用BPhen作基质的铕配合物OLED发光机制研究

用具有良好电子传输/空穴阻挡性能的BPhen(4,7-diphenyl-1,10-phenanthroline)作基质,Eu(DBM)3pyzphen(pyzphen=pyrazino-[2,3-f][1,10]-phenanthroline,DBM=Dibenzoylmethane)作发射材料,成功制得了高效率、高亮度的有机电致发光器件OLED.器件的最大外量子效率为2.5%,最大电流效率为5.3 cd/A,最大亮度为1 320 cd/m2.在亮度为200和1 000 cd/m2时,器件的色坐标分别为(0.66,0.33)和(0.65,0.34).深入研究了该器件的发光机制,发现在电致发光(EL)过程中,载流子直接被Eu(DBM)3pyzphen陷获是主要的发光机制,同时在BPhen与Eu(DBM)3pyzphen间还存在着有效的能量传递.     

Modulation of ambipolar charge transport characteristics in side-chain polystyrenes as host materials for solution processed OLEDs

A series of side-chain polystyrenes was developed as ambipolar hosts for solution processed organic light emitting diodes (OLEDs). The series was derived from the hole-only transport host molecule 1,3-Bis(N-carbazolyl)benzene (mCP). Electron transport ability was incorporated into the host polymers by the introduction of electron-poor heterocycles (pyridine or triazine) and extending delocalization of the lowest unoccupied molecular orbital (LUMO). The materials were tested in Ir-based green OLED devices with all organic layers processed from solution. Devices with the polymer combining triazine and carbazole on its side-chain exhibited a low luminance on-set voltage of 3.0 V and a current efficacy of 28.9 cd/A, which was more than 10 times higher than for devices with the mCP-based polymer (1.6 cd/A). The increase in performance is most likely due to an improvement of charge balance in the emissive layer, showing that our ambipolar polymers are good candidates for further wet-process optoelectronic applications.     

A host material containing tetraphenylsilane for phosphorescent OLEDs with high efficiency and operational stability

A host material containing tetraphenylsilane moiety, 9-(4-triphenylsilanyl-(1,1′,4,1′′)-terphenyl-4′′-yl)-9H-carbazole (TSTC), was synthesized for green phosphorescent organic light emitting diodes. The tetraphenylsilane moiety was introduced to provide high triplet energy level, thermal and chemical stability, and glassy properties leading to high efficiency and operational stability of the devices. Ir(ppy)₃ based OLEDs using the TSTC host and DTBT (2,4-diphenyl-6-(4′-triphenylsilanyl-biphenyl-4-yl)-1,3,5-triazine) hole blocking layer (HBL) resulted in the maximum external quantum efficiency of 19.8% and the power efficiency of 59.4 lm/W. High operational stability with a half lifetime of 160,000 h at an initial luminance of 100 cd/m² was achieved from an electrophosphorescent device using TSTC host and BAlq HBL.     

OLED器件光电性能集成测试系统研制

为方便对OLED器件的各项性能进行测试,研发了一种OLED器件光电性能集成测试系统,实现了在同一个软件下的OLED器件的电压、电流、亮度、光谱、色坐标和寿命等特性的集成测试。介绍了计算机与各测试设备的通信方法,通过计算机控制测量仪器对OLED器件进行测量。使用了Microsoft Visual 2005开发工具,利用MFC(Microsoft Foundation Classes)开发出了图形用户界面下的应用程序。利用TeeChart(西班牙Steema公司研发的图表控件)控件实现了OLED器件性能特性曲线的实时动态显示,并能够对不同器件的测试结果进行性能曲线的对比。编写了色坐标助手软件,实现对测试软件测试的光谱数据的分析显示功能。     

Configuring device architecture with new solution-processable host for high performance low color-temperature OLEDs with ultra-low driving voltage

After the revelation of nonvisual lighting impact on human health, the lighting engineers are more concerned about the human benign light with low cost and high efficiency. The solution-processed fabrication technique with smart device engineering for high efficacy OLED devices is being anticipated to drastically reduce the fabrication cost leading to affordable desired end product. The co-host matrix could be a potential solution to improve device performance multi-folds with suitable band-gap engineering and most effective energy transfer from mixed host to guest. Here, rationally configured device architecture with two novel host materials possessing wide energy gap, high triplet energy, and excellent thermal and morphological stability resulted in highly-efficient solution-processed green, red and low color temperature (CT) OLEDs with sub-bandgap level driving voltage of 2.1 V i.e. record lowest within its own category. Perfect triplet energy match of our newly developed host materials with commercial p-type host m-MTDATA and the common phosphors enabled efficient energy transfer with very low energy loss led to high efficiency of resulting OLED. The resultant solution-processed triplet emitter based green and red OLED devices displayed a maximum efficacy of 75.0 and 30.2 lm W⁻¹ without using light extraction out-coupling techniques, respectively. The designed blue-hazard free 2048 K low CT OLED exhibited a η_PE of 44.5 lmW⁻¹, a η_CE of 47.6 cdA^-1 and an EQE of 20.7% as the maximum value, the highest known so far within its own category. The melatonin suppression sensitivity (MSS) of the engineered low CT OLED is only 1.0% to that of the 480 nm blue light, which is much safer compared to other light sources. The impact of our design engineering was established by fabricating 1 cm × 1 cm device area prototype.     

Fast field solver for the simulation of large-area OLEDs

Lighting purpose organic light-emitting devices need special engineering because of the high electrical and thermal requirements of the operation. Our electro-thermal field simulation software is better to satisfy these special demands than the widely used commercial tools. This article surveys the special simulation needs of lighting purpose OLEDs, presents the electro-thermal extension of the FDM-based SUNRED thermal field simulator and the significant algorithmic changes for speed up the program and make it more flexible. The simulation of an existing OLED closes the paper.     

Nonlinear electro-thermal modeling and field-simulation of OLEDs for lighting applications II: Luminosity and failure analysis

In recent years great effort has been put into development of lighting purpose Organic Light Emitting Diodes (OLEDs) worldwide. Among many concerns of developers is heat-removal from the thin film structure of the active layers of OLEDs which are typically realized on low thermal conductivity substrates such as glass or polymer foils. The other issue is to provide the OLEDs with transparent, yet high electrical conductivity electric power supply structure, therefore metallic shunting grids are added to the layer stack of OLEDs. These two major issues necessitate self-consistent electro-thermal simulation of large area OLEDs in which the temperature dependent I–V characteristics of the light emitting polymer layers are also considered. Our first article discussed the details of the algorithmic fundamentals of our nonlinear electro-thermal field solver. This second paper presents the new, temperature dependent radiance and luminance distribution map calculation extension of the algorithm. Using this feature the inhomogeneity of large area OLEDs in free convection environment can be estimated; such calculations for glass-based research OLED samples are also presented. Because of the operational degradation of the OLED, non-emissive “dark” spots can appear. Cause of these spots can be e.g. manufacturing problem, damage of the surface protection, etc. Electro-thermal and luminance simulation of this failure type is demonstrated and is compared with measured results. Thermal runaway as the possible physical phenomenon behind the appearances of dark spots is proved by simulations.     

Lanthanide rare earth oxide thin film as an alternative gate oxide

An ultrathin gate oxide is needed for future nanoscale technology due to the density of integrated circuits will increase exponentially every two to three years as predicted by Moore's Law. Some problems were occurred in conventional silicon dioxide gate oxide during applications such as high leakage current density, low reliability issues, and undesirable power dissipation. Lanthanide rare earth oxides was attracted as one of potential candidates to replace conventional silicon dioxide due to their superior properties. Each rare earth oxides in lanthanide group was reviewed and discussed in terms of physical, chemical, and electrical properties and also its common deposition methods. Sm₂O₃ is one of the promising candidate materials among rare earth oxides because of some outstanding properties such as high κ (7–22), high breakdown electric field (5–7 MV cm^-1), relatively large bandgap (4.33 eV), low leakage current, large conduction offset with Si, high thermal stability, small frequency dispersion, low trapping rate, and low hygroscopic characteristic. The literatures of Sm₂O₃ was paid particular attention in the last section. The previous deposition methods of the Sm₂O₃ as gate oxide were reviewed and compared.     

Efficient Bipolar Blue AIEgens for High‐Performance Nondoped Blue OLEDs and Hybrid White OLEDs

Blue organic luminescent materials play a crucial role in full‐color display and white lighting but efficient ones meeting commercial demands are very rare. Herein, the design and synthesis of tailor‐made bipolar blue luminogens with an anthracene core and various functional groups are reported. The thermal stabilities, photophysical properties, electronic structures, electrochemical behaviors, carrier transport abilities, and electroluminescence performances are systematically investigated. The luminogen TPE‐TAPBI containing a tetraphenylethene moiety shows aggregation‐induced emission, while another luminogen TriPE‐TAPBI bearing a triphenylethene unit exhibits light aggregation‐caused quenching. In comparison with TriPE‐TAPBI, TPE‐TAPBI has stronger blue emission in neat film and functions more efficiently in nondoped organic light‐emitting diodes (OLEDs). High maxima current, power, and external quantum efficiencies of 7.21 cd A^?1, 6.78 lm W^?1, and 5.73%, respectively, are attained by the nondoped blue OLED of TPE‐TAPBI (CIE_x,y = 0.15, 0.16). Moreover, efficient two‐color hybrid warm white OLEDs (CIE_x,y = 0.457, 0.470) are achieved using TPE‐TAPBI neat film as the blue‐emitting component, which provide total current, power, external quantum efficiencies of up to 70.5 lm W^?1, 76.0 cd A^?1, and 28% at 1000 cd m^?2, respectively. These blue and white OLEDs are among the most efficient devices with similar colors in the literature.     

Efficient blue emitters based on 1,3,5-triazine for nondoped organic light emitting diode applications

Two novel efficient blue emitters (TTT-1, TTT-2) containing 1,3,5-triazine, thiophene and triphenylamine have been designed and synthesized. Organic light emitting diodes (OLEDs) using these new triazine derivatives as emissive layers, ITO/TAPC (60 nm)/TTT-1 (Device A) or TTT-2 (Device B) (40 nm)/TPBi (60 nm)/LiF (1 nm)/Al (100 nm), were fabricated and tested. The OLEDs exhibited good performances with low turn-on voltage of 3 V, maximum luminance of ca. 8990 cd/m² for TTT-1 and 15,980 cd/m² for TTT-2, and maximum luminance efficiency of 4.7 cd/A for TTT-1 and 4.0 cd/A for TTT-2, respectively.     

Surface Control of Planarization Layer on Embossed Glass for Light Extraction in OLEDs

We developed a highly refractive index planarization layer showing a very smooth surface for organic light‐emitting diode (OLED) light extraction, and we successfully prepared a highly efficient white OLED device with an embossed nano‐structure and highly refractive index planarization layers. White OLEDs act as an internal out‐coupling layer. We used a spin‐coating method and two types of TiO₂ solutions for a planarization of the embossed nano‐structure on a glass substrate. The first TiO₂ solution was TiO₂ sol, which consists of TiO₂ colloidal particles in an acidic aqueous solution and several organic additives. The second solution was an organic and inorganic hybrid solution of TiO₂. The surface roughness (R_a) and refractive index of the TiO₂ planarization films on a flat glass were 0.4 nm and 2.0 at 550 nm, respectively. The J–V characteristics of the OLED including the embossed nano‐structure and the TiO₂ planarization film were almost the same as those of an OLED with a flat glass, and the luminous efficacy of the aforementioned OLED was enhanced by 34% compared to that of an OLED with a flat glass.     

功能层界面制备方法对OLED性能的影响

在功能层界面处采用各功能材料共蒸的方法,制备了典型的绿光有机发光器件(OLED)。器件的结构为ITO/NPB(37nm)/(NPB:Alq3)(3nm)/Alq3(27nm):C545T(3%)/Alq3(20nm)/LiF(1nm)/Al(100nm),并与传统的制备方法进行了比较。结果发现,起亮电压从4.5V降低到2.5V,最高耐压从16V提高到21V,最大亮度从13 940cd/m2提高到24 630cd/m2,发光效率由7.0cd/A提高到11.4cd/A。结果表明,本文方法有利于载流子传输,可以有效提高激子形成概率,提高了OLED发光效率。     

Investigation of TDAPBs as hole‐transporting materials for organic light‐emitting devices (OLEDs)

The performance of organic light‐emitting devices (OLEDs) is strongly influenced by the electronic properties of the employed materials. In order to determine the effect of these materials' parameters, several different hole‐transporting 1,3,5‐tris(4‐diphenylaminophenyl)benzenes (TDAPBs) were synthesised. These TDAPBs contained different substituents, different numbers of substituents and different positions of theses substituents. For the evaluation of the electronic properties, cyclic voltammetry was employed in order to determine the HOMO values, and time‐of‐flight (TOF) measurements to obtain the hole mobilities. OLEDs were prepared consisting of the TDAPBs blended in a polymer matrix, and of Alq₃ as electron‐conducting and light‐emitting layer. These devices were investigated regarding their current density/voltage characteristics, efficiencies, onset voltages for electroluminescence, and lifetimes. For hole‐transporting blend systems an exponential relationship between the current density and the HOMO levels of the TDAPBs was found. However, even though the HOMO values cover a range from −5.09 to −5.35 eV, no effects on the performance of the OLEDs were detected for electroluminescent two‐layer systems. In this case the initial voltage seems to be a determining parameter for the behaviour of the devices during operation. Copyright © 1999 John Wiley & Sons, Ltd.     

Aminoborane-based bipolar host material for blue and white-emitting electrophosphorescence devices

A novel aminoborane-based host material, 9-(dimesitylboryl)-9′-phenyl-9H, 9′H-3,3′-bicarbazole (BCzBMes) was developed for blue and white phosphorescent OLEDs (PHOLEDs). The thermal, photophysical and electrochemical properties were systematically investigated. BCzBMes not only has a high triplet energy but also shows a bipolar behavior. To validate the superior properties of BCzBMes, blue and white PHOLEDs were fabricated using BCzBMes as a bipolar host material. A blue PHOLED containing Bis(4,6-difluorophenylpyridinato-N,C2)picolinatoiridium (FIrPic) as a dopant exhibited excellent performance with a maximum external quantum efficiency (EQE) of 16.7%. In particular, the blue PHOLED exhibited an extraordinary low efficiency roll-off of 10.1% at a brightness of 5000 cd/m². Meanwhile, an all-phosphor near-white device hosted by BCzBMes was also fabricated, and a high EQE of 18.8% was achieved. This excellent performance suggests that BCzBMes is a potential bipolar host material for the PHOLEDs.     

Optimization of Al2O3/ZrO2 nanolaminate structure for thin-film encapsulation of OLEDs

We report thin-film moisture barriers based on Al₂O₃/ZrO₂ nanolaminates grown by ALD for an encapsulation of OLEDs. In order to optimize the moisture-barrier performance of the nanolaminates, the most important factors affecting the performance were sought by measuring WVTR of the nanolaminates via an electrical Ca test. We found out that both the number of interfaces in the nanolaminates and the thickness of ZrO₂ in a unit layer were responsible for the performance. By optimizing the nanolaminate structure, the moisture-barrier performance was enhanced up to 350% from a single layer of the same thickness. The WVTR of 30-nm-thick optimized nanolaminate barrier was 2 × 10⁻⁴ g/(m² day) or less at ambient condition. A storage-lifetime measurement of an OLED with a 100-nm-thick encapsulation layer showed that it could exceed 70,000 h if stored at ambient condition.     

制作有机LED的新型材料

在介绍有机LED产品开发动态的基础上引入了两种用于有机LED制作的新材料。对这两种新材料的结构，制作工艺和主要特性进行了详细说明。     

Pyridoindole modified carbazole compounds as high triplet energy host materials of imidazole derived blue triplet emitters for high quantum efficiency

Carbazole compounds modified with a pyridoindole moiety were examined as thermally stable high triplet energy host materials for tris[1-(2,4-diisopropyldibenzo[b,d]furan-3-yl)-2-phenylimidazole] (Ir(dbi)₃) based blue phosphorescent organic light-emitting diodes. A well-known carbazole compound, N,N′-dicarbazolyl-3,5-benzene, was substituted with one or two pyridoindole moieties to develop the thermally stable host materials for Ir(dbi)₃ blue triplet emitters. Remarkably high glass transition temperature of 196 °C and thermal decomposition temperature of 486 °C in addition to high triplet energy of 2.89 eV were achieved by the pyridoindole modification. The pyridoindole modified carbazole compounds also delivered high quantum efficiency of 25.4% in the blue phosphorescent devices by doping Ir(dbi)₃.     

Hydrofluoroethers as heat-transfer fluids for OLEDs: Operational range, stability, and efficiency improvement

In this work we introduce a simple yet very efficient method of heat dissipation by immersing OLED device into hydrofluoroether (HFE) fluids. It is shown that due to highly fluorous nature of this class of fluids, HFE do not damage organic semiconductors which are comprised in the OLED stack and therefore can be used as encapsulation media. HFE also have high thermal conductivity, low viscosity and can efficiently dissipate the heat by means of natural convection with laminar flow. By employing HFE we were able to significantly improve the OLED operating dynamic range. Lifetimes of OLEDs operating in HFE at high currents can be improved by about a factor of 8. Furthermore, HFE fluid significantly improves the light outcoupling by a factor of 70% due to higher than air refractive index (n = 1.3).     

基于OLED灰度显示的新方法

介绍了有机发光二极管(OLED)技术特点、彩色实现方式和驱动方式.针对OLED灰度显示,介绍了实现灰度显示的两种常用方法即脉宽调制和帧灰度调制,并分析了各自的特点.在此基础上,尝试了一种新的方法,将二者结合起来共同实现灰度显示.这种方法不仅可以保持脉宽调制灰度显示的高速度,还可以保持帧灰度方式的均匀、稳定和足够的响应速度,而且可以大大提高灰度级别数.介绍了利用这种新方法实现OLED灰度显示数据的具体方式,该方法在硬件实现上简单易行,节约面积成本.