高效叠层OLED白光器件进展

叠层有机发光二极管（Organic Light-Emitting Diode,OLED）白光器件具备低功耗、高亮度、高色域等性能优势。然而,由于效率、寿命及驱动电压等性能仍有较大改进空间,叠层结构的材料及电学结构仍需进一步优化。本文重点介绍叠层OLED白光器件的最新研究进展,总结了三类电荷产生层（Charge Generation Layer,CGL）在工程化应用中存在的问题以及其非破坏性检测方法;综述高效叠层OLED白光器件的“全磷光体系”、“并行通道激子收集”及“混合磷光热活性型延迟荧光（Thermally Activated Delayed Fluorescence,TADF）体系”最新研究成果,对器件寿命问题进行总结,探讨分析“分级掺杂”、“四色混合TADF体系”等从结构方面提出优化方案,并针对不同发光材料体系中的CGL材料及结构综述叠层OLED白光器件实现较低工作电压的技术方法,最后对叠层OLED白光器件的材料和结构提出改进建议。     

Efficient solution-processed blue phosphorescent organic light-emitting diodes with halogen-free solvent to optimize the emissive layer morphology

Efficient solution-processed blue phosphorescent organic light-emitting diodes (OLEDs) featuring with halogen-free solvent processing are fabricated in this study. The organic molecule 3,6-bis(diphenylphosphoryl)-9-(4′-(diphenylphosphoryl) phenyl)-carbazole (TPCz) that possesses good solubility in halogen-free polar solvents is selected to serve as the host of blue phosphorescent iridium(III) [bis(4,6-difluorophenyl)-pyridinato-N,C²]-picolinate (FIrpic) dopant. The morphology of the TPCz:FIrpic emissive layer prepared with different polar solvents including chlorobenzene (CB), n-butanol (ButA) and isopropanol (IPA) and the effect on their electroluminescent performance have been investigated in detail. It is found that the more polar halogen-free solvent IPA restrains the FIrpic aggregation and renders a more densely packed emissive layer as compared to the CB-processed counterpart, which results in the enhanced electroluminescent performance. The luminous efficiency and power efficiency of the blue phosphorescent OLEDs prepared with CB are merely 5.7 cd/A and 3.3 lm/W, respectively. When using more polar halogen-free solvent IPA, the efficiencies are enhanced to 22.3 cd/A and 15.6 lm/W, about 2.9 and 3.7-time increment, respectively. This work provides an approach to fabricate efficient solution-processed phosphorescent OLEDs with environmental-friendly solvents, which is highly required in large-scale solution-processed manufacturing.     

Bright and efficient inverted organic light-emitting diodes with improved solution-processed electron-transport interlayers

Highly efficient inverted organic light-emitting diodes (iOLEDs) are reported by including in the structure a surface modifier, polyethylenimine-ethoxylated (PEIE), to decrease the cathode work function and a hole blocking layer, 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBi) to increase the efficiency of the device. The two compounds have been processed in a single step, by using a mixture PEIE:TPBi spun from the same solution. It is demonstrated by time-of-flight secondary-ion mass spectrometry (TOF-SIMS) that a bilayer is formed and same performances as the separately processed materials are obtained. This technic enables to reach high luminances (40 000 cd m⁻²) and high current efficiencies (13 cd/A) using the conjugated Super Yellow (SY) polymer as the emissive layer while reducing the number of processing steps.     

Near infrared electroluminescence from Nd(TTA)3phen in solution-processed small molecule organic light-emitting diodes

We report on the near infrared electroluminescence properties of a Nd³⁺ complex with thenoyltrifluoroacetone and 1,10-phenantroline ligands in solution-processed organic light-emitting diodes. Spin-coated blends containing a 1,3-bis(9-carbazolyl)benzene host doped with the Nd³⁺ complex were found to exhibit a photoluminescence quantum yield of about 0.5%, regardless of the doping concentration level. Electroluminescent devices based on these small molecule blends showed the characteristic emission of Nd³⁺ at 890, 1060 and 1330 nm with an external quantum efficiency as high as 0.022%. These improved performances were mainly attributed to direct charge trapping and exciton formation on the near infrared emitter. Importantly, the efficiency roll-off at high current densities due to triplet-triplet exciton annihilation in the device containing 20 wt% of the complex was lower than what is typically observed in lanthanide complex-based electroluminescent devices. This is presumably due to the high triplet energy of the host material, which prevents guest-to-host energy-back transfer and thus host-guest triplet-triplet exciton annihilation.     

Electron injection and interfacial trap passivation in solution-processed organic light-emitting diodes using a polymer zwitterion interlayer

Here we describe the use of a polymer zwitterion as a solution-processable material that serves as the key component of the electron injection layer (EIL) in solution processed organic light-emitting diodes (OLEDs). Poly(sulfobetaine methacrylate) (PSBMA) was employed in both regular and inverted device configurations as a work-function modifier for Al and ZnO cathodes, respectively. For both architectures, PSBMA significantly improved the OLED performance when compared to reference devices without EIL in terms of turn-on voltage and luminance. In inverted devices, PSBMA showed a passivation effect on ZnO surface trap states, producing better performing and more stable devices.     

Fabrication of highly efficient blue top-emission organic light-emitting diodes on different reflective electrodes

The performances of top-emission organic light-emitting diodes (TEOLEDs) with various P-dopant (PD) contents in the injection layer were studied by thinning or removing an indium tin oxide (ITO) film sputtered on the anode. On adjusting the thickness of the active TBPDA (N4,N4,N4′,N4′-tetra ([1,1′-biphenyl]-4-yl)-[1,1′-biphenyl]-4,4′-diamine) film used as hole transport layer, the International Commission on Illumination (CIE) coordinates of blue TEOLEDs did not change and the same CIE coordinates (0.14, 0.04) were maintained. The blue index of device I (PD of 3%) without an indium tin oxide (ITO) layer was 139.9 cd/A/CIEy at a current density of 10 mA/cm². This value was 28% higher than that of the device B (PD of 2%), which had a 15-nm thick ITO film, and 19% higher than that of device E (PD of 2%), which had a 7-nm thick ITO film. Devices B, E, and I achieved similar voltages of approximately 3.9 V. Thus, in the optimized TEOLEDs with suitable PD contents, efficiency was improved by silver without the use of ITO as an anode.     

Boosting the performance of solution-processed quantum dots light-emitting diodes by a hybrid emissive layer via doping small molecule hole transport materials into quantum dots

Solution-processed colloidal quantum dot light-emitting diodes (QLED) have attracted many attentions with significant progress in recent years. However, QLED devices still face some challenges. The energy barrier between Cd-base quantum dots (QDs) and commonly used hole transport materials is larger than that between QDs and electron transport materials, which leads to the imbalance of carriers in the light emitting layer (EML) and the low performance of QLED devices. Herein, we report a simple strategy to improve the device performance by doping small molecule transport material 4,4′-cyclohexylidenebis[N,N-bis(p-tolyl)aniline] (TAPC) into red CdSe/ZnS QDs. The optimized red QLED devices with TAPC-doped emissive layer at a ratio of 3.2 wt% achieve 20.0 cd/A of maximum current efficiency, 16.6 lm/W of power efficiency and 15.7% of external quantum efficiency, which is 30%, 58% and 33% higher than the control device. The improved performance of devices can be ascribed to the increase of hole current density, decrease of leakage electrons and more balanced quantity of carriers in EML. This work put forward a viewpoint to improve the performance of QLED devices via doping high hole mobility materials into emission layer.     

Ink formulation of in-situ crosslinkable hole-transporting composite for multilayer inkjet-printed organic light-emitting diodes

Inkjet printing is considered to be the most promising technique for high-resolution, large-scale and low-cost organic light-emitting diode (OLED) displays. However, the device performance with multilayer printing is still a challenge that needs to be tackled, because of the serious re-dissolving problem of bottom film into the subsequent ink during printing processes. This work demonstrates an in-situ crosslinkable composite of hole-transporting polymer poly(N-vinylcarbazole) (PVK) and oxidative coupling agent phosphomolybdic acid (PMA) without ultra-violet irradiation or high temperature annealing treatment. The hole-transporting ink is formulated by adding high-boiling point solvents including o-dichlorobenzene, butyl benzoate, cyclohexylbenzene and 1-chloronaphthalene to eliminate the coffee ring effect. Their influence on the ink property is systematically investigated, and the corresponding solidification mechanism is also proposed. The modified PVK:PMA ink leads to a crosslinked hole-transporting layer (HTL) with an excellent solvent resistance and temperature-independent property. Finally, the emitting layer is successfully inkjet-printed onto this HTL, and multilayer inkjet-printed OLEDs are achieved with a current efficiency of 21.7 cd/A. In summary, this in-situ crosslinkable hole-transporting composite ink is facile and effective for multilayer inkjet-printed OLEDs.     

Efficient nondoped blue organic light-emitting diodes based on phenanthroimidazole-substituted anthracene derivatives

A series of new blue materials based on highly fluorescent di(aryl)anthracene and electron-transporting phenanthroimidazole functional cores: 2-(4-(anthracen-9-yl)phenyl)-1-phenyl-1H-phenanthro[9,10-d]imidazole (ACPI), 2-(4-(10-(naphthalen-1-yl)anthracen-9-yl)phenyl)-1-p-henyl-1H-phenanthro[9,10-d]imidazole (1-NaCPI), 2-(4-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)-1-phenyl-1H-phenanthro[9,10-d]imidazole (2-NaCPI) were designed and synthesized. These materials exhibit good film-forming and thermal properties as well as strong blue emission in the solid state. To explore the electroluminescence properties of these materials, three layer, two layer and single layer organic light-emitting devices were fabricated. With respect to the three layer device 4 using ACPI as the emitting layer, its maximum current efficiency reaches 4.36 cd A⁻¹ with Commission Internationale del’Eclairage (CIE) coordinates of (0.156, 0.155). In the single layer device 10 based on ACPI, maximum current efficiency reaches 1.59 cd A⁻¹ with Commission Internationale del’Eclairage (CIE) coordinates of (0.169, 0.177). Interestingly, both device 4 and 10 has low turn on voltage and negligible efficiency roll off at high current densities.     

Efficient blue organic light-emitting diodes based on triphenylimidazole substituted anthracene derivatives

A series of new blue emissive materials based on the conjugates of highly fluorescent diaryl anthracene and electron-transporting triphenylimidazole moieties: 2-(4-(anthracen-9-yl)phenyl)-1,4,5-triphenyl-1H-imidazole (ACBI), 2-(4-(10-(naphthalen-1-yl)anthracen-9-yl)phenyl)-1,4,5-triphenyl-1H-imidazole (1-NaCBI), 2-(4-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)-1,4,5-triphenyl-1H-imidazole (2-NaCBI) were designed and synthesized successfully. These materials exhibit good film-forming properties and excellent thermal stabilities. Meanwhile, the decreased π-conjugation in these compounds compared with phenanthroimidazole derivatives leads to obvious hypsochromic shift. To explore the electroluminescence properties of these materials, typical three-layer organic light-emitting devices were fabricated. With respect to the three layer device 2 using 1-NaCBI as the emitting layer, its maximum current efficiency reaches 3.06 cd A⁻¹ with Commission Internationale del’Eclairage (CIE) coordinates of (0.149, 0.092). More interestingly, sky blue doped device 5 based on 1-NaCBI achieved a maximum current efficiency of 15.53 cd A⁻¹ and a maximum external quantum efficiency of 8.15%, high EQE has been proved to be induced by the up-conversion of a triplet excited state.     

Phenylimidazole-based homoleptic iridium(III) compounds for blue phosphorescent organic light-emitting diodes with high efficiency and long lifetime

In order to obtain triplet emitters with high stability and efficiency, three homoleptic iridium(III) compounds — specifically, Ir(tpim)₃ (1), Ir(mtpim)₃ (2), and Ir(itpim)₃ (3), where tpim = 1-([1,1′:3′,1″-terphenyl]-2′-yl)-2-(4-fluorophenyl)-1H-imidazole, mtpim = 2-(4-fluorophenyl)-1-(5′-methyl-[1,1′:3′,1″-terphenyl]-2′-yl)-1H-imidazole, and itpim = 2-(4-fluorophenyl)-1-(5′-isopropyl-[1,1′:3′,1″-terphenyl]-2′-yl)-1H-imidazole — were prepared by one-pot reaction of the corresponding phenylimidazole ligand with an Ir(I) complex as a starting material. Compounds 1–3 emit bright sky-blue phosphorescence with λ_max = 459–463 nm and phosphorescent quantum efficiencies of 0.38–0.50. Multi-layer phosphorescent organic light-emitting diodes using compounds 1–3 as the triplet emitters and mCBP (3,3-di(9H-carbazol-9-yl)biphenyl) as the host have been fabricated. Compound 3 doped in the emissive layer demonstrate external quantum efficiency as high as 20.1% at 1000 cd/m². In addition, the device based on compound 1 as an emitter shows a stable lifetime greater than 300 h at 1000 cd/m², which is one of the best results concerning the device lifetime.     

Lifetime extension of blue phosphorescent organic light-emitting diodes by suppressing triplet-polaron annihilation using a triplet emitter doped hole transport layer

A lifetime extending device structure by suppressing positive polaron induced triplet exciton-polaron annihilation was developed for improved lifetime in blue phosphorescent organic light-emitting diodes. A blue triplet emitter doped hole transport layer was introduced to control the triplet exciton-polaron annihilation of blue phosphorescent emitters in the emitting layer, which extended the lifetime of the blue phosphorescent devices. Current and ultraviolet light/current aging tests of hole and electron only devices proved that the lifetime extending mechanism of the blue triplet emitter doped hole transport layer is suppression of triplet exciton-positive polaron annihilation.     

Efficient non-doped monochrome and white phosphorescent organic light-emitting diodes based on ultrathin emissive layers

Efficient red, orange, green and blue monochrome phosphorescent organic light-emitting diodes (OLEDs) with simplified structure were fabricated based on ultrathin emissive layers. The maximum efficiencies of red, orange, green and blue OLEDs are 19.3 cd/A (17.3 lm/W), 45.7 cd/A (43.2 lm/W), 46.3 cd/A (41.6 lm/W) and 11.9 cd/A (9.2 lm/W). Moreover, efficient and color stable white OLEDs based on two complementary colors of orange/blue, three colors of red/orange/blue, and four colors of red/orange/green/blue were demonstrated. The two colors, three colors and four colors white OLEDs have maximum efficiencies of 30.9 cd/A (27.7 lm/W), 30.3 cd/A (27.2 lm/W) and 28.9 cd/A (26.0 lm/W), respectively. And we also discussed the emission mechanism of the designed monochrome and white devices.     

Modification effect of hole injection layer on efficiency performance of wet-processed blue organic light emitting diodes

We examined the performance of solution-processed organic light emitting diodes (OLEDs) by modifying the hole injection layer (HIL), poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS). Atomic force microscopy (AFM) showed morphological changes with surface roughness (R_RMS) of 1.47, 1.73, and 1.37 nm for pristine PEDOT: PSS, PEDOT: PSS modified with a 40 v% deionized water and with a 30 v% acetone, respectively. The surface hydrophobicity of the acetone modified PEDOT:PSS HIL layer was decreased by 34% as comparing with the water modified counterpart. Electrical conductivity was increased to two orders of magnitude for the water and acetone modified PEDOT:PSS as compared to pristine. We observed a low refractive index and high transmittance for the modified HILs. We fabricated and explored electroluminescent properties of bis[2-(4,6-difluorophenyl)pyridinato-C2,N](picolinato)iridium(III) (FIrpic) based sky blue device by utilizing HIL with and without modification. The changes in electrical conductivity, surface roughness, refractive index, and transmittance of the modified HILs strongly influenced the performance of devices. By utilizing a 30% acetone modified HIL, the power efficiency was increased from 14.2 to 24.2 lm/W, an increment of 70% and the EQE from 8.5 to 13.1% at 100 cd/m², an increment of 54%. The maximum luminance also increased from 11,780 to 18,190 cd/m². The findings revealed herein would be helpful in designing and fabricating high efficiency solution processed OLEDs.     

Soluble processed low-voltage and high efficiency blue phosphorescent organic light-emitting devices using small molecule host systems

We report low voltage driving and highly efficient blue phosphorescence organic light emitting diodes (PHOLEDs) fabricated by soluble process. A soluble small molecule mixed host system consisting of hole transporting 4,4’,4’’ tris(N-carbazolyl)triphenylamine (TCTA) and bipolar carrier transporting 2,6-bis(3-(carbazol-9-yl)phenyl)pyridine (26DCzPPy) exhibits high solubility with smooth surface properties. Moreover, this small molecule host shows the smoothest morphological property similar to a vacuum deposited amorphous film. A low driving voltage of 5.4 V at 1000 cd/m² and maximum external quantum efficiency 14.6% obtained in the solution processed blue PHOLEDs are useful for large area low cost manufacturing.     

Properties of non-doped organic light-emitting devices based on an ultrathin iridium complex phosphor layer

Organic light-emitting devices (OLEDs) were constructed with a structure of indium tin oxide (ITO)/N,N'-bis(naphthalen-1-yl)-N'-bis(phenyl)-benzidine (NPB) (50-xnm)/bis[2-(4-tertbutylphenyl)benzothiazolato-N,C2'] iridium (acetylacetonate) [(t-bt)2Ir(acac)] (nm)/NPB (30nm)/Mg:Ag (200nm).A thin blue emission material of NPB was used as a separating layer,and the (t-bt)2Ir(acac) yellow phosphorescent dye was acted as an ultrathin light-emitting layer.TPBI acted as both hole-blocking and electron-transporting layer.By changing the location (x) and the thickness (d) of the phosphor dye,the variation of device performance were investigated.The results showed that all the devices had a turn-on voltage of 2.8V.In the case of d=0.2nm and x=5nm,the OLED had a maximum luminance of 18367cd/m2 and a maximum power efficiency of 5.3lm/W.The high performance is attributed to both direct charge carrier trapping of iridium phosphor dye and the thin NPB separation layer,which effectively confines the recombination zone of charge carriers.     

Highly efficient inverted blue light-emitting diodes by thermal annealing and interfacial modification

Inverted polymer light-emitting diodes (IPLED) were fabricated by using polyfluorene (PF-FSO10) as the emissive layer, polyethyleneimine ethoxylate (PEIE) as the interlayer, and 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI) as the electron-transport layer with the configuration of ITO/ZnO/PEIE/TPBI/PF-FSO10/MoO₃/Al. Thermal annealing PF-FSO10 made the hole transporting ability decreased, the electron transporting ability enhanced, and thus, jointly promoted the carrier balances in the emissive layer. Inserting a TPBI layer between the PEIE and PF-FSO10 much enhanced the electron transportation and reduced the exciton quench on the ZnO interface. Therefore, the inverted blue light-emitting diode was obtained with a luminous efficiency of 6.8 cd A⁻¹ (an external quantum efficiency of 7.1%), and the CIE color coordinates of (0.15, 0.15), which was among the highest efficiency values in solution-processed inverted blue fluorescent light-emitting diodes.     

A study on full color organic light emitting diodes with blue common layer under the patterned emission layer

Color patterning steps for red, green, and blue emission layers (EMLs) are crucial for the production of full color organic light-emitting diodes (OLEDs). The most common method to form individually patterned EMLs is to use a shadow mask as the key component for patterning. However, most pixel defects are caused by such kinds of patterning steps. Therefore, skipping certain color patterning steps could significantly improve the production yield during the fine metal masking process in the OLED fabrication. A representative example of such approach is the top blue common layer (TBCL) structure with a non-patterned BCL on top of both green and red EMLs. However, this structure could cause blue color mixing in green or red devices. To prevent this effect, we propose a newly devised bottom BCL (BBCL) structure with the BCL that is totally separated from both green and red EMLs. In particular, we utilized 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile interlayer (7 nm) between the underlying BCL and the hole injection layer to completely extinguish blue emission. As a result, both green and red devices with the BBCL structure showed relatively better efficiencies compared to those with the TBCL structure without any color mixing.     

High efficiency fluorescent white organic light-emitting diodes having a yellow fluorescent emitter sensitized by a blue thermally activated delayed fluorescent emitter

Fluorescent white organic light-emitting diodes having a blue thermally activated delayed fluorescent emitter and a yellow fluorescent emitter was developed by co-doping the blue and yellow emitters in a single emitting layer. The blue delayed fluorescent device showed high quantum efficiency of 22.6% at a very high doping concentration of 50% and the white devices exhibited a high quantum efficiency of 15.5% even though a fluorescent yellow emitter was doped in the blue thermally activated delayed fluorescent emitting layer. Minimized charge trapping and Dexter energy transfer by low yellow doping concentration of 0.05% as well as efficient Förster energy transfer could develop the high efficiency fluorescent white organic light-emitting diodes.     

双空穴注入层对有机电致蓝光器件性能的改善

CuI/CuPc被采用作为有机电致蓝光CBP:BCzVBi器件 的双空穴注入层。采用双空穴注入层后使得CBP:BCzVBi蓝光器件的启亮电压降低至 3.4 V,较采用CuPc单空穴注入层的CBP:BCzVBi蓝光器件低0.4 V。在驱动电流20 mA/cm²的情况下,与单空穴注入层器件 相比,采用该双空穴注入层结构使得器件电流效率提升约19%,亮度 增加约17%,驱动电压降低0.9 V。采用Fowler -Nordheim (F-N)隧穿注入理论对器件空穴注入电流的影响因素进行了分析,发现双空穴 注入层形成的能级台阶可以有效地改善发光器件的空穴注入效率,进而起到改善器件发光电 流效率和降低驱动电压的目的。