Solution‐Processable,High‐Performance Flexible Electroluminescent Devices Based on High‐k Nanodielectrics

Flexible alternating‐current electroluminescent (ACEL) devices have attracted considerable attention for their ability to produce uniform light emission under bent conditions and have enormous potential for applications in back lighting panels, decorative lighting in automobiles, and panel displays. Nevertheless, flexible ACEL devices generally require a high operating bias, which precludes their implementation in low power devices. Herein, solution‐processed La‐doped barium titanate (BTO:La) nanocuboids (≈150 nm) are presented as high dielectric constant (high‐k) nanodielectrics, which can enhance the dielectric constant of an ACEL device from 2.6 to 21 (at 1 kHz), enabling the fabrication of high‐performance flexible ACEL devices with a lower operating voltage as well as higher brightness (≈57.54 cd m^?2 at 240 V, 1 kHz) than devices using undoped BTO nanodielectrics (≈14.3 cd m^?2 at 240 V, 1 kHz). Furthermore, a uniform brightness across the whole panel surface of the flexible ACEL devices and excellent device reliability are achieved via the use of uniform networks of crossaligned silver nanowires as highly conductive and flexible electrodes. The results offer experimental validation of high‐brightness flexible ACELs using solution‐processed BTO:La nanodielectrics, which constitutes an important milestone toward the implementation of high‐k nanodielectrics in flexible displays.     

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.     

Facile Photo‐Crosslinking of Azide‐Containing Hole‐Transporting Polymers for Highly Efficient,Solution‐Processed,Multilayer Organic Light Emitting Devices

A novel framework of azide containing photo‐crosslinkable, conducting copolymer, that is, poly(azido‐styrene)‐random‐poly(triphenylamine) (X‐PTPA), is reported as a hole‐transporting material for efficient solution‐processed, multi‐layer, organic light emitting diodes (OLEDs). A facile and energy‐efficient crosslinking process is demonstrated with UV irradiation (254 nm, 2 mW/cm²) at a short exposure time (5 min). By careful design of X‐PTPA, in which 5 mol% of the photo‐crosslinkable poly(azido‐styrene) is copolymerized with hole‐transporting poly(triphenylamine) (X‐PTPA‐5), the adverse effect of the crosslinking of azide moieties is prevented to maximize the performances of X‐PTPA‐5. Since the photo‐crosslinking chemistry of azide molecules does not involve any photo‐initiators, superior hole‐transporting ability is achieved, producing efficient devices. To evaluate the performances of X‐PTPA‐5 as a hole‐transporting/electron‐blocking layer, Ir(ppy)₃‐based, solution‐processable OLEDs are fabricated. The results show high EQE (11.8%), luminous efficiency (43.7 cd/A), and power efficiency (10.4 lm/W), which represent about twofold enhancement over the control device without X‐PTPA‐5 film. Furthermore, micro‐patterned OLEDs with the photo‐crosslinkable X‐PTPA‐5 can be fabricated through standard photolithography. The versatility of this approach is also demonstrated by introducing the same azide moiety into other hole‐transporting materials such as poly(carbazole) (X‐PBC).     

Solution‐Processable Ultrathin Black Phosphorus as an Effective Electron Transport Layer in Organic Photovoltaics

2D van der Waals crystals, possessing excellent electronic and physical properties, have been intriguing building blocks for organic optoelectronic devices. Most of the 2D materials are served as hole transport layers in organic devices. Here,it is reported that solution exfoliated few layers black phosphorus (BP) can be served as an effective electron transport layer (ETL) in organic photovoltaics (OPVs) for the first time. The power conversion efficiencies (PCEs) of the BP‐incorporated OPVs can be improved to 8.18% in average with the relative enhancement of 11%. The incorporation of BP flakes with the optimum thickness of ≈10 nm can form cascaded band structure in OPVs, which can facilitate electron transport and enhance the PCEs of the devices. This study opens an avenue in using solution exfoliated BP as a highly efficient ETL for organic optoelectronics.     

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.     

High‐Performance Inverted Polymer Solar Cells: Device Characterization,Optical Modeling,and Hole‐Transporting Modifications

Although high power conversion efficiencies (PCE) have already been demonstrated in conventional structure polymer solar cells (PSCs), the development of high performance inverted structure polymer solar cells is still lagging behind despite their demonstrated superior stability and feasibility for roll‐to‐roll processing. To address this challenge, a detailed study of solution‐processed, inverted‐structure PSCs based on the blends of a low bandgap polymer, poly(indacenodithiophene‐co‐phananthrene‐quinoxaline) (PIDT‐PhanQ) and [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) as the bulk heterojunction (BHJ) layer is carried out. Comprehensive characterization and optical modeling of the resulting devices is performed to understand the effect of device geometry on photovoltaic performance. Excellent device performance can be achieved by optimizing the optical field distribution and spatial profiles of excitons generation within the active layer in different device configurations. In the inverted structure, because the peak of the excitons generation is located farther away from the electron‐collecting electrode, a higher blending ratio of fullerene is required to provide higher electron mobility in the BHJ for achieving good device performance.     

The Mechanism of Charge Generation in Charge‐Generation Units Composed of p‐Doped Hole‐Transporting Layer/HATCN/n‐Doped Electron‐Transporting Layers

The rate‐limiting step of charge generation in charge‐generation units (CGUs) composed of a p‐doped hole‐transporting layer (p‐HTL), 1,4,5,8,9,11‐hexaazatriphenylene hexacarbonitrile (HATCN) and n‐doped electron‐transporting layer (n‐ETL), where 1,1‐bis‐(4‐bis(4‐methyl‐phenyl)‐amino‐phenyl)‐cyclohexane (TAPC) was used as the HTL is reported. Energy level alignment determined by the capacitance–voltage (C–V) measurements and the current density–voltage characteristics of the structure clearly show that the electron injection at the HATCN/n‐ETL junction limits the charge generation in the CGUs rather than charge generation itself at the p‐HTL/HATCN junction. Consequently, the CGUs with 30 mol% Rb₂CO₃‐doped 4,7‐diphenyl‐1,10‐phenanthroline (BPhen) formed with the HATCN layer generates charges very efficiently and the excess voltage required to generate the current density of ±10 mA cm^?2 is around 0.17 V, which is extremely small compared with the literature values reported to date.     

A New Carbazole‐Constructed Hyperbranched Polymer: Convenient One‐Pot Synthesis,Hole‐Transporting Ability,and Field‐Effect Transistor Properties

A new hyperbranched polymer ( HB‐car ), constructed fully by carbazole moieties, is successfully synthesized through a one‐pot Suzuki coupling reaction. The resultant polymer is well‐characterized, and its hole‐transporting ability is studied carefully. The device, in which HB‐car is utilized as a hole‐transporting layer and tris‐(8‐hydroxyquinoline) aluminum as an electron‐emitting layer as well as electron‐transporting layer, gives a much higher efficiency (3.05 cd A^–1), than that of a poly(N‐vinylcarbazole) based device (2.19 cd A^–1) under similar experimental conditions. The remarkable performance is attributed to its low energy barrier and enhanced hole‐drifting ability in the HB‐car based device. In addition, for the first time, a field‐effect transistor (FET) based on the hyperbranched polymer is fabricated, and the organic FET device shows that HB‐car is a typical p‐type FET material with a saturation mobility of 1 × 10^–5 cm² V^–1 s^–1, a threshold voltage of –47.1 V, and an on‐to‐off current ratio of 10³.     

Solution‐Processed Monolayer Organic Crystals for High‐Performance Field‐Effect Transistors and Ultrasensitive Gas Sensors

This work innovatively develops a dual solution‐shearing method utilizing the semiconductor concentration region close to the solubility limit, which successfully generates large‐area and high‐performance semiconductor monolayer crystals on the millimeter scale. The monolayer crystals with poly(methyl methacrylate) encapsulation show the highest mobility of 10.4 cm² V^?1 s^?1 among the mobility values in the reported solution‐processed semiconductor monolayers. With similar mobility to multilayer crystals, light is shed on the charge accumulation mechanism in organic field‐effect transistors (OFETs), where the first layer on interface bears the most carrier transport task, and the other above layers work as carrier suppliers and encapsulations to the first layer. The monolayer crystals show a very low dependency on channel directions with a small anisotropic ratio of 1.3. The positive mobility–temperature correlation reveals a thermally activated carrier transport mode in the monolayer crystals, which is different from the band‐like transport mode in multilayer crystals. Furthermore, because of the direct exposure of highly conductive channels, the monolayer crystal based OFETs can sense ammonia concentrations as low as 10 ppb. The decent sensitivity indicates the monolayer crystals are potential candidates for sensor applications.     

Solution‐Processed,Alkali Metal‐Salt‐Doped,Electron‐Transport Layers for High‐Performance Phosphorescent Organic Light‐Emitting Diodes

High‐performance, blue, phosphorescent organic light‐emitting diodes (PhOLEDs) are achieved by orthogonal solution‐processing of small‐molecule electron‐transport material doped with an alkali metal salt, including cesium carbonate (Cs₂CO₃) or lithium carbonate (Li₂CO₃). Blue PhOLEDs with solution‐processed 4,7‐diphenyl‐1,10‐phenanthroline (BPhen) electron‐transport layer (ETL) doped with Cs₂CO₃ show a luminous efficiency (LE) of 35.1 cd A^?1 with an external quantum efficiency (EQE) of 17.9%, which are two‐fold higher efficiency than a BPhen ETL without a dopant. These solution‐processed blue PhOLEDs are much superior compared to devices with vacuum‐deposited BPhen ETL/alkali metal salt cathode interfacial layer. Blue PhOLEDs with solution‐processed 1,3,5‐tris(m‐pyrid‐3‐yl‐phenyl)benzene (TmPyPB) ETL doped with Cs₂CO₃ have a luminous efficiency of 37.7 cd A^?1 with an EQE of 19.0%, which is the best performance observed to date in all‐solution‐processed blue PhOLEDs. The results show that a small‐molecule ETL doped with alkali metal salt can be realized by solution‐processing to enhance overall device performance. The solution‐processed metal salt‐doped ETLs exhibit a unique rough surface morphology that facilitates enhanced charge‐injection and transport in the devices. These results demonstrate that orthogonal solution‐processing of metal salt‐doped electron‐transport materials is a promising strategy for applications in various solution‐processed multilayered organic electronic devices.     

High‐Performance Red,Green, and Blue Electroluminescent Devices Based on Blue Emitters with Small Singlet–Triplet Splitting and Ambipolar Transport Property

Two coordination complex emitters as well as host materials Be(PPI)₂ and Zn(PPI)₂ (PPI = 2‐(1‐phenyl‐1H‐phenanthro[9,10‐d]imidazol‐2‐yl)phenol) are designed, synthesized, and characterized. The incorporation of the metal atom leads to a twisted conformation and rigid molecular structure, which improve the thermal stability of Be(PPI)₂ and Zn(PPI)₂ with high T_d and T_g at around 475 and 217 °C, respectively. The introduction of the electron‐donating phenol group results in the emission color shifting to the deep‐blue region and the emission maximum appears at around 429 nm. This molecular design strategy ensures that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) HOMO and LUMO of Be(PPI)₂ and Zn(PPI)₂ localize on the different moieties of the molecules. Therefore, the two complexes have an ambipolar transport property and a small singlet–triplet splitting of 0.35 eV for Be(PPI)₂ and 0.21 eV for Zn(PPI)₂. An undoped deep‐blue fluorescent organic light‐emitting device (OLED) that uses Be(PPI)₂ as emitter exhibits a maximum power efficiency of 2.5 lm W^?1 with the CIE coordinates of (0.15, 0.09), which are very close to the National Television Standards Committee (NTSC) blue standard (CIE: 0.14, 0.08). Green and red phosphorescent OLEDs (PhOLEDs) that use Be(PPI)₂ and Zn(PPI)₂ as host materials show high performance. Highest power efficiencies of 67.5 lm W^?1 for green PhOLEDs and 21.7 lm W^?1 for red PhOLEDs are achieved. In addition, the Be(PPI)₂‐based devices show low‐efficiency roll‐off behavior, which is attributed to the more balanced carrier‐transport property of Be(PPI)₂.     

Design,Synthesis, and Versatile Processing of Indolo[3,2‐b]indole‐Based π‐Conjugated Molecules for High‐Performance Organic Field‐Effect Transistors

A series of indolo[3,2‐b]indole (IDID) derivatives comprising the core unit of N,N‐dihexyl‐IDID with different aromatic and aliphatic substituents at 2‐ and 7‐position are designed and synthesized to construct high‐performance organic semiconductors by different processing routes. Structure‐property relationship of the derivatives is comprehensively studied in terms of their photophysical, electrochemical, structural, and electrical characteristics. IDID derivatives are either evaporated in vacuum or dissolved in common organic solvents to ensure applicalbility in different processing routes toward outstanding p‐type semiconductor films. Among others, the excellently soluble compound 4H4TIDID (with 2‐ and 7‐substituents of 5‐hexyl‐2,2′‐bithiophene moiety, solubility >20 wt% in chloroform), shows the highest field‐effect hole mobility of 0.97 cm² V^?1 s^?1 in a device constructed by vacuum‐deposition and 0.18 cm² V^?1 s^?1 in device cosntructed by spin‐coating, respectively. The 2D grazing incidence X‐ray diffraction of 4H4TIDID films in both devices identically show the 2D molecular orientation favorable for the high transistor mobility.     

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.