Multifunctional Fluorene‐Based Oligomers with Novel Spiro‐Annulated Triarylamine: Efficient,Stable Deep‐Blue Electroluminescence,Good Hole Injection,and Transporting Materials with Very High Tg

A series of fluorene‐based oligomers with novel spiro‐annulated triarylamine structures, namely DFSTPA, TFSTPA, and TFSDTC, are synthesized by a Suzuki cross‐coupling reaction. The spiro‐configuration molecular structures lead to very high glass transition temperatures (197–253 °C) and weak intermolecular interactions, and consequently the structures retain good morphological stability and high fluorescence quantum efficiencies(0.69–0.98). This molecular design simultaneously solves the spectral stability problems and hole‐injection and transport issues for fluorene‐based blue‐light‐emitting materials. Simple double‐layer electroluminescence (EL) devices with a configuration of ITO/TFSTPA (device A) or TFSDTC (device B)/ TPBI/LiF/Al, where TFSTPA and TFSDTC serve as hole‐transporting blue‐light‐emitting materials, show a deep‐blue emission with a peak around 432 nm, and CIE coordinates of (0.17, 0.12) for TFSTPA and (0.16, 0.07) for TFSDTC, respectively, which are very close to the National Television System Committee (NTSC) standard for blue (0.15, 0.07). The maximum current efficiency/external quantum efficiencies are 1.63 cd A^?1/1.6% for device A and 1.91 cd A^?1/2.7% for device B, respectively. In addition, a device with the structure ITO/DFSTPA/Alq₃/LiF/Al, where DFSTPA acts as both the hole‐injection and ‐transporting material, is shown to achieve a good performance, with a maximum luminance of 14 047 cd m^?2, and a maximum current efficiency of 5.56 cd A^?1. These values are significantly higher than those of devices based on commonly usedN,N′‐di(1‐naphthyl)‐N,N′‐diphenyl‐[1,1′‐biphenyl]‐4,4′‐diamine (NPB) as the hole‐transporting layer (11 738 cd m^?2 and 3.97 cd A^?1) under identical device conditions.     

Solution‐Processable Hole‐Generation Layer and Electron‐Transporting Layer: Towards High‐Performance,Alternating‐Current‐Driven,Field‐Induced Polymer Electroluminescent Devices

The effect of solution‐processed p‐type doping of hole‐generation layers (HGLs) and electron‐transporting layer (ETLs) are systematically investigated on the performance of solution‐processable alternating current (AC) field‐induced polymer EL (FIPEL) devices in terms of hole‐generation capability of HGLs and electron‐transporting characteristics of ETLs. A variety of p‐type doping conjugated polymers and a series of solution‐processed electron‐transporting small molecules are employed. It is found that the free hole density in p‐type doping HGLs and electron mobility of solution‐processed ETLs are directly related to the device performance, and that the hole‐transporting characteristics of ETLs also play an important role since holes need to be injected from electrode through ETLs to refill the depleted HGLs in the positive half of the AC cycle. As a result, the best FIPEL device exhibits exceptional performance: a low turn‐on voltage of 12 V, a maximum luminance of 20 500 cd m^?2, a maximum current and power efficiency of 110.7 cd A^?1 and 29.3 lm W^?1. To the best of the authors' knowledge, this is the highest report to date among FIPEL devices driven by AC voltage.     

A Hole‐Transporting Material with Controllable Morphology Containing Binaphthyl and Triphenylamine Chromophores

An organic compound with two triphenylamine moieties linked with binaphthyl at the 3,3′‐positions (2,2′‐dimethoxyl‐3,3′‐ di(phenyl‐4‐yl‐diphenyl‐amine)‐[1,1′]‐binaphthyl, TPA–BN–TPA) can be synthesized by Suzuki coupling. Amorphous and homogeneous films are obtained by either vacuum deposition or spin‐coating from solution in good solvents, while single crystals are grown in an appropriate polar solvent. X‐ray crystallography showed that a TPA–BN–TPA crystal is a multichannel structure containing solvent molecules in the channels. The intramolecular charge‐transfer state resulting from amino conjugation effects is observed by solvatochromic experiments. The high glass‐transition temperature (130 °C) and decomposition temperature (439 °C) of this material, in combination with its reversible oxidation property, make it a promising candidate as a hole‐transport material for light‐emitting diodes. With TPA–BN–TPA as the hole‐transporting layer in an indium tin oxide/TPA–BN–TPA/aluminum tris(8‐hydroxyquinoline)/Mg:Ag device, a brightness of about 10 100 cd m^–2 at 15.6 V with a maximum efficiency of 3.85 cd A^–1 is achieved, which is superior to a device with N,N′‐di(1‐naphthyl)‐N,N′‐diphenyl‐[1,1′‐biphenyl]‐4,4′‐diamine as the hole‐transporting layer under the same conditions. Other devices with TPA–BN–TPA as the blue‐light‐emitting layer or host for a blue dye emitter are also studied.     

Polymeric Light‐Emitting Diodes Based on Poly(p‐phenylene ethynylene), Poly(triphenyldiamine), and Spiroquinoxaline

In this paper polymeric light‐emitting diodes (LEDs) based on alkoxy‐substituted poly(p‐phenylene ethynylene) EHO‐OPPE as emitter material in combination with poly(triphenyldiamine) as hole transport material are demonstrated. Different device configurations such as single‐layer devices, two‐layer devices, and blend devices were investigated. Device improvement and optimization were obtained through careful design of the device structure and composition. Furthermore, the influence of an additional electron transporting and hole blocking layer (ETHBL), spiroquinoxaline (spiro‐qux), on top of the optimized blend device was investigated using a combinatorial method, which allows the preparation of a number of devices characterized by different layer thicknesses in one deposition step. The maximum brightness of the investigated devices increased from 4 cd/m² for a device of pure EHO‐OPPE to 260 cd/m² in a device with 25 % EHO‐OPPE + 75 % poly(N,N′‐diphenylbenzidine diphenylether) (poly‐TPD) as the emitting/hole‐transporting layer and an additional electron‐transport/hole‐blocking spiro‐qux layer of 48 nm thickness.     

Nanodot‐Enhanced High‐Efficiency Pure‐White Organic Light‐Emitting Diodes with Mixed‐Host Structures

A relatively high‐efficiency, fluorescent pure‐white organic light‐emitting diode was fabricated using a polysilicic acid (PSA) nanodot‐embedded polymeric hole‐transporting layer (HTL). The diode employed a mixed host in the single emissive layer, which comprised 0.5 wt % yellow 5,6,11,12‐tetra‐phenylnaphthacene doped in the mixed host of 50 % 2‐(N,N‐diphenyl‐amino)‐6‐[4‐(N,N‐diphenylamino)styryl]naphthalene and 50 % N,N′‐bis‐(1‐naphthyl)‐N,N′‐diphenyl‐1,10‐biphenyl‐4‐4′‐diamine. By incorporating 7 wt % 3 nm PSA nanodot into the HTL of poly(3,4‐ethylene‐dioxythiophene)‐poly‐(styrenesulfonate), the efficiency at 100 cd m^–2 was increased from 13.5 lm W^–1 (14.7 cd A^–1; EQE: 7.2 %) to 17.1 lm W^–1 (17.6 cd A^–1; EQE: 8.3 %). The marked efficiency improvement may be attributed to the introduction of the PSA nanodot, leading to a better carrier‐injection‐balance.     

Unexpected Propeller‐Like Hexakis(fluoren‐2‐yl)benzene Cores for Six‐Arm Star‐Shaped Oligofluorenes: Highly Efficient Deep‐Blue Fluorescent Emitters and Good Hole‐Transporting Materials

Grafting six fluorene units to a benzene ring generates a new highly twisted core of hexakis(fluoren‐2‐yl)benzene. Based on the new core, six‐arm star‐shaped oligofluorenes from the first generation T1 to third generation T3 are constructed. Their thermal, photophysical, and electrochemical properties are studied, and the relationship between the structures and properties is discussed. Simple double‐layer electroluminescence (EL) devices using T1–T3 as non‐doped solution‐processed emitters display deep‐blue emissions with Commission Internationale de l'Eclairage (CIE) coordinates of (0.17, 0.08) for T1 , (0.16, 0.08) for T2 , and (0.16, 0.07) for T3 . These devices exhibit excellent performance, with maximum current efficiency of up to 5.4 cd A^?1, and maximum external quantum efficiency of up to 6.8%, which is the highest efficiency for non‐doped solution‐processed deep‐blue organic light‐emitting diodes (OLEDs) based on starburst oligofluorenes, and is even comparable with other solution‐processed deep‐blue fluorescent OLEDs. Furthermore, T2‐ and T3‐ based devices show striking blue EL color stability independent of driving voltage. In addition, using T0–T3 as hole‐transporting materials, the devices of indium tin oxide (ITO)/poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS)/ T0–T3 /tris(8‐hydroxyquinolinato)aluminium (Alq₃)/LiF/Al achieve maximum current efficiencies of 5.51–6.62 cd A^?1, which are among the highest for hole‐transporting materials in identical device structure.     

End‐Capping as a Method for Improving Carrier Injection in Electrophosphorescent Light‐Emitting Diodes

The electronic properties, carrier injection, and transport into poly(9,9‐dioctylfluorene) (PFO), PFO end‐capped with hole‐transporting moieties (HTM), PFO–HTM, and PFO end‐capped with electron‐transporting moieties (ETM), PFO–ETM, were investigated. The data demonstrate that charge injection and transport can be tuned by end‐capping with HTM and ETM, without significantly altering the electronic properties of the conjugated backbone. End‐capping with ETM resulted in more closely balanced charge injection and transport. Single‐layer electrophosphorescent light‐emitting diodes (LEDs), fabricated from PFO, PFO–HTM and PFO–ETM as hosts and tris[2,5‐bis‐2′‐(9′,9′‐dihexylfluorene)pyridine‐κ²NC_3′]iridium(III ), Ir(HFP)₃ as the guest, emitted red light with brightnesses of 2040 cd m^–2, 1940 cd m^–2 and 2490 cd m^–2 at 290 mA cm^–2 (16 V) and with luminance efficiencies of 1.4 cd A^–1, 1.4 cd A^–1 and 1.8 cd A^–1 at 4.5 mA cm^–2 for PFO, PFO–HTM, and PFO–ETM, respectively.     

White Electroluminescence from a Single‐Polymer System with Simultaneous Two‐Color Emission: Polyfluorene as the Blue Host and a 2,1,3‐Benzothiadiazole Derivative as the Orange Dopant

New single‐polymer electroluminescent systems containing two individual emission species—polyfluorenes as a blue host and 2,1,3‐benzothiadiazole derivative units as an orange dopant on the main chain—have been designed and synthesized. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue (λ_max = 421 nm/445 nm) and orange emission (λ_max = 564 nm) from the corresponding emitting species. The influence of the photoluminescence (PL) efficiencies of both the blue and orange species on the electroluminescence (EL) efficiencies of white polymer light‐emitting diodes (PLEDs) based on the single‐polymer systems has been investigated. The introduction of the highly efficient 4,7‐bis(4‐(N‐phenyl‐N‐(4‐methylphenyl)amino)phenyl)‐2,1,3‐benzothiadiazole unit to the main chain of polyfluorene provides significant improvement in EL efficiency. For a single‐layer device fabricated in air (indium tin oxide/poly(3,4‐ethylenedioxythiophene): poly(styrene sulfonic acid/polymer/Ca/Al), pure‐white electroluminescence with Commission Internationale de l'Eclairage (CIE) coordinates of (0.35,0.32), maximum brightness of 12 300 cd m^–2, luminance efficiency of 7.30 cd A^–1, and power efficiency of 3.34 lm W^–1 can be obtained. This device is approximately two times more efficient than that utilizing a single polyfluorene containing 1,8‐naphthalimide moieties, and shows remarkable improvement over the corresponding blend systems in terms of efficiency and color stability. Thermal treatment of the single‐layer device before cathode deposition leads to the further improvement of the device performance, with CIE coordinates of (0.35,0.34), turn‐on voltage of 3.5 V, luminance efficiency of 8.99 cd A^–1, power efficiency of 5.75 lm W^–1, external quantum efficiency of 3.8 %, and maximum brightness of 12 680 cd m^–2. This performance is roughly comparable to that of white organic light‐emitting diodes (WOLEDs) with multilayer device structures and complicated fabrication processes.     

High‐Throughput Combinatorial Optimizations of Perovskite Light‐Emitting Diodes Based on All‐Vacuum Deposition

Light‐emitting diodes (LEDs) based on lead halide perovskites demonstrate outstanding optoelectronic properties and are strong competitors for display and lighting applications. While previous halide perovskite LEDs are mainly produced via solution processing, here an all‐vacuum processing method is employed to construct CsPbBr₃ LEDs because vacuum processing exhibits high reliability and easy integration with existing OLED facilities for mass production. The high‐throughput combinatorial strategies are further adopted to study perovskite composition, annealing temperature, and functional layer thickness, thus significantly speeding up the optimization process. The best rigid device shows a current efficiency (CE) of 4.8 cd A^?1 (EQE of 1.45%) at 2358 cd m^?2, and best flexible device shows a CE of 4.16 cd A^?1 (EQE of 1.37%) at 2012 cd m^?2 with good bending tolerance. Moreover, by choosing NiO_x as the hole‐injection layer, the CE is improved to 10.15 cd A^?1 and EQE is improved to a record of 3.26% for perovskite LEDs produced by vacuum deposition. The time efficient combinatorial approaches can also be applied to optimize other perovskite LEDs.     

Monodisperse Starburst Oligofluorene‐Functionalized 4,4′,4″‐Tris(carbazol‐9‐yl)‐triphenylamines: Their Synthesis and Deep‐Blue Fluorescent Properties for Organic Light‐Emitting Diode Applications

Four monodisperse starburst oligomers bearing a 4,4′,4″‐tris(carbazol‐9‐yl)‐triphenylamine (TCTA) core and six oligofluorene arms are synthesized and characterized. The lengths of oligofluorene arms vary from one to four fluorene units, giving the starburst oligomers molecular weights ranging from 3072 to 10 068 Da (1 Da = 1.66 × 10^–27 kg). All of the starburst oligomers have good film‐forming capabilities, and display bright, deep‐blue fluorescence (λ_max = 395–416 nm) both in solution and in the solid state, with the quantum efficiencies of the films (Φ_PL) varying between 27 and 88 %. Electrochemical studies demonstrate that these materials have large energy gaps, and are stable for both p‐doping and n‐doping processes. Electroluminescent devices are successfully fabricated using these materials as hole‐transporting emitters, and emit deep‐blue light. Devices with luminance values up to 1025 cd m^–2 at 11 V and luminous efficiencies of 0.47 cd A^–1 at 100 cd m^–2 have been produced, which translates to an external quantum efficiency of 1.4 %. In addition, these large‐energy‐gap starburst oligomers are good host materials for red electrophosphorescence. The luminance of the red electrophosphorescent devices is as high as 4452 cd m^–2, with a luminous efficiency of 4.31 cd A^–1 at 15 mA cm^–2: This value is much higher than those obtained from the commonly used hole‐transporting materials, such as poly(vinyl carbazole) (PVK) (1.10 cd A^–1 at 16 mA cm^–2).     

Stable and Efficient White Electroluminescent Devices Based on a Single Emitting Layer of Polymer Blends

An efficient orange‐light‐emitting polymer (PFTO‐BSeD5) has been developed through the incorporation of low‐bandgap benzoselenadiazole (BSeD) moieties into the backbone of a blue‐light‐emitting polyfluorene copolymer (PFTO poly{[9,9‐bis(4‐(5‐(4‐tert‐butylphenyl)‐[1,3,4]‐oxadiazol‐2‐yl)phenyl)‐9′,9′‐di‐n‐octyl‐[2,2′]‐bifluoren‐7,7′‐diyl]‐stat‐[9,9‐bis(4‐(N,N‐di(4‐n‐butylphenyl)amino)phenyl)‐9′,9′‐di‐n‐octyl‐[2,2′]‐bifluoren‐7,7′‐diyl]}) that contains hole‐transporting triphenylamine and electron‐transporting oxadiazole pendent groups. A polymer light‐emitting device based on this copolymer exhibits a strong, bright‐orange emission with Commission Internationale de L'Eclairage (CIE) color coordinates (0.45,0.52). The maximum brightness is 13 716 cd m^–2 and the maximum luminance efficiency is 5.53 cd A^–1. The use of blends of PFTO‐BSeD5 in PFTO leads to efficient and stable white‐light‐emitting diodes—at a doping concentration of 9 wt %, the device reaches its maximum external quantum efficiency of 1.64 % (4.08 cd A^–1). The emission color remains almost unchanged under different bias conditions: the CIE coordinates are (0.32,0.33) at 11.0 V (2.54 mA cm^–2, 102 cd m^–2) and (0.31,0.33) at 21.0 V (281 mA cm^–2, 7328 cd m^–2). These values are very close to the ideal CIE chromaticity coordinates for a pure white color (0.33,0.33).     

Cover Picture: White Electroluminescence from a Single‐Polymer System with Simultaneous Two‐Color Emission: Polyfluorene as the Blue Host and a 2,1,3‐Benzothiadiazole Derivative as the Orange Dopant (Adv. Funct. Mater. 7/2006)

New single‐polymer electroluminescent systems containing two individual emission species—polyfluorenes as a blue host and 2,1,3‐benzothiadiazole derivative units as an orange dopant on the main chain—have been designed and synthesized by Wang and co‐workers on p. 957. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue and orange emission from the corresponding emitting species. A single‐layer device has been fabricated that has performance characteristics roughly comparable to those of organic white‐light‐emitting diodes with multilayer device structures. New single‐polymer electroluminescent systems containing two individual emission species—polyfluorenes as a blue host and 2,1,3‐benzothiadiazole derivative units as an orange dopant on the main chain—have been designed and synthesized. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue (λ_max = 421 nm/445 nm) and orange emission (λ_max = 564 nm) from the corresponding emitting species. The influence of the photoluminescence (PL) efficiencies of both the blue and orange species on the electroluminescence (EL) efficiencies of white polymer light‐emitting diodes (PLEDs) based on the single‐polymer systems has been investigated. The introduction of the highly efficient 4,7‐bis(4‐(N‐phenyl‐N‐(4‐methylphenyl)amino)phenyl)‐2,1,3‐benzothiadiazole unit to the main chain of polyfluorene provides significant improvement in EL efficiency. For a single‐layer device fabricated in air (indium tin oxide/poly(3,4‐ethylenedioxythiophene): poly(styrene sulfonic acid/polymer/Ca/Al), pure‐white electroluminescence with Commission Internationale de l'Eclairage (CIE) coordinates of (0.35,0.32), maximum brightness of 12 300 cd m^–2, luminance efficiency of 7.30 cd A^–1, and power efficiency of 3.34 lm W^–1 can be obtained. This device is approximately two times more efficient than that utilizing a single polyfluorene containing 1,8‐naphthalimide moieties, and shows remarkable improvement over the corresponding blend systems in terms of efficiency and color stability. Thermal treatment of the single‐layer device before cathode deposition leads to the further improvement of the device performance, with CIE coordinates of (0.35,0.34), turn‐on voltage of 3.5 V, luminance efficiency of 8.99 cd A^–1, power efficiency of 5.75 lm W^–1, external quantum efficiency of 3.8 %, and maximum brightness of 12 680 cd m^–2. This performance is roughly comparable to that of white organic light‐emitting diodes (WOLEDs) with multilayer device structures and complicated fabrication processes.     

Fluorescent,Carrier‐Trapping Dopants for Highly Efficient Single‐Layer Polyfluorene LEDs

Two fluorescent molecules with an alkynylanthracene core and pyrene end‐cappers have been synthesized and fully characterized. Carbazole moieties are introduced into one molecule at the C9 position of the fluorene linkages to enhance the hole‐transport ability of the molecule and to reduce intermolecular interactions. Both compounds exhibit high thermal stabilities and narrow energy bandgaps. Single‐layer polymer light‐emitting diodes (PLEDs) based on poly(9,9‐dioctylfluorene) (PFO) doped with the synthesized compounds exhibit excellent performance. A PLED with 0.2 % of dopant 7 had a high luminance efficiency of 10.7 ± 0.3 cd A^–1 as well as a brightness of 1400 cd m^–2 at a current density of 13 mA cm^–2, and a low turn on voltage (3.1 V) at a brightness of 10 cd m^–2. A maximum brightness of 20 500 ± 1400 cd m^–2 at 7 V was also measured. The high efficiency of the device's performance is attributed to the good electron and hole trapping ability of the dopants, which possess suitable energy levels as compared to those of PFO.     

Solution‐Processed Thermally Activated Delayed Fluorescent OLED with High EQE as 31% Using High Triplet Energy Crosslinkable Hole Transport Materials

Solution‐processed organic light‐emitting diodes (OLEDs) with thermally activated delayed fluorescent (TADF) material as emitter have attracted much attention because of their low cost and high performance. However, exciton quench at the interface between the hole injection layer, poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), and emitting layer (EML) in devices can lead to low device performance. Here, a novel high triplet energy (2.89 eV) and crosslinkable hole‐transporting material grafted with oxetane groups, N,N‐bis(4‐(6‐((3‐ethyloxetan‐3‐yl)methoxy)hexyloxy)phenyl)‐3,5‐di(9H‐carbazol‐9‐yl)benzenamine (Oxe‐DCDPA)), as crosslinked hole transport layer (HTL) into the interface of PEDOT:PSS layer and EML is proposed for prevention of exciton quenching, and among the reported devices with single HTL in solution‐processed TADF‐OLED, the highest external quantum efficiency (EQE)/luminous efficiency (η_L) of 26.1%/94.8 cd A^?1 and 24.0%/74.0 cd A^?1 are achieved for green emission (DACT‐II as emitter) and bluish‐green emission (DMAC‐TRZ as emitter), respectively. Further improvement, using double HTLs, composed of N,N′‐bis(4‐(6‐((3‐ethyloxetan‐3‐yl)methoxy))‐hexylphenyl)‐N,N′‐diphenyl‐4,4′‐diamine with high hole mobility and Oxe‐DCDPA with high triplet energy, leads to the highest EQE/η_L of 30.8%/111.9 cd A^?1 and 27.2%/83.8 cd A^?1 for green emission and bluish‐green emission, respectively. These two devices show the high maximum brightness of 81 100 and 70 000 cd m^?2, respectively.     

Characteristics of Solution‐Processed Small‐Molecule Organic Films and Light‐Emitting Diodes Compared with their Vacuum‐Deposited Counterparts

Although significant progress has been made in the development of vacuum‐deposited small‐molecule organic light‐emitting diodes (OLEDs), one of the most desired research goals is still to produce flexible displays by low‐cost solution processing. The development of solution‐processed OLEDs based on small molecules could potentially be a good approach but no intensive studies on this topic have been conducted so far. To fabricate high‐performance devices based on solution‐processed small molecules, the underlying nature of the produced films and devices must be elucidated. Here, the distinctive characteristics of solution‐processed small‐molecule films and devices compared to their vacuum‐deposited counterparts are reported. Solution‐processed blue OLEDs show a very high luminous efficiency (of about 8.9 cd A^–1) despite their simplified structure. A better hole‐blocking and electron‐transporting layer is essential for achieving high‐efficiency solution‐processed devices because the solution‐processed emitting layer gives the devices a better hole‐transporting capability and more electron traps than the vacuum‐deposited layer. It is found that the lower density of the solution‐processed films (compared to the vacuum‐deposited films) can be a major cause for the short lifetimes observed for the corresponding devices.     

2,5‐Functionalized Spiro‐Bisiloles as Highly Efficient Yellow‐Light Emitters in Electroluminescent Devices

New spiro‐bisilole molecules functionalized with nitrogen‐containing heterocyclic groups including 7‐azaindolyl, indolyl, and 2,2′‐dipyridylamino have been synthesized. These molecules are found to display good chemical and thermal stability. They are luminescent in solution and in the solid state with an emission color ranging from blue–green to yellow, depending on the functional group. In the solid state, they display high photoluminescence quantum efficiency (32–40 %). The electroluminescence properties for one of the new molecules, 2,3,3′,4,4′,5‐hexaphenyl‐2′,5′‐bis(p‐2,2′‐dipyridylaminophenyl)spiro‐bisilole, have been investigated by fabricating single‐layer and double‐layer electroluminescent devices. The double‐layer device, in which N,N′‐bis(1‐naphthyl)‐N,N′‐diphenylbenzidine acts as the hole‐transport layer and the functionalized spiro‐bisilole functions as the emitter (emission wavelength = 566 nm) and the electron‐transport layer, displays a brightness of 8440 cd m^–2 at 9 V with a current efficiency of 1.71 cd A^–1. No evidence of exiplex emission is observed.     

Self‐Organized Gradient Hole Injection to Improve the Performance of Polymer Electroluminescent Devices

A new approach to forming a gradient hole‐injection layer in polymer light‐emitting diodes (PLEDs) is demonstrated. Single spin‐coating of hole‐injecting conducting polymer compositions with a perfluorinated ionomer results in a work function gradient through the layer formed by self‐organization, which leads to remarkably efficient single‐layer PLEDs (ca. 21 cd A^–1). The device lifetime is significantly improved (ca. 50 times) compared with the conventional hole‐injection layer, poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonate). These results are a good example for demonstrating that the shorter lifetime of PLEDs compared with small‐molecule‐based organic LEDs (SM‐OLEDs) is not mainly due to the inherent degradation of the polymeric emitter itself. Hence, the results open the way to further improvements of PLEDs for real applications to large‐area, high‐resolution, and full‐color flexible displays.     

An Alternative Approach to Constructing Solution Processable Multifunctional Materials: Their Structure,Properties, and Application in High‐Performance Organic Light‐Emitting Diodes

A new series of full hydrocarbons, namely 4,4′‐(9,9′‐(1,3‐phenylene)bis(9H‐fluorene‐9,9‐diyl))bis(N,N‐diphenylaniline) (DTPAFB), N,N′‐(4,4′‐(9,9′‐(1,3‐phenylene)bis(9H‐fluorene‐9,9‐diyl))bis(4,1‐phenylene))bis(N‐phenylnaphthalen‐1‐amine) (DNPAFB), 1,3‐bis(9‐(4‐(9H‐carbazol‐9‐yl)phenyl)‐9H‐fluoren‐9‐yl)benzene, and 1,3‐bis(9‐(4‐(3,6‐di‐tert‐butyl‐9H‐carbazol‐9‐yl)phenyl)‐9H‐fluoren‐9‐yl)benzene, featuring a highly twisted tetrahedral conformation, are designed and synthesized. Organic light‐emitting diodes (OLEDs) comprising DNPAFB and DTPAFB as hole transporting layers and tris(quinolin‐8‐yloxy)aluminum as an emitter are made either by vacuum deposition or by solution processing, and show much higher maximum efficiencies than the commonly used N,N′‐di(naphthalen‐1‐yl)‐N,N′‐diphenylbiphenyl‐4,4′‐diamine device (3.6 cd A^?1) of 7.0 cd A^?1 and 6.9 cd A^?1, respectively. In addition, the solution processed blue phosphorescent OLEDs employing the synthesized materials as hosts and iridium (III) bis[(4,6‐di‐fluorophenyl)‐pyridinato‐N, C²] picolinate (FIrpic) phosphor as an emitter present exciting results. For example, the DTPAFB device exhibits a brightness of 47 902 cd m^?2, a maximum luminescent efficiency of 24.3 cd A^?1, and a power efficiency of 13.0 lm W^?1. These results show that the devices are among the best solution processable blue phosphorescent OLEDs based on small molecules. Moreover, a new approach to constructing solution processable small molecules is proposed based on rigid and bulky fluorene and carbazole moieties combined in a highly twisted configuration, resulting in excellent solubility as well as chemical miscibility, without the need to introduce any solubilizing group such as an alkyl or alkoxy chain.     

Solution‐Processible Multi‐component Cyclometalated Iridium Phosphors for High‐Efficiency Orange‐Emitting OLEDs and Their Potential Use as White Light Sources

The synthesis and photophysical studies of several multifunctional phosphorescent iridium(III) cyclometalated complexes consisting of the hole‐transporting carbazole and fluorene‐based 2‐phenylpyridine moieties are reported. All of them are isolated as thermally and morphological stable amorphous solids. Extension of the π‐conjugation through incorporation of electron‐pushing carbazole units to the fluorene fragment leads to bathochromic shifts in the emission profile, increases the highest occupied molecular orbital levels and improves the charge balance in the resulting complexes because of the propensity of the carbazole unit to facilitate hole transport. These iridium‐based triplet emitters give a strong orange phosphorescence light at room temperature with relatively short lifetimes in the solution phase. The photo‐ and electroluminescence properties of these phosphorescent carbazolylfluorene‐functionalized metalated complexes have been studied in terms of the coordinating position of carbazole to the fluorene unit. Organic light‐emitting diodes (OLEDs) using these complexes as the solution‐processed emissive layers have been fabricated which show very high efficiencies even without the need for the typical hole‐transporting layer. These orange‐emitting devices can produce a maximum current efficiency of ～ 30 cd A^–1 corresponding to an external quantum efficiency of ～ 10 % ph/el (photons per electron) and a power efficiency of ～ 14 lm W^–1. The homoleptic iridium phosphors generally outperform the heteroleptic counterparts in device performance. The potential of exploiting these orange phosphor dyes in the realization of white OLEDs is also discussed.     

Highly Efficient Electron‐Transporting/Injecting and Thermally Stable Naphthyridines for Organic Electrophosphorescent Devices

A series of 1,8‐naphthyridine derivatives is synthesized and their electron‐transporting/injecting (ET/EI) properties are investigated via a multilayered electrophosphorescent organic light‐emitting device (OLED) using fac‐tris(2‐phenylpyridine)iridium [Ir(ppy)₃] as a green phosphorescent emitter doped into a 4,4′‐N,N′‐dicarbazolebiphenyl (CBP) host with 4,4′‐bis[N‐(1‐naphthyl)‐N‐phenylamino]biphenyl (a‐NPD) as the hole‐transporting layer, and poly(arylene ether sulfone) containing tetraphenylbenzidine (TPDPES) doped with tris(4‐bromophenyl)ammonium hexachloroantimonate (TBPAH) as the hole‐injecting layer. The turn‐on voltage of the device is 2.5 V using 2,7‐bis[3‐(2‐phenyl)‐1,8‐naphthyridinyl]‐9,9‐dimethylfluorene (DNPF), lower than that of 3.0 V for the device using a conventional ET material. The maximum current efficiency (CE) and power efficiency (PE) of the DNPF device are much higher than those of a conventional device. With the aid of a hole‐blocking (HB) and exciton‐blocking layer of bathocuproine (BCP), 13.2–13.7% of the maximum external quantum efficiency (EQE) and a maximum PE of 50.2–54.5 lm W^?1 are obtained using the naphthyridine derivatives; these values are comparable with or even higher than the 13.6% for conventional ET material. The naphthyridine derivatives show high thermal stabilities, glass‐transition temperatures much higher than that of aluminum(III) bis(2‐methyl‐8‐quinolinato)‐4‐phenylphenolate (BAlq), and decomposition temperatures of 510–518 °C, comparable to or even higher than those of Alq₃.