Organometal Halide Perovskite Quantum Dot Light‐Emitting Diodes

Organometal halide perovskites quantum dots (OHP‐QDs) with bright, color‐tunable, and narrow‐band photoluminescence have significant advantages in display, lighting, and laser applications. Due to sparse concentrations and difficulties in the enrichment of OHP‐QDs, production of large‐area uniform films of OHP‐QDs is a challenging task, which largely impedes their use in electroluminescence devices. Here, a simple dip‐coating method has been reported to effectively fabricate large‐area uniform films of OHP‐QDs. Using this technique, multicolor OHP‐QDs light‐emitting diodes (OQ‐LEDs) emitting in blue, blue‐green, green, orange, and red color have been successfully produced by simply tuning the halide composition or size of QDs. The blue, green, and red OQ‐LEDs exhibited, respectively, a maximum luminance of 2673, 2398, and 986 cd m^?2 at a current efficiency of 4.01, 3.72, and 1.52 cd A^?1, and an external quantum efficiency of 1.38%, 1.06%, and 0.53%, which are much better than most LEDs based on OHP films. The packaged OQ‐LEDs show long‐term stability in air (humidity ≈50%) for at least 7 d. The results demonstrate the great potential of the dip‐coating method to fabricate large‐area uniform films for various QDs. The high‐efficiency OQ‐LEDs also demonstrate the promising potential of OHP‐QDs for low‐cost display, lighting, and optical communication applications.     

Facile Assembly of High‐Quality Organic–Inorganic Hybrid Perovskite Quantum Dot Thin Films for Bright Light‐Emitting Diodes

Organic‐inorganic hybrid perovskite (CH₃NH₃PbX₃, X = Cl, Br or I) quantum dots (QDs) have shown superior optoelectronic properties and have been regarded as a most ideal material for next‐generation optoelectronic devices, particularly for QDs‐based light‐emitting diodes (QLEDs). However, there are only a few reports on CH₃NH₃PbX₃ QLEDs and the reported performance is still very poor, primarily due to the difficulties in the fabrication of high‐quality compact QDs thin films. In this work, an electric‐field‐assisted strategy is developed for efficient fabrication of uniform CH₃NH₃PbBr₃ QDs thin films with high photoluminescence quantum yields (PLQY, 80%–90%) from dilute CH₃NH₃PbBr₃ QDs suspensions (≈0.1 mg mL^‐1) within 5 mins. Benefited from the high‐quality CH₃NH₃PbBr₃ QDs thin films, the corresponding QLEDs deliver a highly bright green emission with maximum luminances of 12450 cd m². Furthermore, a current efficiency of 12.7 cd A^‐1, a power efficiency of 9.7 lm W^‐1, and an external quantum efficiency (EQE) of 3.2% were acheived by enhancing the hole injection. This performance represents the best results for CH₃NH₃PbBr₃ QDs‐based QLEDs reported to date. These results indicate an important progress in the fabrication of high‐performance CH₃NH₃PbX₃ QLEDs and demonstrate their huge potential for next‐generation displays and lighting.     

Suppressing Ion Migration Enables Stable Perovskite Light‐Emitting Diodes with All‐Inorganic Strategy

Stability issue is one of the major concerns that limit emergent perovskite light‐emitting diodes (PeLEDs) techniques. Generally, ion migration is considered as the most important origin of PeLEDs degradation. In this work, an all‐inorganic device architecture, LiF/perovskite/LiF/ZnS/ZnSe, is proposed to address this imperative problem. The inorganic (Cs_1?xRb_x)_1?yK_yPbBr₃ perovskite is optimized with achieving a photoluminescence quantum yield of 67%. Depth profile analysis of X‐ray photoelectron spectroscopy indicates that the LiF/perovskite/LiF structure and the ZnS/ZnSe cascade electron transport layers significantly suppress the electric‐field‐induced ion migrations of the perovskite layers, and impede the diffusion of metallic atoms from cathode into perovskites. The as‐prepared PeLEDs display excellent shelf stability (maintaining 90% of the initial external quantum efficiency [EQE] after 264 h) and operational stability (half‐lifetime of about 255 h at an initial luminance of 120 cd m^?2). The devices also exhibit a maximum brightness of 15 6155 cd m^?2 and an EQE of 11.05%.     

Polarized Optoelectronics of CsPbX3 (X = Cl,Br, I) Perovskite Nanoplates with Tunable Size and Thickness

Low dimensional semiconductor nanomaterials have shown their tailorable properties for a variety of promising applications in decades. Here a general strategy to synthesize all‐inorganic CsPbX₃ (X = Cl, Br, I or their mixture) perovskite 2D nanoplates by introducing additional metal halides MX'₂ or MX'₃ (M = Cu, Zn, Al or Pb, etc.; X' = Cl, Br or I) is reported. These CsPbX₃ perovskite nanoplates have uniform thickness and tunable size, which can be feasibly controlled by the component and ratio of the metal halides, temperature, time, and ligands. The well‐defined morphology of the nanoplates makes them ideal building blocks for the self‐assembly in the face‐to‐face and column‐by‐column arrangement. Compared to the optically isotropic CsPbX₃ nanocubes, the 2D CsPbX₃ nanoplates exhibit remarkable polarized UV–vis absorption and photoluminescence not only in liquid solvent and solid resin matrix, but also in self‐assembled films. An optoelectronic photodetector sensitive for linear polarized light is fabricated to demonstrate the proof‐of‐concept.     

Co‐Interlayer Engineering toward Efficient Green Quasi‐Two‐Dimensional Perovskite Light‐Emitting Diodes

With respect to three‐dimensional (3D) perovskites, quasi‐two‐dimensional (quasi‐2D) perovskites have unique advantages in light‐emitting devices (LEDs), such as strong exciton binding energy and good phase stability. Interlayer ligand engineering is a key issue to endow them with these properties. Rational design principles for interlayer materials and their processing techniques remain open to investigation. A co‐interlayer engineering strategy is developed to give efficient quasi‐2D perovskites by employing phenylbutylammonium bromide (PBABr) and propylammonium bromide (PABr) as the ligand materials. Preparation of these co‐interlayer quasi‐2D perovskite films is simple and highly controllable without using antisolvent treatment. Crystallization and morphology are readily manipulated by tuning the ratio of co‐interlayer components. Various optical techniques, including steady and ultrafast transient absorption and photoluminescence spectroscopies, are used to investigate their excitonic properties. Photoluminescence quantum yield (PLQY) of the perovskite film is dramatically improved to 89% due to the combined optimization of exciton binding energy and suppression of trap state formation. Accordingly, a high current efficiency of 66.1 cd A^?1 and an external quantum efficiency of 15.1% are achieved for green co‐interlayer quasi‐2D perovskite LEDs without using any light out‐coupling techniques, indicating that co‐interlayer engineering is a simple and effective approach to develop high‐performance perovskite electroluminescence devices.     

Layer‐by‐Layer All‐Inorganic Quantum‐Dot‐Based LEDs: A Simple Procedure with Robust Performance

A novel all‐inorganic electroluminescent device is demonstrated based on highly luminescent CdTe nanocrystals intercalated within a laminar hydrotalcite‐like structure. The laminar scaffold acts to both support and distribute the CdTe nanocrystals. The device is synthesized using simple wet chemical processes at room temperature in ambient conditions. It has high thermal stability, operating continuously up to 90 °C, and a maximum efficiency at J = 0.12 A cm^?2. The device is targeted at the automotive industry.     

Localized Surface Plasmon Enhanced All‐Inorganic Perovskite Quantum Dot Light‐Emitting Diodes Based on Coaxial Core/Shell Heterojunction Architecture

This work presents a strategy of combining the concepts of localized surface plasmons (LSPs) and core/shell nanostructure configuration in a single perovskite light‐emitting diode (PeLED) to addresses simultaneously the emission efficiency and stability issues facing current PeLEDs' challenges. Wide bandgap n‐ZnO nanowires and p‐NiO are employed as the carrier injectors, and also the bottom/upper protection layers to construct coaxial core/shell heterostructured CsPbBr₃ quantum dots LEDs. Through embedding plasmonic Au nanoparticles into the device and thickness optimization of the MgZnO spacer layer, an emission enhancement ratio of 1.55 is achieved. The best‐performing plasmonic PeLED reaches up a luminance of 10 206 cd m^?2, an external quantum efficiency of ≈4.626%, and a current efficiency of 8.736 cd A^?1. The underlying mechanisms for electroluminescence enhancement are associated with the increased spontaneous emission rate and improved internal quantum efficiency induced by exciton–LSP coupling. More importantly, the proposed PeLEDs, even without encapsulation, present a substantially improved operation stability against water and oxygen degradation (30‐day storage in air ambient, 85% humidity) compared with any previous reports. It is believed that the experimental results obtained will provide an effective strategy to enhance the performance of PeLEDs, which may push forward the application of such kind of LEDs.     

All‐Inorganic CsPbI3 Perovskite Phase‐Stabilized by Poly(ethylene oxide) for Red‐Light‐Emitting Diodes

Despite the excellent photoelectronic properties of the all‐inorganic cesium lead iodide (CsPbI₃) perovskite, which does not contain volatile and hygroscopic organic components, only a few CsPbI₃ devices are developed mainly owing to the frequent formation of an undesirable yellow δ‐phase at room temperature. Herein, it is demonstrated that a small quantity of poly(ethylene oxide) (PEO) added to the precursor solution effectively inhibits the formation of the yellow δ‐phase during film preparation, and promotes the development of a black α‐phase at a low crystallization temperature. A systematic study reveals that a thin, dense, pinhole‐free CsPbI₃ film is produced in the α‐phase and is stabilized with PEO that effectively reduces the grain size during crystallization. A thin α‐phase CsPbI₃ film with excellent photoluminescence is successfully employed in a light‐emitting diode with an inverted configuration of glass substrate/indium tin oxide/zinc oxide/poly(ethyleneimine)/α‐CsPbI₃/poly(4‐butylphenyl‐diphenyl‐amine)/WO₃/Al, yielding the characteristic red emission of the perovskite film at 695 nm with brightness, external quantum efficiency, and emission band width of ≈101 cd m^?2, 1.12%, and 32 nm, respectively.     

Resonant‐Enhanced Full‐Color Emission of Quantum‐Dot‐Based Display Technology Using a Pulsed Spray Method

Colloidal quantum‐dot light‐emitting diodes (QDLEDs) with the HfO₂/SiO₂‐distributed Bragg reflector (DBR) structure are fabricated using a pulsed spray coating method. Pixelated RGB arrays, 2‐in. wafer‐scale white light emission, and an integrated small footprint white light device are demonstrated. The experimental results show that the intensity of red, green, and blue (RGB) emission exhibited considerable enhancement because of the high reflectivity in the UV region by the DBR structure, which subsequently increases the use in the UV optical pumping of RGB QDs. A pulsed spray coating method is crucial in providing uniform RGB layers, and the polydimethylsiloxane (PDMS) film is used as the interface layer between each RGB color to avoid cross‐contamination and self‐assembly of QDs. Furthermore, the chromaticity coordinates of QDLEDs with the DBR structure remain constant under various pumping powers in the large area sample, whereas a larger shift toward high color temperatures is observed in the integrated device. The resulting color gamut of the proposed QDLEDs covers an area 1.2 times larger than that of the NTSC standard, which is favorable for the next generation of high‐quality display technology.     

Low Roll‐Off Perovskite Quantum Dot Light‐Emitting Diodes Achieved by Augmenting Hole Mobility

The external quantum efficiencies (EQEs) of perovskite quantum dot light‐emitting diodes (QD‐LEDs) are close to the out‐coupling efficiency limitation. However, these high‐performance QD‐LEDs still suffer from a serious issue of efficiency roll‐off at high current density. More injected carriers produce photons less efficiently, strongly suggesting the variation of ratio between radiative and non‐radiative recombination. An approach is proposed to balance the carrier distribution and achieve high EQE at high current density. The average interdot distance between QDs is reduced and this facilitates carrier transport in QD films and thus electrons and holes have a balanced distribution in QD layers. Such encouraging results augment the proportion of radiative recombination, make devices with peak EQE of 12.7%, and present a great device performance at high current density with an EQE roll‐off of 11% at 500 mA cm^?2 (the lowest roll‐off known so far) where the EQE is still over 11%.     

High‐Temperature Photoluminescence of CsPbX3 (X = Cl,Br, I) Nanocrystals

Recent synthetic developments have generated intense interest in the use of cesium lead halide perovskite nanocrystals for light‐emitting applications. This work presents the photoluminescence (PL) of cesium lead halide perovskite nanocrystals with tunable halide composition recorded as function of temperature from 80 to 550 K. CsPbBr₃ nanocrystals show the highest resilience to temperature while chloride‐containing samples show relatively poorer preservation of photoluminescence at elevated temperatures. Thermal cycling experiments show that PL loss of CsPbBr₃ is largely reversible at temperatures below 450 K, but shows irreversible degradation at higher temperatures. Time‐resolved measurements of CsPbX₃ samples show an increase in the PL lifetime with temperature elevation, consistent with exciton fission to form free carriers, followed by a decrease in the apparent PL lifetime due to trapping. PL persistence measurements and time‐resolved spectroscopies implicate thermally assisted trapping, most likely to halogen vacancy traps, as the mechanism of reversible PL loss.     

All‐Inorganic Perovskite Nanocrystals for High‐Efficiency Light Emitting Diodes: Dual‐Phase CsPbBr3‐CsPb2Br5 Composites

A dual‐phase all‐inorganic composite CsPbBr₃‐CsPb₂Br₅ is developed and applied as the emitting layer in LEDs, which exhibited a maximum luminance of 3853 cd m^–2, with current density (CE) of ≈8.98 cd A^–1 and external quantum efficiency (EQE) of ≈2.21%, respectively. The parasite of secondary phase CsPb₂Br₅ nanoparticles on the cubic CsPbBr₃ nanocrystals could enhance the current efficiency by reducing diffusion length of excitons on one side, and decrease the trap density in the band gap on the other side. In addition, the introduction of CsPb₂Br₅ nanoparticles could increase the ionic conductivity by reducing the barrier against the electronic and ionic transport, and improve emission lifetime by decreasing nonradiative energy transfer to the trap states via controlling the trap density. The dual‐phase all‐inorganic CsPbBr₃‐CsPb₂Br₅ composite nanocrystals present a new route of perovskite material for advanced light emission applications.     

Improved Performance and Stability of All‐Inorganic Perovskite Light‐Emitting Diodes by Antisolvent Vapor Treatment

All‐inorganic perovskite light‐emitting diodes (LEDs) reveal efficient luminescence with high color purity, but their modest brightness and poor stability are still critical drawbacks. Here, the luminescent efficiency and the stability of perovskite LEDs (PeLEDs) are boosted by antisolvent vapor treatment of CsPbBr₃ embedded in a dielectric polymer matrix of polyethylene oxide (PEO). A unique method is developed to obtain high quality CsPbBr₃ emitting layers with low defects by controlling their grain sizes. CsPbBr₃ in PEO matrix is post‐treated with antisolvent of chloroform (CF), leading to microcrystals with a size of ≈5 µm along the in‐plane direction with active emitting composite of 90%. A device based on CF post‐treatment (CsPbBr₃‐PEO‐CF) film displays a brightness of up to 51890 cd m^?2 with an external quantum efficiency of 4.76%. CsPbBr₃‐PEO‐CF PeLED still maintains 82% of its initial efficiency after 80 h continuous operation in ambient air, which indicates relatively good device stability. This work highlights that film quality is not only key to promoting fluorescence in CsPbBr₃, but also to achieving higher performance PeLEDs.     

Highly Efficient,Bright, and Stable Colloidal Quantum Dot Short‐Wave Infrared Light‐Emitting Diodes

Unbalanced charge injection is deleterious for the performance of colloidal quantum dot (CQD) light‐emitting diodes (LEDs) as it deteriorates the quantum efficiency, brightness, and operational lifetime. CQD LEDs emitting in the infrared have previously achieved high quantum efficiencies but only when driven to emit in the low‐radiance regime. At higher radiance levels, required for practical applications, the efficiency decreased dramatically in view of the notorious efficiency droop. Here, a novel methodology is reported to regulate charge supply in multinary bandgap CQD composites that facilitates improved charge balance. The current approach is based on engineering the energetic potential landscape at the supra‐nanocrystalline level that has allowed to report short‐wave infrared PbS CQD LEDs with record‐high external quantum efficiency in excess of 8%, most importantly, at a radiance level of ≈5 W sr^?1 m², an order of magnitude higher than prior reports. Furthermore, the balanced charge injection and Auger recombination reduction has led to unprecedentedly high operational stability with radiance half‐life of 26 068 h at a radiance of 1 W sr^?1 m^?2.     

Core/Shell Perovskite Nanocrystals: Synthesis of Highly Efficient and Environmentally Stable FAPbBr3/CsPbBr3 for LED Applications

Lead halide perovskite nanocrystals (PeNCs) are promising materials for applications in optoelectronics. However, their environmental instability remains to be addressed to enable their advancement into industry. Here the development of a novel synthesis method is reported for monodispersed PeNCs coated with all inorganic shell of cesium lead bromide (CsPbBr₃) grown epitaxially on the surface of formamidinium lead bromide (FAPbBr₃) NCs. The formed FAPbBr₃/CsPbBr₃ NCs have photoluminescence in the visible range 460–560 nm with narrow emission linewidth (20 nm) and high optical quantum yield, photoluminescence quantum yield (PLQY) up to 93%. The core/shell perovskites have enhanced optical stability under ambient conditions (70 d) and under ultraviolet radiation (50 h). The enhanced properties are attributed to overgrowth of FAPbBr₃ with all‐inorganic CsPbBr₃ shell, which acts as a protective layer and enables effective passivation of the surface defects. The use of these green‐emitting core/shell FAPbBr₃/CsPbBr₃ NCs is demonstrated in light‐emitting diodes (LEDs) and significant enhancement of their performance is achieved compared to core only FAPbBr₃‐LEDs. The maximum current efficiency observed in core/shell NC LED is 19.75 cd A^‐1 and the external quantum efficiency of 8.1%, which are approximately four times and approximately eight times higher, respectively, compared to core‐only devices.     

Unprecedented Homoleptic Bis‐Tridentate Iridium(III) Phosphors: Facile,Scaled‐Up Production,and Superior Chemical Stability

Bis‐tridentate Ir(III) metal complexes are expected to show great potential in organic light‐emitting diode (OLED) applications due to the anticipated, superb chemical and photochemical stability. Unfortunately, their exploitation has long been hampered by lack of adequate methodology and with inferior synthetic yields. This hurdle can be overcome by design of the first homoleptic, bis‐tridentate Ir(III) complex [Ir(pzpyph)(pz^Hpyph)] ( 1 ), for which the abbreviation (pzpyph)H (or pz^Hpyph) stands for the parent 2‐pyrazolyl‐6‐phenyl pyridine chelate. After that, methylation and double methylation of 1 afford the charge‐neutral Ir(III) complex [Ir(pzpyph)(pz^Mepyph)] ( 2 ) and cationic complex [Ir(pz^Mepyph)₂][PF₆] ( 3 ), while deprotonation of 1 gives formation of anionic [Ir(pzpyph)₂][NBu₄] ( 4 ), all in high yields. These bis‐tridentate Ir(III) complexes 2 – 4 are highly emitted in solution and solid states, while the charge‐neutral 2 and corresponding t ‐butyl substituted derivative [Ir(pzpy^Buph)(pz^Mepy^Buph)] ( 5 ) exhibit superior photostability versus the tris‐bidentate references [Ir(ppy)₂(acac)] and [Ir(ppy)₃] in toluene under argon, making them ideal OLED emitters. For the track record, phosphor 5 gives very small efficiency roll‐off and excellent overall efficiencies of 20.7%, 66.8 cd A^?1, and 52.8 lm W^?1 at high brightness of 1000 cd m^?2. These results are expected to inspire further studies on the bis‐tridentate Ir(III) complexes, which are judged to be more stable than their tris‐bidentate counterparts from the entropic point of view.     

Solvent‐Polarity‐Engineered Controllable Synthesis of Highly Fluorescent Cesium Lead Halide Perovskite Quantum Dots and Their Use in White Light‐Emitting Diodes

Cesium lead halide quantum dots (QDs) have tunable photoluminescence that is capable of covering the entire visible spectrum and have high quantum yields, which make them a new fluorescent materials for various applications. Here, the synthesis of CsPbX₃ (X = Cl, Br, I, or mixed Cl/Br and Br/I) QDs by direct ion reactions in ether solvents is reported, and for the first time the synergetic effects of solvent polarity and reaction temperature on the nucleation and growth of QDs are demonstrated. The use of solvent with a low polarity enables controlled growth of QDs, which facilitates the synthesis of high‐quality CsPbX₃ QDs with broadly tunable luminescence, narrow emission width, and high quantum yield. A QD white LED (WLED) is demonstrated by coating the highly fluorescent green‐emissive CsPbBr₃ QDs together with red phosphors on a blue InGaN chip, which presents excellent warm white light emission with a high rendering index of 93.2 and color temperature of 5447 K, suggesting the potential applications of highly fluorescent cesium lead halide perovskite QDs as an alternative color converter in the fabrication of WLEDs.