Synthesis and photoluminescence properties of Eu doped Sr9Sc(PO4)7 phosphors for white light-emitting diodes

A series of Eu²⁺-activated Sr₉Sc(PO₄)₇ yellowish-green emitting phosphors were synthesized by conventional solid-state reaction. The photoluminescence (PL) properties and concentration quenching mechanism of the as-prepared phosphors were investigated. The emission spectrum exhibits a broad and asymmetric band peaking at 510 nm, which corresponds to the 4f⁶5d¹→4f⁷ transition of Eu²⁺. The excitation spectrum exhibits a broad band extending from 250 to 450 nm, which matches well with the emission of near ultraviolet (n-UV) chips (350–430 nm). Non-radiative transitions between Eu²⁺ ions in the Sr₉Sc(PO₄)₇ host have been demonstrated to be attributable to dipole–dipole interactions, and the critical distance was calculated to be 23.1 Å. These results indicate that Sr₉Sc(PO₄)₇:Eu²⁺ phosphor could serve as a promising candidate for application in n-UV white-light LEDs.     

The doping concentration dependent tunable yellow luminescence of Sr5(PO4)2(SiO4):Eu

Color tunable yellow-emitting phosphors of Sr_5−5xEu_5x(PO₄)₂SiO₄ (x = 0.05-0.15) were prepared by conventional solid-state reaction method. The X-ray powder diffraction patterns, the photoluminescence excitation and emission spectra were measured. The main excitation bands of the phosphors locate at a broad band extending from 300 to 500 nm, which can match the emission of ultraviolet- and blue-emitting diode chips. The tunable luminescence color was realized by the changing Eu²⁺ doping in Sr₅(PO₄)₂SiO₄. The structure and luminescence properties were investigated. Sr_5−5x(PO₄)₂SiO₄:Eu_5x displays two typical luminescence centers, which originate from two different Sr²⁺ (Eu²⁺) sites in the host. The site-occupation, the luminescence intensity and energy transfer between the Eu²⁺ ions occupying two different crystallographic Sr²⁺ sites were discussed on the base of the luminescence spectra and crystal structure. This is helpful to improve this phosphor for a potential application as a white light emitting diode phosphor.     

Potential red-emitting NaGd(MO4)2:R (M=W,Mo, R=Eu,Sm, Bi) phosphors for white light emitting diodes applications

NaGd(MO₄)₂:R (M=W, Mo, R=Eu³⁺, Sm³⁺, Bi³⁺) phosphors were synthesized by solid-state reaction. The structure and photoluminescence properties of the samples were characterized using X-ray powder diffraction and fluorescence spectrophotometry. The ⁵D₀→⁷F₂ transition of Eu³⁺, which led to a red emission of the phosphors, was dominantly observed in the photoluminescence spectra. The doped Bi³⁺ and Sm³⁺ efficiently sensitized the emission of Eu³⁺ and effectively extended and strengthened the absorption of near-UV light with wavelengths ranging from 395 to 405 nm. In addition, energy transfers from Bi³⁺ to Eu³⁺ and from Sm³⁺ to Eu³⁺ occurred. The chromaticity coordinates of the obtained phosphors were close to the standard values of the National Television Standard Committee (x=0.670, y=0.330). The results suggest that NaGd(WO₄)_2−y(MoO₄)_y:Eu³⁺, Sm³⁺, Bi³⁺ is an efficient red-emitting phosphor for light-emitting diode applications.     

Preparation,structural and luminescent properties of YAl3(BO3)4:Dy phosphor for white light-emission under UV excitation

A series of YAl₃(BO₃)₄ phosphors doped with different concentrations of Dy₂O₃ (0.1≤x≤5 mol%) were prepared by solid-state reaction method. The crystallization process of the precursor has been examined by differential thermal analysis (DTA) measurements. The phase purity and surface morphological features were characterized by X-ray diffraction (XRD) and scanning electron microscopic (SEM) investigations. The YAl₃(BO₃)₄ nanocrystals obtained were found to be about 45 nm in size and have the trigonal structure with some agglomeration. Fourier transform infrared (FTIR) and energy dispersive X-ray spectra (EDS) measurements were carried out to understand the compositional and elemental analysis. The characteristics emission peaks of Dy³⁺ ion corresponding to the transitions of ⁴F_9/2→⁶H_15/2 at 485 nm and ⁴F_9/2→⁶H_13/2 at 576 nm were observed in the emission spectra. The luminescence quenching noticed at higher Dy₂O₃ concentrations is due to the exchange interaction among the excited Dy³⁺ ions.     

Dielectric,magnetic and magnetoelectric properties of Ni0.5Zn0.5Fe2O4+Pb(Zr0.48Ti0.52)O3 composite ceramics

Magnetoelectric composite ceramics of spinel ferrite Ni_0.5Zn_0.5Fe₂O₄ (NZFO) with high magnetic permeability and tetragonal perovskite Pb(Zr_0.48Ti_0.52)O₃ (PZT) with high piezoelectric constant were synthesized by common solid state reaction method. XRD and SEM showed that high dense composite ceramics without any foreign phases were obtained. The ceramics showed excellent dielectric and magnetic properties, which were stable in a large frequency range. The dielectric peak became wider with the ferrite content in the permittivity spectrum with temperature. With the increase in the ferrite content, the magnetic Curie temperature shifted to higher temperature and closed to that of the pure ferrite. In addition, the magnetoelectric coefficient enhanced as the increase in the ferrite content. The properties of the composite ceramics could be adjusted by the ferrite content. These research results provided a powerful experimental basis for the sensor and transducer in microelectronic and microwave devices.     

Improvement of the luminescence properties of CaTiO3:Pr obtained by modified solid-state reaction

Using tetra-n-butyl titanate and nitrates as starting materials, the red persistent phosphor CaTiO₃:Pr has been successfully synthesized by modified solid-state reaction. In order to improve the luminescent properties of the phosphor, boric acid as flux regent and aluminum ion as charge compensator were added in, and the influences of partially replacing Ca²⁺ in CaTiO₃ with Zn²⁺ or Mg²⁺ on the long persistent properties were studied. The results of luminescence spectrometer (PL), X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed that a certain quantity of boric acid, Al³⁺, Mg²⁺ or Zn²⁺ was effective in improving the photoluminescence intensity of CaTiO₃:Pr phosphor particles, and the optimum molar ratios of Al³⁺ and boric acid to Ca²⁺ were about 0.1% and 30%, respectively. The photoluminescence brightness and decay curves showed that the sample of Ca_0.8Zn_0.2TiO₃:Pr with 0.l% Al³⁺ and 30% H₃BO₃ obtained at the sintering temperature of 900 °C exhibited the optimal luminescent properties.     

Effect of reduction agent on the performance of Li3V2(PO4)3/C positive material by one-step solid-state reaction

The effects of reduction agent on the electrochemical properties of Li₃V₂(PO₄)₃/C positive materials were studied. An one-step solid-state reaction route was applied to synthesize Li₃V₂(PO₄)₃/C samples. The humic acid, glucose and carbon were used as reduction agent. SEM images show that the particles of sample with humic acid as reduction agent merge with each other and form a porous structure, and yet the particles of sample synthesized using carbon as reduction agent are wrapped with small carbon particles and separate each other. Electrochemical tests show that the samples using humic acid and glucose as reduction agents have better cyclic performance than the one using carbon as reduction agent. At the 200th cycle, the sample using humic acid as reduction agent still keeps 145.2 mAh g⁻¹ at 1 C charge and discharge rates. However, the sample using carbon as reduction agent shows a fast decline in capacity during cycling and has 54.5% capacity loss of the initial value after 200 cycles. The results indicate that different reduction agents can obviously affect the morphologies and electrochemical properties of the products.     

Electrical properties of Li1.3Ge1.4Ti0.3Al0.3(PO4)3 superionic ceramics

Preparation and electrical characterization of NASICON-type compound, Li_1.3Ge_1.4Ti_0.3Al_0.3(PO₄)₃, are described. The solid solution is obtained with Ge⁴⁺ → Ti⁴⁺ and Ge⁴⁺ → Al³⁺ substitutions in LiGe₂(PO₄)₃. The powder has been fabricated by a solid state reaction and the structural characteristics of it have been studied by X-ray. Ceramic samples have been sintered by varying the sintering duration from 1 to 3 h. Samples were studied by complex impedance spectroscopy in the frequency range 1 MHz-1.2 GHz and temperature range 300-600 K. Two regions of relaxation dispersion were found. The dispersions were related to the fast Li⁺ ion transport in the grains and grain boundaries. Variation of the sintering duration has no considerable effect on electrical properties of the ceramics.     

Preparation of Ca4Mg5(PO4)6:Eu,Mn phosphor and its photoluminescence properties

Eu²⁺ and Mn²⁺ singly doped and Eu²⁺/Mn²⁺-codoped Ca₄Mg₅(PO₄)₆ phosphors were synthesized via combustion synthesis. Mn²⁺-singly doped Ca₄Mg₅(PO₄)₆ phosphor exhibits a single red emission in the wavelength range of 500–700 nm due to the ⁴T₁(⁴G)→⁶A₁(⁶S) transition of Mn²⁺. Eu²⁺/Mn²⁺ co-doped phosphor emits two distinctive luminescence bands: a blue one centered at 442 nm originating from Eu²⁺ and a broad red-emitting one peaked at 609 nm from Mn²⁺. Energy transfers from Eu²⁺ to Mn²⁺ were discovered by directly observing significant overlap of the excitation spectrum of Mn²⁺ and the emission spectrum of Eu²⁺ as well as the systematic relative decline and growth of emission bands of Eu²⁺ and Mn²⁺, respectively. Based on the principle of energy transfer, the relative intensities of blue and red emission could be tuned by adjusting the contents of Eu²⁺ and Mn²⁺.     

A reddish orange stoichiometric phosphor LiEu(PO3)4 for white light-emitting diodes

Stoichiometric phosphors LiGd_1−xEu_x(PO₃)₄(x=0, 0.2, 0.4, 0.6, 0.8, 1.0) were synthesized via traditional solid state reactions. The X-ray powder diffraction measurements show that all prepared samples are isostructural with LiNd(PO₃)₄. Eu³⁺ doped phosphors can emit intense reddish orange light under the excitation of near ultraviolet light from 370 to 410 nm. The strongest two at 591 and 613 nm can be attributed to the transitions from excited state ⁵D₀ to ground states ⁷F₁ and ⁷F₂, respectively. The typical chromaticity coordinates (x=0.620, y=0.368) of Eu³⁺ doped phosphors are in red area. The recorded absorbance spectra indicate that there is effective absorbance in the near UV region for all Eu³⁺ doped samples. Present research indicates that LiGd_1–xEu_x(PO₃)₄ is a promising phosphor for white light-emitting diodes.     

Synthesis and characterization of carbon-coated Li3V2(PO4)3 cathode materials with different carbon sources

The carbon-coated monoclinic Li₃V₂(PO₄)₃ (LVP) cathode materials were synthesized by a solid-state reaction process under the same conditions using citric acid, glucose, PVDF and starch, respectively, as both reduction agents and carbon coating sources. The carbon coating can enhance the conductivity of the composite materials and hinder the growth of Li₃V₂(PO₄)₃ particles. Their structures and physicochemical properties were investigated using X-ray diffraction (XRD), thermogravimetric (TG), scanning electron microscopy (SEM) and electrochemical methods. In the voltage region of 3.0-4.3 V, the electrochemical cycling of these LVP/C electrodes all presents good rate capability and excellent cycle stability. It is found that the citric acid-derived LVP owns the largest reversible capacity of 118 mAh g⁻¹ with no capacity fading during 100 cycles at the rate of 0.2C, and the PVDF-derived LVP possesses a capacity of 95 mAh g⁻¹ even at the rate of 5C. While in the voltage region of 3.0-4.8 V, all samples exhibit a slightly poorer cycle performance with the capacity retention of about 86% after 50 cycles at the rate of 0.2C. The reasons for electrochemical performance of the carbon coated Li₃V₂(PO₄)₃ composites are also discussed. The solid-state reaction is feasible for the preparation of the carbon coated Li₃V₂(PO₄)₃ composites which can offer favorable properties for commercial applications.     

Sr0.5Zr2(PO4)3陶瓷的力学性能研究

用共沉淀法和低分子有机溶剂分散获得SZP粉体,经干压成型和烧结得到SZP陶瓷.研究了其力学性能与烧结温度烧结时间和添加剂用量的关系.最佳工艺条件为添加MgO6wt%,1300℃或ZnO3wt%,1200℃均烧结1.5小时,SZP陶瓷的抗压强度分别可达244.0MPa和226.2MPa.     

Effect of strontium and phosphorus source on the structure,morphology and luminescence of Sr5(PO4)2SiO4:Euphosphor prepared by solid-state reaction

Sr₅(PO₄)₂SiO₄:Eu²⁺ phosphosilicate phosphor was prepared by high temperature solid-state reaction. Effects of strontium sources (strontium oxide, strontium nitrate and strontium carbonate) and of phosphorus sources (diammonium phosphate, strontium monophosphate) on the reactivity of their mixture during heating and on phase composition, morphology and photoluminescence excitation and emission properties of the phosphors were investigated by TG–DTG–DSC, XRD, SEM and photoluminescence spectroscopy. The sequence of the solid-state reactions when using the different starting reagents was discussed based on the TG–DTG–DSC results. It was found that it is hard to prepare pure Sr₅(PO₄)₂SiO₄:Eu²⁺ phosphor with either of strontium sources studied when stoichiometric (NH₄)₂HPO₄ was used as a phosphorus source. Minor Sr₂SiO₄ impurity phase was present in the phosphors. The content of impurity phase, the morphology and resultant photoluminescence properties of the phosphors were markedly influenced by the strontium source employed. When SrCO₃ was used as the strontium source, the phase purity of the phosphor was improved with the addition of excess (NH₄)₂HPO₄. When (NH₄)₂HPO₄with 5% excess or SrHPO₄ in stoichiometric ratio was used as the phosphorus source a pure phase phosphor was obtained. In addition, the morphology and photoluminescence of the phosphor were also influenced by phosphorus source. The possible reasons causing different properties of the phosphors prepared using different raw materials were discussed based on reaction schemes.     

Photoluminescence properties of Eu-doped WO3-Eu2(WO4)3 composites and single-phase Eu2(WO4)3 powders

The development of highly stable and efficient oxide-based red phosphors is urgently required for next-generation lighting devices. Herein, we report the micro/crystal structures and luminescent properties of single-phase Eu₂(WO₄)₃ and Eu³⁺-doped WO₃-Eu₂(WO₄)₃ composite phosphors prepared by a one-step conventional solid-state reaction method in air atmosphere. As increasing Eu contents in the mixtures of WO₃ and Eu₂O₃, the intensities of the X-ray diffraction peaks of Eu₂(WO₄)₃ increased while that of WO₃ decreased. The photoluminescence intensity of the synthesized phosphors increased with increase in the Eu content when calcined at 900 °C, while it degraded at a higher temperature. Red-emitting single-phase Eu₂(WO₄)₃ powders were successfully obtained when the WO₃ and Eu₂O₃ powders were calcined in the ratio of 3:1. The intensity of the red emission spectra of the Eu₂(WO₄)₃ phosphor was higher than those of the 6, 12, and 24 at.% Eu-added WO₃ composites at excitation wavelengths of 394 and 465 nm. On the other hand, the intensity of emission from the single-phase phosphor was lower than that of the Eu-doped WO₃-Eu₂(WO₄)₃ composites under excitation of UV light at 254 nm. Thus, we propose two prospective phosphors for application as red phosphors at various wavelengths.     

Solution and solid phase electrochemical behaviour of [Os(bpy)3]3[P2W18O62]

[Os(bpy)₃]₃[P₂W₁₈O₆₂] has been synthesised and characterised by elemental analysis, spectroscopic (UV-vis, IR spectroscopy) and electrochemical techniques. In 0.1 M Bu₄NPF₆ DMSO the complex shows a series of redox couples associated with the Os^3+/2+ and bipyridine ligands of the cationic [Os(bpy)₃]²⁺ moiety and the tungsten-oxo framework of the associated Dawson parent heteropolyanion, [P₂W₁₈O₆₂]⁶⁻. At this electrolyte concentration, the Os³⁺ redox form of the complex was seen to adsorb onto the electrode surface. When the electrolyte concentration is lowered to 0.01 M Bu₄NPF₆ in addition to the Os^3+/2+ redox couple, the redox process associated with the [P₂W₁₈O₆₂]^8−/7− couple also exhibited properties indicating surface based processes were present. Electroactive films of the complex were formed on carbon macroelectrodes by the redox switching of the transition metal within the complex. Voltammetric investigations into the film's behaviour in a range of buffer solutions (pH 2.0, 4.5 and 7.0) were performed. The films were found to possess better stability in acidic pH and the same pH dependence for the tungsten-oxo framework of the heteropolyanions as in solution. Solid state electrochemical measurements on mechanically attached microparticles of the complex were performed, with the effect of both the nature and concentration of the aqueous electrolyte on this behaviour being investigated. Upon redox switching between the Os^2+/3+ redox states, there is an associated insertion/expulsion of anions from/to the solution phase. Scanning electron micrographs of these solid state films were attained before and after redox cycling.     

White light emitting from YVO4/Y2O3:Eu3+,Bi3+ composite phosphors for UV light-emitting diodes

A series of (1−x)YVO₄/xY₂O₃:Eu³⁺_0.006,Bi³⁺_0.006 (0≤x≤0.54) composite phosphors was synthesized in one step by high temperature solid state reaction and the photoluminescence properties were investigated. By means of co-doping Eu³⁺ and Bi³⁺ ions into the composite matrices composed of YVO₄ and Y₂O₃ crystals, the YVO₄/Y₂O₃:Eu³⁺,Bi³⁺ phosphor exhibits simultaneously the blue (418 nm), green (540 nm) and orange-red (595, 620 nm) emissions. The broad blue and green emissions are attributed to the ³P₁–¹S₀ transitions of Bi³⁺ ion both in Y₂O₃ and in YVO₄ matrices. Moreover, the sharp orange-red emissions are attributed to the ⁵D₀–⁷F_1,2 transitions of Eu³⁺ ion in YVO₄ matrix. By tuning the mole ratio of YVO₄/Y₂O₃ matrices the white light-emitting could be obtained. The results indicated that when the mole ratio of Y₂O₃ (x) is at 0.11–0.54 mol, the (1−x)YVO₄/xY₂O₃:Eu³⁺_0.006,Bi³⁺_0.006 phosphors emit white light by combining the blue, green and orange-red emissions under the excitation of 360–370 nm wavelength which matches the emission of the commercial UV-LED diode. This implies that the phosphors may be the promising white light materials with broad absorption band for white light-emitting diodes.     

Microwave solid-state synthesis and electrochemical properties of carbon-free Li3V2(PO4)3 as cathode materials for lithium batteries

Monoclinic Li₃V₂(PO₄)₃ can be rapidly synthesized at 750 °C for 5 min (MW5m) by using microwave solid-state synthesis method. The refined cell parameters and atomic coordination of the sample MW5m show some deviations compared with those of the sample synthesized in conventional solid-state synthesis method, especially the coordinate of Li atoms. Compared with the electrochemical properties of the carbon-coating sample Li₃V₂(PO₄)₃, the carbon-free sample MW5m presents well electrochemical properties. In the cut-off voltage of 3.0-4.3 V, MW5m sample presents a specific charge capacity of 132 mAh g⁻¹, almost equivalent to the reversible cycling of two lithium ions per Li₃V₂(PO₄)₃ formula unit (133 mAh g⁻¹), and specific discharge capacity of 126.4 mAh g⁻¹. In the cut-off voltage of 3.0-4.8 V, MW5m shows an initial specific discharge capacity of 183.4 mAh g⁻¹ at 0.1 C, near the theoretical discharge capacity. In the cycle performance, the capacity fade of Li₃V₂(PO₄)₃ is dependent on the cut-off voltage and the preparation method, more capacity lost at relatively higher charge/discharge voltage. The reasons for the excellent electrochemical properties of Li₃V₂(PO₄)₃ rapidly synthesized in microwave field are discussed in detail.     

Low temperature sintering and microwave dielectric properties of Ce2(WO4)3 ceramics

Ce₂(WO₄)₃ ceramics have been synthesized by the conventional solid-state ceramic route. Ce₂(WO₄)₃ ceramics sintered at 1000 °C exhibited ?_r = 12.4, Qxf = 10,500 GHz (at 4.8 GHz) and τ_f = −39 ppm/°C. The effects of B₂O₃, ZnO–B₂O₃, BaO–B₂O₃–SiO₂, ZnO–B₂O₃–SiO₂ and PbO–B₂O₃–SiO₂ glasses on the sintering temperature and microwave dielectric properties of Ce₂(WO₄)₃ were investigated. The Ce₂(WO₄)₃ + 0.2 wt% ZBS sintered at 900 °C/4 h has ?_r = 13.7, Qxf = 20,200 GHz and τ_f = −25 ppm/°C.     

Synthesis and electrochemical properties of Co-doped Li3V2(PO4)3 cathode materials for lithium-ion batteries

Co-doped Li₃V_2−xCo_x(PO₄)₃/C (x = 0.00, 0.03, 0.05, 0.10, 0.13 or 0.15) compounds were prepared via a solid-state reaction. The Rietveld refinement results indicated that single-phase Li₃V_2−xCo_x(PO₄)₃/C (0 ≤ x ≤ 0.15) with a monoclinic structure was obtained. The X-ray photoelectron spectroscopy (XPS) analysis revealed that the cobalt is present in the +2 oxidation state in Li₃V_2−xCo_x(PO₄)₃. XPS studies also revealed that V⁴⁺ and V³⁺ ions were present in the Co²⁺-doped system. The initial specific capacity decreased as the Co-doping content increased, increasing monotonically with Co content for x > 0.10. Differential capacity curves of Li₃V_2−xCo_x(PO₄)₃/C compounds showed that the voltage peaks associated with the extraction of three Li⁺ ions shifted to higher voltages with an increase in Co content, and when the Co²⁺-doping content reached 0.15, the peak positions returned to those of the unsubstituted Li₃V₂(PO₄)₃ phase. For the Li₃V_1.85Co_0.15(PO₄)₃/C compound, the initial capacity was 163.3 mAh/g (109.4% of the initial capacity of the undoped Li₃V₂(PO₄)₃) and 73.4% capacity retention was observed after 50 cycles at a 0.1 C charge/discharge rate. The doping of Co²⁺into V sites should be favorable for the structural stability of Li₃V_2−xCo_x(PO₄)₃/C compounds and so moderate the volume changes (expansion/contraction) seen during the reversible Li⁺ extraction/insertion, thus resulting in the improvement of cell cycling ability.