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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題名:	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
作者:	何睿哲;Ho, Jui-Che
貢獻者:	化學學系
關鍵詞:	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
日期:	2022-09-26
上傳時間:	2022-10-04 11:01:39 (UTC+8)
出版者:	國立中央大學
摘要:	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%。;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.
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