Deep-red-emitting SrLaLiTeO6: Mn4+ double perovskites: Correlation between Mn4+-O2− bonding and photoluminescence

Mn⁴⁺-activated deep red-emitting SrLaLiTeO₆ phosphors are investigated for indoor plant growth LED applications for the first time. The phosphors crystallize in monoclinic (P2₁/n) symmetry is isostructural with SrLaLiTeO₆ host. B-site substitution of Mn⁴⁺ ions is confirmed from the redshift of high energy phonon modes in both Raman and IR spectra. The phosphor exhibited a far-red emission centered at 696 nm corresponding to the ²E_g → ⁴A_2g spin-forbidden transition of the Mn⁴⁺ ions. Approximate crystal field parameters depict the weak influence of neighboring ligand fields on Mn⁴⁺ ions and the least covalence of Mn⁴⁺-ligand bonding compared to other double perovskite phosphors. Moreover, the phosphors exhibit excellent thermal stability with an activation energy of 0.23 eV. Phosphor parameters including CCT, color purity, and quantum yield are evaluated and their values meet the requirements of a red-emitting phosphor for LED applications. Furthermore, the PL emission spectrum of SrLaLiTeO₆: Mn⁴⁺ matches with the absorption spectrum of plant phytochromes denoting the prospects of this phosphor for indoor plant growth LED applications.     

A universal HF-free synthetic method to highly efficient narrow-band red-emitting A2XF6:Mn4+ (A = K,Na, Rb,Cs; X = Si,Ge, Ti) phosphors

Mn⁴⁺-activated fluoride red-emitting narrow-band phosphors have been successfully used in wide color-gamut white LEDs for liquid crystal display (LCD) backlights. However, highly concentrated and toxic HF is usually used in their synthesis, causing environment and safety issues. In this work, we proposed a HF-free green method, that is, using NH₄F/HCl instead of HF, to synthesize a series of A₂XF₆:Mn⁴⁺ (A = K, Na, Rb, Cs; X = Si, Ge, Ti) phosphors. The microstructure, photoluminescence (PL) properties, thermal quenching, and applications of the synthesized phosphors were investigated. Using the proposed approach, the phosphors generally showed a pure phase, a particle size ranging from 5 to 45 μm, and some characteristic sharp emission lines of Mn⁴⁺ in the red spectral range. The internal quantum efficiency was varied in a broad range of 69%-94% under the 460 nm excitation, depending on the composition of the fluoride host. Among these compositions, K₂XF₆:Mn⁴⁺ (X = Ge and Ti) phosphors even had a similar external quantum efficiency (>60%) with commercial ones. By combining K₂GeF₆:Mn⁴⁺ (narrow-band red) and β-sialon:Eu²⁺ (narrow-band green) with a blue LED, a white light-emitting diode (wLED) backlight with a color gamut of 87.7% National Television System Committee Standard, color temperature of 8423 K, and a luminous efficacy of 110.8 lm/W was demonstrated. These results indicate that the synthetic method proposed in this work is universal for preparing highly efficient fluoride phosphors used in wLEDs.     

Deep‐red photoluminescence and long persistent luminescence in double perovstkite‐type La2MgGeO6:Mn4+

A novel non‐rare‐earth doped phosphor La₂MgGeO₆:Mn⁴⁺ (LMG:Mn⁴⁺) with near‐infrared (NIR) long persistent luminescence (LPL) was successfully synthesized by solid‐state reaction. The phosphors can be effectively excited using ultraviolet light, followed by a sharp deep‐red emission peaking at 708 nm, which is originated from ²E_g → ⁴A_2g transition of Mn⁴⁺ ions. The luminescent performance was analyzed by photoluminescence (PL) and photoluminescence excitation (PLE) spectra. The crystal field parameters were calculated to describe the environment of Mn⁴⁺ in LMG host. The LPL behaviors as well as the mechanisms were systematically discussed. This study suggests that the phosphors will broaden new horizons in designing and fabricating novel NIR long phosphorescent materials.     

Structure and Luminescence of New Red‐Emitting Materials‐Eu3+‐Doped Triple Orthovanadates NaALa(VO4)2 (A = Ca,Sr, Ba)

The new red‐emitting phosphors of Eu³⁺‐doped triple orthovanadates NaALa(VO₄)₂ (A = Ca, Sr, Ba) were prepared by the high‐temperature solid‐state reaction. The formation of single phase compound with isostructural structure of Ba₃(VO₄)₂ was verified through X‐ray diffraction (XRD) studies. The photoluminescence excitation and emission spectra, the fluorescence decay curves and the dependence of luminescence intensity on doping level were investigated. The phosphor can be efficiently excited by near UV and blue light to realize an intense red luminescence (613 nm) corresponding to the electric dipole transition ⁵D₀→⁷F₂ of Eu³⁺ ions. Their potential applications as red‐emitting phosphors for solid‐state lighting were evaluated in comparison with the Eu³⁺‐doped lanthanum orthovanadate LaVO₄ and other reported references. The luminescence was discussed in detail on the base of the crystal structures. The luminescence thermal stability on temperature was investigated and the thermal activated energy was calculated. The phosphors can be suggested to be a potential red‐emitting phosphor for the application on white LEDs under irradiation of near‐UV or blue chips.     

Site-selective substitution and resulting magnetism in arc-melted perovskite ATiO3-δ (A = Ca,Sr, Ba)

Magnetic properties in perovskite titanates ATiO_3-δ (A = Ca, Sr, Ba) were investigated before and after arc melting. Crystal structure analysis was conducted by powder synchrotron X-ray diffraction with Rietveld refinements. Quantitative chemical element analysis was carried out by X-ray photoelectron spectroscopy. Magnetic measurements were conducted by vibrating sample magnetometer and X-ray magnetic circular dichroism (XMCD). The magnetic properties are found to be affected by impurities of 3d elements such as Fe, Co, and Ni. Depending on the composition and crystal structure, the occupation of the magnetic ions in perovskite titanates is selectively varied, which is interpreted to be the origin of the different magnetic behaviors in arc-melted perovskite titanates ATiO_3-δ (A = Ca, Sr, Ba). In addition, both formation of oxygen vacancies and the reduction of Ti⁴⁺ to Ti³⁺ during arc-melting also play a role as proven by XMCD. Nevertheless, preferential site occupation of magnetic impurities is dominant in the magnetic properties of arc-melted perovskite ATiO_3-δ (A = Ca, Sr, Ba).     

An efficient far-red emission Sr2InSbO6:Mn4+, M (M = Li+, Na+, and K+) phosphors for plant cultivation LEDs

High-efficiency and far-red light phosphors based on Mn⁴⁺-doped inorganic luminescence materials are beneficial to plant cultivation. However, Mn⁴⁺-doped oxide phosphors have a common problem of low quantum efficiency. Alkali metal ion codoping can effectively improve the luminescence properties of Mn⁴⁺-activated oxide phosphors. Herein, a series of Sr₂InSbO₆:Mn⁴⁺, M (SISO:Mn⁴⁺, M) (M = Li⁺, Na⁺, and K⁺) far-red-emitting phosphors codoped alkali metal ions were first synthesized. Density functional theory calculation indicated that SISO is a kind of indirect bandgap material with a bandgap of ∼1.60 eV. The SISO:Mn⁴⁺ samples showed a far-red light at 698 nm upon 365 nm, which perfectly matched the absorption spectrum of the far-red-phytochrome (Pfr) of plants. The doping concentration of the SISO:Mn⁴⁺ samples was optimized to be 0.006 mol. The concentration quenching mechanism was defined as dipole–dipole interaction by combining the Dexter theory and the Inokuti–Hirayama model. Optimizing the sintering temperature and codoped with alkali metal ions (Li⁺, Na⁺, and K⁺) could improve the luminescent intensity of SISO:Mn⁴⁺. The optimum sintering temperature was 1300°C. The internal quantum efficiencies of SISO:0.006Mn⁴⁺ and SISO:0.006Mn⁴⁺, 0.006Li⁺ phosphors are 22.67% and 60.56%, respectively. SISO:Mn⁴⁺, Li⁺ phosphors-based plant growth light-emitting diodes (LEDs) demonstrate excellent optical stability and long lifetime. Thus, these phosphors are promising candidates for plant cultivation LEDs.     

Achieving highly efficient far-red emission from luminescence-ignorable Ca2MgTeO6:Mn4+ to Ca2-zLnzMgTe1-yWyO6:Mn4+ (Ln = La,Y, Gd) phosphors via solid solution and impurity doping strategies

The Mn⁴⁺-doped Ca2MgTeO6 (CMTO) far-red emitting phosphors with double perovskite-type structure were successfully synthesized. Upon near-ultraviolet (n-UV, 300 nm) light excitation, the as-prepared phosphors showed far-red light at 700 nm attributed to the ²E_g→⁴A_2g transition of Mn⁴⁺ ion. The doping concentration of the CMTO:xMn⁴⁺ samples was optimized to be 0.8 mol%. The relevant mechanism of concentration quenching was demonstrated as the dipole-dipole interaction. Furthermore, solid solution and impurity doping strategies were adopted to improve the far-red emission of the luminescence-ignorable CMTO:Mn⁴⁺ phosphor. Series of Ca₂MgTe_(1−y)W_yO₆:0.8 mol%Mn⁴⁺ (y = 0–100 mol%) solid solution and Ca_2−zLn_zMgTe_0.6W_0.4O₆:Mn⁴⁺ (Ln = La, Y, and Gd, z = 10 mol%) phosphors were synthesized through the above two strategies. The luminescence intensity of the optimal Ca_1.9Gd_0.1MgTe_0.6W_0.4O₆:Mn⁴⁺ phosphor was 13.7 times that of the CMTO:Mn⁴⁺ phosphor and 2.51 times that of red commercial phosphor K₂SiF₆:Mn⁴⁺. Notably, both CMTO:Mn⁴⁺ and Ca_1.9Gd_0.1MgTe_0.6W_0.4O₆:Mn⁴⁺ phosphors exhibited remarkable thermal stability compared with most Mn⁴⁺-doped phosphors. Finally, the highly efficient Ca_1.9Gd_0.1MgTe_0.6W_0.4O₆:Mn⁴⁺ phosphor was successfully applied in fabricating the warm white light diode (w-LED). This working along both lines strategy exhibited great potential for luminescence optimization of Mn⁴⁺-doped oxide phosphors.     

Deep-red-emitting Ca2ScSbO6:Mn4+ phosphors with a double perovskite structure: Synthesis,characterization and potential in plant growth lighting

Mn⁴⁺-activated double-perovskite type Ca₂ScSbO₆ (CSS) phosphors were synthesized via a high-temperature solid-state reaction. The phase purity and crystal structure of obtained samples were investigated by powder X-ray diffraction (XRD). The successful incorporation of Mn⁴⁺ ions into CSS lattice was confirmed by the combination of energy-dispersive X-ray spectra (EDX) and X-ray photoelectron spectra (XPS) results. The luminescent properties of the CSS phosphors, including the photoluminescence (PL) and PL excitation (PLE) spectra, commission international de l'clairage (CIE) chromaticity coordinates, fluorescence decay curves, quantum yields and temperature-dependent PL spectra, were investigated in detail. Under 310-nm excitation, the optimized CSS:0.3%Mn⁴⁺ phosphor exhibited bright deep-red emission covering a narrow band from 640 nm to 720 nm, which overlaps with the absorbance of phytochromes. The Racah parameters B, C, and local crystal strength Dq were calculated to be 870, 2703, and 1984 cm^–1, respectively. Particularly, the emission intensity of CSS:0.3%Mn⁴⁺ still remained 61.4% at 423 K compared with that at room temperature. Therefore, all these outstanding luminescent properties provided the as-synthesized phosphors a great potential in plant growth lighting.     

Computational Analysis of Oxide Ion Conduction in Orthorhombic Perovskite Structured La0.9A0.1InO2.95 (A = Ca,Sr and Ba)

Oxide ion conduction in orthorhombic perovskite structured oxides, La_0.9A_0.1InO_2.95 (A = Ca, Sr and Ba) is analyzed using molecular dynamics simulation. Factors influencing oxide ion conductivity of the compositions considered are analyzed using radial distribution function, bond energies between dopant and oxide ions, and the diffusion path. It is known that perovskite oxides with smaller ion size mismatch between host and dopant ions have higher electrical conductivities. However, exceptions exist, such as a La_0.9A_0.1InO_2.95 (A = Ca, Sr and Ba) system, where high electrical conductivities occur with large ion size mismatches. Based on this study, a dopant with smaller ion than host ion results in the formation of strong ionic bonds with oxide ions, suggesting that the A‐site dopant should be larger than the host ion for forming weaker O–A bonds. Consequently, the trade‐off between ion size mismatch and O–A bond needs to be considered for enhancing oxide ion conductivity of perovskite oxides.     

Novel AMoO4:Eu3+ (A = Ca and Ba) optical thermometer: Investigation of effect of local ionic coordination environment on optical performance and temperature measurement sensitivity

A range of Eu³⁺-doped AMoO₄ (A = Ca and Ba) phosphors were successfully synthetized, and their crystal structures, optical performance, and temperature measurement sensitivities were investigated in detail. Peak doping concentration of CaMoO₄:Eu³⁺ phosphor was 0.18, while peak doping concentration of BaMoO₄:Eu³⁺ phosphor may be greater than 0.18. Then, temperature-dependent photoluminescence emission spectra of representative CaMoO₄:0.09Eu³⁺ and BaMoO₄:0.03Eu³⁺ phosphors were recorded. CaMoO₄:0.09Eu³⁺ phosphor exhibited abnormal thermal quenching, which was attributed to defects caused by heterovalent substitution of ions and increase in the temperature, and good thermal stability. Finally, the possibility of using both phosphors as optical thermometers was discussed, which exhibited good temperature sensitivity. However, CaMoO₄:0.09Eu³⁺ phosphor exhibited two peak absolute (Sa, 1.28 %K⁻¹ and 1.39 %K⁻¹) and relative sensitivities (Sr, 1.21 %K⁻¹ and 1.20 %K⁻¹). In addition, variation trend of Sr value with temperature was considerably peculiar. Two optimum Sa and Sr values were attributed to abnormal thermal quenching of CaMoO₄:0.09Eu³⁺ phosphor. Peak Sa and Sr values of BaMoO₄:0.03Eu³⁺ phosphor was 12.39 %K⁻¹ and 0.89 %K⁻¹, respectively. In addition, Sa of AMoO₄:Eu³⁺ phosphor was negatively related to Eu³⁺ central asymmetry, while peak Sr value was more inclined to appropriate ionic central asymmetry.     

Broadband emission phosphor Sr3Al2O5Cl2:Bi3+: Luminescence modulation and application for a white-light-emitting diode

Bi³⁺ ions can regulate and control the fluorescence of a phosphor by transferring energy to the activating agent or occupying different luminescent centers, which is important for modifying phosphors and revealing fluorescence mechanisms. As a base material, Sr₃Al₂O₅Cl₂ has three types of Sr sites (Sr 1, Sr 2, and Sr 3) that may be occupied by Bi³⁺ ions (Sr²⁺ has a similar radius to Bi³⁺). Herein, we successfully synthesized a series of Sr₃Al₂O₅Cl₂:x%Bi³⁺ phosphors using the high-temperature solid-state method and determined a two-site-occupying emission mechanism. X-ray diffraction patterns indicated that the samples were synthesized well, and Rietveld refinement results provided their structural information. Photoluminescence spectra showed 490 nm (λ_ex = 345 nm) and 556 nm (λ_ex = 376 nm) emission peaks, which might arise from different luminescent centers. The concentration quenching study, peak separation analysis, fluorescence lifetime spectra, and diffuse reflection spectra indicated that the Bi³⁺ ions occupied two of the three Sr sites. Calculations of relative system energies and distortion index proved that the occupation only occurred in the Sr 1 and Sr 3 sites, and crystal splitting analysis determined that Sr 1 site generated 490 nm emission light and Sr 3 site generated 556 nm emission light. The charge compensator and flux were added to enhance the fluorescence intensity of the phosphor, and 5% K⁺ along with 1% BaF₂ is the optimal dosage. Finally, the SrAlSiN₃:Eu²⁺, BaMgAl₁₀O₁₇:Eu²⁺, and optimized Sr₃Al₂O₅Cl₂:5%Bi³⁺ phosphors were combined as a luminous layer and a warm-white light-emitting diode was realized; the color rendering indices were 84.3, 85.8, 86.4, and 86.2 under working currents of 20, 30, 40, and 50 mA, respectively.     

Comparative analysis on the photoluminescence properties of Cs2BF6:Mn4+ (B = Ge,Si, Zr,Ti) red phosphors for WLEDs

A series of Cs₂BF₆:Mn⁴⁺ (B = Ge, Si, Ti, Zr) red phosphors were synthesized by a precipitation-cation exchange route. The phase purity, morphology, and constituent were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Optical properties were investigated by photoluminescence (PL) spectra and high-resolution PL. Temperature-dependent PL examination at the range of both 273-573 K and 10-300 K was performed to investigate the emission mechanism of Mn⁴⁺ in these fluorides. The intensity for both zero-phonon lines (ZPLs) and vibration coupled emission of Mn⁴⁺ in these four systems with different crystal structures was investigated systematically. These phosphors present bright red emission under blue light (467 nm) illumination, among which Cs₂GeF₆:0.1Mn⁴⁺ shows the highest emission intensity with ultrahigh quantum efficiency of 94%. The white light-emitting diodes (WLEDs) fabricated with this sample, blue InGaN chips and commercial YAG:Ce³⁺ phosphor exhibited high luminous efficacy beyond 100 lm/w with high color rendering index (~88.6) and low color temperature (~3684 K).     

Preparation,luminescence properties,and application of temperature sensing and anti-counterfeiting of La2MgTiO6:Yb3+/Ln3+/Mn4+

The doping of transition metal ions in the up-conversion (UC) luminescent material doped with Yb³⁺/Ln³⁺ is a facile way to increase their UC luminescence intensities and alter their colors. In this study, La₂MgTiO₆:Yb³⁺/Mn⁴⁺/Ln³⁺ (Ln³⁺ = Er³⁺, Ho³⁺, and Tm³⁺) phosphors showing excellent luminescence properties were prepared by a solid-state method. The sensitivity of the La₂MgTiO₆:Yb³⁺/Ln³⁺/Mn⁴⁺ phosphor was double that without Mn⁴⁺, because Mn⁴⁺ affects the UC emissions of Ln³⁺ via energy transfer between these ions. Moreover, Mn⁴⁺ also acts as a down-conversion activator, which can combine with UC ions to achieve multi-mode luminescence at different wavelengths. Under 980 nm excitation, these samples emit green light (from Er³⁺ and Ho³⁺) and blue light (from Tm³⁺). In contrast, under 365 nm excitation, they emit red light (from Mn⁴⁺). Further testing revealed that the La₂MgTiO₆:Yb³⁺/Mn⁴⁺/Ln³⁺ phosphors have potential applications in temperature sensing and anti-counterfeiting.     

Bi3+/Mn4+ co-doped dual-emission phosphors for potential plant lighting

Developing environment-friendly dual-emission phosphors of both blue–cyan and deep-red lights is desirable for the utilized indoor plant lighting research. Notably, the naked 6s and 6p Bi³⁺ ions are sensitive to the lattice sites, which emit from Ultraviolet (UV) to red lights in various crystal compounds. Meanwhile, the ²E → ⁴A_2g transition of Mn⁴⁺ ions promises its deep-red light emissions, which satisfies the demand for specific wavelength lights for plants growth. Hence, a Bi³⁺/Mn⁴⁺ co-doped Sr₂LaGaO₅: Bi³⁺, Mn⁴⁺ (SLGO:Bi³⁺:Mn⁴⁺) phosphor was finally synthesized. The phase, micromorphology and luminescent properties were systematically evaluated. Upon excitation at 350 nm light, dual emissions of both blue–cyan (470 nm) and deep-red (718 nm) lights were observed. Besides, due to the pronounced photoluminescence (PL) spectral overlap between Bi³⁺ and Mn⁴⁺ ions, a potential energy transfer process from Bi³⁺ to Mn⁴⁺ ions was confirmed. The relative PL intensities between Bi³⁺ and Mn⁴⁺ ions can be tuned just by adjusting the Mn⁴⁺ ion concentration. Besides, Li⁺ co-doping has been evidenced to improve the deep-red emissions (718 nm) of SLGO:0.005Mn⁴⁺ due to charge compensation and rationally designed lattice distortion, together with the improved thermal stability. Finally, the emissions of SLGO:Bi³⁺, Mn⁴⁺, Li⁺ phosphor suit properly with the absorption of the four fundamental pigments for plant growth, indicating that the prepared phosphorescent materials may have a prospect in plant light-emitting diodes lighting.     

A novel scheelite-type LiCaGd(WO4)3:Eu3+ red phosphors with prominent thermal stability and high quantum efficiency

A series of LiCaGd(WO4)3 : xEu³⁺ (0 ≤ x ≤ 1.0) red phosphors with tetragonal scheelite structure were synthesized via the conventional solid-state reaction. Their crystal structure, photoluminescence excitation (PLE), and photoluminescence (PL) spectra, thermal stability and quantum efficiency were investigated. The phosphors exhibit a typical red light upon 395 nm near ultraviolet excitation, and the strongest emission peak at 617 nm is dominated by the ⁵D₀→⁷F₂ transition of Eu³⁺ ions. The PL intensity of the phosphors gradually increases with the increase of Eu³⁺ doping concentration, and the concentration quenching phenomenon is hardly observed. The quantum efficiency and the color purity of the phosphor reach maximum values of about 94.2 and 96.6% at x = 1.0, respectively. More importantly, LiCaGd(WO₄)₃:xEu³⁺ phosphors have prominent thermal stability. The temperature-dependent PL intensity of the phosphors at 423 K is only reduced to 89.1% of the PL intensity at 303 K, which is superior to that of commercial red phosphors Y₂O₃:Eu³⁺. Finally, LiCaGd(WO₄)₃:Eu³⁺ phosphor is packaged with near ultraviolet InGaN chips to fabricate white light emitting diodes, which has a low color temperature (CCT = 4622 K) and a high color rendering index (CRI= 89.6).     

Electrospinning,optical properties and white LED applications of one-dimensional CaAl12O19:Mn4+ nanofiber phosphors

Non-rare-earth, red-emitting CaAl₁₂O₁₉:Mn⁴⁺ nanofiber phosphors have been successfully prepared by an electrospinning technique followed by an annealing process. The as-prepared precursor fibers have smooth surfaces with an average diameter of 5 µm. After annealing at high temperature, the diameter of the fibers gradually reduces due to the decomposition of the organic polymers. The photoluminescence and crystalline properties of the fibers were investigated as a function of Mn⁴⁺ concentration and the annealing temperature. Under ultraviolet and blue light excitation, CaAl₁₂O₁₉:Mn⁴⁺ exhibits a characteristic red emission at 655 nm with three satellite peaks due to the ²E→⁴A₂ transition of Mn⁴⁺. The highest PL intensity is achieved at a 0.5% Mn⁴⁺ concentration and a firing temperature of 1400 °C. In comparison to CaAl₁₂O₁₉:Mn⁴⁺ prepared by a usual solid-state reaction, the luminescence of the as-prepared nanofiber phosphors in the present work has been strongly enhanced by optimizing the morphology and improving the crystallinity and phase purity. The absorption band in the blue region and a bright emission in the red region make the CaAl₁₂O₁₉:Mn⁴⁺ nanofiber phosphor a candidate for achieving high color rendering in YAG:Ce-based WLEDs. A warm WLED with a high CRI of 88.5 at a CCT of 4553 K has been successfully achieved by coating YAG:Ce with CaAl₁₂O₁₉:Mn⁴⁺ nanofiber phosphors on blue InGaN chips.     

Mn2+/Pr3+/Tb3+ single-doped Mg4Ga4Ge3O16 persistent luminescence materials for optical information storage application

Persistent luminescence (PersL) phosphors are considered as promising candidates for the next generation of information storage medium. Mg₄Ga₄Ge₃O₁₆ (MGG) is an electron trapping material which exhibits defect luminescence, and the luminescent properties are easily tuned via doping various activated ions. In this work, undoped and Mn²⁺/Pr³⁺/Tb³⁺ single-doped MGG phosphors were synthesized via high temperature solid phase reactions. X-ray diffraction and scanning electron microscope results confirm that the activated ions tend to occupy Mg²⁺ sites. Excited at 265 nm, the MGG host exhibits a defect emission band peaked at 450 nm. Red, pink and green emissions are observed in the Mn²⁺/Pr³⁺/Tb³⁺ single-doped MGG samples, which are ascribed to the Mn²⁺: ⁴T₁(G) → ⁶A₁(S), Pr³⁺: ¹D₂ → ³H₄ and Tb³⁺: ⁵D₄ → ⁷F₅ transitions, respectively. All the samples exhibit bright PersL for minutes after the cessation of excitation. The energy transfer, concentration quenching, luminescence decay and afterglow mechanisms are also discussed in detail. The phosphors exhibit efficient thermal and optical stimuli response, showing great potentials in the optical information storage.     

Effect of ligand environment of rare-earth ions on temperature measurement performance of SrAO4:xEu3+ (A = Mo and W) phosphors

Molybdate and tungstate with scheelite-type structure are excellent self-luminescent materials, which can be used as ideal hosts for the doping of rare-earth ions. In this study, a series of Eu³⁺-activated SrAO₄ (A = Mo and W) phosphors were successfully synthesized, and their crystal structures, photoluminescence properties, and temperature measurement performance were analyzed in detail. These phosphors were excited by UV light (291 nm and 247 nm, respectively), with clear energy transfer (ET) (MoO₄^2?→Eu³⁺ or WO₄^2?→Eu³⁺). According to fluorescence intensity ratio (FIR) and Judd–Ofelt (J–O) theory, compared to SrWO₄:0.01Eu³⁺ phosphor, SrMoO₄:0.01Eu³⁺ phosphor exhibited better thermal stability, with relatively low Sa value (maximum values were 5.082 %K^?1 and 20.74 %K^?1, respectively), and their Sr values were not significantly different (maximum values were 0.864 %K^?1 and 0.83 %K^?1, respectively). Sa value was negatively correlated to central asymmetry of Eu³⁺, but the optimal Sr value tended to be more suitable for central asymmetry of Eu³⁺. In addition, Eu³⁺ exhibited stronger central asymmetry as well as covalency of Eu–O bond in SrMoO₄. Results reveal that SrMoO₄:xEu³⁺ and SrWO₄:xEu³⁺ can be used for luminescent thermometers.     

Broadband deep-red-to-near-infrared emission from Mn2+ in strong crystal-field of nitride MgAlSiN3

Broadband near-infrared (NIR) phosphors have received increasing attention for fabricating phosphor-converted light-emitting diodes (pc-LEDs) as NIR light source. Most of the reported broadband NIR phosphors originate from Cr³⁺ in weak crystal field environments. Herein, we report a luminescent material, MgAlSiN₃:Mn²⁺ with CaAlSiN₃-type structure, demonstrating that broadband deep-red-to-NIR emission can be achieved via doping Mn²⁺ into crystallographic sites with strong crystal field in inorganic solids. This phosphor is synthesized via easy-handle solid-state reaction, and the optimized sample, (Mg_0.93Mn_0.07) AlSiN₃ shows an emission band with peak at ~754 nm, FWHM of 150 nm, and internal quantum efficiency of 70.1%. The photoluminescence intensity can further be enhanced by co-doping Eu²⁺ as sensitizer. This work provides a new strategy for discovering new broadband NIR phosphors using Mn²⁺ in strong crystal field as luminescence center.     

Mn ions-activated Gd3(Al,Ga)5O12 garnet solid-solution ceramics: Cation substitution for dual wavelength red-emission

Red-emitting color-convertors have attracted considerable attention for promising applications in solid-state lighting (SSL) to improve color rendition. However, the current nitride and fluoride phosphor powders have encountered several challenges, such as high cost, narrow emission bands, and insufficient stability during operation, which limit the development of high-power full-spectrum SSL. In this study, thermally robust Gd₃(Al,Ga)₅O₁₂:Mn (GAGG:Mn) solid-solution ceramics (SSCs) with dual wavelength red-emission bands were prepared via an oxygen solid-state sintering reaction. The doped Mn ions occupied octahedral Al³⁺ and Ga³⁺ sites to generate Mn⁴⁺ luminescent centers with pronounced deep-red emissions peaking at 698 nm (²E → ⁴A₂), and Mn²⁺ luminescent centers with broad red emissions at 628 nm (⁴T₁ → ⁶A₁). Because the cationic radius matching effect induced the regulation of valence state of Mn, the photoluminescence of the GAGG:Mn SSCs can be tailored by the substitution of Al³⁺ with Ga³⁺. Moreover, the Mn³⁺ also existed in the GAGG lattice host, and their concentration decreased with increasing Ga³⁺ contents owing to the mismatch of ionic radius between Mn³⁺ and Ga³⁺ ions. With the optimization of Al/Ga ratio and concentration of Mn ions, a broad emission band ranging from 550 to 800 nm (bandwidth = 250 nm) was achieved from Gd₃Al₃Ga₂O₁₂:0.3%Mn SSCs upon 465-nm excitation. Moreover, the GAGG:Mn SSC has over 17-fold enhanced thermal conductivity compared with the corresponding phosphor powder. This paper opens a door of regulating the valence state of luminescence centers with cation substitution and the application of oxide red-emitting color-convertors.