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Title: | 以異靛藍衍生物為核心之有機光電材料 設計合成與應用 Design, Synthesis, and Application of Isoindigo Derivative-based Organic Optoelectronic Materials |
Authors: | 廖御婷 Yu-Ting Liao |
Advisor: | 汪根欉 Ken-Tsung Wong |
Keyword: | 異靛藍,非富勒烯受體,有機光偵測器,有機場效電晶體,分子間電荷轉移複合物, Isoindigo,Non-fullerene acceptors,Organic photodetector,Organic field-effect transistor,Intermolecular charge transfer complex, |
Publication Year : | 2022 |
Degree: | 碩士 |
Abstract: | 有機小分子半導體材料因為其成本低廉、可撓曲、易純化、合成再現性高等優 點,已被廣泛利用於各種光電材料領域中。近年來,異靛藍 (isoindigo) 與其衍生 物由於本身為具有良好的電荷傳輸能力、優異的拉電子特性,且容易製備等優勢, 已經在有機光偵測器與有機場效電晶體的應用上,展現出令人驚豔的表現。 本論文的第一部分是以具有拉電子性質的異靛藍為核心,並於兩端修飾上具有 強推電子能力的三苯胺衍生物,建構一系列D-A-D 架構的有機小分子,ISO-PNT、 ISO-SNT、TISO-PNT、TISO-SNT,並應用於有機半導體元件中。隨著分子置換 上噻吩 (thiophene) 的數量增加,一方面使醌型 (quinoid) 性質增加,造成 HOMO LUMO 間的能隙縮小,使分子的最大吸收波長紅移,另一方面也讓分子有更好的 共平面性,從而縮短分子之間的距離,有利於電荷傳輸。其中,以 ISO-PNT 作為 電子予體搭配 PC71BM 作為吸光的主動層應用於有機光偵測器上,具有最優異的 表現,獲得高達 1.8x1013 Jones 的偵測效率 (detectivity);而在做為有機場效電晶體 的半導體層中,以TISO-PNT 獲得最好的元件表現,電洞傳輸效率來到0.89 cm2/Vs。 第二部分,我們以第一部分的四個分子為基礎,在受體中間引入噻吩並[3,2-b] 噻吩 (thienothiophene),合成出共軛性質更為提升的四個 IQTT 系列分子 (IQTT- PNT、IQTT-SNT、ISQTT-PNT、ISQTT -SNT),使其吸收更為紅移。進行三元光 伏電池的應用測試,其中以PM6 : Y6 搭配 IQTT-PNT (1: 1.2: 0.1) 的元件JSC 高達 15.2 (mA/cm2),具有做為近紅外光有機光偵測器的潛力。由於分子溶解度不佳,應 用於有機場效電晶體,造成元件效率差。我們嘗試增加分子的碳鏈,合成出 IQTT- nBuPNT,可以改善溶解度,希望能開發出更高效率的有機小分子場效電晶體材料。 第三部分是以異靛藍衍生物為核心設計出三個非富勒烯受體 (BTICN-IB、 BTTICN-EH 、NSSN-CN),使供體能階的搭配不再受到過往富勒烯受體的限制。 此外,利用異靛藍衍生物消光係數高的特性,使其可以更有效利用太陽能光子。以 非常低 LUMO 能階的 BTICN-IB 為受體,並選用高 HOMO 的 DTA-DTPZ 為供體,在基態下製作共混膜,形成能隙非常窄的分子間電荷轉移複合物,使吸收紅移 到 989 nm 且消光係數極高 (4163 M-1cm-1),對於以有機小分子為設計基礎的紅外 光有機光偵測器材料提供了新的概念。 Small-molecule organic semiconductor materials (OSCs) have been widely used in various optoelectronic applications due to their advantages of low cost, flexibility, easy purification, and high synthetic reproducibility. In recent years, 3-(2-hydroxy-1H-indol- 3-yl)indol-2-one (isoindigo) and its derivatives have been widely applied to the development of organic photodetectors (OPDs) and organic field-effect transistors (OFETs), demonstrating great performance in charge transportability and electron- withdrawing properties for optoelectronic applications. In the first part of this thesis, isoindigo was selected as the core with strong electron- withdrawing ability (A) and was end-capped with triphenylamine derivatives with strong electron-donating properties (D) to construct a series of D-A-D configured small molecules ISO-PNT, ISO-SNT, TISO-PNT, and TISO-SNT for organic optoelectronic applications. As the number of thiophenes in the molecules increases, the enhanced quinoid characters reduces the energy gap between the HOMO and LUMO, resulting in a red-shift in the maximum absorption wavelength of the molecules. In addition, the enhancement of coplanarity shortens the distance between molecules, which is conducive to charge transport. Among them, the use of ISO-PNT and PC71BM blend as the light- absorbing active layer in OPDs displayed the highest detectivity of up to 1.8x1013 Jones. For the semiconductor layers of OFETs, TISO-PNT achieved the best device IV performance, where the hole transporting mobility reached to 0.89 cm2/Vs. In the second part, in order to further extend the conjugation, thieno[3,2-b]thiophene was incorporated as the π-bridge in the four molecules reported in the first part to afford four IQTT-based molecules, IQTT-PNT, IQTT-SNT, ISQTT-PNT, and ISQTT-SNT with bathochromic shift absorptions. When IQTT-PNT was incorporated as the third component in the ternary active layer, the device comprising PM6: Y6: IQTT-PNT (1: 1.2: 0.1) reached a JSC as high as 15.2 mA/cm2, demonstrating the potential in organic photovoltaics (OPVs). Yet, due to the poor solubility of these molecules, the application of OFETs led to unsastisfactory device efficiencies. Therefore, long carbon chains were introduced onto IQTT-PNT to afford IQTT-nBuPNT, where the solubility of the molecule can be improved, that can be used to develop more efficient OFET device. The third part is the design and characterization of three new non-fullerene acceptors based on isoindigo derivatives, BTICN-IB, BTTICN-EH, and NSSN-CN, where the restrictions of choice in electron donors can be lifted without the use of fullerene based acceptors. In addition, the high extinction coefficients of isoindigo derivatives can lead to more efficient utilization of solar photons. By using a deep LUMO energy level molecule BTICN-IB as the acceptor and a high HOMO energy level molecule DTA- DTPZ as the donor, a blended film was fabricated to form an intermolecular charge transfer complex in the ground state with a very narrow energy gap. The red-shifted V maximum absorption of 989 nm and the extremely high extinction coefficient of 4163 M-1 cm-1 provided a new design concept for developing organic small molecule- based near-infrared organic photodetector materials. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/92024 |
DOI: | 10.6342/NTU202202338 |
Fulltext Rights: | 同意授權(全球公開) |
Appears in Collections: | 化學系 |
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ntu-111-1.pdf Until 2024-09-05 | 18.06 MB | Adobe PDF |
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