Low voltage red phosphorescent organic light-emitting devices with triphenylphosphine oxide and 4,4′-bis(2,2′-diphenylvinyl)-1,1′-biphenyl electron transport layers

We have developed red phosphorescent organic light-emitting devices operating at low voltages by using triphenylphosphine oxide (Ph₃PO) and 4,4′-bis(2,2′-diphenylvinyl)-1,1′-biphenyl (DPVBi) electron transport layers. 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP) and tris-(1-phenylisoquinolinolato-C²,N) iridium(III) [Ir(piq)₃] were used as host and guest materials, respectively. Small voltage drops across the electron transport layers and direct injection of holes from 4,4′,4″-tris[N-(2-naphthyl)-N-phenyl-amino]-triphenylamine (2-TNATA) hole transport layer into the Ir(piq)₃ guests are responsible for the high current density at low voltage, resulting in a high luminance of 1000 cd/m² at low voltages of 2.8–3.0 V in devices with a structure of ITO/2-TNATA/CBP:Ir(piq)₃/DPVBi/Ph₃PO/LiF/Al.     

基于量子阱结构的高效磷光有机电致发光器件

采用多重量子阱结构制作了高效红色磷光有机电致发光器件。以4,4'-bis(N-carbazolyl)-1,10-biphenyl (CBP)掺杂bis(1-phenyl-isoquinoline)(Acetylacetonato) iridium(Ⅲ) (Ir(piq)₂(acac))为发光层,4,4'-bis(N-carbazolyl)-1,10-biphenyl(Bphen)为电荷控制层,形成了Ⅱ型双量子阱结构,器件的最大亮度为15 000 cd/m²,最大电流效率为7.4 cd/A,相对于参考器件提高了21%。研究结果表明:以Bphen为电荷控制层形成的Ⅱ型多重量子阱结构能有效地将载流子和激子限制在势阱中,并且使空穴和电子的注入更加平衡,从而提高了载流子复合的几率和器件的效率。     

A study on the characteristics of OLEDs using Ir complex for blue phosphorescence

Several iridium-based complexes were investigated as phosphorescent dopants. They achieved about 100% internal quantum efficiency, due to utilization of both singlet and triplet excitons in the radiative processes. We have fabricated phosphorescent OLEDs with 8% Ir(ppz)₃ as a triplet emissive dopant in various host materials. CBP, which has an efficiency of 0.20 cd/A, is the best host material. Furthermore, we synthesized metal-organic phosphor complexes based on Ir with different ligands as to (Im)₂Ir(acac), (Im-R)₂Ir(acac), and Ir(ppz)₂(acac).     

基于铱配合物材料的高效高稳定性有机发光二极管

使用基于重金属Ir的新磷光材料(tpbi)₂Ir(acac)，制备了多层结构有机发光二极管器件: ITO/CuPc (40 nm)/α-NPD (45 nm)/CBP: (tpbi)₂Ir(acac) (3%, 30nm)/BCP(20 nm)/Alq₃ (20 nm)/LiF (1 nm)/Al (100 nm).测试了材料的寿命、光谱吸收性质和器件的I-V-L特性.器件在低电压下电流符合热发射注入模型，高电压下I-V呈线形关系.不同偏压下器件发光光谱稳定，多峰拟合结果表明器件光谱由α-NPD发光峰(450 nm)，(tpbi)₂Ir(acac)主发光峰(518 nm)和肩峰(543 nm)构成.驱动电压为6 V时，器件效率达到最大12.1 lm/W，此时亮度为136 cd/m²，器件亮度最大为13500 cd/m²，此时效率为0.584 lm/W. 关键词： 有机发光二极管 磷光 效率 I-V-L特性')" href="#">I-V-L特性 光谱     

Solution-processed white organic light-emitting diodes with mixed-host structures

Efficient white light-emitting diodes (WOLEDs) were fabricated with a solution-processed single emission layer composed of a molecular and polymeric material mixed-host (MH). The main host used was a blue-emitting molecular material of 4,4′-bis(2,2′-diphenylvinyl)-1,1′-biphenyl (DPVBi) and the assisting host used was a hole-transport-type polymer of poly(9-vinylcarbazole) (PVK). By co-doping 4,4′-bis[2-(4-(N,N-diphenylamino)phenyl)vinyl]biphenyl and 5,6,11,12-tetraphenylnaphacene into the MH, the performances of the fabricated devices made with different mixing ratio of host materials were investigated, and were to depend on the mixing ratios. Under the optimal PVK:DPVBi ratio (3:7), we achieved a maximum luminance of 14 110 cd/m² and a maximum current efficiency of 9.5 cd/A. These improvements were attributed to the MH structure, which effectively improved the thermal stability of spin-coated film and enhanced the hole-injection/transporting properties of WOLEDs.     

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.     

Electroluminescence of organic light-emitting diodes consisting of an undoped (pbi)2Ir(acac) phosphorescent layer

The electroluminescence (EL) characteristics of phosphorescent organic light-emitting diodes (OLEDs) with an undoped bis(1,2-dipheny1-1H-benzoimidazole) iridium (acetylacetonate) [(pbi)₂Ir(acac)] emissive layer (EML) of various film thicknesses were studied. The results showed that the intensity of green light emission decreased rapidly with the increasing thickness of (pbi)₂Ir(acac), which was relevant to the triplet excimer emission. It suggested that the concentration quenching of monomer emission in the undoped (pbi)₂Ir(acac) film was mainly due to the formation of triplet excimer and partly due to the triplet-triplet annihilation (TTA) and triplet-polaron annihilation (TPA). A green OLED with a maximum luminance of 26,531 cd/m², a current efficiency of 36.2 cd/A, and a power efficiency of 32.4 lm/W was obtained, when the triplet excimer emission was eliminated. Moreover, the white OLED with low efficiency roll-off was realized due to the broadened recombination zone and reduced quenching effects in the EML when no electron blocking layer was employed.     

不同主体双发光层白色有机电致发光器件的性能研究

制备了结构为ITO/NPB/CBP:TBPe:rubrene/BAlq:Ir(piq)₂(acac)/BAlq/Alq₃/Mg:Ag的白色磷光有机电致发光器件.利用两种不同的主体材料,即用双载流子传输型主体材料CBP掺杂荧光染料TBPe及rubrene作为蓝光和橙黄光发光层;用电子传输型主体材料BAlq掺杂磷光染料Ir(piq)₂(acac)作为红色发光层.以上双发光层夹于空穴传输层NPB与具有电子传输性的阻挡层BALq之间.讨论了如何控制 关键词： 有机电致发光 磷光染料 掺杂 白光     

Influence of Dopant Concentration on Electroluminescent Performance of Organic White-Light-Emitting Device with Double-Emissive-Layered Structure

A novel phosphorescent organic white-light-emitting device （WOLED） with contiguration of ITO/NPB/CBP： TBPe：rubrene/Zn（BTZ）2：Ir（piq）2（acac）/Zn（BTZ）2/Mg：Ag is fabricated successfully, where the phosphorescent dye bis （1-（phenyl）isoquinoline） iridium （Ⅲ） acetylanetonate （Ir（piq）2 （acac）） doped into bis-（2-（2-hydroxyphenyl） benzothiazole）zinc （Zn（BTZ）2） （greenish-blue emitting material with electron transport character） as the red emitting layer, and fluorescent dye 2,5,8,11-tetra-tertbutylperylene （TBPe） and 5,6,11,12-tetraphenyl-naphthacene （rubrene） together doped into 4,4＇-N,N＇-dicarbazole-biphenyl （CBP） （ambipolar conductivity material） as the blue-orange emitting layer, respectively. The two emitting layers are sandwiched between the hole-transport layer N ,N＇-biphenyl-N , N＇-bis （1-naph thyl）-（1,1＇-biphenyl）-4, 4 Cdiamine （NP B） and electron-transport layer （Zn（BTZ）2 ） The optimum device turns on at the driving voltage of 4.5 V. A maximum external quantum efficiency of 1.53%. and brightness 15000 cd/m^2 are presented. The best point of the Commission Internationale de 1＇Eclairage （CIE） coordinates locates at （0.335, 0.338） at about 13 V. Moreover, we also discuss how to achieve the bright pure white light through optimizing the doping concentration of each dye from the viewpoint of energy transfer process.     

Efficient red organic light-emitting diode sensitized by a phosphorescent Ir compound

The efficiencies of red organic light-emitting diode (OLED) using tris-(8-hydroxy-quinoline)aluminum (Alq₃) as host and 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as dopant were greatly increased by adding a small amount (0.3 wt%) of Ir compound, iridium(III) bis(3-(2-benzothiazolyl)-7-(diethylamino)-2H-1-benzopyran-2-onato-N′,C⁴) (acetyl acetonate) (Ir(C6)₂(acac)), as a sensitizer. The device has a sandwiched structure of indium tin oxide (ITO)/4,4′,4″-tris(N-(2-naphthyl)-N-phenyl-amino)triphenylamine (T-NATA) (40 nm)/N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′ diamine (NPB) (40 nm)/Alq₃:DCJTB (0.7 wt%):Ir(C6)₂(acac) (0.3 wt%) (40 nm)/Alq₃ (40 nm)/LiF (1 nm)/Al (120 nm). It can be seen that the current efficiencies of this device remained almost (13.8±1) cd/A from 0.1 to 20,000 cd/m² and the Commission International d’Eclairage (CIE) coordinates at (0.60, 0.37) in the range of wide brightness. The significant improvement was attributed to the sensitization effect of the doped Ir(C6)₂(acac), thus the energy of singlet and triplet excitons is simultaneously transferred to the DCJTB.     

Improving the color purity and efficiency of blue organic light-emitting diodes (BOLED) by adding hole-blocking layer

This work demonstrates the fabrication of a bright blue organic light-emitting diode (BOLED) with good color purity using 4,4′-bis(2,2-diphenylvinyl)-1,1′-biphenyl (DPVBi) and bathocuproine (BCP) as the emitting layer (EML) and the hole-blocking layer (HBL), respectively. Devices were prepared by vacuum deposition on indium tin oxide (ITO)-glass substrates. The thickness of DPVBi used in the OLED has an important effect on color and efficiency. The blue luminescence is maximal at 7670 cd/m² when 13 V is applied and the BCP thickness is 2 nm. The CIE coordinate at a luminance of 7670 cd/m² is (0.165, 0.173). Furthermore, the current efficiency is maximum at 4.25 cd/A when 9 V is applied.     

Energy transfer in a thin film of TPD fluorescent molecules doped with PtOEP and Ir(ppy)3 phosphorescent molecules

A thin film of triphenylamine dimer, N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)-benzidine (TPD), doped with fac tris(2-phenylpyridine) iridium (Ir(ppy)₃) and platinum octaethyl porphine (PtOEP) is characterized by photoluminescence emission measurements at several excitation wavelengths and photoluminescence excitation measurements at relevant emission wavelengths in the temperature range from 10 K to room temperature. The investigated film is a phosphorescent OLED material with singlet absorbing host (TPD) and triplet emitting guests [Ir(ppy)₃ and PtOEP]. At short wavelength excitation simultaneous triple band emission from singlet TPD, triplet Ir(ppy)₃ and TPD, and from triplet PtOEP is observed. Förster-type singlet-singlet state energy transfer from TPD to Ir(ppy)₃ and PtOEP, intra-component intersystem crossing, and Dexter-type triplet-triplet energy transfer between the substituents are studied.     

可调色红光有机电致发光器件

介绍了具有可调节发光光谱的高效红光有机发光二极管(OLED)器件,利用具有高三重态能量的9.9-螺二芴二苯基氧化磷(SPPO1)作为发光层的主体材料及空穴阻挡层,二(1-苯基异喹啉)(乙酰丙酮)合铱(III) (Ir(piq)2(acac))作为客体发光材料,在发光层内SPPO1的能量分别由福斯特和迪克斯特传递到Ir(piq)2(acac)的单重态和三重态从而发出红色磷光,通过调节磷光客体材料的比例得到最优器件结构,从而得到具有较好发光效率和发光亮度并可调节色纯的有机发光二极管器件。     

新型双色有机电致磷光器件

所研究的有机电致磷光发光器件(OLED)选用了一种新型金属铱的化合物Ir(C6)₂(acac),这种金属化合物由配位体香豆素C6和乙酰丙酮(acac)与金属铱化合形成。Ir(C6)₂(acac)可同时作为电子传输材料和发光掺杂剂。比较香豆素C6和Ir(C6)₂(acac)固体材料的光致发光谱,可见Ir(C6)₂(acac)明显抑制了有机电致发光材料分子与分子之间的发光猝灭效应。采用ITO/TPD(N,N′-diphenyl-N,N′-bis(3-methyl-phenyl)-1,1′biphenyl-4,4′diamine)/Ir(C6)₂(acac)/BAlq(bis(2-methyl-8-quinolinolato-N₁,O₈)-(1,1′-biphenyl-4-olato)aluminum)/Alq₃aluminum/Liq(8-hydroxyquinolinelithium)/Al结构,可得到CIE(Commission Interationaled′Eclairage)值为x=0.43;y=0.40的橙红色发光器件,最高亮度可达3390cd/m₂,最大电流效率为1.3cd/A。采用同样的器件结构以Ir(C6)₂(acac)掺杂Alq₃主体得到绿色发光器件,发光色的CIE坐标值为x=0.29;y=0.58,最高亮度可达8832cd/m₂,最大电流效率为5.6cd/A。器件的发光机理研究表明Ir(C6)₂(acac)的非掺杂器件发光以Ir(C6)₂(acac)的三线态磷光为主,器件发光为橙色;在Alq₃中的单掺杂器件以Alq₃和Ir(C6)₂(acac)的荧光为主,同时有小比例Ir(C6)₂(acac)的三线态磷光成分存在,器件总体发光为绿色。     

中间层对白色全磷光有机电致发光器件性能的影响

制备了基于蓝色磷光材料bis[3,5-difluoro-2-（2-pridyl）phenyl-（2-earboxypyribyl）iridumⅢ]（FIrpic）、红色磷光材料bis（2-methyldibenzo [f,h]quinoxaline）（acetylacetonate）iridium（Ⅲ）（Ir（MDQ）₂acac）的双波段白光有机电致发光器件。蓝色磷光材料FIrpic被掺杂在一种宽带隙的主体材料1,3-bis（triphenylsilyl）benzene（UGH3）之中,红色磷光材料Ir（MDQ）₂acac被掺杂在主体材料4,4',4"-tris（carbazol-9-yl）triphenylamine（TCTA）之中,并在两发光层之间加入一种宽带隙的空穴传输材料1,3-bis（carbazol-9-yl）benzene（mCP）作为中间层。制备的器件结构为ITO/NPB（40 nm）/TCTA：Ir（MDQ）₂acac 7%（10 nm）/mCP（x nm）/UGH3：Firpic 8%（30 nm）/BPhen（30 nm）/LIF（0.8 nm）/AL（200 nm）。实验结果表明,中间层的加入促进了发光层中电子和空穴的平衡并抑制了发光层之间的能量转移。加入适当厚度的中间层之后,器件的性能得到了明显的提升,相比于无中间层器件,最高电流效率由3.4 cd/A提高到13.2 cd/A。     

不同主体材料对红色磷光OLED器件性能的影响

制作了结构为ITO/2T-NATA (20 nm)/NPB(60 nm)/Zn(BTZ)₂ : Ir(DBQ)₂(acac) (80 nm)/Alq₃(70 nm)/LiF(1 nm)/Al(200 nm)的红光器件,其中2T-NATA是4,4',4″-tris(N-(2-naphthyl)-N-phenyl-amino)-triphenylamine,NPB是N,N'-di(naphthalen-1-yl)-N,N'-diphenyl-benzidine, Zn(BTZ)₂是Bis-(2-(2-hydroxyphenyl) benzothiazole)zinc,Ir(DBQ)₂(acac)是iridium complex,Alq₃ 是tris(8-hydroxyquinolato)aluminum。基于Ir(DBQ)₂(acac) 掺杂的Zn(BTZ)₂体系的器件给出最高电致发光(EL)性能。结果显示:10％Ir(DBQ)₂-(acac) 掺杂Zn(BTZ)₂器件的亮度和效率分别为25 000 cd/m²和12 cd/A,其相应的EL峰位于620 nm,色坐标(x=0.63,y=0.37)。由于未使用激子阻挡层,所以,比通常磷光器件的制作工艺简单并且操作过程容易控制。     

一种多层白色磷光有机电致发光器件的制备及性能研究

制备了一种结构为ITO/NPB/NPB:Ir(piq)₂(acac)/CBP:TBPe/BAlq:rubrene/BAlq/Alq₃/Mg:Ag的白色磷光有机电致发光器件.其中空穴传输型主体NPB掺杂磷光染料Ir(piq)₂(acac)作为红色发光层,双载流子传输型主体4,4′-N,N′-dicarbazole-biphenyl (CBP)掺杂TBPe作为蓝色发光层,电子传输型主体材料BAlq掺杂rubrene作为绿色发光层.以上发光层夹于 关键词： 电致发光 磷光染料 异质结 白光     

Density functional theory and time-dependent density functional study a series of iridium complexes with low-efficiency roll-off properties

ABSTRACT

A series of blue phosphorescent heteroleptic cyclometalated Ir(III) complexes with mesitylphenyl-imidazole ligands for organic light-emitting devices have been theoretically studied. We want to find their electronic structures, spectroscopic properties, and application value for organic light-emitting devices. (fppz)₂Ir(acac), (fppz)₂Ir(tpip), (dfbdp)₂Ir(fppz), (F-fppz)₂Ir(acac), (F-fppz)₂Ir(tpip), and (dfbdp)₂Ir(F-fppz) are investigated with DFT and TD-DFT approaches, where, for (fppz)₂Ir(acac), (fppz denotes 2-(5-(trifluoromethyl)-4H-pyrazol-3-yl)pyridine, and acac denotes acetylacetonate); for (fppz)₂Ir(tpip), tpip denotes tetraphenylimido-diphosphinate; and, for (F-fppz)₂Ir(acac) and (F-fppz)₂Ir(tpip), F-fppz denotes 2-(5-fluoro-4H-pyrazol-3-yl)pyridine.     

Hole transport characteristics in phosphorescent dye-doped NPB films by admittance spectroscopy

Admittance spectroscopy is a powerful tool to determine the carrier mobility. The carrier mobility is a significant parameter to understand the behavior or to optimize the organic light-emitting diode or other organic semiconductor devices. Hole transport in phosphorescent dye, bis[2-(9,9-diethyl-9H-fluoren-2-yl)-1-phenyl-1Hbenzoimidazol-N,C3] iridium(acetylacetonate [(fbi)₂Ir(acac)]) doped into N,N-diphenyl-N,N-bis(1-naphthylphenyl)-1,1-biphenyl-4,4-diamine (NPB) films was investigated by admittance spectroscopy. The results show that doped (fbi)₂Ir(acac) molecules behave as hole traps in NPB, and lower the hole mobility. For thicker films(?300 nm), the electric field dependence of hole mobility is as expected positive, i.e., the mobility increases exponentially with the electric field. However, for thinner films (?300 nm), the electric field dependence of hole mobility is negative, i.e., the hole mobility decreases exponentially with the electric field. Physical mechanisms behind the negative field dependence of hole mobility are discussed. In addition, three frequency regions were divided to analyze the behaviors of the capacitance in the hole-only device and the physical mechanism was explained by trap theory and the parasitic capacitance effect.     

Blue organic light-emitting diodes with 2-methyl-9,10-bis(naphthalen-2-yl)anthracene as hole transport and emitting layer and the impedance spectroscopy analysis

2-methyl-9,10-bis(naphthalen-2-yl)anthracene (MADN) based fluorescent blue organic light-emitting diodes (OLEDs) are demonstrated. With MADN as emitting layer, experiments indicate that thick MADN (40–60 nm) is preferable for constructing efficient blue OLED. With MADN as hole-transport and emitting layer and tris(8-hydroxy-quinolinato)aluminium (Alq₃) as electron-transport layer, the OLED electroluminescent characteristics show a mixture emission of MADN and Alq₃ with Commission Internationale d'Eclairage (CIE) color coordinates of (0.25, 0.34), indicating feasible hole transporting in MADN. Using 4,7-diphenyl-1,10-phenanthroline (BPhen) replacing Alq₃ as electron-transport layer, the OLED shows deep blue emission with a maximum luminous efficiency of 4.8 cd/A and CIE color coordinates of (0.16, 0.09). The hole transport characteristics of MADN are further clarified by constructing hole-only device and performing impedance spectroscopy analysis. The results indicate that MADN shows superior hole-transport ability which is almost comparable to typical hole-transport material of N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-benzidine (NPB), suggesting a promising application for constructing efficient blue OLED with integrated hole-transport layer and emitting layer.