Rapid synthesis and enhancement in down conversion emission properties of BaAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript>,RE<Superscript>3+</Superscript> (RE<Superscript>3+</Superscript>=Y,Pr) nanophosphors

BaAl₂O₄:Eu²⁺,RE³⁺ (RE³⁺=Y, Pr) down conversion nanophosphors were prepared at 600 °C by a rapid gel combustion technique in presence of air using boron as flux and urea as a fuel. A comparative study of the prepared materials was carried out with and without the addition of boric acid. The boric acid was playing the important role of flux and reducer simultaneously. The peaks available in the XPS spectra of BaAl₂O₄:Eu²⁺ at 1126.5 and 1154.8 eV was ascribed to Eu²⁺(3d _5/2) and Eu²⁺(3d _3/2) respectively which confirmed the presence of Eu²⁺ ion in the prepared lattice. Morphology of phosphors was characterized by tunneling electron microscopy. XRD patterns revealed a dominant phase characteristics of hexagonal BaAl₂O₄ compound and the presence of dopants having unrecognizable effects on basic crystal structure of BaAl₂O₄. The addition of boric acid showed a remarkable change in luminescence properties and crystal size of nanophosphors. The emission spectra of phosphors had a broad band with maximum at 490–495 nm due to electron transition from 4f ⁶5d ¹ → 4f ⁷ of Eu²⁺ ion. The codoping of the rare earth (RE³⁺=Y, Pr) ions help in the enhancement of their luminescent properties. The prepared phosphors had brilliant optoelectronic properties that can be properly used for solid state display device applications.     

Temperature effect on the photoluminescence intensity and Eu<Superscript>2+</Superscript> excited state lifetime in EuGa<Subscript>2</Subscript>S<Subscript>4</Subscript> and EuGa<Subscript>2</Subscript>S<Subscript>4</Subscript>:Er<Superscript>3+</Superscript>

The photoluminescence (PL) spectra and Eu²⁺ excited state lifetime of EuGa₂S₄ and EuGa₂S₄:Er³⁺ have been studied in the range 78–500 K. The spectra show a band at 545 nm, due to the 4f ⁶5d → 4f ⁷(⁸ S _7/2) transition. With increasing temperature, the full width at half maximum Γ(T) of the PL band of EuGa₂S₄ and EuGa₂S₄:Er³⁺ crystals increases from 0.15 to 0.22 and from 0.13 to 0.19 eV, respectively. Over the entire temperature range studied, Γ(T) is a linear function of T ^1/2. The 545-nm emission intensity and Eu²⁺ excited state lifetime in EuGa₂S₄ and EuGa₂S₄:Er³⁺ vary exponentially with temperature. The luminescence quenching energies evaluated from the Arrhenius plots of I(10³/T) and τ(10³/T) coincide (0.10 eV) within the error of determination.     

Tunable luminescence properties and energy transfer of single-phase Ca<Subscript>4</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>O: Dy<Superscript>3+</Superscript>, Eu<Superscript>2+</Superscript> multi-color phosphors for warm white light

The novel Ca_4?x(PO₄)₂O: xDy³⁺ and Ca_4?x?y(PO₄)₂O: xDy³⁺, yEu²⁺ multi-color phosphors were synthesized by traditional solid-state reaction. The crystal structure, particle morphology, photoluminescence properties and energy transfer process were investigated in detail. The X-ray diffraction (XRD) results demonstrate that the products showed pure monoclinic phase of Ca₄(PO₄)₂O when x < 0.1. The scanning electron microscopy (SEM) indicated that the phosphors were grain-like morphologies with diameters of ~ 3.7–7.0 μm. Under excitation of 345 nm, Dy³⁺-doped Ca₄(PO₄)₂O phosphors showed multi-color emission bands at 410, 481 and 580 nm originated from oxygen vacancies and Dy³⁺. Interestingly, Ca₄(PO₄)₂O: Dy³⁺, Eu²⁺ phosphors exhibited blue emission band at 481 nm and broad emission band from 530 to 670 nm covering green to red regions. The energy transfer process from Dy³⁺ to Eu²⁺ was observed for the co-doped samples, and the energy transfer efficiency reached to 60% when Eu²⁺ molar concentration was 8%. In particular, warm/cool/day white light with adjustable CCT (2800–6700 K) and high CRI (R_a > 85) can be obtained by changing the Eu²⁺ co-doping contents in Ca₄(PO₄)₂O: Dy³⁺, Eu²⁺ phosphors. The optimized Ca_3.952(PO₄)₂O: 0.04Dy³⁺, 0.008Eu²⁺ phosphor can achieve the typical white light with CCT of 4735 K and CRI of 87.     

Luminescence properties of Bi codoped and P codoped Ca<Subscript>3</Subscript>(VO<Subscript>4</Subscript>)<Subscript>2</Subscript>:Eu<Superscript>3+</Superscript>

New red emitting phosphors, Ca₃(VO₄)₂:Eu³⁺,Bi³⁺, Ca₃((P,V)O₄)₂:Eu³⁺ were synthesized by low temperature solid-state reaction and characterized by X-ray diffraction, scanning electron microscopy, photoluminescence spectra and Fourier transform infrared spectroscopy. The results show that the red emission located at about 613 nm was ascribed to ⁵ D ₀-⁷ F ₂ transition of Eu³⁺. The effect of by Bi doping and by P doping was also investigated systematically.     

High-temperature heat capacity and vibrational spectra of Eu<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Eu₂Sn₂O₇ compound has been prepared by solid-state reaction (by sequentially firing a stoichiometric mixture of Eu₂O₃ and SnO₂ in air at 1273 and 1473 K) and its heat capacity has been determined by differential scanning calorimetry in the temperature range 370–1000 K. The heat capacity data have been used to evaluate the thermodynamic properties of europium stannate: enthalpy increment H°(T)–H°(370 K), entropy change S°(T)–S°(370 K), and reduced Gibbs energy Ф°(T). Raman spectra of Eu₂Sn₂O₇ polycrystals with the pyrochlore structure have been measured in the range 200–1200 cm^–1.     

Enhanced red-emitting phosphor Na<Subscript>2</Subscript>Ca<Subscript>3</Subscript>Si<Subscript>2</Subscript>O<Subscript>8</Subscript>:Eu<Superscript>3+</Superscript> by charge compensation

A series of novel red-emitting Na₂Ca_3???x Si₂O₈:xEu³⁺ phosphors were synthesized by solid state reactions. The phosphors can strongly absorb 395 nm light, and show red emission with a good color purity. The excitation and emission spectra properties of Na₂Ca₃Si₂O₈:Eu³⁺ were characterized. Na₂Ca₃Si₂O₈:Eu³⁺ with self-compensated and alkali metal ions charge compensated approaches (2Ca²⁺→Eu³⁺ + M⁺, M?=?Li⁺, Na⁺, K⁺) have investigated, which found that the red emission of luminescent intensity can be greatly enhanced, and shows superior luminescent property to the commercial Y₂0₃S:Eu³⁺. The present work implies that the efficient charge compensated phosphors are promising candidates as red-emitting phosphor for w-LEDs.     

Influence of isovalent and heterovalent substitution for Bi<Superscript>3+</Superscript> and Fe<Superscript>3+</Superscript> on the properties of Bi<Subscript>2</Subscript>Fe<Subscript>4</Subscript>O<Subscript>9</Subscript>-based solid solutions

Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites have been prepared by solid-state reactions at a temperature of 1073 K. X-ray diffraction data indicate that, in the Bi_2–хLa_хFe₄O₉ system, the limiting degree of La³⁺ substitution for Bi³⁺ ions in Bi₂Fe₄O₉ does not exceed 0.05 and that the limiting degree of substitution in the Bi₂Fe_4–2xTi_xCo_xO₉ system lies in the range 0.05 < x < 0.1. The specific magnetization and specific magnetic susceptibility of the samples have been measured at temperatures from 5 to 300 K in a magnetic field of 0.86 T. The field dependences of magnetization obtained for the Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites at temperatures of 300 and 5 K demonstrate that partial isovalent substitution of La³⁺ for Bi³⁺ ions in Bi₂Fe₄O₉ and heterovalent substitution of Ti⁴⁺ and Co²⁺ ions for two Fe³⁺ ions leads to partial breakdown of the antiferromagnetic state and nucleation of a ferromagnetic state.     

Synthesis,photoluminescence properties of Sr<Subscript>1.95</Subscript>Ba<Subscript>0.05</Subscript>CeO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> for LED applications

The Sr_1.95Ba_0.05 CeO₄:Eu³⁺ phosphors are synthesized by the solid-state reaction method. The samples are characterized using X-ray diffraction (XRD), diffuse reflectance spectroscopy and photoluminescence (PL) spectra. The XRD results reveal that the synthesized phosphors are genuine crystalline and belong to the orthorhombic structure. The intense PL emission is optimized from the PL spectra at various doping concentrations of europium ions. The results indicates that the phosphor can be effectively excited under 264 nm wavelength producing on intense emission spectrum of the synthesis material at 484 nm (blue region). The color purity of the phosphor is confirmed by CIE coordinates (x = 0.217, y = 0.265). The experimental data indicate that the prepared phosphors can be used as blue-emitting material in the field of illuminations and display devices.     

Critical Temperature of Smart Meta-superconducting MgB<Subscript>2</Subscript>

Enhancing the critical temperature (T _C ) is important not only to widen the practical applications but also to expand the theories of superconductivity. Inspired by the meta-material structure, we designed a smart meta-superconductor consisting of MgB₂ microparticles and Y₂O₃/Eu³⁺ nanorods. In the local electric field, Y₂O₃/Eu³⁺ nanorods generate an electroluminescence (EL) that can excite MgB₂ particles, thereby improving the T _C by strengthening the electron–phonon interaction. An MgB₂-based superconductor doped with one of four dopants of different EL intensities was prepared by an ex situ process. Results showed that the T _C of MgB₂ doped with 2 wt% Y₂O₃, which is not an EL material, is 33.1 K. However, replacing Y₂O₃ with Y₂O₃/Eu³⁺II, which displays a strong EL intensity, can improve the T _C by 2.8 to 35.9 K, which is even higher than that of pure MgB₂. The significant increment in T _C results from the EL exciting effect. Apart from EL intensity, the micromorphology and degree of dispersion of the dopants also affected the T _C . This smart meta-superconductor provides a new method to increase T _C .     

Synthesis and High-Temperature Heat Capacity of Sm<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript> and Eu<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Sm₂Ge₂O₇ and Eu₂Ge₂O₇ germanates have been prepared by solid-state reactions via multistep firing of stoichiometric mixtures of Sm₂O₃ (Eu₂O₃) and GeO₂ in air at temperatures from 1273 to 1473 K. The molar heat capacity of the samarium and europium germanates has been determined by differential scanning calorimetry in the range 350–1000 K and the C _p (T) data have been used to evaluate their thermodynamic properties.     

New NaSrPO<Subscript>4</Subscript>:Sm<Superscript>3+</Superscript> phosphor as orange-red emitting material

Sm³⁺-activated NaSrPO₄ phosphors could be efficiently excited at 403 nm, and exhibited a bright red emission mainly including four wavelength peaks of 565, 600, 646 and 710 nm. The highest emission intensity was found for NaSr _1?x PO₄: xSm³⁺ with a composition of x = 0.007. Concentration quenching was observed as the composition of x exceeds 0.007. The decay time values of NaSr_1?x PO ₄ : xSm³⁺ phosphors range from around 2.55 to 3.49 ms. NaSr_1?x PO₄: xSm³⁺ phosphor shows a higher thermally stable luminescence and its thermal quenching temperature T ₅₀ was found to be 350°C, which is higher than that of commercial YAG:Ce³⁺ phosphor and ZnS:(Al, Ag) phosphor. Because NaSr_1?x PO₄: xSm³⁺ phosphor features a high colour-rendering index and chemical stability, it is potentially useful as a new scintillation material for white light-emitting diodes.     

Photoluminescence of Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>:Eu nanocrystals

The photoluminescence (PL) of Ga₂S₃-5 mol % Eu₂O₃ nanocrystals prepared by mechanical comminution of the initial compound has been studied in the temperature range from 77 to 300 K. It is established that the PL spectrum of nanocrystals, in comparison to that of a massive sample, extends over a broader wavelength interval (430–620 nm) and has two maxima (at 507 and 556 nm) instead of one. The intensity of emission from nanocrystals is significantly higher than that from the massive crystal. The halfwidth in both cases varies with the temperature in proportion to T ^1/2. The intensity of emission at 556 nm for nanocrystals depends on the temperature as lgI ～ 1/T, this dependence having three linear portions corresponding to an activation energy of 0.04, 0.16, and 0.43 eV. The PL bands with maxima at 507 and 556 nm are assigned to the intracenter 4f ⁶5d4f ⁷ transitions in Eu²⁺ ions.     

Luminescence performance of Eu<Superscript>3+</Superscript>-doped lead-free zinc phosphate glasses for red emission

In this study, the luminescence performance of zinc phosphate glasses containing Eu³⁺ ion with the chemical compositions (60–x)NH₄H₂PO₄-20ZnO-10BaF₂-10NaF–x Eu₂O₃ (where x = 0.2, 0.5, 1.0 and 1.5 mol%) has been studied. These glasses were characterized by several spectroscopic techniques at room temperature. All the glasses showed relatively broad fluorescence excitation and luminescence spectra. Luminescence spectra of these glasses exhibit characteristic emission of Eu³⁺ ion with an intense and most prominent red emission (614 nm), which is attributed to ⁵D₀ → ⁷F₂ transition. Judd-Ofelt (Ω₂, Ω₄) parameters have been evaluated from the luminescence intensity ratios of ⁵D₀ → ⁷F_J (where J = 2 and 4) to ⁵D₀ → ⁷F₁ transition. Using J-O parameters and excitation spectra, the radiative parameters are calculated for different Eu³⁺-doped glasses. Effect of γ-irradiation at fixed dose has been studied for all the Eu³⁺-doped glass matrices. The lifetimes of the excited level, ⁵D₀, have been measured experimentally through decay profiles. The colour chromaticity coordinates are calculated and represented in the chromaticity diagram for Eu³⁺-doped zinc phosphate glasses for all concentrations.     

Effects of Ge<Superscript>4+</Superscript> acceptor dopant on sintering and electrical properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript> lead-free piezoceramics

Lead-free (K_0.5Na_0.5)(Nb_1-xGe _x )O₃ (KNN-xGe, where x = 0-0.01) piezoelectric ceramics were prepared by conventional ceramic processing. The effects of Ge⁴⁺ cation doping on the phase compositions, microstructure and electrical properties of KNN ceramics were studied. SEM images show that Ge⁴⁺ cation doping improved the sintering and promoted the grain growth of the KNN ceramics. Dielectric and ferroelectric measurements proved that Ge⁴⁺ cations substituted Nb⁵⁺ ions as acceptors, and the Curie temperature (T_C) shows an almost linear decrease with increasing the Ge⁴⁺ content. Combining this result with microstructure observations and electrical measurements, it is concluded that the optimal sintering temperature for KNN-xGe ceramics was 1020°C. Ge⁴⁺ doping less than 0.4 mol.%can improve the compositional homogeneity and piezoelectric properties of KNN ceramics. The KNN-xGe ceramics with x = 0.2% exhibited the best piezoelectric properties: piezoelectric constant d₃₃ = 120 pC/N, planar electromechanical coupling coefficient k_p = 34.7%, mechanical quality factor Q_m = 130, and tanδ = 3.6%.     

Studies of the Local Structure and the g Factors of the Cu<Superscript>2+</Superscript> Site in Y<Subscript>2</Subscript>BaCuO<Subscript>5</Subscript>

The local structure and the g factors (g _x , g _y , and g _z ) of the Cu²⁺ site in Y₂BaCuO₅ are theoretically studied using the perturbation formulas of the g factors for a 3d⁹ ion in orthorhombically elongated octahedra. The orthorhombic field parameters in these formulas are determined from the superposition model and the local geometry of the system. From the calculations, the oxygen octahedron is found to undergo the local elongation ΔZ (≈0.05 Å) along c-axis and the relative bond length variation ΔX (≈0.1 Å) along a- and b-axes, respectively. The calculated g factors based on the above local structure are in good agreement with the experimental data. The relationships between the anisotropies of the g factors and the low symmetrical (orthorhombic) distortions of the Cu²⁺ site in Y₂BaCuO₅ are discussed.     

A new rare-earth borate K<Subscript>3</Subscript>LuB<Subscript>6</Subscript>O<Subscript>12</Subscript>: crystal and electronic structure,and luminescent properties activated by Eu<Superscript>3+</Superscript>

A new potassium lutetium borate, K₃LuB₆O₁₂, was synthesized by a flux method and the crystal structure was determined by the single crystal X-ray diffraction. It crystallizes in non-centrosymmetric space group R3₂ and features a three-dimensional framework that is composed of B₅O₁₀, KO₆, KO₈, LuO₆ and (K|Lu)O₆ groups. Band structure calculations by the density functional theory method indicate that K₃LuB₆O₁₂ has direct bond gap of about 2.84 eV. The optical absorption can be mainly ascribed to the charge transitions from the O-2p states to the Lu-6s and Lu-5d states. Moreover, Eu-doped phosphor K₃Lu_0.95Eu_0.05B₆O₁₂ was synthesized by a solid-state reaction and its photoluminescence properties were studied. Under near-UV excitation (393 nm), K₃Lu_0.95Eu_0.05B₆O₁₂ exhibits an intense red emission centered at around 611 nm with the CIE coordinate of (0.641, 0.357), which can be assigned to the electric dipole ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions. We think that K₃Lu_0.95Eu_0.05B₆O₁₂ may be used as a good red phosphor pumped by near UV light LED chips.     

Strong up-conversion luminescence and electrical properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> multifunctional ceramics by Er<Superscript>3+</Superscript> doping

Novel green-emitting piezoelectric ceramics of SrBi_4?x Er _x Ti₄O₁₅ (SBT-xEr) were prepared. Strong up-conversion with bright green (524 and 548 nm) and a relatively weak red (660 nm) emission bands were obtained under 980 nm excitation at room temperature, which is attributed to the intra 4f–4f electronic transition of (²H_11/2, ⁴S_3/2)–⁴I_15/2 and the transition from ⁴F_9/2 to ⁴I_15/2 of Er³⁺ ions, respectively. Simultaneously, Er³⁺ doping promotes the electrical properties. At 0.8 mol%Er, the optimal electric properties with high Curie temperature of T _c?~527?°C, large remanent polarization of 2P _r?~14.92 μC/cm² and piezoelectric constant of d ₃₃?~17 pC/N was achieved. As a multifunctional material, Er³⁺ doped SBT showed a great potential to be used in 3D-display, bio-imaging, solid state laser and optical temperature sensor.     

Upconversion Luminescence of Gd<Subscript>2</Subscript>O<Subscript>3</Subscript> Nanocrystals Doped with Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> Ions

The upconversion luminescence (UCL) of nanocrystalline gadolinium oxide (Gd₂O₃) doped with Er³⁺ and Yb³⁺ ions has been studied in the temperature range of 90–400 K. The nanocrystals were synthesized by chemical vapor deposition and possessed a cubic crystalline structure with an average particle size within 48–57 nm. It is established that the USL intensity in the red (⁴F_9/2 → ⁴I_15/2 transition in Er3+ ion) and green (⁴S_3/2 → ⁴I_15/2 transition) spectral regions depends on the sample temperature and concentration of dopant ions, as well as on the additional structural defects (anion vacancies) created in the crystal lattice by the introduction of Zn²⁺ ions or irradiation with high-energy (10 MeV) electrons. The luminescence efficiency and spectrum of the upconversion phosphor are determined by energy transfer processes.     

Ionic conductivity of BaF<Subscript>2</Subscript> + ZnF<Subscript>2</Subscript> + CdF<Subscript>2</Subscript> + YbF<Subscript>3</Subscript> optical fluoride ceramic

The electrical conductivity of an optical fluoride ceramic in the quaternary system BaF₂ + ZnF₂ + CdF₂ + YbF₃ has been determined in the temperature range 338–722 K using impedance spectroscopy (5 to 5 × 10⁵ Hz). The 500-K ionic conductivity of the ceramic is σ = 3.3 × 10^–4 S/cm, which corresponds to the electrical characteristics of single crystals of the best conducting nonstoichiometric M_1–x R _x F_{2 + x} (M = Sr, Ba; R = La–Nd; x = 0.3–0.5) fluorite phases. We have observed nonmonotonic variation (breaks) in temperature-dependent σ, which is due to competing fluoride ion transport processes in different parts of the ceramic sample. The highly conductive state of the BaF₂ + ZnF₂ + CdF₂ + YbF₃ fluoride ceramic seems to be due to the formation of structural regions corresponding to a Ba_1–x Yb _x F_{2 + x} solid solution.     

Very high thermal stability with excellent dielectric,and non-ohmics properties of Mg-doped CaCu<Subscript>3</Subscript>Ti<Subscript>4.2</Subscript>O<Subscript>12</Subscript> ceramics

In this work, the nominal CaCu_3?xMg_xTi_4.2O₁₂ (0.00, 0.05 and 0.10) ceramics were prepared by sintering pellets of their precursor powders obtained by a polymer pyrolysis solution method at 1100 °C for different sintering time of 8 and 12 h. Very low loss tangent (tanδ)?<?0.009–0.014 and giant dielectric constant (ε′) ～?1.1?×?10⁴–1.8?×?10⁴ with excellent temperature coefficient (Δε′) less than ±?15% in a temperature range of ??60 to 210 °C were achieved. These excellent performances suggested a potent application of the ceramics for high temperature X8R and X9R capacitors. It was found that tanδ values decreased with increasing Mg²⁺ dopants due to the increase of grain boundary resistance (R_gb) caused by the very high density of grain, resulting from the substitution of small ionic radius Mg²⁺ dopants in the structure. In addition, CaCu_3?xMg_xTi_4.2O₁₂ ceramics displayed non-linear characteristics with the significant enhancements of a non-linear coefficient (α) and a breakdown field (E_b) due to Mg²⁺doping. The high values of ε′ (14012), α (13.64) and E_b (5977.02 V/cm) with very low tanδ value (0.009) were obtained in a CaCu_2.90Mg_0.10Ti_4.2O₁₂ ceramic sintered at 1100 °C for 8 h.