含聯噻吩之環釕金屬染料的設計與合成並應用於染料敏化太陽能電池

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黃柏程(Bo-Chen Huang) 查詢紙本館藏

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論文名稱

含聯噻吩之環釕金屬染料的設計與合成並應用於染料敏化太陽能電池

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摘要(中)

染料敏化太陽能電池 (Dye Sensitized Solar Cell, 簡稱 DSC ) 因成本低廉、製造簡易、色彩多樣化及室內弱光高效率發電的特性，具有發展的潛力。實驗室合成出的染料DUY29有不錯的光伏表現，然而卻仍有兩個缺點：DUY29有高的HOMO能階，不利電解質還原染料；DUY29染料因體積大，在TiO2膜上有低的吸附量，導致元件有低的Jsc值。本研究以DUY29結構為基礎，用dithieno[3,2-b:2’,3’-d] thiophene (簡稱tThp) 取代DUY29中的 thieno-[2,3-b]thiophene (簡稱cis-fThp) 輔助配位基，降低所合成環金屬錯合物的HOMO能階，合成出HBC30；以Thiophene 取代DUY29的 cis-fThp與2,3-dihydro-thieno-[3,4-b][1,4]dioxine (簡稱EDOT)，分別合成出HBC23和HBC31，可縮小錯合物體積。HBC23、HBC30與HBC31 (簡稱HBC系列染料)和實驗室所合成之DUY28與DUY29 (簡稱DUY系列)染料的HOMO能階由高到低為：DUY29 > HBC31 > HBC23 > DUY28 > HBC30。其中HBC23雖然HOMO能階不是最低的，但有最高的染料吸附量，所敏化之元件能將光更有效的轉換成電流，因此元件有最高的光電轉換效率，達8.62%。

摘要(英)

Dye sensitized solar cell (DSC) is known for its low cost, great variety of colors and high efficiency under dim-light condition. Our Lab members previously had synthesized cycloruthenated sensitizer coded DUY29, which performs good photovoltaic properties, but has two drawbacks: First, DUY29’s has high HOMO potential which is unfavorable for dye regeneration; Second, the dye-loading on TiO2 thin film is small due to its large molecular size, resulting in a low short-curcuit current density (Jsc). This work intends to develop high efficient dyes based on DUY29. We replace thieno-[2,3-b]thiophene (cis-fThp) with the dithieno[3,2-b:2’,3’-d] thiophene (tThp) on DUY29 for lowering the HOMO potential to form HBC30; replace cis-fThp with thiophene (Th) or 2,3-dihydro-thieno-[3,4-b][1,4]dioxine (EDOT) with thiophene for decreasing the molecule size to form HBC23 and HBC31, respectively. Compared with the previously prepared DUY28 and DUY29 (DUY series) dyes. The order of the HOMO potential is DUY29 > HBC31 > HBC23 > DUY28 > HBC30. Although the HOMO potential of HBC23 is not the lowest, the dye loading (on TiO2 thin film) is the highest, resulting in the highest Jsc of DSC device. As a result, the power conversion efficiency of HBC23 sensitized solar cell is the highest, reaching 8.62 %.

關鍵字(中)

★ 環釕金屬
★ 染料敏化太陽能電池
★ 聯噻吩

關鍵字(英)

論文目次

摘要 i
Abstract ii
圖片摘要 iv
謝誌 v
第一章、緒論 1
1-1、前言 1
1-2、太陽能電池的發展及分類 1
1-3、染料敏化太陽能電池的架構 3
1-4、染料敏化太陽能電池的工作原理 3
1-5、染料敏化電池的發展與染料種類 5
1-6、釕金屬錯合物染料(Ruthenium Metal Complex) 8
1-6-1、高效率釕金屬錯合物染料的條件 8
1-6-2、具代表性的釕金屬錯合物染料N3和N719 9
1-6-3、環釕金屬錯合物(Cyclometalated Ruthenium Complex)染料的優勢 11
1-7、提高環釕金屬染料所敏化元件光電轉換率的分子設計 14
1-7-1、DSC環金屬染料DUY29的缺點 14
1-7-2、環釕金屬染料HOMO越低所敏化元件有越高的光電轉換效率 15
1-7-3、環金屬配位基取代基雜環Eg越小染料的HOMO能階越低 17
1-7-4、聯噻吩(Fused thiophene)之碳數越多Eg越小 19
1-7-5、環金屬染料輔助配位基含有氧原子在TiO2膜上有低的吸附量 21
1-8 研究動機 24
第二章、實驗部分 25
2-1、實驗藥品 25
2-2、中間產物之結構、分子量與簡稱 27
2-3、最終產物之結構、分子量與簡稱 30
2-4、實驗步驟 32
2-4-1、Et2dcbpy的合成，如圖2-1所示 32
2-4-3、L-23的合成流程，如圖2-3所示 36
2-4-4、L-28的合成流程，如圖2-4所示 39
2-4-5、L-29的合成流程，如圖2-5所示 41
2-4-6、L-30的合成流程，如圖2-6所示 45
2-4-7、L-31的合成流程，如圖2-7所示 48
2-4-8、釕錯合物HBC23的合成流程，如圖2-8所示 50
2-4-9、釕錯合物DUY28的合成流程，如圖2-9所示 52
2-4-10、釕錯合物DUY29的合成流程，如圖2-10所示 55
2-4-11、釕錯合物HBC30的合成流程，如圖2-11所示 57
2-4-12、釕錯合物HBC31的合成流程，如圖2-12所示 59
2-5、儀器分析與樣品製備 62
2-5-1、聚焦微波化學反應系統(CEM) 62
2-5-2、核磁共振光譜儀(Nuclear Magnetic Resonance, NMR) 63
2-5-3、紫外光/可見光吸收光譜儀(Ultraviolet Visible Spectrophoto-meter, UV/Vis Spectrophotometer) 64
2-5-4、電化學分析儀(Electrochemical Analyzer) 65
第三章、結果與討論 67
3-1、光學性質 67
3-2、電化學性質 74
3-3、Density Fuctional Theory (DFT) 理論計算 80
3-3-1、理論計算出的染料的前置軌域分布 80
3-3-2、理論計算出的染料的Oscillator Strength 84
3-3-3、理論計算出的染料的β-LUSO前置軌域分布 94
3-4、HBC系列與DUY系列染料所組裝元件之光伏參數 96
3-4-1、HBC系列與DUY系列染料所組裝成元件J-V曲線圖與IPCE圖 97
3-4-2、HBC系列與DUY系列染料所組裝成元件開路電壓(Voc)的探討 99
3-4-3、HBC系列與DUY系列染料所組裝成元件短路電流(Jsc)的探討 102
第四章結論 104
參考文獻 106
附錄 111

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指導教授

吳春桂

審核日期

2020-8-19

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