Luminescence investigation of red phosphors Ca0.54Sr0.34−1.5xEu0.08Smx(MoO4)y (WO4)1−y for UV-white LED device

Ca_0.54Sr_0.34−1.5xEu_0.08Sm_x(MoO₄)_y (WO₄)_1−y red phosphors were prepared by solid-state reaction using Na⁺ as a charge compensator for light-emitting diodes (LED). The effects of Na⁺ concentration, synthesis temperature, reaction time and Eu³⁺ concentration were studied for the properties of luminescence and crystal structure of red phosphors. The results show that the optimum reaction condition is 6%, 900 °C, 2 h and 8%. The photoluminescence spectra show that red phosphors are effectively excited at 616 nm by 292, 395 and 465 nm. The wavelengths of 465 nm nicely match the widely applied emission wavelengths of blue LED chips.     

Combustion synthesis and luminescence properties of NaY1−xEux(WO4)2 phosphors

The red phosphors NaY_1−xEu_x(WO₄)₂ with different concentrations of Eu³⁺ were synthesized via the combustion synthesis method. As a comparison, NaEu(WO₄)₂ was prepared by the solid-state reaction method. The phase composition and optical properties of as-synthesized samples were studied by X-ray powder diffraction and photoluminescence spectra. The results show that the red light emission intensity of the combustion synthesized samples under 394 nm excitation increases with increase in Eu³⁺ concentrations and calcination temperatures. Without Y ions doping, the emission spectra intensity of the NaEu(WO₄)₂ phosphor prepared by the combustion method fired at 900 °C is higher than that prepared by the solid-state reaction at 1100 °C. NaEu(WO₄)₂ phosphor synthesized by the combustion method at 1100 °C exhibits the strongest red emission under 394 nm excitation and appropriate CIE chromaticity coordinates (x=0.64, y=0.33) close to the NTSC standard value. Thus, its excellent luminescence properties make it a promising phosphor for near UV InGaN chip-based red-emitting LED application.     

Luminescent properties of HTP AgGd1−xW2O8:Eux and AgGd1−x(W1−yMoy)2O8:Eux phosphor for white LED

Intense red phosphors, AgGd_1−xEu_x(W_1−yMo_y)₂O₈ (x=0.0-1.0, y=0.0-1.0), have been synthesized through traditional solid-state reaction and characterized by X-ray diffraction (XRD) and photoluminescence (PL). XRD results reveal that AgGd_1−xEu_xW₂O₈ synthesized at 1000 °C has a tetragonal crystal structure, which is named as high temperature phase (HTP) AgGdW₂O₈. All phosphors compositions with Eu³⁺ show red and green emission on excitation either in the charge-transfer or Eu³⁺ levels. Analysis of the emission spectra with different Eu³⁺ concentrations reveal that the optimum dopant concentration for Eu³⁺ is x=0.6 in the HTP AgGd_1−xEu_xW₂O₈ (x=0.0-1.0). Studies on the AgGd_0.4Eu_0.6(W_1−yMo_y)₂O₈ (y=0.0-1.0) and AgGd_1−xEu_x(W_0.7Mo_0.3)₂O₈ (x=0.0-1.0) show that the emission intensity is maximum for compositions with y=0.3 and x=0.5, respectively, and a decrease in emission intensity is observed for higher y or x values. The Mo⁶⁺ and Eu³⁺ co-doped AgGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped AgGd(WO₄)₂ in UV region. The intense emission of the tungstate/molybdate phosphors under 394 and 465 nm excitations, respectively, suggests that these materials are promising candidates as red-emitting phosphors for near-UV/blue GaN-based white LED for white light generation.     

Effect of sintering atmosphere on the electrical and optical properties of (ZnO)1−x(MnO2)x NTCR ceramics

Nominal composition of (ZnO)_1−x(MnO₂)_x (0.005≤x≤0.2) ceramics have been prepared by the standard solid-state reaction method in three different sintering atmospheres: Ar, air, and reductive atmosphere. The effect of sintering atmosphere on the electron spin resonance (ESR), negative temperature coefficient of resistivity (NTCR), and photoluminescence (PL) properties of (ZnO)_1−x(MnO₂)_x ceramics has been investigated in detail. The results demonstrate that the sintering atmosphere has significant effects on the ESR signals of (ZnO)_1−x(MnO₂)_x; the NTCR of the samples sintered in air is larger than those sintering in Ar and reductive atmosphere; the deep-level PL related to oxygen vacancy increases when sintered in the reductive atmosphere.     

Blue luminescence in Tm-doped KGd(WO4)2 single crystals

Up-conversion blue emissions of trivalent thulium ions in monoclinic KGd(WO₄)₂ single crystals at 454 and 479 nm are reported for a single pump laser source at 688 nm. We grew thulium-doped KGd(WO₄)₂ single crystals at several concentrations from 0.1% to 10%. We recorded a polarized optical absorption spectrum for the ³F₂+³F₃ energy levels of thulium at room temperature and low temperature (6 K). From the low temperature emission spectra we determined the splitting of the ³H₆ ground state. The blue emissions are characterized as a function of the dopant concentration and temperature from 10 K to room temperature. To our knowledge, this is the first time that sequential two-photon excitation process (STEP) generated blue emissions in thulium-doped single crystals with a single excitation wavelength.     

Ionic liquid-assisted hydrothermal synthesis of dendrite-like NaY(MoO4)2:Tb phosphor

Micro-sized NaY(MoO₄)₂:Tb³⁺ phosphors with dendritic morphology was synthesized by a ionic liquid-assisted hydrothermal process. X-ray diffraction (XRD) indicated that the as-prepared product is pure tetragonal phase of NaY(MoO₄)₂. Field emission scanning electron microscopy (FE-SEM) images showed that the as-prepared NaY(MoO₄)₂:Tb³⁺ phosphors have dendritic morphology. The photoluminescent (PL) spectra displayed that the as-prepared NaY(MoO₄)₂:Tb³⁺ phosphors show a stronger green emission with main emission wavelength 545 nm corresponding to the ⁵D₄→⁷F₅ transition of Tb³⁺ ion, and the optimal Tb³⁺ doping concentration for obtaining maximum emission intensity was confirmed to be 10 mol%. Based on Van Uitert's and Dexter's models the electric dipole–dipole (D–D) interaction was confirmed to be responsible for the concentration quenching of ⁵D₄ fluorescence of Tb³⁺ in the NaY(MoO₄)₂:Tb³⁺ phosphors. The intrinsic radiative transition lifetime of ⁵D₄ level is found to be 0.703 ms.     

Spectral characterization and energy levels of Cr:Sc2(MoO4)3 crystal

This paper reports the spectral properties and energy levels of Cr³⁺:Sc₂(MoO₄)₃ crystal. The crystal field strength Dq, Racah parameter B and C were calculated to be 1408 cm⁻¹, 608 cm⁻¹ and 3054 cm⁻¹, respectively. The absorption cross sections σ_α of ⁴A₂→⁴T₁ and ⁴A₂→⁴T₂ transitions were 3.74×10⁻¹⁹ cm² at 499 nm and 3.21×10⁻¹⁹ cm² at 710 nm, respectively. The emission cross section σ_e was 375×10⁻²⁰ cm² at 880 nm. Cr³⁺:Sc₂(MoO₄)₃ crystal has a broad emission band with a broad FWHM of 176 nm (2179 cm⁻¹). Therefore, Cr³⁺:Sc₂(MoO₄)₃ crystal may be regarded as a potential tunable laser gain medium.     

Polarized fluorescence spectra analysis of Yb:KGd(WO4)2

The average fluorescence wavelength of the laser crystal is the most important factor in the radiation-balanced laser (RBL). Polarized fluorescence spectra measurements of the anisotropic laser material ytterbium-doped potassium gadolinium tungstate, Yb³⁺:KGd(WO₄)₂, are carried out along principal refractive index directions m, p, g in three configurations in order to achieve the best design for RBL. The average fluorescence wavelength of g polarization is the shortest, so g should be in the face of fluorescence emission; m polarization should be normal to that face to avoid its strong absorption to fluorescence photons. Fluorescence re-absorption causes the average fluorescence wavelength of the directly measured spectra red-shifted at least 9 nm. Methods for depressing radiation trapping are suggested accordingly, which are high power pumping, low doping concentration, small dimensions and fusing with undoped KGd(WO₄)₂.     

Luminescent properties of nanoparticles YPXV1−XO4:Dy phosphors

Phosphors of nanoparticles YP_XV_1−XO₄:Dy³⁺ (0?X?1) have been prepared by a citrate sol-gel method. X-ray diffraction, transmission electron microscope (TEM), scanning electron microscope (SEM) and photoluminescence excitation and emission spectra were utilized to characterize the phosphors. The results of XRD showed that a solid solution formed in YP_XV_1−XO₄:Dy³⁺ phosphor series from X=0 to X=1 with zircon structure. TEM and SEM studies revealed that the obtained YP_XV_1−XO₄:Dy³⁺ nanocrystals appeared to be spherical with some agglomeration and their sizes ranged from 30 to 80 nm. Upon short ultraviolet excitation, the optical properties of all the powder presented that the characteristic transitions of Dy³⁺ due to ⁴F_9/2-⁶H_15/2 (blue) and ⁴F_9/2-⁶H_13/2 (yellow) were detected. Besides this, in the system of YP_XV_1−XO₄:Dy³⁺, the yellow-to-blue intensity ratio (Y/B) depended on the value of P/V greatly, with the increasing of X value and the decreased Y/B value. The phosphor found to yield white light when the value of X in the range of X=0.775-0.85, the optimum concentration for Dy³⁺ is 1 mol% of Y in the host, and the emission intensity increased with the annealing temperature.     

花状NaY(MoO4)2的合成和(MoO4)2:Eu3+的光学性质

用微波辅助水热-煅烧法成功合成了花状NaY(MoO₄)₂颗粒,用XRD、XPS、FESEM进行了表征,提出了花状NaY(MoO₄)₂颗粒可能的形成机理. 采用相同的方法合成了NaY(MoO₄)₂:Eu³⁺荧光体,该荧光材料在612 nm处有一个强的发射峰,可用作白色发光二极管的红色磷光剂. 此外,微波辅助水热-煅烧法可能发展成为制备其他花状稀土钼酸盐的有效途径.     

Composition-dependent structural and electrical properties of PbSe1−xTex thin films

Polycrystalline PbSe_1−xTe_x ingots were prepared by solid-state microwave synthesis. Thin films of PbSe_1−xTe_x were then deposited onto clean glass substrates using vacuum evaporation technique. Their nanostructure morphologies and stoichiometric ratio were examined using scanning electron microscopy (SEM) and energy dispersive X-ray spectra (EDX). X-ray diffraction (XRD) patterns indicated that the lattice constants of PbSe_1−xTe_x powders and thin films increased with the increasing amount of Te. From the electrical property measurements, the thin films were characterized by n-type behavior.     

Relationship between structural characteristics and photoluminescent properties of (La1−xEux)2M2O7 (M=Zr, Hf, Sn) pyrochlores

Eu-doped pyrochlores, La₂M₂O₇ (M=Zr, Hf, Sn), were synthesized by solid-state reaction at a temperature range of 1473 and 1673 K, and their structures and optical properties were characterized by X-ray Rietveld analysis, field emission scanning electron microscope (FE-SEM), and photoluminescent spectroscopy. The Rietveld analysis indicated that the distortion of the (EuO₈)ⁿ⁻ scalenohedra increased with decreasing ionic radii of the M⁴⁺ ion, and the crystallinity increased with the sintering temperature. The splitting width of ⁵D₀-⁷F₁ transition of Eu³⁺ ions increased with the distortion of the (EuO₈)ⁿ⁻ scalenohedra. The luminescent intensity ratio of magnetic dipole transitions to electronic dipole transitions decreased with the crystallinity, and the chromaticity changed from deep-red to orange-red. The relationship between the chromaticity of phosphors and the crystallinity was clarified, and the control of crystallinity is an important factor that provides phosphors with required chromaticity.     

Conversion of infrared radiation into visible emission in NaY(WO4)2:Yb, Ho crystal

The spectroscopic characteristics and fluorescence dynamics for Yb³⁺/Ho³⁺:NaY(WO₄)₂ crystal were investigated. The parameters of oscillator strengths, the spontaneous transition probabilities, the fluorescence branching ratios, the radiative lifetimes and the stimulated emission cross sections have been calculated based on Judd-Ofelt theory and Füchtbauer-Ladenburg method. The energy transfer efficiency from Yb³⁺ to Ho³⁺ was 65.85%. The green emission (530-570 nm) corresponding to (⁵F₄, ⁵S₂)→⁵I₈ transition, red emission (640-670 nm) due to ⁵F₅→⁵I₈ transition and NIR emission (740-770 nm) attributed to (⁵F₄, ⁵S₂)→⁵I₇ transition were observed on 974 nm excitation at room temperature. Under low pump power, the intensity of green light emission is weaker than that of the red light, while under high pump power, the case is on the contrary. The upconversion is based on the two-photon process either the energy transfer from Yb³⁺ ions or by the excited state absorption. The proposed mechanisms of upconversion emissions were provided.     

Preparation and magnetic properties of the conductive Co(1−x)NixFe2O4/polyaniline microsphere composites

Core-shell Co_(1−x)Ni_xFe₂O₄/polyaniline nanoparticles, where the core was Co_(1−x)Ni_xFe₂O₄ and the shell was polyaniline, were prepared by the combination of sol-gel process and in-situ polymerization methods. Nanoparticles were investigated by Fourier transform spectrometer, X-ray diffraction diffractometer, Scanning electron microscope, Differential thermal analysis and Superconductor quantum interference device. The results showed that the saturation magnetization of pure Co_(1−x)Ni_xFe₂O₄ nanoparticles were 57.57 emu/g, but Co_(1−x)Ni_xFe₂O₄/polyaniline composites were 37.36 emu/g. It was attributed to the lower content (15 wt%), smaller size and their uneven distribution of Co_(1−x)Ni_xFe₂O₄ nanoparticles in the final microsphere composites. Both Co_(1−x)Ni_xFe₂O₄ and PANI/Co_(1−x)Ni_xFe₂O₄ showed superparamagnetism.     

Structure and magnetostriction of Tb0.2Pr0.8(Fe0.4Co0.6)1.93−xCx intermetallic compounds

The structure and magnetostriction of Tb_0.2Pr_0.8(Fe_0.4Co_0.6)_1.93−xC_x intermetallic compounds were studied by X-ray diffraction and magnetic measurements. Almost a single cubic Laves phase forms in the alloys for x ≤0.20, and a small amount of C can inhibit the formation of the 1:3 phase. The lattice parameter increases when 0≤x≤0.15, while the T_c and the spontaneous magnetization decreases with increasing x. The lattice parameter decreases slowly when 0.15≤x≤0.30, while the T_c decreases evidently with increasing x. The magnetostriction λ_a (=λ_∥-λ_⊥) is improved at low magnetic fields at room temperature for the compounds with 0.05≤x≤0.10, indicating that these C-containing compounds are promising magnetostrictive materials.     

Tm3+离子掺杂的钨酸钇钠晶体中浓度猝灭效应的研究

测量了Tm³⁺离子不同浓度(0.5at.%, 3 at.%, 5 at.%)掺杂的NaY(WO₄)₂晶体在800nm激光二极管激发下的上转换发射光谱.结合吸收谱、荧光谱和由Judd-Ofelt理论计算的光谱参数，详细分析了Tm³⁺:NaY(WO₄)₂晶体中上转换能量传递机理和离子浓度对上转换发射的影响.讨论了四种影响上转换发光效率的离子间相互作用机理：³H₅+¹G₄→³H₆+¹D₂，³H₅+³H₅→³H₆+³F₃，¹G₄+³H₆→³F₄+³F₃，¹G₄+³H₆→³F₃+³F₄，并根据Miyakawa-Dexter理论定量计算了各过程的发生概率.论证了交叉弛豫和共协上转换等浓度猝灭效应是影响Tm³⁺离子蓝色上转换荧光发射效率的主要因素. 关键词： 3+离子')" href="#">Tm³⁺离子 4)₂晶体')" href="#">NaY(WO₄)₂晶体 上转换 浓度猝灭     

Photoluminescence and energy transfer of Tm doped LiIn (WO4)2 blue phosphors

Room temperature steady and time resolved emission spectra of LiIn_1−xTm_x(WO4)2 (where thulium concentration is 0, 0.5, 1, 5 and 10 at%) blue phosphors, under UV excitation energy have been investigated. The concentration quenching effect on the blue emission, due to the (WO₄)⁻² groups and ¹G₄→³H₆ emission transition of Tm³⁺ were studied. Two energy transfer mechanisms are shown. The first takes place between excited (WO₄)⁻² groups and the ¹G₄ energy level of Tm³⁺, and is mainly analyzed by phonon-assisted energy transfer. The second mechanism is due to an energy transfer from the excited Tm³⁺ ions to the surrounding ground state Tm³⁺ ions. The non-exponential decay curves of the ¹G₄ level observed for higher concentrations are analyzed by the Inokuti–Hirayama model. We think that the quenching effect between Tm³⁺ ions is mainly linked to the dipole–dipole interactions.     

Field and temperature induced colossal strain in Gd5(SixGe1−x)4

Gd₅(Si_xGe_1−x)₄, known for its giant magnetocaloric effect, also exhibits a colossal strain of the order of 10,000 ppm for a single crystal near its coupled first-order magnetic-structural phase transition, which occurs near room temperature for the compositions 0.41≤x≤0.575. Such colossal strain can be utilised for both magnetic sensor and actuator applications. In this study, various measurements have been carried out on strain as a function of magnetic field strength and as a function of temperature on single crystal Gd₅Si₂Ge₂ (x=0.5), and polycrystalline Gd₅Si_1.95Ge_2.05 (x=0.487) and Gd₅Si_2.09Ge_1.91 (x=0.52). Additionally a giant magnetostriction/thermally induced strain of the order of 1800 ppm in polycrystalline Gd₅Si_2.09Ge_1.91 was observed at its first order phase transition on varying temperature using a Peltier cell without the use of bulky equipment such as cryostat or superconducting magnet.     

Luminescent properties of Tb activated GdTaO4 with M and M′ type structure under UV-VUV excitation

The photoluminescence of Tb³⁺ doped M and M′ type gadolinium orthotantalate Gd_1−xTb_xTaO₄ (0.01≤x≤0.20) was investigated under ultraviolet and vacuum ultraviolet excitation. For the samples of Gd_1−xTb_xTaO₄ with different crystallographic structures, emission spectra were the same in addition to intensity; the optimal concentration for Tb³⁺ was about 10 mol % in M type Gd_1−xTb_xTaO₄ but 5 mol % in M′ type Gd_1−xTb_xTaO₄. These differences could be corresponding with the difference in structures. In addition, compared to commercial Zn₂SiO₄: Mn²⁺, the integrated intensity of M and M′ type GdTaO₄: Tb³⁺ could reach 67% and 85%, respectively, of that at 147 nm excitation, which indicates that GdTaO₄: Tb³⁺ would be a promising vacuum ultraviolet phosphor for application in PDP and Hg-free lamp.     

Eu-activated Ba2Mg(BO3)2 yellow-emitting phosphors for near ultraviolet-based light-emitting diodes

A series of Eu²⁺-activated Ba₂Mg(BO₃)₂ yellow phosphors were prepared by a high temperature solid-state reaction. The phosphor emits intense yellow light under near ultraviolet excitation. Large Stokes shift can be attributed to the asymmetric nature of the Eu site and the lack of rigidity in the host. The concentration self-quenching mechanism of Ba₂Mg(BO₃)₂:Eu²⁺ is d-d interaction and the critical transfer distance is calculated to be about 12.29 Å. Prototype light-emitting diodes were fabricated by coating the Ba₂Mg(BO₃)₂:0.07Eu²⁺ phosphor onto ∼370 nm-emitting InGaN chips. The LEDs exhibit intense yellow-emitting under a forward bias of 20 mA. The results indicate that Eu²⁺-activated Ba₂Mg(BO₃)₂ is a candidate as a yellow component for fabrication of near-UV white light-emitting diodes.