Vapor Phase Growth of Air-Stable Hybrid Perovskite FAPbBr3 Single-Crystalline Nanosheets.

Organic-inorganic hybrid perovskites have attracted tremendous attention owing to their fascinating optoelectronic properties. However, their poor air stability seriously hinders practical applications, which becomes more serious with thickness down to the nanoscale. Here we report a one-step vapor phase growth of HC(NH2)2PbBr3 (FAPbBr3) single-crystalline nanosheets of tunable size up to 50 µm and thickness down to 20 nm. The FAPbBr3 nanosheets demonstrate high stability for over months of exposure to air with no degradation in surface roughness and photoluminescence efficiency. Besides, the FAPbBr3 photodetectors exhibit superior overall performance as compared to previous devices based on nonlayered perovskite nanosheets, such as an ultralow dark current of 24 pA, an ultrahigh responsivity of 1033 A/W, an external quantum efficiency over 3000%, a rapid response time around 25 ms, and a high on/off ratio of 104. This work provides a strategy to tackle the challenges of hybrid perovskites toward integrated optoelectronics with requirements of nanoscale thickness, high stability, and excellent performance.

Degradation Evolution for Li2 ZrCl6 Electrolytes in Humid Air and Enhanced Air Stability via Effective Indium Substitution.

Superionic halides have aroused interests in field of solid electrolytes such as Li2 ZrCl6 . However, they are still facing challenges including poor air stability which lacks in-depth investigation. Here, moisture instability of Li2 ZrCl6 is demonstrated and decomposition mechanism in air is clearly revealed. Li2 ZrCl6 decomposes into Li2 ZrO3 , ZrOCl2 ·xH2 O and LiCl during initial stage as halides upon moisture exposure. Later, these side products evolve into LiCl(H2 O) and Li6 Zr2 O7 after longer time exposure. More importantly, structure of destroyed halides cannot be recovered after postheating. Later, Indium is doped into Li2 ZrCl6 (9.7 × 10-5 S cm-1 ) to explore its effect on structure and properties. Crystal structure of ball-milled In-doped Li2 ZrCl6 electrolytes is converted from the Li3 YCl6 -like to Li3 InCl6 -like with increasing In content and ionic conductivity can also be enhanced (0.768-1.13) × 10-3 S cm-1 ). More importantly, good air stability of optimal Li2.8 Zr0.2 In0.8 Cl6 is achieved since halide hydrates are formed after air exposure instead of total decomposition and the hydrates can be restored to Li2.8 Zr0.2 In0.8 Cl6 after postheating. Moreover, reheated Li2.8 Zr0.2 In0.8 Cl6 after air exposure is successfully applied in solid-state LiNi0.8 Co0.1 Mn0.1 O2 /halides/Li6 PS5 Cl/Li-In battery. The results in this work can provide insights into air instability of Li2 ZrCl6 and effective strategy to regulate air stability of halides.

In-Situ Construction of Electronically Insulating and Air-Stable Ionic Conductor Layer on Electrolyte Surface and Grain Boundary to Enable High-Performance Garnet-Type Solid-State Batteries.

Lithophobic Li2CO3/LiOH contaminants and high-resistance lithium-deficient phases produced from the exposure of garnet electrolyte to air leads to a decrease in electrolyte ion transfer ability. Additionally, garnet electrolyte grain boundaries (GBs) with narrow bandgap and high electron conductivity are potential channels for current leakage, which accelerate Li dendrites generation, ultimately leading to short-circuiting of all-solid-state batteries (ASSBs). Herein, a stably lithiophilic Li2ZO3 is in situ constructed at garnet electrolyte surface and GBs by interfacial modification with ZrO2 and Li2CO3 (Z+C) co-sintering to eliminate the detrimental contaminants and lithium-deficient phases. The Li2ZO3 formed on the modified electrolyte (LLZTO-(Z+C)) surface effectively improves the interfacial compatibility and air stability of the electrolyte. Li2ZO3 formed at GBs broadens the energy bandgaps of LLZTO-(Z+C) and significantly inhibits lithium dendrite generation. More Li+ transport paths found in LLZTO-Z+C by first-principles calculations increase Li+ conductivity from 1.04×10-4 to 7.45×10-4 S cm-1. Eventually, the Li|LLZTO-(Z+C)|Li symmetric cell maintains stable cycling for over 2000 h at 0.8 mA cm-2. The capacity retention of LiFePO4|LLZTO-(Z+C)|Li battery retains 70.5% after 5800 ultralong cycles at 4 C. This work provides a potential solution to simultaneously enhance the air stability and modulate chemical characteristics of the garnet electrolyte surface and GBs for ASSBs.

Conformal Zn-Benzene Dithiol Thin Films for Temperature-Sensitive Electronics Grown via Industry-Feasible Atomic/Molecular Layer Deposition Technique.

The atomic/molecular layer deposition (ALD/MLD) technique combining both inorganic and organic precursors is strongly emerging as a unique tool to design exciting new functional metal-organic thin-film materials. Here, this method is demonstrated to work even at low deposition temperatures and can produce highly stable and conformal thin films, fulfilling the indispensable prerequisites of today's 3D microelectronics and other potential industrial applications. This new ALD/MLD process is developed for Zn-organic thin films grown from non-pyrophoric bis-3-(N,N-dimethylamino)propyl zinc [Zn(DMP)2] and 1,4-benzene dithiol (BDT) precursors. This process yields air-stable Zn-BDT films with appreciably high growth per cycle (GPC) of 4.5 Å at 60 °C. The Zn/S ratio is determined at 0.5 with Rutherford backscattering spectrometry (RBS), in line with the anticipated (Zn─S─C6H6─S─)n bonding scheme. The high degree of conformality is shown using lateral high-aspect-ratio (LHAR) test substrates; scanning electron microscopy (SEM) analysis shows that the film penetration depth (PD) into the LHAR structure with cavity height of 500 nm is over 200 µm (i.e., aspect-ratio of 400). It is anticipated that the electrically insulating metal-organic Zn-BDT thin films grown via the solvent-free ALD/MLD technique, can be excellent barrier layers for temperature-sensitive and flexible electronic devices.

Bilayer Interphase for Air-Stable and Dendrite-Free Lithium Metal Anode Cycling in Carbonate Electrolytes.

The intrinsic reactivity of lithium (Li) toward ambient air, combined with insufficient cycling stability in conventional electrolytes, hinders the practical adoption of Li metal anodes in rechargeable batteries. Here, a bilayer interphase for Li metal is introduced to address both its susceptibility to corrosion in ambient air and its deterioration during cycling in carbonate electrolytes. Initially, the Li metal anode is coated with a conformal bottom layer of polysiloxane bearing methacrylate, followed by further grafting with poly(vinyl ethylene carbonate) (PVEC) to enhance anti-corrosion capability and electrochemical stability. In contrast to single-layer applications of polysiloxane or PVEC, the bilayer design offers a highly uniform coating that effectively resists humid air and prevents dendritic Li growth. Consequently, it demonstrates stable plating/stripping behavior with only a marginal increase in overpotential over 200 cycles in carbonate electrolytes, even after exposure to ambient air with 46% relative humidity. The design concept paves the way for scalable production of high-voltage, long-cycling Li metal batteries.

Design of Solid Polycationic Electrolyte to Enable Durable Chloride-Ion Batteries.

The high energy density and cost-effectiveness of chloride-ion batteries (CIBs) make them promising alternatives to lithium-ion batteries. However, the development of CIBs is greatly restricted by the lack of compatible electrolytes to support cost-effective anodes. Herein, we present a rationally designed solid polycationic electrolyte (SPE) to enable room-temperature chloride-ion batteries utilizing aluminum (Al) metal as an anode. This SPE endows the CIB configuration with improved air stability and safety (i.e. free of flammability and liquid leakage). A high ionic conductivity (1.3×10-2 S cm-1 at 25 °C) has been achieved by the well-tailored coordination structure of the SPE. Meanwhile, the solid polycationic electrolyte ensures stable electrodes|electrolyte interfaces, which effectively inhibit the growth of dendrites on the Al anodes and degradation of the FeOCl cathodes. The Al|SPE|FeOCl chloride-ion batteries showcased a high discharge capacity around 250 mAh g-1 (based on the cathodes) and extended lifespan. Our electrolyte design opens a new avenue for developing low-cost chloride-ion batteries.

Emerging Lithiated Organic Cathode Materials for Lithium-Ion Full Batteries.

Organic electrode materials have application potential in lithium batteries owing to their high capacity, abundant resources, and structural designability. However, most reported organic cathodes are at oxidized states (namely unlithiated compounds) and thus need to couple with Li-rich anodes. In contrast, lithiated organic cathode materials could act as a Li reservoir and match with Li-free anodes such as graphite, showing great promise for practical full-battery applications. Here we summarize the synthesis, stability, and battery applications of lithiated organic cathode materials, including synthetic methods, stability against O2 and H2 O in air, and strategies to improve comprehensive electrochemical performance. Future research should be focused on new redox chemistries and the construction of full batteries with lithiated organic cathodes and commercial anodes under practical conditions. This Minireview will encourage more efforts on lithiated organic cathode materials and finally promote their commercialization.

A convenient ninhydrin assay in 96-well format for amino acid-releasing enzymes using an air-stable reagent.

An improved and convenient ninhydrin assay for aminoacylase activity measurements was developed using the commercial EZ Nin™ reagent. Alternative reagents from literature were also evaluated and compared. The addition of DMSO to the reagent enhanced the solubility of Ruhemann's purple (RP). Furthermore, we found that the use of a basic, aqueous buffer enhances stability of RP. An acidic protocol for the quantification of lysine was developed by addition of glacial acetic acid. The assay allows for parallel processing in a 96-well format with measurements microtiter plates.

Recent Advances and Perspectives of Air Stable Sulfide-Based Solid Electrolytes for All-Solid-State Lithium Batteries.

An all-solid-state battery enabled by the incombustible and highly Li-ion conductive sulfide solid-state electrolyte, is recognized to be a strong candidate for next-generation of lithium-ion batteries. Intensive research efforts have been devoted to developing the well-suited sulfide electrolytes with outstanding performances. Although several types of sulfide electrolytes have achieved superionic conductivities with excellent deformability, the air-sensitive behaviors of them are detrimental to the large-scale production. Considerable efforts are in progress to tackle this issue via various strategies in recent years. This review provides an overview of several classes of promising sulfide solid electrolytes. The principle and strategies for improving the resistance of these sulfide electrolytes against air are thoroughly discussed. We also point out the major challenges that all-solid-state batteries and different types of sulfide electrolytes face for practical applications.

Simultaneous Improvement of Efficiency and Stability of Organic Photovoltaic Cells by using a Cross-Linkable Fullerene Derivative.

Improving power conversion efficiencies (PCEs) and stability are two main tasks for organic photovoltaic (OPV) cells. In the past few years, although the PCE of the OPV cells has been considerably improved, the research on device stability is limited. Herein, a cross-linkable material, cross-linked [6,6]-phenyl-C61-butyric styryl dendron ester (c-PCBSD), is applied as an interfacial modification layer on the surface of zinc oxide and as the third component into the PBDB-TF:Y6-based OPV cells to enhance photovoltaic performance and long-term stability. The PCE of the OPV cells that underwent the two-step modification increased from 15.1 to 16.1%. In particular, such OPV cells exhibited much better stability under both thermal and air conditions because of the decreased number of interfacial defects and stable interfacial and active layer morphologies. The results demonstrated that the introduction of a cross-linkable fullerene derivative into the interfacial and active layers is a feasible method to improve the PCE and stability of OPV cells.

Ultrathin epitaxial Bi film growth on 2D HfTe2template.

Among ultrathin monoelemental two-dimensional (2D) materials, bismuthene, the single layer of heavier group-VΑ element bismuth (Bi), has been predicted to have large non trivial gap. Here, we demonstrate the growth of Bi films by molecular beam epitaxy on 2D-HfTe2template. At the initial stage of Bi deposition (1-2 bilayers, BL), both the pseudocubic Bi(110) and the hexagonal Bi(111) phases are formed. When reaching 3 BL Bi, a transformation to pure hexagonal Bi(111) occurs. The electronic band structure of 3 BL Bi(111) films was measured by angle-resolved photoemission spectroscopy showing very good matching with the density functional theory band structure calculations of 3 BL free standing Bi(111). The grown Bi(111) thin film was capped with a protective Al2O3layer and its stability under ambient conditions, necessary for practical applications and device fabrication, was confirmed by x-ray photoelectron spectroscopy and Raman spectroscopy.

Investigation of exhaled pollutant distribution in the breathing microenvironment in a displacement ventilated room with indoor air stability conditions.

This study experimentally studied the dispersion of exhaled pollutant in the breathing microenvironment (BM) in a room equipped with a displacement ventilation (DV) system and indoor air stability conditions (i.e., stable and unstable conditions). The vertical temperature differences and the carbon dioxide (CO2) concentration in the BM were measured. Results show that when DV is combined with the stable condition (DS), pollutant tends to accumulate in the BM, leading to a high pollutant concentration in this region. Whereas, when DV is combined with the unstable condition (DU), pollutant diffuses to a relatively wider area beyond the BM, thus the pollutant concentration in the BM is substantially reduced. Moreover, increasing the flow rate can reduce the pollutant concentration in the BM of the DS but yields little difference of the DU. In addition, personal exposure intensity increases with time, and the DS has a relatively higher increase rate than DU. The results suggest that indoor air stability will affect the performance of DV systems. DS will lead to a higher health risk for people when they stay in the indoor environment with pollutant sources, and DU is recommended for minimizing pollutant level in the BM in order to reduce the pollutant concentration and providing better air environments for the occupants.

Control of exhaled SARS-CoV-2-laden aerosols in the interpersonal breathing microenvironment in a ventilated room with limited space air stability.

The Coronavirus Disease 2019 (COVID-19) highlights the importance of understanding and controlling the spread of the coronavirus between persons. We experimentally and numerically investigated an advanced engineering and environmental method on controlling the transmission of airborne SARS-CoV-2-laden aerosols in the breathing microenvironment between two persons during interactive breathing process by combining the limited space air stability and a ventilation method. Experiments were carried out in a full-scale ventilated room with different limited space air stability conditions, i.e., stable condition, neutral condition and unstable condition. Two real humans were involved to conducted normal breathing process in the room and the exhaled carbon dioxide was used as the surrogate of infectious airborne SARS-CoV-2-laden aerosols from respiratory activities. A correspondent numerical model was established to visualize the temperature field and contaminated field in the test room. Results show that the performance of a ventilation system on removing infectious airborne SARS-CoV-2-laden aerosols from the interpersonal breathing microenvironment is dependent on the limited space air stability conditions. Appropriate ventilation method should be implemented based on an evaluation of the air condition. It is recommended that total volume ventilation methods are suitable for unstable and neutral conditions and local ventilation methods are preferable for stable conditions. This study provides an insight into the transmission of airborne SARS-CoV-2-laden aerosols between persons in ventilated rooms with different limited space air stability conditions. Useful guidance has been provided to cope with COVID-19 in limited spaces.

Highly Efficient Spin-Filtering Transport in Chiral Hybrid Copper Halides.

Chiral Pb(Sn)-I hybrid organic-inorganic perovskites exhibit outstanding chiral-induced spin selectivity (CISS) performance, but the nontoxic lead-free hybrid materials with high stability are still greatly desired for spin filtering in spintronic applications. We synthesize chiral hybrid copper halides (R/S-MBA)2 CuX4 (MBA=methylbenzylammonium; X=Cl, Br) with characteristic 0D CuX4 tetrahedral structural motifs, combining the low toxicity of Cu2+ and air stability of halide ions (Cl- and Br- ). Despite similar structural and electronic features, (R/S-MBA)2 CuBr4 shows much smaller chiroptical activity than the chloride counterpart. Magnetically conductive atomic force microscopy measurements display a typical spin-polarized charge-transport property with high efficiency up to 90 % for both copper halides. Our work expands the CISS effect into eco-friendly and stable metal-organic halides, which is promising for applications in spintronics based on transition-metal hybrid systems.

Air Stable Organic-Inorganic Perovskite Nanocrystals@Polymer Nanofibers and Waveguide Lasing.

Organic-inorganic hybrid perovskites have been considered as promising gain materials for lasing. Despite previous reports of lasing from nanocrystals, thin films and single crystals, the stability of perovskite lasers has been a challenge for its practical applications. Herein, a scalable strategy to prepare ultrastable perovskite@polymer hybrid fibers by employing a facile emulsion electrospinning approach is demonstrated. During the electrospinning process, polymethyl methacrylate (PMMA) first solidifies into an outer shell layer. Meanwhile, emulsion drops containing poly(vinylidene fluoride) (PVDF) and perovskite precursor are pushed inward and evolve into perovskite nanocrystals covered by PVDF. The PMMA with smooth surface benefits the light transport and the water-resistant PVDF blocks the moisture. The methylammonium lead bromide perovskite-embedded fibers can emit intensive light after storage in humid ambient environment (relative humidity >60%) or even in water. Amplified spontaneous emissions from the fibers network and waveguide lasing from chopped single fiber is demonstrated.

Giant Thickness-Tunable Bandgap and Robust Air Stability of 2D Palladium Diselenide.

Uncovering the thickness-dependent electronic property and environmental stability for 2D materials are crucial issues for promoting their applications in high-performance electronic and optoelectronic devices. Herein, the extrahigh air stability and giant tunable electronic bandgap of chemical vapor deposition (CVD)-derived few-layer PdSe2 on Au foils, by using scanning tunneling microscope/spectroscopy (STM/STS), are reported. The robust stability of 2D PdSe2 is uncovered by the observation of nearly defect/adsorption-free atomic lattices on long-time air-exposed samples. A one-to-one correspondence between the electronic bandgap (from ≈1.15 to ≈0 eV) and thickness of PdSe2 /Au (from bilayer to bulk) is established. It is also revealed that few-layer semiconducting PdSe2 flakes present zero-gap edges, induced by hybridization of Pd 4d and Se 4p orbitals. This work hereby provides straightforward evidence for the thickness-tunable electronic property and air stability of 2D semiconductors, thus shedding light on their applications in next-generation electronic devices.

A Theoretical Analysis on the Oxidation and Water Dissociation Resistance on Group-IV Phosphide Monolayers.

Group-IV phosphide monolayers (MP, M=C, Si, Ge and Sn) provide a versatile platform for photocatalysts, as well as optoelectronic and nanoelectronic devices. Herein, comprehensive first-principles calculations and ab initio molecular dynamics (AIMD) simulations were performed to explore their stabilities in the air. We identified that the MP monolayers have excellent mechanical properties and their carrier mobilities are higher than that of phosphorene. The MP monolayers were predicted to possess superior oxidation resistance than the boron phosphide (BP) monolayer based on the proposed donation-backdonation theory. It was observed that the dissociation and chemisorption of a water molecule on the monolayers are kinetically difficult both in the water and in oxygen-water environments involving energy barriers of 1.28-3.48 eV. We also performed AIMD simulations at 300, 1000, 1200 and 1500 K. It is noteworthy that only the carbon phosphide (CP) monolayer can retain an intact structure at 1500 K, while the other three monolayers can just sustain to 1200 K. These results provide a guidance for their practical application and experimental fabrication.

Facile Generation of Polymer-Alloy Hybrid Layers for Dendrite-Free Lithium-Metal Anodes with Improved Moisture Stability.

Lithium-metal anodes are recognized as the most promising next-generation anodes for high-energy-storage batteries. However, lithium dendrites lead to irreversible capacity decay in lithium-metal batteries (LMBs). Besides, the strict assembly-environment conditions of LMBs are regarded as a challenge for practical applications. In this study, a workable lithium-metal anode with an artificial hybrid layer composed of a polymer and an alloy was designed and prepared by a simple chemical-modification strategy. Treated lithium anodes remained dendrite-free for over 1000 h in a Li-Li symmetric cell and exhibited outstanding cycle performance in high-areal-loading Li-S and Li-LiFePO4 full cells. Moreover, the treated lithium showed improved moisture stability that benefits from the hydrophobicity of the polymer, thus retaining good electrochemical performance after exposure to humid air.

High Electron Mobility of Amorphous Red Phosphorus Thin Films.

Black phosphorus (BP) has been gathering great attention for its electronic and optoelectronic applications due to its high electron mobility and high ION/OFF current switching ratio. The limitations of this material include its low synthetic yield and high cost. One alternative to BP is another type of phosphorus allotrope, red phosphorus (RP), which is much more affordable and easier to process. Although RP has been widely used in industry for hundreds of years and considered as an insulating material, in this study, we demonstrate through field-effect transistors (FET) measurements that amorphous red phosphorus (a-RP) films are semiconductive with a high mobility of 387 cm2 V-1 s-1 and a current switching ratio of ≈103 , which is comparable to the electronic characteristics previously reported for BP. The films were produced via a thermal evaporation method or a facile drop-casting approach onto Si/SiO2 substrates. We also report a study of the oxidation process of the films over time and a method to stabilize the films via doping a-RP with metal oxides. The doped films retain stability for one thousand I-V cycles, with no signs of degradation.

Lithium-Ion Endohedral Fullerene (Li+ @C60 ) Dopants in Stable Perovskite Solar Cells Induce Instant Doping and Anti-Oxidation.

Herein, we report use of [Li+ @C60 ]TFSI- as a dopant for spiro-MeOTAD in lead halide perovskite solar cells. This approach gave an air stability nearly 10-fold that of conventional devices using Li+ TFSI- . Such high stability is attributed to the hydrophobic nature of [Li+ @C60 ]TFSI- repelling moisture and absorbing intruding oxygen, thereby protecting the perovskite device from degradation. Furthermore, [Li+ @C60 ]TFSI- could oxidize spiro-MeOTAD without the need for oxygen. The encapsulated devices exhibited outstanding air stability for more than 1000 h while illuminated under ambient conditions.