亚单层黄色有机发光器件制备与光电性能研究

采用掺杂薄层作为亚单层有机发光技术,利用沉积在有机发光器件发光层中的亚单层分子[2-methyl-6-[2-(2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene]propane-dinitrile(DCM2)作为探针,同时改变DCM2层的位置,制备了四种亚单层结构的有机发光器件,对有机发光器件中激子的形成与扩散进行了研究,通过对各器件不同条件下的电致发光谱、发光强度和发光效率的对比研究,得到在N,N′-bis-(1-naphthyl)-N,N′-diphenyl-1,1′-biph-enyl-4,4′-diamine(NPB)/(8-hydroxyquinoline)aluminium(Alq)异质结界面处引入亚单层DCM2可以使DCM2分子获得的激子数量最多,获得了高效率的黄色有机发光器件.从其中总结规律,对有机发光器件制作有一定的指导作用.     

有机多层阱结构中光谱蓝移的研究

为了研究有机多层阱结构中光谱蓝移的原因,制备了以N,N′-Di-[(1-naphthalenyl)-N,N′-diphenyl]-(1,1′-biphenyl)-4,4′-diamine (NPB) 为垒层和以Tris-(8-quinolinolato)aluminum(Alq3) 为阱层的有机多层阱结构器件.利用光致发光的方法,对具有不同周期及不同阱层厚度的有机多层阱结构器件进行研究.分析认为有机多层阱结构中的光谱蓝移是由于光谱重叠造成的,而并非量子尺寸效应或激子限制效应.     

沉积亚单层荧光染料提高有机发光器件的发光效率

结合掺杂薄层作为发光探针层的方法和亚单层（sub-monolayer）有机发光技术，利用沉积在有机发光器件发光层中的亚单层奎丫啶酮（Quinacridone，QAD）分子作为探针，同时改变QAD层的位置，对有机发光器件中激子的形成与扩散进行了研究，器件结构为ITO/NPB(60 nm)/ Alq3(x nm)/QAD(0.05 nm)/Alq3［(60－x) nm］/LiF/Al（其中x=0，2.5，5，7.5 nm）.通过对各器件不同条件下的电致发光谱、发光强度和发光效率的对比研究，得到在x＝5 nm处引入亚单层QAD可以使QAD分子通过能量转移而获得的激子数量最多，进而可以实现高效率的发光.     

DPVBi为激子阻挡层的亚单层有机发光器件的制备与光电性能研究

结合亚单层的有机发光技术,制备了一种多层有机电致发光器件,其结构为ITO/m-MTDATA (50nm)/ C545T (0.05nm) /DPVBi (d nm)/DCM2(0.05nm)/ Alq (60nm) /LiF(1nm) /Al.荧光材料C545T和DCM2以亚单层的方式插入DPVBi前后,通过改变DPVBi的厚度,观察器件性能的变化,当DPVBi为4 nm时,器件在4V电压下最大发光效率是4.19 cd/A,在13 V电压下最大亮度是17050 cd/m2.分析对比了四种不同厚度器件的电流密度-电压曲线、亮度-电压曲线、电致发光光谱图和色坐标,发现选择合适厚度的激子阻挡层,可以得到效率较高的器件.激子阻挡层一般选择载流子传输能力较差,HOMO能级较低的材料.所得结果对有机发光器件尤其是采用亚单层有机白光器件的设计和制作有一定的指导作用.     

三元铱配合物磷光体系的白光有机电致发光器件光谱特性研究

将黄光磷光材料bis[2-(4-tertbutylphenyl)benzothiazolato-N,C2’]iridium (acetylacetonate) [(t-bt)₂Ir(acac)]超薄层作为黄光发光层,两个蓝光磷光染料iridium(Ⅲ) bis(4’,6’-difluorophenylpyridinato)tetrakis(1-pyrazolyl)borate (FIr6)和bis[(4,6-difluorophenyl)-pyridinato-N,C2’](picolinate) iridium (Ⅲ) (FIrpic)掺杂层作为蓝光发光层,制备了三元发光层的白光有机电致发光器件。该器件具有三元磷光染料分子协同发光特性,并且利用合适厚度的隔层,将三线态激子束缚在各自激子复合区域内,获得了稳定电致发光光谱,CIE色坐标为(0.29±0.01, 0.34±0.01),处于理想的白光区域。通过器件电学特性的测试,验证了磷光染料在三元发光层器件中电致发光作用的机理,同时结果表明,三元发光层器件由于稳定的激子复合区域而有效减弱了器件效率滚降现象。     

掺杂PVK光电特性研究

将磷光材料三-（2-苯基吡啶）-铱[Ir（ppy）3]掺杂在聚乙烯基咔唑（PVK）中作为发光层,制作了多层有机电致发光器件。采用常规的光电测量方法,研究其光致发光及电致发光特性,得到了激子形成截面随电压的变换关系。     

荧光染料和磷光染料激子形成截面的比较

为了比较单线态激子与三线态激子形成截面的大小,作者将荧光染料4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) 和磷光材料factris-(2-phenylpyridine) iridium [Ir(ppy)₃]共掺杂在N-vinylcarbazole (PVK)中作为发光层,制作了多层有机电致发光器件。通过对其光致发光及电致发光特性的研究,计算出Ir(ppy)₃激子的形成截面比DCJTB激子的形成截面大得多。     

插入电荷控制层对蓝色OLED发光性能的提高

用蓝色有机荧光材料N⁶,N⁶,N¹²,N¹²-tetrap-tolylchrysene-6,12-diamine （DNCA）作为发光层,在发光层中间以及发光层与电子传输层之间插入2-methyl-9,10-di（2-napthyl）anthracene （MADN） 和9,10-di（2-naphthyl）anthracene （ADN） 作为电荷控制层,制备了结构为ITO/NPB（40 nm）/DNCA（15 nm）/MADN（3 nm）/DNCA（15 nm）/ADN（3 nm）/Bphen（30 nm）/LiF（0.8 nm）/Al（120 nm）的蓝色有机电致发光器件（OLED）。该器件的最大电流效率和最大亮度分别为5.6 cd/A和23 310 cd/m²。与传统的单发光层器件相比,最大电流效率和最大亮度分别提高了70%和87%。器件发光性能的提高可归结于两个电荷控制层在整个器件中的协同作用。第一电荷控制层MADN的作用主要是将发光层区域分成两个部分,从而扩大了激子在发光层中的复合区域;第二电荷控制层ADN可以有效地将空穴限制在发光层中,避免了激子在电子传输层中形成的无辐射跃迁从而提高了器件的发光性能。     

利用复合色彩转换膜实现白色有机电致发光

利用蓝色有机发光二极管激发荧光色彩转换膜的方法,制备了一种新型的白色有机电致发光器件.蓝色有机发光二极管的发光层采用在4,4′-Bis(carbazol-9-yl)biphenyl(CBP)主体中掺杂高效蓝色荧光染料N-(4-((E)-2-(6-((E)-4-(diphenylamino)styryl)naphthalen-2-yl)vinyl)phenyl)-N-phenylbenzenamine (N-BDAVBi)来制备.有机/无机复合色彩转换膜是将有机荧光颜料VQ-D25和无机荧光粉钇铝石榴石(YAG)按一定的重量比均匀分散到-[CH3CH2COOCH3]n- (PMMA)中经涂敷、固化而成.通过与单纯有机或无机色彩转换膜的比较及调整复合转换膜本身的厚度和荧光颜料的掺杂比例来优化白光器件的发光光谱,获得了色稳定性较高的白色有机电致发光器件.当驱动电压由6 V升至14 V时,器件的色坐标仅在(0.354,0.304)和(0.357,0.312)之间变化,其最高电流效率约为5.8 cd/A(4.35 mA/cm2),最高亮度为16 800 cd/m2(14 V).     

高效率双发光层结构白色有机电致发光器件

采用双极性材料4,4'-bis(carbazol-9-yl)biphenyl(CBP)为主体,蓝色荧光染料N-(4-((E)-2-(6-((E)-4-(diphenylamino)styryl)naphthalen-2-yl)vinyl)phenyl)-N-phenylbenzenamine(N-BDAVBi)和橙色磷光染料Iridium(III)bis(4-phenylthieno[3,2-c]pyridinato-N,C2')acetylacetonate(PO-01)为客体,制备了双发光层结构的白色有机电致发光器件,通过调整发光层的位置及在两个发光层之间引入间隔层,研究了器件的光电特性.间隔层的引入调整了发光层中激子的分布,改善了器件的光电性能.器件的最大电流效率和功率效率分别为19.6cd/A和12.3lm/W.发光亮度从15cd/m2增加至10 310cd/m2的过程中,器件的色坐标从(0.438,0.476)变化至(0.316,0.389),始终处于白光区.     

Red organic light-emitting devices with dotted-line doped emitting layers

High efficiency red organic light-emitting devices (OLEDs) with several dotted-line doped layers (DLDLs) were fabricated by using an ultra-high vacuum organic molecular-beam deposition system. The red OLEDs consisted of indium-tin-oxide (ITO)/N, N′-diphenyl-N, N′-bis(1-naphthyl)-(1, 1′-biphenyl)-4, 4′-diamine (α-NPD): 40 nm/tris(8-hydroxyquinoline)aluminum (Alq₃)+4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetra-methyljuloldyl-9-enyl)-4H-pyran (DCJTB); 3%wt.: x nm/(Alq₃+DCJTB; 3%wt./ Alq₃)_n−1: (30−x) nm/ Alq₃: 30 nm/Mg:Ag with n of 2, 4, 6, or 8, and x=30/(2n−1). The luminance yield of the device with 8 DLDLs was 75% higher than that of the device with a common doped layer. This was attributed to more formation of the excitons formed in a wider region resulting from the existence of the DLDLs. The dominant mechanisms of the dopant emission for the devices with DLDLs were described on the basis of the sequential carrier trapping process.     

Solution-processed white organic light-emitting devices based on small-molecule materials

We investigated solution-processed films of 4,4′-bis(2,2-diphenylvinyl)-1,1′-bibenyl (DPVBi) and its blends with N,N′-bis(3-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TPD) by atomic force microscopy (AFM). The AFM result shows that the solution-processed films are pin-free and their morphology is smooth enough to be used in OLEDs. We have developed a solution-processed white organic light-emitting device (WOLEDs) based on small-molecules, in which the light-emitting layer (EML) was formed by spin-coating the solution of small-molecules on top of the solution-processed hole-transporting layer. This WOLEDs, in which the EML consists of co-host (DPVBi and TPD), the blue dopant (4,4′-bis[2-(4-(N,N-diphenylamino)phenyl)vinyl]biphenyl) and the yellow dye (5,6,11,12-tetraphenylnaphtacene), has a current efficiency of 6.0 cd/A at a practical luminance of 1000 cd/m², a maximum luminance of 22500 cd/m², and its color coordinates are quite stable. Our research shows a possible approach to achieve efficient and low-cost small-molecule-based WOLEDs, which avoids the complexities of the co-evaporation process of multiple dopants and host materials in vacuum depositions.     

Optimal thickness of hole transport layer in doped OLEDs

Current-voltage (I–V) and electroluminescence (EL) characteristics of organic light-emitting devices with N,N’-Di-[(1-naphthalenyl)-N,N’-diphenyl]-(1,1’-biphenyl)-4,4’-diamine (NPB) of various thicknesses as the hole transport layer, and tris(8-hydroxyquinoline)aluminum (Alq₃) selectively doped with 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM) as the electron transport layer, have been investigated. A trapped charge induced band bend model is proposed to explain the I–V characteristics. It is suggested that space charge changes the injection barrier and therefore influences the electron injection process in addition to the carrier transport process. Enhanced external quantum efficiency of the devices due to the electron blocking effect of an inserted NPB layer is observed. The optimal thickness of the NPB layer is experimentally determined to be 12±3 nm in doped devices, a value different from that for undoped devices, which is attributed to the electron trap effect of DCM molecules. This is consistent with the result that the proportion of Alq₃ luminescence in the total electroluminescence (EL) spectra increases with NPB thickness up to 12 nm under a fixed bias. PACS 72.80.Le; 85.60.Jb     

Improved outcoupling of light in organic light emitting devices, utilizing a holographic DFB-structure

In this work organic light emitting devices (OLEDs) were fabricated implementing gratings, in order to extract waveguided electroluminescence (EL). The gratings were recorded by exposing thin films of the molecular azo glass N, N′-bis (4-phenyl)-N, N′-bis [(4-phenylazo)-phenyl] benzidine (AZOPD) to holographic light patterns. The photopatterned AZOPD serves as hole transport material for devices with aluminum-tris(8-hydroxyquinoline) doped with 1% of 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (Alq₃:DCM) as emissive/electron transport layer. The corrugated devices showed enhanced emission in the forward direction. The emitted light is polarized preferably parallel to the grating lines. In addition, we have found a doubling in the total luminance with respect to the unstructured device.     

NaCl/Ca/Al as an efficient cathode in organic light-emitting devices

An efficient cathode NaCl/Ca/Al used to improve the performance of organic light-emitting devices (OLEDs) was reported. Standard N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′ biphenyl 4,4′-dimaine (NPB)/tris-(8-hydroxyquinoline) aluminum (Alq₃) devices with NaCl/Ca/Al cathode showed dramatically enhanced electroluminescent (EL) efficiency. A power efficiency of 4.6 lm/W was obtained for OLEDs with 2 nm of NaCl and 10 nm of Ca, which is much higher than 2.0 lm/W, 3.1 lm/W, 2.1 lm/W and 3.6 lm/W in devices using, respectively, the LiF (1 nm)/Al, LiF (1 nm)/Ca (10 nm)/Al, Ca (10 nm)/Al and NaCl (2 nm)/Al cathodes. The investigation of the electron injection in electron-only devices indicates that the utilization of the NaCl/Ca/Al cathode substantially enhances the electron injection current, which in case of OLEDs leads to the improvement of the brightness and efficiency.     

Characterization of amorphous organic thin films, determination of precise model for spectroscopic ellipsometry measurements

The optical properties of tris(8-hydroxyquinoline) aluminum (Alq₃), N,N′-diphenyl-N,N′-bis(1-naphthyl)-1-1′biphenyl-4,4″diamine (α-NPD) and other amorphous organic materials for OLEDs application, e.g. 4,4-bis(2,2-diphenyl vinyl)-1,1-biphenyl (DPVBI) and Spiro-DPVBI have been studied by multi-angle spectroscopic ellipsometry (SE). The thin films of these materials have been deposited by organic vapor phase deposition (OVPD). The structural characterization has been performed using atomic force microscopy (AFM) and X-ray reflectometry (XRR). Comparison of the measurements using these different independent techniques enables the precise determination of the optical model for dielectric function of these thin films. The detail analyses on Alq₃ and α-NPD show that the Kim model with Gaussian broadening provides a significantly better fit to the ellipsometry data than the frequently used harmonic oscillator model. This conclusion is further proved by performing similar measurements on other amorphous organic samples for OLEDs application, e.g. DPVBI and Spiro-DPVBI. This result can be explained by the characteristic features of electronic states in organic molecules.     

Nondoped phosphorescent organic quantum well light-emitting device based on iridium complex: Synthesis, characterization, photophysical property, and electroluminescence performance

In this paper, we report a phosphorescent Ir(III) emitter of Ir(acac)(F-BT)₂, where acac=acetylacetonate and F-BT=2-(2-fluorophenyl)benzo[d]thiazole, including its crystal structure, electronic nature, photophysical characteristics, thermal, and electrochemical properties. Data suggest that Ir(acac)(F-BT)₂ is a promising emitter with high quantum yield of 0.61 and good thermal stability, along with its proper energy levels for charge carrier transportation. Multiple quantum well (MQW) structured OLEDs using Ir(acac)(F-BT)₂ as emitter are also fabricated, and their electroluminescence (EL) are investigated in detail. The optimal EL device with 4,4′-N,N′-dicarbazole-biphenyl as potential well layer shows a maximum luminance of 85,500 cd/cm² and a peak current efficiency of 31.5 cd/A, and the efficiency roll-off is efficiently reduced.     

White organic light emitting diodes based on DCM dye sandwiched in 2-methyl-8-hydroxyquinolinolatolithium

Stable white electroluminescence (EL) has been achieved from organic LED, in which an ultrathin 4-(dicyanomethylene)-2-methyl-6-(p-dimethyl-aminostyryl)-4H-pyran (DCM) dye layer has been inserted in between two 2-methyl-8-hydroxyquinolinolatolithium [LiMeq] emitter layer and by optimizing the position of the DCM dye layer from the α-NPD/LiMeq interface. Electroluminescence spectra, current-voltage-luminescence (I-V-L) characteristics of the devices have been studied by changing the position of the dye layer. As the distance of DCM layer from α-NPD/LiMeq interface is increased, the intensity of host emission enhances rapidly. Introduction of thin layer of DCM in emissive layer increases the turn on voltage. The best Commission International de L’ Eclairage (CIE) coordinates i.e. (0.32, 0.33) were obtained with device structure ITO/α-NPD(30 nm) /LiMeq(10 nm)/DCM(1 nm)/LiMeq(25 nm)/BCP(6 nm)/Alq₃(28 nm)/LiF(1 nm)/Al(100 nm). The EL spectrum covers the whole visible spectra range 400-700 nm. The color rendering index (CRI) for our best white light (Device 4) is 47.4. The device shows very good color stability in terms of CIE coordinates with voltages. The maximum luminescence 1240 cd/m⁻² has been achieved at 19 V.     

Color-tunable organic light-emitting devices using a thin N,N′-bis-(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine layer at heterojunction interface

Novel types of multilayer color-tunable 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)/aluminum (III)bis(2-methyl-8-quinolinato)4-phenylphenolato (BAlq)/tris-(8-hydroxyquinolate)-aluminum (Alq₃)/Mg:Ag were fabricated. By inserting a thin layer with different thickness of a second NPB layer at the heterojunction interface of BAlq/Alq₃, the emission zone of devices shifted greatly and optoelectronic characteristics underwent large variation. Although BAlq was reported as a very good hole-blocking and blue-light-emission material, results of measurements in this paper suggested that a certain thickness of NPB layer between BAlq and Alq₃ plays an important role to modify device characteristics, which can act as recombination-controlling layer in the multilayer devices. It also provides a simple way to fabricate color-tunable OLEDs by just changing the thickness of this “recombination-controlling” layer rather than doping by co-evaporation.