吡咯[3, 4-b]吲哚雜環的合成研究與在光敏太陽能電池染料的應用

周怡滿(Yi-Man Chou)

指導教授 ： 沙晉康

國立清華大學/理學院/化學系/碩士(2009年)

摘要

本篇論文運用本實驗室所開發的「丙二酸酯脫去反應」（retro-malonate addition reaction），以吡咯吲哚做為共軛架橋連接不同的電子受體和扮演電子予體的氰基乙酸，成功合成了一系列吡咯[3,4-b] 吲哚衍生物IP1~IP4的有機染料分子。並對此系列分子進行光譜、光學元件和電化學等物理性質之測試，應用為光敏太陽能電池之染料。由吸收光譜可知IP1~IP4皆有π-π* transition和charge transition，最大吸收峰和消光係數數值為：IP1（446nm, ε = 22650 M-1 cm-1）、IP2（448nm, ε = 15420 M-1 cm-1）、IP3（451nm, ε = 15394 M-1 cm-1）、IP4（432nm, ε = 9804 M-1 cm-1）。電化學測試結果，四個染料LUMO在- 2.4 eV~ - 2.8 eV，HOMO在- 4.9 eV ~ - 5.2 eV，就其能階表現，皆可以應用於光敏太陽能電池的染料。理論計算結果顯示此系列的共軛性和平面性不足，造成電荷分散能力較不佳。光電轉換效率最高的為IP1（η = 1.70%, Jsc = 4.69 mAcm–2, Voc = 0.51 V, ff = 0.71），IPCE可見光最大吸收波長處轉換率為45%；IP2~IP4效率皆在1％左右，IPCE的可見光最大吸收波長處轉換率為30%。。

關鍵字

吡咯[3, 4-b]吲哚雜環 ； 光敏太陽能電池染料

並列摘要

Using our method of retro-malonate addition reaction, we have synthesized series of dipolar dyes, IP1~IP4, containing pyrrolo[3,4-b] indole conjugate spacers between arylamine donor and the 2-cyanoacrylic acid acceptor. These exhibited both π-π* and charge-transfer transition in the absorption spectra. The maximum absorption peak of IP1~IP3 located at 446nm~451nm, and IP4 was at 432nm which revealed blue shift. By differential pulse voltammetry measurements, we observed that the lowest unoccupied molecular orbital (LUMO) of these dyes located between -2.4 eV and -2.8 eV and the highest occupied molecular orbital (HOMO) located between -4.9 eV and -5.2 eV. According to the HOMO and LUMO potentials, we believed that these compounds could be used on dye-sensitized solar cells. The results from quantum computation indicated that poor planarity and insufficient conjugation diminished the electron-transfer of these dyes. Dye-sensitized solar cells using these materials as the sensitizers exhibited conversion efficiencies ranging from 1.00% to 1.70%.

並列關鍵字

Pyrrolo [3,4-b] indole ； Dye-Sensitized Solar Cells

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