High performance polymer light-emitting diodes doped with a novel phosphorescent iridium complex

High performance polymer light-emitting diodes (PLEDs) based on a phosphor of noble metal complex bis(1,2-dipheny1-1H-benzoimidazole) iridium (acetylacetonate) [(pbi)₂Ir(acac)] doped in poly(N-vinylcarbazole) (PVK) host with various concentration were demonstrated. The photoluminescence (PL) and electroluminescence (EL) spectra of the PLEDs exhibited an emission intensity decrease of PVK and a gradually enhanced feature of (pbi)₂Ir(acac) with increased doping concentration. The device with a 5 wt% (pbi)₂Ir(acac) doped PVK system showed a high power efficiency of 3.84 lm/W and a luminance of 26,006 cd/m². The results indicated that both energy transfer and charge trapping have a significant influence on the performance of PLEDs. The devices have a broadened EL spectrum of full-width at half-maximum (FWHM) more than 100 nm, which can be realized for WOLEDs.     

White organic electroluminescence from fluorescent bis (2-(2-hydroxyphenyl) benzoxazolate)zinc doped with phosphorescent material

Efficient white electroluminescence has been obtained by using an electroluminescent layer comprising of a blue fluorescent bis (2-(2-hydroxyphenyl) benzoxazolate)zinc [Zn(hpb)₂] doped with red phosphorescent bis (2-(2′-benzothienyl) pyridinato-N,C^3′)iridium(acetylacetonate) [Ir(btp)₂acac] molecules. The color coordinates of the white emission spectrum was controlled by optimizing the concentration of red dopant in the blue fluorescent emissive layer. Organic light-emitting diodes were fabricated in the configuration ITO/α-NPD/Zn(hpb)₂:0.01 wt%Ir(btp)₂acac/BCP/Alq₃/LiF/Al. The J-V-L characteristic of the device shows a turn on voltage of 5 V. The electroluminescence (EL) spectra of the device cover a wide range of visible region of the electromagnetic spectrum with three peaks around 450, 485 and 610 nm. A maximum white luminance of 3500 cd/m² with CIE coordinates of (x, y=0.34, 0.27) at 15 V has been achieved. The maximum current efficiency and power efficiency of the device was 5.2 cd/A and 1.43 lm/W respectively at 11.5 V.     

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     

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).     

铱金属配合物磷光材料掺杂聚合物体系的电致发光特性

通过对一种新型贵金属铱的配合物磷光材料(pbi)₂Ir(acac)与咔唑共聚物进行物理掺杂, 制备了结构为indium-tin oxide(ITO)/poly(N-vinylcarbazole)(PVK): (pbi)₂Ir(acac)(x)/2,9-dimethyl-4,7-diphenyl-1,10-phenan throline(BCP)(20nm)/8-Hydroxyquinoline aluminum(Alq₃)(10nm)/Mg:Ag的聚合物电致磷光器件,研究了磷光聚合物掺杂体系在低掺杂浓度时(0.1%和0.5%(质量百分数,全文同))的光致发光(PL)和电致发光(EL)特性. 结果表明, 该掺杂体系的PL光谱和EL光谱中均同时存在主体材料PVK与磷光客体(pbi)₂Ir(acac)的发光光谱, 但主客体的发射强度不同,推测该掺杂体系在电致发光条件下, 同时存在主体材料到客体的不完全的能量传递和载流子直接俘获过程. 磷光掺杂浓度为0.1%的器件在19V电压下实现了白光发射, 色坐标为(0.32, 0.38), 掺杂浓度为0.5%的器件在20.6V电压下的最大发光亮度为11827 cd·m^-2, 而在13.4V电压下的最大流明效率为4.13 cd·A^-1. 关键词： 有机电致发光器件 铱配合物磷光 聚合物掺杂     

Effect of Ir(pq)2acac doping on CBP in phosphorescence organic light-emitting diodes

Doping is one of the most powerful methods amongst the various performance improvement ways. Doping affects the energy levels of the host layer by the energy level of the dopant. This allows the energy bandgap to be adjusted to a desired level and thus generates light corresponding to that energy level. Alternatively, it can act as an energy barrier between the interfaces to change the flow of carriers. In this study, the voltage dependences of undoped and doped devices were observed. Bis(2-phenylquinoline) iridium(III) (acetylacetonate) (Ir(pq)₂acac) was doped in 4,4′-N, N′-dicarbazole-biphenyl (CBP) as the emission layer. The light intensity changes with the doping concentration, and the efficiency was also studied. When a high voltage was applied, the effect of triplet-triplet annihilation (TTA) adversely affected the electron-hole recombination. We analyzed the optimal operating conditions and the effect of doping concentration on OLEDs.     

室温下磁场对基于Alq3的有机电致发光器件的影响

制备了ITO/NPB/LiF/Alq₃/LiF/Al的器件,测量了该组器件效率和亮度的磁效应.结果表明,在50 mT磁场中,当LiF缓冲层厚度为0.8 nm时,器件的效率最大增加了12.4%,磁致亮度最大变化率17%.同时,制备的磷光器件ITO/NPB/LiF/CBP:6 wt% Ir(ppy)₃/BCP/Alq₃/ LiF/Al,在50mT磁场作用下,当LiF缓冲层的厚度为0.8 nm时,器件的效率最大增加12.1%.在Alq_{3 关键词： 有机发光 磁场 效率 磁致亮度}     

Enhancement of Frster energy transfer from thermally activated delayed fluorophores layer to ultrathin phosphor layer for high color stability in non-doped hybrid white organic light-emitting devices

Fluorescence/phosphorescence hybrid white organic light-emitting devices(WOLEDs) based on double emitting layers(EMLs) with high color stability are fabricated.The simplified EMLs consist of a non-doped blue thermally activated delayed fluorescence(TADF) layer using 9,9-dimethyl-9,10-dihydroacridine-diphenylsulfone(DMAC-DPS) and an ultrathin non-doped yellow phosphorescence layer employing bis[2-(4-tertbutylphenyl)benzothiazolato-N,C2']iridium(acetylacetonate)((tbt)_2Ir(acac)).Two kinds of materials of 4,7-diphenyl-1,10-phenanthroline(Bphen) and 1,3,5-tris(2-Nphenylbenzimidazolyl) benzene(TPBi) are selected as the electron transporting layer(ETL),and the thickness of yellow EML is adjusted to optimize device performance.The device based on a 0.3-nm-thick yellow EML and Bphen exhibits high color stability with a slight Commission International de l'Eclairage(CIE) coordinates variation of(0.017,0.009) at a luminance ranging from 52 cd/m~2 to 6998 cd/m~2.The TPBi-based device yields a high efficiency with a maximum external quantum efficiency(EQE),current efficiency,and power efficiency of 10%,21.1 cd/A,and 21.3 lm/W,respectively.The ultrathin yellow EML suppresses hole trapping and short-radius Dexter energy transfer,so that Forster energy transfer(FRET)from DMAC-DPS to(tbt)_2Ir(acac) is dominant,which is beneficial to keep the color stable.The employment of TPBi with higher triplet excited state effectively alleviates the triplet exciton quenching by ETL to improve device efficiency.     

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.     

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。     

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.     

同时掺杂磷光和荧光染料的白色有机电致发光器件性能研究

以磷光染料Ir(piq)₂(acac)作为发光掺杂剂,掺入空穴传输性主体材料NPB中得到红色发光层,荧光材料TBP掺入到主体CBP中作为蓝色发光层,制备了结构为ITO/NPB/NPB：Ir(piq)₂(acac)/CBP/CBP：TBPe/BCP/ALq/Mg：Ag的双发光层白色有机电致发光器件.其中ALq₃、未掺杂的NPB和CBP及BCP层分别作为电子传输层、空穴传输层和激子阻挡层.实验中通过调节发光层厚度及Ir(piq)_{2关键词： 磷光 激子阻挡层 有机电致发光}     

A novel blue-emitting Ir(III) complex with short excited state lifetime: Synthesis,structure, photophysical property,and electrophosphorescence performance

In this paper, we synthesize a triphenylamine-derived cyclometalating ligand of (4-benzothiazol-2-yl-phenyl)-diphenyl-amine (referred as BPDA) and its corresponding Ir(III) complex of (BPDA)₂Ir(acac) (acac=acetylacetone). The photophysical property, molecular structure, thermal property and electroluminescence performance of (BPDA)₂Ir(acac) are investigated in detail. It is found that (BPDA)₂Ir(acac) is an efficient emitter with high thermal stability and short excited state lifetime. The emission of (BPDA)₂Ir(acac) changes from deep blue (417 nm) to bluish green (500 nm) upon addition of different solvents. We also investigate its electrophosphorescence performance. A maximum electroluminance of 8820 cd/m² peaking at 494 nm is achieved, with the highest device efficiency of 1.72 cd/A.     

Emission properties of dopants rubrene and coumarin 6 in Alq3 films

We have investigated the emission properties of dopants 5,6,11,12-tetraphenylnapthacene (rubrene) and 3-(2′-benzothiazolyl)-7-diethylaminocoumarin (coumarin 6) as well as co-doping of these two dopants in tris (8-hydroxyquinolinato) aluminum (Alq₃) films in double-layer organic light emitting diodes (OLEDs). We varied the rubrene (Rb) doping concentration in Alq₃:Rb films up to 10 wt%. The maximum luminescence efficiency of ∼6.5 cd/A was observed for Rb doping concentration of ∼0.7 wt% in Alq₃:Rb film, which was nearly double efficiency compared to pure Alq₃ device. The co-doping of dopants of C-6 and Rb in the ratio of 1:1 and 1:2 in Alq₃ films reduced the bias voltage compared to pure Alq₃ and Alq₃:C-6 devices for the same current density. The maximum luminescence efficiency was improved to ∼7 cd/A in Alq₃:{C-6:Rb(1:2)} film OLED. The direct recombination of holes and electrons in the dopant molecules may be responsible for the improvement of the luminescence efficiency. We also observed the shifting of photoluminescence (PL) and electroluminescence (EL) peaks position from ∼515 to ∼562 nm by co-doping of Rb and C-6 in Alq₃.     

Phosphorescent iridium(III) complexes with hetero (C ˆN) ligands

In order to improve luminescence efficiency, it is necessary to design a phosphorescent material which is capable of transferring the excited energy without triplet–triplet (T–T) annihilation. For this purpose, new types of metal complexes were designed with different species of (C ˆN) ligands. Herein, Ir(ppy)₂(piq), Ir(ppy)₂(piq-F) and Ir(ppy)₂(piq-CF₃) were designed and prepared, where ppy, piq, piq-F and piq-CF₃ represent 2-phenylpyridine, 1-(phenyl)isoquinoline, 1-(4′-fluorophenyl)isoquinoline and 1-(4′-trifluoromethylphenyl)isoquinoline, respectively. These Ir(III) complexes having two different ligands (hetero-Ir complexes) are expected to have a high luminescence efficiency by intramolecular energy transfer from the energy absorbing ligand to the luminescent ligand leading to a decrease in quenching or energy deactivation. To compare luminescent characteristics of these hetero-Ir complexes, homo-Ir complexes Ir(ppy)₃, Ir(piq)₃, Ir(piq-F)₃ and Ir(piq-CF₃)₃ were prepared and investigated photophysically.     

基于咪唑并吡啶类配体新型磷光材料的合成与表征

设计开发了系列新型咪唑并吡啶类铱(Ⅲ)配合物(BIPy)₂Ir(acac)、(PIPy)₂Ir(acac)、 (4'-MPIPy)₂-Ir(acac)。在化合物Ⅲ中,当R=Ph时得到(BIPy)₂Ir(acac)材料,其中BIPy和acac分别表示2-(4-联苯基)咪唑并吡啶和乙酰丙酮。将(BIPy)₂Ir(acac)掺杂在N,N'-二咔唑-(1,1'-联苯)-4,4'-二胺(CBP)中制备了高效OLEDs器件,器件的最大电流效率为26.7 cd/A,最大亮度为18 000 cd/cm²,色坐标为(0.32,0.60),是首次报道的新型苯基咪唑并吡啶类铱(Ⅲ)配合物绿色磷光材料。     

Simultaneous observation of low temperature 4f-4f and 3d-3d emission spectra in a series of Cr(III)(ox)Ln(III) assembly

We report here the low temperature emission spectra in the heterometal dinuclear 3d-4f assembled molecular system [(acac)₂Cr^III(μ-ox)Ln^III(HBpz₃)₂] (Cr(ox)Ln:acac⁻=acetylacetonate, ox²⁻=oxalate, HBpz₃⁻=hydrotris(pyrazol-1-yl)borate; Ln=La, Nd, Ho, Er , Tm and Yb) in comparison with those of Na[Cr(acac)₂(ox)] and [(HBpz₃)₂Ln(μ-ox)Ln(HBpz₃)₂](Ln=Nd and Er). From 10 to 150 K the Cr(ox)Ln complexes show a broad emission band around 800 nm from the ²E state of Cr(III) moiety. At room temperature no ²E-⁴A₂ emission was observed in the Cr(ox)Ln except for the La and Lu complexes. On warming from 10 to 300 K rapid quenching of the ²E-⁴A₂ emission of Cr(III) is suggested to result from the energy transfer from Cr to Ln in the Cr(ox)Ln. The excitation spectra and the life-time were also measured with monitoring the 4f-4f emission peaks of the Cr(ox)Yb complex.     

Study on triplet exciton diffusion length of mCP in phosphorescent organic light-emitting devices using electroluminescent spectra

Electroluminescent (EL) spectra was employed to probe the triplet exciton diffusion length (L_T) of a commonly used host material of N,N′-dicarbazolyl-3,5-benzene (mCP) in phosphorescent organic light-emitting devices (OLEDs). By varying the film thickness of bis [2-(4-tertbutylphenyl) benzothiazolato-N,C²], iridium (acetylacetonate) [(t-bt)₂Ir(acac)] phosphor doped layer within 30 nm thick mCP layer, a series of devices were fabricated to investigate the EL characteristics. The results showed that with the increasing doped layer thickness (d), both (t-bt)₂Ir(acac) emission peaks at 562 nm and mCP emission centered at 403 nm were observed. Moreover, the relationship between mCP EL intensity and d was detected. The L_T was induced by an abrupt decrease in variation of mCP EL intensity when d is increased from 10 to 15 nm, and the reason to cause this phenomenon was investigated. The L_T of mCP approximately to 15 nm was perfectly consistent to the result of 16±1 nm, which was calculated by the traditional steady-state diffusion model.     

Ir(PPY)3掺杂PVK的电致发光机理

近几年来发展起来的电致磷光(electrophosphorescence)是有机发光二极管(OLED)研究的新生长点。对电致磷光发光机理的研究随即得到了人们普遍的关注。比较了不同正向偏压条件下Ir(PPY)₃掺杂聚乙烯基咔唑(PVK)的光致发光(PL)和电致发光(EL)光谱。研究结果显示在电场和注入电流的共同作用下,PL光谱中基质PVK发光的相对强度并没有发生显著的变化。电场或注入载流子不会影响PVK向Ir(PPY)₃的能量传递。磷光掺杂聚合物EL主要是由于载流子在掺杂磷光分子上的直接复合,而不是由基质向磷光掺杂分子的能量传递。     

High-efficiency blue and white phosphorescent organic light-emitting devices

We have significantly improved the efficiency of blue and white phosphorescence from organic light-emitting devices (OLEDs) based on phosphorescent iridium complexes. To improve the emission efficiency, 4,4^′-Bis(9-carbazolyl)-2,2^′-Dimethyl-biphenyl (CDBP), which has a high triplet energy, was used as the carrier-transporting host for the emissive layer. The blue phosphorescent OLED exhibited a maximum external quantum efficiency of 10.4%, which corresponds to a current efficiency of 20.4 cd/A. This result can be explained as due to the efficient confinement of triplet energy on blue phosphorescent molecules, which is consistent with the results of transient photoluminescence experiments. The white phosphorescent OLED with greenish-blue and red emissive layers exhibited a maximum external quantum efficiency of 12% and a luminous efficiency of 18 cd/A. This is primarily attributed to the improvement of greenish-blue emission efficiency as well as the emission efficiency of the blue phosphorescent OLED.