Study of Configuration Differentia and Highly Efficient,Deep‐Blue,Organic Light‐Emitting Diodes Based on Novel Naphtho[1,2‐d]imidazole Derivatives

Two novel naphtho[1,2‐d]imidazole derivatives are developed as deep‐blue, light‐emitting materials for organic light‐emitting diodes (OLEDs). The 1H‐naphtho[1,2‐d]imidazole based compounds exhibit a significantly superior performance than the 3H‐naphtho[1,2‐d]imidazole analogues in the single‐layer devices. This is because they have a much higher capacity for direct electron‐injection from the cathode compared to their isomeric counterparts resulting in a ground‐breaking EQE (external quantum efficiency) of 4.37% and a low turn‐on voltage of 2.7 V, and this is hitherto the best performance for a non‐doped single‐layer fluorescent OLED. Multi‐layer devices consisting of both hole‐ and electron‐transporting layers, result in identically excellent performances with EQE values of 4.12–6.08% and deep‐blue light emission (Commission Internationale de l'Eclairage (CIE) y values of 0.077–0.115) is obtained for both isomers due to the improved carrier injection and confinement within the emissive layer. In addition, they showed a significantly better blue‐color purity than analogous molecules based on benzimidazole or phenanthro[9,10‐d]imidazole segments.     

Highly Efficient Three Primary Color Organic Single‐Crystal Light‐Emitting Devices with Balanced Carrier Injection and Transport

Organic single crystals have a great potential in the field of organic optoelectronics because of their advantages of high carrier mobility and high thermal stability. However, the application of the organic single crystals in light‐emitting devices (OLEDs) has been limited by single‐layered structure with unbalanced carrier injection and transport. Here, fabrication of a multilayered‐structure crystal‐based OLED constitutes a major step toward balanced carrier injection and transport by introducing an anodic buffer layer and electron transport layer into the device structure. Three primary color single‐crystal‐based OLEDs based on the multilayered structure and molecular doping exhibit a maximum luminance and current efficiency of 820 cd cm^?2 and 0.9 cd A^?1, respectively, which are the highest performance to date for organic single‐crystal‐based OLEDs. This work paves the way toward high‐performance organic optoelectronic devices based on the organic single crystals.     

Optimization of Orange‐Emitting Electrophosphorescent Copolymers for Organic Light‐Emitting Diodes

Orange‐emitting phosphorescent copolymers containing iridium complexes and bis(carbazolyl)fluorene groups in their side chains are employed as the emissive layer in multilayer organic light‐emitting diodes (OLEDs). The efficiency of the OLED devices is optimized by varying characteristics of the copolymers: the molecular weight, the iridium loading level, and the nature and length of the linker between the side chains and the polymer backbone. A maximum efficiency of 4.9 ± 0.4%, 8.8 ± 0.7 cd A⁻¹ at 100 cd m⁻² is achieved with an optimized copolymer.     

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.     

Investigating Morphology and Stability of Fac‐tris (2‐phenylpyridyl)iridium(III) Films for OLEDs

Stable film morphology is critical for long‐term high performance organic light‐emitting diodes (OLEDs). Neutron reflectometry (NR) is used to study the out‐of‐plane structure of blended thin films and multilayer structures comprising evaporated small molecules. It is found that as‐prepared blended films of fac‐tris(2‐phenylpyridyl)iridium(III) [Ir(ppy)₃] in 4,4′‐bis(N‐carbazolyl)biphenyl (CBP) are uniformly mixed, but the occurrence of phase separation upon thermal annealing is dependent on the blend ratio. Films comprised of the ratio of 6 wt% of Ir(ppy)₃ in CBP typically used in OLEDs are found to phase separate with moderate heating while a higher weight percent mixture (12 wt%) is found to be stable. Furthermore, it is found that thermal annealing of a multilayer film comprised of typical layers found in efficient devices ([tris(4‐carbazoyl‐9‐ylphenyl)amine (TCTA)/Ir(ppy)₃:CBP/bathocuproine (BCP)]) causes the BCP layer to become mixed with the emissive blend layer, whereas the TCTA interface remains unchanged. This significant structural change causes no appreciable difference in the photo­luminescence of the stack although such a change would have a dramatic effect on the charge transport through the device, leading to changes in performance. These results demonstrate the effect of thermal stress on the delicate interplay between the chemical composition and morphology of OLED films.     

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.     

Solution‐Processed Organic Light‐Emitting Transistors Incorporating Conjugated Polyelectrolytes

Improved performance of p‐type organic light‐emitting transistors (OLETs) is demonstrated by introducing a conjugated polyelectrolyte (CPE) layer and symmetric high work function (WF) source and drain metal electrodes. The OLET comprises a tri‐layer film consisting of a hole transporting layer, an emissive layer, and a CPE layer as an electron injection layer. The thickness of the CPE layer is critical for achieving good performance and provides an important structural handle for consideration in future optimization studies. We also demonstrate for the first time, good performance solution‐processed blue‐emitting OLETs. These results further demonstrate the simplification of device fabrication and improved performance afforded by integrating CPE interlayers into organic optoelectronic devices.     

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.     

Monothiatruxene‐Based,Solution‐Processed Green,Sky‐Blue,and Deep‐Blue Organic Light‐Emitting Diodes with Efficiencies Beyond 5% Limit

The development of blue materials with good efficiency, even at high brightness, with excellent color purity, simple processing, and high thermal stability assuring adequate device lifetime is an important remaining challenge for organic light‐emitting didoes (OLEDs) in displays and lightning applications. Furthermore, these various features are typically mutually exclusive in practice. Herein, four novel green and blue light‐emitting materials based on a monothiatruxene core are reported together with their photophysical and thermal properties, and performance in solution‐processed OLEDs. The materials show excellent thermal properties with high glass transition temperatures ranging from 171 to 336 °C and decomposition temperatures from 352 to 442 °C. High external quantum efficiencies of 3.7% for a deep‐blue emitter with CIE color co‐ordinates (0.16, 0.09) and 7% for green emitter with color co‐ordinates (0.22, 0.40) are achieved at 100 cd m^?2. The efficiencies observed are exceptionally high for fluorescent materials with photoluminescence quantum yields of 24% and 62%, respectively. The performance at higher brightness is very good with only 38% and 17% efficiency roll‐offs at 1000 cd m^?2. The results indicate that utilization of this unique molecular design is promising for efficient deep‐blue highly stable and soluble light‐emitting materials.     

Influences of Connecting Unit Architecture on the Performance of Tandem Organic Light‐Emitting Devices

The present work investigates the influence of the n‐type layer in the connecting unit on the performance of tandem organic light‐emitting devices (OLEDs). The n‐type layer is typically an organic electron‐transporting layer doped with reactive metals. By systematically varying the metal dopants and the electron‐transporting hosts, we have identified the important factors affecting the performance of the tandem OLEDs. Contrary to common belief, device characteristics were found to be insensitive to metal work functions, as supported by the ultraviolet photoemission spectroscopy results that the lowest unoccupied molecular orbitals of all metal‐doped n‐type layers studied here have similar energy levels. It suggests that the electron injection barriers from the connecting units are not sensitive to the metal dopant used. On the other hand, it was found that performance of the n‐type layers depends on their electrical conductivities which can be improved by using an electron‐transporting host with higher electron mobility. This effect is further modulated by the optical transparency of constituent organic layers. The efficiency of tandem OLEDs would decrease as the optical transmittance decreases.     

Mechanistic Study on High Efficiency Deep Blue AIE‐Based Organic Light‐Emitting Diodes by Magneto‐Electroluminescence

Aggregation‐induced emission (AIE) materials are highly attractive because of their excellent properties of high efficiency emission in nondoped organic light‐emitting diodes (OLEDs). Therefore, a deep understanding of the working mechanisms, further improving the electroluminescence (EL) efficiency of the resulting AIE‐based OLEDs, is necessary. Herein, the conversion process from higher energy triplet state (T₂) to the lowest singlet state (SS₁) is found in OLEDs based on a blue AIE material, 4′‐(4‐(diphenylamino)phenyl)‐5′‐phenyl‐[1,1′:2′,1′′‐terphenyl]‐4‐carbonitrile (TPB‐AC), obviously relating to the device efficiency, by magneto‐EL (MEL) measurements. A special line shape with rise at low field and reduction at high field is observed. The phenomenon is further clarified by theoretical calculations, temperature‐dependent MELs, and transient photoluminescence emission properties. On the basis of the T₂‐S₁ conversion process, the EL performances of the blue OLEDs based on TPB‐AC are further enhanced by introducing a phosphorescence doping emitter in the emitting layer, which effectively regulates the excitons on TPB‐AC molecules. The maximum external quantum efficiency (EQE) reaches 7.93% and the EQE keeps 7.57% at the luminance of 1000 cd m^?2. This work establishes a physical insight for designing high‐performance AIE materials and devices in the future.     

Red‐Light‐Emitting Iridium Complexes with Hole‐Transporting 9‐Arylcarbazole Moieties for Electrophosphorescence Efficiency/Color Purity Trade‐off Optimization

The synthesis, structures, photophysics, electrochemistry and electrophosphorescent properties of new red phosphorescent cyclometalated iridium(III) isoquinoline complexes, bearing 9‐arylcarbazolyl chromophores, are reported. The functional properties of these red phosphors correlate well with the results of density functional theory calculations. The highest occupied molecular orbital levels of these complexes are raised by the integration of a carbazole unit to the iridium isoquinoline core so that the hole‐transporting ability is improved in the resulting complexes relative to those with 1‐phenylisoquinoline ligands. All of the complexes are highly thermally stable and emit an intense red light at room temperature with relatively short lifetimes that are beneficial for highly efficient organic light‐emitting diodes (OLEDs). Saturated red OLEDs, fabricated using these dyes as the phosphorescent dopants both as vacuum‐evaporated and spin‐coated emissive layers, have been achieved in a multilayer configuration with outstanding red color purity at Commission International de L'Éclairage (CIE) coordinates of (0.67,0.33) to (0.68,0.32). Some of the devices can show very high efficiencies with a maximum external quantum efficiency of up to 12 % photons per electron. The excellent performance of these red emitters indicates the advantage of the carbazole module in the ligand framework; demonstrated by an improved hole‐transporting ability that facilitates exciton transport. These materials could thus provide a new avenue for the rational design of heavy‐metal electrophosphors that reveal a superior device efficiency/color purity trade‐off necessary for pure red‐light generation.     

Platinum Binuclear Complexes as Phosphorescent Dopants for Monochromatic and White Organic Light‐Emitting Diodes

Efficient blue‐, green‐, and red‐light‐emitting organic diodes are fabricated using binuclear platinum complexes as phosphorescent dopants. The series of complexes used here have pyrazolate bridging ligands and the general formula C^∧NPt(μ‐pz)₂PtC^∧N (where C^∧N = 2‐(4′,6′‐difluorophenyl)pyridinato‐N,C^2′, pz = pyrazole ( 1 ), 3‐methyl‐5‐tert‐butylpyrazole ( 2 ), and 3,5‐bis(tert‐butyl)pyrazole ( 3 )). The Pt–Pt distance in the complexes, which decreases in the order 1 > 2 > 3 , solely determines the electroluminescence color of the organic light‐emitting diodes (OLEDs). Blue OLEDs fabricated using 8 % 1 doped into a 3,5‐bis(N‐carbazolyl)benzene (mCP) host have a quantum efficiency of 4.3 % at 120 Cd m^–2, a brightness of 3900 Cd m^–2 at 12 V, and Commission Internationale de L'Eclairage (CIE) coordinates of (0.11, 0.24). Green and red OLEDs fabricated with 2 and 3 , respectively, also give high quantum efficiencies (～ 6.7 %), with CIE coordinates of (0.31, 0.63) and (0.59, 0.46), respectively. The current‐density–voltage characteristics of devices made using dopants 2 and 3 indicate that hole trapping is enhanced by short Pt–Pt distances (< 3.1 Å). Blue electrophosphorescence is achieved by taking advantage of the binuclear molecular geometry in order to suppress dopant intermolecular interactions. No evidence of low‐energy emission from aggregate states is observed in OLEDs made with 50 % 1 doped into mCP. OLEDs made using 100 % 1 as an emissive layer display red luminescence, which is believed to originate from distorted complexes with compressed Pt–Pt separations located in defect sites within the neat film. White OLEDs are fabricated using 1 and 3 in three different device architectures, either with one or two dopants in dual emissive layers or both dopants in a single emissive layer. All the white OLEDs have high quantum efficiency (～ 5 %) and brightness (～ 600 Cd m^–2 at 10 V).     

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.     

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.     

Achieving High Efficiency and Improved Stability in ITO‐Free Transparent Organic Light‐Emitting Diodes with Conductive Polymer Electrodes

Efficient transparent organic light‐emitting diodes (OLEDs) with improved stability based on conductive, transparent poly(3,4‐ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) electrodes are reported. Based on optical simulations, the device structures are carefully optimized by tuning the thickness of doped transport layers and electrodes. As a result, the performance of PEDOT:PSS‐based OLEDs reaches that of indium tin oxide (ITO)‐based reference devices. The efficiency and the long‐term stability of PEDOT:PSS‐based OLEDs are significantly improved. The structure engineering demonstrated in this study greatly enhances the overall performances of ITO‐free transparent OLEDs in terms of efficiency, lifetime, and transmittance. These results indicate that PEDOT:PSS‐based OLEDs have a promising future for practical applications in low‐cost and flexible device manufacturing.     

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.     

A Multifunctional Blue‐Emitting Material Designed via Tuning Distribution of Hybridized Excited‐State for High‐Performance Blue and Host‐Sensitized OLEDs

Actualizing full singlet exciton yield via a reverse intersystem crossing from the high‐lying triplet state to singlet state, namely, “hot exciton” mechanism, holds great potential for high‐performance fluorescent organic light‐emitting diodes (OLEDs). However, incorporating comprehensive insights into the mechanism and effective molecular design strategies still remains challenging. Herein, three blue emitters (CNNPI, 2TriPE‐CNNPI, and 2CzPh‐CNNPI) with a distinct local excited (LE) state and charge‐transfer (CT) state distributions in excited states are designed and synthesized. They show prominent hybridized local and charge‐transfer (HLCT) states and aggregation‐induced emission enhancement properties. The “hot exciton” mechanism based on these emitters reveals that a balanced LE/CT distribution can simultaneously boost photoluminescence efficiency and exciton utilization. In particular, a nearly 100% exciton utilization is achieved in the electroluminescence (EL) process of 2CzPh‐CNNPI. Moreover, employing 2CzPh‐CNNPI as the emitter, emissive dopant, and sensitizing host, respectively, the EL performances of the corresponding nondoped pure‐blue, doped deep‐blue, and HLCT‐sensitized fluorescent OLEDs are among the most efficient OLEDs with a “hot exciton” mechanism to date. These results could shed light on the design principles for “hot exciton” materials and inspire the development of next‐generation high‐performance OLEDs.     

Water‐Soluble Lacunary Polyoxometalates with Excellent Electron Mobilities and Hole Blocking Capabilities for High Efficiency Fluorescent and Phosphorescent Organic Light Emitting Diodes

High performance solution‐processed fluorescent and phosphorescent organic light emitting diodes (OLEDs) are achieved by water solution processing of lacunary polyoxometalates used as novel electron injection/transport materials with excellent electron mobilities and hole blocking capabilities. Green fluorescent OLEDs using poly[(9,9‐dioctylfluorenyl‐2,7‐diyl)‐co‐(1,4‐benzo‐{2,1′,3}‐thiadiazole)] (F8BT) as the emissive layer and our polyoxometalates as electron transport/hole blocking layers give a luminous efficiency up to 6.7 lm W^?1 and a current efficiency up to 14.0 cd A^?1 which remained nearly stable for about 500 h of operation. In addition, blue phosphorescent OLEDs (PHOLEDs) using poly(9‐vinylcarbazole) (PVK):1,3‐bis[2‐(4‐tert‐butylphenyl)‐1,3,4‐oxadiazo‐5‐yl]benzene (OXD‐7) as a host and 10.0 wt% FIrpic as the blue dopant in the emissive layer and a polyoxometalate as electron transport material give 12.5 lm W^?1 and 30.0 cd A^?1 power and luminous efficiency, respectively, which are among the best performance values observed to date for all‐solution processed blue PHOLEDs. The lacunary polyoxometalates exhibit unique properties such as low electron affinity and high ionization energy (of about 3.0 and 7.5 eV, respectively) which render them as efficient electron injection/hole blocking layers and, most importantly, exceptionally high electron mobility of up to 10^?2 cm² V^?1 s^?1.     

Triplet Harvesting in Hybrid White Organic Light‐Emitting Diodes

White organic light‐emitting diodes (OLEDs) are highly efficient large‐area light sources that may play an important role in solving the global energy crisis, while also opening novel design possibilities in general lighting applications. Usually, highly efficient white OLEDs are designed by combining three phosphorescent emitters for the colors blue, green, and red. However, this procedure is not ideal as it is difficult to find sufficiently stable blue phosphorescent emitters. Here, a novel approach to meet the demanding power efficiency and device stability requirements is discussed: a triplet harvesting concept for hybrid white OLED, which combines a blue fluorophor with red and green phosphors and is capable of reaching an internal quantum efficiency of 100% if a suitable blue emitter with high‐lying triplet transition is used is introduced. Additionally, this concept paves the way towards an extremely simple white OLED design, using only a single emitter layer.