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过渡金属(铼、钌)配合物光电功能材料与器件
Opto-Electro Functional Materials and Devices Based on Transition Metal(Re、Ru) Complexes
【作者】 傅春艳;
【作者基本信息】 东北师范大学 , 无机化学, 2006, 博士
【摘要】 许多过渡金属磷光配合物具有出色的光致发光和理论内量子效率可达100%的电致发光性能,随着有机电致发光研究的不断深入,近年来以过渡金属配合物作为发光中心的研究正逐渐成为该领域的重点。其中以铱、铂配合物为基础的高效有机电致发光器件得到了广泛的研究,而对于铼配合物的研究相对较少。铼配合物具有高的室温磷光量子效率、相对较短的激发态寿命和出色的热稳定性,对它们的发光机理及性能的研究可以加深对电致发光的认识和开发新型高效电致发光材料。有机光伏与电致发光之间存在着密切的联系,是完全相反的两个过程。有机紫外光探测器件是有机光电转换器件的应用领域之一,深入研究有机器件的光伏性能对于化学/生物分析、全彩色数字图像信号检测和高能辐射测量等具有重要意义。本文以含乙烯基砒啶衍生物的铼金属配合物作为发光中心组装了红色有机电致发光器件,最优化浓度为2 wt.-%。首次发现室温下无法观测到光致发光的材料具有良好的电致发光特性。它改变了人们对开发电致发光材料的传统认识,即电致发光材料的选择必须建立在良好的光致发光的基础上,有助于开发新型OLED材料。四氮杂苯并菲衍生物具有出色的载流子传输性能、特别是电子传输性能,本文以化合物DPPz作为配体制备了新型金属铼的配合物。并以此作为发光中心进行了电致磷光器件的组装。相对平衡的载流子注入和主体到客体的高效能量传递提高了电致发光器件的性能。其中Dexter机制起着主导的作用。F?rster能量传递机制和载流子俘获机制相对微弱。器件的最大效率为6.3 cd/A,最大亮度接近1000 cd/m2,相关的机理被讨论。在电致发光研究的基础上我们进一步开展了相应材料的有机光伏器件的研究。利用激基复合物的形成,研究了以m-MTDATA作为电子给体,以Re-DPPz、Tb(acac)3DPPz、Eu(TTA)3DPPz、Eu(DBM)3DPPz作为电子受体所组装的光伏器件的性能。该系列器件的响应范围均位于长波紫外区,是典型的可见盲区的紫外探测器件。研究表明由DPPz所组成的金属配合物不仅具有良好的电致发光性能,而且还可应用于传感。合成了两种新型金属钌表面活性剂配合物,它们与水的混合体系展示良好的溶致液晶行为。以该液晶体系作为模板剂成功地制备出相应结构的介孔分子筛,由此证明了理想液晶模板机理。
【Abstract】 Recently, there has been growing interesting in employment of transition metal complexes as emitters in organic light-emitting diodes (OLEDs), since many of them have excellent photoluminescence (PL) properties and potential advantages of achieving a maximum internal quantum efficiency of 100%. Highly efficient OLEDs based on the Ir complexes and Pt complexes have been extensively studied. Little attention has been devoted to Re(I) complexes. It is well known that they feature high room-temperature phosphorescence quantum yield, relatively short excited state lifetime, and excellent thermal stability. Study these complexes is important to exploit novel types of EL materials and understand the EL mechanism deeply. On the other hand, as an application of organic photovoltaic devices, organic ultraviolet photodetectors present the advantages of low manufacturing cost, large detection area, and easy hybridization, and promise to integrate together with other electronic or optical components including chemical/biomedical analysis, full color digital image sensing and high energy radiation detection.In this work, red organic light-emitting diodes using a rhenium(I) bipyridyl complex, fac-[ClRe(CO)3(trans-4-methyl-4’-(2-4-octadecyloxylphenyl)vinyl)-2,2’- bipyridine] as an emitter were fabricated. The optimized device has a bilayer structure of indium-tin oxide/poly(N-vinylcarbazole): x wt.-% Re-mopvb/2,9-dimethyl-4,7-diphenyl-,10-phen anthroline/LiF/Al. It was found that no photoluminescence from Re-mopvb in room- temperature solution appeared due to photoinduced isomerization, a bright red electrophosphorescence from an intraligand excited state of Re-mopvb was observed at room temperature, indicating promising future of such a class of EL materials. It is helpful to exploit novel types of EL materials. DPPz derivatives have excellent electron-transporting property. Highly efficient orange-yellow organic EL devices based on DPPz have been fabricated. By incorporating Re-DPPz into EL devices with balanced charge injection and efficient host-to-guest energy transfer, the EL performances were significantly improved. For EL device with 7 wt. % Re-DPPz doped emissive layer, maximum efficiency of 6.3 cd/A, and orange-yellow emission with brightness approaching 1000 cd/m2 were achieved. Such improvement is due to efficient Dexter energy transfer between CBP host and Re-DPPz.Metal-DPPz complexes and m-MTDATA were used as electron-acceptors and donors, respectively in the PV devices. The performance of ultraviolet-A photodetectors based on PV has been investigated. The forming of exciplexes makes UV detectors better capability. The absorption spectra of the composite films located at long wave UV area, typical visible-blind UV detector. It indicates that DPPz-containing metal complexes not only possess excellent EL performances, but only find applications in sensors.New surfactant Ru(II) complexs were synthesized and characterized by elemental analysis,mass spectra and 1H NMR. The complex– water mixture displays lyotropic liquid crystalline behaviour. The mesoporous films obtained still retain the corresponding texture of
【Key words】 Electrophosphorescent devices; Organic photovoltaic devices; Transition metal complex; Lyotropic liquid crystalline;