苯駢[de]蒽-10-酮(10)，9-(6-溴-苯駢-2-基)-1,1,6,6-四甲基-2,3,5,6-四氫-1H,4H-11-氧-3a-吖-苯駢[de]蒽-10-酮(10)及2-噻吩硼酸在Pd(PPh3)4及K2CO3下進行Suzuki coupling reaction得1,1,6,6-四甲基-9-(6-噻吩-2-基-苯駢-2-基)-2,3,5,6-四氫-1H,4H-11-氧-3a-吖-苯駢[de]蒽-10-酮(12)，1,1, 6,6-四甲基-9-(6-噻吩-2-基-苯駢-2-基)-2,3,5,6-四氫-1H,4H-11-氧-3a-吖-苯駢[de]蒽-10-酮(12)進行Vilsmeyer-Haack reacti on可得5-[2-(1,1,6,6-四甲基-10-氧-2,3,5,6-四氫-1H,4H,10H-11-氧-3a-吖-苯駢[de]蒽-9-基)-3H-吲哚-5基]-噻吩-2-carbaldehyde (13)，5-[2-(1, 1,6,6-四甲基-10-氧-2,3,5,6-四氫-1H,4H,10H-11-氧-3a-吖-苯駢[de]蒽-9 -基)-3H-吲哚-5基]-噻吩-2- carbaldehyde (13)、Rhodanine-N-acetic ac id、piperidine在酒精溶液下迴流進行反應24小時，結束反應再以管柱層析法純化沉澱物得含薰草素染料(4-氧-5-{5-[2 - (1,1,6,6-四甲基-10-氧-2,3,5,6-四氫-1H,4H,10H-11-氧-3a-吖-苯駢[de]蒽-9-基)-苯駢-6-基]- 噻吩噻唑-2-基亞甲基}-2-硫硐-噻唑-3-基)-乙酸(14) 深咖啡色固體。

AM1.5 100mW/cm2模擬太陽光入射量測所得光電轉換效率（η％）為0.475％，Isc(Short Circuit Current)為0.403mA，開環電壓Voc(Open Circuit Voltage)為0.502V，填充因子（FF）為0.587。

初步的研究結果顯示含薰草素染料運用在應用在有機染料敏化太陽能電池上是相當具有發展性。

We reported here on the synthesis and photophysical properties of a no vel coumarin-based organic dye (14) as well as its application dye-sensiti zed nanocrystalline TiO2 solar cells (DSSCs).

The key step of the synthesis of new coumarin-based organic dye（14）for dye-sensitized solar cell as shown in scheme 1 ,is condensation reacti on of 2-Amino-5-bromobenzenethiol (3) and 3,3,3- triethoxypropionic ethyl ester (5) to give the corresponding (6-Bromo-benzothiazol-2-yl) - ac etic acid ethyl ester (6) in the presence of acetic acid and THF as solven t .Subsequent condensation with 8-hydroxy-1,1,7,7–tetramethyl -2, 3, 6,7 -tetrahydro-1H,5H-pyrido[3,2,1-ij]quinoline-9-carbaldehyde (9) gave 9- (6-Bromo-benzothiazol-2-yl)-1,1,6,6-tetramethyl -2, 3, 5, 6– tetrahydro- 1H,4H-11-oxa-3a-aza-benzo[de]anthracen-10-one(10).Suzuki coupling reaction of the intermediate (10) with 2-thienyl-boronic acid in the presence of Pd(PPh3)4 and K2CO3 gave 1,1,6,6-tetramethyl-9 -(6-thiophen -2–yl-benzothiazol-2-yl)-2,3,5,6-tetrahydro-1H,4H-11-oxa-3a-aza-benzo[de]anthracen-10-one(12). 5-[2-(1,1,6, 6-tetramethy l-10-oxo -2,3, 5,6 – tetrhydro-1H,4H,10H-11 -oxa-3a-a za-benzo[de] anthracen-9-yl) -3H – indol -5-yl]-thiophene-2-carbaldehyde (13) was synthesized from (12) by the Vilsmeyer-Haack reaction .An ethanolic solution including (13) and rhodanine- N-acetic acid was refluxed in the presence of piperidine for 24h.Purificat ion of the resulting precipitates by column chromatography to give deep b rown solids of the coumarin-based dye, (4-oxo -5-{5-[2 -(1,1,6,6- tetra methyl-10-oxo-2,3,5,6 -tetrahydro- 1H,4H,10H-11–oxa -3a-aza-benzo[de]anthracen- 9-yl) -benzothiazol-6-yl] –thiophen -2- ylmethylene}-2-thioxo-thiazolidin-3-yl) acetic acid(14).

A solar-energy-to-electricity conversion efficiency of 0.475％ was attained under AM 1.5 irradiation (100mW/cm2) it’s a Short Circuit Current density (Isc) of 0.403mA，an Open Circuit Voltage (Voc) of 0.502V，and a fill factor (FF) of 0.587.

This preliminary work suggests that the molecular-designed coumarin dye is promising in the application of DSSCS.

目 錄

中文摘要
英文摘要
誌謝
目錄
List of Scheme
List of Figure
List of Table

第一章 緒論……………………………………………………………1
1.1 前言……………………………………………………….…..1
1.2 染料敏化太陽能電池簡介……………………………...........2
1.3 染料敏化太陽能電池的結構及原理………………………...4
1.4 染料敏化太陽能電池的敏化劑……………………………...9
1.5 敏化染料太陽能電池效能.…………………………………15
1.6 研究動機與目的………………………………………….....17

第二章 實驗…………………………………………………………19
2.1 藥品………………………………………………………...19
2.2 實驗儀器與測試方法……………………………………...19
2.3 合成方法…………………………………………………...26

第三章 鑑定…………………………………………………………30
3.1 9-(6-Bromo- benzothiazol-2-yl)-1,1,6,6 –tetramethyl-2,3,5,6 -tetra hydro -1H,4H-11–oxa -3a-aza-benzo[de] anthracen- 10-one 之合成與鑑定…………………………………30
3.2 1,1,6,6-Tetramethyl- 9-(6-thiophen-2-yl -b enzothia zol-2-yl)-2,3,5, 6-tetrahydro- 1H,4H -11 -oxa- 3a-aza- benzo[de]anthracen-10-one之合成與鑑定……………...30
3.3 5-[2-(1,1,6,6-Tetramethyl-10-oxo-2,3,5,6-te trahydro-1H,4H, 10H-11-oxa-3a-aza-benzo [de] anthracen -9-yl)-3H-indol -5-yl]-thiophene-2-carbaldehyde之合成與鑑定…………..31


3.4 (4-Oxo-5-{5-[2-(1, 1,6,6-tetramethyl-10-o xo-2,3,5,6 -tetrahydro-1H,4H,10H-11-oxa-3a-a za-benzo[de] anthracen -9-yl)-benzothiazol-6-yl]-thiophen-2-ylmethylene}-2-thioxo-thiazolidin-3-yl)-acetic acid之合成與鑑定……………........32

第四章 元件製作……………………………………………………...45
4.1 Tio2 溶凝膠製備…………………………………………....45
4.2 Tio2薄膜製備………………………………………………45
4.3 TiO2 薄膜乾燥處理………………………………………..47
4.4 染料敏化太陽電池( DSSC )組裝…………………………48

第五章 結果與討論…………………………………………………52
5.1 紫外光光譜之探討…………………………………………52
5.2 螢光光譜之探討……………………………………………52
5.3 光電轉換效率之探討………………………………………52

第六章 總 結………………………………………………………60

參考資料 ……………………………………………………………61

List of Scheme

Scheme Ⅰ The synthesis of (4-Oxo-5-{5-[2-(1, 1,6,6-tetramethy l-10-oxo-2,3,5,6 -tetrahydro-1H,4H,10H-11-oxa-3a-a za-benzo[de] anthracen -9-yl)-benzothiazol-6-yl]-thio phen-2-ylmethylene}-2-thioxo-thiazolidin-3-yl)-acetic acid……………………………………………………24
List of Figure

Fig.1-1 染料敏化奈米太陽能電池的結構示意圖…………………..4
Fig.1-2 染料敏化奈米晶太陽能電池的工作原理示意圖…………..6
Fig.1-3 染料敏化奈米晶太陽能中電子的損失反映示意圖..............8
Fig.1-4 COOH官能基可能的化學吸附和物理吸附的模型圖........10
Fig.1-5 N-3 Dye化學結構式.................…………………11
Fig.1-6 N719-dye化學結構式…………………………………….12
Fig.1-7 Black dye 化學結構式……………………………………13
Fig.1-8 Coumarin Dye 化學結構式……………………………….14
Fig 1.9 Molecular Structures of Triphenylamine Dyes…………….18
Fig.1.10 Molecular Structures of indoline dye ：(a)D-149 and (b)D-102…………………………………………………...18
Fig.1.11 Molecular Structures of coumarin dye：NKX-2753 and NKX-2586…………………………………………………18
Fig1.12 Molecular Structures of oligothiophene dye：MK-2 and MK-5………………………………………………………18
Fig.2.1 太陽光譜模擬系統架構圖………………………………...21
Fig.2.2 Solar simulator 型號NEWPORT Oriel 91160……………21
Fig.2.3 電漿清洗機………………………………………………...22
Fig.3.1-1 Mass spectrum of compound
9-(6-Bromo-benzothiazol-2-yl)-1,1,6,6-tetramethyl-2,3,5,6-tetrahydro-1H,4H-11-oxa-3a-aza-benzo[de]anthracen-10-one.................................................................................................33
Fig.3.1-2 1H-NMR spectrum of compound 9-(6-Bromo-benzothiazol-2-yl)-1,1,6,6-tetramethyl-2,3,5,6-tetrahydro-1H,4H-11-oxa-3a-aza-benzo[de]anthracen-10-one.................................................................................................34

Fig.3.1-3 FTIR spectrum of compound 9-(6-Bromo–benzothiazol -2-yl)-1,1,6,6-tetramethyl-2,3,5,6-tetrahydro-1H,4H-11-oxa-3a-aza-benzo[de]anthracen-10-one…..................................35
Fig.3.2-1 Mass spectrum of compound 1,1,6,6-Tetramethyl-9- (6-thiophen-2-yl-benzothiazol-2-yl) -2,3,5,6-tetrahydro-1H, 4H- 11-oxa-3a-aza-benzo[de] anthracen-10-one………….36
Fig.3.2-2 1H-NMR spectrum of compound 1,1,6,6- Tetramethyl-9- (6-thiophen-2-yl-benzothiazol-2-yl)-2,3,5,6-tetrahydro-1H, 4H- 11-oxa-3a-aza-benzo[de]anthracen-10-one…………..37
Fig.3.2-3 FTIR spectrum of compound 1,1,6,6-Tetra meth yl-9- (6-thi ophen-2-yl-benzothiazol-2-yl)-2,3,5,6-tetrahydro-1H,4H-11-oxa-3a-aza-benzo[de]anthracen-10-one…………………...38
Fig.3.3-1 Mass spectrum of compound 5-[2-(1,1,6,6- Tetramethyl- 10 -oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-3H-indol-5-yl]-thiophene-2-carbaldehyde45
Fig.3.3-2 1H-NMR spectrum of compound 5-[2-(1,1, 6,6-Tetramethyl -10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-3H-indol-5-yl]-thiophene-2-carbaldehyde……………………………………………………………40
Fig.3.3-3 1 FTIR spectrum of compound 5-[2-(1,1,6,6-Tetramethy l-10 -oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-3H-indol-5-yl]-thiophene-2-carbaldehyde………………………………………………………………..41
Fig.3.4-1 1Mass spectrum of compound (4-Oxo -5-{5 -[2 -(1,1,6,6-t etr amethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-benzothiazol-6-yl]-thiophen-2-ylmethylene}-2-thioxo-thiazolidin-3-yl)-acetic acid………..42
Fig.3.4-2 1H-NMR spectrum of compound (4-Oxo -5-{5-[2 -(1,1,6, 6 -tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-benzothiazol-6-yl]-thiophen-2-ylmethylene}-2-thioxo-thiazolidin-3-yl)-acetic acid……43
Fig.3.4-3 FTIR spectrum of compound (4-Oxo-5-{5 -[2-(1,1,6,6–tetra methyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-benzothiazol-6-yl]-thiophen-2-ylmethylene}-2-thioxo-thiazolidin-3-yl)-acetic acid………..54

Fig.4.1 用電漿清洗機清潔後之 ITO透明導電玻璃………………...46
Fig.4.2 旋轉塗佈法示意圖…………………………………………..46
Fig.4.3 將 TiO2塗佈於 ITO…………………………………………...48
Fig.4.4 TiO2塗佈在 ITO後，將膠帶撕去..................... ……………49
Fig.4.5 將Pt蒸鍍在ITO上…………………………………………49
Fig.4.6 封裝示意圖.............................................................................50
Fig.5.1-1 UV/Vis. Spectrum of compound （10）…………………..54
Fig.5.1-2 UV/Vis. Spectrum of compound （12）…………………..54
Fig.5.1-3 UV/Vis. Spectrum of compound （13）……………………55
Fig.5.1-4 UV/Vis. Spectrum of compound （14）…………………… 55
Fig.5.1-5 TiO2吸收(14) Dye 之UV-Vis……………………………...56
Fig.5.1-6 (14)薄膜紫外線(UV)吸收光譜圖………………………....56
Fig.5.1-6 光電子光譜分析儀(AC2 PESA)測定HOMO軌道能量圖...57
Fig.5.1-7 (14)染料能階圖…………………………………………….57
Fig.5.2-1 absorption and Fluorescence spectra of compound（10）（in THF solvent，C=1.96�e10-5M）………………………..58
Fig.5.2-2 absorption and Fluorescence spectra of compound（12）（in THF solvent，C=1.56�e10-5M）………………………...58
Fig.5.2-3 absorption and Fluorescence spectra of compound （13）（in THF solvent，C=1.85�e10-5M）………………………..59
Fig.5.2-4 absorption and Fluorescence spectra of compound（14）（in THF solvent，C=1.78�e10-5M）…………………………59


List of Table

Table 5.1 UV光譜相關數據與參數………………………………….53
Table 5.2 螢光光譜激發後所得之stokes shift……………………….53
Table 5.3 光電轉換效率………………………………………………53

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