Intense Hydrochromic Photon Upconversion from Lead-Free 0D Metal Halides For Water Detection and Information Encryption.

Hydrochromic materials that change their luminescence color upon exposure to moisture have attracted considerable attention owing to their applications in sensing and information encryption. However, the existing materials lack high hydrochromic response and color tunability. This study reports the development of a new and bright 0D Cs3 GdCl6 metal halide as the host for hydrochromic photon upconversion in the form of polycrystals (PCs) and nanocrystals. Lanthanides co-doped cesium gadolinium chloride metal halides exhibit upconversion luminescence (UCL) in the visible-infrared region upon 980 nm laser excitation. In particular, PCs co-doped with Yb3+ and Er3+ exhibit hydrochromic UCL color change from green to red. These hydrochromic properties are quantitatively confirmed through the sensitive detection of water in tetrahydrofuran solvent via UCL color changes. This water-sensing probe exhibits excellent repeatability and is particularly suitable for real-time and long-term water monitoring. Furthermore, the hydrochromic UCL property is exploited for stimuli-responsive information encryption via cyphertexts. These findings will pave the way for the development of new hydrochromic upconverting materials for emerging applications, such as noncontact sensors, anti-counterfeiting, and information encryption.

Utilizing VO2 as a Hole Injection Layer for Efficient Charge Injection in Quantum Dot Light-Emitting Diodes Enables High Device Performance.

Quantum dot light-emitting diodes (QLEDs) are promising devices for display applications. Polyethylenedioxythiophene:polystyrene sulfonate (PEDOT:PSS) is a common hole injection layer (HIL) material in optoelectronic devices because of its high conductivity and high work function. Nevertheless, PEDOT:PSS-based QLEDs have a high energy barrier for hole injection, which results in low device efficiency. Therefore, a new strategy is needed to improve the device efficiency. Herein, we have demonstrated a bilayer-HIL using VO2 and a PEDOT:PSS-based QLED that exhibits an 18% external quantum efficiency (EQE), 78 cd/A current efficiency (CE), and 25,771 cd/m2 maximum luminance. In contrast, the PEDOT:PSS-based QLED exhibits an EQE of 13%, CE of 54 cd/A, and maximum luminance of 14,817 cd/m2. An increase in EQE was attributed to a reduction in the energy barrier between indium tin oxide (ITO) and PEDOT:PSS, caused by the insertion of a VO2 HIL. Therefore, our results could demonstrate that using a bilayer-HIL is effective in increasing the EQE in QLEDs.

Synthesis of Thermally Stable and Highly Luminescent Cs5 Cu3 Cl6 I2 Nanocrystals with Nonlinear Optical Response.

Low-dimensional Cu(I)-based metal halide materials are gaining attention due to their low toxicity, high stability and unique luminescence mechanism, which is mediated by self-trapped excitons (STEs). Among them, Cs5 Cu3 Cl6 I2 , which emits blue light, is a promising candidate for applications as a next-generation blue-emitting material. In this article, an optimized colloidal process to synthesize uniform Cs5 Cu3 Cl6 I2 nanocrystals (NCs) with a superior quantum yield (QY) is proposed. In addition, precise control of the synthesis parameters, enabling anisotropic growth and emission wavelength shifting is demonstrated. The synthesized Cs5 Cu3 Cl6 I2 NCs have an excellent photoluminescence (PL) retention rate, even at high temperature, and exhibit high stability over multiple heating-cooling cycles under ambient conditions. Moreover, under 850-nm femtosecond laser irradiation, the NCs exhibit three-photon absorption (3PA)-induced PL, highlighting the possibility of utilizing their nonlinear optical properties. Such thermally stable and highly luminescent Cs5 Cu3 Cl6 I2 NCs with nonlinear optical properties overcome the limitations of conventional blue-emitting nanomaterials. These findings provide insights into the mechanism of the colloidal synthesis of Cs5 Cu3 Cl6 I2 NCs and a foundation for further research.

Enhancement of Luminescence Efficiency of Y2O3 Nanophosphor via Core/Shell Structure.

We successfully fabricated Y2O3:RE3+ (RE = Eu, Tb, and Dy) core and core-shell nanophosphors by the molten salt method and sol-gel processes with Y2O3 core size of the order of 100~150 nm. The structural and morphological studies of the RE3+-doped Y2O3 nanophosphors are analyzed by using XRD, SEM and TEM techniques, respectively. The concentration and annealing temperature dependent structural and luminescence characteristics were studied for Y2O3:RE3+ core and core-shell nanophosphors. It is observed that the XRD peaks became narrower as annealing temperature increased in the core-shell nanophosphor. This indicates that annealing at higher temperature improves the crystallinity which in turn enhances the average crystallite size. The emission intensity and quantum yield of the Eu3+-doped Y2O3 core and core-shell nanoparticles increased significantly when annealing temperature is varied from 450 to 550 °C. No considerable variation was noticed in the case of Y2O3:Tb3+ and Y2O3:Dy3+ core and core-shell nanophosphors.

Multimodal Digital X-ray Scanners with Synchronous Mapping of Tactile Pressure Distributions using Perovskites.

Visual and tactile information are the key intuitive perceptions in sensory systems, and the synchronized detection of these two sensory modalities can enhance accuracy of object recognition by providing complementary information between them. Herein, multimodal integration of flexible, high-resolution X-ray detectors with a synchronous mapping of tactile pressure distributions for visualizing internal structures and morphologies of an object simultaneously is reported. As a visual-inspection method, perovskite materials that convert X-rays into charge carriers directly are synthesized. By incorporating pressure-sensitive air-dielectric transistors in the perovskite components, X-ray detectors with dual modalities (i.e., vision and touch) are attained as an active-matrix platform for digital visuotactile examinations. Also, in vivo X-ray imaging and pressure sensing are demonstrated using a live rat. This multiplexed platform has high spatial resolution and good flexibility, thereby providing highly accurate inspection and diagnoses even for the distorted images of nonplanar objects.

Sub-micro droplet reactors for green synthesis of Li3VO4 anode materials in lithium ion batteries.

The conventional solid-state reaction suffers from low diffusivity, high energy consumption, and uncontrolled morphology. These limitations are competed by the presence of water in solution route reaction. Herein, based on concept of combining above methods, we report a facile solid-state reaction conducted in water vapor at low temperature along with calcium doping for modifying lithium vanadate as anode material for lithium-ion batteries. The optimized material, delivers a superior specific capacity of 543.1, 477.1, and 337.2 mAh g-1 after 200 and 1000 cycles at current densities of 100, 1000 and 4000 mA g-1, respectively, which is attributed to the contribution of pseudocapacitance. In this work, we also use experimental and theoretical calculation to demonstrate that the enhancement of doped lithium vanadate is attributed to particles confinement of droplets in water vapor along with the surface and structure variation of calcium doping effect.

Mechanochemistry as a Green Route: Synthesis, Thermal Stability, and Postsynthetic Reversible Phase Transformation of Highly-Luminescent Cesium Copper Halides.

Cesium copper halides (CCHs) show promise for optoelectronic applications, and their syntheses usually involve high-temperatures and hazard solvents. Herein, the synthesis of highly luminescent and phase-pure Cs3Cu2X5 (X = Cl, Br, and I) and CsCu2I3 via a solvent-free mechanochemical approach through manual grinding is demonstrated. This cost-effective approach can produce CCHs on a scale of tens to hundreds of grams. Rietveld refinement analysis of the X-ray diffraction patterns of the as-synthesized CCHs reveals their structural details. Notably, the emission characteristics of green-emitting, chloride-based CCHs remain stable even at elevated temperatures-maintaining 80% of initial PL efficiency at 150 °C. Lastly, a postsynthetic reversible transformation between zero- and one-dimensional CCH materials is demonstrated, indicating the labile nature of their crystal structure. The proposed study suggests that mechanochemistry can be an alternative and promising synthetic tool for fabricating high-quality lead-free metal halides.

Facile Green Synthesis of Pseudocapacitance-Contributed Ultrahigh Capacity Fe2(MoO4)3 as an Anode for Lithium-Ion Batteries.

The investigation into the use of earth-abundant elements as electrode materials for lithium-ion batteries (LIBs) is becoming more urgent because of the high demand for electric vehicles and portable devices. Herein, a new green synthesis strategy, based on a facile solid-state reaction with the assistance of water droplets' vapor, was conducted to prepare Fe2(MoO4)3 nanosheets as anode materials for LIBs. The obtained sample possesses a two-dimensional stacked nanosheet construction with open gaps providing a much higher surface area compared to the bulk sample conventionally synthesized. The nanosheet sample delivers an ultrahigh reversible capacity (1983.6 mA h g-1) at a current density of 100 mA g-1 after 400 cycles, which could be related to the contribution of pseudocapacitance. The enhancement in cyclability and rated performance with an interesting increased capacity could be caused by the effect of electrochemical milling and the in situ formation of metallic particles in its lithium-ion storage mechanism.

Narrow-Band SrMgAl10O17:Eu2+, Mn2+ Green Phosphors for Wide-Color-Gamut Backlight for LCD Displays.

The strength of the photoluminescence excitation (PLE) spectrum of SrMgAl10O17:Eu2+, Mn2+ (SAM:Eu2+, Mn2+) phosphor increased at deep blue (∼430 nm) and red-shifted from violet to deep blue with increasing concentrations of both Eu2+ ions Mn2+ ions. Eu2+-Mn2+ energy transfer between Eu2+ ions in Sr-O layer and Mn2+ ions at Al-O tetrahedral sites was maximized, and the photoluminescence (PL) intensity of the narrow-band Mn2+ emission was improved by optimizing the concentrations of Eu2+ and Mn2+ ions. The PL emission spectrum of the (Sr0.6Eu0.4)(Mg0.4Mn0.6)Al10O17 (SAM:Eu2+, Mn2+) phosphor peaks was optimized at 518 nm at a full width at half-maximum (FWHM) of 26 nm under light-emitting diode (LED) excitation at 432 nm LED. The color gamut area of a color-filtered RGB triangle of down-converted white LEDs (DC-WLEDs) incorporated with optimum SAM:Eu2+, Mn2+ green and K2SiF6:Mn4+ (KSF:Mn4+) red phosphors is enlarged by 114% relative to that of the NTSC standard system in the CIE 1931 color space. The luminous efficacy of our DC-WLED was measured and found to be ∼92 lm/W at 20 mA. Increased energy transfers between dual activators and red-shifted band-edge and enhanced intensity of PLE spectrum indicate the possibility of developing dual-activated narrow-band green phosphors for wide-color gamut in an LCD backlighting system.

Robust, Brighter Red Emission from CsPbI3 Perovskite Nanocrystals via Endotaxial Protection.

Increasing the stability of lead halide perovskites (LHPs) is required for integrating them into light-emitting devices. To date, most studies toward this direction have primarily concentrated on improving the chemical stability of green-emitting LHPs. In this work, red-emitting CsPbI3-Cs4PbI6 hybrid nanocrystals (NCs) were synthesized with a high photoluminescence (PL) quantum yield of ∼90%. Their hybrid structure was examined via structural (Rietveld) refinement analysis and transmission electron microscopy. Rietveld refinement also revealed that the black polymorph of CsPbI3 NCs is an orthorhombic perovskite rather than a cubic one. The thermodynamic stability of the CsPbI3 NCs in Cs4PbI6 matrices is enhanced in both solutions and films for up to several weeks. The enhanced stability of the embedded CsPbI3 NCs is attributed to the lowering of their Gibbs free energy, as determined on the basis of experimental data. Additionally, the hybrid NCs exhibit unprecedented emission stability-maintaining 65% of their original PL efficiency at 150 °C-and improved aqueous stability.

Correction: Highly stable hetero-structured green-emitting cesium lead bromide nanocrystals via ligand-mediated phase control.

Correction for 'Highly stable hetero-structured green-emitting cesium lead bromide nanocrystals via ligand-mediated phase control' by G. Krishnamurthy Grandhi et al., Nanoscale, 2019, 11, 21137-21146.

Zero reduction luminescence of aqueous-phase alloy core/shell quantum dots via rapid ambient-condition ligand exchange.

Quantum dots (QDs) have been widely studied as promising materials for various applications because of their outstanding photoluminescence (PL). Although ligand exchange methods for QDs have been developed over two decades, the PL quantum yield (QY) of aqueous phase QDs is still lower than that of their organic phase and the mechanism of quenching has not been clearly understood. In this study, we demonstrate for the first time that 3-mercaptopropionic-capped CdZnSeS/ZnS core/shell QDs obtained via ligand exchange in a ternary solvent system containing chloroform/water/dimethyl sulfoxide can enable the fast phase transfer and zero reduction of PL under ambient condition. The new solvent system allows the ligand-exchanged QDs to exhibit enhanced QYs up to 8.1% of that of the organic-phase QDs. Based on both theoretical calculation and experiment, it was found that control over the physical/chemical perturbation between the organic/aqueous phases by choosing appropriate solvents for the ligand exchange process is very important to preserve the optical properties of QDs. We believe that our new technologies and theoretical knowledge offer opportunities for the future design and optimization of highly stable and highly luminescent aqueous-phase QDs for various applications.

Mechanoluminescent, Air-Dielectric MoS2 Transistors as Active-Matrix Pressure Sensors for Wide Detection Ranges from Footsteps to Cellular Motions.

Tactile pressure sensors as flexible bioelectronic devices have been regarded as the key component for recently emerging applications in electronic skins, health-monitoring devices, or human-machine interfaces. However, their narrow range of sensible pressure and their difficulty in forming high integrations represent major limitations for various potential applications. Herein, we report fully integrated, active-matrix arrays of pressure-sensitive MoS2 transistors with mechanoluminescent layers and air dielectrics for wide detectable range from footsteps to cellular motions. The inclusion of mechanoluminescent materials as well as air spaces can increase the sensitivity significantly over entire pressure regimes. In addition, the high integration capability of these active-matrix sensory circuitries can enhance their spatial resolution to the level sufficient to analyze the pressure distribution in a single cardiomyocyte. We envision that these wide-range pressure sensors will provide a new strategy toward next-generation electronics at biomachine interfaces to monitor various mechanical and biological phenomena at single-cell resolution.

Rechargeable Intermetallic Calcium-Lithium-O2 Batteries.

The growing demand for rechargeable batteries with high energy density has triggered research on batteries based on polyvalent cations such as Ca2+ , Mg2+ , Al3+ , and Y3+ . Ca is, in particular, a promising anode material as an alternative to Li because of its mechanical strength (ρ=1.55 g cm-3 ), safety in terms of thermal runaway (m.p.=839 °C), earth-abundance (world production of 150 million tons of gypsum in 2012), high specific charge capacity (1.340 mAh g-1 or 2.077 mAh cm-3 ), and standard reduction potential (-2.87 V vs. normal hydrogen electrode, NHE) comparable to that of Li. As with Mg, the practical application of Ca in rechargeable batteries with organic liquid electrolytes has been hindered by the passivation layer resulting from undesirable reactions between metallic Ca and electrolytes, which precludes the possibility of reversible plating of any metal cations on Ca electrodes. Here, a battery system based on intermetallic CaLi2 anodes was developed. Li was used as a host for Ca through the formation of an intermetallic compound, which simultaneously enabled 1) the assembly of a rechargeable battery system with Ca anodes and liquid organic electrolytes and 2) coupling these with an earth-abundant, high-energy-density air cathode without special passivation agents. This strategy is simple and broadly applicable to the other polyvalent cations listed above, opening a new avenue to further engineer the electrode materials required for practical, efficient electrochemical energy-storage systems.

Highly stable hetero-structured green-emitting cesium lead bromide nanocrystals via ligand-mediated phase control.

Green-emissive Cs4PbBr6 shows promise for light-emitting diode devices superior to that of CsPbBr3 NCs owing to their stability and high photoluminescence efficiency. Nevertheless, there is still no consensus regarding the basis of their green emission, which decelerates their advance in light-emitting applications. Herein, a systematic investigation on the concentration of capping ligands (oleylamine and oleic acid), which determines the predominant phase between CsPbBr3 and Cs4PbBr6 for a given Cs to Pb feed ratio, is conducted. This study deduces that oleylamine to oleic acid ratio plays a crucial role in obtaining either green-emissive or non-emissive Cs4PbBr6 NCs. Scrutiny of Cs4PbBr6 microscopic and optical data in addition to their emission quenching study with a hole-withdrawing molecule reveals that the green emission originates from the CsPbBr3 impurity phase. Furthermore, stable green emission is observed for CsPbBr3/Cs4PbBr6 nanocrystals when CsPbBr3 particles are well protected by the Cs4PbBr6 matrix. These CsPbBr3/Cs4PbBr6 films remained highly luminescent even after UV exposure for hours or annealing at ∼150 °C for days in addition to their long-term stability under an ambient atmosphere, which are the desirable properties for various practical applications.

Molecular Cooperative Assembly-Mediated Synthesis of Ultra-High-Performance Hard Carbon Anodes for Dual-Carbon Sodium Hybrid Capacitors.

Although sodium hybrid capacitors (NHCs) have emerged as one of the most promising next-generation energy storage systems, further advancement is delayed primarily by the absence of high-performance battery-type anodes. Herein, we report a nature-inspired synthesis route to prepare hard carbon anodes with high capacity, rate capability, and cycle stability for dual-carbon NHCs. Shape- and size-controllable crystal aggregates of inexpensive triazine molecules are utilized as reactive templates that perform triple duties of structure-directing agent, porogen, and nitrogen source. This enables the fine control of microstructure/morphology/composition and thereby electrochemical reactions toward Na-ion. The resulting hard carbon optimized in terms of lateral size, interlayer spacing, and surface affinity of graphene-like layers achieves a specific capacity of ∼380 mAh/g after 100 cycles at a current density of 250 mA/g mainly via intercalation, the current record of hard carbons. Combined with a commercial microporous carbon fiber cathode, the full cell is able to deliver a volumetric energy density of 2.89 mWh/cm3 and a volumetric power density of 160 mW/cm3, outperforming NHCs based on inorganic Na-ion anode materials. More importantly, such performance could not only be retained for 10000 cycles (4.5 F/cm3 at 10 mA/cm3) with 0.000 028 6% loss per cycle at >97% Coulombic efficiency but also successfully transferred to flexible pouch cells without significant performance loss after 300 bending cycles or during wrapping at a 10R condition. Simple preparation of hard carbon anodes using organic crystal reactive templates, therefore, demonstrates great potential for the manufacture of high-performance flexible NHCs using only carbon electrode materials.

Publisher Correction: Probing molecule-like isolated octahedra via phase stabilization of zero-dimensional cesium lead halide nanocrystals.

The original version of this Article contained an error in the title, which incorrectly read 'Probing molecule-like isolated octahedra via-phase stabilization of zero-dimensional cesium lead halide nanocrystals.' The correct version states 'via phase stabilization' in place of 'via-phase stabilization'. This has been corrected in both the PDF and HTML versions of the Article.

A Phosphosilicate Compound, NaCa3PSiO8: Structure Solution and Luminescence Properties.

NaCa3PSiO8 was synthesized in a microwave-assisted solid-state reaction. The crystal structure of the synthesized compound was solved using a least-squares method, followed by simulated annealing. The compound was crystallized in the orthorhombic space group Pna21, belonging to Laue class mmm. The structure consisted of two layers of cation planes, each of which contained three cation channels. The cation channels in each of the layers ran antiparallel to that of the adjacent layer. All the major cations together constituted four distinct crystallographic sites. The Rietveld refinement of the powder X-ray diffraction data, followed by the maximum-entropy method analysis, confirmed the obtained structure solutions. The electronic band structure of the compound was analyzed through density function theory calculations. Luminescence properties of the compound, upon activating with Eu2+ ions, were analyzed through photoluminescence measurements and decay profile analysis. The compound was found to exhibit green luminescence centered at ∼502 nm, with a typical broadband emission due to the transition from the crystal-field split 4f65d to 4f7 levels.

Colloidal Organolead Halide Perovskite with a High Mn Solubility Limit: A Step Toward Pb-Free Luminescent Quantum Dots.

Organolead halide perovskites have emerged as a promising optoelectronic material for lighting due to its high quantum yield, color-tunable, and narrow emission. Despite their unique properties, toxicity has intensified the search for ecofriendly alternatives through partial or complete replacement of lead. Herein, we report a room-temperature synthesized Mn2+-substituted 3D-organolead perovskite displacing ∼90% of lead, simultaneously retaining its unique excitonic emission, with an additional orange emission of Mn2+ via energy transfer. A high Mn solubility limit of 90% was attained for the first time in lead halide perovskites, facilitated by the flexible organic cation (CH3NH3)+ network, preserving the perovskite structure. The emission intensities of the exciton and Mn were influenced by the halide identity that regulates the energy transfer to Mn. Homogeneous emission and electron spin resonance characteristics of Mn2+ indicate a uniform distribution of Mn. These results suggest that low-toxicity 3D-CH3NH3Pb1-xMnxBr3-(2x+1)Cl2x+1 nanocrystals may be exploited as magnetically doped quantum dots with unique optoelectronic properties.

Engineering the Lattice Site Occupancy of Apatite-Structure Phosphors for Effective Broad-Band Emission through Cation Pairing.

A series of britholite compounds were synthesized by simultaneous introduction of trivalent La3+ and Si4+ ions into an apatite structure. The variations in the average structure, electronic band structure, and microstructural properties resulting from the introduction of cation pairs were analyzed as a function of their concentration. The effects of the structural variance and microstructural properties on the broad-band-emitting activator ions were studied by introducing Eu2+ ions as activators. For the resulting compound, which had dual emission bands in the blue and yellow regions of the spectrum, the emission peak position and strength were dependent upon the concentration of La3+-Si4+ pairs. By engineering the relative sizes of the two possible activator sites in the structure, 4f and 6h, through the introduction of a combination of trivalent La3+ and a polyanion, the preferential site occupancy of the activator ions was favorably altered. Additionally, the activator ions responsible for the lower-Stokes-shifted blue component of the emission functioned as a sensitizer of the larger-Stokes-shifted yellow-emitting activators, and predominantly yellow-emitting phosphors were achieved. The feasibility of developing a white light-emitting solid-state device using the developed phosphor was also demonstrated.