具有氮氧化吡啶錨定基推拉電子BODIPY染料之合成與鑑定及其在染料敏化太陽能電池之應用

Abstract

本論文第一部分主要目的是合成BODIPY ( 4,4- difluoro-4-bora-3a, 4a-diaza-s -indancene ) 衍生物，其結構設計採Donor-π-Acceptor ( D-π-A ) 共軛系統，引進 新穎的拉電子基團N-氧化吡啶，以BODIPY 為π-conjugation system，在BODIPY 之β 位取代上分別與bis-(4-methoxy-phenyl)-phenyl-amine unit、具有長碳鏈的 bis-(4- ethylhexyl oxy-phenyl)-phenyl-amine unit 二種不同之推電子基鍵結以及不 同位置的拉電子基團N-氧化吡啶。 在第二部分，將合成出來的染料進行鑑定與物性分析。鑑定化合物方式主要以 核磁共振光譜儀( NMR )、質譜儀( Mass )量測;在光物理量測方面也有深入的探討， 藉由紫外-可見光光譜儀測量化合物之吸收光譜圖、使用循環電位儀與光電子光 譜儀測量與計算得知化合物之HOMO 和LUMO 能階、利用DFT 理論計算出染 料分子最穩定之結構以及HOMO 與LUMO 能階分子軌域的分佈與其相對應 之能階，並且模擬染料在激發態時電子躍遷之情形；最後將染料利用液滴式 (dropping)與浸泡式(dipping)吸附在二氧化鈦上並應用於DSSCs 探討其元件表現 性能，而染料以液滴式吸附大幅改善染料之吸附能力，進而提升元件效率，其中 EHPTTpN 具有最高之能量轉換效率( Jsc = 9.99mA / cm2, Voc = 0.63 V, FF = 0.58, η = 3.65 % )。

In this thesis’s first part , we pay attention to synthesize the derivatives of BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s- indancene).We use conjugated system of Donor-π-Acceptor (D-π-A) and new acceptor pyridine-N-oxide on the design. BODIPY play the role of π-conjugation system, bounding with different donor substituent such as bis-(4-methoxy-phenyl)-phenyl-amine unit , bis-(4- ethylhexyl oxy-phenyl)-phenyl-amine unit, and acceptor substituent is pyridine-N-oxide which has a different position on the β-substituent of BODIPY. At second part, we apply these dye in dye sensitized solar cells. These compounds are characterized by 1H NMR, 13C NMR, mass spectrometry, their absorption spectrum was estimated by UV-visible spectrometer, and their energy level of HOMO and LUMO in solution and adsorb on TiO2 were estimated by cyclic voltammetry and low-energy photoelectron spectrometer, respectively, use density functional theory and time-dependent density functional theory to imitate the orbital and energy levels of HOMO and LUMO.Finally,we try to adsorb these dyes on TiO2 by using dip and drop method and apply in DSSCs. And we find that using the drop method improves these dye adsorption. The highest power conversion efficiency in this thesis is EHPTTpN ( Jsc = 9.99mA / cm2, Voc = 0.63V, FF = 0.58, η = 3.65% ).