高色饱和度的微腔结构蓝色顶发射有机发光器件的光谱分析

制作了具有微腔结构的蓝色有机顶发射电致发光器件。利用TBADN∶3%DSAPh为发光材料,结构为Ag/ITO/CuPc/NPB/TBADN∶3%DSAPh/Alq₃/LiF/Al(Ag)。在玻璃基片上,制备Ag为阳极反射层,CuPc作为空穴注入层,NPB作为空穴传输层,ITO为光程调节层;Al/Ag作为半透明阴极,电极的透射率在30％左右。得到了半高宽仅为17nm发光光谱,实现了窄带发射。通过改变ITO的厚度,得到了纯度较高的蓝色发光光谱,色坐标为(0.141,0.049),实现了高色饱和度的发射。在文章中,作者研究了微腔器件的发光强度,当选择合适的阴极透射率时可以使发光强度达到最大。根据相关的公式,计算出了发光强度随阴极透射率(或者反射率)变化的近似曲线。     

Efficient and color-saturated inverted bottom-emitting organic light-emitting devices with a semi-transparent metal-assisted electron injection layer

We report the development of highly efficient and color-saturated green fluorescent 10-(2-benzothiazolyl)-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-benzo[l]pyrano-[6,7,8-ij]quinolizin-11-one dye-doped inverted bottom-emitting organic light-emitting diode (IBOLED). This was enabled by the insertion of a silver (Ag) based semi-transparent metal-assisted electron injection layer between the ITO cathode and n-doped electron transporting layer. This IBOLED with ITO/Ag bilayer cathode with its synergistic microcavity effect achieved luminous efficiencies of 20.7 cd/A and 12.4 lm/W and a saturated CIE_x,y of (0.22, 0.72) at 20 mA/cm², which are twice better than those of the conventional OLED and have over 60% improvement on IBOLED without ITO/Ag bilayer cathode.     

Color tunable high efficiency microcavity organic light-emitting diodes

Color tunable microcavity organic light-emitting diodes (OLEDs) with structure of distributed Bragg reflectors (DBR)/indium-tin-oxide (ITO)/N,N′-di(naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPB)/tris(8-hydroxyquinoline) aluminum (Alq₃)/LiF/Al were fabricated. Orange red and green light emissions with full width at half maximum (FWHM) of less than 20 nm were obtained through simply changing the thickness of NPB layer. Furthermore, due to the effective modification of the spontaneous emission within microcavity, the brightness and electroluminescent (EL) efficiency of the microcavity OLEDs were significantly enhanced. The maximum brightness and current efficiency, respectively, reached 31000 cd/m² at a current density of 480.0 mA/cm² and 8.3 cd/A at a current density of 110.0 mA/cm² for green devices, and 9700 cd/m² at a current density of 180.0 mA/cm² and 6.6 cd/A at a current density of 36.4 mA/cm² for red devices, which are over 1.5 times higher than those of noncavity OLEDs.      

有机微腔绿色发光二极管

光学微腔是指尺寸在光波长量级的光学微型谐振腔。微腔结构可以使腔内物质和光场的相互作用与体材料相比发生很大变化,出现了自发辐射谱线窄化和增强等腔效应。利用这些腔效应,可以改善有机发光器件的性能。采用微腔结构,优化设计并研制了有机微腔绿色发光二极管,器件结构为Glass/DBR/ITO/NPB/Alq∶Rubrene/Alq/MgAg,获得了最大亮度40100 cd/m2、最大发光效率为6.44 cd/A、半峰全宽为28 nm的纯绿色有机微腔电致发光器件。而与之比较的无腔器件最大亮度为22580 cd/m2、最大发光效率为2.98 cd/A、半峰全宽为120 nm。相同电流密度下微腔电致发光谱的峰值发射强度是无腔器件的4.2倍。结果表明将微腔结构引入有机电致发光器件中,不但改善了发光的色纯度,而且使器件的发光效率和亮度都得到明显增强。     

基于一种新型有机金属配合物的量子阱结构有机电致白光器件的性能研究

利用一种新型有机金属配合物二(2-(4-三氟甲基-2-羟基苯基)苯并噻唑锌(Zn(4-TfmBTZ)₂),基于NPB/Zn(4-TfmBTZ)₂界面电致激基复合物,制备了一系列异质结量子阱结构有机电致白光器件.结果表明,量子阱结构可以有效提高界面电致激基复合物的发光效率以及器件的显色指数和色度稳定性.得出器件ITO/NPB (60 nm)/Zn(4-TfmBTZ)₂(3.0 nm)/NPB (4.0 nm)/Zn(4-TfmBTZ)_{关键词： 二(2-(4-三氟甲基-2-羟基苯基)苯并噻唑锌 电致激基复合物 量子阱 白光}     

Pure red emission of dye-doped organic molecules from microcavity organic light emitting diode

Organic red emitting diode was fabricated by using 4-dicyanomethylene-2-methyl-6-[2-(2,3,6,7-tetrahydro-1 H,5H-benzo[ij]quinolizin-8-yl)vinyl]-4H-pyran (DCM)-doped tri-(8-quinolitolato) aluminum (Alq₃) as emitter with the structure of G/ITO/NPB(25 nm)/DCM:Alq₃(55 nm)/Alq₃(20 nm)/LiF (1.2 nm)/Al(84 nm), (glass/indium–tin-oxide/4,4-bis-[N-(1-naphthyl)-N-phenyl-amino]biphenyl, G/ITO/NPB), the wavelength of the maximal emission of which is 615 nm. By introducing cavity to Organic light emitting diode (OLED), we got pure red emitting diode with wavelength of the maximal emission of 621 nm and full-width at half-maximum (FWHM) of 27 nm. As far as we know, it is the best result in the dye-doped organic red emitting diode. We also made a device of G/ITO/NPB(25 nm)/DCM:Alq₃(29 nm)/DCM:PBD(26 nm)/Alq₃(20 nm)/LiF(1.2 nm)/Al(84 nm), in order to compare the performance of Alq₃ with that of 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) as host material. It was found that the performance of device A is better than that of C both in brightness and color purity,as well as in EL efficiency.     

Diffusion study of multi-organic layers in OLEDs by ToF-SIMS

A model organic light-emitting diodes (OLEDs) with structure of tris(8-hydroxyquinoline) aluminum (Alq₃)/N,N′-diphenyl-N,N′-bis[1-naphthy-(1,1′-diphenyl)]-4,4′-diamine (NPB)/indium tin oxide (ITO)-coated glass was fabricated for diffusion study by ToF-SIMS. The results demonstrate that ToF-SIMS is capable of delineating the structure of multi-organic layers in OLEDs and providing specific molecular information to aid deciphering the diffusion phenomena. Upon heat treatment, the solidity or hardness of the device was reduced. Complicated chemical reaction might occur at the NPB/ITO interface and results in the formation of a buffer layer, which terminates the upper diffusion of ions from underlying ITO.     

基于PVK的高色纯度高稳定性有机电致红光器件

利用旋涂法和真空蒸镀法相结合的方法,根据能量空间传递的原理制备了PVK ∶ Ir(piq)₂(acac)体系的红色有机电致发光显示器件。器件的结构为ITO/CuPc/PVK ∶ Ir(piq)₂(acac)/BCP/Alq₃/LiF/Al。研究了不同主客体掺杂比对器件发光性能的影响,得到了高色纯度、单色性较好的红光器件。当Ir(piq)₂(acac)掺杂的质量比为1 ∶ 0.08时,器件的综合性能达到最佳,发光峰位于625 nm,CIE坐标为(x=0.66,y=0.33)。通过对各层厚度的合理选择,形成相对优化的微腔结构,充分利用其对光谱的窄化效应,使得器件的EL光谱的发射半峰全宽仅为55 nm,提高了器件的发光性能。器件光谱具有很好的单色性,色纯度达到98.2%。     

The roles of zinc selenide sandwiched between organic layers and its applications in white light-emitting diodes

In this paper, the roles of zinc selenide (ZnSe) sandwiched between organic layers, i.e. organic/ZnSe/aluminum quinoline (Alq₃), have been studied by varying device structure. A broad band emission was observed from ITO/poly(N-vinylcarbazole)(PVK)(80 nm)/ZnSe(120 nm)/ Alq₃(15 nm)/Al under electric fields and it combined the emissions from the bulk of PVK, ZnSe and Alq₃, however, emission from only Alq₃ was observed from trilayer device ITO/N,N^′-bis-(1-naphthyl)-N,N^′-diphenyl-1, 1^′-biphenyl-4, 4^′-diamine (NPB) (40 nm)/ZnSe(120 nm)/ Alq₃(15 nm)/Al. Consequently the luminescence mechanism in the ZnSe layer is suggested to be charge carrier injection and recombination. By thermal co-evaporating Alq₃ and 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB), we get white light emission with a Commission Internationale de l’E clairage (C.I.E) co-ordinates of (0.32, 0.38) from device ITO/PVK(80 nm)/ZnSe(120 nm)/ Alq₃:DCJTB(0.5 wt% DCJTB)(15 nm)/Al at 15 V and the device performs stably with increasing applied voltages.     

发光层和空穴传输层对白色电致发光器件性能的影响

利用电子传输性能良好的苯并噻唑螯合锌(Zn(BTZ)₂)作为蓝光层，通过设计不同类型的空穴传输层并试验不同厚度的发光层后，制作了一种最佳厚度的双发光层白色电致发光器件：氧化铟锡(ITO)/N-N′-双(3-甲基苯基)-N-N′-二苯基-1-1′-二苯基-4-4′-二胺(TPD)∶N,N′-二(1-萘基)-N,N′-二苯基-1,1′-联苯-4-4′-二胺(NPB)(1∶0.0 关键词： 厚度 空穴传输层 白光 载流子     

电致发光色纯性增强的硅基有机微腔

报道了硅基有机微腔的电致发光（EL）.该微腔由上半透明金属膜、中心有源多层膜和多孔硅分布Bragg反射镜（PS DBR）组成.半透明金属膜由Ag（２０nm）构成，充当发光器件的负电极和微腔的上反射镜.有源多层膜由Al (1 nm) / LiF(05 nm) /Alq3/Alq3:DCJTB/NPB/CuPc/ITO/SiO2组成，其中的Al/LiF为电子注入层，ITO为正电极，SiO2为使正、负电极电隔离的介质层.该PS DBR是采用设备简单、成本低廉且非常省时的电化学腐蚀法用单晶Si来制备的；该PS 关键词： 电化学腐蚀 电致发光 窄峰发射 硅基有机微腔     

Modification of the organic/La0.7Sr0.3MnO3 interface by in situ gas treatment

La_0.7Sr_0.3MnO₃ (LSMO) can act as a spin injection electrode in organic spin-valves and organic light-emitting devices. For the latter application, good control of the electronic structure of the organic/LSMO interface is a key issue to ensure sufficient current injection in the device. By exposing cleaned LSMO surfaces to activated oxygen and hydrogen, the work function of the samples can reach 5.15 and 4.3 eV, respectively, as shown by in situ photoemission measurements. The initial stage of formation of the organic/LSMO interface upon deposition of N,N′-bis-(1-naphyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) onto the oxygen-treated LSMO surface is examined. We find that the NPB molecules evenly cover the LSMO surface and that the interface barrier height is 0.8 eV, which is comparable to that at the NPB/indium tin oxide (ITO) interface with the ITO surface pretreated in situ by oxygen plasma.     

白光微腔有机电致发光器件的结构设计与制备

采用一种宽谱带绿光发光材料,通过两个颜色互补的谐振模式结构设计实现了白光发射的微腔OLED.与普通结构的OLED相比,器件的电致发光效率提高了0.7倍.优化后的白光微腔OLED的色坐标为(0.34,0.33),且颜色不随工作电压变化.进一步改善显色指数性能则需要构建多个模式的微腔结构.     

高效高亮度有机红色微腔发光二极管

采用普通的Alq:DCM红光发光材料体系,制作了结构为Glass/DBR/ITO/NPB/Alq:DCM/MgAg的有机红光微腔发光器件,实现了纯红光发射,器件发射峰位于600 nm.与无腔器件相比,微腔器件光谱半峰全宽（FWHM）从92 nm压缩为32 nm,色度从X=0.58,Y=0.41改善为X=0.6,Y=0.4,微腔器件的最大发光效率为3.1 cd/A,最大亮度为32 010 cd/m2.     

Hole-transporting property of a chemically hybridized poly(vinylcarbazole)-fullerene

We synthesized a star copolymer of poly(vinylcarbazole) (PVK) branched from a fullerene (C₆₀) center, and investigated its optical absorption and photoluminescence properties. The chemically hybridized PVK-C₆₀ was then employed as a hole-transporting layer of the electroluminescent device with a poly(9,9^′-dihexylfluorene-2,7-divinylene-m-phenylenevinylene-stat-p-phenylenevinylene) (CPDHFPV) emitting layer. The ITO/PVK-C₆₀/CPDHFPV/LiF/Al device showed a strong electroluminescence quenching due to a direct contact of the PVK-C₆₀ and the CPDHFPV layers. In contrast, when an additional PVK layer was introduced between the two layers, the electroluminescence was largely enhanced. The emitted light power of the ITO/PVK-C₆₀/PVK/CPDHFPV/LiF/Al device was improved by 3 times compared with the device without the PVK-C₆₀ layer.     

Study of the electronic structure of Al(III) and Zn(II) complexes with organic ligands by quantum chemistry and photoelectron spectroscopy methods

Photoelectron spectra of aluminum complexes with 8-oxyquinoline (Alq ₃) and zinc complexes with N, N′-(o-phenylene)-bis(salicylidenediamine) (ZnSaloph) were measured on a photoelectron spectroscopy station at the Kurchatov Centre for Synchrotronic Radiation over the range of photon energies from 10 to 100 eV. Thin films of these compounds (∼20 nm thick) prepared by thermal evaporation onto glass substrates covered with transparent electroconductive layer of solid solution of tin and indium oxides (In₂O₃, SnO₂, ITO) were used as the objects of this study. The spectra of the valence band of these compounds and Al 2p level were measured. The data of quantum chemical calculations of the electronic structure obtained by the density functional theory are in good agreement with the experimental photoelectron spectra. Analysis of performance efficiency of the device was carried out on the basis of the results of calculation. This procedure does not result in decomposition of samples in the process of investigation and may be used for studying the electronic structure of coordination compounds with organic ligands in films.     

Electrical characteristics and efficiency of organic light-emitting diodes depending on hole-injection layer

In a device structure of ITO/hole-injection layer/N,N′-biphenyl-N,N′-bis-(1-naphenyl)-[1,1′-biphthyl]4,4′-diamine(NPB)/tris(8-hydroxyquinoline)aluminum(Alq₃)/Al, we investigated the effect of the hole-injection layer on the electrical characteristics and external quantum efficiency of organic light-emitting diodes. Thermal evaporation was performed to make a thickness of NPB layer with a rate of 0.5–1.0 Å/s at a base pressure of 5 × 10⁻⁶ Torr. We measured current–voltage characteristics and external quantum efficiency with a thickness variation of the hole-injection layer. CuPc and PVK buffer layers improve the performance of the device in several aspects, such as good mechanical junction, reducing the operating voltage, and energy band adjustment. Compared with devices without a hole-injection layer, we found that the optimal thickness of NPB was 20 nm in the device structure of ITO/NPB/Alq₃/Al. By using a CuPc or PVK buffer layer, the external quantum efficiencies of the devices were improved by 28.9% and 51.3%, respectively.     

一种新型有机电致微腔结构的双模发射

采用结构Glass／DBR／ITO／NPB／NPB：Alq／Alq／Al制作了有机微腔电致发光器件。将空穴传输材料与发光材料以一定比例混合作为发光层，为了便于对比，在不改变有机层的膜厚的情况下同时制作了传统的异质结微腔器件，发现两种器件的发光光谱有很大不同，器件的复合效率与传统的异质结器件相比也得到了很大提高，这是因为将两种有机材料混合能消除界面势垒，提高器件的复合效率，从而提高了器件的发光性能，实现了微腔双模发射，且两个模式的半峰全宽分别为8nm和12nm。通过进一步优化器件结构可以实现微腔白光发射。     

4,4′,4″-三(N-3-甲基苯基-N-苯基氨基)三苯胺掺杂MoOx作为空穴传输层对有机太阳电池性能的影响

通过采用4,4′,4″-三(N-3-甲基苯基-N-苯基氨基)三苯胺 (m-MTDATA)掺入MoO_x作为器件的空穴传输层来提高酞菁铜(CuPc)/C₆₀小分子 有机太阳电池的效率. 采用真空蒸镀的方法制备了一系列器件, 其中结构为铟锡氧化物 (ITO)/m-MTDATA:MoO_x(3:1)(30 nm)/CuPc(20 nm)/C₆₀(40 nm)/4,7-二苯 基-1,10-菲罗啉 (Bphen)(8 nm)/LiF(0.8 nm)/Al(100 nm)的器件, 在AM1.5 (100 mW/cm²)模拟太阳光的照射条件下, 开路电压V_oc=0.40 V, 短路电流J_sc=6.59 mA/cm², 填充因子为0.55, 光电转换效率达1.46%, 比没有空穴传输层的器件ITO/CuPc(20 nm)/C₆₀(40 nm)/Bphen(8 nm)/LiF(0.8 nm)/Al(100 nm) 光电转换效率提高了38%. 研究表明, 加入m-MTDATA:MoO_x(3:1)(30 nm)空穴传输层减小了有机层和ITO电极之间的接触电阻, 从而减小了整个器件的串联电阻, 提高了器件的光电转换效率.     

Modification of anode surface in organic light-emitting diodes by chalcogenes

Influence of thin chalcogen X (S, Se, Te) interlayer between anode (indium-tin oxide, ITO) and a layer of N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD) used as a hole-transport layer (HTL) on the operating characteristics of organic light-emitting diodes (OLEDs) of composition ITO/X/TPD/Alq₃/Yb (Alq₃ - aluminum 8-quinolinolate) has been investigated. It was found that the sulphur layer decreases operating voltage and enhances operating stability of a device while the selenium or tellurium interlayers impair these characteristics.