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標題: | 合成與探索發色團光物理性質在離子遷移和激發態分子內質子轉移之應用 Synthesis and Exploitation of Photophysics of Chromophores and Applications in Ion-Migration and Excited State Intramolecular Proton Transfer |
作者: | 楊雨軒 Yu-Hsuan Yang |
指導教授: | 周必泰 Pi-Tai Chou |
關鍵字: | 鈣鈦礦太陽能電池,兩性離子鈍化,供體-受體添加劑,平衡電荷傳輸,增強穩定性,ESIPT,質子轉移,兩性離子,離子遷移,電荷轉移,溶劑化顯色,多氫鍵腔體,OLED發射器,基於ESIPT的TADF,主/客系統,複合物, perovskite solar cell,zwitterionic passivation,donor−acceptor additives,balanced charge transport,enhanced stability,ESIPT,proton transfer,zwitterion,ion-migration,charge transfer,solvatochromism,multiple hydrogen bond cavity,OLED emitter,ESIPT-based TADF,host/guest system,complex, |
出版年 : | 2023 |
學位: | 博士 |
摘要: | 摘要-第一部分
倒置鈣鈦礦太陽能電池(PSCs)因其微弱的遲滯現象和低溫製造工藝而引起了廣泛關注。但是倒置PSCs的效率仍然不如商業化的矽太陽能電池好。而且較差的穩定性是實現PSCs商業化的主要障礙之一。在本文中我們設計並合成了一系列新的兩性離子作為邊界調節劑,分別以R,R-二苯氨基和嘧啶-(CH2)n-磺酸鹽為電子供體和受體,並有系統地研究了它們在PSCs中相關的界面性質。詳細的物理和光電研究證實,這些兩性離子具有四合一的功能,暨平衡電荷載體傳輸、抑制不太協調的Pb2+缺陷、增強防潮性和減少離子遷移。儘管由特定的鈍化分子改善單一功能的相關研究已有被報告,但同時調節電荷轉移平衡和其他三種功能的策略仍尚未被開發。結果表明這種策略對PSCs的性能有全方位的改進。在所有兩性離子中,OMeZC3表現出較為優異的性能,其平衡空穴/電子遷移率鈣鈦礦含量降至0.91,相應PSCs的功率轉換效率(PCE)高達23.15%,且無滯後現象,為倒置結構中的最佳PSCs之一。更重要的是,OMeZC3修飾的PSCs表現出出色的長期穩定性,在 80% 相對濕度下儲存35天後幾乎仍保持其初始PCE值。 摘要-第二部分 我們在此報告分子3-(4λ2-嗎啉-3-基)-4'-(吡啶-4-基)-[1,1'-聯苯]-4-醇吡啶-4-基-[1,1'-聯苯]-4 -ol, (6c)的設計和合成,探測其激發態分子內質子轉移(ESIPT)性質。6c顯示幾乎與溶劑無關的吸收光譜,而發射峰波長從環己烷中的370 nm急劇紅移到CH2Cl2中的500 nm和CH3CN中的545 nm。峰值波數與溶劑極性的線性Lippert 圖無法擬合表面上看起來的溶劑化變色效應,此外經計算得出吸收到發射之間的0-0起點值大至分別在600 cm-1(在CH2Cl2中)和800 cm-1(在CH3CN中),而它在環己烷中幾乎重疊。通過改變環己烷/ CH2Cl2的比率來連續調節介電常數,將發射從藍色(100% 環己烷)到白色(雙發射)再到黃色(100% CH2Cl2)有著顯著的變化。相比之下,在甲氧基衍生物5cOMe表現有輕微的溶劑化變色變化出規則的發射,發射從330(環己烷)到350(CH2Cl2)再到390 nm(CH3CN)只有輕微的溶劑化變色變化。結果使我們得出6c中有激發態分子內質子轉移(ESIPT)的發生,這顛覆了大多數在非極性溶劑中發生質子轉移的傳統ESIPT系統,6c的ESIPT可以隨著溶劑極性的增加而從“關閉”到“開啟”。6c中的ESIPT的耦合電荷轉移特性使這一非常規結果合理化,其中ESIPT中兩性離子的形成起著關鍵作用。兩性離子互變異構體及其誘導的電荷轉移會產生大的偶極變化,這需要大的介電穩定性並且在非極性環境中是不利的。3-(嗎啉代甲基)-[1,1':4',1''-三聯苯]-4-醇 (6d)和2-(嗎啉代甲基)-4-(吡啶-4-基)苯酚(6a),分別作為沒有電子轉移的兩性離子型ESIPT和6c類似物但沒有橋接苯環的參考。在實驗上,6d和6c在非極性溶劑中表現出開和關的ESIPT,並且可以通過兩性離子ESIPT耦合電荷轉移很好地合理化。因此,該結果設置了具有通用機制的非常規ESIPT開啟(非極性介質)到關閉(極性介質)開關的範例。 摘要-第三部分 在此報導我們設計並合成的具有多氫鍵結合位點的剛性腔體7,8,10,11,18,20-六氫吡啶並[3',2':6,7]吲哚[3,2-c]吡啶並[3' ,2':6,7]吲哚[2,3-h]吖啶-2,16-二胺(NH2-DPI)。我們通過將客體2,4-二氨基-6-苯基-1,3,5-三嗪(DCPT)引入NH2-DPI並通過氫鍵鍵結生成NH2DPI-DCPT複合物的方式,將之設計為基於ESIPT的TADF發射體。接著再利用理論計算進一步證實了我們的想法,與NH2-DPI和DCPT相比,NH2DPI-DCPT複合物的穩定能量為-14.5 kcal/mol,這歸因於吡咯與DCPT中的N-H分別形成的2.77 Å和2.30 Å的弱氫鍵。此外該複合物可導致分子軌道分離,分別將HOMO定位在主體上,LUMO分佈在客體上。將NH2-DPI與NH2DPI-DCPT複合物相比,發射光由藍光紅移到黃光並且溶解度和熒光量子產率增加。因此我們認為NH2DPI-DCPT複合物作為OLED發射體具有巨大的潛力。 Abstract-Part I Inverted perovskite solar cells (PSCs) have attracted intense attention because of their insignificant hysteresis and low-temperature fabrication process. However, the efficiencies of inverted PSCs are still inferior to those of commercialized silicon solar cells. Also, the poor stability of PSCs is one of the major impedances to commercialization. Herein, we rationally designed and synthesized a new series of electron donor (R,R-diphenylamino) and acceptor (pyridimium-(CH2)n-sulfonates) zwitterions as a boundary modulator and systematically investigated their associated interface properties. Comprehensive physical and optoelectronic studies verify that these zwitterions provide a four-in-one functionality: balancing charge carrier transport, suppressing less-coordinated Pb2+ defects, enhancing moisture resistance, and reducing ion migration. Although each functionality may have been reported by specific passivating molecules, a strategy that simultaneously regulates the charge-transfer balance and three other functionalities has not yet been developed. The results are to make an omnidirectional improvement of PSCs. Among all zwitterions, 4-(4-(4-(di-(4-methoxylphenyl)amino)phenyl)propane-1-ium-1-yl)butane-1-sulfonate (OMeZC3) optimizes the balance hole/electron mobility ratio of perovskite to 0.91, and the corresponding PSCs demonstrate a high power conversion efficiency (PCE) of up to 23.15% free from hysteresis, standing out as one of the champion PSCs with an inverted structure. Importantly, the OMeZC3-modified PSC exhibits excellent long-term stability, maintaining almost its initial PCE after being stored at 80% relative humidity for 35 days. Abstract-Part II We report herein the design and synthesis of molecule 3-(4λ2-morpholin-3-yl)-4'-(pyridin-4-yl)-[1,1'-biphenyl]-4-olpyridin-4-yl-[1,1'-biphenyl]-4-ol, 6c to probe its excited-state intramolecular proton transfer (ESIPT) property. 6c shows nearly solvent independent absorption spectra, while the emission peak wavelength red shifts drastically from 370 nm in cyclohexane to 500 nm in CH2Cl2 and 545 nm in CH3CN. The seemly solvatochromic effect cannot be fit by the linear Lippert’s plot for peak wavenumber versus the solvent polarity. Moreover, the 0-0 onset between absorption to emission is calculated to be as large as 600 cm-1 (in CH2Cl2) and 800 cm-1 (in CH3CN) whereas it is nearly overlapped in cyclohexane. Continuously tuning the dielectric constant by varying cyclohexane/ CH2Cl2 ratio, the emission changes remarkably from blue (100% cyclohexane), white (dual emission) and yellow (100% CH3CN). In comparison, its methoxyl derivative 5cOMe exhibits regular emission with slight solvatochromic shift from 330 (cyclohexane), 350 (CH2Cl2) to 390 nm (CH3CN). The results lead us to conclude the occurrence of excited-state intramolecular proton transfer (ESIPT) in 6c. Subverting most of conventional ESIPT systems where proton transfer takes place in nonpolar solvents, ESIPT of 6c is “off” and then is turned “on” as increasing the solvent polarity. This unconventional result is rationalized by ESIPT coupled charge transfer in 6c where zwitterion formation amid ESIPT plays a key role. The zwitterionic tautomer, together with its inducing charge transfer, creates large dipolar changes that requires large dielectric stabilization and is unfavourable in nonpolar environment. The generality of this mechanism is further supported by 3-(morpholinomethyl)-[1,1':4',1''-terphenyl]-4-ol (6d) and 2-(morpholinomethyl)-4-(pyridin-4-yl)phenol (6a), which, respectively, serves as a reference for the zwitterionic-type ESIPT without electron transfer, and an analogue of 6c but without the bridging phenyl ring. Experimentally, 6d and 6a show on- and off- ESIPT in nonpolar solvent and can be well rationalized by the zwitterionic ESIPT coupled charge transfer. The results thus set a paradigm of unconventional ESIPT on(nonpolar medium)-to-off(polar medium) switch with a generalized mechanism. Abstract-Part III We reported herein designed and synthesized a multiple hydrogen-binding sites rigid cavity 7,8,10,11,18,20-hexahydropyrido[3',2':6,7]indolo[3,2-c]pyrido[3',2':6,7]indolo [2,3-h]acridine-2,16-diamine (NH2-DPI). NH2-DPI was designed as an ESIPT-based TADF emitter by introducing the guest 2,4-diamino-6-phenyl-1,3,5-triazine (DCPT) into NH2-DPI and generating the NH2DPI-DCPT complex through hydrogen bonding. Our ideas are further confirmed by theoretical calculations, the stabilization energy is -14.5 kcal/mol for the generation of the NH2DPI-DCPT complex when compare to NH2-DPI and DCPT, which is ascribed to the weak hydrogen bonds of 2.77 Å and 2.30 Å for NH in pyrrole and DCPT, respectively. Furthermore, the complex gives rise to molecular orbital separation with HOMO and localization in the host and LUMO distribution on the guest, respectively. Compared to NH2-DPI after the NH2DPI-DCPT complex was generated, the emission red-shift from blue to yellow, and the solubility and fluorescence quantum yield increased. Therefore, we considered the NH2DPI-DCPT complex has great potential as an OLED emitter. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/90702 |
DOI: | 10.6342/NTU202303516 |
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顯示於系所單位: | 化學系 |
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