Influence of Poly(methylmethacrylate) on 8-hydroxyquinoline Derivative-Metal Complexes Electroluminescence

A new method is presented of enhancing the organic electroluminescent(EL) efficiency by using poly (methylmethacrylaie) (PMMA) as barrier layers which play the role of controlling the electron-hole recombination in the organic EL materials. The organic EL device with one layer of 8-hydroxyquinoline derivalive-metal complexes-(Alq3, Znq2) as the EL-emitting layers, and two layers of EL emitting materials deposited on PMMA Langmuir-Blodgett films (PMMA/Alq3, PMMA/Znq2) sandwiched between indium/tin oxide (ITO) and aluminum electrodes have been fabricated, respectively. The evidence reveals that the LB film takes an importance to raising the 8-hydroxyquinoline derivative-metal complexes EL efficiency.     

Chemistry between magnesium and multiple molecules in tris(8-hydroxyquinoline) aluminum films

Metal organic contacts are at the basis of devices such as organic light emitting diodes (OLEDs). Here, we report a theoretical investigation of the chemical interaction between a Mg atom and an organic film made of tris(8-hydroxyquinoline)aluminum (Alq3) molecules. The latter is modeled either by an isolated molecule or by a bulk crystal. Using first-principles molecular dynamics for structural optimization, we find that an isolated Alq3 molecule and a Mg atom form an ion-pair. However, when the metal atom interacts with molecules in a bulk crystalline environment, we find that an organometallic complex is energetically preferred over the ion-pair. The complex formation is an effect of the environment which makes possible the interaction of the metal atom with several adjacent molecules. Here, our calculated O(1s) and N(1s) core level shifts agree well with recent experimental data on Alq3 films exposed to Mg. Our results resolve the apparent contradiction between experiment and predictions made in previous calculations in which a single Alq3 molecule was used to model a thin film.     

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...     

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%.     

Simulating charge transport in tris(8-hydroxyquinoline) aluminium (Alq(3))

We present a model of charge transport in organic solids which explicitly considers the packing and electronic structure of individual molecules. We simulate the time-of-flight mobility measurement in crystalline and disordered films of tris(8-hydroxyquinoline) aluminium (Alq(3)). The morphology of disordered Alq(3) is modelled on a molecular scale, and density functional theory is used to determine the electronic couplings between molecules. Without any fitting parameters we predict electron mobilities in the crystalline and disordered phases of approximately 1 and approximately 10(-4) cm(2) V(-1) s(-1), respectively. In good agreement with experiment we find that electron mobilities are two orders of magnitude greater than those of holes. We explain this difference in terms of the spatial extent of the frontier orbitals. Our results suggest that charge transport in disordered Alq(3) is dominated by a few highly conducting pathways.     

High-efficiency tris(8-hydroxyquinoline)aluminum (Alq3) complexes for organic white-light-emitting diodes and solid-state lighting

Combinations of electron-withdrawing and -donating substituents on the 8-hydroxyquinoline ligand of the tris(8-hydroxyquinoline)aluminum (Alq(3)) complexes allow for control of the HOMO and LUMO energies and the HOMO-LUMO gap responsible for emission from the complexes. Here, we present a systematic study on tuning the emission and electroluminescence (EL) from Alq(3) complexes from the green to blue region. In this study, we explored the combination of electron-donating substituents on C4 and C6. Compounds 1-6 displayed the emission tuning between 478 and 526 nm, and fluorescence quantum yield between 0.15 and 0.57. The compounds 2-6 were used as emitters and hosts in organic light-emitting diodes (OLEDs). The highest OLED external quantum efficiency (EQE) observed was 4.6%, which is among the highest observed for Alq(3) complexes. Also, the compounds 3-5 were used as hosts for red phosphorescent dopants to obtain white light-emitting diodes (WOLED). The WOLEDs displayed high efficiency (EQE up to 19%) and high white color purity (color rendering index (CRI≈85).     

Triarylboron-functionalized 8-hydroxyquinolines and their aluminium(III) complexes

The first examples of triarylboron-functionalized 8-hydroxyquinoline ligands and their aluminium complexes have been synthesized. These luminescent derivatives of the well-known electron transport material tris(8-hydroxyquinoline)aluminium (Alq(3)) display enhanced electron-accepting ability relative to Alq(3), and can also be used as an indicator for small F(-) and CN(-) anions.     

Novel four-pyridylbenzene-armed biphenyls as electron-transport materials for phosphorescent OLEDs

A series of four-pyridylbenzene-armed biphenyl derivatives were designed and synthesized as an electron-transport and exciton- and hole-block layer for the fac-tris(2-phenylpyridine)iridium (Ir(PPy)3)-based green phosphorescent organic light-emitting devices (OLEDs), giving improved efficiency in comparison to that with both the electron-transport layer of tris(8-hydroxyquinoline)aluminum (Alq3) and the exciton- and hole-block layer of 2,9-dimethyl-4,7-diphenylphenathroline (BCP).     

含有Alq3和Znq2的可交联聚合物的合成与表征

合成了溶解性优良、带有可聚合链段的8-羟基喹啉金属螯合物(Alq3和Znq2)单体,在室温下通过紫外光照射,形成热力学性能稳定、8-羟基喹啉金属螯合物含量高(50(wt)%以上)的交联聚合物.这种材料可以解决使用旋涂的方法制备器件带来的底层溶解的问题,从而实现大面积、多层电致发光器件的制备,还可以通过光刻手段实现器件涂层图案化,是器件实现全彩色、超像素方法之一.其光致发光和电致发光性质证明这种材料本身以及其加工性能在有机/高分子平面显示技术领域有一定应用价值.     

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.     

八-羟基喹啉铝薄膜光致发光的厚度依赖性质

In situ thickness dependent photoluminescence (PL) measurements of tris(8-hydroxyquinoline) aluminum(Alq3) film were performed. At the beginning of Alq3 deposition on the glass substrate, the Alq3 emission showed a sharp red-shift. Further deposition of Alq3 resulted slight red-shift, and finally tended to saturated value. The total red-shift of about 12 nm was observed for the Alq3 film thickness range from 2 to 500 nm.This red-shift was attributed to the change from the 2D to 3D exciton state with increasing Alq3 film thickness. Meanwhile, the PL intensity of Alq3 emission increased continuously, and showed a rate change at the initial deposition of Alq3 due to non-rediative decay of excitons arised from the interaction between excitons and the substrate, and finally tended to saturation with the Alq3 thickness.     

Optimization of high-performance blue organic light-emitting diodes containing tetraphenylsilane molecular glass materials

Molecular glass material (4-(5-(4-(diphenylamino)phenyl)-2-oxadiazolyl)phenyl)triphenylsilane (Ph(3)Si(PhTPAOXD)) was used as the blue light-emitting material in the fabrication of high-performance organic light-emitting diodes (OLEDs). In the optimization of performance, five types of OLEDs were constructed from Ph(3)Si(PhTPAOXD): device I, ITO/NPB/Ph(3)Si(PhTPAOXD)/Alq(3)/Mg:Ag, where NPB and Alq(3) are 1,4-bis(1-naphylphenylamino)biphenyl and tris(8-hydroxyquinoline)aluminum, respectively; device II, ITO/NPB/Ph(3)Si(PhTPAOXD)/TPBI/Mg:Ag, where TPBI is 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene; device III, ITO/Ph(2)Si(Ph(NPA)(2))(2)/Ph(3)Si(PhTPAOXD)/TPBI/Mg:Ag, where Ph(2)Si(Ph(NPA)(2))(2) is bis(3,5-bis(1-naphylphenylamino)phenyl)-diphenylsilane, a newly synthesized tetraphenylsilane-containing triarylamine as hole-transporting material; device IV, ITO/Ph(2)Si(Ph(NPA)(2))(2)/NPB/Ph(3)Si(PhTPAOXD)/TPBI/Mg:Ag; device V, ITO/CuPc/NPB /Ph(3)Si(PhTPAOXD)/Alq(3)/LiF/Al, where CuPc is Cu(II) phthalocyanine. Device performances, including blue color purity, electroluminescence (EL) intensity, current density, and efficiency, vary drastically by changing the device thickness (100-600 A of the light-emitting layer) and materials for hole-transporting layer (NPB and/or Ph(2)Si(Ph(NPA)(2))(2)) or electron-transporting material (Alq(3) or TPBI). One of the superior OLEDs is device IV, showing maximum EL near 19 000 cd/m(2) with relatively low current density of 674 mA/cm(2) (or near 3000 cd/m(2) at 100 mA/cm(2)) and high external quantum efficiency of 2.4% (1.1 lm/W or 3.1 cd/A). The device possesses good blue color purity with EL emission maximum (lambda(max)(EL)) at 460 nm, corresponding to (0.16, 0.18) of blue color chromaticity on CIE coordinates. In addition, the device is reasonably stable and sustains heating over 100 degrees C with no loss of luminance on the basis of the annealing data for device V. Formation of the exciplex at the interface of NPB and Ph(3)Si(PhTPAOXD) layers is verified by EL and photoluminescence (PL) spectra studies on the devices with a combination of different charge transporting materials. The EL due to the exciplex (lambda(max)(EL) at 490-510 nm) can be properly avoided by using a 200 A layer of Ph(3)Si(PhTPAOXD) in device I, which limits the charge-recombination zone away from the interface area.     

Highly luminescent zinc(II)-bis(8-hydroxyquinoline) complex nanorods: sonochemical synthesis, characterizations, and protein sensing

Highly luminescent zinc(II)-bis(8-hydroxyquinoline) (Znq(2)) complex nanorods have been synthesized via a sonochemical route from the microemulsion containing zinc acetate and 8-hydroxyquinoline. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed that the products were rod-like morphology with a diameter of about 200-450 nm and a length of about 1-3 microm. A possible mechanism for the formation of Znq(2) nanorods is proposed that the ultrasound wave might urge the collision and fusion of initial Znq(2) nuclei to form nanorods. The photoluminescence (PL) and resonance light scattering (RLS) of the products were also investigated. The Znq(2) nanorods were found to be sensitive to several proteins, such as human serum albumin (HSA), bovine serum albumin (BSA), bovine hemoglobin (Hb), and egg albumin (EA), displaying an increase in intensities of both PL and RLS. The protein-concentration dependence of the PL and RLS intensities can be well described as a Langmuir-type binding isotherm. This is the first report on the enhancement of PL and RLS intensities of Znq(2) nanorods by proteins. On the basis of enhanced PL and RLS intensities, the protein could be detected at the nanogram per milliliter level. The experimental results clearly showed that the Znq(2) nanorods were good protein probes for easy and highly sensitive detection.     

基于N-对甲氧苯基咔唑-2-乙烯基-8-羟基喹啉锌的白色和黄色有机电致发光器件的性能

通过研究新型荧光染料N-对甲氧苯基咔唑-2-乙烯基-8-羟基喹啉锌(MoBCzHQZn)的电致发光(EL)特性, 发现MoBCzHQZn具有较强的发光特性和空穴传输特性, 利用此特性制备了非掺杂型的有机电致白光器件和掺杂型的有机电致黄光器件. 白光器件的结构为ITO/2T-NATA(20 nm)/MoBCzHQZn(25 nm)/NPBX(13 nm)/BCP(8nm)/Alq3(34 nm)/LiF(0.5 nm)/Al, 器件在15 V电压下实现了白光发射, 色坐标为(0.3719, 0.3275), 最大发光亮度为3414 cd·m-2, 在14 V 电压下的最大发光效率为1.69 cd·A-1、黄光器件的结构为ITO/2T-NATA(20 nm)/CBP:6%Ir(ppy)3:10%MoBCzHQZn(25 nm)/TPBi:6%Ir(ppy)3(47 nm)/LiF(0.5 nm)/Al, 器件在15 V电压下实现了黄绿光发射, 色坐标为(0.3590, 0.5787), 最大发光亮度为11073 cd·m-2, 在9 V电压下的最大发光效率为2.51 cd·A-1.     

Synthesis, crystal structure, and luminescent properties of a binuclear gallium complex with mixed ligands

By introducing tridentate Schiff base ligands, a binuclear gallium complex with mixed ligands, bis(salicylidene-o-aminophenolato)-bis(8-quinolinolato)-bis-gallium(III) [Ga(2)(saph)(2)q(2)], has been synthesized and structurally characterized by single-crystal X-ray crystallography. Crystal data for C(44)H(30)Ga(2)N(4)O(6) are as follows: space group, triclinic, P; a = 11.357(3) A, b = 12.945(3) A, c = 12.947(3) A, alpha = 103.461(15) degrees, beta = 100.070(7) degrees, gamma = 96.107(18) degrees, Z = 2. This complex was identified as a dimeric complex of hexacoordinated gallium with strong intermolecular and intramolecular pi-pi stacking interactions between the pyridyl/pyridyl rings. The thermal analysis showed that Ga(2)(saph)(2)q(2) can readily form a stable amorphous glass with a high glass transition temperature (T(g) = 204 degrees C), which is 27 degrees C higher than that of tris(8-hydroxyquinolinolate)aluminum (Alq(3)). In addition, a high photoluminescence efficiency (phi(PL)) of 0.318 in DMF has been demonstrated, although the central gallium atom can result in heavy-atom quenching. Organic light-emitting diodes (OLEDs) based on this complex displayed a turn-on voltage as low as 2.5 V and a high efficiency. Even at a low doping concentration of 1%, the doped Ga(2)(saph)(2)q(2) devices with 4-(dicyanomethylene)-2-tert-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as the dopant exhibited excellent red emission centered at 628 nm with improved durability, compared with the case of Alq(3) as the host. These distinguishing properties of Ga(2)(saph)(2)q(2) make it a good candidate as a novel electron-transporting and emitting material for OLEDs.     

Neutral copper(I) phosphorescent complexes from their ionic counterparts with 2-(2'-quinolyl)benzimidazole and phosphine mixed ligands

Neutral mononuclear Cu(I) complexes and their counterparts with counterion, i.e. Cu(qbm)(PPh(3))(2), Cu(qbm)(DPEphos), [Cu(Hqbm)(PPh(3))(2)](BF(4)) and [Cu(Hqbm)(DPEphos)](BF(4)), where Hqbm = 2-(2'-quinolyl)benzimidazole, DPEphos = bis[2-(diphenylphosphino)phenyl]ether, have been synthesized and characterized by X-ray structure analyses. All of the four complexes in solid state exhibit a strong phosphorescence band in the orange spectral region at room temperature. The photophysical properties of these complexes in both methylene chloride solution and poly(methyl methacrylate) film have been studied. Compared to the related cationic complexes, the neutral ones show blue-shifted emissions and longer lifetimes that can be attributed to the additional ligand-centered π-π* transition beside traditional metal-to-ligand charge-transfer (MLCT). By doping these complexes in N-(4-(carbazol-9-yl)phenyl)-3,6-bis(carbazol-9-yl) carbazole (TCCz), multilayer organic light-emitting diodes (OLEDs) were fabricated with the device structure of ITO/PEDOT/TCCz: Cu(I) (10 wt%)/BCP/Alq(3)/LiF/Al. The neutral complex Cu(qbm)(DPEphos) exhibits a higher current efficiency, up to 8.87 cd A(-1), than that (5.58 cd A(-1)) of its counterpart [Cu(Hqbm)(DPEphos)](BF(4)).     

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.     

Generation and decay dynamics of triplet excitons in Alq3 thin films under high-density excitation conditions

We studied the generation and decay dynamics of triplet excitons in tris-(8-hydroxyquinoline) aluminum (Alq3) thin films by using transient absorption spectroscopy. Absorption spectra of both singlet and triplet excitons in the film were identified by comparison with transient absorption spectra of the ligand molecule (8-hydroxyquinoline) itself and the excited triplet state in solution previously reported. By measuring the excitation light intensity dependence of the absorption, we found that exciton annihilation dominated under high-density excitation conditions. Annihilation rate constants were estimated to be gammaSS = (6 +/- 3) x 10(-11) cm3 s(-1) for single excitons and gammaTT = (4 +/- 2) x 10(-13) cm3 s(-1) for triplet excitons. From detailed analysis of the light intensity dependence of the quantum yield of triplet excitons under high-density conditions, triplet excitons were mainly generated through fission from highly excited singlet states populated by singlet-singlet exciton annihilation. We estimated that 30% of the highly excited states underwent fission.     

Design Strategy Towards Horizontally Oriented Luminescent Tetradentate-Ligand-Containing Gold(III) Systems

Phosphorescent dopants are promising candidates for organic light-emitting diodes (OLEDs). Although it has been established that the out-coupling efficiency and overall performances of vacuum-deposited OLEDs can be significantly improved by a horizontal orientation of the dopants, no horizontally oriented gold(III) complexes have been reported to date. Herein, a novel class of tetradentate C^C^N^N ligand-containing gold(III) complexes with a preferential horizontal orientation successfully generated through a one-pot reaction is reported. These complexes demonstrate high photoluminescence quantum yields of 70 % and a high horizontal dipole ratio of 0.87 in solid-state thin films. Green-emitting OLEDs based on these complexes operate with a maximum external quantum efficiency of 20.6 % with an estimated out-coupling efficiency of around 30 %. A promising device stability has been achieved in the vacuum-deposited OLEDs, with operational half-lifetimes of around 37 500 h at 100 cd m⁻².     

侧链含8-羟基喹啉铝配合物的聚苯乙烯的合成与发光性能研究

通过高分子反应法研究制备了高分子化的8-羟基喹啉铝发光材料.首先使用自制的氯甲基化试剂1,4-二氯甲氧基丁烷(BCMB),制备了5-氯甲基-8-羟基喹啉(CHQ);通过聚苯乙烯(PS)与CHQ之间的Friedel-Crafts烷基化反应,制得侧链键合有8-羟基喹啉(HQ)的改性聚苯乙烯HQ-PS;再使HQ-PS与二配体...