【摘要】：支化大分子有機(jī)光電材料不僅同時(shí)具有小分子和聚合物材料的優(yōu)點(diǎn),而且具有獨(dú)特的光電特性,使其有機(jī)光電器件、生物傳感(自組裝調(diào)控?zé)晒夤舱衲芰哭D(zhuǎn)移)等方面的應(yīng)用得到了人們廣泛的關(guān)注。作為界面材料,其在光捕獲系統(tǒng)中對(duì)自組裝調(diào)控的給受體之間的熒光共振能量轉(zhuǎn)移(FRET)為共軛材料光電轉(zhuǎn)化機(jī)制的研究提供了不錯(cuò)的思路;在有機(jī)光電器件的研究中其主要具有以下作用:(1)調(diào)節(jié)電極功函數(shù),減少界面缺陷,降低電荷收集勢(shì)壘;(2)在電極的界面選擇性的傳輸和收集電荷;(3)調(diào)控器件的相對(duì)極性;(4)影響界面薄膜形貌進(jìn)而改善表面性能;(5)減少漏電流的產(chǎn)生;(6)作為光學(xué)間隔層等。同樣,支化大分子有機(jī)光電材料在有機(jī)電致發(fā)光二極管(OLEDs)中作為發(fā)光層,有機(jī)太陽能電池中作為活性材料以及在機(jī)激光領(lǐng)域作為增益介質(zhì)都得到了廣泛的關(guān)注和應(yīng)用。為了系統(tǒng)的研究支化大分子在光捕獲系統(tǒng)中熒光共振能量轉(zhuǎn)移機(jī)制,進(jìn)而通過合理的分子設(shè)計(jì)提高光電器件性能,在本課題組前期工作的基礎(chǔ)上,設(shè)計(jì)合成了一系列支化大分子有機(jī)光電材料,系統(tǒng)的研究了水/醇溶性支化大分子界面材料在光捕獲系統(tǒng)中的自組裝調(diào)控的熒光共振能量轉(zhuǎn)移機(jī)制、水/醇溶性支化大分子界面材料對(duì)于器件界面性能的改善、支化大分子多臂結(jié)構(gòu)功能材料在OLEDs和有機(jī)激光領(lǐng)域的應(yīng)用。首先,通過Suzuki偶聯(lián)設(shè)計(jì)合成了以三苯胺為核,三苯胺芴基為臂的支化大分子;Stille多重偶聯(lián)設(shè)計(jì)合成了以噻吩苯噻唑?yàn)楹巳桨窞闃蜍虨楸鄣闹Щ蠓肿雨庪x子(4FNaT)、中性離子(4FNOHT)以及陽離子(4FNBrT)界面材料,并研究了其光物理特性和電化學(xué)特性,發(fā)現(xiàn)離子基團(tuán)的不同對(duì)材料的光物理特性及其電化學(xué)特性沒有明顯的影響,則主要是由其共軛骨架結(jié)構(gòu)所決定的。其次,系統(tǒng)的研究了支化大分子4FNaT、4FNOHT以及4FNBrT界面材料作為受體在光捕獲系統(tǒng)中的由自組裝調(diào)控的熒光共振能量轉(zhuǎn)移機(jī)制,研究發(fā)現(xiàn)陰陽離子間由于強(qiáng)的靜電作用在低濃度(10-6 M)狀態(tài)下能夠形成自組裝結(jié)構(gòu)調(diào)控給受體間熒光共振能量轉(zhuǎn)移,然而在陽-中性離子以及陽-陽離子之間則沒有這種現(xiàn)象。我們進(jìn)一步的通過動(dòng)態(tài)光散射(DLS)和透射電子顯微鏡(TEM)證明了這一結(jié)論。最后,設(shè)計(jì)合成了以螺芴和芘為核的四臂支化大分子材料SF-PyF和Py-PyF,研究了其在有機(jī)電致發(fā)光二極管和有機(jī)激光領(lǐng)域的應(yīng)用。兩種材料均表現(xiàn)出較低的ASE閾值,其中SF-PyF為6.6μJ/cm2(1.3 kW/cm2),Py-PyF為5.4μJ/cm2(1.1 kW/cm2),其均具有很好的熱穩(wěn)定性和水氧穩(wěn)定性。
[Abstract]:Branched macromolecular organic optoelectronic materials not only have the advantages of small molecules and polymer materials, but also have unique optoelectronic properties, which make them organic optoelectronic devices. The application of biosensor (self-assembly regulated fluorescence resonance energy transfer) has been paid more and more attention. As an interface material, the fluorescence resonance energy transfer (FRET) between the self-assembled and regulated receptors in the optical capture system provides a good idea for the study of the photoelectric conversion mechanism of conjugated materials. In the research of organic optoelectronic devices, the main functions are as follows: (1) adjusting the work function of the electrode, reducing the interface defect and reducing the charge collection barrier; (2) transferring and collecting charge selectively at the interface of the electrode; (3) controlling the relative polarity of the device; (4) influencing the morphology of the interface film to improve the surface performance; (5) reducing the leakage current generation; (6) acting as the optical spacer layer. In the same way, branched macromolecular organic optoelectronic materials are widely used as light-emitting layers in organic light-emitting diode (OLEDs), organic solar cells as active materials and laser as gain media. In order to systematically study the mechanism of fluorescence resonance energy transfer of branched macromolecules in the optical capture system, and then improve the performance of optoelectronic devices through reasonable molecular design, based on the previous work of our group, A series of branched macromolecular organic optoelectronic materials were designed and synthesized. The fluorescence resonance energy transfer mechanism of self-assembly of water / alcohol-soluble branched macromolecular interface materials in photocapture system was studied systematically. The interface properties of water / alcohol-soluble branched macromolecules are improved. The applications of branched macromolecular Dobby functional materials in the field of OLEDs and organic laser are discussed. Firstly, the branched macromolecules with trianiline as nucleus and trianiline fluorene as arm were synthesized by Suzuki coupling design. The interface materials of branched macromolecular anions (4FNaT), neutral ions (4FNOHT) and cations (4FNBrT) with thiophene benzothiazole as nuclear trianiline as bridge fluorene were designed and synthesized by Stille multiple coupling. The photophysical and electrochemical properties of these materials were studied. It is found that the different ionic groups have no obvious influence on the photophysical and electrochemical properties of the materials, but are mainly determined by their conjugated skeleton structure. Secondly, the self-assembled fluorescence resonance energy transfer mechanism of the branched macromolecule 4FNaTN 4FNOHT and the interface material of 4FNBrT as the receptor in the photocapture system is studied systematically. It has been found that due to strong electrostatic interaction between anion and anion at low concentration (10-6 M), self-assembled structure can be formed to regulate the fluorescence resonance energy transfer between the receptors. However, there is no such phenomenon between cationic and cationic ions. We further prove this conclusion by dynamic light scattering (DLS) and transmission electron microscopy (TEM). Finally, SF-PyF and Py-PyF, with spirofluorene and pyrene as nuclei were designed and synthesized to study their applications in organic light-emitting diodes (OLEDs) and organic lasers. The two materials showed low ASE threshold, including SF-PyF of 6.6 渭 J/cm2 (1.3 kW/cm2) and Py-PyF of 5.4 渭 J/cm2 (1.1 kW/cm2). Both of them had good thermal stability and hydrothermal stability.
【學(xué)位授予單位】：南京郵電大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TN383.1;O621.2

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