基于新型电荷生成层的P-i-N结构白色有机叠层电致发光器件

采用2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline(BCP): 5 wt.% cesium carbonate(Cs₂CO₃)和N, N'-Bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine(NPB): 20 wt.% molybdenum oxide(MoO₃)分别作为器件的电子注入层和空穴注入层,研究了N型和P-i-N结构有机电致发光器件的载流子传输特性.载流子传输层中BCP: Cs₂CO₃和NPB:MoO₃的引入有效增强了载流子注入能力,从而降低了器件的驱动电压.基于新型电荷生成层BCP: 5 wt.% Cs₂CO₃/ NPB: 20 wt.% MoO₃制备了色稳定、高效率P-i-N结构有机叠层器件.与单元器件相比,引入新电荷生成层有机叠层器件的最大电流效率增大了2.5倍,表明该电荷生成层可以有效地将电子和空穴分别注入到相邻发光单元中.采用该电荷生成层制备了P-i-N结构白色有机叠层器件,器件的上下发光单元分别为橙光和蓝光发射.当发光亮度从500增加到5 000 cd/m²时,器件的色坐标稳定在(0.33, 0.29)附近,接近白光等能点.利用单色发光单元堆叠制备白色有机叠层器件的方法为实现色稳定、高效率的白色有机电致发光器件提供了一种有效的途径.     

Twisted penta‐Carbazole/Benzophenone Hybrid Compound as Multifunctional Organic Host,Dopant or Non‐doped Emitter for Highly Efficient Solution‐Processed Delayed Fluorescence OLEDs

A new multi‐functional penta‐carbazole/benzophenone hybrid compound 5CzBP was designed and synthesized through a simple one‐step catalyst‐free C—N coupling reaction by using 2,3,4,5,6‐pentafluorobenzophenone and carbazole as starting materials. 5CzBP is very soluble in tetrahydrofuran (THF), which brings an environmentally friendly device fabrication for solution‐processed OLEDs instead of most widely used chlorinated solvents when 5CzBP is employed as the bulk‐phase of organic host or non‐doped emitter in the emissive layer. 5CzBP exhibits thermally activated delayed fluorescence (TADF) characteristic with relatively high triplet energy of 2.60 eV and a low ΔE_ST of 0.01 eV. By using the new TADF material as organic host for another green TADF emitter, maximum external quantum efficiency (EQE) of 12.5% has been achieved in simple solution‐processed OLED device. Besides, a maximum EQE of 8.9% and 5.7% was further obtained in TADF devices based on 5CzBP as dopant and non‐doped emitter, respectively. The simultaneously acting as efficient TADF host and non‐doped TADF emitter provides the potential guidance of the future simple single‐layer two‐color white OLEDs based on low‐cost pure organic TADF materials.     

Regulation of Multiple Resonance Delayed Fluorescence via Through-Space Charge Transfer Excited State towards High-Efficiency and Stable Narrowband Electroluminescence

B- and N-embedded multiple resonance (MR) type thermally activated delayed fluorescence (TADF) emitters usually suffer from slow reverse intersystem crossing (RISC) process and aggregation-caused emission quenching. Here, we report the design of a sandwich structure by placing the B−N MR core between two electron-donating moieties, inducing through-space charge transfer (TSCT) states. The proper adjusting of the energy levels brings about a 10-fold higher RISC rate in comparison with the parent B−N molecule. In the meantime, a high photoluminescence quantum yield of 91 % and a good color purity were maintained. Organic light-emitting diodes based on the new MR emitter achieved a maximum external quantum efficiency of 31.7 % and small roll-offs at high brightness. High device efficiencies were also obtained for a wide range of doping concentrations of up to 20 wt % thanks to the steric shielding of the B−N core. A good operational stability with LT₉₅ of 85.2 h has also been revealed. The dual steric and electronic effects resulting from the introduction of a TSCT state offer an effective molecular design to address the critical challenges of MR-TADF emitters.     

Synthesis, structural characterization, and initial electroluminescent properties of bis-cycloiridiated complexes of 2-(3,5-bis(trifluoromethyl)phenyl)-4-methylpyridine

A series of bis-cyclometalated Ir(III) complexes (8-10, 12, 15, 17, 19, 21, 23, 25, 28, 29 and 33) bearing two chromophoric N^∧C cyclometalated ligands derived from 2-(3,5-bis(trifluoromethyl)phenyl)-4-methylpyridine (1) and a third nonchromophoric ligand has been synthesized. A palladium-catalyzed cross-coupling reaction between 2-chloro-4-methylpyridine (2) and 3,5-bis(trifluoromethyl)phenylboronic acid (3) was used to prepare 2-(3,5-bis(trifluoromethyl)phenyl)-4-methylpyridine (1). Cyclometalation of (1) by IrCl₃ was carried out in (MeO)₃PO, with the formation of chloro-bridged dimer [N^∧C]₂Ir(μ-Cl)₂Ir[C^∧N]₂ (8). Reaction of (8) with lithium 2,4-pentanedionate, lithium 2,2,6,6-tetramethyl-heptane-3,5-dionate (13), dipivaloyltrimethylsilylphosphine (14), 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octadione (16), 1,1,1,3,3,3-hexafluoro-2-pyridin-2-yl-propan-2-ol (18), 1,1,1,3,3,3-hexafluoro-2-pyrazol-1-ylmethyl-propan-2-ol (20), 2-diphenylphosphanylethanol (22), and 1-diphenylphosphanylpropan-2-ol (24), afforded octahedral iridium complexes 9, 12, 15, 17, 19, 21, 23 and 25, respectively. Complex 10, which contains three different ligands (L₁ = N^∧C of 1; L₂ = N^∧C of 4,4′-dimethyl-[2,2′]bipyridinyl 4; L₃ = O^∧O of 2,4-pentanedione), and complex 11, which contains no cyclometalated ligands (L₁ = 4; L₂ = L₃ = Cl; L₄ = O^∧O of 2,4-pentanedione) were also isolated as minor products in a one-pot reaction between a 94:5 mixture of 1 and 4, IrCl₃ and lithium 2,4-pentanedionate. Reaction of 8 with diphenylphosphanylmethanol (27) in 1,2-dichloroethane unexpectedly led to complexes 28 and 29. The reactions of 8 with benzoylformic acid resulted in the formation of hydroxyl-bridged dimer [N^∧C]₂Ir(μ-OH)₂Ir[C^∧N]₂ (33). According to X-ray analyses, Ir-to-Ir distances in the crystal cell increase from 6.86 Å for 10 to 13.31 Å for 33. The angle theta, which represents the twisting of two cyclometalated C-Ir-N planes relative to each other, varies from 97.5° for 21 to 90.76 for complex 28. OLED devices were fabricated from several Ir complexes and preliminary results are discussed.     

Probing Electron Excitation Characters of Carboline-Based Bis-Tridentate Ir(III) Complexes

In this work, we report a series of bis-tridentate Ir(III) metal complexes, comprising a dianionic pyrazole-pyridine-phenyl tridentate chelate and a monoanionic chelate bearing a peripheral carbene and carboline coordination fragment that is linked to the central phenyl group. All these Ir(III) complexes were synthesized with an efficient one-pot and two-step method, and their emission hue was fine-tuned by variation of the substituent at the central coordination entity (i.e., pyridinyl and phenyl group) of each of the tridentate chelates. Their photophysical and electrochemical properties, thermal stabilities and electroluminescence performances are examined and discussed comprehensively. The doped devices based on [Ir(cbF)(phyz1)] (Cb1) and [Ir(cbB)(phyz1)] (Cb4) give a maximum external quantum efficiency (current efficiency) of 16.6% (55.2 cd/A) and 13.9% (43.8 cd/A), respectively. The relatively high electroluminescence efficiencies indicate that bis-tridentate Ir(III) complexes are promising candidates for OLED applications.     

基于红色荧光染料3-(dicyanomethylene)-5, 5-dimethyl-1-(4-dimethylamino-styryl) cyclohexene的高性能白色有机电致发光器件

研究了基于红色荧光染料3-（dicyanomethylene）-5, 5-dimethyl-1-（4-dimethylamino-styryl） cyclohexene（DCDDC）的白色有机电致发光器件的性能,分别制备了基于DCDDC超薄层和DCDDC掺杂主体材料的两种器件结构: 1）indium-tin oxide（ITO）/N, N′-diphenyl-N, N′-bis（1-naphthyl-pheny1）-1, 1′-biphenyl-4, 关键词： 有机电致发光器件 白色发光 红色荧光染料 掺杂     

可弯曲式有机电玫发光器件的出光率

基于几何光学模型及其原理,推导出在不同弯曲情况下可弯曲式有机电致发光器件的出光率表达式,分析了器件出光率受基板曲率、厚度及有机层折射率的影响,并与平整有机电致发光器件的出光情况作了比较.结果表明:当器件向外弯曲时,出光率随着基板曲率与基板厚度的增大而增大,随着有机层折射率的增大而减小;当器件向内弯曲时,出光率随着基板曲率与基板厚度的增大而减小,随着有机层折射率的增大而减小.对于平整器件,其出光率随有机层折射率的增大而减小.     

OLED with Hole-Transporting Layer Fabricated by Ink-Jet Printing

we report about the fabrication of organic light-emitting diodes (OLEDs) ink-jet printing a hole-transporting polymer (PF6, poly(9,9-dihexyl-9H-fluorene-2,7-diyl)) on flexible substrate (PET) and performing the other layers through vacuum thermal evaporation. The aim of the work is to employ the ink-jet printing (IJP) technology, familiar as a method for printing on paper, in optoelectronic applications and to determine how the deposition method affects the functional material film properties and hence the ultimate device performances. In this line of work, ink-jet printed polymer films are compared to same spin-coated polymer from the electro-optical point of view: both prepared materials are adopted as HTLs of electroluminescent devices. All manufactured OLEDs are characterized and their behaviours are investigated and analyzed with theoretical models. The results show differences in current density and optical behaviours between the devices fabricated by means of the above mentioned technologies which can be justified in terms of different trap distribution induced by impurity energy levels associated to each process.     

柔性衬底白色有机电致发光器件的制备及其性能

采用以ITO为导电层的柔性透明PET基片作为衬底,以2-(2-羟基苯基)苯并噻唑螯合锌(Zn(BTZ),)作为发光层制备出结构为PET／ITO／PVK：TPD／Zn(BTZ)2／Al明亮的近白色柔性有机小分子电致发光器件。发光的色坐标值为x=0．242,y=0．359,在25V的直流电压驱动下,亮度为1000cd／m^2,量子效率达到了0．30％。并进一步在Zn(BTZ)2中掺入橙红色染料Rubrene,制成PET／ITO／PVK：TPD／Zn(BTZ)2：Rubrene／Al结构器件。实现了纯白色发光(色坐标值：x=0．339,y=0．339),非常接近于白色等能点,驱动电压为25V时器件的亮度达1200cd／m^2,且量子效率达0．35％。最后对器件的发光性能及机理进行了深入的研究和探讨。     

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。