Sr和Ba替代对Eu掺杂Ca2.955Si2O7的结构和发光特性的影响研究

利用固相反应法制备了Sr和Ba替代的Ca_2.955-xM_xSi₂O₇: 0.045Eu²⁺ (M= Sr, Ba, x= 0.1-0.5)系列荧光粉, 利用较大离子半径的Sr和Ba元素替代Eu掺杂Ca_2.955-xM_xSi₂O₇ 中的Ca元素,研究Sr和Ba替代对样品结构和发光特性的影响. X射线衍射测试结果表明,少量Sr和Ba替代不会改变基质的晶体结构, 样品仍然为单斜晶系.未替代前, Ca_2.955Si₂O₇: 0.045Eu²⁺ 样品的发射峰在574 nm左右,随着Sr含量的增加,样品的发射峰发生蓝移; 而Ba含量在x= 0.1-0.4时不会引起发射峰位置的移动, 但x= 0.5样品的发射峰发生蓝移.同等含量的Sr和Ba部分替代样品中的Ca元素, Ba替代样品的光谱强度较强.     

Tunable luminescent properties by adjusting the Sr/Ba ratio in Sr1.97−xBaxMgSi2O7:Eu0.01, Dy0.02 phosphors

The long afterglow phosphors Sr_1.97−xBa_xMgSi₂O₇:Eu²⁺_0.01, Dy³⁺_0.02 (x=0, 0.4, 0.8, 1.2, 1.6 and 1.97) were synthesized via high temperature solid-state reaction. The phase identification reveals that the crystal plane spacing becomes greater with the decrease in the Sr/Ba ratio. Phase transition occurs when x=1.97. A nonlinear relationship between the emission peak and the crystal plane spacing is obtained with the decrease of the Sr/Ba ratio. This ascribes to the splitting of the 5d level of the Eu²⁺ and the change of the crystal field strength. The duration of the afterglow becomes shorter with the decrease of the Sr/Ba ratio. It may ascribe to deeper trap depth, lower trap concentration and the embarrassment of the transfer of carriers.     

Preparation and optical properties of Ce activated (Ca1 − x,Srx)Al2Si2O8 phosphors

(Ca_1 − x, Sr_x)Al₂Si₂O₈:0.06Ce³⁺, M⁺ (M⁺ = Li⁺, Na⁺, K⁺) phosphors have been prepared by conventional solid-state reaction method. The structural and optical properties of the phosphors were characterized by X-ray diffraction (XRD) technique and spectrophotometer, respectively. A regular variation was found among the XRD patterns of (Ca_1 − x, Sr_x)Al₂Si₂O₈:0.06Ce³⁺ phosphors based on the changing of Sr content. With the increase of Sr content, the maximum of emission band presented slight blue shifts (~ 15 nm). The luminescence intensity of CaAl₂Si₂O₈:0.06Ce³⁺ and SrAl₂Si₂O₈:0.06Ce³⁺ were significantly enhanced when K⁺ and Li⁺ were incorporated, respectively.     

Defect chemistry and oxygen transport of (La0.6Sr0.4 − xMx)0.99Co0.2Fe0.8O3 − δ, M = Ca (x = 0.05, 0.1), Ba (x = 0.1, 0.2), Sr: Part I: Defect chemistry

This paper is the first part of a two part series, where the effects of varying the A-site dopant on the defect chemistry, the diffusion coefficient and the surface catalytic properties of the materials (La_0.6Sr_0.4 − xM_x)_0.99Co_0.2Fe_0.8O_3 − δ, M = Sr, Ca (x = 0.05, 0.1), Ba (x = 0.1, 0.2) (LSMFC) have been investigated. In part I, the findings on the defect chemistry are reported, while the transport properties are reported in part II. Substitution of Sr²⁺ ions with Ca²⁺ ions (smaller ionic radius) and Ba²⁺ ions (larger ionic radius) strains the crystal structure differently for each composition while keeping the average valence of the cations constant. The Ba²⁺ containing materials show the largest oxygen loss at elevated temperatures, while the purely Sr²⁺ doped material showed the smallest oxygen loss. This was reflected in the partial oxidation entropy of the materials. The measured oxygen loss was modelled with point defect chemistry models. Measurements at very low p_O2 showed several phase transitions.     

Green Eu-doped Ba3Si6O12N2 phosphor for white light-emitting diodes: Synthesis, characterization and theoretical simulation

The Eu²⁺-doped Ba₃Si₆O₁₂N₂ green phosphor (Eu_xBa_3−xSi₆O₁₂N₂) was synthesized by a conventional solid state reaction method. It could be efficiently excited by UV-blue light (250-470 nm) and shows a single intense broadband emission (480-580 nm). The phosphor has a concentration quenching effect at x=0.20 and a systematic red-shift in emission wavelength with increasing Eu²⁺ concentration. High quantum efficiency and suitable excitation range make it match well with the emission of near-UV LEDs or blue LEDs. First-principles calculations indicate that Ba₃Si₆O₁₂N₂:Eu²⁺ phosphor exhibits a direct band gap, and low band energy dispersion, leading to a high luminescence intensity. The origin of the experimental absorption peaks is clearly identified based on the analysis of the density of states (DOS) and absorption spectra. The photoluminescence properties are related to the transition between 4f levels of Eu and 5d levels of both Eu and Ba atoms. The 5d energy level of Ba plays an important role in the photoluminescence of Ba₃Si₆O₁₂N₂:Eu²⁺ phosphor. The high quantum efficiency and long-wavelength excitation are mainly attributed to the existence of Ba atoms. Our results give a new explanation of photoluminescence properties and could direct future designation of novel phosphors for white light LED.     

The structure of mixed fluorides Ca1?xSrxF2 and Sr1?xBaxF2 and the luminescence of Eu2+ in these crystals

The structure of the mixed fluorites Ca_1−x Sr_xF₂ and Sr_1−x Ba_xF₂, as well as the structure of the Eu²⁺ impurity center in these crystals, is calculated within the framework of the virtual-crystal method realized in the shell model and pair-potential approximation. The phenomenological dependence of the position of the lower level of the 4f ⁶5d configuration of the Eu²⁺ ion on distance to the Eu²⁺-ligand is derived. The dependences of the Stokes shift and the Huang-Rhys factor on x are calculated for the yellow luminescence in Sr_1−x Ba_xF₂:Eu²⁺. The value of x at which the lower level of the 4f ⁶5d configuration of the Eu²⁺ ion in Sr_1−x Ba_xF₂:Eu²⁺ falls within the conduction band is found. __________ Translated from Fizika Tverdogo Tela, Vol. 45, No. 5, 2003, pp. 823–826. Original Russian Text Copyright ? 2003 by Nikiforov, Zakharov, Chernyshev, Ugryumov, Kotomanov.     

Enhanced luminescent properties of long-persistent Sr2MgSi2O7:Eu, Dy phosphor prepared by the co-precipitation method

Sr₂MgSi₂O₇:Eu²⁺, Dy³⁺ phosphors were prepared by the (aminopropyl)-triethoxysilane (APTES) co-precipitation method. Effects of synthesis temperature on the crystal characteristics, luminescent properties and afterglow performance of Sr₂MgSi₂O₇:Eu²⁺, Dy³⁺ phosphors have been discussed in detail and compared with the corresponding commercial product. The experimental results indicated that the sample could be synthesized at a relatively lower temperature and had better performance on the above-mentioned properties using the co-precipitation method.     

Highly Efficient pc-LED Phosphors Sr1-xBaxSi2O2N2:Eu2+ (0 x 1) - Crystal Structures and Luminescence Properties Revisited

Due to their excellent luminescence properties in the blue-green to green-yellow spectral region, oxonitridosilicates Sr_1-xBa_xSi₂O₂N₂:Eu²⁺ (0 x 1) are promising conversion materials for application in phosphor-converted high-power LED devices. In order to understand the properties and thus to fully exploit the potential of these materials, detailed knowledge of corresponding (local) crystal structures is indispensable. Detailed insights into real structures have been achieved by combining X-ray diffraction and electron-microscopy methods. A major reason for the excellent luminescence properties of the phases Sr_1-xBa_xSi₂O₂N₂:Eu²⁺ (0 x 1) is the rigid silicate substructure built up of two-dimensionally condensed SiON₃ tetrahedra. The general topology of these layers is analogous for all members. However, there is no complete solid-solution series. Crystal-structure determination was frequently not straightforward because several real-structure effects had to be considered. The relative orientation of the silicate layers and the metal-atom layers inserted between them can differ without changing the chemical composition. As a consequence, polytypes are formed. The differentiation between such closely related structures was only possible by a thorough analysis of crystallographic data. The same applies for phases which differ in their composition as all Sr_1-xBa_xSi₂O₂N₂:Eu²⁺ (0 x 1) phases are very similar. The literature on these compounds is critically discussed with respect to phase analysis and structure determination. Different synthesis routes are reviewed and the results of luminescence investigations are discussed in this contribution. Beyond thermal as well as chemical stability and high transparency, electron-phonon coupling is effectively suppressed in Sr_1-xBa_xSi₂O₂N₂:Eu²⁺ (0 x 1) phases. Therefore, primary UV to blue light (GaN based semiconductor LEDs) is efficiently converted into visible components of the spectrum. Sr_1-xBa_xSi₂O₂N₂:Eu²⁺ (0 x 1) phases are therefore promising oxonitridosilicate phosphors for application in LED industry.     

Synthesis and luminous characteristics of Ba2MgSi2−xAlxO7: 0.1Eu, 0.1Mn phosphor for WLED

The shift of the emission band to longer wavelength (yellow-orange) of the Ba₂MgSi_2−xAl_xO₇: 0.1Eu²⁺ phosphor under the 350-450 nm excitation range has been achieved by adding the codoping element (Mn²⁺) in the host. The single-host silicate phosphor for WLED, Ba₂MgSi_2−xAl_xO₇: 0.1Eu²⁺, 0.1Mn²⁺ was prepared by high-temperature solid-state reaction. It was found experimentally that, its three-color emission peaks are situated at 623, 501 and 438 nm, respectively, under excitation of 350-450 nm irradiation. The emission peaks at 438 and 501 nm originate from the transition 5d to 4f of Eu²⁺ ions that occupy the two Ba²⁺ sites in the crystal of Ba₂MgSi_2−x Al_xO₇, while the 623 nm emission is attributed to the energy transfer from Eu²⁺ ions to Mn²⁺ ions. The white light can be obtained by mixing the three emission colors of blue (438 nm), green (501 nm) and red (623 nm) in the single host. When the concentrations of the Al³⁺, Eu²⁺ and Mn²⁺ ions were 0.4, 0.1 and 0.1 mol, respectively, the sample presented intense white emission. The addition of Al ion to the host leads to a substantial change of intensity ratio between blue and green emissions. White light could be obtained by combining this phosphor with 405 nm light-emitting diodes. The near-ultraviolet GaN-based Ba₂MgSi_1.7 Al_0.3O₇: 0.1Eu²⁺, 0.1Mn²⁺ LED achieves good color rendering of over 85.     

Relation between highT c superconductivity and structure: A study of Ba3+x Cu6O14+δ and YBa2Cu3O7−δ systems

Superconductivity is found in tetragonal La_3−x Ba_3+x Cu₆O_14+δ and La, Ba)_6−x Sr _x Cu₆O_14+δ even though they do not possess Cu-O chains or the K₂NiF₄ structure. Resistivity measurements confirm the occurrence of a transformation from chain-superconductivity to sheet-superconductivity in YBa₂Cu₃O_7−δ as δ is varied in the range 0.0–0.5. Contribution No. 481 from the Solid State and Structural Chemistry Unit     

发光二极管用红色荧光粉Sr0.8-xBaxEu0.2WO4的制备和性质研究

采用化学共沉淀法制备了不同Ba²⁺掺杂浓度、 不同煅烧温度的Sr_0.8-xBa_xEu_0.2WO₄红色荧光粉. 研究了样品的晶体取向和晶格 畸变对发光性质的影响, 实验结果表明: 合成的Sr_0.8-xBa_xEu_0.2WO₄红色荧光粉为四方相, 样品中Eu³⁺的⁵D₀–⁷F₂跃迁的红光能被近紫外光和蓝光有效激发. 适量的Ba²⁺离子取代部分的Sr²⁺提高了Sr_0.8Eu_0.2WO₄荧光粉的发光强度, Ba²⁺掺杂浓度的改变对基质的晶格参数、晶体对称性和发光性能影响较大, Ba²⁺的最佳掺杂量为30%.     

Synthesis and Luminescent Properties of M<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript>: Eu (M=Sr,Ba) Nanophosphors

A solution combustion route for the synthesis of Eu³⁺-activated M₂V₂O₇ (M = Sr, Ba) and their luminescent properties have been investigated. Structure and luminescent characteristics of Sr₂V₂O₇:Eu³⁺ and Ba₂V₂O₇:Eu³⁺ nanophosphors have been studied by x-ray diffraction, scanning electron microscopy, transmission electron microscopy, fluorescence spectrometry and Fourier transform infra-red spectroscopy. The incorporation of Eu³⁺ activator in these nanoparticles has been checked by luminescence characteristics. These nanoparticles have displayed red color under a UV source which is due to characteristics transition of Eu³⁺ from ⁵D₀ → ⁷F₂ at 613 nm in both Sr₂V₂O₇:Eu³⁺ and Ba₂V₂O₇:Eu³⁺ nanophosphors. In addition, the optimal Eu³⁺ - doped contents of Sr_2(1-x)Eu_2xV₂O₇ and Ba_2(1-x)Eu_2xV₂O₇ nanophosphors for both were 4 mol%.     

Structure and ferroelectric properties of BaBi3.8M0.2(Ti3.8Nb0.2)O15 (M=Mg, Ca, Sr and Ba) ceramics

Bismuth layer structured compounds BaBi_3.8M_0.2(Ti_3.8Nb_0.2)O₁₅, with M=Mg, Ca, Sr and Ba, were synthesized through a modified chemical route. Phase and structure of the compounds were analyzed by X-ray diffraction. The structure of Mg²⁺ based compound was orthorhombic, while it was tetragonal for the other three compositions. Experimental results indicate that Mg²⁺ prefers to substitute in the Bi₂O₂ layer. The room temperature permittivity was maximum for Ba²⁺ based compound (∼432). The piezoelectric coefficient was significantly enhanced in Mg²⁺ based compound. The Curie temperature was found to decrease gradually in the order Mg>Ca>Sr>Ba based compound. There was a marked improvement in the relaxor behavior and remnant polarization for Ba²⁺ based compound. The structural changes and dielectric, ferroelectric and piezoelectric properties of all the compounds was discussed and co-related.     

Structural, magnetic and transport properties of double perovskite compounds (Sr2−3xLa2xBax)FeMoO6

The crystal structure and magnetic properties of a series of ordered double perovskite oxides (Sr_2−3xLa_2xBa_x)FeMoO₆ (0x0.3) have been investigated. X-ray powder diffraction reveals that the crystal structure of the compounds changes from a tetragonal I4/m lattice to a cubic lattice around x=0.2. Though the nominal average size of the A site cation of (Sr_2−3xLa_2xBa_x)FeMoO₆ is designed to be almost independent of x, the refinements of the crystal structure show that the lattice constants increase with x in both the tetragonal and the cubic phase regions due to electron doping. As the x increases, the degree of cationic ordering on the B site is decreased pronouncedly, while the Curie temperature of the compounds is nearly unchanged. The saturation magnetization of the compounds decreases with x and shows a linear dependence on the degree of cation ordering. The resistivity of the parent compound shows a semiconducting behavior below room temperature, but those of the doped samples exhibit a metal–semiconductor transition. A correlation between the resistivity and metal-semiconducting transition temperature (T_M−S) is observed. The resistivity and T_M−S of the compounds decrease with x for x0.2 and increase for x0.2. Magnetoresistance of the compounds is reduced by the La/Ba doping. All these observations can be understood based on the interplay of the electron doping, change in bandwidth and the anti-site defect concentration.     

掺Ba对Bi系2212相超导电性的影响

研究了掺Ｂａ对Bi₂Sr_2-xBa_xCaCu₂O_y（０≤ｘ≤０．１５，０．３）单晶和多晶样品超导电性的影响，结果表明，有少量Ｂａ^２＋离子进入了超导相，且有固溶度极限．对于２２１２相单晶，ｃ轴参数和Ｔ_c均随Ｂａ含量增加而增加；对于慢冷多晶样品，掺Ｂａ可明显提高Ｔ_c；然而对于淬大多晶样品，Ｔ_c没有明显变化，用掺Ｂａ 关键词：     

Probing lattice defects in Sr2MgSi2O7:Eu2+,Dy3+

The Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺ materials were prepared with a solid state reaction and their microscopic structure (at 295 K only) and luminescence were studied at selected temperatures between 150 and 295 K. Undisturbed Sr crystal planes were common in the TEM images of the undoped Sr₂MgSi₂O₇ material, whereas with Eu²⁺ doping more disturbed planes were observed even in the nanometer scale. With Dy³⁺ co-doping, a large number of small lattice domains created by the discontinuities in the crystal structure was observed. The domains with different orientations seem to be centered around point defects. The decay curves of Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺ showed fast (ms scale) persistent luminescence. The intensity of persistent luminescence increased considerably between 200 and 250 K while remaining constant in the ranges of 150–200 and 250–295 K. The changes were used to study the depth of the traps. In general, Dy³⁺ co-doping was found to deepen the traps.     

Investigation on Eu doped Sr2MgSi2O7 red-emitting phosphors for white-light-emitting diodes

In this work, we report the high temperature solid-state synthesis of red phosphors Sr₂MgSi₂O₇: Eu³⁺ with various Eu³⁺ concentrations. Their luminescent properties at room temperature are investigated. The X-ray diffraction patterns indicate that the red phosphors powder conforms to the tetragonal Sr₂MgSi₂O₇. Impurity structure appears when more than 20% Eu³⁺ is doped. The samples show a strong emission line at 615 nm and the intensity increases with the increase of Eu³⁺ concentration until concentration quenching occurs. Charge compensation assists in the reduction of the impurity structure and vacancies; hence the luminescent intensity is enhanced. The decay measurement indicates that the lifetime of Eu³⁺ emission is about 2-3 ms. Some of the Eu³⁺ can be reduced to Eu²⁺; this is also discussed.     

A tunable green alkaline-earth silicon-oxynitride solid solution (Ca1? x Sr x )Si2O2N2:Eu2+ and its application in LED

A series of (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺ (x=0.0–0.97, y=0.03) phosphors were synthesized by high-temperature solid-state reaction. The XRD patterns confirm the formation of a solid solution of (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺. An intense tunable green light is observed with the increasing ratio of Sr/Ca. With an increase in x, the excitation and emission spectra show a redshift and blueshift, respectively, due to large centroid shift and small Stokes shift. The temperature dependent luminescence is also investigated in the temperature range of 77–450 K. The Huang–Rhys factor and the thermal-quenching temperature are determined. Intense green LEDs were successfully fabricated based on the (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺ phosphor and near-ultraviolet (∼395 nm) GaN/blue (460 nm) InGaN chips. All the results indicate that the solid solution (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺ is a promising phosphor applicable to near-UV and blue LEDs for solid-state lighting.     

Strontium diffusion in Sr3−3x La2x □x(VO4)2 solid solutions

Layer-by-layer radiometric analysis in the temperature range 800–950 °C was used to measure the diffusion coefficients of ⁹⁰Sr, ⁴⁵Ca, ¹³³Ba radionuclides in Sr_3−3x La_2x □_x(VO₄)₂ (x=0,0.1,0.15,0.2,0.25) solid solutions. It was established that D _Ca ^* >D _Sr ^* >D _Ba ^* . An increase in the concentrations of vacancies (□) in the strontium sublattice leads to increased coefficients of diffusion of rare-earth metal cations. The activation energies for radionuclide diffusion were determined. It was shown that M²⁺ cations migrate via Sr(2) positions. Fiz. Tverd. Tela (St. Petersburg) 40, 223–226 (February 1998)     

Superconductivity in Sr<Subscript>0.75</Subscript>Y<Subscript>0.75</Subscript>Ba<Subscript>1.5</Subscript>Cu<Subscript>3</Subscript> O<Subscript>7−<Emphasis Type="Italic">d</Emphasis></Subscript> compounds

The effect of simultaneous Sr substitution at the Ba and Y sites has been studied in the Sr_0.75Y_0.75Ba_1.5Cu₃O_7–dsystem. Attempts to replace 25% Y and 25% Ba have been successful and superconductivity was observed above 78 K for Sr_0.75Y_0.75Ba_1.5Cu₃O_7–d compound with high oxygen content, i.e., O_6.76, and having orthorhombic crystal symmetry. The compound was treated in argon gas at 800°C to reduce the oxygen content and to induce some structural changes. The Sr_0.75Y_0.75Ba_1.5Cu₃O_6.1 compound thus obtained has tetragonal symmetry and low oxygen content, O_6.1. It has also shown superconductivity at 28 K. The paper presents a careful comparison of the structural and electrical properties and infrared absorbance spectra of the two compounds with the same metallic composition, Sr_0.75Y_0.75Ba_1.5Cu₃, but with different oxygen content and crystal symmetry. The study clearly establishes the occurrence of superconductivity in tetragonal Sr-substituted (both at Y and Ba sites in) YBCO.