Phase transition of Eu2Ti2O7 under high pressure and a new ferroelectric phase with perovskite‐like layered structure

Ferroelectrics with perovskite‐like layered (PL) structure are well‐known for their high T_c and the application prospect of high‐temperature‐piezoelectric sensing. In this study, the PL‐structure Eu₂Ti₂O₇ was prepared by 1‐step high‐pressure sintering, which show the pyrochlore structure of Eu₂Ti₂O₇ would change into PL structure at 11 GPa, 1300°C. The PL‐structure Eu₂Ti₂O₇ is metastable, which will change back to pyrochlore structure at about 900°C in the air. The PL‐structure Eu₂Ti₂O₇ was confirmed as a high‐temperature ferroelectric material for the first time. The ferroelectric domain switching was directly observed using piezoelectric force microscope. The piezoelectric constant of the PL Eu₂Ti₂O₇ ceramic was measured as 0.7‐0.9 pC/N and its thermal depoling temperature (T_d) was determined as 800°C, which is associated with the PL‐pyrochlore transition.     

Tuning the Color Emission of Sr2P2O7: Tb3+, Eu3+ Phosphors Based on Energy Transfer

A series of color tunable Tb³⁺‐ and Eu³⁺‐activated Sr₂P₂O₇ phosphors were synthesized by a traditional solid‐state reaction method in air atmosphere. The crystal structure, photoluminescence (PL) properties, energy transfer, thermal stability, and luminous efficiency were investigated. A series of characteristic emission of Tb³⁺ and Eu³⁺ were observed in the PL spectra and the variation in the emission intensities of the three emission peaks at around 416 nm (blue), 545 nm (green), and 593 nm (orange‐red) induced the multicolor emission evolution by tuning the Tb³⁺/Eu³⁺ content ratio. The energy‐transfer mechanism from Tb³⁺ to Eu³⁺ ion was determined to be dipole–dipole interaction, and the energy‐transfer efficiency was about 90%. The novel phosphors have excellent thermal stability in the temperature range of 77–473 K and the Commission International De L'Eclairage 1931 chromaticity coordinates of Sr₂P₂O₇: Tb³⁺, Eu³⁺ (λ_ex = 378 nm) move toward the ideal white light coordinates.     

Crystallographic Structure and Ferroelectricity of (AxLa1−x)2Ti2O7 (A = Sm and Eu) Solid Solutions with High Tc

The solubility and ferroelectric properties of (A_xLa_1?x)₂Ti₂O₇ (A = Sm and Eu) solid solutions were investigated. The crystallographic structure of the solid solutions was studied using X‐ray diffraction and Raman spectroscopy. The solubility limits of Eu and Sm in (A_xLa_1?x) ₂Ti₂O₇ were found to be greater than x = 0.5 and 0.8, respectively. The solid solutions had a monoclinic perovskite‐like layered structure (PLS), similar to that of the pure La₂Ti₂O₇, when x was less than the solubility limit. When x was above the solubility limit the materials were biphase. The biphases of (Sm_xLa_1?x)Ti₂O₇ (x = 0.9) consisted of (Sm_xLa_1?x)₂Ti₂O₇ with PLS and pure Sm₂Ti₂O₇ with pyrochlore structure, and the biphases of (Eu_xLa_1?x)Ti₂O₇ (x = 0.6, 0.7, and 0.8) consisted of (Eu_xLa_1?x)₂Ti₂O₇ with PLS structure and La³⁺ doped Eu₂Ti₂O₇ with pyrochlore structure. The effect of A‐site substitution on the properties of La₂Ti₂O₇ was investigated by measuring the dielectric permittivity and loss at different frequencies and temperatures. The highest piezoelectric constant d₃₃ was 2.8 pC/N for (Sm_0.1La_0.9)Ti₂O₇.     

Structure and luminescence properties of Eu3+ doped TiO2 nanocrystals and prolate nanospheroids synthesized by the hydrothermal processing

We report on a new approach to the synthesis of Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids. They were synthesized by shape transformation of hydrothermally treated titania nanotubes at different pH and in the presence of Eu³⁺ ions. The use of nanotubes as a precursor to the synthesis of Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids opens the possibility of overcoming the problems related to molecular precursors. The shapes and sizes of the nanotubes, Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids were characterized by transmission electron microscopy (TEM) technique. Crystal structures of the resultant powders were investigated by X-ray diffraction (XRD) analysis. The percentage ratio of Eu³⁺ to Ti⁴⁺ ions in doped nanocrystals was determined using inductively coupled plasma atomic emission spectroscopy. The optical characterization was done by using fluorescence and ultraviolet-visible reflection spectroscopies. An average size of faceted Eu³⁺ doped TiO₂ nanocrystals was 13 nm. The lateral dimensions of Eu³⁺ doped TiO₂ prolate nanospheroids varied from 14 to 20 nm, while the length varied from 40 to 80 nm, depending on precursor concentrations. The XRD patterns revealed the homogeneous anatase crystal phase of Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids independently of the amount of dopant. A postsynthetic treatment (filtration or dialysis) was applied on the dispersions of the doped nanoparticles in order to study the influence of the dopant position on photoluminescence (PL) spectra. In the red spectral region, room temperature PL signals associated with ⁵D₀ → ⁷F_J (J = 1–4) transitions of Eu³⁺ were observed in all samples. The increased contribution of dopants from the interior region of dialyzed nanocrystals to photoluminescence was confirmed by the increase of R value.     

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).     

Preparation and Luminescence Properties of Blue‐emitting Phosphor Ba2Ca(PO4)2:Eu2+

Using the conventional high temperature solid‐state reaction method Ba₂Ca(PO₄)₂:Eu²⁺ phosphors were prepared. The phase structure, photoluminescence (PL) properties, and the PL thermal stability of the samples were investigated, respectively. Under the excitation at 365 nm, the phosphor exhibited an asymmetric broad‐band blue emission with peak at 454 nm, which is ascribed to the 4f–5d transition of Eu²⁺. It was further proved that the dipole–dipole interactions results in the concentration quenching of Eu²⁺ in Ba₂Ca_1?x (PO₄)₂:xEu²⁺ phosphors. When the temperature turned up to 150°C, the emission intensity of Ba₂Ca_0.99(PO₄)₂:0.01Eu²⁺ phosphor was 59.07% of the initial value at room temperature. The activation energy ΔE was calculated to be 0.30 eV, which proved the good thermal stability of the sample. All the properties indicated that the blue‐emitting Ba₂Ca(PO₄)₂:Eu²⁺ phosphor has potential application in white LEDs.     

Enhanced electrical properties and strong red light‐emitting in Eu3+‐doped Sr1.90Ca0.15Na0.9Nb5O15 ceramics

The luminescent‐ferroelectic materials based on Sr_1.90Ca_0.15Na_0.9Nb₅O₁₅ (SCNN) matrix doping with Eu³⁺ were synthesized by the conventional solid‐state reaction method. The crystal structure, photoluminescence, thermal stability, dielectric, ferroelectric, and piezoelectric behaviors were systematically investigated. XRD results revealed that Eu³⁺ introduction could induce the tungsten bronze phase transition from orthorhombic to tetragonal structures. The dielectric spectra of all specimens showed two broad dielectric anomalies: a high‐temperature ferroelectric phase transition (T_c) and a low‐temperature ferroelastic phase transition (T_s), both of which were suppressed at higher Eu³⁺ concentrations. The enhanced electrical properties were obtained in a proper Eu³⁺ concentration range of 0.03‐0.05. For all SCNN:xEu³⁺ samples, the strong red emission peak at 617 nm originating from the electric dipole transition of ⁵D₀ →⁷F₂ was excited by different light excitations of 395 or 463 nm. Our results demonstrated that Eu³⁺‐doped SCNN materials might have promising potential in advanced multifunctional optoelectronic applications.     

Phase formation and spectral evolution of (Sr,Ba)2Si(O,N)4:Eu2+ phosphors

Sr_2‐xBa_xSi(O,N)₄:Eu²⁺ (SB_xSON:Eu²⁺) oxynitridosilicate phosphors were prepared via incorporation of N^3?, Eu²⁺, and Ba²⁺ ions into Sr₂SiO₄ (SSO) lattices. X‐ray diffraction patterns of the prepared powders revealed that SB_xSON:Eu²⁺ was a solid‐solution form of SSO. An increase in x values caused a phase transition and an expansion of the unit cell. The photoluminescence excitation (PLE) spectra of SB_xSON:Eu²⁺ were broad, covering the ultraviolet range to the visible range. Corresponding PL emission spectra strongly depended on the excitation wavelengths and consisted of two emission bands, one in the green‐blue region (A‐band) and the other in the red region (B‐band), which were assigned to Eu(I) and Eu(II), respectively. The B‐band resulted from a dramatic red‐shift of the green emission band assigned to Eu(II) of SSO:Eu²⁺, revealing that the nitridation process preferentially affected the Eu(II) sites. This behavior was explained by crystal field splitting, the fluorescence decay time, and thermal quenching. The Ba²⁺ substitution caused evolution of the PL spectra, and its effects on the spectra were discussed under consideration of ionic size and covalence.     

Structural and emission properties of Eu3+‐doped alkaline earth zinc‐phosphate glasses for white LED applications

Quaternary alkaline earth zinc‐phosphate glasses in molar composition (40 ? x)ZnO – 35P₂O₅ – 20RO – 5TiO₂ – xEu₂O₃ (where x=1 and R=Mg, Ca, Sr, and Ba) were prepared by melt quenching technique. These glasses were studied with respect to their thermal, structural, and photoluminescent properties. The maximum value of the glass transition temperature (T_g) was observed for BaO network modifier mixed glass and minimum was observed for MgO network modifier glass. All the glasses were found to be amorphous in nature. The FT‐IR suggested the glasses to be in pyrophosphate structure, which matches with the theoretical estimation of O/P atomic ratio and the maximum depolymerization was observed for glass mixed with BaO network modifier. The intense emission peak was observed at 613 nm (⁵D₀→⁷F₂) under excitation of 392 nm, which matches well with excitation of commercial n‐UV LED chips. The highest emission intensity and quantum efficiency was observed for the glass mixed with BaO network modifier. Based on these results, another set of glass samples was prepared with molar composition (40 ? x)ZnO – 35P₂O₅ – 20BaO – 5TiO₂ – xEu₂O₃ (x=3, 5, 7, and 9) to investigate the optimized emission intensity in these glasses. The glasses exhibited crystalline features along with amorphous nature and a drastic variation in asymmetric ratio at higher concentration (7 and 9 mol%) of Eu₂O₃. The color of emission also shifted from red to reddish orange with increase in the concentration of Eu₂O₃. These glasses are potential candidates to use as a red photoluminsecent component in the field of solid‐state lighting devices.     

Effects of crystallization and dopant concentration on the emission behavior of TiO2:Eu nanophosphors

Uniform, spherical-shaped TiO₂:Eu nanoparticles with different doping concentrations have been synthesized through controlled hydrolysis of titanium tetrabutoxide under appropriate pH and temperature in the presence of EuCl₃·6H₂O. Through air annealing at 500°C for 2 h, the amorphous, as-grown nanoparticles could be converted to a pure anatase phase. The morphology, structural, and optical properties of the annealed nanostructures were studied using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy [EDS], and UV-Visible diffuse reflectance spectroscopy techniques. Optoelectronic behaviors of the nanostructures were studied using micro-Raman and photoluminescence [PL] spectroscopies at room temperature. EDS results confirmed a systematic increase of Eu content in the as-prepared samples with the increase of nominal europium content in the reaction solution. With the increasing dopant concentration, crystallinity and crystallite size of the titania particles decreased gradually. Incorporation of europium in the titania particles induced a structural deformation and a blueshift of their absorption edge. While the room-temperature PL emission of the as-grown samples is dominated by the ⁵D₀ - ⁷F _j transition of Eu⁺³ ions, the emission intensity reduced drastically after thermal annealing due to outwards segregation of dopant ions.     

Structural and Photoluminescence Study of Eu3+/TiO2 Xerogels as a Function of the Temperature Using Optical Techniques

Eu³⁺/TiO₂ xerogels have been obtained from colloidal sols by drying at room conditions. Anatase with traces of brookite phases are obtained from the synthesis and the stability of both with temperature is higher (from 400°C up to 800°C) when Eu³⁺ is present. Raman phonons have been used to detect the different phases and follow the structural transitions. The observed changes with calcination temperature of anatase modes (E_g,1, B_1g,₁ A_g/B_1g,2, and E_g,3) are found to be mainly related to the grain size. The anatase grain size increases more and at lower temperatures for undoped than for Eu³⁺‐doped samples favoring the transition to rutile. The stability of the brookite phase is also influenced by the doping being higher in the doped xerogels (700°C) than in the undoped ones (400°C). No concentration quenching of the f–f Eu³⁺ emission bands is observed up to 3% Eu³⁺ at low temperatures but the maximum emission is found at lower temperatures for higher Eu³⁺ content may be due to quenching related to Eu³⁺ migration. The narrower f–f emission bands of the as‐prepared samples are consistent with the presence of Eu³⁺ ions at the surface with a weak interaction with the TiO₂ nanoparticles. A diffusion process of Eu³⁺ ions occurs during calcination from the surface to different positions of the anatase lattice close to the surface producing an inhomogeneous broadening. Finally, the formation of the pyrochlore phase Eu₂Ti₂O₇ is detected which explains the decrease on the emission efficiency and the increase of the Eu³⁺ environment symmetry.     

Controllable synthesis of bifunctional material Ca2Ti2O6:Eu3+ and its comparative study on luminescence and photocatalytic properties with CaTiO3:Eu3+

Pure pyrochlore Ca₂Ti₂O₆, perovskite CaTiO₃, and their mixed crystalline phases with different proportions were controllably synthesized via a solvothermal method, followed by a subsequent calcination process. RIR (reference intensity ratio) data of Ca₂Ti₂O₆ were first obtained by X-ray diffraction (XRD), which can be used to quantitatively analyze the phase composition. When Eu³⁺ is doped into these calcium titanium oxides, they can be used as luminescent and photocatalytic materials. The structure, luminescence, and photocatalytic properties of pure pyrochlore Ca₂Ti₂O₆:Eu³⁺ and perovskite CaTiO₃:Eu³⁺ were comparatively studied in detail. The relative intensities of the excitation peaks and the emission peaks in Ca₂Ti₂O₆:Eu³⁺ and CaTiO₃:Eu³⁺ are different, which is attributed to the different symmetries of Eu³⁺ inhabiting the two kinds of lattices. In addition, although the luminescence intensity of CaTiO₃:3%Eu³⁺ is higher than that of Ca₂Ti₂O₆:3%Eu³⁺ under excitation at 394 nm, the luminescence intensity of Ca₂Ti₂O₆:3%Eu³⁺ is superior to that of CaTiO₃:3%Eu³⁺ under excitation at 464 nm and 533 nm. Photocatalytic experiments show that Ca₂Ti₂O₆:3%Eu³⁺ has better photocatalytic performance than CaTiO₃:3%Eu³⁺, which is mainly due to its smaller crystallite size, higher specific surface area and pyrochlore structure. In addition, biphase (Ca₂Ti₂O₆–CaTiO₃):3%Eu³⁺ has the best photocatalytic activity compared with the single phase Ca₂Ti₂O₆:3%Eu³⁺ and CaTiO₃:3%Eu³⁺, owing to the presence of heterojunctions that significantly reduced the band gap. It is anticipated that the discovery of this bifunctional Ca₂Ti₂O₆:Eu³⁺ would expand the application of rare earth-doped calcium titanium oxide materials.     

Relationship between valence of titania and apatite mineralization behavior in simulated body environment

Titania-based materials are attractive for hard tissue repair due to their bone-bonding ability induced by apatite formation in the body environment. Various surface treatments have therefore been developed to produce a hydrated titania layer on Ti and its alloys. Titania takes various valences, such as TiO (Ti²⁺) and Ti₂O₃ (Ti³⁺), as well as typical TiO₂ (Ti⁴⁺); however, there is no comprehensive study of structural effects on the apatite-forming ability of these titanias. In this study, we investigated apatite formation on titania powders with various valences in simulated body fluid. Anatase- and rutile-type TiO₂ formed apatite in simulated body fluid within 7 days, but TiO and Ti₂O₃ did not. In contrast, when the titania powders were treated with NaOH solution, the surface converted to tetravalent titania and all samples formed apatite. It is proposed that the surface electrical states of TiO and Ti₂O₃ are strongly affected by their bulk conductivity and that these behaved like pure Ti metal, which has poor apatite-forming ability. Apatite formation was favorable when the titania had a high absolute value and exhibited high fluctuations of zeta potential during initial stages in simulated body fluid, owing to adsorption of large amounts of Ca²⁺ and HPO₄²⁻.     

Efficient red‐emitting phosphor of Eu3+‐activated (Na0.5Gd1.5)(TiSb)O7 derived via cation‐substitutions in Gd‐Pyrochlore

Rare‐earth (RE) titanate pyrochlore with perovskite‐layered structure is a well‐known engineering material in applied in many field. In this work, a red‐emitting phosphor of Gd_2?xNa_xTi_2?2xSb_2xO₇:Eu³⁺ (x = 0‐0.5) was developed via cation substitutions of (Sb⁵⁺→Ti⁴⁺) and (Na⁺→Gd³⁺) in Gd₂Ti₂O₇. The motivation is based on the fact that the introduction of cation‐disorders has been regarded to be an effective approach for improving the luminescent efficiency and thermal stability of RE‐activated materials. All the samples were synthesized via facile solid‐state reaction method. The morphology properties were measured via SEM and EDS measurements. The structural Rietveld refinement was performed to investigate the microstructure in pyrochlore lattices. The luminescence properties of Gd_2?xNa_xTi_2?2xSb_2xO₇:0.15Eu³⁺ (x = 0‐0.5) has a strict dependence on the cation substitution levels. The band energy of Gd₂Ti₂O₇ is 2.9 eV with a direct transition nature. The incorporation of Sb⁵⁺ and Na⁺ in the lattices moves the optical absorption to a longer wavelength. The cation disorder results in significant improvements of luminescence intensity, excitation efficiency in the blue region, longer emission lifetime and thermal stability.     

Probing Site Symmetry Around Eu3+ in Nanocrystalline ThO2 Using Time Resolved Emission Spectroscopy

ThO₂:Eu³⁺ nanoparticles were synthesized at 300°C by combustion route using urea as a fuel and characterized by thermogravimetric/differential thermal analysis, X‐ray diffraction, transmission electron microscopy, and photoluminescence techniques. To investigate the effect of annealing temperature, as synthesized powder were heated further at 500°C, 700°C, and 900°C. It was observed that extent of asymmetry around Eu³⁺ at 700°C/900°C is very high as compared to as‐prepared or 500°C annealed sample. Based on the time resolved emission spectroscopic investigations, it was inferred that two different types of Eu³⁺ ions were present in the ThO₂ nanoparticles. In ThO₂ structure, Eu³⁺ ions occupy two sites; cubic (O_h) and noncubic (<C_2v) as can be confirmed from our emission studies. Short‐lived species T₁ (~1.3–3.4 ms) predominates at higher annealing temperature arises because of Eu³⁺ ions occupying noncubic (<C_2v) sites without inversion symmetry, whereas long‐lived species T₂ (~4.6–6.6 ms) can be ascribed to Eu³⁺ ions occupying cubic sites (O_h) with inversion symmetry.     

Crystal structure and luminescence properties of a single‐component white‐light‐emitting phosphor Ca8ZnLa(PO4)7:Eu2+,Mn2+

A series of novel green emission Whitlockite‐type Ca₈ZnLa(PO₄)₇:Eu²⁺ and color tunable Ca₈ZnLa(PO₄)₇:Eu²⁺,Mn²⁺ phosphors were prepared by the solid‐state reaction method in a reducing atmosphere. Its crystal structure and phase composition were identified by high‐resolution transmission electron microscopy, selected area electronic diffraction, X‐ray photoelectron spectroscopy, and X‐ray powder diffraction Rietveld refinement, and it was found to be trigonal, belonging to R‐3c(161) space group. The luminescence properties of Eu²⁺ singly doped and Eu²⁺/Mn²⁺ codoped Ca₈ZnLa(PO₄)₇ phosphors were revealed in detail. Ca₈ZnLa(PO₄)₇:Eu²⁺ is excitable over a broad range from 200 to 450 nm with a prominent green emitting. With varied Eu²⁺/Mn²⁺ ratios, fine‐tune emission under 365 nm excitation can be achieved from green (0.221, 0.468) to magenta (0.391, 0.276), especially the warm white light (0.392, 0.352), and CCT 3500 K can be obtained by the process of energy transfer between Eu²⁺ and Mn²⁺. The ET mechanism in this system is managed via the dipole‐dipole interaction with the maximum energy‐transfer efficiency 82.8% based on the decay lifetime data. These results suggest that as‐prepared phosphors can serve as promising candidates of UV‐pumped w‐LEDs.     

Luminescence and Quantum Efficiencies of Eu3+‐Doped Vanadate Garnets

Nondoped and 5.0 mol% Eu³⁺‐doped vanadate garnets Ca₅Mg₄(VO₄)₆, NaCa₂Mg₂[VO₄]₃, KCa₂Mg₂[VO₄]₃, and NaSr₂Mg₂[VO₄]₃ were synthesized by solid‐state reactions. The formation of single‐phase compound with garnet structure is confirmed by X‐ray diffraction. The photoluminescence (PL) and PL excitation (PLE) spectra are investigated together with color coordinates. The luminescence process is discussed on the charge‐transfer transitions in [VO₄]^3? ions and the crystal structure. The PL quantum efficiencies (QE) are measured for nondoped and Eu³⁺‐doped samples. The Eu³⁺‐doped samples have higher QEs than the corresponding nondoped ones although the energy transfer occurs from [VO₄]^3? to Eu³⁺. Broad emission band due to [VO₄]^3? with intense sharp lines due to Eu³⁺, which gives white color, is observed in Eu³⁺‐doped NaCa₂Mg₂[VO₄]₃ and NaSr₂Mg₂[VO₄]₃ under excitation with UV light. These materials are suggested to be useful for lighting under the excitation with near‐UV LED.     

Synthesis and luminescent properties of Sr4−xSi3O8Cl4: xEu3+ red phosphor by hydrothermal method

Sr_4‐xSi₃O₈Cl₄:xEu³⁺ (SSOC:Eu³⁺) phosphors were successfully synthesized by hydrothermal method. The crystallization of this phosphor was analyzed by means of X‐ray diffraction patterns. The size and morphology were recorded using SEM patterns of samples. And the PLE and PL spectra were characterized by a PL spectrophotometer. Excited by 394 nm UV light, the intense red emission is recognized in SSOC:Eu³⁺ phosphor and the main emission peak located at 620 nm. The influences of Eu³⁺ concentration, pH value of reaction solution, and charge compensator on PL spectra of SSOC:Eu³⁺ phosphors were investigated. The results revealed that this red phosphor had potential applications for white LEDs.     

In Situ Diffraction from Levitated Solids Under Extreme Conditions—Structure and Thermal Expansion in the Eu2O3–ZrO2 System

The accurate determination of structure and thermal expansion of refractory materials at temperatures above 1500°C is challenging. Here, for the first time, we demonstrate the ability to reliably refine the structure and thermal expansion coefficient of oxides at temperatures to 2200°C using in situ synchrotron diffraction coupled with aerodynamic levitation. Solid solutions in the Eu₂O₃–ZrO₂ binary system were investigated, including the high‐temperature order–disorder transformation in Eu₂Zr₂O₇. The disordered fluorite phase is found to be stable above 1900°C, and a reversible phase transition to the pyrochlore phase is noticed during cooling. Site occupancies in Eu₂Zr₂O₇ show a gradual increase in disorder on both cation and anion sublattices with increasing temperature. The thermal expansion coefficients of all cubic solid solutions are relatively similar, falling in the range 8.6–12.0 × 10^?6 C^?1. These studies open new vistas for in situ exploration of complex structural changes in high‐temperature materials.     

Design of Eu2+-activated broadband orange-emitting phosphors with excellent luminescent performance for warm WLEDs

We report orange-emitting Sr₈La_0.5Na_0.5Mg_1.5(PO₄)₇:Eu²⁺ (SLNMPO-0.5:Eu²⁺) and Sr₇LaNaMg_1.5(PO₄)₇:Eu²⁺ (SLNMPO-1:Eu²⁺) phosphors with broad emission bands covering from 450 to 800 nm. The phosphors can be excited by n-ultraviolet and blue light efficiently. Their crystal structure, diffuse reflection spectra, photoluminescence (PL) spectra, fluorescence decay curves and thermal stability were investigated systematically. Under the excitation of 365 and 400 nm, SLNMPO-0.5:Eu²⁺ and SLNMPO-1:Eu²⁺ both exhibit better PL properties and contain more red emissions than SMPO:Eu²⁺. CIE coordinates of SLNMPO-0.5:Eu²⁺ and SLNMPO-1:Eu²⁺ under 365 nm excitation are (0.460, 0.497) and (0.457, 0.494), respectively. Furthermore, high-quality warm white light can be generated by fabricating warm white light-emitting diode (WLED) devices with 370 nm LED chips, BaMgAl₁₀O₁₇:Eu²⁺ commercial blue phosphor and orange-emitting SLNMPO-0.5:Eu²⁺ (or SLNMPO-1:Eu²⁺) phosphor. The correlated color temperature, R_a and color coordinates are 3880 K, 94.05, (0.3895, 0.3922) and 3736 K, 91.73, (0.4005, 0.4078) for the fabricated WLED devices with SLNMPO-0.5:Eu²⁺ and SLNMPO-1:Eu²⁺, respectively. The excellent performances indicate that SLNMPO-0.5:Eu²⁺ and SLNMPO-1:Eu²⁺ have great potential to be attractive candidates in the application of warm WLEDs.