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研究生： 顏夢華
Meng-hua Yan
論文名稱： 新型含香豆素基團的光敏化有機太陽能電池染料2-氰基-3-{5-[2-（1,1,6,6-四甲基-10-氧-2,3,5,6 -四氫-1H，4H，10H-11-氧雜-3a-氮雜苯並[de]蒽-9-基）-苯並噻唑-6-基]-噻吩- 2 -基）}-丙烯酸之合成與性質研究
Synthesis and Characterization of a Novel Coumarin -based Organic Dye 2-Cyano-3-{5-[2-(1,1,6,6-Tetrame thyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-benzothiazol-6-yl]-thiophen-2-yl}-acrylic Acid for Organic Dye-Sensitized Solar Cell
指導教授： 廖本瑞
Ben-Ruey Liaw
口試委員: 曾文祺
Wen-Chi Tseng
黃炳綜
Ping-Tsung Huang
學位類別： 碩士
Master
系所名稱： 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年： 2008
畢業學年度： 96
語文別： 中文
論文頁數： 66
中文關鍵詞： 染料敏化太陽能電池 、香豆素
外文關鍵詞： Dye-Sensitized Solar Cell, Coumarin
相關次數： 點閱：325  下載：1 
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    • 此報告對合成和光物理性質一新型香豆素為基礎的有機染料（14）以及其應用染料敏化奈米二氧化鈦太陽能電池（DSSCs）。
    關鍵的步驟合成出一個新的香豆素為基礎的有機染料（14），如圖I為染料敏化太陽能電池流程圖，2-胺基-5-溴-苯硫醇（3）和3,3,3-三乙氧基丙酸乙酯（4）冷凝反應，醋酸和四氫呋喃作為溶劑，因此可得（6-溴-苯並噻唑-2-基）-醋酸乙酯（6）。濃縮8 -羥基- 1 ,1,7,7 -四甲基-2,3,6,7 -四氫-1H，5H-吡啶並[3,2,1-ij]喹啉-9-甲醛（9）可得9-（ 6 -苯並噻唑-2-基）- 1,1,6,6-四甲基-2,3,5,6 -四氫-1H，4H-11-氧雜- 3a-氮雜苯並[de]蒽-1 0-酮（10）。中間物（10）、2-噻吩硼酸，Pd(PPh3)4 與碳酸鉀，利用Suzuki coupling反應，可得1,1,6,6-四甲基-9-（6-噻吩-2-基-苯並噻唑-2-基）-2,3,5,6-四氫-1H，4H-11-氧雜-3a-氮雜苯並[de] 蒽-10-酮（12）。
    利用Vilsmeyer-Haack 反應，可由(12)合成出5-[2-（1,1,6,6-四甲基-10-氧-2,3,5,6-四氫-1H，4H，10H-11-氧雜-3a-氮雜苯並[de]蒽- 9 -基）-3H-吲哚- 5-基]-噻吩-2-甲醛（13）。將（13）和氰醋酸與哌啶回流24小時。利用管柱層析法純化，最後可得到深橘紅色固體，2-氰基-3-{5-[2-（1,1,
    6,6-四甲基-10-氧-2,3,5,6 -四氫-1H，4H， 10H-11-氧雜-3a-氮雜苯並[de]蒽-9-基）-苯並噻唑-6-基]-噻吩- 2 -基）}-丙烯酸（14） 。
    光電轉換效率（η）達到0.413 ％ ，短路電流密度（ISC）為0.309 mA/cm-2 ，開環電壓（Voc）為0.502V，以及填充因子（FF）為0.665 。這個初步的結果表示，香豆素染料應用在染料敏化太陽能電池上，在將來是有前瞻性的。

    We reported here on the synthesis and photophysical properties of a
    novel coumarin-based organic dye (14) as well as its application in dye-
    sensitized nanocrystalline TiO2 solar cells (DSSCs).
    The key step of the synthesis of a new coumarin-based organic dye(14)
    for dye-sensitized solar cell as shown in scheme I, is the condensation
    reaction of 2-Amino-5-bromobenzenethiol (3) and 3,3,3-triethoxypropio
    nic ethyl ester (4) to give the corresponding (6-Bromo-benzothiazol-2-yl
    )acetic acid ethyl ester (6) in the presence of acetic acid and THF as solv
    ent. Subsquent 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 re-
    action of the intermediate (10) with 2-thiopheneboronic acid in the pres-
    ence of Pd(PPh3)4 and K2CO3 gave 1,1,6,6-tetramethyl-9-(6-thiophen-2-y
    l-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-tetramethyl-10-oxo-2,3,5,6-tetrahyd
    ro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-3H-indol-5-yl]t
    hiophene-2-carbaldehyde (13) was synthesized from (12) by the Vilsme-
    yer-Haack reaction. An ethanolic solution including (13)and cyanoacetic
    acid was refluxed in the presence of piperidine for 24h.Purification of the
    resulting precipitates by column chromatography to give deep orange-red
    solids of the coumarin-based dye, 2-cyano-3-{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-yl}acrylic acid (14) .
    A solar-energy-to-electricity conversion efficiency (η) of 0.413% was
    attained AM 1.5 radiation (100 mW/cm-2), short-circuit current density
    (Isc) of 0.309 mA/cm-2, an open-circuit voltage (Voc) of 0.502V, and
    a fill factor (FF) of 0.665.
    This prelimiary 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 致謝 目錄 List of Scheme List of Figure List of Table 第一章 緒論....................................................................................................1 1.1 前言....................................................................................................1 1.2 研究動機與目的....................................................................................................2 第二章 理論原理與文獻回顧....................................................................................................5 2.1 有機太陽能電池....................................................................................................5 2.2 染料敏化太陽能電池發展及構造原理....................................................................................................9 2.3 染料敏化太陽能電池的敏化劑............................................................................13 2.4 染料敏化太陽能電池電流-電壓輸出特性...........................................................18 第三章 實驗........................................................................................21 3.1 藥品.......................................................................................21 3.2 實驗儀器與測試方法...........................................................21 3.3 合成方法...............................................................................25 3.4 染料敏化太陽電池組裝.......................................................46 第三章 鑑定........................................................................................49 3.1 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 之合成與鑑定..........................................................49 3.2 1,1,6,6-Tetramethyl-9-(6-thiophen-2-yl-benzothia 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..........................50 3.3 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之合成與鑑定...................51 3.4 2-Cyano-3-{5-[2-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahy dro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-benzothiazol-6-yl]-thiophen-2-yl}-acrylic acid 之合成與鑑定..52 第五章 結果與討論............................................................................53 5.1 紫外光光譜之探討................................................................53 5.2 螢光光譜之探討...................................................................53 5.3 光電轉換效率之探討.............................................................54 第六章 結 論...................................................................................63 參考資料 ............................................................................................64 List of Scheme Scheme Ⅰ The synthesis of 2-cyano-3-{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-yl}-acrylic acid...................................................24 List of Figure Fig. 1.2-1 Molecular Structures of Triphenylamine Dyes.......................3 Fig. 1.2-2 Molecular Structures of indoline dye......................................4 Fig. 1.2-3 Molecular Structures of coumarin dye....................................4 Fig. 1.2-4 Molecular Structures of oligothiophene dye...........................4 Fig. 2.2-1 DSSC工作原理示意圖...........................................................9 Fig. 2.2-2 染料敏化太陽能電池中產生電子再結合的機制...............12 Fig. 2.2-3 DSSC電子能階示意圖........................................................12 Fig. 2.3-1 化學吸附和物理吸附的模型圖...........................................14 Fig. 2.3-2 N3化學結構式......................................................................15 Fig. 2.3-3 N719化學結構式..................................................................16 Fig. 2.3-4 Black dye化學結構式...........................................................17 Fig. 2.3-5 coumarin dye化學結構式.....................................................18 Fig. 3.3-1 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...................................................34 Fig. 3.3-2 1H NMR 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. 3.3-3 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...................................................36 Fig. 3.3-4 Mass spectrum of compound 1,1,6,6-Tetramethyl-9-(6-thiope n-2-yl-benzothiazol-2-yl)-2,3,5,6-tetrahydro-1H,4H-11-oxa-3a-aza-benzo[de]anthracen-10-one.........................................37 Fig. 3.3-5 1H NMR of compound 1,1,6,6-Tetramethyl-9-(6-thiopen-2-y l-benzothiazol-2-yl)-2,3,5,6-tetrahydro-1H,4H-11-oxa-3a-aza-benzo[de]anthracen-10-one............................................38 Fig. 3.3-6 FTIR spectrum of compound 1,1,6,6-Tetramethyl-9-(6-thio pen-2-yl-benzothiazol-2-yl)-2,3,5,6-tetrahydro-1H,4H-11-oxa-3a-aza-benzo[de]anthracen-10-one...............................39 Fig. 3.3-7 Mass spectrum of compound 5-[2-(1,1,6,6-Tetramethyl-10-ox o-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-benzothiazol-6-yl]-thiophene-2-carbaldehyde ...............................................................................................40 Fig. 3.3-8 1H NMR 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)-benzothiazol-6-yl]-thiophene-2-carbaldehyde.........41 Fig. 3.3-9 FTIR spectrum of compound 5-[2-(1,1,6,6-Tetramethyl-10-o xo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de] anthracen-9-yl)-benzothiazol-6-yl]-thiophene-2-carbaldehyde ..............................................................................................42 Fig. 3.3-10 Mass spectrum of compound 2-Cyano-3-{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-yl}-a crylic acid................................................................................43 Fig. 3.3-11 1H NMR of compound 2-Cyano-3-{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)-benzothiazol-6-yl]-thiophen-2-yl}-acrylic acid....................................................................................44 Fig. 3.3-12 FTIR spectrum of compound 2-Cyano-3-{5-[2-(1,1,6,6-tetr 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-yl}-acrylic acid.........................................................................45 Fig. 3.4-1 將TiO2塗佈於 ITO.............................................................47 Fig. 3.4-2 TiO2塗佈在 ITO後，將膠帶撕去.......................................47 Fig. 3.4-3 將Pt蒸鍍在ITO上..............................................................48 Fig. 3.4-4 封裝示意圖...........................................................................48 Fig. 5.1-1 UV/VIS 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...........................................55 Fig. 5.1-2 UV/VIS spectrum of compound1,1,6,6-Tetramethyl-9-(6-thi open-2-yl-benzothiazol-2-yl)-2,3,5,6-tetrahydro-1H,4H-11-oxa-3a-aza-benzo[de]anthracen-10-one.................................55 Fig. 5.1-3 UV/VIS 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)-benzothiazol-6-yl]-thiophene-2-carbaldehyde.............................................................................................56 Fig. 5.1-4 UV/VIS spectrum of compound 2-Cyano-3-{5-[2-(1,1,6,6-tet ramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-benzothiazol-6-yl]-thiophen-2-yl}-acrylic acid........................................................................56 Fig. 5.1-5 薄膜紫外線(UV)吸收光譜圖of compound 2-Cyano-3-{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-yl}-acrylic acid....................................................57 Fig. 5.1-6 TiO2吸收compound 2-Cyano-3-{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-yl}-acrylic acid之UV/VIS......................................................................57 Fig. 5.1-7 光電子光譜分析儀(AC2 PESA)測定HOMO軌道能量圖 of compound 2-Cyano-3-{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-yl}-acrylic acid ...............................................................................................58 Fig. 5.1-8 compound 2-Cyano-3-{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-yl}-acrylic acid染料能階圖...................................................................................58 Fig. 5.2-1 Absorption and Fluorescence spectram of compound9-(6-Bro mo-benzothiazol-2-yl)-1,1,6,6-tetramethyl-2,3,5,6-tetrahydro-1H,4H-11-oxa-3a-aza-benzo[de]anthracen-10-one............59 Fig. 5.2-2 Absorption and Fluorescence spectram of compound 1,1,6,6- Tetramethyl-9-(6-thiopen-2-yl-benzothiazol-2-yl)-2,3,5,6-tetrahydro-1H,4H-11-oxa-3a-aza-benzo[de]anthracen-10-one ...............................................................................................60 Fig. 5.2-3 Absorption and Fluorescence spectra 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)-benzothiazol-6-yl]-thiophene-2-carbaldehyde.............................................................60 Fig. 5.2-3 Absorption and Fluorescence spectram of compound 2-Cyano -3-{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-yl}-acrylic acid............................................61 List of Table Table 5.1 Absorption of four compounds..................59 Table 5.2 Photoluminescent of four compounds.....................................61 Table 5.3 光電轉換率.............................................................................62

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