Synthesis,structure and luminescent properties of Eu3+ doped Ca3LiMgV3O12 color-tunable phosphor

A new vanadate Ca₃LiMgV₃O₁₂ and its Eu³⁺-doped counterparts were synthesized. Rietveld confinement result of Ca₃LiMgV₃O₁₂ host indicates that it belongs to cubic space group Ia-3d with parameters of a =?12.4300?Å, V =?1920.49?ų, Z?=?8. Under UV excitation, pure Ca₃LiMgV₃O₁₂ exhibits a bluish-green broadband emission at 490?nm, while Eu³⁺ doped Ca₃LiMgV₃O₁₂ shows one bluish-green broad band with a series of red sharp peaks, which originate from the V⁵⁺-O^2- charge transfer and the Eu³⁺ intra-4f transitions, respectively. The occurrence of VO₄→Eu³⁺ energy transfer is confirmed by decay lifetime analysis and time-resolved emission spectra. It is found that emitting color varies from bluish-green to orange-red with increasing Eu³⁺ concentration. VO₄ bluish-green and Eu³⁺ red emission shows different thermal quenching response with increasing temperature, due to their different activation energy.     

Color-tunable up-conversion luminescence of Zn(AlxGa1-x)2O4:Yb3+,Tm3+,Er3+ powders

Color-tunable up-conversion powder phosphors Zn(Al_xGa_1-x)₂O₄: Yb³⁺,Tm³⁺,Er³⁺ were synthesized via high temperature solid-state reaction. Also, the morphological and structural characterization, up-conversion luminescent properties were all investigated in this paper. In brief, under the excitation of a 980?nm laser, all powders have same emission peaks containing blue emission at 477?nm (attributed to ¹G₄→³H₆ transition of Tm³⁺ ions), green emission at 526?nm and 549?nm (attributed to ²H_11/2→ ⁴I_15/2 and ⁴S_3/2→⁴I_15/2 transition of Er³⁺ ions respectively), red emission at about 659?nm and 694?nm (attributed to ⁴F_9/2→⁴I_15/2 transition of Er³⁺ ions and ³F₃→³H₆ transition of Tm³⁺ ions, respectively), which are not changed after the doping of Al³⁺ ions. However, the doping of Al³⁺ ions can enhance the up-conversion luminescent intensity and efficiency, while the emission color of as-prepared powder phosphors can be tunable by controlling the doping amount of Al³⁺ ions. Taking Zn(Al_0.5Ga_0.5)₂O₄:Yb,Tm,Er as the cut-off value, the emissions have clear blue-shift firstly and then show obvious red-shift with the increasing doping of Al³⁺ ions. Stated thus, pink emission in ZnAl₂O₄:Yb,Tm,Er, purplish pink emission in ZnGa₂O₄:Yb,Tm,Er and Zn(Al_0.9Ga_0.1)₂O₄:Yb,Tm,Er, purple emission in Zn(Al_0.1Ga_0.9)₂O₄:Yb,Tm,Er and Zn(Al_0.3Ga_0.7)₂O₄:Yb,Tm,Er, purplish blue emission in Zn(Al_0.7Ga_0.3)₂O₄:Yb,Tm,Er, blue emission in Zn(Al_0.5Ga_0.5)₂O₄:Yb,Tm,Er can be observed, which confirm the potential applications of as-prepared Zn(Al_xGa_1-x)₂O₄:Yb³⁺,Tm³⁺,Er³⁺ powder phosphors in luminous paint, infrared detection and so on.     

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.     

Color tunable Ba3Lu(PO4)3:Tb3+,Mn2+ phosphor via Tb3+→Mn2+ energy transfer for white LEDs

Series of UV excited Ba₃Lu(PO₄)₃:Tb³⁺,Mn²⁺ phosphors with tunable green to red emissions had been prepared using solid state reactions. Powder X-ray diffraction and Rietveld structure refinement were used to investigate the phase purity and crystal structure of the prepared samples. Under UV excitation, the Ba₃Lu(PO₄)₃:Tb³⁺,Mn²⁺ samples exhibited not only the typical Tb³⁺ emission peaks but also the broad emission band of Mn²⁺ ions due to the efficient Tb³⁺→Mn²⁺ energy transfer which had been verified by luminescence spectra and decay curves. Utilizing the Inokuti-Hirayama model, the Tb³⁺→Mn²⁺ energy transfer mechanism was determined to be the electronic dipole–quadrupole interaction. Moreover, the emission spectra of Ba₃Lu(PO₄)₃:0.80Tb³⁺,0.015Mn²⁺ sample at different temperatures manifested that our prepared phosphors possessed good thermal stability. The luminescence properties investigation results revealed the potential value of Ba₃Lu(PO₄)₃F:Tb³⁺,Mn²⁺ in application for UV excited phosphor converted white light emitting diodes.     

Synthesis and photoluminescence enhancement of Ca3Sr3(VO4)4:Eu3+ red phosphors by co-doping with La3+

In this study, a series of red-emitting Ca₃Sr₃(VO₄)₄:Eu³⁺ phosphors co-doped with La³⁺ was prepared using the combustion method. The microstructures, morphologies, and photoluminescence properties of the phosphors were investigated. All Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ samples synthesized at temperatures greater than 700 ℃ exhibited the same standard rhombohedral structure of Ca₃Sr₃(VO₄)₄. Furthermore, the Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ phosphor was effectively excited by near-ultraviolet light of 393 nm and blue light of 464 nm. The strong excitation peak at 464 nm corresponded to the ⁷F₀→⁵D₂ electron transition of Eu³⁺. The strong emission peak observed at 619 nm corresponded to the ⁵D₀→⁷F₂ electron transition of Eu³⁺. Co-doping with La³⁺ significantly improved the emission intensity of Ca₃Sr₃(VO₄)₄:Eu³⁺ red phosphors. The optimum luminescence of the phosphor was observed at Eu³⁺ and La³⁺ concentrations of 5% and 6%, respectively. Moreover, co-doping with La³⁺ also improved the fluorescence lifetime and thermal stability of the Ca₃Sr₃(VO₄)₄:Eu³⁺ phosphor. The CIE chromaticity coordinate of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺, 0.06La³⁺ was closer to the NTSC standard for red phosphors than those of other commercial phosphors; moreover, it had greater color purity than that of all the samples tested. The red emission intensity of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺, 0.06La³⁺ at 619 nm was ~1.53 times that of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺ and 2.63 times that of SrS:Eu²⁺. The introduction of charge compensators could further increase the emission intensity of Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ red phosphors. The phosphors synthesized herein are promising red-emitting phosphors for applications in white light-emitting diodes under irradiation by blue chips.     

Multicolour tunable luminescence of thermal-stable Ce3+/Tb3+/Eu3+-triactivated Ca3Gd(GaO)3(BO3)4 phosphors via Ce3+ → Tb3+ → Eu3+ energy transfer for near-UV WLEDs applications

A series of single-component blue, green and red phosphors have been fabricated based on the Ca₃Gd(GaO)₃(BO₃)₄ host through doping of the Ce³⁺/Tb³⁺/Eu³⁺ ions, and their crystal structure and photoluminescence properties have been discussed in detail. A terbium bridge model via Ce³⁺ → Tb³⁺ → Eu³⁺ energy transfer has been studied. The emission colours of the phosphors can be tuned from blue (0.1661, 0.0686) to green (0.3263, 0.4791) and eventually to red (0.5284, 0.4040) under a single 344 nm UV excitation as the result of the Ce³⁺ → Tb³⁺ → Eu³⁺ energy transfer. The energy transfer mechanisms of Ce³⁺ → Tb³⁺ and Tb³⁺ → Eu³⁺ were found to be dipole-dipole interactions. Importantly, Ca₃Gd(GaO)₃(BO₃)_4:Ce³⁺,Tb³⁺,Eu³⁺ phosphors had high internal quantum efficiency. Moreover, the study on the temperature-dependent emission spectra revealed that the Ca₃Gd(GaO)₃(BO₃)_4:Ce³⁺,Tb³⁺,Eu³⁺ phosphors possessed good thermal stability. The above results indicate that the phosphors can be applied into white light-emitting diodes as single-component multi-colour phosphors.     

Ca3(PO4)2 coating of spherical Ni(OH)2 cathode materials for Ni-MH batteries at elevated temperature

Calcium phosphate was used for surface modification of spherical nickel hydroxide to improve its high temperature performance at the first time due to its low cost. The Ca₃(PO₄)₂ and Co(OH)₂ coated nickel hydroxides were prepared by precipitation of Ca₃(PO₄)₂ on the surface of spherical nickel hydroxide, followed by precipitation of Co(OH)₂ on its surface. The optimum coating content of calcium was around 2% (atomic concentration) to obtain high discharge capacity both at 25 and 60 °C. It was shown that the discharge capacity of nickel hydroxide at higher temperatures was improved by coating of Ca₃(PO₄)₂ and cobalt hydroxide. The high temperature performances of the sealed AA-sized nickel-metal hydride (Ni-MH) batteries using Ca/Co coated nickel hydroxide as positive electrodes were carried out, showing much better than those using uncoated or only Co(OH)₂ coated nickel hydroxide electrodes. The charge acceptance of the battery using 2% Ca and 2% Co coated nickel hydroxide reached 81% at 60 °C, where the charge acceptances for uncoated and only Co(OH)₂ coated nickel hydroxide were only 42 and 48%, respectively. It has shown that the Ca/Co coating is an effective way to improve the high temperature performance of nickel hydroxide for nickel-metal hydride batteries. It is a promising cathode material of Ni-MH batteries for EV applications due to the cost.     

Photoluminescence properties of a double perovskite tungstate based red-emitting phosphor NaLaMgWO6:Sm3+

In this work, the conventional solid-state method was applied to synthesize a series of red-emitting NaLaMgWO₆:Sm³⁺ phosphors. The crystal structure, phase purity, morphology, particle size distribution as well as elemental composition of the as-prepared phosphors were investigated carefully with the aid of XRD, SEM, EDS, FT-IR analyses, indicating the high-purity and micron-sized NaLaMgWO₆:Sm³⁺ phosphors with monoclinic structure were prepared successfully. The spectroscopic properties of Sm³⁺ in NaLaMgWO₆ host including UV–vis diffuse reflection spectrum, photoluminescence excitation and emission spectra, decay curves, chromaticity coordinates and internal quantum efficiency were investigated in detail. Upon excitation with UV (290 nm) and n-UV (406 nm), NaLaMgWO₆:Sm³⁺ phosphor presented red emission corresponding to the ⁴G_5/2→⁶H_J (J = 5/2, 7/2, 9/2, and 11/2) transitions of Sm³⁺, in which the hypersensitive electronic dipole transition ⁴G_5/2→⁶H_9/2 (645 nm) was with the strongest emission intensity because Sm³⁺ ions were located at a lattice site with anti-inversion symmetry. The optimal concentration of Sm³⁺ was different for the given excitation wavelength such as 290 nm and 406 nm, which was interpreted by the extra effect of the energy transfer from W⁶⁺-O^2- group to Sm³⁺. The decay lifetime for ⁴G_5/2→⁶H_9/2 transition of Sm³⁺ was very short (< 1 ms) and decreased with the increasing Sm³⁺ concentration. The present investigation indicates that NaLaMgWO₆:Sm³⁺ phosphor could be a potential red component for application in w-LEDs.     

Luminescence characteristics and energy transfer of Eu2+/Tb3+ doped single phase multi-color phosphor

The investigation on single phase multi-color phosphors is highly meaningful for near-ultraviolet chip based white light emitting diodes. In this work, a series of Eu²⁺ and Tb³⁺ singly doped and Eu²⁺/Tb³⁺ codoped Sr₅(PO₄)₃Cl phosphors were synthesized via a high-temperature solid state reaction method. The luminescence spectra and decay curves of Eu²⁺ and Tb³⁺ singly doped samples were discussed, the optimal doping concentrations were determined. Thanks to the spectra overlap between Eu²⁺ and Tb³⁺, nonradiative energy transfer from Eu²⁺ to Tb³⁺ was investigated. It is found electric dipole-dipole interaction played the main role for the energy transfer in codoped samples, the highest energy transfer efficiency was calculated to be 60.98%. Tunable emissions are observed for codoped samples by adjusting doping concentration. The thermal quenching properties were discussed and the activation energy (ΔE) was estimated in the present work.     

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.     

Synthesis and characterization of nanocrystalline merwinite (Ca3Mg(SiO4)2) via sol-gel method

In this research, the synthesis of nanocrystalline merwinite (2SiO₂-3CaO-MgO) bioactive ceramic was carried out by the sol-gel method. After crushing, obtained sol-gel derived bioceramic powder pressed uniaxially to produce cylindrical-like pellets, followed by sintering at 1300 °C. Via immersion in simulated body fluid (SBF) for various time intervals, the formation of apatite was characterized. Scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), and Fourier transform infrared spectroscopy (FT-IR) studies were conducted both before and after immersion in SBF. The crystallization temperature of the merwinite was determined by thermal analysis. Attained results confirmed formation of apatite layer within the first day of soaking. Accordingly it can be concluded that merwinite is bioactive and might be used for preparation of implantable biomaterials.     

Solid solution between Al-ettringite and Fe-ettringite (Ca6[Al1 − xFex(OH)6]2(SO4)3·26H2O)

The solid solution between Al- and Fe-ettringite Ca₆[Al_1 − xFe_x(OH)₆]₂(SO₄)₃·26H₂O was investigated. Ettringite phases were synthesized at different Al/(Al + Fe)-ratios (= X_Al,total), so that X_Al increased from 0.0 to 1.0 in 0.1 unit steps. After 8 months of equilibration, the solid phases were analyzed by X-ray diffraction (XRD) and thermogravimetric analysis (TGA), while the aqueous solutions were analyzed by inductively coupled plasma optical emission spectroscopy (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). XRD analyses of the solid phases indicated the existence of a miscibility gap between X_Al,total = 0.3-0.6. Some of the XRD reflections showed two overlapping peaks at these molar ratios. The composition of the aqueous solutions, however, would have been in agreement with both, the existence of a miscibility gap or a continuous solid solution between Al- and Fe-ettringite, based on thermodynamic modeling, simulating the experimental conditions.     

The formation and thermal stability of spurrite,Ca5(SiO4)2CO3

The reversible equilibrium: 2Ca₂SiO₄ + CaO + CO₂ ? Ca₅(SiO₄)₂CO₃ has been studied using F^? and C?^? ions as mineralizers. A pressure-temperature curve is given for the reaction in the range of CO₂ pressures between 0.08 and 1 atmosphere. At these pressures, the decomposition temperatures of spurrite are 790 ± 5°C and 912 ± 5°C respectively. At a given CO₂ pressure the thermal stability of spurrite is greater than that of CaCO₃.     

Photoluminescence properties of Pr3+ ion-doped YInGe2O7 phosphor under an ultraviolet irradiation

Pr³⁺ ion-doped YinGe₂O₇ phosphors are synthesized by a vibrating milled solid state reaction. There is a red shift for the excitation peak for the charge transfer transition between In³⁺ and O^2- ion because the numbers of oxygen vacancies change the structure, which leads to a change in the crystal field. The results indicate that the emission spectra for the YinGe₂O₇:Pr samples under an excitation of 263 nm exhibit two dominant peaks at 486 and 604 nm, which are respectively assigned to the ³P₀→³H₄ and ¹D₂→³H₄ transitions. The chromaticity coordinate for (Y_1?xPr_x)InGe₂O₇ phosphors varies with the Pr³⁺ doping concentration, from white, to greenish, to blueish. This has a potential application as a white light emitting phosphor for ultraviolet light-emitting diodes.     

Ionic conduction and dielectric properties of yttrium doped LiZr2(PO4)3 obtained by a Pechini-type polymerizable complex route

We report on the ion transport properties of Li_1+xZr_2-xY_x(PO₄)₃ (0.05?≤ x?≤?0.2) NASICON type nanocrystalline compounds prepared through a Pechini-type polymerizable complex method. Structural properties were characterized by means of powder X-ray diffraction, Raman spectroscopy and electron microscopy with selected area electron diffraction. Impedance spectroscopy was utilised to investigate the lithium ion transport properties. Y³⁺ doped LiZr₂(PO₄)₃ compounds showed stabilized rhombohedral structure with enhanced total ionic conductivity at 30?°C from 2.87?×?10^?7 S?cm^?1 to 0.65?×?10^?5 S?cm^?1 for x=0.05 to 0.20 respectively. The activation energies of Li_1+xZr_2-xY_x(PO₄)₃ show a decreasing trend from 0.45?eV to 0.35?eV with increasing x from 0.05 to 0.20. The total conductivity of these compounds is thermally activated, with activation energies and pre-exponential factors following the Meyer-Neldel rule. The tanδ peak position shifts to the high-frequency side with increasing yttrium content. Scaling in AC conductivity spectra shows that the electrical relaxation mechanisms are independent of temperature.     

Enhanced mechanical property of Ca5(PO4)2SiO4 bioceramic by a biocompatible sintering aid of zinc oxide

In the present work, a biocompatible additive ZnO was used to enhance the sintering of calcium phosphate silicate (CPS)¹ bioceramic and improve its mechanical property. Sol-gel prepared CPS powders were mechanically mixed with various amount of ZnO and then sintered at high temperatures to prepare Zn-CPS bioceramics. The effects of ZnO content and sintering temperature on microstructure and bending strength of Zn-CPS bioceramics were investigated and the related mechanism was also discussed. The results showed that ZnO could significantly enhance the sintering of CPS and improve its bending strength accordingly. The Zn-CPS bioceramic with 1?wt% ZnO sintered at 1300?°C exhibited a highest bending strength of 80.8?MPa. The enhanced densification of Zn-CPS bioceramics might be attributed to the liquid phase appeared during the sintering process and the formation of Ca₂ZnSi₂O₇² (HT) nano-grains at grain boundaries. It is expected that Zn-CPS bioceramics could have both good mechanical property and excellent bioactivity.     

Effects of B-site ion (M) substitution on the ionic conductivity of (Li3xLa2/3−x)1+y/2(MyTi1−y)O3 (M=Al, Cr)

Effect on the ionic conductivity of B-site ion (M) substitution in (Li_3xLa_2/3−x)_1+y/2M_yTi_1−yO₃ (M=Al, Cr) has been investigated. It has been found that partial substitution of smaller Al³⁺ for Ti⁴⁺ is effective to enhance the ionic conductivity of Li_3xLa_2/3−xTiO₃. At 300 K, the maximum bulk conductivity of (1.58±0.01)×10⁻³ S cm⁻¹ is observed from the composition of (Li_0.39La_0.54)_1−y/2Al_yTi_1−yO₃ with y=0.02 (x=0.13), that is the highest yet reported for known perovskite solutions at room temperature. The conductivity enhancement is interpreted as being due to the substitution-induced bond-strength change rather than due to bottleneck size change for Li migration, TiO₆-octahedron tilting or A-site cation ordering.     

浸渍Ca3(PO4)2溶液对SiC窑具材料抗氧化性的影响

SiC窑具材料浸渍Ca3(PO4)2饱和溶液,能填充气孔,降低气孔率,阻碍O2的扩散,能增加SiC窑具抗氧化性和延长使用寿命.浸渍次数越多,氧化速度越小,其中浸渍4次最佳,浸渍1-4次氧化速度常数的比值=K1K2K3K4=10.30×10-78.94×10-74.17×10-72.65×10-7=3.893.371.571.     

Alkali metal ion substitution induced luminescence enhancement of NaLaMgWO6:Eu3+ red phosphor for white light-emitting diodes

Alkali metal ion substitution is an effective strategy to improve the luminescence properties of phosphors. In this work, a series of red-emitting phosphors Na_1-xLi_x/2K_x/2La_0.6Eu_0.4MgWO₆ were prepared by a traditional high-temperature solid-state reaction. Their phase structure, microstructure, luminescence properties and potential application in phosphor-converted white light-emitting diodes (pc-WLEDs) were investigated in detail. X-ray diffraction (XRD) result revealed the formation of a solid solution when x?≤?0.3, which kept monoclinic structure of NaLaMgWO₆. Photoluminescence investigation indicated that the partial substitution of Li⁺/K⁺ ions for Na⁺ ions improved largely the red emission of Eu³⁺. Based on the optimized Na_0.7Li_0.15K_0.15La_0.6Eu_0.4MgWO₆ sample with relatively good thermal stability, a WLED device was fabricated by combining a near-ultraviolet (NUV) chip (~400?nm) with the phosphor mixture of commercial green/blue phosphors and the optimized red phosphor. The results indicated that the optimized red phosphor in this work could be a potential candidate for WLEDs pumped by NUV chips.