Robust and orange-yellow-emitting Sr-rich polytypoid α-SiAlON (Sr3Si24Al6N40:Eu2+) phosphor for white LEDs.

Nitrides and oxynitrides isostructural to α-Si3N4 (M-α-SiAlON, M = Sr, Ca, Li) possess superb thermally stable photoluminescence (PL) properties, making them reliable phosphors for high-power solid-state lighting. However, the synthesis of phase-pure Sr-α-SiAlON still remains a great challenge and has only been reported for Sr below 1.35 at.% as the large size of Sr2+ ions tends to destabilize the α-SiAlON structure. Here, we succeeded to synthesize the single-phase powders of a unique 'Sr-rich' polytypoid α-SiAlON (Sr3Si24Al6N40:Eu2+) phosphor with three distinctive Sr/Eu luminescence sites using a solid-state remixing-reannealing process. The Sr content of this polytypoid structure exceeds those of a few previously reported structures by over 200%. The phase purity, composition, structure, and PL properties of this phosphor were investigated. A single phase can be obtained by firing the stoichiometric mixtures of all-nitride precursors at 2050°C under a 0.92 MPa N2 atmosphere. The Sr3Si24Al6N40:Eu2+ shows an intense orange-yellow emission, with the emission maximum of 590 nm and internal/external quantum efficiency of 66%/52% under 400 nm excitation. It also has a quite small thermal quenching, maintaining 93% emission intensity at 150°C. In comparison to Ca-α-SiAlON:Eu2+, this Sr counterpart shows superior quantum efficiency and thermal stability, enabling it to be an interesting orange-yellow down-conversion luminescent material for white LEDs. The experimental confirmation of the existence of such 'Sr-rich' SiAlON systems, in a single-phase powder form, paves the way for the design and synthesis of novel 'Sr-rich' SiAlON-based phosphor powders with unparalleled properties.

A distinctive orange-yellow-emitting 'Sr-rich' α-SiAlON-based phosphor with quite small thermal quenching (93% PL intensity at 150°C) that can surprisingly be synthesized in a single-phase powder form for white LEDs.

Enabling Visible-Light-Charged Near-Infrared Persistent Luminescence in Organics by Intermolecular Charge Transfer.

Visible light is a universal and user-friendly excitation source; however, its use to generate persistent luminescence (PersL) in materials remains a huge challenge. Herein, the concept of intermolecular charge transfer (xCT) is applied in typical host-guest molecular systems, which allows for a much lower energy requirement for charge separation, thus enabling efficient charging of near-infrared (NIR) PersL in organics by visible light (425-700 nm). Importantly, NIR PersL in organics occurs via the trapping of electrons from charge-transfer aggregates (CTAs) into constructed trap states with trap depths of 0.63-1.17 eV, followed by the detrapping of these electrons by thermal stimulation, resulting in a unique light-storage effect and long-lasting emission up to 4.6 h at room temperature. The xCT absorption range is modulated by changing the electron-donating ability of a series of acenaphtho[1,2-b]pyrazine-8,9-dicarbonitrile-based CTAs, and the organic PersL is tuned from 681 to 722 nm. This study on xCT interaction-induced NIR PersL in organic materials provides a major step forward in understanding the underlying luminescence mechanism of organic semiconductors and these findings are expected to promote their applications in optoelectronics, energy storage, and medical diagnosis.

Quantifying the interfacial triboelectricity in inorganic-organic composite mechanoluminescent materials.

Mechanoluminescence (ML) sensing technologies open up new opportunities for intelligent sensors, self-powered displays and wearable devices. However, the emission efficiency of ML materials reported so far still fails to meet the growing application requirements due to the insufficiently understood mechano-to-photon conversion mechanism. Herein, we propose to quantify the ability of different phases to gain or lose electrons under friction (defined as triboelectric series), and reveal that the inorganic-organic interfacial triboelectricity is a key factor in determining the ML in inorganic-organic composites. A positive correlation between the difference in triboelectric series and the ML intensity is established in a series of composites, and a 20-fold increase in ML intensity is finally obtained by selecting an appropriate inorganic-organic combination. The interfacial triboelectricity-regulated ML is further demonstrated in multi-interface systems that include an inorganic phosphor-organic matrix and organic matrix-force applicator interfaces, and again confirmed by self-oxidization and reduction of emission centers under continuous mechanical stimulus. This work not only gives direct experimental evidences for the underlying mechanism of ML, but also provides guidelines for rationally designing high-efficiency ML materials.

Tunable Emission of Low-Dimensional Organic Metal Halides by Stoichiometric Ratio and Metal Center.

Low-dimensional (LD) organic metal halides (OMHs) have a bright future due to their excellent photoelectric characteristics and unique structure. However, the synthesis and emission control of LD-OMHs are still unclear. Herein, the different dimensional (zero-dimensional (0D), one-dimensional (1D), and three-dimensional (3D)) of OMHs were obtained by the reaction of 1,4-diazabicyclo (2.2.2) octane with PbBr2 in different stoichiometric ratios. This discovery shows that the structure and properties of OMHs can be regulated while maintaining the functional organic cations of OMHs, which broadens the path for the development of functional LD-OMHs. Among them, 0D-OMH 1 and 1D-OMH 3 have narrow-band (full width at half-maximum (fwhm) = 74 nm) and broad-band (fwhm = 201 nm) emission, respectively. We found that when organic cations have no contribution to the formation of conduction band minimum and valence band maximum, and the distances between polyhedrons are larger than the van der Waals diameter of the halogen atom, the effect of phonons on exciton transitions can be reduced to achieve a narrow-band emission. Further, Cu(I)- and Mn (II)-based 0D-OMHs were synthesized, which have high photoluminescence quantum yield (PLQY) (33.97 and 47.33%, respectively). When the emitting of 0D-OMHs produced by the interaction of the metal-center and halogens, the asymmetric planar metal-halogen structure will result in a higher PLQY.

Water-Soluble Quantum Dots for Inkjet Printing Color Conversion Films with Simultaneous High Efficiency and Stability.

Water-soluble quantum dots (QDs) are necessary to prepare patterned pixels or films for high-resolution displays with less environmental burden but are very limited by the trade-off between photoluminescence and stability of QDs. In this work, we proposed synthesizing water-soluble QDs with simultaneous excellent luminescence properties and high stability by coating the amphiphilic poly(maleic anhydride-alt-1-octadecene)-ethanol amine (PMAO-EA) polymer on the surface of silane-treated QDs. These coated QDs show a photoluminescence quantum yield (PLQY) as high as 94%, and they have good photoluminescence stability against light irradiation and thermal attacks, owing to the suppression of the nonradiative recombination by the polymer layer and the isolation of oxygen and water by the silica layer. The water-soluble QDs, mixed with ethylene glycol, enable inkjet printing of QD color conversion films (QD-CCFs) with an average diameter of 68 µm for each pixel and a high PLQY of 91%. The QD-CCFs are demonstrated to fabricate red-emitting mini-LEDs by combining with blue mini-LED chips, which have an external quantum efficiency as high as 25.86% and a luminance of 2.44 × 107 cd/m2. We believe that the proposed strategy is applicable to other water-soluble QDs and paves an avenue for inkjet printing environmentally friendly QD-CCFs for mini/micro-LED displays.

Correction: A super-high brightness and excellent colour quality laser-driven white light source enables miniaturized endoscopy.

Correction for 'A super-high brightness and excellent colour quality laser-driven white light source enables miniaturized endoscopy' by Shuxing Li et al., Mater. Horiz., 2023, 10, 4581-4588, https://doi.org/10.1039/D3MH01170D.

Ligand Engineering Enables Efficient Pure Red Tin-Based Perovskite Light-Emitting Diodes.

With increasing ecological and environmental concerns, tin (Sn)-based perovskite light-emitting diodes (PeLEDs) are competitive candidates for future displays because of their environmental friendliness, excellent photoelectric properties, and low-cost solution-processed fabrication. Nonetheless, their electroluminescence (EL) performance still lags behind that of lead (Pb)-based PeLEDs due to the fast crystallization rate of Sn-based perovskite films and undesired oxidation from Sn2+ to Sn4+ , leading to poor film morphology and coverage, as well as high density defects. Here, we propose a ligand engineering strategy to construct high-quality phenethylammonium tin iodide (PEA2 SnI4 ) perovskite films by using L-glutathione reduced (GSH) as surface ligands toward efficient pure red PEA2 SnI4 -based PeLEDs. We show that the hydrogen-bond and coordinate interactions between GSH and PEA2 SnI4 effectively reduce the crystallization rate of the perovskites and suppress the oxidation of Sn2+ and formation of defects. The improved pure red perovskite films not only show excellent uniformity, density, and coverage but also exhibit enhanced optical properties and stability. Finally, state-of-the-art pure red PeLEDs achieve a record external quantum efficiency of 9.32 % in the field of PEA2 SnI4 -based devices. This work demonstrates that ligand engineering represents a feasible route to enhance the EL performance of Sn-based PeLEDs.

A super-high brightness and excellent colour quality laser-driven white light source enables miniaturized endoscopy.

A laser-driven white light source promises intrinsic advantages for miniaturized endoscopic illumination. However, it remains a great challenge to simultaneously achieve high brightness and excellent colour rendition due to the shortage of highly efficient and thermally robust red-emitting laser phosphor converters. Here, we designed CaAlSiN3:Eu@Al (CASN@Al) converters with neglectable efficiency loss by tightly bonding all-inorganic phosphor films on an aluminium substrate. A layer-by-layer phosphor converter (LuAG/CASN@Al), i.e., stacking a green-emitting Lu3Al5O12:Ce (LuAG) layer on CASN@Al, was constructed to enhance light conversion efficiency and reduce reabsorption loss under blue laser excitation, which thus produces an excellent white light source with a luminous efficacy of 258 lm W-1 and a colour rendering index of 91. A miniaturized endoscopy with a coupling efficiency twice that of the commercial white LEDs was demonstrated by using the laser-driven white light and showed a central illuminance as high as 52 730 lx, more vivid images and long-term reliability.

Constructing Perovskite/Polymer Core/Shell Nanocrystals with Simultaneous High Efficiency and Stability for Mini-LED Backlights.

Lead halide perovskite nanocrystals (NCs) have been the star material in lighting and displays owing to their excellent photoelectrical properties, but they have not simultaneously realized high photoluminescence quantum yield (PLQY) and high stability. To solve this problem, we propose a perovskite/linear low-density polyethylene (perovskite/LLDPE) core/shell NC by the synergistic role of the pressure effect and steric effect. Green CsPbBr3/LLDPE core/shell NCs with near-unity PLQY and nonblinking behavior were synthesized through an in situ hot-injection process. The mechanism of the improved photoluminescence (PL) properties is the enhanced pressure effect resulting in increased radiative recombination and interaction between the ligand and perovskite crystals, as confirmed by the PL spectra and finite element calculations. Meanwhile, the NCs show high stability under ambient conditions (with a PLQY of 92.5% after 166 days) and against 365 nm UV light (maintaining 61.74% of the initial PL intensity after continuous radiation for 1000 min). This strategy also works well in the blue and red perovskite/LLDPE NCs and red InP/ZnSeS/ZnS/LLDPE NCs. Finally, white-emitting Mini-LEDs were fabricated by combining the green CsPbBr3/LLDPE and red CsPbBr1.2I1.8/LLDPE core/shell NCs with blue Mini-LED chips. The white-emitting Mini-LEDs exhibit super wide color gamut (∼129% of the National Television Standards Committee or 97% of the Rec. 2020 standards).

Perovskite Light-Emitting Diodes with an External Quantum Efficiency Exceeding 30.

Perovskite light-emitting diodes (PeLEDs) are strong candidates for next-generation display and lighting technologies due to their high color purity and low-cost solution-processed fabrication. However, PeLEDs are not superior to commercial organic light-emitting diodes (OLEDs) in efficiency, as some key parameters affecting their efficiency, such as the charge carrier transport and light outcoupling efficiency, are usually overlooked and not well optimized. Here, ultrahigh-efficiency green PeLEDs are reported with quantum efficiencies surpassing a milestone of 30% by regulating the charge carrier transport and near-field light distribution to reduce electron leakage and achieve a high light outcoupling efficiency of 41.82%. Ni0.9 Mg0.1 Ox films are applied with a high refractive index and increased hole carrier mobility as the hole injection layer to balance the charge carrier injection and insert the polyethylene glycol layer between the hole transport layer and the perovskite emissive layer to block the electron leakage and reduce the photon loss. Therefore, with the modified structure, the state-of-the-art green PeLEDs achieve a world record external quantum efficiency of 30.84% (average =  29.05 ± 0.77%) at a luminance of 6514 cd m-2 . This study provides an interesting idea to construct super high-efficiency PeLEDs by balancing the electron-hole recombination and enhancing the light outcoupling.

Organic Sulfonium-Stabilized High-Efficiency Cesium or Methylammonium Lead Bromide Perovskite Nanocrystals.

Herein, we report a new X-type ligand, i.e., organic sulfonium bromide, for high-efficiency CsPbBr3 and MAPbBr3 (MA=methylammonium) perovskite nanocrystals (PNCs). We first confirmed the facile synthesis of the titled ligands in N,N-dimethylformamide at room temperature. By reacting dodecylmethylsulfide with allyl bromide, (3-bromopropyl)trimethoxysilane, and 1,4-dibromobutane, respectively, three representative ligands (named DAM, DSM, and DMM) are acquired. All of them result in CsPbBr3 and MAPbBr3 PNCs with near-unity photoluminescence quantum yield (PLQY) and decent ambient stability (no less than 90 % PLQY after 2 months) using a room-temperature ligand-assisted reprecipitation technique. Among them, DSM and DMM endow CsPbBr3 PNCs with higher thermal/light stability arising from the cross-linkable or bidentate ligand structure. Further, DSM-CsPbBr3 PNCs can be incorporated into polystyrene through in situ thermal polymerization and the composite shows a record-high PLQY of 93.8 %.

Visualizing Dynamic Mechanical Actions with High Sensitivity and High Resolution by Near-Distance Mechanoluminescence Imaging.

Proportionally converting the applied mechanical energy into photons by individual mechanoluminescent (ML) micrometer-sized particles opens a new way to develop intelligent electronic skins as it promises high-resolution stress distribution visualization and fast response. However, a big challenge for ML sensing technology is its low sensitivity in detecting stress. In this work, a novel stress distribution sensor with the detection sensitivity enhanced by two orders of magnitude is developed by combining a proposed near-distance ML imaging scheme with an improved mechano-to-photon convertor. The enhanced sensitivity is the main contributor to the realization of a maximum photon harvesting rate of ≈80% in the near-distance ML imaging scheme. The developed near-distance ML sensor shows a high sensitivity with a detection limit down to ≈kPa level, high spatial resolution of 254 dpi, and fast response with an interval of 3.3 ms, which allows for high-resolution and real-time visualization of complex mechanical actions such as irregular solid contacts or fluid impacts, and thus enables use in intelligent electronic skin, structural health monitoring, and human-computer interaction.

Time-Gated Imaging of Latent Fingerprints with Level 3 Details Achieved by Persistent Luminescent Fluoride Nanoparticles.

The discovery of X-ray-charged persistent luminescence (PersL) in fluoride nanoparticles enables these materials to emit photons without real-time excitation, which provides a great possibility for the development of new luminescent nanotechnologies. In this work, we developed NaLuF4:Mn nanoparticles with intense green PersL and functionalized surfaces and accordingly achieved time-gated imaging of latent fingerprints (LFPs) with Level 3 details. These surface-modified NaLuF4:Mn nanoparticles exhibited near-spherical morphology, long-lasting emission for several hours, appropriate trap depth distribution, and tight chemical bonding with amino acids from fingerprints, thus greatly improving the accuracy of LFP imaging in a variety of environments. The developed NaLuF4:Mn PersL nanoparticles are expected to find broad applications in the fields of LFP imaging and in vivo biological imaging.

Passivation Layer of Potassium Iodide Yielding High Efficiency and Stable Deep Red Perovskite Light-Emitting Diodes.

Perovskite light-emitting diodes (PeLEDs) are promising candidates used for superthin emissive displays with high resolution, high brightness, and wide color gamut, but the CsPbI3 nanocrystal (NC) based ones usually have an external quantum efficiency (EQE) of less than 20%, which needs further enhancement to minimize the gap between their counterparts. Herein, we propose to improve optical properties of the CsPbI3:Sr emissive layer (EML) by inserting an additional potassium iodide (KI) passivation layer between the hole transport layer and EML to increase the film quality, photoluminescence quantum yield, and thermal stability of the EML. The KI layer can also increase the carrier mobility to balance the charge injection in PeLEDs, leading to a reduction in Auger recombination and Joule heating. An interesting deep-red-emitting PeLED (λem = 687 nm) with a record EQE of 21.8% and a lifetime T50 of 69 min is obtained by applying the additional KI passivation layer. Moreover, a flexible PeLED consisting of the KI layer is also demonstrated to have a record EQE of 12.7%. These results indicate that the use of a functional KI layer is a feasible way to develop high-performance electroluminescent devices.

In Situ Inkjet Printing Patterned Lead Halide Perovskite Quantum Dot Color Conversion Films by Using Cheap and Eco-Friendly Aqueous Inks.

Inkjet-printed perovskite quantum dot (PQD) color conversion films (CCFs) have great potentials for mini/micro-LED displays because of their ultrahigh color purity, tunable emissions, high efficiency, and high-resolution. However, current PQD inks mainly use expensive, toxic, and flammable organic substances as solvents. In this work, water is proposed to be used as the solvent for inkjet printing PQD/polymer CCFs. The green-emitting patterned MAPbBr3 /polyvinyl alcohol (PVA) films are in situ prepared by using halides and the PVA-based aqueous ink. The as-printed CCFs exhibit a high-resolution dot matrix of 90 µm with a bright green emission (λem  = 526 nm), a high photoluminescence quantum yield of 85%, and a narrow full width at half maximum of 22 nm. They have both air- and photo-stabilities under ambient conditions, and each pixel of CCFs is relatively uniform in morphology and fluorescence when the substrate temperature is 80 °C. The patterned blue-emitting MAPbClx Br3-x /PVA and red-emitting Cs0.3 MA0.7 PbBrx I3-x /PVA can also be printed by aqueous inks. These results indicate that the designed aqueous inks are promising for in situ inkjet printing high resolution and reliability PQD CCFs for mini/micro-LED displays.

X-ray-charged bright persistent luminescence in NaYF4:Ln3+@NaYF4 nanoparticles for multidimensional optical information storage.

NaYF4:Ln3+, due to its outstanding upconversion characteristics, has become one of the most important luminescent nanomaterials in biological imaging, optical information storage, and anticounterfeiting applications. However, the large specific surface area of NaYF4:Ln3+ nanoparticles generally leads to serious nonradiative transitions, which may greatly hinder the discovery of new optical functionality with promising applications. In this paper, we report that monodispersed nanoscale NaYF4:Ln3+, unexpectedly, can also be an excellent persistent luminescent (PersL) material. The NaYF4:Ln3+ nanoparticles with surface-passivated core-shell structures exhibit intense X-ray-charged PersL and narrow-band emissions tunable from 480 to 1060 nm. A mechanism for PersL in NaYF4:Ln3+ is proposed by means of thermoluminescence measurements and host-referred binding energy (HRBE) scheme, which suggests that some lanthanide ions (such as Tb) may also act as effective electron traps to achieve intense PersL. The uniform and spherical NaYF4:Ln3+ nanoparticles are dispersible in solvents, thus enabling many applications that are not accessible for traditional PersL phosphors. A new 3-dimensional (2 dimensions of planar space and 1 dimension of wavelength) optical information-storage application is demonstrated by inkjet-printing multicolor PersL nanoparticles. The multicolor persistent luminescence, as an emerging and promising emissive mode in NaYF4:Ln3+, will provide great opportunities for nanomaterials to be applied to a wider range of fields.

Phosphorus-Doped Metal-Organic Framework-Derived CoS2 Nanoboxes with Improved Adsorption-Catalysis Effect for Li-S Batteries.

Lithium-sulfur (Li-S) batteries are regarded as one of the most promising next-generation battery technologies owing to their ultrahigh energy density up to 2600 W h kg-1 and low cost. However, major challenges still remain in the application of Li-S batteries, such as shuttle effect and sluggish redox kinetics. Herein, it is demonstrated that phosphorus doping can not only significantly improve the polysulfide adsorption but also enhance the catalysis effects of metal-organic framework-derived CoS2 nanoboxes in Li-S batteries. Consequently, a modified separator integrated with P-CoS2 and carbon nanotubes effectively suppresses the polysulfide shuttle and propels the redox kinetics of polysulfides, thus promising higher specific discharge capacity, better rate, and stable cycle performance. Even under the high sulfur loading condition (4.8 mg cm-2), the areal discharge capacity of the cell with the functional separator can still remain at 4.5 mA h cm-2 after 100 cycles at 0.2 C. More importantly, this work may encourage more effort on anion doping for engineering the polar surface of transition-metal compounds to further mediate the interfacial redox chemistry between transition-metal compounds and polysulfides in Li-S batteries.

Mechanoluminescence Rebrightening the Prospects of Stress Sensing: A Review.

The emergence of new applications, such as in artificial intelligence, the internet of things, and biotechnology, has driven the evolution of stress sensing technology. For these emerging applications, stretchability, remoteness, stress distribution, a multimodal nature, and biocompatibility are important performance characteristics of stress sensors. Mechanoluminescence (ML)-based stress sensing has attracted widespread attention because of its characteristics of remoteness and having a distributed response to mechanical stimuli as well as its great potential for stretchability, biocompatibility, and self-powering. In the past few decades, great progress has been made in the discovery of ML materials, analysis of mechanisms, design of devices, and exploration of applications. One can find that with this progress, the focus of ML research has shifted from the phenomenon in the earliest stage to materials and recently toward devices. At the present stage, while showing great prospects for advanced stress sensing applications, ML-based sensing still faces major challenges in material optimization, device design, and system integration.

In situ TEM study of edge reconstruction and evolution in monolayer black phosphorus.

As symmetry-breaking interfaces, edges inevitably influence material properties, particularly for low-dimensional materials such as two-dimensional (2D) graphene and black phosphorus (BP). Hence, exploiting pristine edge structures and the associated edge reconstruction is important. In this study, we revealed edge reconstruction and evolution in monolayer BP (ML-BP) via in situ high-resolution transmission electron microscopy. Under our typical experimental conditions, spontaneous edge reconstruction occurred in all types of as-prepared edges that include zigzag, Klein zigzag, diagonal, and Klein diagonal edges. Reconstruction induces a periodic variation of the bond length and bond angles of edge atoms: an out-of-plane bending for zigzag and diagonal edge atoms and a dimerization for two neighboring edge atoms on the Klein edge, respectively. Surface atom diffusion can also induce edge structural evolution as evidenced by the atomic scale dynamics captured for the zigzag edge. Experimentally resolved edge configurations and reconstruction were further corroborated by ab initio first-principles calculations. This study explores the understanding of the edge stability in 2D BP materials and may provide routes for precisely controlled edge structure engineering.

Force-induced charge carrier storage: a new route for stress recording.

Stress sensing is the basis of human-machine interface, biomedical engineering, and mechanical structure detection systems. Stress sensing based on mechanoluminescence (ML) shows significant advantages of distributed detection and remote response to mechanical stimuli and is thus expected to be a key technology of next-generation tactile sensors and stress recorders. However, the instantaneous photon emission in ML materials generally requires real-time recording with a photodetector, thus limiting their application fields to real-time stress sensing. In this paper, we report a force-induced charge carrier storage (FICS) effect in deep-trap ML materials, which enables storage of the applied mechanical energy in deep traps and then release of the stored energy as photon emission under thermal stimulation. The FICS effect was confirmed in five ML materials with piezoelectric structures, efficient emission centres and deep trap distributions, and its mechanism was investigated through detailed spectroscopic characterizations. Furthermore, we demonstrated three applications of the FICS effect in electronic signature recording, falling point monitoring and vehicle collision recording, which exhibited outstanding advantages of distributed recording, long-term storage, and no need for a continuous power supply. The FICS effect reported in this paper provides not only a breakthrough for ML materials in the field of stress recording but also a new idea for developing mechanical energy storage and conversion systems.