含高度共軛芳香雜環之釕錯合物的合成以應用於染料敏化太陽能電池

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蔡源寧(Yuan-ning tsai) 查詢紙本館藏

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化學學系

論文名稱

含高度共軛芳香雜環之釕錯合物的合成以應用於染料敏化太陽能電池

相關論文

★ 含3,4-乙烯二氧噻吩輔助配位基之鋨、釕金屬錯合物合成與其在染料敏化太陽能電池的應用	★ 應用於染料敏化太陽能電池之釕金屬錯合物合成與其性質探討
★ 含共軛配位基之釕錯合物合成與其在染料敏化太陽能電池的應用	★ 新型三吡啶釕錯合物光敏化染料的合成與性質探討
★ 釕錯合物敏化太陽能電池元件優化與光伏特性探討	★ 金屬錯合物染料敏化太陽能電池的元件優化
★ 新型三吡啶鋨錯合物染料合成與配位基效應之探討	★ 多聯吡啶釕錯合物光敏化染料的合成與性質探討
★ 優化含氯元素之多聯吡啶釕錯合物敏化太陽能電池與元件特性探討	★ 釕與鋨錯合物染料敏化太陽能電池性能優化與特性探討
★ 有機共吸附染料的合成與性質探討

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摘要(中)

染料敏化太陽能電池(Dye-sensitized solar cells，DSCs)，由於其光電轉換機制的獨特性、材料的多樣性、元件的低製造成本與良好的光電轉換效率，相關研究極為眾多，其中，使用雙吡啶配位的釕錯合物染料因為可使元件同時具有高效率與高穩定性而備受重視，儘管如此，該類型染料的研發至今仍無法有效增加分子在近紅外光的吸收能力。本研究為求突破此限制，設計合成兩個新的雙吡啶配位釕錯合物(CYC-53及CYC-55)，其分子設計不僅採用芳香雜環同時延長輔助配位基與固著配位基的共軛長度，在固著配位基更首次分別引入selenophene及thienothiophene單元。與固著配位基使用thiophene共軛單元的CYC-21相比，CYC-53及CYC-55在DMF溶液中的吸收光譜皆紅位移、吸收強度也增加 (CYC-53及CYC-55的起始吸收波長比CYC-21 (747 nm)分別紅位移了19 nm及14 nm)。而從電化學氧化峰得知三者的HOMO位能皆為+0.84 V (vs. NHE)，透過搭配吸收光譜所得之能隙可得知：CYC-53的LUMO位能(-0.78 V vs. NHE)、CYC-55的LUMO位能(-0.79 V vs. NHE)皆低於CYC-21之LUMO位能(-0.82 V vs. NHE)。在所敏化元件的效率比較中，CYC-53及CYC-55的Jsc值均大於CYC-21 (11.61 mA·cm-2)所敏化之元件，且其中以CYC-55所敏化之元件具最高效率(6.85%)，此結果顯示在釕錯合物染料分子的固著配位基引入重原子及延長共軛單元，能夠有效降低釕錯合物的能隙、拓寬吸光範圍、與提高吸收係數，以利進一步提高所敏化元件的光電轉換效率。

摘要(英)

Dye-sensitized solar cells (DSCs) have attracted significant attention due to their unique working mechanism, diverse materials, low manufacturing costs, and good efficiency. Bipyridyl ruthenium (Ru)-based sensitizers have received considerable attention for attending high efficiency and stability of the corresponding DSCs. However, to date, their development has not effectively increased the near-infrared light absorption capacity. To breakthrough this limitation, two new bipyridyl Ru complexes (CYC-53 and CYC-55) are designed and synthesized. They have the heterocycles to simultaneously extend the conjugation length of both ancillary and anchoring ligands. Additionally, for the first time, selenophene and thienothiophene moieties are introduced in the anchoring ligands to extent their conjugate length. Compared with CYC-21 (747 nm) using thiophene in the anchoring ligand, CYC-53 and CYC-55 in DMF exhibit a red-shifted (by 19 nm and 14 nm, respectively), and increased absorption intensity. Moreover, all of the three complexes have the same HOMO energy level of +0.84 V (vs. NHE). LUMO energy levels for CYC-53 (-0.78 V vs. NHE) and CYC-55 (-0.79 V vs. NHE) are lower than that of CYC-21 (-0.82 V vs. NHE). Both of CYC-53 and CYC-55 dyed DSCs exhibit higher Jsc values than that based on CYC-21 (11.61 mA·cm-2). CYC-55-sensitized device achieves the highest efficiency of 6.85%. These results indicate that introducing heavy atoms and extending the conjugation length in the anchoring ligands of Ru complexes can effectively reduce the energy gap, broaden the absorption profile, and enhance the absorption coefficient, thereby improving the power conversion efficiency of the correspondry devices.

關鍵字(中)

★ 釕錯合物
★ 芳香雜環

關鍵字(英)

論文目次

摘要 I
Abstract II
謝誌 III
目錄 IV
圖目錄 VII
表目錄 XVI
附錄目錄 XVIII
第一章緒論 1
1-1 前言 1
1-2 太陽光譜與太陽能電池的光伏參數 1
1-3 太陽能電池的發展歷史簡介 6
1-4 染料敏化太陽能電池的工作原理 8
1-5 釕錯合物分子設計 11
1-5-1 均配型(Homoleptic)釕錯合物染料 12
1-5-2 異配型(Heteroleptic)釕錯合物染料 14
1-6 釕錯合物染料設計相關文獻探討 30
1-6-1 含Selenophene單元之染料 30
1-6-2 含Thienothiophene之染料 36
1-7研究動機 39
第二章實驗部分 41
2-1 實驗藥品 41
2-2 中間產物之結構與簡稱 45
2-3 最終產物之結構與簡稱 48
2-4 儀器分析與樣品製備 49
2-5 合成流程及實驗 54
2-5-1 雙牙輔助配位基Ligand-20之合成 54
2-5-2 雙牙固著配位基Ligand-53-ester之合成 58
2-5-3 雙牙固著配位基Ligand-55-ester之合成 64
2-5-4 釕錯合物CYC-53之合成 74
2-5-5 釕錯合物CYC-55之合成 79
2-6 元件組裝與光電轉換效率量測 83
2-6-1 DSCs元件組裝流程 83
2-6-2 DSCs光電轉換效率量測系統 86
第三章結果與討論 88
3-1 合成相關探討 88
3-1-1 雙牙固著配位基Ligand-53-ester合成所遇到之問題與解決方法 88
3-1-2 雙牙固著配位基Ligand-55-ester合成所遇到之問題與解決方法 93
3-2 釕錯合物染料純化、結構鑑定與光物理性質探討 101
3-2-1 釕錯合物染料純化、結構鑑定相關討論 101
3-2-2 釕錯合物的光物理性質探討 116
3-3 釕錯合物染料的電化學性質與前置分子軌域位能 120
3-4 釕錯合物染料敏化電池元件的性能探討 124
第四章結論 127
參考文獻 128
附錄 136
附錄1：雙牙固著配位基Ligand-55(Te)-ester之合成 172
附錄2：雙牙固著配位基Ligand-58-ester之合成 179
附錄3：雙牙固著配位基Ligand-55(Te)-ester合成所遇到之問題 190
附錄4：釕錯合物CYC-58合成所遇到之問題 196

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指導教授

陳家原(Chia-Yuan Chen)

審核日期

2023-8-9

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