Effect of Sr and Ca substitution of Ba on the photoluminescence properties of the Eu2+ activated Ba2MgSi2O7 phosphor

The effects of Sr and Ca substitution of Ba on the Ba_1.98-xSr_x(Ca_x)MgSi₂O₇:Eu²⁺ photoluminescence properties have been investigated. The physical mechanisms for the photoluminescence variations are discussed. With Rietveld refinement method, the crystal structure of Ba_1.98MgSi₂O₇:0.02Eu²⁺ and the lattice parameters of Sr and Ca substituted phosphors were refined. The emission band shift, the photoluminescence intensity variation, the phosphor chromaticity evolution, the Eu²⁺ lifetime distribution and the thermal stability elevation were investigated. With Sr and Ca substitution, the cell is shrinks. The cell shrinkage is resulting in the increase of the Eu²⁺ 5d electron crystal field splitting intensity, which is the reason for the emission band shift towards the long wavelength band. The photoluminescence intensity is increased firstly and then decreased. The intensity variation is the competitive result between the increase of the crystal structure rigidity and the rise of the lattice defect. The correlated color temperature can be cut down and the color purity can be adjusted. The photoluminescence life time of Eu²⁺ is raised firstly and then decreased. For Sr and Ca substitution, the thermal stability can be elevated. With the forbidden band gap calculation, the reason for the thermal stability elevation was investigated that for the substituted phosphors the forbidden band gap is enlarged and then limits the Eu²⁺ 5d self-ionization from the splitting levels to the conduction band. This work reveals that the Sr and Ca substitution of Ba can elevate the Ba_1.98-xSr_x(Ca_x)MgSi₂O₇:Eu²⁺ photoluminescence properties and improve the applications for the White Light Emitting Diode.     

Preparation and characterization of a green emitting Li2Ca0.4Sr0.6SiO4:Tb3+ phosphor with afterglow behavior

A novel green emitting long afterglow phosphor Li₂Ca_0.4Sr_0.6SiO₄:Tb³⁺ was obtained via a high temperature solid-state reaction in air atmosphere. X-ray diffraction (XRD), photoluminescence spectroscope (PLS), long afterglow spectroscope (LAS) and thermal luminescence spectroscope (TLS) were performed to characterize the physical properties of the phosphors. Typical ⁵D₄-⁷F_j transitions of Tb³⁺ ions were detected by PL spectra, corresponding to CIE chromaticity coordinates of x =0.3456, y =0.5745. An optimal concentration of Tb³⁺ in the substrate was determined as 0.8 at%. The Li₂Ca_0.4Sr_0.6SiO₄ phosphors showed a typical afterglow behavior when the UV source was switched off. A typical triple exponential decay behavior was confirmed after fitting the experimental data. Thermal simulated luminescence study further indicated that the afterglow behavior of Li₂Ca_0.4Sr_0.6SiO₄:Tb³⁺ phosphors was generated by the recombination of electrons with the holes resulted from the doping of rare-earth ions (Tb³⁺) in Li₂Ca_0.4Sr_0.6SiO₄ host. The long afterglow luminescence mechanism of Li₂Ca_0.4Sr_0.6SiO₄:Tb³⁺ is illustrated and discussed in detail on the basis of experimental results.     

Green and red upconversion luminescence of Er-doped K0.5Na0.5NbO3 ceramics

Er³⁺ doped K_0.5Na_0.5NbO₃ (KNN) lead-free piezoelectric ceramics were synthesized by the solid-state reaction method. The upconversion emission properties of Er³⁺ doped KNN ceramics were investigated as a function of Er³⁺ concentration and incident pumping power intensity. Bright green (~555 nm) and red (670 nm) upconversion emission bands were obtained under 980 nm excitation at room temperature, which are attributed to (²H_11/2, ⁴S_3/2)→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions, respectively. The upconversion emission intensity can be adjusted by changing Er³⁺ concentration, and the mechanism of upconversion processes involve not only a two-photon absorption but also a three-photon absorption. In addition to the admirable intrinsic piezoelectric properties of KNN, this kind of material may have potential application as a multifunctional device by integrating its upconversion and piezoelectric property.     

Improvement of photoluminescence properties of Ce3+- doped CaSrAl2SiO7 phosphors by charge compensation with Li+ and Na+

In this work, we prepared CaSr_1-xAl₂SiO₇:xCe³⁺ (0.03 ≤ x ≤ 0.12) and CaSr_0.94Al₂SiO₇:0.03Ce³⁺,0.03 M⁺ (M⁺ = Li⁺ and Na⁺) phosphors via solid-state reaction method. Structural and photoluminescence (PL) properties of the phosphors were also investigated. The prepared phosphors formed an orthorhombic crystal structure with the P2₁2₁2₁ space group. CaSr_1-xAl₂SiO₇:xCe³⁺ phosphors were effectively excited by near-ultraviolet (UV) light (345 nm), which is suitable with the emission of near-UV light emitting diode chips. A broad blue emission (402 nm) was detected in CaSr_1-xAl₂SiO₇:xCe³⁺ and CaSr_0.94Al₂SiO₇:0.03Ce³⁺,0.03 M⁺ phosphors; this was attributed to the 4f⁰5d¹ → 4f¹ transition of Ce³⁺. To maintain charge equilibrium, charge compensators, such as monovalent Li⁺ and Na⁺ ions, were doped into the CaSr_0.97Al₂SiO₇:0.03Ce³⁺ phosphor, significantly improving its PL properties. The strongest emission intensity was achieved in CaSr_0.94Al₂SiO₇:0.03Ce³⁺,0.03Li⁺ phosphor. Addition of Li⁺ charge compensator was highly effective in improving PL properties of CaSr_0.97Al₂SiO₇:0.03Ce³⁺ phosphors.     

Solid state reaction preparation and enhanced red luminescence of S-doped La2Mo2O9:Prphosphors

Red-light-emitting phosphors of La₂Mo₂O₉:Pr³⁺ and S-doped La₂Mo₂O₉:Pr³⁺ were prepared by high temperature solid state reaction. Under the excitation of 450 nm blue light, all samples produced a red emission peak at 650 nm corresponding to the characteristic transition of Pr³⁺ (³P₀→³F₂). The dependence of Pr³⁺ doping content (x) on the luminescent intensity was analyzed, and the optimal doping content of Pr³⁺ was x=0.07. After a small quantity of sulfur was introduced into the system, the luminescence intensity of phosphors was obviously enhanced. The reasons for the enhancement of luminescence are due to improved crystallization after S doping and the relatively large electronegativity difference between S and Mo. Additionally, the coincidence of the excitation wavelength with the emission of GaN chips may recommend this phosphor system as a potential candidate for use in white light-emitting diodes.     

Preparation and infrared to visible upconversion luminescence of Yb2O3:Ho3+ nanocrystalline powders

Yb₂O₃:Ho³⁺ nanocrystalline powders were synthesized through a solid state reaction method. X-ray diffraction analysis and field emission scanning electron microscopy were used to analyze the phase composition and morphology of the powders. Then under the 980 nm excitation of laser diode, the fluorescence of the crystals was studied via a fluorescence spectrometer. The green and red emissions centered on 551 and 668 nm were observed, and the green band dominated the emission spectrum. The effect of the concentration of Ho³⁺ on the upconversion luminescence intensity was discussed and the possible upconversion emission mechanism was explained. It indicates that like other metal oxide nanoparticles, Yb₂O₃ could also be a potential host material for doping to prepare the upconversion phosphor.     

Synthesis and photoluminescence properties of a novel red phosphor SrLaGaO4:Mn4+

A novel Mn⁴⁺-doped strontium lanthanum gallate red phosphor SrLaGaO₄:Mn⁴⁺ has been successfully prepared via the conventional solid-state reaction method. Phase purity, photoluminescence excitation/emission spectra, concentration quenching, decay curves, and temperature-dependent photoluminescence have been investigated systematically. SrLaGaO₄:Mn⁴⁺ phosphor exhibits broad excitation band from 250 to 600 nm and emits intense red light centered at 716 nm arising from spin-forbidden transition, ²E → ⁴A₂ of Mn⁴⁺. The optimal dopant concentration of Mn⁴⁺ is determined to be 0.2 mol%. Dipole-dipole interaction is supposed to be the mechanism of concentration quenching. The crystal-field strength Dq, the Racah parameters B and C, and the nephelauxetic ratio β₁ of SrLaGaO₄:Mn⁴⁺ have been calculated according to its luminescent spectra. Our systematic investigation on this new phosphor can provide a reference for the development of red-emitting phosphor.     

Modulations in relaxor nature due to Sr2+ doping in 0.68PMN-0.32PT ceramic

Substitution of alkali earth metal ion of Sr²⁺, in the Pb²⁺ site of Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ is expected to induce functional modulations in the system. Doping of 4 at.% of Sr²⁺ in 0.68PMN-0.32PT was carried out to lower the transition temperature, and to investigate the intended ferroelectric and dielectric variations. Excellent relaxor property was observed in the doped sample without appreciable reduction in remnant polarization. Doping with Sr²⁺ led to a reduction in transition temperature from 165 °C to 117 °C. Doped sample exhibited remnant polarization P_r = 16.2 μC/cm², Squareness factor (Rsq) = 1.05 and Relaxor exponent (γ) around 2. Modulation in the functional response was exhibited by the doped composition, having low transition temperature, and its prospect in electrocaloric applications was analyzed.     

Luminescent properties of Eu-doped YTaO4 powders

YTaO₄:Eu³⁺ powders were synthesized by a flux method with LiCl. The use of a flux in the synthesis of M′–YTaO₄ facilitated the reaction of raw materials, leading to lowering the heating temperature, but not effective at the high firing temperature. The red emission peaks were observed around 613 nm with an excitation wavelength of 254 nm. Emission peaks were composed of two sets around 613 nm and 590 nm, which originated from ⁵D₀–⁷F₂ and ⁵D₀–⁷F₁, respectively. PL intensity of YTaO₄:Eu³⁺ prepared with a small amount of LiCl (10 wt%) significantly depended on the firing temperatures, while that with a larger amount of LiCl (40 wt%) slightly relied on firing temperatures. The highest PL intensity could be obtained at the firing conditions of 1300 °C and 10 wt% LiCl.     

Investigation of Eu2+ luminescence in barium tetraphosphate Ba3P4O13 polycrystalline ceramics

In this paper, Ba₃P₄O₁₃:Eu²⁺ phosphor was synthesized by a solid-state reaction. The photoluminescence (PL) emission spectrum and luminescence decay kinetics confirm that the doped Eu²⁺ ions can occupy two different Ba²⁺ sites. The PL excitation spectrum shows a broad band matching well with the emission of near-UV chip. Ba₃P₄O₁₃:Eu²⁺ is a promising phosphor for near-UV chip excited white LEDs. The doped Eu³⁺ ions can also be reduced to Eu²⁺ ions in air atmosphere at high temperature. Charge compensation mechanism is applied to explain this kind of abnormal reduction.     

Synthesis and dielectric properties of layered-perovskite KCa2Nan-3NbnO3n+1 ceramics

KCa₂NaNb₄O₁₃ (4KCNNO)¹ ceramics are well-sintered at 1325 °C without any secondary phase. However, K₂O evaporation occurs in KCa₂Na₂Nb₅O₁₆ (5KCNNO)² ceramics calcined at temperatures higher than 1200 °C, resulting in the formation of the KCa₂Na₃Nb₆O₁₉ (6KCNNO)³ secondary phase. Excess-K₂O was added to the 5KCNNO specimen to synthesize pure 5KCNNO ceramics by compensating for the evaporated K₂O. The 5KCNNO ceramic containing 20 mol% excess-K₂O sintered well at 1325 °C without any secondary phase. However, the 6KCNNO secondary phase also developed in specimens containing a large excess of K₂O, owing to the reaction between excess-K₂O and the 5KCNNO phase. Dielectric constant (ɛ_r) of the 4KCNNO ceramic is 62 with a dielectric loss (tan δ) of 0.6% at 100 kHz and the 5KCNNO ceramic showed increased ɛ_r of 70 with tan δ of 0.3% at 100 kHz. The increase in the ɛ_r value is rationalized by the inc_reased number of NbO₆ octahedral layers between the K⁺ layers. In addition, the structural and dielectric properties of the 5KCNNO ceramic are more important than those of the 4KCNNO ceramic from the application point of view, because the ε_r value of the 5KCNNO ceramic is larger than that of the 4KCNNO ceramic.     

Electronic structure and electrical conduction by polaron hopping mechanism in A2LuTaO6 (A= Ba,Sr, Ca) double perovskite oxides

Impedance spectroscopy has been applied to explore electrical properties of polycrystalline double perovskite oxides A₂LuTaO₆ (A = Ba, Sr, Ca; ALT). The phase purity and microstructural analysis of the samples are obtained from XRD and SEM. Ba₂LuTaO₆ (BLT) crystallizes in a single phase whereas in Sr₂LuTaO₆ (SLT) and Ca₂LuTaO₆ (CLT) a small secondary phase of Lu₂O₃ was detected. The Nyquist plots for ALT reveals the rising dominance of the grain boundary contribution to the conduction process with increasing temperature. The complex modulus plots confirm the presence of both the grain and grain boundary contributions to the relaxation process at low temperatures. The relaxation mechanism is seen to be shifted from its ideal character as observed in the Nyquist plots. The frequency dependent conductivity spectra follow the power law behavior. Small polaron hopping is responsible for the electrical conduction in these materials in the entire temperature range. Density functional theory calculations are performed to understand the electronic structure of the materials. The density of states (DOS) for BLT, SLT and CLT establishes the semiconducting ground state of the materials. The conductivity mechanism is analysed on the basis of the calculated DOS.     

Intermediate ferroelectric phase driven ferroelectric-relaxor crossover and superior storage properties in phase boundary engineered BCZT ceramics

Compositional tuning in materials at the morphotropic phase boundary has been a novel strategy to realize unprecedented and exotic physical properties. This work reports the structural, dielectric, electrical, and energy storage properties in lead-free BCZT (Ba_0.85Ca_0.15Zr_0.1Ti_0.9O₃) at the morphotropic phase boundary (MPB) through compositional engineering at Ba-site. The polycrystalline samples of Ba_0.85(1-x)(La_1/2Na_1/2)_0.85xCa_0.15Zr_0.1Ti_0.9O₃ (x = 0.0, 0.05, 0.075, 0.1) are synthesized by mechanical alloying followed by heating the samples at elevated temperatures. Rietveld refinement of powder X-ray diffraction patterns unveils coexisting ferroelectric P4mm (tetragonal) and ferroelectric R3m (Rhombohedral) symmetries, for samples x = 0.0–0.075. Intriguingly, the sample with x = 0.10 supports the inclusion of an intermediate ferroelectric phase with orthorhombic (Amm2) symmetry along with P4mm and R3m symmetries. Dielectric studies reveal a structurally coherent normal ferroelectric-ergodic relaxor crossover with Vogel-Fulcher type freezing of polar-nano-regions. Furthermore, the La/Na co-doping substantially enhances the recoverable energy density (W_rec); from 357 mJ/cm³ to 664 mJ/cm³, reduces the loss energy density (W_L); from 101 mJ/cm³ to 42 mJ/cm³ and increases the storage efficiency (η); from 77.9% to 94%. The doping-induced enhanced dielectric and storage properties are elucidated by impedance spectroscopy and density functional theory (DFT)-based calculations.     

The effect of calcination atmosphere on structural properties of Y-doped SrTiO3 perovskite anode for SOFC prepared by solid-state reaction

Recently Y-doped SrTiO₃ (YST) perovskite has been reported as a promising alternative for Ni/YSZ cermets as anode material for solid oxide fuel cells due to its mixed, ionic and electronic conduction. In this work SrTiO₃ was synthesized by solid-state reaction method, calcined, and sinterized to obtain undoped (ST), 4% (YST04) and 8% (YST08) of Y-dopant and as a heterojunction with yttria-stabilized zirconia (YST08/YSZ). The effects of calcination atmosphere and dopant concentration on formation of the perovskite and grain size distribution of the material were investigated. It was observed that calcination under Ar/5%H₂ atmosphere have increased the dopant maximum concentration in the SrTiO₃ cubic crystal structure when compared to inert atmosphere. When the Y solubility limit was exceeded, a pyrochlore phase Y₂Ti₂O₇ was formed at the intergranular region due to the deficiency of oxygen vacancies, especially in the presence of inert atmosphere. TGA and DTA curves present a peak of water desorption and two overlapping peaks of SrCO₃ phase change and decomposition. Ceramic microstructure was studied by SEM-EDS and the results showed that Y incorporation inhibits the grain growth in sintering step; reaching a smallest amount value of grain size in YST08/YSZ heterojunction under Ar/5%H₂ atmosphere.     

Mn4+ activated dodec-fluoride red phosphor Na3Li3In2F12:Mn4+ with excellent waterproof stability for WLEDs

Mn⁴⁺ activated fluoride red phosphors, as candidate red materials in white light-emitting diodes (WLEDs), have received widespread attention. However, the poor water stability limits their application. Herein, a novel dodec-fluoride red phosphor Na₃Li₃In₂F₁₂:Mn⁴⁺ with good waterproof stability was successfully synthesized by solvothermal method. The crystal structure, optical property, micro-morphology, element composition, waterproof property and thermal behavior of Na₃Li₃In₂F₁₂:Mn⁴⁺ phosphor were analyzed. Under the 468 nm blue light excitation, the Na₃Li₃In₂F₁₂:Mn⁴⁺ phosphor has narrow emission bands in the area of 590–680 nm. Compared with commercial red phosphor K₂SiF₆:Mn⁴⁺, the Na₃Li₃In₂F₁₂:Mn⁴⁺ phosphor possesses better waterproof stability. When soaked in water for 360 min, the PL intensity of the Na₃Li₃In₂F₁₂:Mn⁴⁺ phosphor remains at initial 80%. Finally, warm WLEDs with CRI of 87 and CCT of 3386 K have been fabricated using blue InGaN chip, YAG:Ce³⁺ yellow phosphor and Na₃Li₃In₂F₁₂:Mn⁴⁺ red phosphor.     

Synthesis,crystal structure and temperature dependent luminescence of Eu3+ doped SrGd2O4 host: An approach towards tunable red emissions for display applications

In the present paper, an investigation on the structural and photoluminescence (PL) properties of SrGd₂O₄:Eu³⁺ ceramic phosphors synthesized by homogeneous precipitation method followed by combustion process has been reported. The samples, annealed at 1200 °C, were crystallized into orthorhombic phase without any impurities. Microscopic studies revealed the irregular morphology of the obtained ceramic phosphor particles having sizes in the range of 0.3–3 µm. The characteristic photoluminescence properties and decay curves were studied in detail as a function of Eu³⁺ concentration and temperature. The Eu³⁺ doped ceramic samples illuminated with UV light revealed the characteristic red luminescence corresponding to ⁵D₀→⁷F_J transitions of Eu³⁺. The concentration quenching phenomenon of Eu³⁺ ions in the present host, analyzed in the light of ion-ion interaction, indicated multipolar interaction between Eu³⁺ ions. Finally, the intensity parameters (Ω₂, Ω₄) and various radiative properties such as stimulated emission cross-section (σ_e), gain band-width (σ_e×Δλ_eff) and optical gain (σ_e×τ_exp) of Eu³⁺ in the SrGd₂O₄ ceramic phosphors have been calculated by using Judd-Ofelt theory. The present phosphor system exhibited efficient red emission with high red color purity (95%) and adequate thermal stability even at 200 °C. Present research broadly indicated the suitability of SrGd₂O₄:Eu³⁺ ceramic phosphor for display applications.     

LED-pumped intense red luminescence based on Ba2LaTaO6: Mn4+ double perovskite phosphor

Non-rare earth Mn⁴⁺ ion-doped red oxide phosphors have great potential for applications in warm white light-emitting diodes (wLEDs) due to their low cost and stable physicochemical properties. Herein, a series of Ba₂LaTaO₆ (BLTO): Mn⁴⁺ phosphors were successfully synthesized by the high-temperature solid-state method. The theoretical values of the band gap calculated by the density functional theory are close to the experimental values obtained by the absorption spectroscopy. In addition, the phosphors have a broad excitation band in the wavelength range of 280–550 nm and emit red light at the peak wavelength of 681 nm under excitation. The concentration quenching of the BLTO: Mn⁴⁺ phosphor was caused by dipole-dipole interactions. The activation energy and the average decay lifetimes of the samples were calculated. Meanwhile, the effects of synthesis temperature and Li⁺ ion doping on the luminescence performance of the samples were also investigated. Satisfactorily, the color purity and internal quantum efficiency of the phosphor reached 98.3% and 26.8%, respectively. Further, the samples were prepared as red-light components for warm wLEDs. The correlated color temperature, color rendering index, and luminous efficiency of the representative devices driven by 60 mA current were 5190 K, 83.3, and 81.59 lm/W, respectively. This work shows that the BLTO: Mn⁴⁺ red phosphor with excellent luminescence performance can be well applied to warm wLEDs.     

Synthesis and characterization of MgAl2O4 micro-rods by a molten salt method

Large amounts of MgAl₂O₄ micro-rods were successfully synthesized using the molten-salt technology. The effect of KCl contents on the formation of MgAl₂O₄ micro-rods was investigated. The structure and morphology of MgAl₂O₄ were investigated by means of powder X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy, respectively. The experimental results showed that the contents of KCl significantly influenced the formation of MgAl₂O₄ micro-rods. MgAl₂O₄ micro-rods could be prepared at 1150 °C with a weight ratio of 100:1 between the salt and the starting materials. The formation of MgAl₂O₄ micro-rods could be suggested to be due to the inhomogeneous nucleation and orientated growth perpendicularly to the surfaces of Al₂O₃ grains. An impedance-type humidity sensor was finally fabricated based on the as-prepared MgAl₂O₄ micro-rods. According to tests of the humidity performance, MgAl₂O₄ micro-rods might be suitable for high-performance humidity sensors.     

Calorimetric study of ytterbium orthovanadate YbVO4 polycrystalline ceramics

The heat capacity of ytterbium orthovanadate was first measured by adiabatic calorimetry in the temperature range T?=?12.28–344.06?K. No obvious anomalies were observed on the curve obtained. The values of standard thermodynamic functions in the temperature range T?=?0–400 K were calculated. Based on low-temperature calorimetry data obtained, previously published data on the high-temperature heat capacity of ytterbium orthovanadate were corrected. The anomalous contribution to heat capacity for YbVO₄ was compared with the data known for YbPO₄.     

Synthesis, formation and characterization of ZnTiO3 ceramics

Zinc titanate (ZnTiO₃) powders of perovskite structure were synthesized by conventional solid state reaction using metal oxides. Powders of ZnO and TiO₂ in a molar ratio of 1:1 were mixed in a ball mill and then heated at temperatures from 700 to 1000 °C for various time periods in air. The crystallization temperature of ZnTiO₃ powder was 820 °C, activation energy for crystallization was 327.14 kJ/mol and for grain growth was 48.84 kJ/mol. A transition point was observed when the electrical resistivity was measured versus temperature. Like some ferroelectric materials, a PTCR behavior above the transition temperature was observed with Curie temperature of 5 °C.