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Long-wavelength near-infrared (LWNIR) imaging technology has exciting application potential across various fields due to its ability of deeper penetration and unique properties related to its emission wavelength, when compared to short-wavelength near-infrared imaging. However, the limited availability of materials for LWNIR light sources, due to the lack of suitable host materials that constitute luminescence centers, has been a major challenge and technical obstacle in realizing such applications. Here, we developed MgIn2O4:Ni2+ phosphors with an antispinel structure and LWNIR luminescence properties through a sol-gel combustion method. Under excitation at 365 nm, its emission wavelength covers the range of 1000-2000 nm, with a peak emission at approximately 1520 nm, a full width at half-maximum of â¼340 nm, and an optimized photoluminescence quantum yield of â¼21.22%, when an optimal Ni2+ doping content of 1 mol % was used. Studies on the crystal structure of MgIn2O4 have shown that Ni2+ ions preferentially replace the lattice position occupied by Mg2+ ions in the [MgO6] octahedrons, which provides a crystal field microenvironment of weak strength to the Ni2+ luminescence centers and promotes their LWNIR emission with a large Stokes shift. A LWNIR pc-LED device was assembled using the optimized MgIn2O4:Ni2+ phosphor and a near-ultraviolet LED chip (@ 365 nm), and its potential applications, including NIR night vision imaging, nonvisual detection, and anticounterfeiting displays, were demonstrated. Our results show that the antispinel MgIn2O4:Ni2+ phosphor prepared by the sol-gel combustion method is a promising LWNIR luminescence material.
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Exploring strategies to improve the near-infrared response of photocatalysts is an urgent challenge that can be overcome by utilizing upconversion (UC) luminescence to enhance photocatalysis. This paper reports the fabrication of a ZnO/Bi3Ti2O8F:Yb3+, Er3+ (ZnO/BTOFYE) Z-scheme heterojunction based on a Bi3Ti2O8F:Yb3+, Er3+ (BTOFYE) UC photocatalyst via electrostatic self-assembly. Fermi energy difference at the interface of BTOFYE and ZnO generates a strong internal electric field (IEF) in the Z-scheme heterojunction, offering a novel charge transfer mode that promotes carrier transfer and separation while retaining the strong redox capability. These results are confirmed through in situ X-ray photoelectron spectroscopy, in situ Kelvin probe force microscopy, electron spin resonance, and density functional theory calculations. In addition, the effect of the IEF on the UC luminescence process of Er3+ enhances the luminescence intensity, considerably improving the UC utilization efficiency. The optimal ZnO/BTOFYE degrades 64 % of ciprofloxacin in 120 min, which is 2.3 times more than that degraded by BTOFYE. Overall, the results of this study offer a reference for the rational development of high efficiency UC photocatalysts by generating IEF in Z-scheme heterojunctions.
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Lanthanide-based NIR-II-emitting materials (1000-1700 nm) show promise for optoelectronic devices, phototherapy, and bioimaging. However, one major bottleneck to prevent their widespread use lies in low quantum efficiencies, which are significantly constrained by various quenching effects. Here, a highly oriented (222) facet is achieved via facet engineering for Cs2NaErCl6 double perovskites, enabling near-complete suppression of NIR-II luminescence quenching. The optimally (222)-oriented Cs2Ag0.10Na0.90ErCl6 microcrystals emit Er3+ 1540 nm light with unprecedented high quantum efficiencies of 90 ± 6% under 379 nm UV excitation (ultralarge Stokes shift >1000 nm), and a record near-unity quantum yield of 98.6% is also obtained for (222)-based Cs2NaYb0.40Er0.60Cl6 microcrystallites under 980 nm excitation. With combined experimental and theoretical studies, the underlying mechanism of facet-dependent Er3+ 1540 nm emissions is revealed, which can contribute to surface asymmetry-induced breakdown of parity-forbidden transition and suppression of undesired non-radiative processes. Further, the role of surface quenching is reexamined by molecular dynamics based on two facets, highlighting the drastic two-phonon coupling effect of a hydroxyl group to 4I13/2 level of Er3+. Surface-functionalized facets will provide new insights for tunable luminescence in double perovskites, and open up a new avenue for developing highly efficient NIR-II emitters toward broad applications.
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Upconversion luminescence plays a crucial role in various technological applications, and among the various valence states of lanthanide elements, Ln3+ has the highest stability. The 4f orbitals of these elements are in a fully empty, semifull, or full state. This special 4f electron configuration allows them to exhibit rich discrete energy levels. However, the 4f-4f transition of Ln3+ rare earth ions itself is prohibited, resulting in a lower luminescence efficiency. This limitation greatly hinders the practical application of upconversion luminescence. In this study, we report nanostructured luminescence-enhanced substrate platforms with both semiconductive local surface plasmons and spatially confined domain effects on a single defect semiconductor substrate. By coupling NaYF4:Yb-Er nanoparticle emitters to the surface of Ti3O5 NC-arrays plasmonic nanostructures, an ultrabright luminescence with a 32-fold increase in green emission and a 40-fold increase in red emission was achieved. Furthermore, the fluorescence resonance energy transfer characteristics observed in the R6G/NaYF4/Ti3O5 NC-array composite film enable accurate detection of fluorescent molecules. The results provide an innovative and intelligent approach to enhance the upconversion luminescence intensity of rare-doped nanoparticles and develop highly sensitive molecular detection systems based on the above luminescence enhancement.
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Near-infrared (NIR) phosphor conversion light-emitting diodes (pc-LEDs) have great application potential as NIR light sources in many fields such as food analysis, night vision illumination, and bioimaging for noninvasive medical diagnosis. In general, phosphors synthesized by a high-temperature solid-phase method have large particle sizes and have to be processed to fine powders by a grinding process, which may introduce surface defects and lower the luminous efficiency. Here, we report a sol-gel sintering method with ammonium nitrate and citric acid as the sacrificing agents to synthesize high purity, nanosized (less than 50 nm) Zr4+/Ni2+ codoped MgAl2O4 spinel NIR phosphors, in which MgAl2O4 spinel is the matrix, Ni2+ is the luminous center, and Zr4+ acts as the charge compensator. We systematically characterized the crystal structures and NIR luminescence properties of the Ni2+-doped MgAl2O4 and the Zr4+/Ni2+ codoped MgAl2O4. Under 390 nm light excitation, the emission spectrum of the Ni2+-doped MgAl2O4 phosphor covers 900-1600 nm, the half-peak width is 251 nm, and the peak position is located at 1230 nm. We demonstrated that by incorporating small amounts of Zr4+ as the charge compensator, the NIR emission intensity of the Zr4+/Ni2+ codoped MgAl2O4 nanosized phosphor was doubled over that of the Ni2+-doped MgAl2O4 phosphor. The optimal content of the charge compensator was 2 mol %. More importantly, the inclusion of Zr4+ led to a NIR phosphor with improved thermal stability in luminous properties, and the luminous intensity measured at 100 °C was 33.83% of that measured at room temperature (20 °C). This study demonstrates that NIR phosphor nanomaterials with high-purity and enhanced optical properties can be designed and synthesized through the charge compensation strategy by a sol-gel sintering method.
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X-ray radiation information storage, characterized by its ability to detect radiation with delayed readings, shows great promise in enabling reliable and readily accessible X-ray imaging and dosimetry in situations where conventional detectors may not be feasible. However, the lack of specific strategies to enhance the memory capability dramatically hampers its further development. Here, we present an effective anion substitution strategy to enhance the storage capability of NaLuF4:Tb3+ nanocrystals attributed to the increased concentration of trapping centers under X-ray irradiation. The stored radiation information can be read out as optical brightness via thermal, 980 nm laser, or mechanical stimulation, avoiding real-time measurement under ionizing radiation. Moreover, the radiation information can be maintained for more than 13 days, and the imaging resolution reaches 14.3 lp mm-1. These results demonstrate that anion substitution methods can effectively achieve high storage capability and broaden the application scope of X-ray information storage.
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Tissue engineered bracket materials provide essential support for the physiological protection and therapeutics of patients. Unfortunately, the implantation process of such devices poses the risk of surgical complications and infection. In this study, an upconversion nanoparticles (UCNPs)-assisted 3D bioprinting approach is developed to realize in vivo molding that is free from invasive surgery. Reasonably designed UCNPs, which convert near-infrared (NIR) photons that penetrate skin tissues into blue-violet emission (300-500 nm), induce a monomer polymerization curing procedure in vivo. Using a fused deposition modeling coordination framework, a precisely predetermined trajectory of the NIR laser enables the manufacture of implantable medical devices with tailored shapes. A proof of the 3D bioprinting of a noninvasive fracture fixation scaffold is achieved successfully, thus demonstrating an entirely new method of in vivo molding for biomedical treatment.
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Bioimpressão , Nanopartículas , Humanos , Luz , Próteses e ImplantesRESUMO
Water plays a vital role in all aspects of life. Recently, water pollution has increased exponentially due to various organic and inorganic pollutants. Organic pollutants are hard to degrade; therefore, cost-effective and sustainable approaches are needed to degrade these pollutants. Organic dyes are the major source of organic pollutants from coloring industries. The photoactive metal-organic frameworks (MOFs) offer an ultimate strategy for constructing photocatalysts to degrade pollutants present in wastewater. Therefore, tuning the metal ions/clusters and organic ligands for the better photocatalytic activity of MOFs is a tremendous approach for wastewater treatment. This review comprehensively reports various MOFs and their composites, especially POM-based MOF composites, for the enhanced photocatalytic degradation of organic pollutants in the aqueous phase. A brief discussion on various theoretical aspects such as density functional theory (DFT) and machine learning (ML) related to MOF and MOF composite-based photocatalysts has been presented. Thus, this article may eventually pave the way for applying different structural features to modulate novel porous materials for enhanced photodegradation properties toward organic pollutants.
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Lead-free metal halide perovskites have attracted attention because of their excellent optical properties and nontoxicity. Here, we report the synthesis of Sb3+-doped indium halide perovskite Cs2InCl5·H2O:Sb3+ by an improved solution coprecipitation method. The treatment of the Sb3+-doped indium halide perovskite with selected monovalent cation halides led to Cs2MInCl6 (Ag+, K+, Na+) in different crystal structures or phases. Sb3+ has an isolated ns2 electron, and Sb3+-doped metal halide acts as the luminescence center and exhibits bright broadband emission that originated from self-trapped excitons. Under UV light excitation, these phosphors with different crystal structures emitted multicolored luminescence ranging from blue, green, yellow, and red depending on whether or not or which monovalent metal ion was used. The phosphor samples were used to print high-resolution 2D color barcodes for security and anticounterfeiting applications. The study presented here provides a new approach for the design and synthesis of lead-free metal halide perovskites with different crystal structures and unique optical properties.
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The roles of Mn2+ ions in the MnCO3 compound, leading to the formation of an Mn2+-Yb3+ dimer and affecting the gain coefficient for the 4I13/2 â 4I15/2 transition of Er3+ ions and near-infrared (NIR) emission bandwidth flatness of Er3+/Tm3+/Yb3+ co-doped in SiO2-ZnO-BaO (SZB) barium zinc silicate glasses, were investigated in this work. The composition of all elements from the original raw materials that exist in the host glasses was determined using energy-dispersive X-ray spectroscopy (EDS). Under the excitation of a 980 nm laser diode (LD), the NIR emission of Er3+/Tm3+/Yb3+-co-doped SZB glasses produced a bandwidth of about 430 nm covering the O, E, and C bands. The effects of Mn2+ ions and the Mn2+-Yb3+ dimer on the gain coefficient for the 4I13/2 â 4I15/2 transition of Er3+ ions and bandwidth flatness of NIR emission of Er3+/Tm3+-co-doped and Er3+/Tm3+/Yb3+-co-doped SZB glasses were also assigned. The optimal molar concentration of Mn2+ ions was determined such that the NIR bandwidth flatness of Er3+/Tm3+/Yb3+-co-doped SZB glasses was the flattest. In addition, the role of Mn2+ ions in reducing the gain coefficient for the 4I13/2 â 4I15/2 transition of Er3+ ions was also calculated and discussed.
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Two-dimensional (2D) layered double perovskites have attracted much attention because of their excellent photoelectric properties. However, few reports have been published on the synthesis of 2D layered double perovskites from halide perovskites as precursors. Here, we report that CsCdCl3 and Cs3Bi2Cl9 were synthesized by the coprecipitation method, and a two-dimensional layered double perovskite Cs4CdBi2Cl12 was readily synthesized by mixing the two halide perovskites. We doped different amounts of Mn2+ into CsCdCl3 to form CsCd1-xMnxCl3, which introduced impurity states into the energy level and exhibited an orange-red light emission that is characteristic of Mn2+. A series of 2D layered double perovskites Cs4Cd1-xMnxBi2Cl12 were synthesized from CsCd1-xMnxCl3 and Cs3Bi2Cl9, which showed a bright orange-yellow luminescence under ultraviolet excitation. The presence of high concentrations of Cd2+ in the two-dimensional layered double perovskites weakened the strong Mn-Mn coupling and suppressed the energy transfer to defects, thus minimizing nonradiative decay and promoting efficient energy transfer. Our work provides a new concept for the synthesis of low-dimensional metal halide perovskites with unique optical properties.
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Lanthanide ions are widely used as dopants for halide perovskites for their broad energy level coverage from the visible to near-infrared (NIR) range. In this work, Cs2NaScCl6:Er3+ was synthesized by an improved solid-state reaction method, which showed effective NIR emission under ultraviolet excitation. Through calculations based on density functional theory and Bader charge analysis, it is shown that [ErCl6]3- octahedra show a strong localization effect in the Cs2NaScCl6:Er3+ lattice, which is conducive to the charge transfer process of Cl-Er3+, and charge transfer sensitization is responsible for the efficient visible to NIR luminescence of Er3+, where the NIR emission around λem = 1540 nm originated from the Er3+:4I13/2 â 4I15/2 transition with an ultrahigh photoluminescence quantum yield that reached â¼28.3%. Notably, Cs2NaScCl6:Er3+ also exhibited bright upconversion luminescence of green light (at 540 nm) under excitation by a variety of NIR laser diodes (808, 980, and 1550 nm) via self-sensitization processes.
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Capacitive deionization (CDI) is an electrochemical method of extracting ions from solution at potentials below electrolysis. It has various applications ranging from water remediation and desalination to heavy metal removal and selective resource recovery. A CDI device applies an electrical charge across two porous electrodes to attract and remove ions without producing waste products. It is generally considered environmentally friendly and promising for sustainability, yet ion removal efficiency still falls short of more established filtration methods. Commercially available activated carbon is typically used for CDI, and its ion adsorption capacity is low at approximately 20-30 mg g-1. Recently, much interest has been in the highly porous and well-structured family of materials known as metal-organic frameworks (MOFs). Most MOFs are poor conductors of electricity and cannot be directly used to make electrodes. A common workaround is to pyrolyze the MOF to convert its organic components to carbon while maintaining its underlying microstructure. However, most MOF-derived materials only retain partial microstructure after pyrolysis and cannot inherit the robust porosity of the parent MOFs. This review provides a systematic breakdown of structure-performance relationships between a MOF-derived material and its CDI performance based on recent works. This review also serves as a starting point for researchers interested in developing MOF-derived materials for CDI applications.
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X-ray dose detection plays a critical role in various scientific fields, including chemistry, materials, and medicine. However, the current materials used for this purpose face challenges in both immediate and delayed radiation detections. Here, we present a visual X-ray dosimetry method for multienvironment applications, utilizing NaLuF4 nanocrystals (NCs) that undergo a color change from green to red upon X-ray irradiation. By adjustment of the concentrations of Ho3+, the emission color of the NCs can be tuned thanks to the cross-relaxation effects. Furthermore, X-ray irradiation induces generation of trapping centers in NaLuF4:Ho3+ NCs, endowing the generation of mechanoluminescence (ML) behavior upon mechanical stimulation after X-ray irradiation ceases. The ML intensity shows a linear correlation with the X-ray dose, facilitating the detection of delayed radiation. This breakthrough facilitates X-ray dose inspection in flaw detection, nuclear medicine, customs, and civil protection, thereby enhancing opportunities for radiation monitoring and control.
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Near-infrared phosphor-converted light-emitting diodes (NIR pc-LEDs) offer numerous advantages, including compact size, tunable emission spectra, energy efficiency, and high integration potential. These features make them highly promising for various applications, such as night vision monitoring, food safety inspection, biomedical imaging, and theragnostics. All-inorganic halide double-perovskite materials, known for their large absorption cross section, excellent defect tolerance, and long carrier diffusion radius, serve as unique matrices for constructing near-infrared fluorescent materials. In this study, we successfully prepared the all-inorganic metal halide double-perovskite Cs2NaYCl6:Cr3+ using a grinding-sintering method. A small fraction of the [YCl6] octahedra within the host material's lattice was substituted with Cr3+ ions, resulting in the creation of the Cs2NaYCl6:Cr3+ phosphor. When excited with λ = 310 nm UV light, the phosphor exhibited a broad emission range spanning from 800 to 1400 nm, covering the NIR-I and NIR-II regions. It had a broad bandwidth emission of 185 nm and achieved a fluorescence quantum yield of 20.2%. The unique broadband emission of the phosphor originates from the weak crystal field environment provided by the Cs2NaYCl6 host matrix, which enhances the luminescence properties of the Cr3+ ions. To create NIR pc-LEDs, the phosphor was encapsulated onto a commercially available UV LED chip operating at 310 nm. The potential application of these NIR pc-LEDs in night vision imaging was successfully validated.
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Transmission near-infrared (NIR) imaging technology has great potential for biomedical imaging because of its lower water absorption coefficient and highly reduced photon scattering effect in biological tissues compared to visible light. The extent of biological tissue photon scattering is inversely proportional to wavelength; therefore, in principle, imaging with long-wavelength NIR helps improve the resolution of the optical image, but deep tissue high-resolution luminescence imaging is still very challenging technically. Here, we report the discovery of a Ba2MgWO6:Ni2+ double perovskite phosphor that emits broadband long-wavelength NIR (1200-2000 nm) under 365 nm near-ultraviolet (UV) excitation, with a full width at half-maximum of 255 nm. The luminescence quantum efficiency of the phosphor with optimized composition reached 16.67%. The analysis of the crystal structure of Ba2MgWO6:Ni2+ suggests that Ni2+ ions preferentially occupy the W6+ site in octahedrons with a weak crystal field, which leads to a large Stokes shift. An as-prepared long-wavelength NIR pc-LED device was built by packaging an optimized phosphor with a low-power near-UV-LED chip, which was tested to generate clear imaging of venous vessels in human fingers. These unique properties of the Ba2MgWO6:Ni2+ double perovskite phosphor makes it a promising application in the field of imaging sources for body tissue..
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Níquel , Óxidos , Humanos , Água , Compostos de CálcioRESUMO
Featured with a tunable excitation/emission wavelength and excellent physicochemical stability, inorganic fluorescent materials are widely used in the fields of anti-counterfeiting. Here, we design a multi-stimuli-responsive dynamic fluorescence and phosphorescence anti-counterfeiting material by introducing Eu3+ ions in NaGdGeO4: Bi3+ to tailor the trap structure. The photoluminescence (PL), long persistent luminescence (LPL), and photo-stimulated luminescence (PSL) colors of NaGdGeO4: Bi3+, Eu3+ can be switched by varying the excitation modes (ultraviolet, near infrared, and X-ray light). Especially, the LPL and PSL colors of NaGdGeO4: Bi3+, Eu3+ vary with increasing decay and stimulation times. In addition, X-ray excitation ensures the specificity of the luminescence of NaGdGeO4: Bi3+, Eu3+ compared with ultraviolet excitation. This rapidly-changing-color fluorescent material offers the possibility of sophisticated anti-counterfeiting applications in the future.
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The sluggish redox kinetics and shuttle effect seriously impede the large application of room-temperature sodium-sulfur (RT Na-S) batteries. Designing effective catalysts into cathode material is a promising approach to overcome the above issues. However, considering the multistep and multiphase transformations of sulfur redox process, it is impractical to achieve the effective catalysis of the entire S8 âNa2 Sx âNa2 S conversion through applying a single catalyst. Herein, this work fabricates a nitrogen-doped core-shell carbon nanosphere integrated with two different catalysts (ZnS-NC@Ni-N4 ), where isolated Ni-N4 sites and ZnS nanocrystals are distributed in the shell and core, respectively. ZnS nanocrystals ensure the rapid reduction of S8 into Na2 Sx (4 < x ≤ 8), while Ni-N4 sites realize the efficient conversion of Na2 Sx into Na2 S, bridged by the diffusion of Na2 Sx from the core to shell. Besides, Ni-N4 sites on the shell can also induce an inorganic-rich cathode-electrolyte interface (CEI) on ZnS-NC@Ni-N4 to further inhibit the shuttle effect. As a result, ZnS-NC@Ni-N4 /S cathode exhibits an excellent rate-performance (650 mAh g-1 at 5 A g-1 ) and ultralong cycling stability for 2000 cycles with a low capacity-decay rate of 0.011% per cycle. This work will guide the rational design of multicatalysts for high-performance RT Na-S batteries.
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Pervasive mechanical force in nature and human activities is closely related to intriguing physics and widespread applications. However, describing stress distribution timely and precisely in three dimensions to avoid "groping in the dark" is still a formidable challenge, especially for nonplanar structures. Herein, we realize three-dimensional (3D) stress imaging for sharp arbitrary targets via advanced 3D printing, owing to the use of fluoride nanocrystal(NC)-based ink. Notably, a fascinating mechano-luminescence (ML) is observed for the homogeneously dispersed NaLuF4:Tb3+ NCs (â¼25 nm) with rationally designed deep traps (at 0.88 and 1.02 eV) via incorporating Cs+ ions and using X-ray irradiation. Carriers captured in the corresponding traps are steadily released under mechanical stimulations, which enables a ratio metric luminescence intensity based on the applied force. As a result, a significant mechano-optical conversion and superior optical waveguide of the corresponding transparent printed targets demonstrate stress in 3D with a high spatial and temporal resolution based on stereovision. These results highlight the optical function of the 3D-printed fluoride NCs, which cast light into the black boxes of stress described in space, benefiting us in understanding the ubiquitous force relevant to most natural and engineering processes.
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High-temperature scintillation detectors play a significant role in oil exploration. However, traditional scintillators have limited ability to meet the requirements of practical applications owing to their low thermal stability. In this study, we designed and developed a one-dimensional (1D) Cs5Cu3Cl6I2 scintillator with high thermal stability. In addition, by preparing Cs5Cu3Cl7I, we proved that the Cs5Cu3Cl6I2 scintillator exhibits high thermal stability because the bridges linking the structural units in the 1D chain structure are only formed by I- ions, which improve their structural rigidity. The scintillator has a high steady-state light yield (59,700 photons MeV-1) and exhibits the highest spatial resolution for powder-based scintillation screens (18 lp mm-1) after cyclic treatment within the temperature range of 298-423 K. The Cs5Cu3Cl6I2 scintillator allows the visualization of alloy melting, indicating that it has significant potential for application in high-temperature environments. This study provides a new perspective toward the design of scintillators with high thermal stability.