支化大分子有机光电材料的设计合成及性能研究
发布时间：2019-01-21 16:26
【摘要】：支化大分子有机光电材料不仅同时具有小分子和聚合物材料的优点,而且具有独特的光电特性,使其有机光电器件、生物传感(自组装调控荧光共振能量转移)等方面的应用得到了人们广泛的关注。作为界面材料,其在光捕获系统中对自组装调控的给受体之间的荧光共振能量转移(FRET)为共轭材料光电转化机制的研究提供了不错的思路;在有机光电器件的研究中其主要具有以下作用:(1)调节电极功函数,减少界面缺陷,降低电荷收集势垒;(2)在电极的界面选择性的传输和收集电荷;(3)调控器件的相对极性;(4)影响界面薄膜形貌进而改善表面性能;(5)减少漏电流的产生;(6)作为光学间隔层等。同样,支化大分子有机光电材料在有机电致发光二极管(OLEDs)中作为发光层,有机太阳能电池中作为活性材料以及在机激光领域作为增益介质都得到了广泛的关注和应用。为了系统的研究支化大分子在光捕获系统中荧光共振能量转移机制,进而通过合理的分子设计提高光电器件性能,在本课题组前期工作的基础上,设计合成了一系列支化大分子有机光电材料,系统的研究了水/醇溶性支化大分子界面材料在光捕获系统中的自组装调控的荧光共振能量转移机制、水/醇溶性支化大分子界面材料对于器件界面性能的改善、支化大分子多臂结构功能材料在OLEDs和有机激光领域的应用。首先,通过Suzuki偶联设计合成了以三苯胺为核,三苯胺芴基为臂的支化大分子;Stille多重偶联设计合成了以噻吩苯噻唑为核三苯胺为桥芴为臂的支化大分子阴离子(4FNaT)、中性离子(4FNOHT)以及阳离子(4FNBrT)界面材料,并研究了其光物理特性和电化学特性,发现离子基团的不同对材料的光物理特性及其电化学特性没有明显的影响,则主要是由其共轭骨架结构所决定的。其次,系统的研究了支化大分子4FNaT、4FNOHT以及4FNBrT界面材料作为受体在光捕获系统中的由自组装调控的荧光共振能量转移机制,研究发现阴阳离子间由于强的静电作用在低浓度(10-6 M)状态下能够形成自组装结构调控给受体间荧光共振能量转移,然而在阳-中性离子以及阳-阳离子之间则没有这种现象。我们进一步的通过动态光散射(DLS)和透射电子显微镜(TEM)证明了这一结论。最后,设计合成了以螺芴和芘为核的四臂支化大分子材料SF-PyF和Py-PyF,研究了其在有机电致发光二极管和有机激光领域的应用。两种材料均表现出较低的ASE阈值,其中SF-PyF为6.6μJ/cm2(1.3 kW/cm2),Py-PyF为5.4μJ/cm2(1.1 kW/cm2),其均具有很好的热稳定性和水氧稳定性。
[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.
【学位授予单位】：南京邮电大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TN383.1;O621.2
[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.
【学位授予单位】：南京邮电大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TN383.1;O621.2
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