Characterization and photoluminescence properties of some MLn2(1−x)O4:2xEu or 2xTb systems (M=Ba or Sr, Ln=Gd or La)

BaGd₂O₄, BaLa₂O₄ and SrLa₂O₄ powders doped with different concentrations of Eu³⁺ or Tb³⁺ are prepared by combustion synthesis method and the samples were further heated to 500, 700 and 900 °C to improve the crystallinity of the materials. The structure and morphology of materials have been examined by X-ray diffraction and scanning electron microscopy. It is remarkable that all the samples of BaGd₂O₄, BaLa₂O₄ and SrLa₂O₄ have similar morphology. The SEM images show homogeneous aggregates of varying shapes and sizes, which are composed of a large number of small elliptical shaped crystallites with an average diameter of about 0.5-3.0 μm. Photoluminescence for all materials increases with increase of temperature and shows a maximum for the samples heated to 900 °C with 4 mole% doping of Eu³⁺ or Tb³⁺ ions. The luminescence is almost same for all powders when doped with same concentration of Eu³⁺.     

Dyand Mn emission in KMgSO4Cl phosphor

In the present paper, KMgSO₄Cl:Ce³⁺, KMgSO₄Cl:Ce³⁺,Dy³⁺, and KMgSO₄Cl:Ce³⁺,Mn²⁺, new halosulphate phosphors were synthesized by wet chemical method. X-ray powder diffraction (XRD) and photoluminescence (PL) characterization of phosphors have been reported in this paper. The effects of Dy³⁺ co-doping on the PL characteristics of KMgSO₄Cl:Ce phosphor were studied. Energy transfer from Ce³⁺→Dy³⁺and Ce³⁺→Mn²⁺ results in increase in PL peak intensity suggesting that Ce³⁺ plays an important role in PL emission in the present matrix. The PL emission spectra have two peaks (482 and 571 nm) and a single peak (564 nm), which could be attributed to the Ce³⁺→Dy³⁺and Ce³⁺→Mn²⁺ emissions, respectively.     

Correlated ESR, PL and TL studies on Sr5(PO4)3Cl:Eu thermoluminescence dosimetry phosphor

Electron spin resonance (ESR), thermoluminescence and photoluminescence studies in Eu²⁺ activated Sr₅(PO₄)₃Cl phosphor are reported in this paper. The Sr₅(PO₄)₃Cl:Eu²⁺ phosphor is twice as sensitive as the conventional CaSO₄:Dy phosphor used in thermoluminescence dosimetry of ionizing radiations. It has a linear response, simple glow curve, emission peaking at 456 nm. The defect centers formed in the Sr₅(PO₄)₃Cl:Eu²⁺phosphor are studied by using the technique of ESR. A dominant TL glow peak at 430 K with a smaller shoulder at 410 K is observed in the phosphor. ESR studies indicate the presence at three centers at room temperature. Step annealing measurements show a connection between one of the centers and the dominant glow peak at 430 K. The 430 K TL peak is well correlated with center I, which is tentatively identified as (PO₄)²⁻ radical.     

Up and down conversion fluorescence studies on combustion synthesized Yb/Yb: MO-Al2O3 (M=Ca, Sr and Ba) phosphors

The ytterbium ions doped MO-Al₂O₃ (M=Ca, Sr and Ba) phosphors have been synthesized through combustion technique and their up and down conversion fluorescence properties have been studied and compared. The samples were calcinated at different temperatures and their FTIR and XRD spectra have shown a close relationship. With 976 nm excitation all these phosphors show cooperative upconversion emission at 488 nm from the pairs of two Yb³⁺ ions along with an unexpected broad upconversion band in the blue green region and has been assigned to arise from the defect centers. Contrary to this upconversion emission, calcium aluminate phosphor exhibits bright and very broad down-conversion fluorescence (FWHM≈160 nm) upon UV (266 nm) excitation due to Yb²⁺ ions. The inter-conversion between the 3+ and 2+ valence states of Yb ion has been observed on calcinations of samples in open atmosphere and has been correlated to the emission properties. The Yb²⁺ ions containing calcium aluminate phosphor has been found suitable for producing broad band light in the visible region (white light). Lifetime of the emitting states of Yb³⁺ and Yb²⁺ ions have also been measured and discussed.     

Magnetoresistance in Parent Pnictide AFe2As2(A=Sr, Ba)

Magnetoresistances of SrFe₂As₂ and BaFe₂As₂ in the magnetic ordered state are studied. Positive magnetoresistance is observed in the magnetic fields H applied in the azimuthes of θta = 0°and 30° with respect to the c-axis. The magnetoresistance can reach 20% for SrFe₂As₂ and 12% for BaFe₂As₂ at H = 9 T with θ= 0°(H || c). Above the magnetic transition temperature, the magnetoresistance becomes negligible. The data in the magnetic ordered state could be described by a modified two-band galvanomagnetic model including the enhancement effect of the applied magnetic field on the spin-density-wave gap. The field enhanced spin-density-wave gaps for different types of carriers are different. Temperature dependencies of the fitting parameters are discussed.     

Enhanced luminescence of Tb by efficient energy transfer from Ce in Sr2B5O9Cl host

Ce³⁺ and Tb³⁺ co-doped Sr₂B₅O₉Cl phosphors with intense green emission were prepared by the conventional high-temperature solid-state reaction technique. A broad band centered at about 315 nm was found in phosphor Sr₂B₅O₉Cl: Ce³⁺, Tb³⁺ excitation spectrum, which was attributed to the 4f-5d transition of Ce³⁺. The typical sharp line emissions ranging from 450 to 650 nm were originated from the ⁵D₄ → ⁷F_J (J = 6, 5, 4, 3) transitions of Tb³⁺ ions. The photoluminescence (PL) intensity of green emission from Tb³⁺ was enhanced remarkably by co-doping Ce³⁺ in the Tb³⁺ solely doped Sr₂B₅O₉Cl phosphor because of the dipole-dipole mechanism resonant energy transfer from Ce³⁺ to Tb³⁺ ions. The energy transfer process was investigated in detail. In light of the energy transfer principles, the optimal composition of phosphor with the maximum green light output was established to be Sr_1.64Ce_0.08Tb_0.1Li_0.18B₅O₉Cl by the appropriate adjustment of dopant concentrations. The PL intensity of Tb³⁺ in the phosphor was enhanced about 40 times than that of the Tb³⁺ single doped phosphor under the excitation of their optimal excitation wavelengths.     

Synthesis and effect of Ce co-doping on photoluminescence characteristics of KZnSO4Cl: M (M=Dy or Mn) new phosphors

In the present paper KZnSO₄Cl:Ce³⁺, KZnSO₄Cl:Ce³⁺, Dy³⁺ and KZnSO₄Cl:Ce³⁺, Mn²⁺ new halosulfate phosphors were synthesized by wet chemical method. XRD and photoluminescence characterization of phosphors has been reported in this paper.     

LED用荧光粉Sr(S_(1-x)Se_x)∶Eu~(2 )的合成和光谱性质研究

采用高温固相法合成了Sr(S1-xSex)系列硫属化合物掺Eu2 荧光粉。XRD表明荧光粉的组成为单相,而且体系Sr(S1-xSex)∶0.005Eu2 中晶胞参数随着组成的变化呈现良好的线性关系,遵守韦加定律。漫反射光谱与激发光谱吻合,说明荧光粉吸收的能量能够有效地激发发光中心而发光,激发光谱中较低能量区域覆盖了400~500nm的光谱范围,与蓝光LED芯片的发射光匹配。发射光谱呈现的是Eu2 离子的5d→4f特征跃迁发射带,当x由0增加到1.0的过程中,发射峰值波长由617nm逐渐蓝移到571nm。不同基质中掺杂的Eu2 离子的荧光寿命均为微秒数量级,与Eu2 离子的4f65d1→4f7跃迁相符合。将荧光粉封装在发蓝色光(λ=460nm)的GaN芯片上制作了LED器件,测量了器件的发光强度、色纯度和色坐标等参数。Sr(S1-xSex)∶Eu2 系列硫属化合物掺铕荧光粉能够有效地被GaN芯片发出的蓝色光激发,发出从橙色到红色的可见光,是一类较好的LED用荧光粉。     

Excitation mechanisms and effects of dopant concentration in Gd2O2S:Tb phosphor

Gadolinium oxysulfide powders doped with different Tb³⁺ concentrations were prepared from sulfur vaporization on rare earths’ basic carbonate precursors. Single-phase Gd₂O₂S samples were obtained, with Tb³⁺ doping up to 9 at%. The study of the excitation mechanisms revealed that the Tb³⁺ emission might occur after the direct Tb³⁺ excitation either by energy transfer from Gd³⁺ or from the phosphor host. The characteristic terbium emission lines were observed, resulting from the radiative decay from ⁵D₃ or ⁵D₄ to ⁷F_j levels. The cross-relaxation phenomenon was observed and its effects on the materials emission color were discussed based on the CIE diagram. By using time-resolved spectroscopy, ⁵D₃→⁷F_J and ⁵D₄→⁷F_J transitions were separated.     

Luminescent properties of a novel red-emitting phosphor: Eu-activated Ca3Sr3(VO4)4

A new luminescent material, Eu³⁺ activated Ca₃Sr₃(VO₄)₄, was investigated. This compound shows a strong red emission centered at 618 nm under near-UV light with two distinct absorption bands; charge transfer state of VO₄³⁻ and f-f transitions of europium ions. As the europium concentration is increased, an additional red-emitting phosphor, EuVO₄, which is known to be a prominent luminescent material in the near-UV region can be traced. The UV excited luminescent properties of this material may find application in the production of red phosphors for white light-emitting diodes.     

Orange emission enhancement by energy transfer in Sr3Al2O5Cl2:Ce, Eu phosphor for solid-state lighting

Orange-emissive Ce³⁺/Eu²⁺ co-doped Sr₃Al₂O₅Cl₂ phosphors were synthesized by a solid-state reaction. The large overlap between the emission spectrum of blue Sr₃Al₂O₅Cl₂:Ce³⁺ and the excitation spectrum of orange Sr₃Al₂O₅Cl₂:Eu²⁺, and the shortening trend in lifetime of Ce³⁺ donors with increasing Eu²⁺ concentration in Sr₃Al₂O₅Cl₂:Ce³⁺, Eu²⁺ provide the strong evidence of energy transfer from Ce³⁺ to Eu²⁺ ions. It supports that the orange emission intensity of the optimal co-doped phosphor is 1.5 times stronger than that of single Eu²⁺-doped one. The Sr₃Al₂O₅Cl₂:Ce³⁺, Eu²⁺ phosphor is a promising orange-emitting phosphor for warm-white-light-emitting diode because of its effective excitation in the near ultraviolet range.     

Electronic structures and ferroelectric properties of ABi2Ta2O9 (A=Ca, Sr, and Ba)

The electronic structures of ABi₂Ta₂O₉ (A=Ca, Sr, and Ba) were calculated by using first-principles under optimized structure. As the size of A-site cation decreases from that of Ba²⁺ to Ca²⁺, the band-gap between O 2p and Ta 5d increases from 2.0 to 2.9 eV, which responses to the stronger orbital hybridizations between Ta 5d and O 2p orbits favoring improvement of the ferroelectric property, decrease in leakage current, and increase in both spontaneous polarization and Curie temperature by the structural distortion. In contrast to CaBi₂Ta₂O₉ and SrBi₂Ta₂O₉, the hybridization between Ba 5p orbits and O 2p orbits in BaBi₂Ta₂O₉ has better structural stability.     

LnZr(BO3)2:Eu3+(Ln=Ba,Sr)的真空紫外光谱特性的研究

采用高温固相法合成了Ba(1-x)SrxZr(BO3)2:Eu3 系列样品,样品Ba(1-x)SrxZr(BO3)2:Eu3 激发谱在130～170nm和230 nm区域有两个很强的吸收带,位于130～170nm的吸收带主要是硼酸盐基质的吸收;位于230nm附近的吸收主要是Eu3 电荷转移态的吸收.当在样品中以Al部分取代Zr时,电荷转移态的吸收明显增强,并且Ba(1-x)SrxZr(BO3)2:Eu3 发射强度也会明显增强;随着x的增大,硼酸盐基质的吸收强度减弱,基质吸收带的主峰值向低能方向移动了大约30 nm.样品Ba(1-x)SrxZr(BO3)2:Eu3 在147nm激发下,发射出主峰值位于616nm的强红光,对应Eu3 电偶极(5D0→7F2)跃迁发射.     

Synthesis, luminescence and crystallographic structure of Eu-doped garnet-type yafsoanite Ca3Te2(ZnO4)3

A red-emitting phosphor of Eu³⁺-doped calcium–tellurium–zinc oxide, Ca₃Te₂(ZnO₄)₃, with a garnet-type structure was synthesized by high temperature solid-state reactions. This phosphor exhibited a strong red emission. The photoluminescence excitation spectrum showed that Ca₃Te₂(ZnO₄)₃:Eu³⁺ can be effectively excited by UV–visible light. The property of long-wavelength excitation for this material has a benefit as a red phosphor in application of white light-emitting diodes. The colour coordinates were calculated. The excitation and emission spectra and luminescence decay curves were obtained using a pulsed, tunable, narrowband dye laser. Crystallographic sites and charge compensation mechanism of Eu³⁺ ions were discussed. The emission line from Eu³⁺ in intrinsic crystallographic site in the lattice was located at 579.56 nm. The emission line from Eu³⁺ in another disturbed site, which is created by the defects created by the charge-compensation, was located at 580.88 nm. The disordered crystallographic sites of Eu³⁺ are benefit for their strong red luminescence corresponding to the ⁵D₀→⁷F₂ transition.     

NaEu0.96Sm0.04(MoO4)2 as a promising red-emitting phosphor for LED solid-state lighting prepared by the Pechini process

NaEu_0.96Sm_0.04(MoO₄)₂ was prepared by the Pechini method (P phosphor) and as a comparison, also by solid-state reaction technique (S phosphor). The photo-luminescent properties, the morphology and the grain size were investigated. The phosphors show broadened excitation band around 400 nm, high intensity of Eu³⁺⁵D₀→⁷F₂ emission upon excitation around 400 nm, and appropriate CIE chromaticity coordinates. Intensive red light-emitting diodes (LEDs) were fabricated by combining the phosphor and a 400 nm InGaN chip for the first time, which confirm that the phosphor is a good candidate for near UV LED. The luminescent intensity of P phosphor prepared at 700 °C is near that of S phosphor prepared at 800 °C. In addition, P phosphor shows advantages of lower calcining temperature, shorter heating time, and smaller grain size. Considering all these factors, the suitable method for preparing the promising near UV LED phosphor NaEu_0.96Sm_0.04(MoO₄)₂ is recommended to be the Pechini process at 700 °C.     

Photoluminescence studies of NaCaPO4:RE (RE=Dy, Mn or Gd)

The purpose of the present study is to develop an understanding of photoluminescence properties of Dy³⁺, Mn²⁺ or Gd³⁺doped NaCaPO₄ phosphors, which have served as efficient phosphors in many industrial applications. The phase formation was confirmed by the X-ray powder diffraction (XRD) measurement. Photoluminescence (PL) excitation spectrum measurement of NaCaPO₄:Dy³⁺ shows this phosphor can be efficiently excited by near-ultraviolet (UV) light from 300 to 400 nm and presents dominant luminescence band centered at 480 nm (blue) and 573 nm (yellow). The PL excitation of NaCaPO₄:Mn²⁺ and Gd³⁺ under UV wavelength shows the emissions at 520 and 313 nm, respectively. A scanning electron microscope (SEM) shows an average crystallite size in sub-micrometer range. The obtained results show that the phosphors have the potential for application in the lamp industry and medical applications.     

Emission properties of Eu, Mn in MAl2Si2O8 (M=Sr, Ba)

The emission properties of Eu²⁺ and Mn²⁺ in monoclinic SrAl₂Si₂O₈ (M-SAS) and hexagonal BaAl₂Si₂O₈ (H-BAS), both of which have only one alkaline-earth site, were studied. The emission peaks of both Eu²⁺ (405 nm) and Mn²⁺ (564 nm) in SrAl₂Si₂O₈, are located at longer wavelengths, compared with those in H-BAS (373 nm for Eu²⁺ and 518 nm for Mn²⁺), because of the stronger crystal field strength at the Sr site. EPR spectra showed that the g values of Mn²⁺ are 4.5065 in M-SAS:Mn and 2.0247 in H-BAS:Mn. Magnetic measurements proved that Mn²⁺ was at high-spin state in both hosts. The large g value of Mn²⁺ in M-SAS was ascribed to the mixing of the first excitation state to the ground state, both of which have lower d orbital degeneracy due to the lower symmetry of Mn²⁺ site. The transfer efficiency from Eu²⁺ to Mn²⁺was about 10% in M-SAS, higher than that in H-BAS (5%). This was probably because Eu²⁺ emission overlaps the relatively low excitation level of Mn²⁺ in M-SAS. In order to obtain high transfer efficiency, it was necessary for the Eu²⁺ emission to overlap the lowest excitation level of Mn²⁺. The results obtained in this work may be helpful to design the new white or red phosphors for white-light emitting diode (w-LED) applications.     

Relaxor behavior of (Sr,Ba,Bi)TiO3 ferroelectric ceramic

The dielectric behavior of (Sr_0.4Ba_0.6)_0.925Bi_0.05TiO₃ (SBBT) ceramic was investigated in the temperature range from 100 K to 450 K. Broad dielectric maxima, which shift to higher temperature with increasing frequency, and the value of the relaxation parameter γ=1.6-2 estimated from the linear fit of the modified Curie-Weiss law, indicated the relaxor nature of the SBBT ceramic. The dielectric relaxation which follows the Vogel-Fulcher relationship with  K, E_a=0.0392 eV, and ν_o=2.98×10¹¹ Hz, further supports such a relaxor nature. The P-E hysteresis loop at different temperatures and ‘butterfly’ shape dc bias field dependence of permittivity at T>T_m (the temperature of permittivity maximum) signifies the occurrence of nanopolar clusters, which is the typical characteristic of relaxor ferroelectrics. At 300 K and 10 kHz, the dielectric constant and loss tgδ are ∼2210 and 0.00118, respectively. The tunability (28%) and figure of merit (237) at room temperature show that the SBBT ceramic could be a promising candidate for tunable capacitor applications.     

Synthesis, structure and luminescence properties of Y(V,P)O4:Eu,Bi phosphors

YVO₄:Eu³⁺-based red-emitting phosphors with the compositions of Y_0.95−xVO₄:0.05Eu³⁺,xBi³⁺ (x=0.01, 0.03, 0.05, 0.07 and 0.09) and Y_0.90(V_1−zP_z)O₄:0.05Eu³⁺,0.05Bi³⁺ (z=0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1.0) were synthesized by the high temperature solid-state method. The as-prepared phosphors have the similar tetragonal phase structure and their morphologies varied with the relative content ratio of V to P. The photoluminescence spectra for the as-synthesized phosphors show that a dominant red emission line at around 619 nm, which is due to the Eu³⁺ electric dipole transition of ⁵D₀-⁷F₂, is observed under different excitation wavelengths (254 and 365 nm). Further, the emission intensities of ⁵D₀-⁷F₂ transition upon 365 nm excitation increase sharply owing to the Bi³⁺ doping. Energy transfer process, luminescent lifetime and quantum efficiency for the selected Y_0.90(V_1−yP_y)O₄:0.05Eu³⁺,xBi³⁺phosphors were also studied in detail.     

Continuous nano-coating of Y2O3:Eu phosphor shell on SiO2 core particles and its photoluminescence properties

In order to investigate the effects of the crystallite size on the photoluminescence (PL) properties of a phosphor, monodisperse spherical SiO₂/Y₂O₃:Eu³⁺ phosphor core/shell particles were synthesized. On the surface of the core particles prepared by the Stöber method, the phosphor shell was continuously coated by a heterogeneous precipitation method. Because the growth of the crystallite was restricted by the shell thickness, the crystallite size could be successfully controlled at the same firing conditions. The PL intensity, the asymmetric ratio and thus the color purity were significantly decreased with the decrease of the crystallite size. In addition, the position of charge transfer band in the PL excitation spectrum was red-shifted with the decrease of the crystallite size.