基于磷氧基团的铱配合物和电子传输材料的合成及性能研究

发布时间：2018-01-13 08:12

本文关键词：基于磷氧基团的铱配合物和电子传输材料的合成及性能研究　出处：《南京大学》2017年博士论文　论文类型：学位论文

【摘要】：近年来,有机电致发光器件(OLEDs)的研究引起了广泛关注并取得了一系列重要进展,使其在平板显示和固态照明领域步入了实用化阶段。目前,作为有机电子领域的研究热点,OLEDs新材料的开发仍然如火如荼进行着。本论文通过将磷氧基团合理的引入分子结构中,设计开发了新的蓝光铱配合物客体掺杂材料和电子传输材料,制备了高性能的OLEDs器件,同时,该思路为设计合成高性能的电致发光材料提供了切实可行的途径。1.通过设计含磷氧基团的吡啶磷酸辅助配体,合成了两个新型的蓝光铱配合物(dfppy)2Ir(ppp)和(dfppy)2Ir(dpp)。它们均表现出较短的磷光寿命,优秀的热稳定性和高的电子迁移率,并以它们为客体掺杂材料,制备了蓝光器件。基于(dfppy)2Ir(ppp)的器件优化结构为 ITO/MoO3(3 nm)/TAPC(50 nm)/(dfppy)2Ir(ppp)(10 wt%):26DCzPPy(15 nm)/TmPyPB(50 nm)/LiF(1 nm)/Al(100 nm),该器件展现出良好性能:启动电压2.9 V,最大电流效率52.49 cd A-1,最大外量子效率25.2%,最大功率效率51.50 lmW-1。基于(dfppy)2Ir(dpp)的器件结构为ITO/Mo03(3 nm)/TAPC(50 nm)/TcTa(5 nm)/(dfppy)2Ir(dpp)(10%):26DCzPPy(15 nm)/TmPyPB(50nm)/LiF(1nm)/A1(100nm),并显示出优异的性能:最大电流效率58.78 cdA-1,最大外量子效率28.3%,最大功率效率52.74 lm W-1,效率滚降很低。它们优异的性能得益于磷氧基团的引入,使新的蓝光铱配合物具有合适的HOMO/LUMO能级和高的电子迁移率,平衡了载流子的注入与传输,扩大了激子的复合面积,提高了器件效率。高效的性能使其在OLEDs中具有重要的潜在应用价值。2.通过对主配体2-(2,4-二氟苯基)吡啶结构进行改造:一方面用缺电子的吡啶环取代苯环,另一方面在苯环上引入强吸电子基团氰基,从而来降低它的HOMO能级,实现发光蓝移。基于此,设计合成了四个新的深蓝光铱配合物(dfpypy)2Ir(ppp),(dfpypy)2Ir(dpp),FCNIr(ppp),FCNIr(dpp),最大发射波长分别为458nm,453nm,459nm,458nm。选择了(dfpypy)2Ir(ppp),FCNIr(ppp)作为客体掺杂材料,制备了深蓝光器件:ITO/Mo03(3 nm)/TAPC(50 nm)/(dfpypy)2Ir(ppp)or FCNIr(ppp)(10%):TcTa(5 nm)/(dfpypy)2Ir(ppp)or FCNIr(ppp)(10%):26DCzPPy(15 nm)/TmPyPB(50 nm)/LiF(1 nm)/Al(100 nm)。两个器件的最大电流效率分别为24.51和16.27cdA-1,最大外量子效率为12.4%和8.0,最大功率效率为21.99和13.101m W-1。3.以炔丙胺作为一种新的自由基受体,在醋酸银或光催化剂作用下,通过串联的磷化、环化、氧化、芳构化过程合成了一系列新型的磷氧喹啉化合物。该反应原料易得、条件温和,原子经济性高。其中化合物QDPO用作电子传输材料制备了有机发光器件,结构为:ITO/MoO3(5nm)/TAPC(30nm)/Ir(tfmppy)2tpip(8 wt%):mCP(10nm)/QDPO(30nm)/LiF(1 nm)/Al(100nm)。器件表现出优异性能:最大电流效率83.53 cd A-1,最大外量子效率21.9%,最大功率效率67.27 lm W-1,效率滚降很小。
[Abstract]:In recent years, the research of organic electroluminescent devices (OLEDss) has attracted extensive attention and made a series of important progress, which has made it into the practical stage in the field of flat panel display and solid-state lighting. As a research hotspot in the field of organic electronics, the development of new materials of OLEDs is still in full swing. A new blue iridium complex guest doped material and electron transport material were designed and developed, and high performance OLEDs devices were fabricated at the same time. This idea provides a feasible way for the design and synthesis of high performance electroluminescent materials. 1. Through the design of pyridine phosphoric acid auxiliary ligands containing phosphorous groups. Two new blue iridium complexes, dfppyn 2Irzppp) and dfppy2 Ir1 dppp, have been synthesized. They all exhibit short phosphorescence lifetimes. Excellent thermal stability and high electron mobility, and they as guest doped materials. A blue light device was prepared. The optimized structure of the device is ITO/MoO3(3 nm)/TAPC(50 NMU / dfppy based on DFP / 2IrPPP). 210 wt%):26DCzPPy(15 nm)/TmPyPB(50 nm)/LiF(1 nm)/Al(100 NM. The device shows good performance: starting voltage 2.9 V, maximum current efficiency 52.49 CD A-1, maximum external quantum efficiency 25.2%. Maximum power efficiency 51.50 lmW-1. The device structure based on Dfppy2 Irnmp) is ITO/Mo03(3 nm)/TAPC(50 NM). / Tc Ta5 nm)/(dfppy)2Ir(dpp)(10%):26DCzPPy(15 NM / T m PyPB50 nmM / L F 1 nm). / A1 / 100nm). The maximum current efficiency is 58.78 cdA-1, the maximum external quantum efficiency is 28.3 and the maximum power efficiency is 52.74 lm W-1. Their excellent properties are due to the introduction of phosphor groups, which make the new blue iridium complexes have the appropriate HOMO/LUMO energy level and high electron mobility. The injection and transport of carriers are balanced and the complex area of excitons is enlarged. It improves the device efficiency and makes it have important potential application value in OLEDs due to its high performance. The structure of 4- difluorophenyl) pyridine was modified: on the one hand, the ring of benzene was replaced by the ring of pyridine lacking electrons; on the other hand, the strong electron-absorbing group cyanide was introduced into the ring of benzene to reduce its HOMO energy level. Based on the blue shift of luminescence, four new deep blue iridium complexes, dfpypyn 2Irpypy1, dfpypyn 2Irp Dppp, have been designed and synthesized. The maximum emission wavelengths are 458nm, 453nm and 459nm, respectively. 458nm. the DfpypyO2IrPPU (FCNIrirppp) was chosen as the guest doped material. A dark blue optical device, 1: ITO / Mo033 nm)/TAPC(50 nm)/(dfpypy)2Ir(ppp)or FCNIrppp 10, has been fabricated. Tc Taer 5 nm)/(dfpypy)2Ir(ppp)or FCNIr(ppp)(10%):26DCzPPy(15 NMU / TmPyPB5. The maximum current efficiency of the two devices is 24.51 and 16.27cdA-1, respectively. The maximum external quantum efficiency was 12.4% and 8.0, and the maximum power efficiency was 21.99 and 13.101m W-1.3 respectively. Propargmine was used as a new free radical receptor. A series of new phosphoroquinoline compounds were synthesized by series phosphating, cyclization, oxidation and aromatization under the action of silver acetate or photocatalyst. The compound QDPO is used as electron transport material to prepare organic luminescent devices. The structure is:: ITO / MoO3 / 5nmN / TAPC-30nmN / / Irtfmppy2 / 2tpipa / 8wt / 10nmb / QDPO(). The device exhibits excellent performance: the maximum current efficiency is 83.53 CD A-1. The maximum external quantum efficiency is 21.9, the maximum power efficiency is 67.27 lm W-1, and the efficiency rolling down is very small.
【学位授予单位】：南京大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TN383.1;O641.4

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