Excitation-Selective and Double-Emissive Lead-Free Binary Hybrid Metal Halides for White Light-Emitting Diode and X-Ray Scintillation.

Zero-dimensional (0D) organic metal halides comprising heterogeneous metal cations in single phase can achieve multiple luminous emissions enabling them toward multifunctional light-emitting applications. Herein, A novel single crystal of (C8H20N)4SbMnCl9 containing two luminescent centers of [SbCl5]2- pentahedrons and [MnCl4]2- tetrahedrons is reported. The large distance between Sb-Sb, Mn-Mn, and Sb-Mn as well as theory calculation indicate negligible interaction between individual centers, thus endowing (C8H20N)4SbMnCl9 with excitation-dependable and efficient luminescence. Under near-UV excitation, only orange emission originates from self-trapped excitons recombination in [SbCl5]2- pentahedron occurs with photoluminescence quantum yield (PLQY) of 91.5%. Under blue-light excitation, only green emission originating from 4T1-6A1 transition of Mn2+ in [MnCl4]2- tetrahedrons occurs with PLQY of 66.8%. Interestingly, upon X-ray illumination, both emissions can be fully achieved due to the high-energy photon absorption. Consequently, (C8H20N)4SbMnCl9 is employed as phosphors to fabricate white light-emitting diodes optically pumped by n-UV chip and blue-chip thanks to its excitation-dependable property. Moreover, it also shows promising performance as X-ray scintillator with low detection limit of 60.79 nGyair S-1, steady-state light yield ≈54% of commerical scintillaotr LuAG:Ce, high resolution of 13.5 lp mm-1 for X-ray imaging. This work presents a new structural design to fabricate 0D hybrids with multicolor emissions.

Suppressed Concentration Quenching Brightens Short-Wave Infrared Emitters.

The brightness of doped luminescent materials is usually limited by the ubiquitous concentration quenching phenomenon resulting in an intractable tradeoff between internal quantum efficiency and excitation efficiency. Here, an intrinsic suppression of concentration quenching in sensitized luminescent systems, by exploiting the competitive relationship between light emitters and quenchers in trapping excitation energies from sensitizers, is reported. Although Cr3+ sensitizers and trivalent lanthanide (Ln3+ , Ln = Yb, Nd, and Er) emitters themselves are highly susceptible to concentration quenching, the unprecedentedly high-brightness luminescence of Cr3+ -Ln3+ systems is demonstrated in the short-wave infrared (SWIR) range employing high concentrations of Cr3+ , whereby a record photoelectric efficiency of 23% is achieved for SWIR phosphor-converted light-emitting diodes, which is about twice as high as those previously reported. The results underscore the beneficial role of emitters in terminating excitation energies, opening up a new dimension for developing efficient sensitized luminescent materials.

Toughening oxide glasses through paracrystallization.

Glasses, unlike crystals, are intrinsically brittle due to the absence of microstructure-controlled toughening, creating fundamental constraints for their technological applications. Consequently, strategies for toughening glasses without compromising their other advantageous properties have been long sought after but elusive. Here we report exceptional toughening in oxide glasses via paracrystallization, using aluminosilicate glass as an example. By combining experiments and computational modelling, we demonstrate the uniform formation of crystal-like medium-range order clusters pervading the glass structure as a result of paracrystallization under high-pressure and high-temperature conditions. The paracrystalline oxide glasses display superior toughness, reaching up to 1.99 ± 0.06 MPa m1/2, surpassing any other reported bulk oxide glasses, to the best of our knowledge. We attribute this exceptional toughening to the excitation of multiple shear bands caused by a stress-induced inverse transformation from the paracrystalline to amorphous states, revealing plastic deformation characteristics. This discovery presents a potent strategy for designing highly damage-tolerant glass materials and emphasizes the substantial influence of atomic-level structural variation on the properties of oxide glasses.

Glass-Crystallized Luminescence Translucent Ceramics toward High-Performance Broadband NIR LEDs.

Near-infrared (NIR) phosphor-converted light-emitting diodes (pc-LEDs) are newly emergent broadband light sources for miniaturizing optical systems like spectrometers. However, traditional converters with NIR phosphors encapsulated by organic resins suffer from low external quantum efficiency (EQE), strong thermal quenching as well as low thermal conductivity, thus limiting the device efficiency and output power. Through pressureless crystallization from the designed aluminosilicate glasses, here broadband Near-infrared (NIR) emitting translucent ceramics are developed with high EQE (59.5%) and excellent thermal stability (<10% intensity loss and negligible variation of emission profile at 150 °C) to serve as all-inorganic visible-to-NIR converters. A high-performance NIR phosphor-converted light emitting diodes is further demonstrated with a record NIR photoelectric efficiency (output power) of 21.2% (62.6 mW) at 100 mA and a luminescence saturation threshold up to 184 W cm-2 . The results can substantially expand the applications of pc-LEDs, and may open up new opportunity to design efficient broadband emitting materials.

Low-dose real-time X-ray imaging with nontoxic double perovskite scintillators.

X-rays are widely used in probing inside information nondestructively, enabling broad applications in the medical radiography and electronic industries. X-ray imaging based on emerging lead halide perovskite scintillators has received extensive attention recently. However, the strong self-absorption, relatively low light yield and lead toxicity of these perovskites restrict their practical applications. Here, we report a series of nontoxic double-perovskite scintillators of Cs2Ag0.6Na0.4In1-yBiyCl6. By controlling the content of the heavy atom Bi3+, the X-ray absorption coefficient, radiative emission efficiency, light yield and light decay were manipulated to maximise the scintillator performance. A light yield of up to 39,000 ± 7000 photons/MeV for Cs2Ag0.6Na0.4In0.85Bi0.15Cl6 was obtained, which is much higher than that for the previously reported lead halide perovskite colloidal CsPbBr3 (21,000 photons/MeV). The large Stokes shift between the radioluminescence (RL) and absorption spectra benefiting from self-trapped excitons (STEs) led to a negligible self-absorption effect. Given the high light output and fast light decay of this scintillator, static X-ray imaging was attained under an extremely low dose of ∼1 µGyair, and dynamic X-ray imaging of finger bending without a ghosting effect was demonstrated under a low-dose rate of 47.2 µGyair s-1. After thermal treatment at 85 °C for 50 h followed by X-ray irradiation for 50 h in ambient air, the scintillator performance in terms of the RL intensity and X-ray image quality remained almost unchanged. Our results shed light on exploring highly competitive scintillators beyond the scope of lead halide perovskites, not only for avoiding toxicity but also for better performance.

Highly efficient phosphor-glass composites by pressureless sintering.

The development of high-power white light-emitting diodes demands highly efficient and stable all-inorganic color converters. In this respect, phosphor-glass/ceramic composites show great promise as they could combine the merits of high quantum efficiency of phosphors and high chemical and thermal stabilities of glass/ceramic matrices. However, strong interfacial reaction between phosphors and matrices at high temperature results in quantum efficiency loss of the embedded phosphors, and traditional solutions rely on high-pressure consolidation techniques. Here we report the intrinsic inhibition of interfacial reaction by using silica glass rather than multicomponent glasses as the matrix. The embedment of phosphors is achieved via a pressureless sintering method, rendering these color-tunable phosphor-glass composites not only accessible to three-dimensional printing technique, but also highly efficient (internal quantum efficiency >90.0%), thermally stable at 1200 °C and hydrothermally stable at 200 °C. Our results provide a facile and general strategy for developing all-inorganic functional composites.

Efficient Visible-to-NIR Spectral Conversion for Polycrystalline Si Solar Cells and Revisiting the Energy Transfer Mechanism from Ce3+ to Yb3+ in Lu3Al5O12 Host.

The so-called Shockley-Queisser converting efficiency limit of Si solar cells is believed to be surpassed by using the spectral converter. However, searching for efficient spectral converting materials is still a challenging task. In this paper, efficient visible-to-NIR spectral conversion for polycrystalline Si solar cells has been demonstrated in Ce3+ and Yb3+ codoped Lu3Al5O12. Moreover, the underlying energy transfermechanism from Ce3+ to Yb3+ is systematically re-investigated by the detailed excitation and emission spectra as well as fluorescent decay curves, and our results demonstrate that fast metal-to-metal charge transfer from Ce3+ to nearby Yb3+ is the dominant energy transfermechanism. Finally, we provide new evidence that Ce4+-Yb2+ charge-transfer state is responsible for the relatively low quantum efficiency of NIR emission in Ce3+ and Yb3+ codoped system.

The Inductive Effect of Neighboring Cations in Tuning Luminescence Properties of the Solid Solution Phosphors.

Forming solid solutions through cation substitution is an efficient way to improve the luminescence properties of Ce3+ or Eu2+ activated phosphors and even to develop new ones, which is badly needed for phosphor-converted white LEDs. Here, we report new color tunable solid solution phosphors based on Eu2+ activated K2Al2B2O7 as a typical case to demonstrate that, besides crystal field splitting of 5d levels, centroid shift and Stokes shift can be dominant in tuning excitation and emission spectra as well as thermal stability of solid solution phosphors, both of which were previously considered to be negligible. Moreover, a general model involving the inductive effect of neighboring cations is proposed to explain the obvious variations in centroid shift and Stokes shift with cation substitution. Our work is propitious for the construction of more reasonable structure-property relations and thus offers theoretical guidance for designing solid solution phosphors.

Highly Efficient Green-Emitting Phosphors Ba2Y5B5O17 with Low Thermal Quenching Due to Fast Energy Transfer from Ce3+ to Tb3.

This paper demonstrates a highly thermally stable and efficient green-emitting Ba2Y5B5O17:Ce3+, Tb3+ phosphor prepared by high-temperature solid-state reaction. The phosphor exhibits a blue emission band of Ce3+ and green emission lines of Tb3+ upon Ce3+ excitation in the near-UV spectral region. The effect of Ce3+ to Tb3+ energy transfer on blue to green emission color tuning and on luminescence thermal stability is studied in the samples codoped with 1% Ce3+ and various concentrations (0-40%) of Tb3+. The green emission of Tb3+ upon Ce3+ excitation at 150 °C can keep, on average, 92% of its intensity at room temperature, with the best one showing no intensity decreasing up to 210 °C for 30% Tb3+. Meanwhile, Ce3+ emission intensity only keeps 42% on average at 150 °C. The high thermal stability of the green emission is attributed to suppression of Ce3+ thermal de-excitation through fast energy transfer to Tb3+, which in the green-emitting excited states is highly thermally stable such that no lifetime shortening is observed with raising temperature to 210 °C. The predominant green emission is observed for Tb3+ concentration of at least 10% due to efficient energy transfer with the transfer efficiency approaching 100% for 40% Tb3+. The internal and external quantum yield of the sample with Tb3+ concentration of 20% can be as high as 76% and 55%, respectively. The green phosphor, thus, shows attractive performance for near-UV-based white-light-emitting diodes applications.

Blue-emitting K2Al2B2O7:Eu(2+) phosphor with high thermal stability and high color purity for near-UV-pumped white light-emitting diodes.

Novel blue-emitting K2Al2B2O7:Eu(2+) (KAB:Eu(2+)) phosphor was synthesized by solid state reaction. The crystal structural and photoluminescence (PL) properties of KAB:Eu(2+) phosphor, as well as its thermal properties of the photoluminescence, were investigated. The KAB:Eu(2+) phosphor exhibits broad excitation spectra ranging from 230 to 420 nm, and an intense asymmetric blue emission band centered at 450 nm under λex = 325 nm. Two different Eu(2+) emission centers in KAB:Eu(2+) phosphor were confirmed via their fluorescence decay lifetimes. The optimal concentration of Eu(2+) ions in K2-xEuxAl2B2O7 was determined to be x = 0.04 (2 mol %), and the corresponding concentration quenching mechanism was verified to be the electric dipole-dipole interactions. The PL intensity of the nonoptimized KAB:0.04Eu(2+) phosphor was measured to be ∼58% that of the commercial blue-emitting BaMgAl10O17:Eu(2+) phosphor, and this phosphor has high color purity with the CIE coordinate (0.147, 0.051). When heated up to 150 °C, the KAB:0.04Eu(2+) phosphor still has 82% of the initial PL intensity at room temperature, indicating its high thermal stability. These results suggest that the KAB:Eu(2+) is a promising candidate as a blue-emitting n-UV convertible phosphor for application in white light emitting diodes.