Controlling Interfacial Amidation Reaction Rate to Regulate Crystal Growth toward High-Performance FAPbBr3-Based Inverted Light-Emitting Diodes.

Controlling interfacial reactions is critical for zinc oxide (ZnO)-based inverted perovskite light-emitting diodes (PeLEDs), boosting the external quantum efficiency (EQE) of the near-infrared device to above 20%. However, violent interfacial reactions between the bromine-based perovskites and ZnO-based films severely limit the performance of inverted green PeLEDs, whose efficiency and stability lag far behind those of their near-infrared counterparts. Here, a controllable interfacial amidation between the bromine-based perovskites and magnesium-doped ZnO (ZnMgO) film utilizing caprylyl sulfobetaine (SFB) is realized. The SFB molecules strongly interact with formamidinium bromide, decelerating the amidation reaction between formamidinium and carboxylate groups on the ZnMgO film, thus regulating the crystallization of FAPbBr3. Combined with the passivation of benzylamine, a FAPbBr3 bulk film directly deposited on a ZnMgO substrate with single-crystal characteristics is obtained, exhibiting a high photoluminescence quantum yield of above 80%. The resultant PeLEDs demonstrate a peak EQE of exceeding 20% at a high luminance of 120,000 cd m-2 and a half lifetime of 26 min at 11,000 cd m-2, representing the state-of-the-art inverted green electroluminescence. This work resolves the crucial issues of violent interfacial reactions and provides a strategy toward inverted green PeLEDs with outstanding performance.

High-Performance All-Inorganic Architecture Perovskite Light-Emitting Diodes Based on Tens-of-Nanometers-Sized CsPbBr3 Emitters in a Carrier-Confined Heterostructure.

Developing green perovskite light-emitting diodes (PeLEDs) with a high external quantum efficiency (EQE) and low efficiency roll-off at high brightness remains a critical challenge. Nanostructured emitter-based devices have shown high efficiency but restricted ascending luminance at high current densities, while devices based on large-sized crystals exhibit low efficiency roll-off but face great challenges to high efficiency. Herein, we develop an all-inorganic device architecture combined with utilizing tens-of-nanometers-sized CsPbBr3 (TNS-CsPbBr3) emitters in a carrier-confined heterostructure to realize green PeLEDs that exhibit high EQEs and low efficiency roll-off. A typical type-I heterojunction containing TNS-CsPbBr3 crystals and wide-bandgap Cs4PbBr6 within a grain is formed by carefully controlling the precursor ratio. These heterostructured TNS-CsPbBr3 emitters simultaneously enhance carrier confinement and retain low Auger recombination under a large injected carrier density. Benefiting from a simple device architecture consisting of an emissive layer and an oxide electron-transporting layer, the PeLEDs exhibit a sub-bandgap turn-on voltage of 2.0 V and steeply rising luminance. In consequence, we achieved green PeLEDs demonstrating a peak EQE of 17.0% at the brightness of 36,000 cd m-2, and the EQE remained at 15.7% and 12.6% at the brightness of 100,000 and 200,000 cd m-2, respectively. In addition, our results underscore the role of interface degradation during device operation as a factor in device failure.

Bilayer phosphine oxide modification toward efficient and large-area pure-blue perovskite quantum dot light-emitting diodes.

Blue emissive halide perovskite light-emitting diodes (LEDs) are gaining increasing attention. Reducing defects in halide perovskites to improve the performance of the resulting LEDs is a main research direction, but there are limited passivation methods for achieving efficient and spectrally-stable pure-blue LEDs based on mixed-halide perovskites. In this work, double modification layers containing phosphine oxides, i.e., diphenyl[4-(triphenylsilyl)phenyl]phosphine oxide (TSPO1) and 2,7-bis(diphenylphosphoryl)-9,9'-spirobifluorene (SPPO13), are developed to passivate mixed-halide perovskite quantum dot (QD) films. The comprehensive spectroscopic and structural characterization results indicate the presence of strong interactions between TSPO1/SPPO13 and the QDs. Besides, the combination of the bilayer exhibits a synergistic hole-blocking effect, improving the charge balance of the LEDs. LEDs based on the QD/TSPO1/SPPO13 films deliver stable electroluminesence at 469 nm and present a maximum external quantum efficiency (EQE) and luminance of 4.87% and 560 cd m-2, respectively. Benefiting from the uniform QD/TSPO1/SPPO13 film over a large area, LEDs with an area of 64 mm2 show a maximum EQE of 3.91%, which represents the first efficient large-area mixed-halide perovskite LED with stable pure-blue emission. This work provides a method to improve the perovskite QDs-based film quality and optoelectronic properties, and is a step toward the fabrication of highly-efficient large-area blue perovskite LEDs.

In Situ Generated UiO-66/Cotton Fabric Easily Recyclable for Reactive Dye Adsorption.

In view of the environmental pollution caused by the widespread use of reactive dyes in the printing and dyeing industry, the modified cotton fabric was loaded with the extremely stable metal-organic frame (MOF) material UiO-66 for removing reactive dyes from colored wastewater. UiO-66/cotton fabric was prepared by in situ synthesis, and its surface morphology and structure were analyzed by XRD, SEM, BET, and XPS. The adsorption performance of UiO-66/cotton fabric on reactive dyes was investigated by adsorbent dosage, adsorption time and temperature, dye concentration, pH, and so on. The results indicated that the adsorption equilibrium time of UiO-66/cotton fabric on reactive orange 16 was 120 min, and the removal rate was about 98%. The adsorption process belongs to simple molecular layer chemisorption and can be regarded as a spontaneous heat absorption reaction, which was consistent with the proposed secondary kinetic model and Langmuir isothermal adsorption model. In addition, the reactive dyes with a higher molecular weight of each sulfonic acid group are more hydrophobic, and the dyes are more likely to aggregate and deposit on the adsorbent surface by electrostatic attraction, hydrogen bonding, and π-π accumulation. Therefore, this work provides a potential UiO-66/cotton fabric application for the effective adsorption of reactive dyes in textile wastewater.

Preparation of zeolitic imidazolate framework-67/wool fabric and its adsorption capacity for reactive dyes.

Zeolitic imidazolate framework-67 (ZIF-67) formed by Co2+ and 2-methylimidazole (MIM) is widely used for adsorption and separation of pollutants. However, there are some disadvantages for ZIF-67 powder, such as strong electrostatic interaction and difficulty in recovery from the liquid phase. The available way to solve the above problems is choosing a suitable substrate to load ZIF-67. The amino and hydroxyl of wool fabrics effectively capture and fix ZIF-67, making it easy to separate ZIF-67 by taking out the composite materials from aqueous solution. In this study, ZIF-67/Wool fabric (ZW) was successfully prepared. The results show that ZIF-67 has better adsorption performance for reactive dyes with more sulfonic groups, higher molecular weight and lower steric resistance. The equilibrium adsorption capacity of ZW for reactive red 195 was 4.15 mg g-1. The adsorption accorded with pseudo-second-order kinetic model and Langmuir isotherm. This study improved the application of ZIF-67, which provided a treatment method for dyeing wastewater and made it possible to recycle waste wool.

Flower-Shaped Ni/Co MOF with the Highest Adsorption Capacity for Reactive Dyes.

Reactive dyes are widely used in textile industry, but their excessive use has caused several water pollution problems. In order to reasonably treat printing and dyeing wastewater, the highly efficient adsorbent for reactive dyes employed in this study is a new type metal-organic framework (MOF) material. Ni/Co MOF (NCM) was synthesized using the solvothermal method; then, the materials were analyzed by a series of characterization methods. This study mainly investigated the adsorption properties of NCM toward reactive dyes, and the adsorption capacities of NCM toward reactive red 218 were up to 200 mg·g-1. The results were found to conform to the Langmuir isotherm model, and the pseudo-second-order kinetic model by performing kinetic and isotherm studies on the adsorption process of reactive red 218 on NCM. The results of the intraparticle diffusion model suggest that the binding of reactive red 218 to NCM was mainly divided into three steps: adsorption, diffusion, and saturation. Moreover, it was concluded by thermodynamic fitting of the adsorption process that the adsorption of reactive red 218 by NCM proceeded spontaneously and was accompanied by an endothermic reaction, in which the adsorption of both occurred mainly by electrostatic attraction. The NCM has good reusability and still has good adsorption performance after being reused 5 times. Therefore, NCM is a very promising and excellent adsorbent for the treatment of dye wastewater because of its high efficiency and reusability.

Decoupling the Positive and Negative Aging Processes of Perovskite Light-Emitting Diodes Using a Thin Interlayer of Ionic Liquid.

A positive aging phenomenon, that is, enhancement of the electroluminescence performance at the beginning of electrical aging, is commonly observed for the state-of-the-art perovskite light-emitting diodes (PeLEDs). The origins of positive aging could fundamentally interfere with those of the operational deterioration processes of PeLEDs (namely negative aging), bringing difficulty in analyzing the degradation mechanisms. This work decouples the positive and negative aging processes of PeLEDs by inserting a thin ionic liquid interlayer between the hole-injection layer and the perovskite layer. This interlayer inhibits ions migration by passivating the halogen vacancies of perovskite films and suppresses interfacial exciton quenching, enabling us to decouple the positive and negative aging processes of PeLEDs while increasing the device efficiency. Inserting an ionic liquid interlayer is also demonstrated to be effective for iodide-based PeLEDs and applicable with the use of other ionic liquids. Our work provides an ideal system for fundamental studies on the degradation mechanisms of PeLEDs.

Effects of masting on seedling establishment of a rodent-dispersed tree species in a warm-temperate region, northern China.

Masting is an evolutionary strategy used by plants to promote seed survival and/or seed dispersal under animal predation, but its effects on seedling establishment in field condition are rarely tested by long-term experiments incorporating combined effects of seed and animal abundance. Here, we tracked seed production, rodent-mediated seed dispersal, and seedling establishment in Armeniaca sibirica from 2005 to 2014 in a warm-temperate forest in northern China, and examined the effects of seed abundance and per capita seed availability on seed fate and seedling recruitment rate. Our results showed that seed abundance or per capita seed availability generally benefited the seedling recruitment of A. sibirica through increasing dispersal intensity, supporting predator dispersal hypothesis. However, seedling recruitment showed satiated or even dome-shaped association with per capita seed availability, suggesting the benefit to trees would be decreased when seed abundance were too high as compared to rodent abundance (a satiated effect). Our results suggest that the predator dispersal and satiation effects of masting on seedling recruitment can operate together in one system and conditionally change with seed and animal abundance.

Efficient and High-Color-Purity Light-Emitting Diodes Based on In Situ Grown Films of CsPbX3 (X = Br, I) Nanoplates with Controlled Thicknesses.

We report a facile solution-based approach to the in situ growth of perovskite films consisting of monolayers of CsPbBr3 nanoplates passivated by bulky phenylbutylammonium (PBA) cations, that is, two-dimensional layered PBA2(CsPbBr3)n-1PbBr4 perovskites. Optimizing film formation processes leads to layered perovskites with controlled n values in the range of 12-16. The layered perovskite emitters show quantum-confined band gap energies with a narrow distribution, suggesting the formation of thickness-controlled quantum-well (TCQW) structures. The TCQW CsPbBr3 films exhibit smooth surface features, narrow emission line widths, low trap densities, and high room-temperature photoluminance quantum yields, resulting in high-color-purity green light-emitting diodes (LEDs) with remarkably high external quantum efficiencies (EQEs) of up to 10.4%. The solution-based approach is extended to the preparation of TCQW CsPbI3 films for high-color-purity red perovskite LEDs with high EQEs of up to 7.3%.

Simple Approach to Improving the Amplified Spontaneous Emission Properties of Perovskite Films.

Organo-lead halide perovskite has emerged as a promising optical gain media. However, continuous efforts are needed to improve the amplified spontaneous emission (ASE) even lasing properties to evade the poor photostability and thermal instability of the perovskites. Herein, we report that simply through the coating of polymer layer, the CH3NH3PbBr3 polycrystalline films prepared by a modified sequential deposition process show remarkably enhanced photoluminescence and prolonged decay lifetime. As a result, under nanosecond pulse pumping, the ASE threshold of the perovskite films is significantly reduced from 303 to 140 µJ/cm2. Furthermore, the light exposure stability is improved greatly after the polymer coating. We confirmed that the polymer layer plays the roles of both surface passivation and symmetric waveguides. Our results may shed light upon the stable and sustained output of laser from perovskite materials.

Iodomethane-Mediated Organometal Halide Perovskite with Record Photoluminescence Lifetime.

Organometallic lead halide perovskites are excellent light harvesters for high-efficiency photovoltaic devices. However, as the key component in these devices, a perovskite thin film with good morphology and minimal trap states is still difficult to obtain. Herein we show that by incorporating a low boiling point alkyl halide such as iodomethane (CH3I) into the precursor solution, a perovskite (CH3NH3PbI3-xClx) film with improved grain size and orientation can be easily achieved. More importantly, these films exhibit a significantly reduced amount of trap states. Record photoluminescence lifetimes of more than 4 µs are achieved; these lifetimes are significantly longer than that of pristine CH3NH3PbI3-xClx films. Planar heterojunction solar cells incorporating these CH3I-mediated perovskites have demonstrated a dramatically increased power conversion efficiency compared to the ones using pristine CH3NH3PbI3-xClx. Photoluminescence, transient absorption, and microwave detected photoconductivity measurements all provide consistent evidence that CH3I addition increases the number of excitons generated and their diffusion length, both of which assist efficient carrier transport in the photovoltaic device. The simple incorporation of alkyl halide to enhance perovskite surface passivation introduces an important direction for future progress on high efficiency perovskite optoelectronic devices.

Exciton localization in solution-processed organolead trihalide perovskites.

Organolead trihalide perovskites have attracted great attention due to the stunning advances in both photovoltaic and light-emitting devices. However, the photophysical properties, especially the recombination dynamics of photogenerated carriers, of this class of materials are controversial. Here we report that under an excitation level close to the working regime of solar cells, the recombination of photogenerated carriers in solution-processed methylammonium-lead-halide films is dominated by excitons weakly localized in band tail states. This scenario is evidenced by experiments of spectral-dependent luminescence decay, excitation density-dependent luminescence and frequency-dependent terahertz photoconductivity. The exciton localization effect is found to be general for several solution-processed hybrid perovskite films prepared by different methods. Our results provide insights into the charge transport and recombination mechanism in perovskite films and help to unravel their potential for high-performance optoelectronic devices.

Interfacial control toward efficient and low-voltage perovskite light-emitting diodes.

High-performance perovskite light-emitting diodes are achieved by an interfacial engineering approach, leading to the most efficient near-infrared devices produced using solution-processed emitters and efficient green devices at high brightness conditions.

Rigorous microlens design using vector electromagnetic method combined with simulated annealing optimization.

In this paper, finite-aperture diffractive optical element with its critical dimension smaller than illumination wavelength is modeled and optimized using an integrated method. This method employs rigorous analysis model based on Finite Difference Time Domain (FDTD), and simulated annealing (SA) global search algorithm. Numerical results reveal that the diffraction efficiency of the 8-step microlens quickly climbs to its global optimum along with the optimization process, which manifests its global search ability. The design algorithm and implementation are discussed in details. Considering its time consuming efficiency and global search ability, our method provides valuable reference value in practical multistep microlens design.

Counter-countermeasure identification based on multi-element dual band infrared detector.

An infrared (IR) dual band multi-element detector with the abilities of dual band IR counter-countermeasure (IRCCM) and spatial filtering is presented for effective target detection in a complex tactical environment. The detection elements of the detector are specially arranged like a conventional reticle pattern. With special design, the ratio of radiation intensity from two IR bands can be calculated to distinguish the target from the IR target-flare mixed signal and the two detection bands use a common aperture in the seeker. Without a reticle in the optical system of the IR seeker, the dual band detector can still perform spatial filtering to eliminate background noise effectively. The design details of the detector are presented. The performance of the detector's dual band IRCCM and spatial filtering are analyzed. Simulation results are presented verifying validity of the presented method.

Athermal silica-based interferometer-type planar light-wave circuits realized by a multicore fabrication method.

Athermal silica-based interferometer-type planar light-wave circuits were realized by a newly developed multicore fabrication method. In this method, inductively coupled chemical-vapor deposition and polishing technologies are adopted on a silica substrate with a trench-type waveguide pattern prepared by reactive ion etching. Two kinds of deposited core material, 10GeO2-90SiO2 (mol. %) and 8GeO2-5B2O3-87SiO2 (mol. %), which show wavelength temperature dependence of 9.7 and 8.1 pm/degree C, respectively, were used to prepare the waveguide sections in a device. By adjustment of the lengths of waveguide sections with these two different core materials, athermal characteristics of less than 0.5 pm/degree C were achieved for Mach-Zehnder interferometer filter devices at the 1.55-microm wavelength range while the temperature varied from -20 to 80 degrees C. The new method is also applicable for the preparation of many other kinds of functional devices.