Efficient red light phosphorescence emission in simple bi-layered structure organic devices with fluorescent host-phosphorescent guest system

Highly efficient red phosphorescent devices comprising a simple bi-layered structure using tris(1-phenylisoquinoline)iridium (Ir(piq)₃) doped in a narrow band-gap fluorescent host material, bis(10-hydroxybenzo [h] quinolinato)beryllium complex (Bebq₂) are reported. The driving voltage to reach 1000 cd/m² is 3.5 V in Bebq₂:Ir(piq)₃ red phosphorescent device. With a dopant concentration of as low as 4%, the current and power efficiency values of 8.41 cd/A and 7.34 lm/W are obtained in this PHOLEDs, respectively. External quantum efficiency (EQE) of 14.5% is noticed in this red phosphorescent device, promising to high brightness applications.     

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.     

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.     

Study of different roles phosphorescent material played in different positions of organic light emitting diodes

Phosphorescent materials are crucial to improve the luminescence and efficiency of organic light emitting diodes (OLED), because its internal quantum efficiency can reach 100%. So the studying of optical and electrical properties of phosphorescent materials is propitious for the further development of phosphorescent OLED. Phosphorescent materials were generally doped into different host materials as emitting components, not only played an important role in emitting light but also had a profound influence on carrier transport properties. We studied the optical and electrical properties of the blue 4,4′-bis(2,2-diphenylvinyl)-1,1′-biphenyl (DPVBi)-based devices, adding a common yellow phosphorescent material bis[2-(4-tert-butylphenyl)benzothiazolato-N,C2′] iridium(acetylacetonate) [(t-bt)₂Ir(acac)] in different positions. The results showed (t-bt)₂Ir(acac) has remarkable hole-trapping ability. Especially the ultrathin structure device, compared to the device without (t-bt)₂Ir(acac), had increased the luminance by about 60%, and the efficiency by about 97%. Then introduced thin 4,4′-bis(carbazol-9-yl)biphenyl (CBP) host layer between DPVBi and (t-bt)₂Ir(acac), and got devices with stable white color.     

Synthesis and characterization of phosphorescent iridium complexes of 6-chloro-3-phenylpyridazine and 3-chloro-6-(3′-methoxy-phenyl)-4-methyl-pyridazine

The preparation and photophysics of organometallic Ir(III) complexes with 3-phenylpyridazine (H6Clppdz) and its derivative are reported. IrCl₃ · nH₂O reacts with H6Clppdz, and 3-chloro-6-(3^′-methoxyphenyl)-4-methyl-pyridazine (MCOMppdz) to give the corresponding chloride-bridged dimers, (6Clppdz)₂Ir(μ-Cl)₂Ir(6Clppdz)₂ and (MCOMppdz)₂Ir(μ-Cl)₂Ir(MCOMppdz)₂ in good yields. These chloride-bridged dimers are cleaved with 2-pyrazinecarboxylic acid (Hpyzc), 2-picolinic acid (Hpic), acetylacetone (Hacac), and 2,2,6,6-tetramethyl-3,5-heptanedione (Htmd) to give the corresponding monomer, (6Clppdz)₂Ir(pyzc), (6Clppdz)₂Ir(pic), (6Clppdz)₂Ir(acac), (6Clppdz)₂Ir(tmd), (MCOMppdz)₂Ir(acac), and (MCOMppdz)₂Ir(tmd), respectively. The complexes show bright orange to red luminescence at room temperature and the emission wavelenghts are affected by the ancillary ligands as well as cyclometalating ligands (593–664 nm).     

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.     

New red electrophosphor based on Ir(III) complex of 2,3,4-triphenylquinoline

2,3,4-Triphenylquinoline (tpq) ligand and its Ir(III) complex Ir(tpq)₂(acac) were prepared and their photonic properties were investigated as red electrophosphorescent material. The photoluminescence (PL) spectra of tpq and Ir(tpq)₂(acac) in dichloromethane showed a peak at 450 nm and 607 nm, respectively, at room temperature. The small Stokes shift between the ³MLCT absorption and emission bands shows that Ir(tpq)₂(acac) emits from a predominantly ³MLCT excited state. The theoretical calculation of the Ir(III) complex was performed by an ab initio method, and the result calculated by time dependent density functional theory (TD-DFT) showed that the Ir(III) complex underwent a strong ³MLCT transition because of the strong coupling between the 5d-orbital of Ir atom and the highest occupied molecular orbital (HOMO) of tpq ligand. Thus, it is concluded that this complex is a good candidate for a highly efficient electrophosphorescent material.     

On the photophysics of four heteroleptic iridium(III) phenylpyridyl complexes investigated by relativistic multi-configuration methods

ABSTRACT

In this work, we present a detailed analysis of the photophysical properties of four phosphorescent iridium(III) complexes, i.e. trans-N,N- and cis-N,N-(ppy)₂Ir^III(acac) as well as their fluorinated derivatives trans-N,N- and cis-N,N-(F₂ppy)₂Ir^III(acac). These properties include absorption and emission characteristics, intersystem crossing rates from the lowest singlet excited state, phosphorescence lifetimes of the individual triplet sublevels as well as the orientations of the transition dipole vectors. To this end, we have carried out combined density functional theory and multi-reference configuration interaction studies including spin–orbit coupling by perturbational as well as variational procedures. For the experimentally known complexes, we observe excellent agreement between our computed data and literature data. Also the blueshifts of the emission maxima occurring upon fluorination of the (ppy)₂Ir(acac) compounds are well reproduced. To our surprise, we find the experimentally not yet investigated cis-N,N-(F₂ppy)₂Ir(acac) isomer to be thermodynamically more stable than the well-known blue phosphorescent emitter trans-N,N-(F₂ppy)₂Ir(acac).     

Synthesis,photophysical and electro-optical properties of bis-carbazolyl methane based host material for pure-blue phosphorescent OLED

A new high triplet-energy host material, 9-(4-(bis(9-ethyl-9H-carbazol-3-yl)methyl)phenyl)-9H-carbazole (bis-CMPC), was synthesized and its device performance of phosphorescent organic light-emitting diode was investigated. This host material showed a high triplet energy (～2.95 eV) and good thermal stability. Highly efficient pure-blue PHOLED was obtained when employing bis-CMPC as the host material and bis((3,5-difluoro-4-cyanophenyl)pyridine) iridium picolinate as the guest material. The maximum external quantum efficiency of the device reached as high as 13.3% with a pure-blue color coordinate of (0.14, 0.21).     

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.     

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     

Combined host–guest doping and host-free systems for high-efficiency white organic light-emitting devices

Highly efficient white organic light-emitting devices (WOLEDs) with a four-layer structure were realized by utilizing phosphorescent blue and yellow emitters. The key concept of device construction is to combine host–guest doping system of the blue emitting layer (EML) and the host-free system of yellow EML. Two kinds of WOLEDs incorporated with distinct host materials, namely N,N'-dicarbazolyl-3,5-benzene (mCP) and p-bis(triphenylsilyly)benzene (UGH2), were fabricated. Without using light out-coupling technology, a maximum current efficiency (η_C) of 58.8 cd/A and a maximum external quantum efficiency (η_EQE) of 18.77% were obtained for the mCP-based WOLED; while a maximum η_C of 65.3 cd/A and a maximum η_EQE of 19.04% were achieved for the UGH2-based WOLED. Meanwhile, both WOLEDs presented higher performance than that of conventionally full-doping WOLEDs. Furthermore, systematic studies of the high-efficiency WOLEDs were progressed.     

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.     

Synthesis and characterization of L10 FePt nanoparticles from Pt–Fe3O4 core-shell nanoparticles

Pt/Fe₃O₄ core-shell nanoparticles have been prepared by a modified polyol method. Pt nanoparticles were first prepared via the reduction of Pt(acac)₂ by polyethylene glycol-200 (PEG-200), and layers of iron oxide were subsequently deposited on the surface of Pt nanoparticles by the thermal decomposition of Fe(acac)₃. The nanoparticles were characterized by XRD and HR-TEM. The as-prepared Pt/Fe₃O₄ nanoparticles have a chemically disordered FCC structure and transformed into chemically ordered fct structure after annealing in reducing atmosphere (4% H₂, 96% Ar) at 700 °C. The ordered fct FePt phase has high magnetic anisotropy with coercivity reaching 7.5 kOe at room temperature and 9.3 kOe at 10 K.     

Synthesis and photophysics of a new deep red soluble phosphorescent iridium(III) complex based on chlorine-methyl-substituted 2,4 diphenyl quinoline

A new iridium complex with a chlorine-methyl-substituted 2,4 diphenyl quinoline, (Cl-MDPQ) ligand has been synthesized. The synthesized iridium metal complex, Ir(Cl-MDPQ)₂(acac) where Cl-MDPQ=chlorine-methyl substituted, 2,4 diphenyl quinoline, acac=acetyl acetone is characterized by employing different techniques such as mass spectrometry, ¹H NMR, DTA/TGA, XRD, and FTIR. The molecular structures of Cl-MDPQ and Ir(Cl-MDPQ)₂(acac) complexes are confirmed by the FTIR spectra. Strong singlet metal-to-ligand charge-transfer (¹MLCT) and triplet metal-to-ligand charge-transfer (³MLCT) absorption peaks at 353 and 437 nm in tetrahydrofuran (THF) are reported in the synthesized complex, respectively. A deep red emitting Ir(Cl-MDPQ)₂(acac) complex at 662 nm is promising for flexible organic devices.     

基于CBP:BCzVB:Btp2Ir(acac)体系的白色有机电致发光器件色度飘移研究

以苯乙烯类化合物BCzVB为蓝色荧光染料,以铱配合物Btp_2Ir(acac)为红色磷光染料,共掺杂到CBP基质中作为发光层,制备了白色有机电致发光器件,研究了该体系发光色度漂移的原因。器件在掺杂CBP:6?zVB: 0．2%Btp_2Ir(acac),在．驱动电流从4～200 mA/cm~2变化范围内,发光色坐标从(0．340,0．273)飘移到(0．308, 0．273),色坐标轻微蓝移。对器件发光光谱和亮度-电流密度曲线等分析表明:器件色度的轻微蓝移是由于CBP基质向Btp_2Ir(acac)掺杂剂完全的能量传递、荧光染料BCzVB向磷光染料Btp_2Ir(acac)不完全的能量传递等内在物理过程和磷光染料Btp_2Ir(acac)自身发光饱和等特性共同决定的。     

A new type of iridium (III) phenylpyrazole complexes: synthesis, photophysical characterization

New heteroleptic iridium(III) complexes (ppz)2Ir(LX), which consist of two cyclometalated ligands ppz(1-phenylpyrazole) together with an ancillary ligand LX (LX= 2-(2'-hydroxylphenyl)benzothiazole (BTZ), 2-(3'-methyl-2'-hydroxylphenyl) benzothiazole (3-MeBTZ), 2-(4'-methyl-2'-hydroxylphenyl) benzothiazole (4-MeBTZ) and 2-(4'-Trifluoromethyl-2'hydroxylphenyl) benzothiazole (4-tfmBTZ)), were synthesized and characterized. The molecular structures and photophysical properties were characterized and analyzed comparatively. The results show that the four complexes have basically similar UV-Vis absorption spectra, fluorescence excitation and emission spectra. Their maximum emission peaks are located at 583-615 nm, and accompanied by a lower intensity emission band around 400 nm. The weak emissions around 400 nm are ascribed to the radi ation transition of single state excition from ancillary ligand BTZ perturbed by metallic ion, and light emission around long-wave-length to the radiation transition of 3MLCT of Ir(BTZ) fragment. While the triplet state 3 MLCT of Ir(ppz)2 fragment might be quenched at room temperature. For all complexes, the excitations with maximum efficiency are located at 250-310 nm, which indicates that main contributor to light emitting is ligand-centered absorption (1pi-pi*) of ppz and BTZ rather than 3MLCT transitions, and thus provides a striking evidence that there is intersystem crossing from 1pi-pi* state to 3MLCT state in these complexes. Compared with Ir(ppz)3, these complexes not only have stronger phosphorescence at room temperature but also their emission color can be tuned by modifying ancillary ligand.     

Synthesis,measurements, and theoretical analysis of carbazole derivatives with high-triplet-energy

In order to obtain the blue light-emitting organic materials with high triplet state energy, two 3,5-diphenyl-4H-1,2,4-triazole (Tz) containing carbazole (Cz) derivatives of 9-(4-(3,5-diphenyl-4H-1,2,4-triazol-4-yl)phenyl)-9H-carbazole (TzCz1) and 3,6-di-tert-butyl-9-(4-(3,5-diphenyl-4H-1,2,4-triazol-4-yl)phenyl)-9H-carbazole (TzCz2) are synthesized using Cz acting as the starting material, as well as characterized by the ¹H NMR spectra, ultraviolet–visible (UV–vis) absorption spectra, and the IR absorption spectra. The luminescence quantum yields (LQYs) of TzCz1 and TzCz2 are measured in CH₂Cl₂ solution to be 32.1% and 47.5%, respectively. The electrochemical analysis and the photophysical measurements suggest that the triplet energy levels and the energy gaps of the highest-occupied orbital and the lowest-unoccupied orbital are 2.83 eV and 3.59 eV for TzCz1, and 2.80 eV and 3.43 eV for TzCz2. At last, the theoretical analyses of their ground state geometries and the simulated UV–vis absorption spectra are carried out at B3LYP1/6-31G? level. The studies mentioned above indicate that both TzCz1 and TzCz2 are suitable for the host materials of blue light-emitting diodes.     

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.