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.     

Luminescence Study of LiY<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Eu<Subscript>x</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The luminescence spectra of LiY_{1 − x} Eu_x(MoO₄)₂ (x = 0.0005, 0.001, 0.01, 0.05, 0.1, 0.5, 1) scheelite solid solutions are measured under laser excitation at 337.1 nm. The effect of Eu³⁺ concentration on the luminescence behavior of the solid solutions is examined. The highest integrated emission intensity is offered by LiY_0.5Eu_0.5(MoO₄)₂. Eu³⁺ substitution for Y³⁺ has no effect on the symmetry of the emission centers involved. Eu³⁺ is shown to occupy only one site in the structure of the solid solutions. X-ray diffraction and luminescence data indicate that all of the solid solutions have an undistorted scheelite structure.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 7, 2005, pp. 871–875.Original Russian Text Copyright © 2005 by Zaushitsyn, Mikhailin, Romanenko, Khaikina, Basovich, Morozov, Lazoryak.     

Roles of doping ions in persistent luminescence of SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript>, RE<Superscript>3+</Superscript> phosphors

The polycrystalline Eu²⁺ and RE³⁺ co-doped strontium aluminates SrAl₂O₄:Eu²⁺, RE³⁺ were prepared by solid state reactions. The UV-excited photoluminescence, persistent luminescence and thermo-luminescence of the SrAl₂O₄:Eu²⁺, RE³⁺ phosphors with different composition and doping ions were studied and compared. The results showed that the doped Eu²⁺ ion in SrAl₂O₄:Eu²⁺, Dy³⁺ phosphors works as not only the UV-excited luminescent center but also the persistent luminescent center. The doped Dy³⁺ ion can hardly yield any luminescence under UV-excitation, but can form a electron trap with appropriate depth and greatly enhance the persistent luminescence and thermo-luminescence of SrAl₂O₄:Eu²⁺. Different co-doping RE³⁺ ions showed different effects on persistent luminescence. Only the RE³⁺ ion (e.g. Dy³⁺, Nd³⁺), which has a suitable optical electro-negativity, can form the appropriate electron trap and greatly improve the persistent luminescence of SrAl₂O₄:Eu²⁺. Based on above observations, a persistent luminescence mechanism, electron transfer model, was proposed and illustrated.     

Ionic Conductivity of Ln<Subscript>2 + <Emphasis Type="Italic">x</Emphasis></Subscript>Zr<Subscript>2 − <Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>7 − <Emphasis Type="Italic">x</Emphasis>/2</Subscript> (Ln = Sm-Gd) Solid Solutions

The electrical conductivity of Ln_{2 + x} Zr_{2 − x} O_{7 − x/2} (Ln = Sm-Gd) solid solutions prepared from mechanically activated Ln₂O₃ and ZrO₂ is shown to correlate with their structural properties. In the three systems, the x-T regions are determined in which electrical transport is dominated by oxygen-ion conduction. In the Sm₂O₃-ZrO₂ system, ionic conductivities from 5 × 10⁻⁴ to 6 × 10⁻³ S/cm at 740°C are found in Sm_{2 + x} Zr_{2 − x} O_{7 − x/2} with 26.6, 33.3, 35.5, 37, and 40 mol % Sm₂O₃ prepared at 1450, 1530, and 1600°C. Eu_{2 + x} Zr_{2 − x} O_{7 − x/2} and Gd_{2 + x} Zr_{2 − x} O_{7 − x/2} containing 33.3 to 37 mol % Ln₂O₃ have 740°C ionic conductivities of 10⁻³ to ∼7.5 × 10⁻³ and 10⁻³ to 7 × 10⁻³ S/cm, respectively. The activation energy of conduction in Ln_{2 + x} Zr_{2 − x} O_{7 − x/2} (Ln = Sm-Gd), E _a = 0.84–1.04 eV, increases with the atomic number of Ln and x. The highest ionic conductivity is offered by the stoichiometric Ln₂Zr₂O₇ (Ln = Sm-Gd) pyrochlores prepared at 1600°C, owing to the optimal concentration of Ln_Zr + Zr_Ln antistructure pairs (∼5–22%). The grains in the ceramic samples studied range in size from 0.5 to 2 µm.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 8, 2005, pp. 975–984.Original Russian Text Copyright © 2005 by Shlyakhtina, Kolbanev, Knotko, Boguslavskii, Stefanovich, Karyagina, Shcherbakova.     

Electrical and Structural Properties of RE<Subscript>3</Subscript>Ba<Subscript>5</Subscript>Cu<Subscript>8</Subscript>O<Subscript>18</Subscript> (RE=Y,Sm and Nd) Superconductors

This paper presents the synthesis and characterization of the new superconducting compounds with nominal composition, RE₃Ba₅Cu₈O₁₈, RE=Y, Sm and Nd. The onset critical temperatures of the present samples are 97.5, 97 and 95 K for the RE=Y, Sm and Nd, respectively. The first two values are the highest for the RE–Ba–Cu–O superconductors recorded to date. The RE₃Ba₅Cu₈O₁₈ samples crystallize in the orthorhombic system, with increased unit cell volume as Sm and Nd replace the element Y.     

Luminescent properties of Yb<Superscript>3+</Superscript>-doped hexagonal Ln<Subscript>3</Subscript>BWO<Subscript>9</Subscript> (Ln = Gd,Y)

We report the synthesis and spectroscopic characterization of polycrystalline Yb³⁺-doped (1, 2, and 5 at %) Ln₃BWO₉ (Ln = Gd and Y) borotungstates as candidate gain media for diode-pumped near-IR and visible solid-state lasers. Unpolarized luminescence and absorption spectra for the Yb^{3+ 2} F _7/2→² F _5/2 transition are measured at T = 77 and 300 K, the lifetime of the ² F _5/2 excited state is determined, and the emission cross section of the stimulated Yb^{3+ 2} F _5/2→² F _7/2 transition in these compounds is evaluated. Offering a combination of nonlinear optical and lasing properties, the Ln₃BWO₉ (Ln = Gd, Y) hexagonal borotung-states can be used as bifunctional media for diode-pumped lasers with nonlinear laser frequency self-conversion.     

Synthesis and photoluminescence properties of LiEu(W,Mo)<Subscript>2</Subscript>O<Subscript>8</Subscript>:Bi<Superscript>3+</Superscript> red-emitting phosphor for white-LEDs

LiEu_1−x (W_2−y Mo _y )O₈:xBi³⁺ series red-emitting phosphors were synthesized by solid state reaction. The structure, morphology, and photoluminescent properties of phosphors were studied by X-ray powder diffraction, scanning electron microscopy, and photoluminescence spectrum, respectively. X-ray powder diffraction analysis showed that the as-obtained phosphors belong to the scheelite structure. The average particle size of the investigated phosphor was about 8 μm. The excitation spectrum exhibits a charge-transfer broad band along with some sharp peaks from the typical 4f–4f transitions of Eu³⁺. Under excitation of UV, near-UV, or blue light, these phosphors showed strong red emission at 615 nm due to ⁵D₀–⁷F₂ transition of Eu³⁺. The incorporation of Mo⁶⁺ into LiEuW₂O₈:Bi³⁺ could induce red-shift of the charge-transfer broad band and a remarkable increase of photoluminescence. The highest red-emission intensity was observed with LiEu_0.80Mo₂O₈:0.20Bi³⁺. Compared with the commercial red-emitting phosphor, Y₂O₂S:Eu³⁺, the emission intensity of LiEu_0.80Mo₂O₈:0.20Bi³⁺ phosphor is much stronger than that of Y₂O₂S:Eu³⁺ and its chromaticity coordinates are closer to the standard values than that of the commercial phosphor. The optical properties of LiEu_0.80Mo₂O₈:0.20Bi³⁺ phosphor make it attractive for the application in white-light-emitting diodes (LEDs), in particular for near-UV InGaN-based white-LEDs.     

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.     

Effect of secondary heat treatment on the spectroscopic properties of Na<Subscript>2</Subscript>O-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

We have studied the optical absorption and luminescence spectra of 45Na₂O · xNb₂O₅ · (55 − x)P₂O₅ glasses containing 5, 10, 20, 25, 30, and 35 mol % Nb₂O₅. The results indicate that the absorption band around 26000 cm⁻¹, responsible for the yellow color of the glasses, is due to the [Nb^(5+)--O⁻] center and disappears upon secondary heat treatment. Heat treatment of europium-doped glasses increases the concentration of Eu³⁺ centers in an asymmetric environment, which is accompanied by an increase in luminescence efficiency. The reason for this is that the Eu³⁺ ions are located outside the niobate subsystem of the glass matrix. The europium in the glasses studied acts as a protector ion.     

Enhanced Superconducting Properties of Air-Processed GdBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7-δ</Subscript> Single Domains with BaCO<Subscript>3</Subscript>/BaCuO<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript> Addition

Single domain GdBa₂Cu_7-δ (Gd123) bulk superconductors were fabricated in air by top-seeding melt-texture growth. Performance of the air-processed Gd123 was successfully enhanced by addition of both BaCO₃ and BaCuO_2−x , which suppress the formation of Gd_1+x Ba_2−x Cu₃O_7-δ solid solutions. The optimum doping amount ranges from 0.05 to 0.15, M BaCO₃ and 0.05 to 0.1, M BaCuO_2−x per molar Gd123. The distribution of the second phase particles was observed by scanning electron microscopy. A narrow band formed by Gd₂BaCuO₅ particle concentration appeared around the seeding zone in both a–b plane and c-growth sector in Gd123 single grain. Trapped magnetic field density reached 0.67, T for sample with 24 mm in diameter and 8, mm in thickness and a high critical current density J _c up to 91,200, A/cm² was achieved at 77, K under self-field.     

Synthesis and annealing effects on the optical spectroscopy properties of red-emitting Gd(P<Subscript>0.5</Subscript>V<Subscript>0.5</Subscript>)O<Subscript>4</Subscript>: x at.% Eu<Superscript>3+</Superscript>

In this work, Gd(P_0.5V_0.5)O₄: x at.% Eu³⁺ phosphors with different dopant concentrations (x?=?1, 3, 5, 6, 7, 9) were synthesized through chemical coprecipitation method. The phosphors were characterized by XRD, SEM, infrared spectroscopy, photoluminescence excitation, emission spectra and CIE. The results of XRD indicate that the obtained phosphors have the tetragonal phase structure. Eu³⁺ emission transitions arise mainly from the ⁵D₀ level to the ⁷F_J (J?=?0, 1, 2, 3, 4) manifolds. The emission intensity and crystalline of Gd(P_0.5V_0.5)O₄:x at% Eu³⁺ powders are increasing with annealing temperature at 600, 800, 1000, 1100, and 1200 °C, respectively. The introduction of VO₄^3? can broaden the range of UV excitation spectrum wavelength and enhance the transition between ⁵D₀ → ⁷F₁ to ⁵D₀ → ⁷F₂ for long wavelength emission. And the most dominant emission peak of Eu³⁺ for ⁵D₀ → ⁷F₂ transition is closer to pure red light at 622 nm. The maximum emission intensity of the phosphors is the concentration of 6 at.% Eu³⁺ because of the distance of the neighbor Eu³⁺ ions reaching a certain critical value and the influence of multipolar interaction. Compared to commercial phosphors Y₂O₃:Eu³⁺ and (Y,Gd)BO₃:Eu³⁺, our work yielded a longer wavelength red light emission intensity and a higher proportion of red light to orange light. All our results indicate that color purity of this phosphor turns it into a promising red phosphor in ultraviolet-pumped light-emitting diodes.     

Study of the effect of Li<Superscript>+</Superscript> concentration on the photoluminescence properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphors

Y₂O₃:Eu³⁺ phosphors were prepared by hydrothermal method. Effect of the doping concentration of Eu³⁺ on the photoluminescence properties of Y₂O₃:Eu³⁺ phosphor was studied in details. It was found that the strongest emission intensity is achieved as atomic ratio of Y³⁺ to Eu³⁺ is 8. As concentration of Eu³⁺ exceeds the critical concentration, the emission intensity decreases dramatically due to the concentration quenching of Eu³⁺. Also, the effect of Li⁺ on the photoluminescence performance of the Y₂O₃:Eu³⁺ phosphor is studied in this work. According to the results, the doping of Li⁺ may greatly improve the PL performance of the Y₂O₃:Eu³⁺ phosphors due to the flux effect and improved crystallinity caused by the doping of Li⁺.     

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.     

Combusion synthesis,structural and photo-physical characteristics of Eu<Superscript>2+</Superscript> and Dy<Superscript>3+</Superscript> co-doped SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript> phosphor nanopowders

In this research, we reported the synthesis of Eu²⁺ and Dy³⁺ co-doped SrAl₂O₄ phosphor nanopowders with high brightness and long afterglow by urea-nitrate solution combustion synthesis (SCS) at 600 °C, followed by heating the resultant combustion ash at 1,200 °C in a weak reductive atmosphere (5% H₂ + 95% N₂). The broad-band UV-excited luminescence of the SrAl₂O₄: Eu²⁺, Dy³⁺ nanopowders was observed at λ _max = 517 nm due to transitions from the 4f⁶5d¹ to the 4f⁷ configuration of the emission center (Eu²⁺ ions). The excitation spectra consist of 240- and 254 nm broad peaks. Finally, it was found that the optimum ratio of urea is 2.5 times higher than theoretical quantities for the best emission condition of SrAl₂O₄: Eu²⁺, Dy³⁺ phosphor nanopowders.     

Synthesis,photoluminescence and mechanoluminescence properties of Eu<Superscript>3+</Superscript> ions activated Ca<Subscript>2</Subscript>Gd<Subscript>2</Subscript>W<Subscript>3</Subscript>O<Subscript>14</Subscript> phosphors

A new series of Eu³⁺ ions-activated calcium gadolinium tungstate [Ca₂Gd₂W₃O₁₄] phosphors were synthesized by conventional solid-state reaction method. The X-ray diffraction patterns of the powder samples indicate that the Eu³⁺: Ca₂Gd₂W₃O₁₄ phosphors are of tetragonal structure. The prepared phosphors were well characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), Fourier transform infrared spectroscopy (FTIR), photoluminescence (PL), and mechanoluminescence (ML) spectra. PL spectra of Eu³⁺: Ca₂Gd₂W₃O₁₄ powder phosphors have shown strong red emission at 615 nm (⁵D₀ → ⁷F₂) with an excitation wavelength λ _exci = 392 nm (⁷F₀ → ⁵L₆). The energy transfer from tungstate groups to europium ions has also reported. Mechanoluminescence studies of Eu³⁺: Ca₂Gd₂W₃O₁₄ phosphors have also been explained systematically.     

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.     

Optical properties of Eu<Superscript>3+</Superscript> activated SrLa<Subscript>2</Subscript>O<Subscript>4</Subscript> red-emitting phosphors for WLED applications

The SrLa_2?xO₄:xEu³⁺ phosphors are synthesized through high-temperature solid-state reaction method at 1473 K with various doping concentration. Their phase structures, absorption spectra, and luminescence properties are investigated by X-ray diffraction (XRD), UV–Vis spectrophotometer and photoluminescence spectrometry. The intense absorption of SrLa_2?xO₄:xEu³⁺ phosphors have occurred around 400 nm. The prominent luminescence spectra of the prepared phosphors exhibited bright red emission at 626 nm. The doping concentration 0.12 mol% of Eu³⁺ is shown to be optimal for prominent red emission and chromaticity coordinates are x?=?0.692, y?=?0.3072. Considering the high colour purity and appropriate emission intensity of Eu³⁺ doped SrLa₂O₄ can be used as red phosphors for white light emitting diodes (WLEDs).     

K<Superscript>+</Superscript> ion conducting properties in the R<Subscript>2</Subscript>O<Subscript>3</Subscript>-KNO<Subscript>3</Subscript> (R: Rare earths) solid solution series

A new type of polycrystalline potassium ion conducting solid electrolyte doped with potassium nitrite as the starting material, was developed. Since cubic rare earth oxides hold reasonably enough interstitial space for bulky K⁺ ion migration in the crystal lattice, an extraordinary high K⁺ ion conductivity was successfully achieved by forming a polycrystalline (1 − x)R₂O₃-xKNO₃ solid solution, which was realized by doping KNO₂ as the KNO₃ state into the interstitial site of cubic rare earth oxide crystal lattice. The potassium ion conductivity of the (1 − x)R₂O₃-xKNO₃ (R: rare earths) solid solution linearly increased with expanding the R₂O₃ crystal lattice and the highest K⁺ ion conductivity was obtained for the 0.653Gd₂O₃-0.347KNO₃ solid solution, which is three orders of magnitude higher than that of a well-known polycrystalline K⁺ ion conducting K₂SO₄ solid and the value exceeds that in the ab conducting plane of a K⁺-β ”-Al₂O₃ single crystal.     

The synthesis and the magnetic properties of Sm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>BiY<Subscript>2–<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript>5</Subscript>O<Subscript>12 </Subscript>nanoparticles

Sm _x BiY_2–x Fe₅O₁₂ (x = 0, 0.1, 0.2, 0.4, 0.6, 0.8) nanocrystals were fabricated by sol–gel method. Samples were characterized by powder X-ray diffraction (XRD), thermal gravity analysis (TGA) and differential thermal analysis (DTA), transmission electron microscopy (TEM), vibrating sample magnetometer(VSM). The samples were calcined at 850 °C and 1000 °C and the average size of the particles were determined by Scherrer’s formula . In this paper, we discussed the effect of Sm³⁺ substitution for Y³⁺ on magnetic properties of BiY₂Fe₅O₁₂. The magnetic properties of Sm _x BiY_2−x Fe₅O₁₂ are decreased with increasing content of Sm ion.     

Photoluminescence properties of a novel red-emitting phosphor Ba<Subscript>2</Subscript>LaV<Subscript>3</Subscript>O<Subscript>11</Subscript>:Eu<Superscript>3+</Superscript>

Ba₂LaV₃O₁₁:Eu³⁺ phosphors were firstly synthesized by the traditional solid-state reaction method at 1100 °C. Their luminescence properties were investigated by photoluminescence excitation and emission spectra. The excitation spectrum shows a broad band centered at about 275 nm in the region from 200 to 370 nm, which is attributed to an overlap of the charge transfer transitions of O^2??→?V⁵⁺ and O^2??→?Eu³⁺. The phosphors exhibit the red emissions of Eu³⁺ and the emission intensity ratio of ⁵D₀?→?⁷F₂ to ⁵D₀?→?⁷F₁ is dependent on the Eu³⁺ concentration due to an environment change about Eu³⁺ ions. Concentration quenching occurs at 30 mol% in the phosphors and exchange interaction is its main mechanism. Ba₂LaV₃O₁₁:Eu³⁺ displays tunable CIE color coordinates from yellow orange to red depended on Eu³⁺ content, which may have a potential application for illuminating and display devices.