Highly efficient and low turn-on voltage quantum-dot light-emitting diodes using a ZnMgO/ZnO double electron transport layer

A ZnMgO and ZnO double-layered structure was prepared to create a stepwise interfacial electronic structure to improve the electron-injection and electron-transport behaviors in quantum-dot light-emitting diodes (QLEDs). The current density of the electron-only device (EOD) with ZnMgO/ZnO was higher than that of the EOD with only ZnMgO. The detailed QLED interfacial electronic structure was measured using X-ray and ultraviolet photoelectron spectroscopy. A stepwise interfacial electronic structure for electron injection and electron transport was observed connecting the aluminum cathode to the ZnMgO conduction band minimum (CBM) via the ZnO CBM. The QLEDs with the ZnMgO/ZnO double electron transport layer showed an improved performance, with a maximum luminance and current efficiency of 90,892 cd m⁻² and 19.2 cd A⁻¹, respectively. Moreover, the turn-on voltage of the device was significantly reduced to 2.6 V due to the stepwise interfacial electronic structure between the aluminum cathode and ZnMgO CBM. This research provides a useful method for developing highly efficient and low turn-on voltage QLEDs using a ZnMgO/ZnO double ETL for next-generation display.     

Low-temperature and solution-processable inorganic hole injection layer for flexible quantum-dot light-emitting diodes

A low-temperature solution-processable inorganic vanadium oxide (V₂O₅) hole injection layer (HIL) was synthesized for flexible quantum-dot light-emitting diodes (QLEDs). Efficient hole injection characteristics were observed in the hole-only devices; furthermore, the process temperature of V₂O₅ was as low as 30 °C. We investigated the source of the efficient hole injection behavior using ultraviolet and x-ray photoelectron spectroscopy. The density of gap states was found to increase in accordance with process temperature reduction. Therefore, QLEDs with low-temperature solution-processable V₂O₅ HILs were fabricated on a glass substrate, which showed excellent characteristics. The maximum luminance and luminous efficiency of the device were 56,717 Cd/m² and 4.03 Cd/A, respectively. Due to the low-temperature process of the V₂O₅ HIL, it was also possible to fabricate QLEDs on a flexible plastic substrate without mechanical or thermal deformation of the substrate. Our results suggest that the low-temperature V₂O₅ inorganic HIL is a feasible alternative to organic HILs for flexible QLEDs.     

Improving hole injection ability using a newly proposed WO3/NiOx bilayer in solution processed quantum dot light-emitting diodes

We propose a novel device structure with a WO₃/NiO_x bilayer to improve the hole injection ability in QLEDs fabricated mainly by a solution-based process. First, we employed a spin-coated NiO_x thin film as a hole injection layer (HIL) to replace Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) PEDOT:PSS which corrodes indium tin oxide (ITO) used as an anode in QLEDs. We showed a simply optimized annealing process, instead of a rather complicated process like doping, can improve the electrical conductivity of the NiO_x thin film. The reason for the dependency of conductivity on the post-metallization annealing is because of the change of the total amount of Ni vacancy in the NiO_x thin film as a function of annealing temperature: The electrical conductivity of the NiO_x thin film annealed at 275 °C was the best in this work. Second, we inserted the WO₃ thin film in between ITO electrode and NiO_x HIL to form an ITO/WO₃/NiO_x structure which reduces the hole injection barrier to 0.35 eV, resulting in the excellent characteristic in view of charge balance. Finally, we measured the properties of QLEDs with the WO₃/NiO_x bilayer to check the effects of the proposed device structure and showed the substantial improvement of the electrical conductivity of NiO_x, the luminance, and the current efficiency of the QLEDs.     

Quantum dot light emitting diodes using size-controlled ZnO NPs

The particle size and trap energy level of ZnO were adjusted by varying the concentration of precursors using a sol–gel process, and the energy transport properties of the electron transport layer in quantum dot light-emitting diodes (QD-LEDs) were analyzed. Thus far, no study has considered the efficient electron transport properties of quantum dot light-emitting devices with respect to trap energy levels owing to the oxygen vacancies of ZnO. The particle size and trap energy levels of ZnO were analyzed based on optical properties such as photoluminescence and absorbance. The optimized device showed excellent performance, with a maximum luminance of 50,120 cd/m², a high efficiency of 5.85 cd/A, and a threshold voltage of 2.5 V. The Y-ZnO (yellow photoluminescence ZnO)-based QD-LEDs not only enhanced the injection efficiency of electrons into the emitting layer but also confined the holes in the emitting layer due to the shallow trap level of Y-ZnO, in contrast to the deep trap levels of G-ZnO (green photoluminescence ZnO) and B-ZnO (blue photoluminescence ZnO). Here, we present the first attempt to analyze the electron transport behavior of the electron transport layer of the resulting device.     

氧化锌作为电子传输层的量子点发光二极管

为降低量子点发光二极管(QLED)的开启电压,提高器件性能,利用电子传输性能良好的氧化锌(ZnO)作为电子传输层,制备了结构为ITO/PEDOT∶PSS/poly-TPD/QDs/ZnO/Al的QLED样品。在该器件结构基础上,采用隧穿注入和空间电荷限制电流模型仿真分析了载流子在量子点(QDs)层的电流密度。研究发现,当ZnO厚度为50 nm时,poly-TPD的理论最优厚度为40 nm,载流子在QDs层的注入达到相对平衡。通过测试器件的电流密度-电压-亮度-发光效率特性,研究了空穴传输层厚度对QLED器件性能的影响。实验结果表明,当空穴传输层厚度为40 nm时,器件的开启电压为1.7 V,最大发光效率为1.18 cd/A。在9 V电压下,器件最大亮度达到5 225 cd/m~2,远优于其他厚度的器件。实验结果与仿真结果基本吻合。     

Improved blue quantum dot light-emitting diodes via chlorine passivated ZnO nanoparticle layer

In blue quantum dot light emitting diodes (QLEDs), electron injection is insufficient, which would degrade device efficiency and stability. Herein, we employ chlorine passivated ZnO nanoparticles as electron transport layer to facilitate electron injection into QDs effectively. Moreover, it suppresses exciton quenching at the QD/ZnO interface by blocking charge transfer channel. As a result, the maximum external quantum efficiency of blue QLED was increased from 2.55% to 4.60%, and the operation lifetime of blue QLED was nearly 4 times longer than that of the control device. Our work indicates that election injection plays an important role in blue QLED efficiency and stability.     

Improved electron emission characteristics of ZnO nano-gap with Pd films

The properties of the surface-conduction electron-emitter display (SED) are mainly decided by the surface-conduction electron emitters (SCEs). Pd is mostly used to fabricate the surface-conduction electron emitters, which are normally obtained by generating a nano-scale gap from PdO conductive film. ZnO is a potential material for electron emission and the research work has proved that ZnO film can act as the electron-emitter material. In this study, we propose to use the ZnO-Pd two-layer film as the conductive film. Both the multi-layer device electrode film and conductive film were deposited by a magnetron sputter, and SCEs are formed by the electro-forming process as used in SED. The results revealed that the Pd film on ZnO film surface increases the electron emission efficiency from 0.36‰ to 3.85‰.     

Non-vacuum, single-step conductive transparent ZnO patterning by ultra-short pulsed laser annealing of solution-deposited nanoparticles

A solution-processable, high-concentration transparent ZnO nanoparticle (NP) solution was successfully synthesized in a new process. A highly transparent ZnO thin film was fabricated by spin coating without vacuum deposition. Subsequent ultra-short-pulsed laser annealing at room temperature was performed to change the film properties without using a blanket high temperature heating process. Although the as-deposited NP thin film was not electrically conductive, laser annealing imparted a large conductivity increase and furthermore enabled selective annealing to write conductive patterns directly on the NP thin film without a photolithographic process. Conductivity enhancement could be obtained by altering the laser annealing parameters. Parametric studies including the sheet resistance and optical transmittance of the annealed ZnO NP thin film were conducted for various laser powers, scanning speeds and background gas conditions. The lowest resistivity from laser-annealed ZnO thin film was about 4.75×10⁻² Ω cm, exhibiting a factor of 10⁵ higher conductivity than the previously reported furnace-annealed ZnO NP film and is even comparable to that of vacuum-deposited, impurity-doped ZnO films within a factor of 10. The process developed in this work was applied to the fabrication of a thin film transistor (TFT) device that showed enhanced performance compared with furnace-annealed devices. A ZnO TFT performance test revealed that by just changing the laser parameters, the solution-deposited ZnO thin film can also perform as a semiconductor, demonstrating that laser annealing offers tunability of ZnO thin film properties for both transparent conductors and semiconductors.     

基于石墨烯/PEDOT：PSS叠层薄膜的柔性OLED器件

石墨烯具有独特的电学性能、优异的机械延展性和良好的化学稳定性,是制备高性能导电薄膜的理想材料,但是当前石墨烯的高电阻率限制了它的实际应用。本文采用喷涂方法制备了石墨烯/聚（3,4-亚乙二氧基噻吩）-聚（苯乙烯磺酸）（PEDOT：PSS）复合导电薄膜,对复合薄膜的表面形貌与光电性能进行了研究。PEDOT：PSS的引入不仅降低了石墨烯薄膜的表面电阻,同时还平滑了薄膜表面。在此基础上,成功制备了柔性黄光有机电致发光器件,器件在12 V时达到效率最大值0.9 cd/A。器件在曲率半径为10 mm时弯曲了100次后,发光亮度并无明显变化。该复合薄膜可实际应用于柔性有机电致发光显示器件。     

银纳米颗粒对聚合物太阳能电池性能的提高

采用水溶性银纳米颗粒附着在反型太阳能电池的电子传输层上,用以提高有机太阳能电池的短路电流。所制备的器件结构为ITO/ZnO/Ag NPs/P3HT(Poly 3-hexylthiophene):PC_[60]BM/MoO₃/Ag。其金属银纳米颗粒的表面等离激元在410 nm处出现了共振吸收峰,半峰全宽约为60 nm。器件的光电流在可见光范围内均有所增加,短路电流相对于标准器件提高了20.2%,光电转化效率相对提高了17.2%。     

分步磁控溅射ZnO和/或功能化碳纳米粒子修饰ZnO电子传输层增强聚合物太阳能电池效率

氧化锌具有良好电子传输性和高透光性,ZnO作为电子传输层已被广泛应用于聚合物太阳能电池。但采用溶胶凝胶法和真空镀膜制备ZnO电子传输层,因ZnO界面具有大量缺陷,极大增加载流子复合。抑制ZnO界面复合电流和改善ZnO界面接触性能,是提高ZnO基电子传输层聚合物太阳能电池性能关键所在。基于P3HT:PCBM反转型聚合物太阳能电池,采用磁控溅射ZnO层,研究了离子液功能化碳纳米粒子(ILCNs)修饰层或Ar/O₂混合气体溅射沉积ZnO修饰层,以及Ar/O₂溅射ZnO界面层与ILCNs联合修饰ZnO界面的聚合物太阳能电池性能。纯Ar和Ar/O₂混合气体下一步溅射沉积ZnO电子传输层,其电池效率分别为2.2%和2.8%。经ILCNs修饰或Ar/O₂溅射ZnO修饰层,电池效率分别达到3.4%和3.1%,并且分步溅射ZnO层并联合ILCNs修饰ZnO界面,聚合物太阳能电池效率可提高到3.8%。ZnO修饰型聚合物太阳能电池克服了电化学阻抗负阻效应,降低了反向暗电流并显示出更好的整流特性。研究表明,采用ILCNs修饰ZnO层和分步溅射ZnO层能有效抑制ZnO界面缺陷和改善界面接触性能,而采用分步溅射ZnO层与ILCNs联合修饰ZnO界面,这种联合修饰ZnO界面方案,更能增强ZnO层电子传输和提取能力,是提高聚合物太阳能电池效率更为有效方案。     

全湿法制备聚合物白光器件

使用全溶液法制备聚合物白光器件,通过引入修饰层并改变各层薄膜厚度来优化器件性能。针对ITO 阴极功函数较高的问题,引入功函数较低的蓝光聚芴衍生物：聚[9,9-二辛基芴-9,9-双（N,N-二甲基胺丙基）芴]（PFN）,有效地降低了阴极的复合功函数。同时PFN也是电子注入材料和发光材料。为降低器件的启动电压,引入Cs₂CO₃作为修饰层,同时也提高了电子传输能力。使用MEH-PPV作为橙红光材料。使用二次溶剂掺杂获得的高导PEDOT：PSS聚合物并通过滴膜的方法制备阳极取代了传统的金属电极真空镀膜法,从而使器件制备简单、快捷。最终得到了湿法制作的聚合物白光器件的光谱范围为400~800 nm,涵盖了整个可见光区域。器件的启亮电压为4 V,亮度为1 500 cd/m²,电流效率为0.55 cd/A。     

PTCDI-C8作为阴极修饰层提高钙钛矿太阳能电池的性能

采用N,N'-二正辛烷基-3,4,9,10-苝四甲酰二亚胺（PTCDI-C₈）对钙钛矿电池电子传输层（PCBM）进行界面修饰以减少PCBM与Al电极之间的漏电流,提高阴极的电子收集效率。通过调节PTCDI-C₈薄膜的厚度优化界面接触和电子传输性能。实验结果表明：当PTCDI-C₈薄膜的厚度为20 nm时得到的器件性能最优。光电转换效率（PCE）由5.26%提高到了8.65%,开路电压（V_oc）为0.92 V,短路电流（J_sc）为15.68 mA/cm²,填充因子（FF）为60%。PTCDI-C₈能够有效阻挡空穴向阴极传输,同时PTCDI-C₈具有较高的电子迁移率以及较高的稳定性,在增加电子传输的同时,可减少环境对PCBM的侵蚀,提高了器件的稳定性。     

混合界面对溶液制备的磷光OLED器件性能的影响

利用混蒸的方法、将空穴阻挡材料2,9-Dimethyl-4,7-diphenyl-1,10-phenanhroline及电子传输材料Tris(8-hydroxy-quinolinato)aluminium混合,在电子传输层及空穴阻挡层之间制备了薄层的混合界面.在相同驱动电压下,采用混合界面的器件比常规器件的电流密度和亮...     

Effect of ethanolamine passivation of ZnO nanoparticles in quantum dot light emitting diode structure

The aging of ZnO nanoparticles in quantum dot light-emitting diode (QD-LED) structures was studied. Coarsening of as-synthesized ZnO nanoparticles is observed in both solution and thin film structures, which potentially deteriorates the performance of QD-LED devices over time. First, the temperature effect on ZnO coarsening was investigated, and it was revealed that aging of ZnO nanoparticles is faster at higher temperature due to a diffusion-controlled mechanism of nanoparticle coarsening. To observe aggregation of ZnO in the film state, the electron transporting part (ZnO/Al) of the QD-LED structure was prepared. The current density of a ZnO film and an electron-only device (QD/ZnO between two electrodes) was also measured. Resistance of the film increased as a function of aging time, which corresponded with observations of the ZnO film by optical microscopy. Aggregation of ZnO nanoparticles was directly measured by the root-mean-square value using atomic force microscopy. Ethanolamine (EA) stabilizer was added to the ZnO solution to disperse the ZnO nanoparticles without aggregation. The effect of EA on the surface passivation of the ZnO found to suppress pinhole formation, as revealed by scanning electron microscopy observations. Finally, the device lifetime was measured for QD-LEDs with EA-stabilized ZnO to understand the effect of ZnO aging on long-term QD-LED device operation.     

Interpretation of transport measurements in ZnO-thin films

In order to interpret results of temperature dependent Hall measurements in heteroepitaxial ZnO-thin films, we adopted a multilayer conductivity model considering carrier-transport through the interfacial layer with degenerate electron gas as well as the upper part of ZnO layers with lower conductivity. This model was applied to the temperature dependence of the carrier concentration and mobility measured by Hall effect in a ZnO-layer grown on c-sapphire with conventional high-temperature MgO and low-temperature ZnO buffer. We also compared our results with the results of maximum entropy mobility-spectrum analysis (MEMSA). The formation of the highly conductive interfacial layer was explained by analysis of transmission electron microscopy (TEM) images taken from similar layers.     

Ag-ZnO混合薄膜在聚合物太阳能电池中的应用

采用旋涂法研制了Ag浆SC100-ZnO混合薄膜,系统研究了不同混合比例SC100∶ZnO薄膜作为电子传输层或光散射层对聚合物太阳能电池器件性能的影响,并讨论了其中存在的物理机制。研究发现,采用少量SC100(1%和2.5%)混合的薄膜作为光散射层,可以提高器件的性能参数(短路电流密度和填充因子),器件的光电转换效率分别提高了4.4%和5%。     

Resistive switching of in situ and ex situ oxygen plasma treated ZnO thin film deposited by atomic layer deposition

In situ and ex situ oxygen plasma treatment (OPT) were applied to treat ZnO thin films deposited by thermal atomic layer deposition (T-ALD), and the resistive switching (RS) behaviors of the films were investigated. For the in situ OPT, the treatment was applied after each T-ALD cycle. For the ex situ OPT, the treatment was applied on the as-grown film. The T-ALD-grown ZnO films were defect-rich and conductive with no RS behavior. After the OPT process, the resistivity of the films increased drastically, which is believed to be mainly due to the removal of hydrogen impurities, and the films showed bipolar RS characteristics. The dominant conduction mechanisms are the trap-controlled space charge limited current and ohmic behavior at different field regions. The RS behavior was induced upon the formation/disruption of the conducting filaments. Owing to the homogeneous chemical composition and fewer defects, the resistance ratio of the in situ OPT ZnO film is higher than that of the ex situ OPT film, implying that the in situ OPT method is an efficient way to fabricate resistive random access memory devices using the ALD-grown ZnO films.     

高度取向的半导体聚合物薄膜的溶液浸涂法生长及其电荷传输特性研究

有效地控制有机半导体分子取向和堆积特性对实现高性能电子器件具有非常重要的意义,而发展简便高效的溶液相成膜技术是实现这一目的的重要途径.本文采用改进的溶液浸涂法,成功地成长出大面积宏观取向的半导体聚合物P(NDI2OD-T2)和PTHBDTP薄膜.偏光显微镜和极化的紫外-可见光吸收谱测量显示,薄膜中聚合物分子主链骨架沿成膜时液面下移方向择优取向.原子力显微镜观察到聚合物薄膜由纳米尺度的取向有序晶畴构成,畴的取向与分子链的取向一致.采用衬底-溶液界面处表面张力和溶剂蒸发诱导的分子自组织过程来解释浸涂法生长聚合物取向薄膜的微观机理.使用取向的P(NDI2OD-T2)薄膜制备场效应晶体管,显著地提高了电子迁移率(可达4倍),并实现高达19的迁移率各向异性度.这可归因于共轭的聚合物主链骨架择优取向引起电荷传导通路的变化.     

量子点发光二极管稳定性提高策略

量子点发光二极管(QLEDs)由于具有独特的光电特性,可应用于照明和显示行业,其外量子效率(EQEs)正迅速接近商业化要求。然而,器件的稳定性和工作寿命仍然是QLEDs商业化应用面临的关键问题。本文将影响QLEDs寿命的主要因素分为功能层材料的稳定性和电荷注入不平衡两大方面,从提高量子点、电荷传输层(CTLs)的稳定性以及促进电荷平衡等方面讨论了近年来提高QLEDs稳定性的各种策略。随着人们对QLEDs降解机制认识的加深,更稳定的量子点和QLEDs器件得以开发,但是将QLEDs器件商业化仍存在很大的挑战,比如Cd的高毒性以及蓝光QLEDs的寿命和效率远低于绿光和红光相对应的水平,此外,QLEDs在高亮度(1000 cd m^-2)下的稳定性较差,这些因素均限制了QLEDs的发展。因此,应进一步加大QLEDs在光电器件领域的研发力度,克服这些技术劣势,实现QLEDs未来的商业化。