四(8-羟基喹啉)硼锂作为电子注入层的高效有机发光二极管

采用四(8-羟基喹啉)硼锂(LiBq4)代替LiF 作为电子注入材料, 以金属铝作为阴极, 制备了有机电致发光器件. 器件采用N,N'-(α-萘基)-N,N'-苯基联苯二胺(NPB)作为空穴传输层, 三(8-羟基喹啉)铝(Alq3)作为电子传输层和发光层. 采用LiBq4作为电子注入层, 实验结果表明, 器件的亮度、电流效率和起亮电压等性能均有改善, 超过了采用LiF作为电子注入层的器件.器件性能的提升可以用电子注入增强和电荷平衡来解释.     

中位四(1-苯基吡唑-4-基)卟啉掺杂空穴传输材料的红色有机电致发光器件(英文)

使用中位-四(1-苯基吡唑-4-基)卟啉(TPPyPH2)掺杂空穴传输材料N,N′-二苯基-N,N′-双(4-甲苯基)-1,1′-二苯基-4,4′-二胺(TPD)制备了红色有机电致发光器件.因为TPD的发射光谱与TPPyPH2的吸收光谱具有更大的光谱重叠,为了得到更为有效的从主体材料TPD向红光染料TPPyPH2的能量传递,我们使用TPD代替传统的8-羟基喹啉铝(Alq3)作为主体发光材料.器件在680nm处具有纯的红光发射峰;通过使用Alq3电子传输层以及使用Alq3共掺杂发光层的方法,使器件的发光性能得到了改善,结构为ITO/Alq3+TPPyPH2+TPD(50nm)/Alq3(30nm)/Al的器件的最大发光亮度为177cd/m2.     

四氮杂大环化合物在有机电致发光器件中的应用(英文)

合成了四氮杂大环化合物,Tetraazamacrocycliccompound,6,12,19,25 tetramethyl 7,11:20,24 dinitrilo dibenzo［b,m］［1,4,12,15］tetra azacyclo docosine(TMCD).TMCD作为电子传送材料,探讨了它在有机电致发光器件中的应用.制作了结构为:玻璃基板／ITO阳极／NPD／Alq／TMCD／LiF／Al阴极的器件.评价的结果显示:该有机电致发光器件在538nm的绿色发光来源于Alq层.它的最大外部量子效率为0.84%,视感效率为1.30lm／W.最先提出了四氮杂大环化合物做为电子传送材料,可应用于电致发光领域.     

可溶性聚合物电致发光材料PDHPV的合成及单、双层发光二极管器件的发光性能比较

可溶性聚合物电致发光材料ＰＤＨＰＶ的合成及单、双层发光二极管器件的发光性能比较李晨曦，尹春，黄文强，印寿根，张会旗，何炳林，郑军，华玉林（南开大学高分子化学研究所，天津，３０００７１）（天津理工学院材料物理研究所）关键词ＰＤＨＰＶ共轭聚合物；电致发光...     

Alkali metal salts doped pluronic block polymers as electron injection/transport layers for high performance polymer light-emitting diodes

A series of alkali metal salts doped pluronic block copolymer F127 were used as electron injection/transport layers (ETLs) for polymer light-emitting diodes with poly[2-(4-(3′,7′-dimethyloctyloxy)-phenyl)-p-phenylenevinylene] (P-PPV) as the emission layer. It was found that the electron transport capability of F127 can be effectively enhanced by doping with alkali metal salts. By using Li2CO3 (15%) doped F127 as ETL, the resulting device exhibited improved performance with a maximum luminous efficiency (LE) of 13.59 cd/A and a maximum brightness of 5529 cd/m2, while the device with undoped F127 as ETL only showed a maximum LE of 8.78 cd/A and a maximum brightness of 2952 cd/m2. The effects of the doping concentration, cations and anions of the alkali metal salts on the performance of the resulting devices were investigated. It was found that most of the alkali metal salt dopants can dramatically enhance the electron transport capability of F127 ETL and the performance of the resulting devices was greatly improved.     

White and Red Organic Light Emitting Materials

Derivatives of 2,3-(1,4-dialkoxyaceno)norbornadiene underwent ring-opening metathesis polymerization (ROMP) upon the catalysis of a ruthenium complex to afford the corresponding polymers. The polymeric materials containing anthracene chromophores emit white electro-luminescence, which can be fabricated into light-emitting diodes (LED). The broad emission band is composed of a blue emission from anthracene and a red emission from aggregates. A single layer device, ITO/polymer/Ca/Al, can be turned on at 7V and exhibits maximum intensity 427 cd/m2 at 15 V. A double layer device, ITO/polymer/TPBI/Mg:Ag (TPBI = (2,2′,2"-(1,3,5-benzenetriyl)-tris(1-phenyl-1H-benzimidazole)) displayed blue light with turn-on voltage 6 V and maximal intensity 930 cd/m2 at 15 V.Derivatives of bisindolylmaleimide were found to form amorphous solid films which exhibit intensive red luminescence. The property of forming glasses can be ascribed to the nonplanar geometry of these molecules. LED devices were fabricated by a layer of pure dye sandwiched between two charge transporting films. The yellow emission spectrum of the devices utilizing Alq (tris(8-hydoxyquinolinato)aluminum) contains a green component from Alq. Pure red emissions can be achieved by replacing Alq with TPBI. Typical devices can be turned on at ～3 V with maximal intensity 2000 cd/m2. White color devices are under current investigation, in which the green Alq layer is replaced by its blue derivative (bis(2-methyl-8-hydoxyquinolinato)(phenolato)aluminum).     

超薄铝/碳酸锂修饰氧化铟锡阴极制备蓝色磷光反转底发光有机发光二极管

在氧化铟锡（ITO）阴极上依次蒸镀2 nm铝和2 nm碳酸锂（Li2CO3）薄膜作为电子注入层,成功制备出器件结构为ITO/Al/Li2CO3/SPPO13/SPPO13∶FIrpic/TCTA/MoO3/Al(SPPO13：2,7-双（二苯基磷）-9,9′-螺二[芴];FIrpic：双(4,6-二氟苯基吡啶-N,C2)吡啶甲酰合铱;TCTA：4,4′,4″-三(咔唑-9-基)三苯胺)的蓝色磷光反转底发光有机发光二极管（IBOLED）。 结果表明,Al/Li2CO3作为电子注入层可以有效降低ITO与有机材料之间的电子注入势垒,蓝色磷光IBOLED的起亮电压由11 V降至4.2 V,器件的发光效率也得到有效提高。 蓝光磷光IBOLED的最大电流效率与功率效率分别达到了28.2 cd/A和19.6 lm/W,制备出的反转结构器件性能可与传统正置结构比美,说明Al/Li2CO3可以作为反转有机发光二极管优良的电子注入层。     

超薄层在白色有机电致发光器件中的应用

以DCJTB为掺杂剂, 以BCP为空穴阻挡层, 研究了两种结构的有机电致发光器件ITO/NPB/BCP/Alq3:DCJTB/Alq3/Al(结构A)和ITO/NPB/BCP/Alq3/Alq3:DCJTB/Alq3/Al(结构B)的电致发光光谱. 实验结果显示, 在结构A器件的电致发光光谱中, 绿光的相对发光强度较弱,增加Alq3层的厚度对绿光的相对发光强度的影响也很小; 而在结构B器件的电致发光光谱中, BCP层与掺杂层(Alq3:DCJTB)之间的Alq3薄层对绿光的相对发光强度影响显著, 用很薄的Alq3层就可以得到强的绿光发射. 进一步改变器件结构, 利用有机超薄层就可以得到稳定的白光器件ITO/NPB(50 nm)/BCP(3 nm)/Alq3(3 nm)/Alq3:DCJTB(1%(w))(5 nm)/Alq3(7 nm)/Al. 随着电压的增加(14-18 V), 该器件的色坐标基本保持在(0.33, 0.37)处不动; 在432 mA·cm-2的电流密度下, 该器件的发光亮度可达11521 cd·m-2.     

基于N-乙基咔唑-2-乙烯基-8-羟基喹啉锌的黄绿色有机电致发光器件的性能

通过用一种既具有空穴传输特性又具有发光特性的新型荧光染料N-乙基咔唑-2-乙烯基-8-羟基喹啉锌((E)-2-(2-(9-ethyl-9H-carbazol-3-yl)vinyl) quinolato-zinc, CzHQZn)作为受主, 制备了结构为ITO/2T-NATA (30 nm)/CBP: 6%Ir(ppy)3:wCzHQZn(20 nm)/Alq3(50 nm)/LiF/Al(ITO: indium-tin oxide, 2T-NATA: 4,4',4'-{N,N-(2-naphthyl)-N-phenylamino}-triphenylamine, CBP: 4,4-N,N'-dicarbazole-biphenyl, Ir(ppy)3: factris (2-phenylpyridine) iridium, Alq3: tris(8-quinolinolato) aluminum; w 是CzHQZn 的质量分数)的黄绿色有机电致发光器件(OLEDs). 研究了掺杂体系在不同掺杂浓度(w=5%、10%、12%、15%)时的电致发光(EL)特性. 结果表明, CzHQZn 掺杂浓度为10%的器件在11 V 电压下实现了黄绿光发射, 色坐标为(0.4045, 0.5113), 最大发光亮度为16110 cd·m-2; 而在7 V电压下的最大发光效率为2.19 cd·A-1, 最大外量子效率为0.775%.     

氧化石墨烯掺杂PEDOT:PSS作为空穴注入层对有机发光二极管发光性能的影响

研究了氧化石墨烯(GO)掺杂聚(3,4-亚乙二氧基噻吩):聚(苯乙烯磺酸) (PEDOT:PSS)作为空穴注入层对有机发光二极管发光性能的影响. 在PEDOT:PSS水溶液中掺入GO, 经过湿法旋涂和退火成膜后, 不仅提高了空穴注入层的空穴注入能力和导电率, 透光率也得到了相应的提高, 从而使得有机发光二极管(OLED)器件的发光性能得到了提升. 通过优化GO掺杂量发现, 当GO掺杂量为0.8%(质量分数)时, 空穴注入层的透光率达到最大值(96.8%), 此时获得的OLED器件性能最佳, 其最大发光亮度和最大发光效率分别达到17939 cd·m^-2和3.74 cd·A^-1. 与PEDOT:PSS 作为空穴注入层的器件相比, 掺杂GO后器件的最大发光亮度和最大发光效率分别提高了46.6%和67.6%.     

氟化吡唑啉蓝色电致发光器件的制备

自从Tang等[1]首次报道了多层有机电致发光器件以来, 人们研究了大量的新型材料[2,3], 其中较吸引人的方法是将高量子产率的荧光染料掺杂于传输层中制备电致发光器件[4～9]. 三芳基吡唑啉化合物具有较高的荧光产率和蓝色发射特性. 这些化合物具有分子内电荷传输性能, 在激发状态下分子可发生扭曲形成电子给体-受体结构[10], 因此在EL器件制备过程中既可以作为载流子传输材料, 又可以作为发光材料来应用. 虽然吡唑啉类化合物在固态下具有空穴传输特性[11], 也有较高的荧光产率, 但它们的玻璃转化转变温度较低, 在制备EL器件时, 如单独作为传输层或发射层时, 该类材料易于结晶, 从而使得器件的性能快速衰减. 如果将它们分散于聚合物等主体中, 就会避免重结晶问题. 我们在三苯基吡唑啉中引入强吸电子基团CF3, 导致分子的刚性增强和荧光强度增加, 熔点升高. 将氟化三苯基吡唑啉(FTPP)作为发光中心制作了两类EL器件, 均获得蓝光发射. FTPP分子结构见图1.     

MULTILAYER ORGANIC LEDS BASED ON A NEW DYE-DOPED POLYMER*

A blue dye, l-benzothiazoly-3-phenyl-pyrazoline (BTPP) was found to function as bright lightemitting dye in organic electroluminescent devices. This heterocyclic compound exhibits good characteristicsof blue photoluminescence and electroluminescence, which has emission peak at 445 nm.The thin films offluorescent dye dispersed in poly(N-vinylcarbazole) (PVK) could serve as light-emitting layers in multilayerorganic LEDs. 2-(4-Biphenyl)-5-(4-tert-butylpheynyl)-1,3,4-oxadiazole (PBD) and tris-(8-hydroxyquinoline)aluminum (Alq3) were introduced into double-layer and three-layer devices respectively. The introduction ofelectron transport material Alq_3 enhanced the electron injection and luminous efficiency, as compared withdouble-layer devices. Maximum brightness and luminous efficiency can be reached up to 190 cd/m~2 and0.31 m/W, respectively.     

Bright White Organic Light-emitting Device Based on 1,2,3,4,5,6-Hexakis（9,9-diethyl-9H-fluoren-2-yl）benzene

Organic light-emitting devices(OLEDs) with the structure of indium-tin-oxide(ITO)/N,N'-bis-(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine(NPB)/2,9-dimenthyl-4,7-diphenyl-1,10-phenanthroline(BCP)/tris(8-hydroxyquinoline)aluminum(Alq3)/Mg:Ag or that of ITO/NPB/1,2,3,4,5,6-hexakis(9,9-diethyl-9H-fluoren-2-yl)benzene(HKEthFLYPh)/Alq3/Mg:Ag were studied.White light emission was achieved with the two devices when the thicknesses of BCP and HKEthFLYPh were 1.5 nm(device B) and 5 nm(device II),respectively...     

不同电子传输层的蓝光有机电致发光器件的性能研究

自从Tang等^[1]首次报道多层有机电致发光器件（OLED）以来,其在亮度和效率上有了质的飞跃,表明器件的结构对提高发光亮度和发光效率起着至关重要的作用,单层器件虽然具有制作简单的优点,但却存在明显缺点：（1）复合发光区靠近金属电极,该处缺陷很多,非辐射复合几率大,导致器件效率降低;（2）由于两种载流子注入不平衡,载流子的复合几率较低,因而影响器件的发光效率,要使发光层中具有高的载流子辐射复合效率,两种载流子的注入及传输能力应相当,否则传输快的一方就会直接穿过发光层到达对电极被猝灭,平衡电子和空穴的注入与传输可通过在电极和发光层之间加入载流子输运层或限制层制作多层器件的途径来实现,基于上述考虑,我们以PPCP为发光层（PPCP是一种荧光效率较高的蓝光材料^[2-4],对其进行深入研究尚未见有文献报道＿,设计了4种不同电子传输层（ETL)的三层 结构的OLED,为研究电子传输层对器件性能的影响,我们还制备了不含电子传输层的双层器件,结果表明,通过选择合适的ETL,OLED的发光亮度及发光效率会有很大程度的改善。     

Interface modification of 8-hydroxyquinoline aluminium with combined effects in quasi-solid dye-sensitized solar cells

In this paper, 8-hydroxyquinoline aluminium (Alq(3)) was used in interface modification of dye-sensitized solar cells (DSCs). Alq(3) was the first discovered interface modification material with combined effects of retarding charge recombination and F?rster resonant energy transfer (FRET). Results of dark current curve and AC impedance showed that Alq(3) could retard charge recombination in DSCs. I-V curves showed that conversion efficiency increased with Alq(3) modification. Besides the interface modification effect, it was discovered that Alq(3) also acted as energy relay dye with the FRET effect between itself and N3, which increased photoresponse and electron injection. The application of Alq(3) with combined effects opened a new door to explore more novel multi-functional interface modification materials to improve the performance of DSCs.     

混合蓝色和绿色发射的高亮度白色有机电致发光器件

使用星形六苯芴类新材料1,2,3,4,5,6-hexakis(9,9-diethyl-9H-fluoren-2-yl)benzene (HKEthFLYPh)分别制备了三种不同结构的有机电致发光器件. 在结构为indium-tin oxide (ITO)/NPB (40 nm)/HKEthFLYPh (10 nm)/Alq3(50 nm)/Mg:Ag (200 nm)的器件中, 获得了两个电致发光谱峰分别位于435 和530 nm处的明亮白光. HKEth-FLYPh是能量传输层; N,N’-bis-(1-naphthyl)-N,N’-diphenyl-(1,1’-biphenyl)-4,4’-diamine (NPB)是空穴传输层和蓝色发光层; tris(8-hydroxyquinoline)aluminum (Alq3)是电子传输层和绿色发光层. 结果表明, 当驱动电压为15 V时, 器件的最大亮度达到8523 cd·m-2; 在5.5 V时, 器件达到最大流明效率为1.0 lm·W-1. 在电压为9 V时, CIE色坐标为(0.29, 0.34). 此外, 通过改变HKEthFLYPh层的厚度, 发现蓝色发射的相对强度随着HKEthFLYPh层厚度的增加而增强.     

Blue-light-emitting multifunctional triphenylamine-centered starburst quinolines: synthesis, electrochemical and photophysical properties

A series of triphenylamine-centered starburst quinolines (1a-1g) have been synthesized by Friedl?nder condensation of the 4,4',4'-triacetyltriphenylamine (2) and 2-aminophenyl ketones (3a-3g) in the presence of catalytic sulfuric acid and characterized well. They are thermally robust with high glass transition temperatures (above 176.4 °C) and decomposition temperatures (above 406 °C). These compounds emit blue fluorescence with λ(max)(Em) ranging from 433 to 446 nm in dilute toluene solution and 461 to 502 nm in the solid-state and have a relatively high efficiency (Φ(u) = 0.98-0.57). 1a-1g have estimated ionization potentials (IP) of 4.54 to 6.45 eV which are significantly near or higher than those of well-known electron transport materials (ETMs), including tris(8-hydroxyquinoline)aluminium (Alq(3)) (IP = 5.7-5.9 eV), and previously reported oligoquinolines (IP = 5.53-5.81 eV). Quantum chemical calculations using DFT B3LYP/6-31G* showed the highest occupied molecular orbital (HOMO) of -5.05 to -4.81 eV, which is close to the work function of indium tin oxide (ITO). These results demonstrate the potential of 1a-1g as hole-transporting/light-emitting/electron-transport materials and the host-materials of a dopant for hole-injecting for applications in organic light-emitting devices.     

Red electrophosphorescence from a soluble binaphthol derivative as host and iridium complex as guest

The investigation of the optical properties, carrier injection, and transport into a soluble small molecule, 6,6'-dicarbazolyl-2,2'-dihexyloxy-1,1'-binaphthol (BA), was reported. The results demonstrated that BA is a blue-emitting molecule, which can be used as a host for the fabrication of electrophosphorescent light-emitting diodes (LEDs). The single-layer electrophosphorescent LEDs fabricated from toluene solution containing BA with tris[2,5-bis-2'-(9',9'-dihexylfluorene)pyridine-kappa(2)NC(3)(')]iridium(III) [Ir(HFP)(3)] emitted red light from Ir(HFP)(3) triplet emission. The results from photoluminescence (PL) and electroluminescence (EL) demonstrated that the dominated operational mechanism in EL was charge trapping rather than F?rster transfer, which was the dominated mechanism in PL. The single-layer OLEDs with 1wt % of Ir(HFP)(3) have a luminance (L) of 1000 cd/m(2) at 22 V and a luminous efficiency (LE) of 0.88 cd/A at 11 mA/cm(2). Double-layer electrophosphorescent LEDs fabricated by casting the emitting layer from a solution of BA blended with Ir(HFP)(3) and subsequently thermally depositing tris(8-hydroxyquinoline) aluminum (Alq(3)) film as an electron injection and transport layer yielded L = 1830 cd/m(2) at 30 V and LE = 2.47 cd/A at 18 mA/cm(2). These results demonstrated that electrophosphorescent LEDs can be fabricated from BA via solution processing and that L and LE can be enhanced by changing the device architecture with the goal of better balancing the electron and hole currents.     

1,8-Naphthalimides in phosphorescent organic LEDs: the interplay between dopant,exciplex, and host emission

Four different 1,8-naphthalimide derivatives were examined in phosphorescent organic light emitting diodes (OLEDs), i.e., 1,8-naphthalimide, N-phenyl-1,8-naphthalimide, N-2,6-dibromophenyl-1,8-naphthalimide (niBr), and bis-N,N-1,8-naphthalimide. Photoluminescence from all four naphthalimides have violet-blue fluorescence and phosphorescent bands between 550 and 650 nm (visible at 77 K). While all four compounds gave good glassy films when doped with a phosphorescent dopant, only the niBr films remained glassy for extended periods. OLED studies focused on niBr, with two different architectures. One OLED structure (type 1) had the niBr layer as a doped luminescent layer and an undoped niBr layer to act as a hole-blocking layer. The alternate structure (type 2) utilizes a doped CBP layer as the luminescent layer and the niBr layer is used as a hole-blocking layer only (CBP = 4,4'-N,N'-dicarbazolylbiphenyl). Type 1 and 2 OLEDs were prepared with green, yellow, and red emissive phosphorescent dopants (Irppy, btIr, and btpIr, respectively). The dopants were organometallic Ir complexes, previously shown to give highly efficient OLEDs. Of the three dopants, the btpIr-based OLEDs showed the best device performance in both structures (peak efficiencies for type 2: 3.2% and 2.3 lum/W at 6.3 V; type 1: 1.7% and 1.3 lm/W at 6.1 V). The green and yellow dopants gave very similar performance in both type 1 and 2 devices (peak efficiencies are 0.2-0.3%), which were significantly poorer than the btpIr-based OLEDs. The emission spectrum of the btIr- and btpIr-based devices (type 1 and 2) are the same as the solution photoluminescence spectrum of the dopant alone, while the Irppy device gives a broad red emission line (lambda(max) = 640 nm). The red Irppy.niBr emission line is assigned to an Irppy.niBr exciplex. The type 2 Irppy-based device gave a voltage-dependent spectrum, with the red emission observed at low bias (4-8 V), switching over to strong green emission as the bias was raised. All other devices showed bias-independent spectra. Estimates of HOMO, LUMO, and excited-state energies (dopant, niBr, and exciplex) were used to explain the observed spectral properties of these devices. btpIr-based devices emit efficiently from isolated dopant states (external efficiencies = 3.2 %, 2.3 lum/W). Irppy-based devices emit only from exciplex states, with low efficiency (external efficiency = 0.3%). btIr.niBr films have very similar energies for the dopant, exciplex, and niBr triplet states, such that relaxation can go through any of these states, leading to low device efficiency (external efficiency = 0.4%). High device efficiency is achieved only when dopant emission is the dominant pathway for relaxation, since exciplex and niBr triplet states give either weak or no electroluminescence.     

Modulation of spontaneous emission characteristics of Alq3 in three‐dimensional PMMA photonic crystals

The effect of the photonic stop bands (PSBs) on the spontaneous emission from tris(8‐hydroxyquinolinato)aluminum (Alq3) doped in the beads of polymethylmethacrylate opal photonic crystals (PCs) is investigated in detail. The structure of PSBs in PCs has been analyzed. The steady emission data exhibits that the first‐ and second‐order PSB could effectively influence the spectral characteristics of Alq3 through changing the incident angles. The emission dynamic data is also investigated by using the Kohlrausch strengthened exponential model, which shows that the emission decay rate of Alq3 can be decelerated as the PSB of PC approaches the emission peak of Alq3. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 842–847