吸收達近紅外光釕錯合物染料的合成並應用於染料敏化太陽能電池

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何睿哲(Jui-Che Ho) 查詢紙本館藏

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論文名稱

吸收達近紅外光釕錯合物染料的合成並應用於染料敏化太陽能電池

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至系統瀏覽論文 (2025-9-26以後開放)

摘要(中)

染料敏化太陽能電池(Dye sensitized solar cells, 簡稱DSCs)大部分所使用的釕金屬染料其吸收波段大部份在可見光區，若是能增加染料在近紅外光區波段的吸收就能有更多的光子被利用，提高元件光電轉換效率。本研究將具有重原子效應的磷作為輔助配位基的配位原子以增加染料在近紅外光區的吸收。我們以羧酸三芽聯吡啶作為固著配位基，輔助配位基則有Triphenylphosphine、triethylphosphite、triphenylphosphite、2-Diphenylphosphine-5-hexylthiophene、2-Diphenylphosphine-5-hexylthieno[3,2-b]thiophene、4-Diphenylphosphine-triphenylamine等6個、合成出PPh、POEt 、POPh、PTR、PTTR及PTPA六個染料。染料的吸收波段皆涵蓋紫外光區至近紅外光區，起始吸收波長皆約為850 nm，染料的Highest occupied molecular orbital (HOMO) 能階皆坐落於0.88 V至0.71 V與碘電解質的氧化還原電位(0.4 V)還有至少0.3 V的差距，因此再以含有強推電子能力的矽(如1,2-Bis(dimethylsilyl)benzene及Triethylsilane)作為輔助配位基，矽為配位點可以提高染料的HOMO能階，然而在嘗試各種反應條件後含矽之化合物無法與釕金屬進行鍵結，推測可能是矽為sp3的混成軌域其上的烷基會與固著配位基產生空間立體障礙所導致。6個染料中以POEt所敏化之元件有最高的光電轉換效率為6.38%。

摘要(英)

Most of the dye molecules used in Dye sensitized solar cells (DSCs) absorb only visible light. One of the strategy to enhance the photovoltaic performance of the DSCs is to red-shift the absorption of the sensitizer. In this study we used the ancillary ligand containing phosphorus, which has heavy atom effect, to enhance the absorption of the dye in near-infrared region. Six ruthenium complexes (PPh、POEt、POPh、PTR、PTTR, and PTPA) using [2,2′:6′,2′′-terpyridine]-4,4′,4′′-tricarboxylic acid as the anchoring ligand and Triphenylphosphine、triethylphosphite、triphenylphosphite、2-Diphenylphosphine-5-hexylthiophene、2-Diphenylphosphine-5-hexylthieno[3,2-b]thiophene as am ancillary ligand. The onset absorption of the six dyes is all longer than 850 nm. The HOMO (highest occupied molecular orbital) level at 0.88 V ~ 0.71 V, can be reduced by iodine redox couple when oxidized. The highest power conversion efficiency of 6.38% was achieved by POEt dye. The HOMO of the six dyes are much lower than the redox potential of the iodine electroiyte. Therefore silicon containing ligands, such as 1,2-Bis(dimethylsilyl)benzene and Triethylsilane were used to replace phorphine ligand to rise the HOMO of the dye molecule. Unfortunately, maybe due to the steric effect, we are not able to use silicon as a coordination site to the ruthenium metal center.

關鍵字(中)

★ 三重態吸收
★ 紅外光吸收
★ 釕錯合物染料
★ 染料敏化太陽能電池

關鍵字(英)

論文目次

摘要 II
Abstract II
圖摘要 III
謝誌 IV
目錄 V
圖目錄 VIII
表目錄 XI
第一章、緒論 1
1-1、前言 1
1-2、太陽能電池的發展與分類 1
1-3、染料敏化太陽能電池的架構、工作原理與光伏參數 3
1-3-1、染料敏化太陽能電池的架構 3
1-3-2、染料敏化太陽能電池的工作原理 6
1-3-3、染料敏化太陽能電池的光伏參數 9
1-4、染料敏化太陽能電池於室內弱光環境下有高的光電轉換效率 14
1-5、染料敏化太陽能電池用的染料種類 15
1-6、釕金屬錯合物染料(Ruthenium Metal Complex) 18
1-7、研究動機 32
第二章、實驗部分 33
2-1、實驗藥品 33
2-2、產物之結構、簡稱與分子量 36
2-3、實驗步驟 41
2-3-1、Me3tctpy的合成 41
2-3-2、1,2-Bis(dimethylsilyl)benzene的合成 44
2-3-3、2-Diphenylphosphine-5-hexylthiophene的合成 45
2-3-4、2-Diphenylphosphine-5-hexylthieno[3,2-b]thiophene的合成 48
2-3-5、4-Diphenylphosphine-triphenylamine的合成 53
2-3-6、Me3tctpy-Ru-Cl3的合成 55
2-3-7、PPh的合成 56
2-3-8、POPh的合成 57
2-3-9、POEt的合成 59
2-3-10、PTR的合成 60
2-3-11、PTTR的合成 62
2-3-12、PTPA的合成 63
2-4、儀器分析與樣品製備 65
2-4-1、核磁共振光譜儀(Nuclear Magnetic Resonance, NMR) 65
2-4-2、紫外光/可見光吸收光譜儀 (Ultraviolet Visible Spectrophoto-meter, UV/Vis Spectrophotometer) 66
2-4-4、光致螢光光譜儀 (Photoluminescence Spectrometer) 67
2-4-3、電化學分析儀 (Electrochemical Analyzer) 68
第三章、結果與討論 70
3-1、染料合成途徑與結構鑑定 70
3-2、光學性質 74
3-3、電化學性質 79
3-4、理論計算 86
3-5、元件數據 89
3-6、含矽的輔助配位基與釕金屬進行配位之反應探討 93
第四章、結論 103
參考文獻 104
附錄 113

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指導教授

吳春桂(Chun-Geuy Wu)

審核日期

2022-9-26

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