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.     

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.     

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.     

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.     

Photoluminescence and electroluminescence of a novel green-yellow emitting material-5,6-Bis-[4-(naphthalene-1-yl-phenyl-amino)-phenyl]-pyrazine-2,3-dicarbonitrile

A new compound with intramolecular charge transfer (ICT) property—5,6-Bis-[4-(naphthalene-1-yl-phenyl-amino)-phenyl]-pyrazine-2,3-dicarbonitrile(BNPPDC) was synthesized. The new compound was strongly fluorescent in non-polar and moderately polar solvents, as well as in thin solid film. The absorption and emission maxima shifted to longer wavelength with increasing solvent polarity. The fluorescence quantum yield also increased with increasing solvent polarity from non-polar to moderately polar solvents, then decreased with further increase of solvent polarity. This indicates both “positive” and “negative” solvatokinetic effects co-existed. Using this material as hole-transporting emitter and host emitter, we fabricated two electroluminescent (EL) devices with structures of A (ITO/BNPPDC (45 nm)/1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI) (45 nm)/Mg:Ag (200 nm) and B (ITO/N,N′-diphenyl-N,N′-bis-(3-methylphenyl) (1,1′-diphenyl)4,4′-diamine (TPD) (50 nm)/BNPPDC (20 nm)/1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI) (45 nm)/Mg:Ag (200 nm). The devices showed green-yellow EL emission with good efficiency and high brightness. For example, the device A exhibited a high brightness of 17400 cd/m² at a driving voltage of 11 V and a very low turn-on voltage (2.9 V), as well as a maximum luminous efficiency 3.61 cd/A. The device B showed a similar performance with a high brightness of 12650 cd/m² at a driving voltage of 13 V and a maximum luminous efficiency 3.62 cd/A. In addition, the EL devices using BNPPDC as a host and 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as a dopant (configuration: ITO/TPD (60 nm)/BNPPDC:DCJTB (2%) (30 nm)/TPBI (35 nm)/Mg:Ag (200 nm)) showed a good performance with a brightness of 150 cd/m² at 4.5 V, a maximum brightness of 12600 cd/m² at 11.5 V, and a maximum luminous efficiency of 3.30 cd/A.     

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.     

Synthesis and electroluminescent properties of a carbozole-functionalized europium(III) complex

A novel europium(III) complex, tris(dibenzoylmethanate){1-[9-hexyl-9H-carbazole]-2-(2-pyridyl)-benzimidazole}europium(III) [Eu(DBM)₃(CAR-PyBM)] functionalized by a carbozole fragment, was synthesized and used as emitting material in organic electroluminescent (EL) devices. Compared with the device based on an unfunctional Eu(III) complex, [Eu(DBM)₃HPyBM] (HPyBM=2-(2-pyridyl)benzimidazole), the EL performances of the device using [Eu(DBM)₃(CAR-PyBM)] as an emitter was significantly enhanced due to the improvement of hole-transporting ability. The maximum efficiency and luminance of red emission achieved from the device with the configuration of ITO/N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′diamine (TPD, 50 nm)/ [Eu(DBM)₃(CAR-PyBM)] (30 nm)/1,3,5-tirs-(N-phenylbenzimidazol-2-yl)benzene (TPBI, 20 nm)/LiF (1.5 nm)/Al were 4.2 cd/A and 200 cd/m², respectively.     

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.     

High performance Europium(III) based emitters for electroluminescence: Synthesis,crystal structures,photophysical and electroluminescent properties

In this paper, we synthesize two 1,10-phenanline derived ligands, along with their corresponding Eu(III) complexes. Their crystal structures, photophysical characteristics, including UV–vis absorption, photoluminescence (PL), quantum yields, excited state lifetimes, and thermal stability, are discussed in detail. In addition, we also investigate their potential application in electroluminescence (EL) devices. Experimental data suggest that the two Eu(III) complexes are promising emitters for EL application: pure red emissions with a maximum EL brightness of 850 cd/m² and a maximum current efficiency of 3.67 cd/A are achieved. It is found that the elimination of active hydrogen in ligand favors most PL and EL factors, including PL quantum efficiency, thermal stability, and current efficiency, but not for maximum EL brightness. An emitter with shorter excited state lifetime leads to a higher EL brightness, regardless of its relatively lower device efficiency.     

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}     

Highly efficient greenish blue-emitting organic diodes based on pyrene derivatives

We report the synthesis of pyrene derivatives as the light emissive layer for highly efficient organic electroluminescence (EL) diodes. Multilayer devices were fabricated with pyrene derivatives (ITO/NPB (50 nm)/blue material (30 nm)/BCP (10 nm)/Alq₃ (30 nm)/LiF (1 nm)/Al). By using 1,1′-dipyrene (DP) and 1,4-dipyrenyl benzene (DPB), the devices produced the blue EL emissions with 1931 Commission International de L’Eclairage coordinates of (x=0.21, y=0.35) and (x=0.19, y=0.25), respectively. The device with DPB shows a maximum brightness of 42,445 cd/m² at 400 mA/cm² and the luminance efficiency of 8.57 cd/A and 5.18 lm/W at 20 mA/cm².     

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).     

Characterization and emissive property of microfibers doped with fluorine functionalized iridium complex

In this paper, we used two fluorine-containing ligands of 2-(2-fluorophenyl)benzo[d]thiazole (F-BT) and 1,1,1,5,5,5-hexafluoropentane-2,4-dione (acac-F6) to construct an Ir complex of Ir(acac-F6)(F-BT)₂. The single crystal of Ir(acac-F6)(F-BT)₂ is observed, which confirms its identity. Ir(acac-F6)(F-BT)₂ single crystal belongs to monoclinic system with two molecules in each unit cell. Theoretical calculation is performed on Ir(acac-F6)(F-BT)₂ to investigate its electronic nature, which suggests that the first electronic transition owns a mixed character of metal-to-ligand-charge-transfer and ligand-to-ligand-charge-transfer. We select a polymer matrix of poly(vinylpyrrolidone) (PVP) to explore the photophysical property of Ir(acac-F6)(F-BT)₂ within microfibers. Results indicate that the photophysical performances of Ir(acac-F6)(F-BT)₂ within microfibers are improved compared with those of Ir(acac-F6)(F-BT)₂ powder, including microfiber sample's higher emission energy, longer excited state lifetime, and better photostability.     

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     

Improved performance and stability by an Al/Ni bilayer cathode in organic light-emitting diodes

Al/Ni bilayer cathode was used to improve the electroluminescent (EL) efficiency and stability in N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′ biphenyl 4,4′-dimaine (NPB)/tris-(8-hydroxyquinoline) aluminum (Alq₃)-based organic light-emitting diodes. The device with LiF/Al/Ni cathode achieved a maximum power efficiency of 2.8 lm/W at current density of 1.2 mA/cm², which is 1.4 times the efficiency of device with the state-of-the-art LiF/Al cathode. Importantly, the device stability was significantly enhanced due to the utilization of LiF/Al/Ni cathode. The lifetime at 30% decay in luminance for LiF/Al/Ni cathode was extrapolated to 400 h at an initial luminance of 100 cd/m², which is 10 times better than the LiF/Al cathode.     

The effect of iridium precursor on oxide-supported iridium catalysts prepared by atomic layer deposition

Alumina, silica and beta zeolite supported iridium catalysts were prepared by atomic layer deposition (ALD) from two different metal precursors, Ir(acac)₃ and Ir(thd)(COD). The use of Ir(thd)(COD) in ALD is reported for the first time. The aim was to investigate the effect of the precursor on catalyst surface species, chemical state and characteristics.Controllable ALD reaction was successful with both iridium precursors on alumina and with Ir(acac)₃ on β zeolite. On these catalysts, iridium particle sizes were very small (1-3 nm). Instead, some thermal decomposition of both precursors was observed during deposition on silica. At conditions, where no or very little decomposition of the precursors took place, the differences in the chemical state and characteristics of the as-prepared Ir/support samples were negligible, In ALD, Ir(acac)₃ is slightly more stable at high deposition temperatures (>200 °C) while Ir(thd)(COD) enables the utilization of larger temperature range since it vaporizes at lower temperature compared to Ir(acac)₃. The results thus indicate that Ir(thd)(COD) is a suitable new precursor for ALD.     

Efficient small molecular and polymer organic devices using bis[2-(4-tert-butylphenyl)benzothiazolato-N,C′] iridium (III) (acetylacetonate) dye as emitter

Small molecular organic light-emitting diodes (MOLED) and polymer organic light-emitting diodes (POLED) were fabricated with yellow light emission phosphorescent dye bis[2-(4-tert-butylphenyl)benzothiazolato-N,C²′] iridium (III) (acetylacetonate) doped in different hosts. The electroluminescent (EL) spectra of both devices shown two peaks generated from iridium dye but the position of main peak changed and became broader for POLED. The maximum luminance of 10,500 cd/m² achieved at 12.5 V for MOLED is higher than maximum luminance of 9996 cd/m² at 20 V for POLED. The maximum power efficiency of small molecular device is 6.4 lm/W, which is higher than 2.3 lm/W of polymer device, but the efficiency of both devices will roll off at large current density.     

New heteroleptic cyclometalated iridium(III) complexes containing 2-(2′,4′-difluorophenyl)-4-methylpyridine for organic light-emitting diode applications

Two phosphorescent iridium(III) complexes (dfpmpy)₂Ir(ppc) and (dfpmpy)₂Ir(prz) [dfpmpy=2-(2′,4′-difluorophenyl)-4-methylpyridine, ppc=pipecolinate, prz=2-pyrazine carboxylate] were synthesized from the reaction of the chloro-bridged dimeric complex [(dfpmpy)₂Ir(μ-Cl)]₂ and the ancillary ligand. Their structures and photoluminescence properties were investigated and device performances for application in organic light-emitting diodes (OLEDs) were studied. The complexes adopt a distorted, octahedral geometry around the iridium metal, exhibiting cis C-C and trans N-N arrangements. The photoluminescent (PL) properties reveal that (dfpmpy)₂Ir(ppc) emits in the blue-green region (λ_max=497 nm), whereas (dfpmpy)₂Ir(prz) shows red phosphorescence (λ_max=543 nm) in the film state (5% wt. doped in PMMA). The (dfpmpy)₂Ir(ppc)- and (dfpmpy)₂Ir(prz)-based OLEDs exhibited sky-blue and greenish-yellow electroluminescence with similar current-voltage characteristics, repectively. Maximum current efficiency of (dfpmpy)₂Ir(ppc) and (dfpmpy)₂Ir(prz) were 4.4 and 7.4 cd/A, respectively. Maximum luminance values were approximately 10,000 cd/m² for the both compounds.     

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     

Blue organic electroluminescent devices based on a distyrylarylene derivative as emitting layer and a terbium complex as electron-transporting layer

With a blue distyrylarylene derivative, 4,4′-bis(2,2-di(2-methoxyphenyl)ethenyl)-1,1′-biphenyl (CBS) as emitting material, double-layer and triple-layer electroluminescent (EL) devices were fabricated. For the device using tris-(1-phenyl-3-methyl-4-isobutyryl-5-pyrozolone)-bis(triphenyl phosphine oxide) terbium (Tb(PMIP)₃(TPPO)₂) as the electron-transporting layer, blue EL emission with a maximum luminance of 253 cd/m² was achieved at 19 V. The difference of Tb(PMIP)₃(TPPO)₂ and tris(8-hydroxyquinolinate)aluminum (AlQ) as the electron-transporting materials in these devices were compared and discussed.