Engineering Efficiency Roll‐Off in Organic Light‐Emitting Devices

Previous studies have identified triplet‐triplet annihilation and triplet‐polaron quenching as the exciton density‐dependent mechanisms which give rise to the efficiency roll‐off observed in phosphorescent organic light‐emitting devices (OLEDs). In this work, these quenching processes are independently probed, and the impact of the exciton recombination zone width on the severity of quenching in various OLED architectures is examined directly. It is found that in devices employing a graded‐emissive layer (G‐EML) architecture the efficiency roll‐off is due to both triplet‐triplet annihilation and triplet‐polaron quenching, while in devices which employ a conventional double‐emissive layer (D‐EML) architecture, the roll‐off is dominated by triplet‐triplet annihilation. Overall, the efficiency roll‐off in G‐EML devices is found to be much less severe than in the D‐EML device. This result is well accounted for by the larger exciton recombination zone measured in G‐EML devices, which serves to reduce exciton density‐driven loss pathways at high excitation levels. Indeed, a predictive model of the device efficiency based on the quantitatively measured quenching parameters shows the role a large exciton recombination zone plays in mitigating the roll‐off.     

High‐Transconductance Organic Thin‐Film Electrochemical Transistors for Driving Low‐Voltage Red‐Green‐Blue Active Matrix Organic Light‐Emitting Devices

Switching and control of efficient red, green, and blue active matrix organic light‐emitting devices (AMOLEDs) by printed organic thin‐film electrochemical transistors (OETs) are demonstrated. These all‐organic pixels are characterized by high luminance at low operating voltages and by extremely small transistor dimensions with respect to the OLED active area. A maximum brightness of ≈900 cd m^?2 is achieved at diode supply voltages near 4 V and pixel selector (gate) voltages below 1 V. The ratio of OLED to OET area is greater than 100:1 and the pixels may be switched at rates up to 100 Hz. Essential to this demonstration are the use of a high capacitance electrolyte as the gate dielectric layer in the OETs, which affords extremely large transistor transconductances, and novel graded emissive layer (G‐EML) OLED architectures that exhibit low turn‐on voltages and high luminescence efficiency. Collectively, these results suggest that printed OETs, combined with efficient, low voltage OLEDs, could be employed in the fabrication of flexible full‐color AMOLED displays.     

Designing Host Materials for the Emissive Layer of Single-Layer Phosphorescent Organic Light-Emitting Diodes: Toward Simplified Organic Devices

Thanks to the tremendous effort over the last 20 years, phosphorescent organic light-emitting diodes (PhOLEDs) represent a prevalent technology. In this technology, all the high-efficiency PhOLEDs are multi-layer devices constituting, in addition to the emissive layer (EML), of a stack of functional organic layers. These layers play a crucial role in the device performance as they improve the injection, transport, and recombination of charges within the EML. Single-layer PhOLEDs (SL-PhOLEDs) represent ideal OLEDs, consisting only of the electrodes and the EML. However, reaching high-performance SL-PhOLED is far from easy, as removing the functional layers of an OLED stack dramatically decreases the performance. To achieve high SL-PhOLED efficiency, the efficient injection, transport, and recombination of charges should be insured by the EML, and particularly, by the host material. In the present exhaustive review, the different molecular design strategies are analyzed, which have been used to construct high-efficiency hosts for SL-PhOLED. The impact of the electronic properties (triplet energy, HOMO/LUMO energy, mobility etc.) on the device characteristics (threshold voltage, electroluminescent spectrum, external quantum efficiency, etc.) are discussed. This allows to draw a structure/properties/device performance relationship map of interest for the future design of functional materials for SL-PhOLEDs.     

Blue Single‐Layer Organic Light‐Emitting Diodes Using Fluorescent Materials: A Molecular Design View Point

Since the beginning of organic light‐emitting diodes (OLEDs), blue emission has attracted the most attention and many research groups worldwide have worked on the design of materials for stable and highly efficient blue OLEDs. However, almost all the high‐efficiency blue OLEDs using fluorescent materials are multilayer devices, which are constituted of a stack of organic layers to improve the injection, transport, and recombination of charges within the emissive layer. Although the technology has been mastered, it suffers from real complexity and high cost and is time‐consuming. Simplifying the multilayer structure with a single‐layer one, the simplest devices made only of electrodes and the emissive layer have appeared as an appealing strategy for this technology. However, removing the functional organic layers of an OLED stack leads to a dramatic decrease of the performance and achieving high‐efficiency blue single‐layer OLEDs requires intense research especially in terms of materials design. Herein, an exhaustive review of blue emitting fluorophores that have been incorporated in single‐layer OLEDs is reported, and the links between their electronic properties and the device performance are discussed. Thus, a structure/properties/device performance relationship map is drawn, which is of interest for the future design of organic materials.     

加入激子阻挡层增强白色有机发光器件效率

通过在发光层（EBL）与电子注入层之间增加激子阻挡层（EBL）制备了新型白色有机发光器件（WOLED）。有EBL的新型器件效率和亮度均比传统结构器件高50％,在电流密度为4mA／cm^2时效率达到3．42cd／A,最大亮度为11000cd／m^2（16V）,色坐标为x=0．34、y=0．36;而具有相同EBL厚度的传统结构器件,在电流密度为4mA／cm^2时效率为2．15cd／A,最大亮度为6259cd／m^2（16V）。效率的提高是由于EBL的限制作用而提高了激子浓度。测量了器件的效率与电流密度关系,随电流密度增加电流效率的衰减缓慢,说明短寿命红色搀杂剂的激子-激子湮灭很弱。     

Exciton–Polaron‐Induced Aggregation of Wide‐Bandgap Materials and its Implication on the Electroluminescence Stability of Phosphorescent Organic Light‐Emitting Devices

The degradation mechanisms of phosphorescent organic light‐emitting devices (PhOLEDs) are studied. The results show that PhOLED degradation is closely linked to interactions between excitons and positive polarons in the host material of the emitter layer (EML), which lead to its aggregation near the EML/electron transport layer (ETL) interface. This exciton–polaron‐induced aggregation (EPIA) is associated with the emergence of new emission bands at longer wavelengths in the electroluminescence spectra of these materials, which can be detected after prolonged device operation. Such EPIA processes are found to occur in a variety of wide‐bandgap materials commonly used as hosts in PhOLEDs and are correlated with device degradation. Quite notably, the extent of EPIA appears to correlate with the material's bandgap rather than with the glass‐transition temperature. The findings uncover a new degradation mechanism, caused by polaron‐exciton interactions, that appears to be behind the lower stability of OLEDs utilizing wide‐bandgap materials in general. The same degradation mechanism can be expected to be present in other organic optoelectronic devices.     

Improved efficiency in fluorescent blue organic light emitting diode with a carrier confining structure

A blue organic light emitting device (OLED) with improved efficiency and good color purity is reported. The highest occupied molecular orbital (HOMO) level of the hole transport layer (HTL) and that of the emissive layer (EML) differs by 0.3 eV. This energy level mismatch confines the carriers at the HTL/EML interface. Conventional devices have only one HTL/EML interface, with a current efficiency of 2.9 cd/A. Without adding a separate hole blocking layer, incorporating multi-layers of the same HTL and EML increases this efficiency to 5.8 cd/A, with only a small increase in operating voltage yielding increased power efficiency also. But, there are an optimum number of layers, beyond which efficiency loss results. Also, including the multilayer structure simultaneously improves the blue color co-ordinates. To gain insight into the role of multilayer structures in modifying charge transport and recombination zone a simulator was developed. The simulated results could qualitatively explain the experimental observations.     

有机电致发光器件中复合发光区域的移动

采用在OLED有机层中夹入与主发光材料不同的发光材料薄层标记发光区域，介绍了复合发光区域位置随电压变化而移动的现象。在以Alq为发光材料的单层器件中夹入0．5nm厚的红光材料DCJTB层，或在两个位置分别夹入0．5nm厚的橙光材料QA层和红光材料DCJTB层，研究分析了电压升高时发光颜色的变化。结果表明，复合发光区域位置随电压升高由阳极一侧有机层向阴极方向移动；在有空穴阻挡层BCP层的器件中。在电子传输层与BCP层之间夹入10nm厚的DCJTB掺杂发光层，研究了不同电压时器件的发光颜色，发光区域位置在较低的电压范围内被BCP层限定，但发光区域在驱动电压很高时可越过BCP层进入电子传输层。     

Correlation between interlayer thickness and device performance in blue phosphorescent organic light emitting diodes with a quantum well structure

We systematically examined the effects of interlayer (ITL) thickness variation in an emission layer (EML) on electrical and optical characteristics of blue phosphorescent organic light-emitting diodes. The EML consisted of a quantum well structure using a hole transport material 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC) as an ITL. This ITL facilitated the confinement of charge carriers in the recombination zone (RZ), adjusted the charge carrier balance in the EML, and prevented the triplet exciton loss to adjacent transport layers. The thickness variation in the ITL greatly influenced the size and location of the RZ and the exciton density (ED), which is related to charge balance and exciton diffusion in the EML. A micro-cavity effect around 500 nm and the corresponding redshift/blueshift in the electroluminescent spectrum arose from different ITL thicknesses. Remarkably, the device having a 5-nm-thick TAPC ITL showed better current and power efficiencies than those of any other devices because of the rearrangement of the locations of excitons and ED through control of the hole/electron charge density.     

Light Out‐Coupling Efficiencies of Organic Light‐Emitting Diode Structures and the Effect of Photoluminescence Quantum Yield

Results obtained from modeling the light out‐coupling efficiency of an organic light‐emitting diode (OLED) structure containing the recently developed first‐generation fac‐tris(2‐phenylpyridine) iridium‐cored dendrimer (Ir‐G1) as the emissive organic layer are reported. Comparison of the results obtained for this material with those of corresponding structures based upon small‐molecule and polymer emissive materials is made. The calculations of out‐coupling efficiency performed here take account of many factors, including the photoluminescence quantum yield (PLQY) of the emissive materials. Further, how each material system might perform with regard to out‐coupling efficiency when a range of possible PLQYs are considered is shown. The calculations show that the very high efficiency of dendrimer‐based OLEDs can be attributed primarily to their high PLQY.     

Device Physics of White Polymer Light‐Emitting Diodes

The charge transport and recombination in white‐emitting polymer light‐ emitting diodes (PLEDs) are studied. The PLED investigated has a single emissive layer consisting of a copolymer in which a green and red dye are incorporated in a blue backbone. From single‐carrier devices the effect of the green‐ and red‐emitting dyes on the hole and electron transport is determined. The red dye acts as a deep electron trap thereby strongly reducing the electron transport. By incorporating trap‐assisted recombination for the red emission and bimolecular Langevin recombination for the blue emission, the current and light output of the white PLED can be consistently described. The color shift of single‐layer white‐emitting PLEDs can be explained by the different voltage dependencies of trap‐assisted and bimolecular recombination.     

Organic Light‐Emitting Transistors Containing a Laterally Arranged Heterojunction

An approach to produce organic light‐emitting transistors (OLETs) containing a laterally arranged heterojunction structure, which minimizes exciton quenching at the metal electrodes, is described. This device configuration provides an organic light‐emitting diode (OLED) structure where the anode (source) electrode, hole‐transport material (field‐effect material), light‐emitting material, and cathode (drain) electrode are laterally arranged, thus offering a chance to control the electroluminescent intensity by changing the gate bias. Pentacene and tris(8‐quinolinolato)aluminum (Alq₃) are employed as the field‐effect and light‐emitting materials, respectively. The laterally arranged heterojunction structures are achieved by successively inclined deposition of the field‐effect and light‐emitting materials. After deposition of pentacene, a narrow gap of about 10–20 nm between the drain electrode and pentacene was obtained, thereby creating an opportunity to fabricate a laterally arranged heterojunction. In the OLETs, unsymmetrical source and drain electrodes, that is, Au and LiF/Al ones, are used to ensure efficient injection of holes and electrons. Visible‐light emission from OLETs is observed under ambient atmosphere. This result is ascribed to efficient carrier injection and transport, formation of a heterojunction, as well as good luminescence from the organic emissive layer. The device structure serves as an excellent model system for OLETs and demonstrates a general concept of adjusting the charge‐carrier injection and transport, as well as the electroluminescent properties, by forming laterally arranged heterojunctions.     

基于超薄发光层的有机发光二极管器件的研究

文章采用具有电子捕捉能力的橙红色磷光材料iridium(Ⅲ)bis(2-methyldibenzo-[f,h] quinoxaline) (acetylacetonate) (Ir(MDQ)2 (acac))作为超薄发光层应用于有机发光二极管中.通过对其厚度的优化,发现当发光层厚度为0.1 nm时,器件性能最好,最大电流效率达到了28.1 cd/A,明显优于采用掺杂发光层的器件.分析了发光材料的载流子捕捉作用对器件载流子平衡及器件电流效率的影响,发现超薄发光层结构几乎不改变器件的电学特性,不会进一步破坏器件载流子平衡,正因如此,大多数磷光材料都可以采用超薄发光层获得很高的效率.     

Effect of Hole Mobility Through Emissive Layer on Temporal Stability of Blue Organic Light‐Emitting Diodes

Light‐emitting conjugated oligomers comprising anthracene, naphthalene, and fluorene units have been synthesized to investigate three configurations of blue organic light‐emitting diodes (OLEDs) that are designed to identify the origins of device instability. The transient OLED technique is employed to measure hole mobilities, which are found to be 3.1 × 10^–4, 8.9 × 10^–5, and 3.6 × 10^–5 cm² V^–1 s^–1 for three different blue‐light‐emitting model compounds with varying fluorene content. A higher hole mobility through the emissive layer results in a wider recombination zone, which, in turn, is responsible for a longer device lifetime and a lower drive voltage at the expense of luminance yield.     

Novel Heterolayer Organic Light‐Emitting Diodes Based on a Conjugated Dendrimer

We demonstrate a novel organic light‐emitting diode (LED) heterolayer structure that contains a conjugated dendrimer as the light‐emitting molecule. The LED was prepared by spin‐coating two dendrimer layers from the same solvent. The device consists of a graded bilayer structure formed from a neat dendrimer film covered with a film consisting of the same dendrimer but doped with the electron‐transporting material 2‐(4‐biphenylyl)‐5‐phenyl‐1,3,4‐oxadiazole (PBD). In this device, the heterojunction interface present in conventional bilayer organic light‐emitting diodes is eliminated, and is replaced by a graded interlayer. By optimizing the concentration of PBD in the dendrimer, a peak electroluminescence (EL) external quantum efficiency of 0.16 % at 600 cd m^–2 was obtained. The EL quantum efficiency is significantly enhanced in comparison with devices based on a single layer, a conventional bilayer, and a single‐layer doped with PBD. The EL quantum efficiency is a factor of eight larger than that of a conventional bilayer LED made with the conjugated dendrimer as the emissive layer and poly(methylmethacrylate) (PMMA) doped with PBD as the electron‐transporting layer. The best blended device exhibited only one third of the efficiency of the graded device. The improvement in the operating characteristics of the graded device is attributed to the efficient device structure, in which exciton formation is improved by a graded doping profile of electron‐ and hole‐transporting components.     

Improving device efficiencies of solid-state white light-emitting electrochemical cells by adjusting the emissive-layer thickness

Exciton quenching in the recombination zone close to electrochemically doped regions would be one of the bottlenecks for improving device efficiencies of solid-state white light-emitting electrochemical cells (LECs). To further enhance device efficiencies of white LECs for practical applications, we adjust the emissive-layer thickness to reduce exciton quenching. In white LECs with properly thickened emissive-layer thickness, the recombination zone can be situated near the center of the emissive layer, rendering mitigated exciton quenching and thus enhanced device efficiencies. High external quantum efficiencies and power efficiencies of optimized devices reach ca. 11% and 20 lm/W, respectively, which are among the highest reported for white LECs. These results confirm that tailoring the thickness of the emissive layer to avoid exciton quenching would be a feasible approach to improve device efficiencies of white LECs.     

Interlayer Engineering with Different Host Material Properties in Blue Phosphorescent Organic Light‐Emitting Diodes

We investigated the light‐emitting performances of blue phosphorescent organic light‐emitting diodes, known as PHOLEDs, by incorporating an N,N’‐dicarbazolyl‐3,5‐benzen interlayer between the hole transporting layer and emitting layer (EML). We found that the effects of the introduced interlayer for triplet exciton confinement and hole/electron balance in the EML were exceptionally dependent on the host materials: 9‐(4‐tert‐butylphenyl)‐3.6‐bis(triphenylsilyl)‐9H‐carbazole, 9‐(4‐tert‐butylphenyl)‐3.6‐ditrityl‐9H‐carbazole, and 4,4’‐bis‐triphenylsilanyl‐biphenyl. When an appropriate interlayer and host material were combined, the peak external quantum efficiency was greatly enhanced by over 21 times from 0.79% to 17.1%. Studies on the recombination zone using a series of host materials were also conducted.     

Achieving a Significantly Increased Efficiency in Nondoped Pure Blue Fluorescent OLED: A Quasi‐Equivalent Hybridized Excited State

Excited state characters and components play a decisive role in photoluminescence (PL) and electroluminescence (EL) properties of organic light‐emitting materials (OLEDS). Charge‐transfer (CT) state is beneficial to enhance the singlet exciton utilizations in fluorescent OLEDs by an activated reverse intersystem crossing process, due to the minimized singlet and triplet energy splitting in CT excitons. However, the dominant CT component in the emissive state significantly reduces the PL efficiency in such materials. Here, the strategy is to carry out a fine excited state modulation, aiming to reach a golden combination of the high PL efficiency locally emissive (LE) component and the high exciton utilizing CT component in one excited state. As a result, a quasi‐equivalent hybridization of LE and CT components is obtained in the emissive state upon the addition of only an extra phenyl ring in the newly synthesized material 4‐[2‐(4′‐diphenylamino‐biphenyl‐4‐yl)‐phenanthro[9,10‐d]imidazol‐1‐yl]‐benzonitrile (TBPMCN), and the nondoped OLED of TBPMCN exhibited a record‐setting performance: a pure blue emission with a Commission Internationale de L'Eclairage coordinate of (0.16, 0.16), a high external quantum efficiency of 7.8%, and a high yield of singlet exciton of 97% without delayed fluorescence phenomenon. The excited state modulation could be a practical way to design low‐cost, high‐efficiency fluorescent OLED materials.     

Solution‐Processed Full‐Color Polymer Organic Light‐Emitting Diode Displays Fabricated by Direct Photolithography

The first full‐color polymer organic light‐emitting diode (OLED) display is reported, fabricated by a direct photolithography process, that is, a process that allows direct structuring of the electroluminescent layer of the OLED by exposure to UV light. The required photosensitivity is introduced by attaching oxetane side groups to the backbone of red‐, green‐, and blue‐light‐emitting polymers. This allows for the use of photolithography to selectively crosslink thin films of these polymers. Hence the solution‐based process requires neither an additional etching step, as is the case for conventional photoresist lithography, nor does it rely on the use of prestructured substrates, which are required if ink‐jet printing is used to pixilate the emissive layer. The process allows for low‐cost display fabrication without sacrificing resolution: Structures with features in the range of 2 μm are obtained by patterning the emitting polymers via UV illumination through an ultrafine shadow mask. Compared to state‐of‐the‐art fluorescent OLEDs, the display prototype (pixel size 200 μm × 600 μm) presented here shows very good efficiency as well as good color saturation for all three colors. The application in solid‐state lighting is also possible: Pure white light [Commision Internationale de l'Éclairage (CIE) values of 0.33, 0.33 and color rendering index (CRI) of 76] is obtained at an efficiency of 5 cd A^–1 by mixing the three colors in the appropriate ratio. For further enhancement of the device efficiency, an additional hole‐transport layer (HTL), which is also photo‐crosslinkable and therefore suitable to fabricate multilayer devices from solution, is embedded between the anode and the electroluminescent layer.     

ZnO Nanorod Arrays as Electron Injection Layers for Efficient Organic Light Emitting Diodes

Nanostructured oxide arrays have received significant attention as charge injection and collection electrodes in numerous optoelectronic devices. Zinc oxide (ZnO) nanorods have received particular interest owing to the ease of fabrication using scalable, solution processes with a high degree of control of rod dimension and density. Here, vertical ZnO nanorods as electron injection layers in organic light emitting diodes are implemented for display and lighting purposes. Implementing nanorods into devices with an emissive polymer, poly(9,9‐dioctyluorene‐alt‐benzothiadiazole) (F8BT) and poly(9,9‐di‐n‐octylfluorene‐alt‐N‐(4‐butylphenyl)dipheny‐lamine) (TFB) as an electron blocking layer, brightness and efficiencies up to 8602 cd m^?2 and 1.66 cd A^?1 are achieved. Simple solution processing methodologies combined with postdeposition thermal processing are highlighted to achieve complete wetting of the nanorod arrays with the emissive polymer. The introduction of TFB to minimize charge leakage and nonradiative exciton decay results in dramatic increases to device yields and provides an insight into the operating mechanism of these devices. It is demonstrated that the detected emission originates from within the polymer layers with no evidence of ZnO band edge or defect emission. The work represents a significant development for the ongoing implementation of ZnO nanorod arrays into efficient light emitting devices.