【作者】 陈善勇；

【导师】 王悦；

【作者基本信息】 吉林大学 ， 有机化学， 2014， 博士

【摘要】 近年来，有机发光二极管（OLEDs）发展迅速并已进入商业化阶段，OLEDs产品大量应用到手机、电视等电子产品上。但目前报道的高效率器件大都具有复杂的材料体系和器件结构，这会增加加工难度和成本，不利于其产业化。同时，随着主要层材料的逐步成熟，人们对以前甚少关注的材料如电极、注入材料等加大了研究力度并取得了不少最新成果。本论文中，我们首先在吲哚并咔唑和联咔唑基团的基础上构建了多功能材料并研究了它们结构与性能的关系。然后，我们设计了新型噻唑类空穴注入材料并将它们用来改进我们的多功能材料器件。1、第二章中，我们合成了DPDT-ICZ、DNDT-ICZ和DPA-PCTP-CA三个分子，并用核磁、质谱、元素分析等对它们进行了表征。晶体结构研究发现它们分子之间的作用力较弱。这有利于它们蒸镀时形成均匀薄膜，同时使它们有成为优异发光材料、空穴传输材料和主体材料的潜力。我们研究了BTDA-TCNQ、TDA-TCNNQ和TDA-TCNAQ三个空穴注入材料。这些材料合成简单便宜，溶解性也比常见空穴注入材料HATCN好很多，这扩展了它们的应用范围。2、第三章中，DPDT-ICZ、DNDT-ICZ以及DPA-PCTP-CA的热力学、光谱学和电化学研究表明它们可能是非常稳定的优异深蓝色发光材料和从绿色到红色的磷光主体材料。电化学和光谱学研究也显示它们的HOMO能级在-5.0eV左右，LUMO能级在-2.10eV左右。能级数据表明它们有成为优异空穴传输材料的潜力。BTDA-TCNQ、TDA-TCNNQ和TDA-TCNAQ的热力学、电化学以及光谱数据表明它们可能是非常稳定的具有强吸电子性质的空穴注入材料。3、第四章中，我们把并咔唑类化合物DPDT-ICZ和DNDT-ICZ应用到器件中。单载流子器件表明它们是以空穴传输为主的材料并且传输能力比NPB弱，这有利于它们在器件中实现电荷平衡。它们的非掺杂器件发深蓝光，器件亮度、稳定性都很好，但器件效率限制了它们的应用。以它们作为空穴传输材料的喹吖啶酮器件效率以及效率滚降均比以NPB制备的器件好，这说明它们是良好的空穴传输材料。以它们作为主体制备的黄色和红色磷光器件的高效率和低效率滚降表明它们是良好的主体材料。因此，我们同时用它们作为空穴传输材料和主体材料制备了多功能材料器件。器件的优异性能表明它们是优秀的多功能材料。4、第五章中我们把联咔唑类化合物DPA-PCTP-CA应用到器件中。空穴单载流子器件表明它的空穴传输能力比NPB低很多，甚至比Alq3的电子传输能力还弱。以它作为空穴传输材料先后在荧光和磷光器件中取得应用。虽然比用NPB和DPDT-ICZ制备的器件性能低，但是器件较优异的性能表明它仍是一个较优异的空穴传输材料。在此基础上，以它同时作为空穴传输材料和主体材料制备了多功能材料器件。但是器件糟糕的性能表明它不是一个优良的多功能材料。5、第六章中，以BTDA-TCNQ、TDA-TCNNQ、TDA-TCNAQ、MoO3、HATCN作为空穴注入材料制作的底接触、顶接触以及掺杂接触的NPB单载流子器件以及以它们制作的底接触荧光器件中显著提升的性能表明它们是比MoO3和HATCN更优异的空穴注入材料。但在将它们用以改进前面的多功能材料器件时，器件效率仅有小幅提升。这与发光层的空穴传输限制有关。器件的电流密度-电压曲线表明它们仍是良好的空穴注入材料。综上所述，我们设计了三个多功能材料和三个空穴注入材料并研究了它们的物理性质和器件性能，同时我们还将空穴注入材料引入到多功能材料器件中改进其性能。结果表明，DPDT-ICZ和DNDT-ICZ是优良的多功能材料，BTDA-TCNQ、TDA-TCNNQ和TDA-TCNAQ是优良的空穴注入材料。这与我们在研究思路中一步一步设计分子希望它们具备的性能基本一致。这些结果表明我们从所需性能出发设计改进分子的思路是合理的。我们的研究为研究结构与功能的关系提供了一些素材，同时也开发出一些优良的OLEDs材料。更多还原

【Abstract】 In recent years, with rapid development and further reseach, commercialization of organic light emitting diodes (OLEDs) has appeared (mobile phones, TVs etc.). However, most high efficient devices reported have complicated material system/device structures that render them much difficult and expensive to fabricate. Meanwhile, with mature research of main-layer materials, people give more attention to materials (such as electrodes, injecting materials etc.) whose research are scarce, and have achieved some breakthroughs. In this thesis, we built multifunctional materials based on groups of indole-carbazole and carbazole-carbazole, and studied relationships between structures and properties. Then, we designed novel hole-injection materials based on thiazole and used them to improve performance of devices with multifunctional materials.1. In chapter II, we synthesized three multifunctional compounds of DPDT-ICZ, DNDT-ICZ and DPA-PCTP-CA. NMR, mass spectrometry, elemental analysis etc. were used for characterization. Studies of crystal structures revealed molecular interactions were weak. With such properties, these materials could form uniform thin films during evaporation and have the possibility of being excellent luminescent materials, hole-transport materials and hosts. We investigated three hole-injection materials of BTDA-TCNQ, TDA-TCNNQ and TDA-TCNAQ. Their simple and cheap process of synthesis, good solubilities which are much better than common hole-injection material HATCN extend their range of application.2. In chapter Ⅲ, thermodynamic, spectroscopic and electrochemical studies of DPDT-ICZ, DNDT-ICZ and DPA-PCTP-CA showed they might be very stable and excellent deep-blue luminescent materials and hosts for phosphorescent devices from green to red. According to electrochemical and spectroscopic studies, their HOMO energy levels were about-5.0eV and LUMO energy levels were about-2.10eV which made them to have the potentiality of excellent hole-transport materials. Thermodynamic, spectroscopic and electrochemical studies of BTDA-TCNQ, TDA-TCNNQ and TDA-TCNAQ indicated they might be stable hole-injection materials with strong electron-withdrawing characteristics.3. In chapter Ⅳ, we applied DPDT-ICZ and DNDT-ICZ of indole-carbazole compounds to devices. Single-carrier devices figured out they were typical hole-transport materials and their hole-transport capabilities were weaker than NPB which was beneficial for them to achieve charge balance in devices. Their non-doped devices emitted deep-blue light and showed high brightness and stabilities, while their low efficiencies limited their application. In quinacridone’s devices which used them as hole-transport materials, high efficiencies and low roll-off of efficiencies indicated they were good hole-transport materials. In yellow and red phosphorescent devices which used them as hosts, high efficiencies and low roll-off of efficiencies proved they were good hosts. Based on facts mentioned above, we used them as both hole-transport materials and hosts to build multifunctional-material devices. Good performance of devices revealed they were excellent multifunctional materials.4. In chapter V, devices with DPA-PCTP-CA of carbazole-carbazole compounds were carried out. Hole-only devices revealed that its hole-transport capability was much lower than NPB, even lower than electron-transport ability of Alq3. Moreover, we applied it to fluorescent and phosphorescent devices as hole-transport material. Although efficiencies of these devices were lower than devices which used NPB and DPDT-ICZ as hole-transport materials, their fairly good performance indicated it was still a suitable hole-transport material. As a result, we used it as hole-transport material and host simultaneously in multifunctional-material devices. However, bad performance of devices indicated that it was not a good multifunctional material. 5. In chapter VI, single-carrier devices of NPB of bottom contact, top contact and doped contact or fluorescent devices which used BTDA-TCNQ, TDA-TCNNQ, TDA-TCNAQ, MoO3, HATCN as hole-injection materials indicated BTDA-TCNQ, TDA-TCNNQ, TDA-TCNAQ were better hole-injection materials than MoO3and HATCN. However, efficiencies of devices which used them as hole-injection materials to improve devices of multifunctional materials above were only slightly increased. This might be due to limited hole-transport abilities of emitting layers. At the same time, current density-voltage curves indicated they were still good hole-injection materials.To sum up, we designed three multifunctional materials and three hole-injection materials, and studied their physical and electroluminescent properties. Furthermore, we used our hole-injection materials to revise multifunctional-material devices. Results showed DPDT-ICZ and DNDT-ICZ were excellent multifunctional materials; BTDA-TCNQ, TDA-TCNNQ and TDA-TCNAQ were excellent hole-injection materials. These properties were consistent with properties that we hoped our materials had when we designed them step by step. The results indicate ideas that designing and modifying molecules from properties which we need are reasonable. Our studies provide some materials that are about relationships between structures and properties, and also produce some excellent materials of OLEDs.更多还原