Phosphorescent dye-doped hole transporting layer for organic light-emitting diodes

Hole transport materials are critical to the performance of organic light-emitting diodes (OLEDs). While 1,1-bis(di-4-tolylaminophenyl)cyclohexane (TAPC) with a high triplet energy is widely used for high efficiency phosphorescent OLEDs, devices using TAPC as a hole transport layer (HTL) have a short operating lifetime due to the build-up of trapped charges at the TAPC/emitting layer (EML) interface during device operation. In this work, to solve the operating stability problem, instead of using conventional HTLs, we use a(fac-tris(2-phenylpyridine)iridium (III))(Ir(ppy)₃) doped layer as an HTL to replace the conventional HTLs. Because of the hole injecting and transporting abilities of the phosphorescent dye, holes can be directly injected into the emitting layer without an injection barrier. OLEDs based on a phosphorescent dye-doped HTL show significant improvement in operational stability without loss of efficiency.     

Highly efficient all-solution processed blue quantum dot light-emitting diodes based on balanced charge injection achieved by double hole transport layers

Solution-processed blue quantum dot light-emitting diodes (QLEDs) suffer from low device efficiency, whereas the balance of electron and hole injection is critical for obtaining high efficiency. Herein, synergistical double hole transport layers (D-HTLs) are employed, which use poly(9-vinylcarbazole) (PVK) stacked on poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-(4,4'-(N-(4-butylphenyl) (TFB). The fabrication of D-HTLs is achieved by using dimethyl formamide (DMF) as the solvent for PVK, with which the underlying TFB layer almost remains unwashed and undamaged during the spin-coating process of PVK layer. TFB/PVK D-HTLs form the stepwise energy level for hole injection, which reduces the hole injection barrier and favors the carrier balance in the emission layer (EML). The optimized blue QLED with TFB/PVK D-HTLs shows a maximum external quantum efficiency (EQE) of 13.7%, which is 3-fold enhancement compared to that of the control device with single TFB HTL. The enhancement of the QLED performance can be attributed to the improvement of surface morphology and charge injection balance for the stepwise D-HTLs based QLEDs. This work manifests the positive effect on performance boost by selecting appropriate solvents towards stepwise D-HTLs formation and paves the way to fabricate highly efficient all-solution processed light emitting diodes.     

High-performance azure blue quantum dot light-emitting diodes via doping PVK in emitting layer

Highly bright and efficient azure blue quantum dot-based light-emitting diodes (QD-LEDs) have been demonstrated by employing ZnCdSe core/multishell QDs as emitters and the crucial development we report here is the ability to dramatically enhance the efficiency and brightness through doping poly vinyl(N-carbazole) (PVK) in the emissive layer to balance the charge injection. The best device displays remarkable features like maximum luminance of 13,800 cd/m², luminous efficiency of 6.41 cd/A, and external quantum efficiency (EQE) of 8.76%, without detectable red-shift and broadening in electroluminescence (EL) spectra with increasing voltage as well as good spectral matching between photoluminescence (PL) and EL. Such azure blue quantum-dot LEDs show a 140% increase in external quantum efficiency compared with QD-LEDs without PVK. More important, the peak efficiency of the QD-LEDs with PVK dopant is achieved at luminance of about 1000 cd/m², and high efficiency (EQE > 8%) can be maintained with brightness ranging from 200 to 2400 cd/m². There are two main aspects of the role of PVK in the proposed system. Firstly, the lower HOMO of PVK than (poly[9,9-dioctylfluorene-co-N-[4-(3-methylpropyl)]-diphenylamine] (TFB) can reduce the potential barrier for 0.4 eV at the interface of QDs and hole transport layer which could result in higher hole injection efficiency along with good EQE as compared to TFB-only HTLs. Secondly, with PVK acting as buffer layer of TFB and QDs, the exciton energy transfer from the organic host to the QDs can be effectively improved.     

Cadmium-free quantum dots based violet light-emitting diodes: High-efficiency and brightness via optimization of organic hole transport layers

Bright and efficient violet quantum dot (QD) based light-emitting diodes (QD-LEDs) with heavy-metal-free ZnSe/ZnS have been demonstrated by choosing different hole transport layers, including poly(4-butyl-phenyl-diphenyl-amine) (poly-TPD), poly[9,9-dioctylfluorene-co-N-[4-(3-methylpropyl)]-diphenylamine] (TFB), and poly-N-vinylcarbazole (PVK). Violet QD-LEDs with maximum luminance of about 930 cd/m², the maximum current efficiency of 0.18 cd/A, and the peak EQE of 1.02% when poly-TPD was used as HTL. Higher brightness and low turn-on voltage (3.8 V) violet QD-LEDs could be fabricated when TFB was used as hole transport material. Although the maximum luminance could reach up to 2691 cd/m², the devices exhibited only low current efficiency (∼0.51 cd/A) and EQE (∼2.88%). If PVK is used as hole transport material, highly efficient violet QD-LEDs can be fabricated with lower maximum luminance and higher turn-on voltages compared with counterpart using TFB. Therefore, TFB and PVK mixture in a certain proportion has been used as HTL, turn-on voltage, brightness, and efficiency all have been improved greatly. The QD-LEDs is fabricated with 7.39% of EQE and 2856 cd/m² of maximum brightness with narrow FWHM less than 21 nm. These results represent significant improvements in the performance of heavy-metal-free violet QD-LEDs in terms of efficiency, brightness, and color purity.     

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.     

Highly efficient and stable blue quantum-dot light-emitting diodes based on polyfluorenes with carbazole pendent groups as hole-transporting materials

Highly efficient and stable blue quantum-dot light-emitting diodes (QD-LEDs) have been realized by using poly (9,9-bis(N-(2′-ethylhexyl)-carbazole-3-yl)-2,7-fluorene) (PFCz) as hole-transporting layers (HTLs). Due to the carbazole units as substituents at the 9-position of polyfluorene, PFCz shows higher hole mobility and better electrochemical stability than poly (N-vinlycarbazole) (PVK). As a result, the maximum current efficiency (CE) and external quantum efficiency (EQE) of the blue QD-LEDs increased from 4.32 cd A⁻¹ to 7.9% for PVK HTL to 7.38 cd A⁻¹ and 12.61% for PFCz HTL, respectively. Furthermore, the PFCz-based blue QD-LED exhibited lower turn-on voltage and longer device lifetime than the PVK-based device. The improvement performance of blue QD-LED should be attributed to the conjugated fluorene backbone and the substituents of the carbazole active sites, thus enhancing hole mobility and electrochemical stability. This result demonstrates that polyfluorenes with pendent carbazole groups is a promising hole-transporting materials for improving performance of blue QD-LEDs.     

有机/聚合物异质结电致发光器件的光电性能

器件结构是影响有机发光器件(OLED)性能的重要因素之一.采用8-hydroxyquinoline-aluminum(AlQ)作为发光层(EML)和电子传输层(ETL),polyvinylcarbazole (PVK)作为空穴传输层(HTL),制备了具有有机小分子/聚合物异质结结构的OLED器件,通过其电压-电流-发光亮度(V-J-B)特性测试,研究了HTL的引入及其膜厚对器件性能的影响.实验结果表明,HTL的引入有效地改善了OLED的光电性能,同时HTL膜厚对器件性能具有显著影响,当HTL膜厚为20 nm时,所制备的OLED器件具有最小的驱动电压和启亮电压、最大的发光亮度和发光效率.

Abstract：

The device construction plays an important role in improving the optoelectronic performance of organic electroluminescence devices (OLEDs). Heterojunction OLEDs with a configuration of glass/ITO/PVK/AlQ/Mg/Al were fabricated by using 8-hydroxyquinoline-aluminum (AlQ) as the emission layer (EML) and electron transport layer (ETL) and polyvinylcarbazole (PVK) as the hole transport layer (HTL). The effect of the HTL thickness on the performance of OLEDs was investigated with respect to the driving voltage, turn-on voltage, electroluminescence brightness and efficiency of the devices. Experimental results demonstrate that the optical and electrical properies of OLEDs are closely related to the HTL thickness. The device fabricated with the HTL thickness of 20 nm possesses the best photoelectric properties such as the minimum driving voltage and turn-on voltage, and the maximum electroluminescence brightness and efficiency.     

Improved photovoltaic characteristics of organic cells with heterointerface layer as a hole-extraction layer inserted between ITO anode and donor layer

We have fabricated an improved organic photovoltaic (OPV) cell in which organic heterointerface layer is inserted between indium-tin-oxide (ITO) anode and copper-phthalocyanine (CuPc) donor layer in the conventional OPV cell of ITO/CuPc/fullerene (C₆₀)/bathophenanthroline (Bphen)/Al to enhance the power conversion efficiency (PCE) and fill factor (FF). The inserted ITO-buffer layer consists of electron-transporting layer (ETL) and hole-transporting layer (HTL). We have changed the ETL and HTL materials variously and also changed their layer thickness variously. It is confirmed that ETL materials with higher LUMO level than the work function of ITO give low PCE and FF. All the double layer buffers give higher PCE than a single layer buffer of TAPC. The highest PCE of 1.67% and FF of 0.57% are obtained from an ITO buffer consisted of 3 nm thick ETL of hexadecafkluoro-copper-phthalocyanine (F₁₆CuPc) and 3 nm thick HTL of 1,1-bis-(4-methyl-phenyl)-aminophenylcyclohexane (TAPC). This PCE is 1.64 times higher than PCE of the cell without ITO buffer and 2.98 times higher than PCE of the cell with single layer ITO buffer of TAPC. PCE is found to increase with increasing energy difference (ΔE) between the HOMO level of HTL and LUMO level of F₁₆CuPc in a range of ΔE < 0.6 eV. From the ΔE dependence of PCE, it is suggested that electrons moved from ITO to the LUMO level of the electron-transporting F₁₆CuPc are recombined, at the F₁₆CuPc/HTL-interface, with holes transported from CuPc to the HOMO level of HTL in the double layer ITO buffer ETL, leading to efficient extraction of holes photo-generated in CuPc donor layer.     

基于电荷传输层优化的量子点发光二极管

采用溶液法旋涂薄膜、真空蒸镀铝电极,制备了ITO/PEDOT∶PSS/空穴传输材料/量子点/纳米氧化锌(ZnO Nanoparticles)/Al结构的量子点发光二极管(QLED)器件。对比了不同纳米氧化锌分散剂对器件性能的影响。当用乙醇和乙醇胺分散氧化锌时,对量子点层破坏较小,器件的亮度最高达22 940cd/m2,电流效率达28.9cd/A。研究了在聚乙烯咔唑(PVK)中掺杂不同比例4,4′-环己基二[N,N-二(4-甲基苯基)苯胺](TAPC)器件的发光特性。在PVK中掺杂TAPC材料能够促进器件空穴传输以及电子空穴注入平衡,当PVK∶TAPC=3∶1时,器件的空穴传输层形貌较为平整,亮度较高;当PVK∶TAPC=1∶1时,器件的开启电压最低。通过对器件膜层表面形貌以及电学、光学性能的对比,分析了电荷传输层优化对器件特性改善的原因。     

量子点发光器件的制备与仿真分析

为研究量子点发光器件结构与性能的关系,制备了以CdSe/ZnS量子点作为发光层、poly-TPD作为空穴传输层,Alq3作为电子传输层的量子点发光二极管,对器件结构及性能参数进行了表征,结果显示器件具有开启电压低、色纯度高等特点.结合测试数据,对量子点发光二极管进行了器件结构建模,利用隧穿模型及空间电荷限制电流模型对实验结果进行了分析,研究了器件中载流子的注入与传输机理.器件测试与仿真结果表明:各功能层厚度会影响载流子在量子点层的注入平衡,同时器件中载流子的注入与传输存在一转变电压,当外加电压低于转变电压时,器件中载流子的注入主要符合隧穿模型;当外加电压高于转变电压时,器件中载流子的注入主要符合空间电荷限制电流模型.研究结果验证了器件结构建模的合理性,可以利用仿真的方法进行器件结构优化并确定相关参数,这对器件性能的提高具有指导意义.     

Enhanced device performance of quantum-dot light-emitting diodes via 2,2′-Bipyridyl ligand exchange

Quantum dots (QDs) are electroluminescent (EL) materials that have been developed as promising emitters in next-generation displays. The amount of charge carriers that travel to the light-emitting layer located at the interface between the hole- and electron-transport layers must be balanced in these displays to achieve maximum luminous efficiency. An existing amine ligand (oleylamine), which was coordinated on the surface of red-emitting InP/ZnSeS/ZnS QDs, was partially exchanged with two 2,2′-bipyridyl derivatives to enhance the EL properties; the QD light-emitting diode (QD-LED) performance was also investigated. Thermogravimetric and ¹H nuclear magnetic resonance analyses were used to examine the bipyridyl-ligand-partially-substituted QDs. Photoluminescence spectroscopy and transmission electron microscopy revealed that the emission wavelength (630 nm) and size (7.3 nm) of the QDs were not altered upon ligand exchange. Significant improvements were observed in the electronic properties of QD-LED devices fabricated using the bipyridyl-ligand-substituted QDs. The bipyridyl ligands lowered the charge-injection barrier and improved the charge balance in the QDs. High-performance QD-LED devices were consequently realized with an augmentation of two times in current density, and three times in brightness, external quantum efficiency, and current efficiency.     

All-solution-processed multilayer polymer/dendrimer light emitting diodes

A fully solution-processed deep-blue emitting organic light emitting diode (OLED) based on a highly efficient fluorescent dendritic material with a pyrene core, a phenylene shell and triphenylamine surface groups coupled with polymeric hole (HTL) and electron (ETL) transport layers is demonstrated. Each layer formed smooth and pinhole-free films as demonstrated by Atomic Force Microscopy (AFM) as well as by X-ray Photoelectron Spectroscopy (XPS). Furthermore, detailed Ultraviolet Photoelectron Spectroscopy (UPS) surveys revealed a beneficial energy level alignment and hence improved charge carrier confinement. The resulting triple-layer device saw a 7.7-fold increase in current efficiency compared to a single-layer device while maintaining a deep-blue emission color characterized by the CIE1931 coordinates of x = 0.153 and y = 0.155.     

载流子平衡方法提高量子点发光二极管效率的研究

尝试采用三种方式来平衡载流子的浓度,以提高量子点发光二极管(QLED)的外量子效率等性能:在正装结构(ITO/HIL/HTL/QD/ETL/EIL/金属阴极)的QLED的发光层和电子传输层中间插入超薄聚甲基丙烯酸甲脂(PMMA)电子阻挡层;在空穴注入和传输层方面,通过使用更加优化的HIL等来提高空穴注入和传输几率;在QD发光层方面,用短链配体来置换量子点的长链配体以增加载流子向量子点发光层中的传输效率等。在进行量子点配体交换的同时带来了量子点在正交溶剂中的可溶性优势,有利于QLED器件的全溶液法制备。     

Revisiting Hole Injection in Quantum Dot Light-Emitting Diodes

Injecting holes from the hole transport layer (HTL) into the quantum dot (QD) emitting layer in quantum dot light-emitting diodes (QLEDs) is considered challenging due to the presence of a relatively high hole injection barrier at the HTL/QD interface. However, QLEDs with exceptional brightness and efficiency are achieved, prompting a reevaluation of the traditional hole injection mechanisms. This study examines the hole injection mechanism in QLEDs using a combination of experiments and simulations. The results demonstrate that the applied bias significantly reduces the barrier height between the highest occupied molecular orbital level of the HTL and the valence band (VB) of the QDs, facilitating hole injection. The bending of the lowest unoccupied molecular orbital energy level of the HTL at the HTL/QD interface confines electrons within the QD, effectively minimizing leakage current. Additionally, the triangle-shaped potential barrier arising from the bending of the VB energy level of the QDs creates favorable conditions for hole–tunneling injection. Moreover, both simulations and experiments consistently demonstrate that the predominant pathway for hole injection from the HTL to the QDs in the QLED device involved thermally assisted tunneling. This study is important to understand the hole injection mechanism in QLEDs.     

量子点发光二极管中载流子注入机理的研究

针对量子点(QDs)发光二极管(QLED)中载流子注 入不平衡的问题,对载流子的注入机理进行了研 究。在隧穿注入和空间电荷限制电流(SCLC)模型的基础上,仿真分析了空穴和电子在QDs 层的注入情况,制备 了QLED的样品。CdSe/CdS作为QDs层,PEDOT:PSS作为空穴注入层(HIL),TPD作为 空穴传输层(HTL),Alq₃作为电子传输层(ETL)。优选的QDs层厚为25nm时,确定了TPD和Alq₃的理论最优厚分别为48nm。研究发现, 当驱动电压低于6.5V时,隧穿注入电流在载流子的传输过 程中起主导作用;高于6.5V时,SCLC在载流子的传输过程中起主导 作用。实验结果表明,当 Alq₃厚为20nm时,器件发出QDs的红光,随着Alq₃厚度的增加, 器件开始出现绿光,实验结果与仿 真结果基本吻合。研究结果对QLED的制备具有理论借鉴意义。     

Improved performance of CdSe/ZnS quantum dot light-emitting diodes through doping with small molecule CBP

The poor film formation of CdSe/ZnS quantum dots (QDs) during spin-coating makes a substantial impact on the device performance of quantum dot light-emitting diodes (QLEDs). This work proposes a method to improve the morphology of the quantum dot light-emitting layer (EML) by adding small organic molecular 4,4''-Bis(9H-carbazol-9-yl) biphenyl (CBP) into the layer. Its surface roughness reduces from 6.21 nm to 2.71 nm, which guarantees a good contact between hole transport layer (HTL) and EML. Consequently, the CdSe/ZnS QDs:CBP based QLED achieves maximum external quantum efficiency (EQE) of 5.86%, and maximum brightness of 10 363 cd/m2. It is demonstrated that the additive of small organic molecules could be an effective way to improve the brightness and the efficiency of QLEDs.     

Highly efficient green phosphorescent organic light emitting diodes with simple structure

A series of simple structures is investigated for realization of the highly efficient green phosphorescent organic light emitting diodes with relatively low voltage operation. All the devices were fabricated with mixed host system by using 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC) and 1,3,5-tri(p-pyrid-3-yl-phenyl)benzene (TpPyPB) which were known to be hole and electron type host materials due to their great hole and electron mobilities [μ_h(TAPC): 1 × 10^?2 cm²/V s and μ_e(TpPyPB): 7.9 × 10^?3 cm²/V s] [1]. The optimized device with thin TAPC (5–10 nm) as an anode buffer layer showed relatively high current and power efficiency with low roll-off characteristic up to 10,000 cd/m². The performances of the devices; with buffer layer were compared to those of simple devices with single layer and three layers. Very interestingly, the double layer device with TAPC buffer layer showed better current and power efficiency behavior compared to that of three layer device with both hole and electron buffer layers (TAPC, TpPyPB, respectively).     

具有新型电子传输层的有机薄膜电致发光器件

将8-hydroxy-quinolinato lithium(Liq)掺入4'7-diphyenyl-1,10-phenanthroline(BPhen)作为n型电子传输层(ETL),将tetrafluro-tetracyano-quinodimethane(F4-TCNQ)掺入4,4',4"-tris(3-methylphenylphenylamono)triphenylamine(m-MTDATA)作为p型空穴传输层(HTL),制作了p-i-n结构有机电致发光器件.为了检验传输层传导率的改善情况,制备了一系列单一空穴器件和单一电子器件.在引入BPhen:33wt% Liq作为ETL后,x% F4-TCNQ:m-MTDATA作为HTL后,器件的电流和功率效率明显改善.与控制器件(未掺杂)相比,性能最佳的掺杂器件的电流及功率效率分别提高了51%和89%,电压下降了29%.这是由于传输层传导能力的提高使得载流子在发光区域达到有效平衡.     

具有新型电子传输层的有机薄膜电致发光器件

将8-hydroxy-quinolinato lithium(Liq)掺入4'7-diphyenyl-1,10-phenanthroline(BPhen)作为n型电子传输层(ETL),将tetrafluro-tetracyano-quinodimethane(F4-TCNQ)掺入4,4',4"-tris(3-methylphenylphenylamono)triphenylamine(m-MTDATA)作为p型空穴传输层(HTL),制作了p-i-n结构有机电致发光器件.为了检验传输层传导率的改善情况,制备了一系列单一空穴器件和单一电子器件.在引入BPhen:33wt% Liq作为ETL后,x% F4-TCNQ:m-MTDATA作为HTL后,器件的电流和功率效率明显改善.与控制器件(未掺杂)相比,性能最佳的掺杂器件的电流及功率效率分别提高了51%和89%,电压下降了29%.这是由于传输层传导能力的提高使得载流子在发光区域达到有效平衡.     

Insights into charge balance and its limitations in simplified phosphorescent organic light-emitting devices

Simplified phosphorescent organic light-emitting device (PHOLED), which utilizes only two organic layers, showed record-high efficiency when first introduced. It is quite surprising that this device can have such high efficiency without the use of complex carrier and exciton confinement layers that are common in the state-of-the-art PHOLEDs nowadays. Therefore, it is important to understand how good charge balance is in simplified PHOLED and why. In this work, we study the effects of altering charge balance in simplified PHOLED through means of changing layer thickness in the hole transport layer (HTL) and electron transport layer (ETL) as well as intentionally doping hole and electron traps in the HTL and ETL, respectively, on device efficiency. The results show that when using high carrier mobility charge transport materials, changing layer thickness does not impact charge balance appreciably. On the other hand, introducing charge traps in a thin layer within the HTL or ETL can, in comparison, influence charge balance more significantly, and proves to be a more effective approach for studying the factors limiting charge balance in these devices. The results reveal that simplified PHOLEDs are generally hole-rich, and that the leakage of electrons to the counter electrode is also a major mechanism behind the poor charge balance and efficiency loss in these devices. In order to optimize charge balance in simplified PHOLED, it is important to reduce hole transport in the device so that e-h ratio can be brought closer to unity, as well as eliminate electron leakage. Finally, we show that by simply using an electron blocking HTL, the efficiency of the device can be enhanced by as much as 25%, representing the highest reported for simplified PHOLEDs.