Ultra-bright alternating current organic electroluminescence

We report on an alternating current (AC) field induced organic electroluminescence (EL) device with internal charge carrier generation and recombination luminance of over 5000 cd m^?2 under AC drive without charge carrier injection from external electrodes. The ultra-bright AC-EL is attributed to an optical optimization performed on the devices via numerical optical simulations based on an optical thin film model as well as an increase in the number of charge carriers achieved via the concept of molecular doping within the device. The luminance levels achieved are highest reported so far in literature for AC organic light emitting devices.     

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.     

Solution Processable Fluorenyl Hexa‐peri‐hexabenzocoronenes in Organic Field‐Effect Transistors and Solar Cells

The organization of organic semiconductor molecules in the active layer of organic electronic devices has important consequences to overall device performance. This is due to the fact that molecular organization directly affects charge carrier mobility of the material. Organic field‐effect transistor (OFET) performance is driven by high charge carrier mobility while bulk heterojunction (BHJ) solar cells require balanced hole and electron transport. By investigating the properties and device performance of three structural variations of the fluorenyl hexa‐peri‐hexabenzocoronene (FHBC) material, the importance of molecular organization to device performance was highlighted. It is clear from ¹H NMR and 2D wide‐angle X‐ray scattering (2D WAXS) experiments that the sterically demanding 9,9‐dioctylfluorene groups are preventing π–π intermolecular contact in the hexakis‐substituted FHBC 4 . For bis‐substituted FHBC compounds 5 and 6 , π–π intermolecular contact was observed in solution and hexagonal columnar ordering was observed in solid state. Furthermore, in atomic force microscopy (AFM) experiments, nanoscale phase separation was observed in thin films of FHBC and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC₆₁BM) blends. The differences in molecular and bulk structural features were found to correlate with OFET and BHJ solar cell performance. Poor OFET and BHJ solar cells devices were obtained for FHBC compound 4 while compounds 5 and 6 gave excellent devices. In particular, the field‐effect mobility of FHBC 6 , deposited by spin‐casting, reached 2.8 × 10^?3 cm² V^?1 s and a power conversion efficiency of 1.5% was recorded for the BHJ solar cell containing FHBC 6 and PC₆₁BM.     

Non‐Volatile Polymer Electroluminescence Programmable with Ferroelectric Field‐Induced Charge Injection Gate

Electroluminescence (EL) of organic and polymeric fluorescent materials programmable in the luminance is extremely useful as a non‐volatile EL memory with the great potential in the variety of emerging information storage applications for imaging and motion sensors. In this work, a novel non‐volatile EL memory in which arbitrarily chosen EL states are programmed and erased repetitively with long EL retention is demonstrated. The memory is based on utilizing the built‐in electric field arising from the remnant polarization of a ferroelectric polymer which in turn controls the carrier injection of an EL device. A device with vertically stacked components of a transparent bottom electrode/a ferroelectric polymer/a hole injection layer/a light emitting layer/a top electrode successfully emits light upon alternating current (AC) operation. Interestingly, the device exhibits two distinctive non‐volatile EL intensities at constant reading AC voltage, depending upon the programmed direct current (DC) voltage on the ferroelectric layer. DC programmed and AC read EL memories are also realized with different EL colors of red, green and blue. Furthermore, more than four distinguishable EL states are precisely addressed upon the programmed voltage input each of which shows excellent EL retention and multiple cycle endurance of more than 10⁵ s and 10² cycles, respectively.     

Layered,Nanonetwork Composite Cathodes for Flexible,High‐Efficiency,Organic Light Emitting Devices

In this work, the application of an aluminum (Al)/multiwall carbon nanotube (MWCNT)/Al, multilayered electrode to flexible, high‐efficiency, alternating current driven organic electroluminescent devices (AC‐OEL), is reported. The electrode is fabricated by sandwiching a spray‐cast nanonetwork film of MWCNTs between two evaporated layers of Al. The resulting composite film facilitates a uniform charge distribution across a robust crack‐free electrode under various bending angles. It is demonstrated that these composite electrodes stabilize the power efficiency of flexible devices for bending angles up to 120°, with AC‐OEL device power efficiencies of ≈22 lm W^?1 at luminances of ≈4000 cd m^?2 (using no output coupling). Microscopic examination of the Al/MWCNTs/Al electrode after bending of up to 1300 cycles suggests that the nanotubes significantly enhance the mechanical properties of the thin Al layers while providing a moderate modification to the work function of the metal. While the realization of robust, high‐brightness, and high‐efficiency AC‐OEL devices is potentially important in their future lighting applications, it is anticipated that this to also have significant impact in standard organic light emitting diodes lighting applications.     

Highly Efficient Greenish‐Yellow Phosphorescent Organic Light‐Emitting Diodes Based on Interzone Exciton Transfer

Phosphorescent organic light emitting diodes (PHOLEDs) have undergone tremendous growth over the past two decades. Indeed, they are already prevalent in the form of mobile displays, and are expected to be used in large‐area flat panels recently. To become a viable technology for next generation solid‐state light source however, PHOLEDs face the challenge of achieving concurrently a high color rendering index (CRI) and a high efficiency at high luminance. To improve the CRI of a standard three color white PHOLED, one can use a greenish‐yellow emitter to replace the green emitter such that the gap in emission wavelength between standard green and red emitters is eliminated. However, there are relatively few studies on greenish‐yellow emitters for PHOLEDs, and as a result, the performance of greenish‐yellow PHOLEDs is significantly inferior to those emitting in the three primary colors, which are driven strongly by the display industry. Herein, a newly synthesized greenish‐yellow emitter is synthesized and a novel device concept is introduced featuring interzone exciton transfer to considerably enhance the device efficiency. In particular, high external quantum efficiencies (current efficiencies) of 21.5% (77.4 cd/A) and 20.2% (72.8 cd/A) at a luminance of 1000 cd/m² and 5000 cd/m², respectively, have been achieved. These efficiencies are the highest reported to date for greenish‐yellow emitting PHOLEDs. A model for this unique design is also proposed. This design could potentially be applied to enhance the efficiency of even longer wavelength yellow and red emitters, thereby paving the way for a new avenue of tandem white PHOLEDs for solid‐state lighting.     

Inkjet‐Printed Organic Electrodes for Bottom‐Contact Organic Field‐Effect Transistors

A graphite thin film was investigated as the drain and source electrodes for bottom‐contact organic field‐effect transistors (BC OFETs). Highly conducting electrodes (10² S cm^?1) at room temperature were obtained from pyrolyzed poly(l,3,4‐oxadiazole) (PPOD) thin films that were prepatterned with a low‐cost inkjet printing method. Compared to the devices with traditional Au electrodes, the BC OFETs showed rather high performances when using these source/drain electrodes without any further modification. Being based on a graphite‐like material these electrodes possess excellent compatibility and proper energy matching with both p‐ and n‐type organic semiconductors, which results in an improved electrode/organic‐layer contact and homogeneous morphology of the organic semiconductors in the conducting channel, and finally a significant reduction of the contact resistance and enhancement of the charge‐carrier mobility of the devices is displayed. This work demonstrates that with the advantages of low‐cost, high‐performance, and printability, PPOD could serve as an excellent electrode material for BC OFETs.     

The role of local potential minima on charge transport in thin organic semiconductor layers

We have performed a systematic study of dependence of time-resolved photocurrent on the point of charge excitation within the organic semiconductor channel formed by two coplanar metal electrodes. The results confirm that spatial variation of electric field between the electrodes crucially determines transport of photogenerated charge carriers through the organic layer. Time-of-flight measurements of photocurrent demonstrate that the transit time of photogenerated charge carrier packets drifting between the two electrodes decreases with increasing travelling distance. Such counterintuitive result cannot be reconciled with the spatial distribution of electric field between coplanar electrodes, alone. It is also in contrast to expected role of space-charge screening of external electric field. Supported by Monte Carlo simulations of hopping transport in disordered organic semiconductor layer, we submit that the space-charge screens the external electric field and captures slower charge carriers from the photogenerated charge carrier packet. The remaining faster carriers, exhibit velocity distribution with significantly higher mean value and shorter transit time.     

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.     

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.     

Solution‐Processed Highly Efficient Alternating Current‐Driven Field‐Induced Polymer Electroluminescent Devices Employing High‐k Relaxor Ferroelectric Polymer Dielectric

Organic thin‐film electroluminescent (EL) devices, such as organic light‐emitting diodes (OLEDs), typically operate using constant voltage or direct current (DC) power sources. Such approaches require power converters (introducing power losses) and make devices sensitive to dimensional variations that lead to run away currents at imperfections. Devices driven by time‐dependent voltages or alternating current (AC) may offer an alternative to standard OLED technologies. However, very little is known about how this might translate into overall performance of such devices. Here, a solution‐processed route to creating highly efficient AC field‐induced polymer EL (FIPEL) devices is demonstrated. Such solution‐processed FIPEL devices show maximum luminance, current efficiency, and power efficiency of 3000 cd m^?2, 15.8 cd A^?1, and 3.1 lm W^?1 for blue emission, 13 800 cd m^?2, 76.4 cd A^?1, and 17.1 lm W^?1 for green emission, and 1600 cd m^?2, 8.8 cd A^?1, and 1.8 lm W^?1 for orange‐red emission. The high luminance and efficiency, and solution process pave the way to industrial roll‐to‐roll manufacturing of solid state lighting and display.     

Efficient Light‐Emitting Devices Based on Phosphorescent Polyhedral Oligomeric Silsesquioxane Materials

Synthesis, photophysical, and electrochemical characterizations of iridium‐complex anchored polyhedral oligomeric silsesquioxane (POSS) macromolecules are reported. Monochromatic organic light‐emitting devices based on these phosphorescent POSS materials show peak external quantum efficiencies in the range of 5–9%, which can be driven at a voltage less than 10 V for a luminance of 1000 cd m^?2. The white‐emitting devices with POSS emitters show an external quantum efficiency of 8%, a power efficiency of 8.1 lm W^?1, and Commission International de'lÉclairage coordinates of (0.36, 0.39) at 1000 cd m^?2. Encouraging efficiency is achieved in the devices based on hole‐transporting and Ir‐complex moieties dual‐functionalized POSS materials without using host materials, demonstrating that triplet‐dye and carrier‐transporting moieties functionalized POSS material is a viable approach for the development of solution‐processable electrophosphorescent devices.     

Charge‐Carrier Balance and Color Purity in Polyfluorene Polymer Blends for Blue Light‐Emitting Diodes

A study of an efficient blue light‐emitting diode based on a fluorescent aryl polyfluorene (aryl‐F8) homopolymer in an inverted device architecture is presented, with ZnO and MoO₃ as electron‐ and hole‐injecting electrodes, respectively. Charge‐carrier balance and color purity in these structures are achieved by incorporating poly(9,9‐dioctylfluorene‐co‐N‐(4‐butylphenyl)‐diphenylamine (TFB) into aryl‐F8. TFB is known to be a hole‐transporting material but it is found to act as a hole trap on mixing with aryl‐F8. Luminance efficiency of ≈6 cd A^?1 and external quantum efficiency (EQE) of 3.1% are obtained by adding a small amount (0.5% by weight) of TFB into aryl‐F8. Study of charge injection and transport in the single‐carrier devices shows that the addition of a small fraction of hole traps is necessary for charge‐carrier balance. Optical studies using UV–vis and fluorescence spectroscopic measurements, photoluminescence quantum yield, and fluorescence decay time measurements indicate that TFB does not affect the optical properties of the aryl‐F8, which is the emitting material in these devices. Luminance efficiency of up to ≈11 cd A^?1 and EQE values of 5.7% are achieved in these structures with the aid of improved out‐coupling using index‐matched hemispheres.     

Unraveling Doping Capability of Conjugated Polymers for Strategic Manipulation of Electric Dipole Layer toward Efficient Charge Collection in Perovskite Solar Cells

Developing electrical organic conductors is challenging because of the difficulties involved in generating free charge carriers through chemical doping. To devise a novel doping platform, the doping capabilities of four designed conjugated polymers (CPs) are quantitatively characterized using an AC Hall‐effect device. The resulting carrier density is related to the degree of electronic coupling between the CP repeating unit and 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4‐TCNQ), and doped PIDF‐BT provides an outstanding electrical conductivity, exceeding 210 S cm^?1, mainly due to the doping‐assisted facile carrier generation and relatively fast carrier mobility. In addition, it is noted that a slight increment in the electron‐withdrawing ability of the repeating unit in each CP diminishes electronic coupling with F4‐TCNQ, and severely deteriorates the doping efficiency including the alteration of operating doping mechanism for the CPs. Furthermore, when PIDF‐BT with high doping capability is applied to the hole transporting layer, with F4‐TCNQ as the interfacial doping layer at the interface with perovskite, the power conversion efficiency of the perovskite solar cell improves significantly, from 17.4% to over 20%, owing to the ameliorated charge‐collection efficiency. X‐ray photoelectron spectroscopy and Kelvin probe analyses verify that the improved solar cell performance originates from the increase in the built‐in potential because of the generation of electric dipole layer.     

Light‐Emitting Field‐Effect Transistors Consisting of Bilayer‐Crystal Organic Semiconductors

A novel device structure for organic light‐emitting field‐effect transistors has been developed. The devices comprise bilayer‐crystal organic semiconductors of a p‐type and an n‐type. The pn‐junction can readily be formed by successively laminating two crystals on top of a gate insulator. This structure enables the efficient injection and transport of electrons and holes, leading to their effective recombination. As a result, bright emissions are attained. The devices are operated by AC gate voltages. Gate‐voltage phase‐resolved drain‐current and emission‐intensity measurements enable us to study the relationship between the emissions and carrier transport. The maximum external quantum efficiency reaches 0.045%.     

Integration of a Rib Waveguide Distributed Feedback Structure into a Light‐Emitting Polymer Field‐Effect Transistor

Ambipolar light‐emitting organic field‐effect transistors (LEFETs) possess the ability to efficiently emit light due to charge recombination in the channel. Since the emission can be made to occur far from the metal electrodes, the LEFET structure has been proposed as a potential architecture for electrically pumped organic lasers. Here, a rib waveguide distributed feedback structure consisting of tantalum pentoxide (Ta₂O₅) integrated within the channel of a top gate/bottom contact LEFET based on poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) (F8BT) is demonstrated. The emitted light is coupled efficiently into the resonant mode of the DFB waveguide when the recombination zone of the LEFET is placed directly above the waveguide ridge. This architecture provides strong mode confinement in two dimensions. Mode simulations are used to optimize the dielectric thickness and gate electrode material. It is shown that electrode absorption losses within the device can be eliminated and that the lasing threshold for optical pumping of the LEFET structure with all electrodes (4.5 µJ cm^?2) is as low as that of reference devices without electrodes. These results enable quantitative judgement of the prospects for realizing an electrically pumped organic laser based on ambipolar LEFETs. The proposed device provides a powerful, low‐loss architecture for integrating high‐performance ambipolar organic semiconductor materials into electrically pumped lasing structures.     

An Electrical Switch‐Driven Flexible Electromagnetic Absorber

The development of a thin, tunable, and high‐performance flexible electromagnetic (EM) absorbing device that aims to solve signal interference or EM pollution is highly desirable but remains a great challenge. Herein, demonstrated is a flexible electrical‐driven device constructed by an insulated organic‐polymer substrate, carrier transmission layer, and core–shell structured absorber, enabling a narrow and tunable effective absorption region (f_E < 2.0 GHz) by controlling the external voltage toward this challenge. As a key design element, the selected absorber consists of an Sn/SnS/SnO₂ core and C shell, which exhibits an exceptional dielectric‐response ability at a small voltage, which is attributed to desirable carrier mobility and excitable carriers. Multiple f_E‐tuning regions (maximum up to 7.0), covering 90% of C‐band can be achieved for Sn/SnS/SnO₂@C‐based flexible device by selecting a low voltage (2–12 V). The strategy developed here may open a new avenue toward the design of flexible intelligent EM device for practical applications.     

Solution‐Processible Red Iridium Dendrimers based on Oligocarbazole Host Dendrons: Synthesis,Properties, and their Applications in Organic Light‐Emitting Diodes

A series of novel red‐emitting iridium dendrimers functionalized with oligocarbazole host dendrons up to the third generation ( red‐G3 ) have been synthesized by a convergent method, and their photophysical, electrochemical, and electroluminescent properties have been investigated. In addition to controlling the intermolecular interactions, oligocarbazole‐based dendrons could also participate in the electrochemical and charge‐transporting process. As a result, highly efficient electrophosphorescent devices can be fabricated by spin‐coating from chlorobenzene solution in different device configurations. The maximum external quantum efficiency (EQE) based on the non‐doped device configuration increases monotonically with increasing dendron generation. An EQE as high as 6.3% was obtained as for the third generation dendrimer red‐G3 , which is about 30 times higher than that of the prototype red‐G0 . Further optimization of the device configuration gave an EQE of 11.8% (13.0 cd A^?1, 7.2 lm W^?1) at 100 cd m^?2 with CIE coordinates of (0.65, 0.35). The state‐of‐the‐art performance indicated the potential of these oligocarbazole‐based red iridium dendrimers as solution processible emissive materials for organic light‐emitting diode applications.     

Exciton and Polaron Quenching in Doping‐Free Phosphorescent Organic Light‐Emitting Diodes from a Pt(II)‐Based Fast Phosphor

By introducing a neat Pt(II)‐based phosphor with a remarkably short decay lifetime, a simplified doping‐free phosphorescent organic light‐emitting diode (OLED) with a forward viewing external quantum efficiency (EQE) and power efficiency of 20.3 ± 0.5% and 63.0 ± 0.4 lm W^?1, respectively, is demonstrated. A quantitative analysis of how triplet‐triplet annihilation (TTA) and triplet‐polaron annihilation (TPA) affect the device EQE roll‐off at high current densities is performed. The contributions from loss of charge balance associated with charge leakage and field‐induced exciton dissociation are found negligible. The rate constants k_TTA and k_TPA are determined by time‐resolved photoluminescence experiments of a thin film and an electrically‐driven unipolar device, respectively. Using the parameters extracted experimentally, the EQE is modeled versus electric current characteristics of the OLEDs by taking both TTA and TPA into account. Based on this model, the impacts of the emitter lifetime, quenching rate constants, and exciton formation zone upon device efficiency are analyzed. It is found that the short lifetime of the neat emitter is key for the reduction of triplet quenching.     

Tetradentate Platinum Complexes for Efficient and Stable Excimer‐Based White OLEDs

A series of tetradentate platinum complexes that exhibit both efficient monomer and excimer emission are synthesized. Via small modifications to the cyclometalating ligands, both the monomer and excimer emission energy can be separately tuned. Devices employing all of the developed emitters demonstrate impressively high external quantum efficiencies (EQEs) within the range of 22% to 27% for concentrations between 2% and 16%. The halogen‐free design of the complexes also enables the fabrication of single, doped, white organic light‐emitting diodes (OLEDs) with long operational lifetimes. A balanced white device employing the complex Pt2O2, achieves a device operational lifetime to 80% of the initial luminance estimated at over 200 h at 1000 cd m^–2, while also achieving 12.5% peak EQE for a warm white light with a color rendering index of 80. Furthermore, a highly doped device exhibiting nearly exclusive excimer emission showed an impressive operational lifetime, which is estimated at more than 400 h for 1000 cd m^‐2.