等价Ca、Sr离子固溶对CaTiO3:0.002Pr3+发光特性的影响

利用高温固相反应法,制备了不同Sr/Ca比的(Ca1-xSrx)TiO30.002Pr3+(x=0～0.6)红色发光材料.荧光光谱与XRD测试结果表明所有样品均发出源于pr3+的1D2→3H4跃迁的612m红色光;发光强度与晶胞a轴均随固溶取代量x改变而连续变化,并在x=0.15的出现极值发光强度提高约三倍,a轴则最小.研究揭示除不等价离子取代产生的电荷缺陷外,等价离子取代导致的固溶结构变化也是改变发光强度的有效途径.     

Nd3+A位置换对(Pb0.5Ca0.5)(Fe0.5Nb0.5)O3陶瓷微波介电性能的影响

研究了Nd³⁺离子A位置换改性(Pb_0.5Ca_0.5)(Fe_0.5Nb_0.5)O₃陶瓷的微波介电性能.[(Pb_0.5Ca_0.5)_1-xNd_x](Fe_0.5Nb_0.5)O₃(PCNFN)陶瓷的微波介电性能得到改善是由于少量过剩的Nd³⁺与(Pb,Ca)²⁺的固溶能够消除氧空位.当x=0.02时,能够形成单相的钙钛矿相,随着Nd³⁺置换量的增加,过剩的Nd³⁺将导致第二相焦绿石的形成,焦绿石会恶化PCNFN的微波介电性能.PCNFN介电性能随x的增加而下降是由于焦绿石相随x增加的结果.当x=0.02-0.05,PCNFN陶瓷有很好的微波介电性能,介电常数K>100,Qf值为5385-5797GHz,频率温度系数TCF随Nd³⁺含量的增加从正的变为负的.     

Yb3+掺杂SiO2-Bi2O3-B2O3玻璃的物理性质及光谱性质

选取玻璃组分60SiO₂-xBi₂O₃-(30-x)B₂O₃-2K₂O-7Na₂O-1Yb₂O₃(以mol％记,x=0,5,10,15,20,25,30)为研究对象。通过测试试样的物理性质和光谱性质,应用倒易法(reciprocity method)计算Yb³⁺离子的受激发射截面(σ_emi),并且计算了Yb³⁺的自发辐射几率(A_rad),²F_5/2能级的辐射寿命(T_rad)。讨论了玻璃中Bi₂O₃和B₂O₃的组成变化对其物理性质、Yb³⁺离子的吸收特性、发光特性以及OH^-离子对实测Yb³⁺荧光寿命(T_f)的影响。结果表明:Yb³⁺掺杂的Si₂-Bi₂O₃-B₂O₃具有较好的光谱性能,是一种新型的Yb³⁺掺杂双包层光纤候选基质材料。     

钡过量非化学计量M型铁氧体的合成与表征

采用并加共沉淀工艺在900℃热处理2h的条件下合成了单相钡过量非化学计量M型铁氧体Ba_1+xCoTiFe₁₀O_19+x(x=0.00、0.05、0.10、0.15、0.20), 并用XRD、SEM、TEM和VSM表征了这种新的非化学计量M型铁氧体的结构和磁学特性. 结果表明: 当0c和剩余磁化强度σ_r均随x增大而显著增大(Δσ_r=5.36A·m^2·kg^-1, ΔH_c=16.99 kA·m^-1, 但比饱和磁化强度σ_s基本不变; 0.053+离子被稀释导致σ_s、H_c和σ_r均随x增大而持续降低. 同时证实钡过量并不会导致晶体对称性破坏, 02+离子分布于平行于a轴方向的大孔隙位?置, 不仅具有助熔剂作用, 而且对磁畴壁产生了钉扎效应.     

掺铒碲酸盐玻璃的热力学稳定性和光谱性质的研究

分析了掺Er³⁺碲酸盐玻璃的热力学稳定性能,研究了掺Er3+碲酸盐玻璃的吸收和荧光光谱性质;应用Judd-Ofelt理论计算了碲酸盐玻璃中Er3+离子的强度参数Ω(Ω₂=4.79×10^-20cm², Ω₄=1.52×10^-20cm²,Ω₆=0.66×10^-20_cm2),计算了离子的自发跃迁几率,荧光分支比;应用McCumber理论计算了Er3+的受激发射截面(σ_e=10.40×10^-21cm²)、Er³⁺离子⁴I_13/2→⁴I_15/2 发射谱的荧光半高宽(FWHM=65.5nm)及各能级的荧光寿命(⁴I_13/2能级为τ_rad=3.99ms);比较了不同基质玻璃中Er3+离子的光谱特性,结果表明掺铒碲酸盐玻璃更适合于掺Er³⁺光纤放大器实现宽带和高增益放大.     

Dy3+激活的LiCaBO3材料发光特性研究

采用固相法制备了LiCaBO₃∶Dy³⁺发光材料. 材料的发射光谱为一多峰宽谱, 主峰分别为484、577和668nm; 监测577nm发射峰, 对应的激发光谱为一主峰位于331、368、397、433、462和478nm的宽谱. 研究了Dy³⁺浓度对材料发射光谱及发光强度的影响, 结果随Dy³⁺浓度的增大, 材料的黄、蓝发射峰强度比(Y/B)逐渐增大; 同时, 发光强度呈现先增大后减小的趋势, 最大值对应的Dy³⁺浓度为3.00mol%, 其浓度猝灭机理为电偶极电偶极相互作用. 引入Li⁺、Na⁺或K⁺可增强材料的发射强度. InGaN管芯激发下的LiCaBO₃∶Dy³⁺材料呈现很好的白光发射, 色坐标为x=0.3001, y=0.3152.     

B位异价离子(Al,Cr)置换对Li3xLa2/3-xTiO3离子电导率的影响

研究了B位Al,Cr异价离子置换对Li_3xLa_2/3-xTiO₃(x=0.13)离子电导率的影响。结果表明:用适量离子半径较小的Al³⁺(0.535A)置换Ti⁴⁺(0.605A)可有效地提高其离子电导率,当B位铝离子的置换量为y=0.02时,组分为(Li_0.39La_0.54)_1+y/2Al_yTi_1-yO₃的材料其室温下的体离子电导率σ_b=(1.58±0.01)×10^-3S·cm^-1,这一结果是迄今为止钙钛矿锂离子导体材料文献报道的最好水平。然而,分析结果表明,离子电导率的提高难以用锂离子迁移“瓶颈”尺寸的变化,TiO₆八面体张缩能力及A位阳离子和空位的有序性来解释,因B位异价离子置换而引发的Li⁺离子键强度的变化被认为是导致锂离子电导率提高的原因。     

Ba3BPO7的合成及其水解、热稳定性和稀土掺杂发光性能的研究

采用多种高温固相反应途径合成了纯相Ba₃BPO₇并研究了Ba₃BPO₇的水解和热稳定性能.研究表明:Ba₃BPO₇遇水水解,生成Ba₃(PO₄)₂、Ba₅(PO₄)₃OH和Ba(OH)₂;TG-DTA表明它是一致熔化合物,熔点在1353℃左右;同时,初步研究了X射线激发Ba₃BPO₇:RE(RE=Eu³⁺、Sm³⁺)的发光性能,表明基质Ba₃BPO₇与稀土离子之间存在着能量传递.     

Gd3+为敏化剂的掺Tb3+硅酸盐闪烁玻璃

实验制备了以Tb³⁺为激活剂、Gd³⁺为敏化剂的硅酸盐闪烁玻璃, 研究了Tb₂O₃和Gd₂O₃含量对玻璃密度和玻璃折射率, 以及对玻璃在紫外光激发和X射线激发条件下的光学光谱特性的影响. 通过研究Tb³⁺/Gd³⁺共掺闪烁玻璃的激发与发光特性、荧光寿命, 结合稀土离子能级结构, 分析了Gd³⁺→Tb³⁺离子之间的能量转移与传递机制. 结果表明：在紫外激发条件下, 大量引入Tb₂O₃和Gd₂O₃可提高Gd³⁺→Tb³⁺离子之间的能量传递效率, 有利于Tb³⁺离子的绿色发光; 但是在X射线激发条件下大量引入Tb³⁺离子, 由于缺陷数增加而弱化Tb³⁺离子荧光.     

Nb掺杂Bi4Ti3O12层状结构铁电陶瓷的电行为特性研究

采用固相烧结工艺制备了Nb⁵⁺掺杂的Bi₄Ti₃O₁₂层状结构铁电陶瓷.运用XRD 和AFM对Bi₄Ti_3-xNb_xO_12+x/2材料的微观结构进行表征,发现所制备的陶瓷均具有单一的正交相结构,抛光热腐蚀表面晶粒的显微形貌表现为随机排列的棒状结构.通过对材料直流电导率与温度关系的Arrhenius拟合,分析丁Bi₄Ti_3-xNb_xO_12+x/2的导电机理. Nb⁵⁺掺杂提高了材料的介电常数,但居里温度随掺杂含量的增加呈线性下降趋势.DSC结果显示Bi₄Ti_3-xNb_xO_12+x/2材料在居里温度处经历了一级铁电相变.样品的铁电性能测试结果表明, Nb⁵⁺掺杂Bi₄Ti₃O₁₂提高了材料的剩余极化Pr,这主要是由于^_Nb5+取代Ti⁴⁺大大降低了材料中氧空位的浓度,使得氧空位对畴的钉扎作用减弱的缘故.     

Ba6-3x(Sm1-yPry)8+2x Ti18O54微波介质陶瓷结构及性能的研究

本文研究了Ｂａ６－３ｘ（Ｓｍ１－ｙＰｒｙ）８＋２ｘＴｉ１８Ｏ５４（ｘ＝０．５,ｙ＝０．０、０．１、０．２）微波介质陶瓷的结构和性能。结果表明,在Ｓｍ－Ｐｒ系中Ｐｒ取代Ｓｍ形成了钨青铜结构的固溶体,随Ｐｒ取代量的增多,晶格常数呈线性增加趋势。最佳烧结温度确定为１４００℃。同时,随Ｐｒ的取代,介电常数得到提高,同时保持了低的损耗,并可以找到ｆ恰为零的最佳成分点。     

Luminescence characteristics of Pr3+ ion doped CaTiO3 nanopowder phosphors synthesized by solvothermal method

In display applications, each displays technique needs different phosphors according to its applications. So, in this paper, nano-sized red emitting CaTiO3:Pr3+ powder phosphors were prepared by solvothermal reaction method. The phase purity and the structure of the phosphors were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM). The particles show the spherical morphology, which indicates the good luminescent characteristics. The luminescent properties of CaTiO3:Pr3+ powder phosphors have been carried out by the measurement of their phototluminescence (PL) and phototluminescence excitation (PLE) spectra. The PL spectra shows the strong red emission due to 1D2 --> 3H4 transition. The emissions of intra-4f transitions from the excited states (1D2) to the ground state (3H4) of Pr3+ are mainly observed around from 612 to 618 nm. The effect of the Pr3+ concentration on their photoluminescent properties was investigated extensively. These luminescent powders are expected to find potential applications such as optical display systems.     

Ca10K（PO4）7:Eu3+红色荧光粉的制备及其发光性质

高温固相法合成了Ca10-xK(PO4)7:xEu3+(x=0.02,0.04,0.06,0.08,0.10,0.12,0.14和0.16)的红色荧光粉。X射线衍射表明,样品具有标准的Ca10K(PO4)7六角晶体结构,且无第二相存在。在393nm的波长激发下,样品获得由Eu3+的4f-4f跃迁产生红光发射,其中以613nm附近的5 D0→7F2电偶极跃迁发射为最强。通过调节Eu3+的掺杂浓度,获得了色坐标与商业化Y2O2S:Eu3+荧光粉十分接近的接近纯色的红色荧光粉。Ca10K(PO4)7:Eu3+是一种可望应用于紫外激发的白光LED的红色荧光粉。     

Characterization and luminescence of Eu3+ ions doped 12CaO 7Al2O3 nanopowders

Eu3+ ions doped 12CaO 7Al2O3 (C12A7) powders with different Eu3+ concentrations were prepared by sol-gel combined with solid state reaction method. The results of XRD and Raman spectra showed that single cubic phase polycrystalline C12A7:Eu3+ powders were prepared. The absorption peaks attributed to f-f transition of Eu3+ ion can be observed, indicating that Eu3+ had been incorporated into C12A7 lattice site. Visible PL peaks around 578, 588, 614 nm were ascribed to 5D0 --> 7FJ (J = 0, 1, 2) transitions of Eu3+ under the excitation of 488 nm line. The PL of C12A7:Eu3+ showed the strongest emission intensity at Eu3+ concentration of 0.5 at%. Two different types of Eu3+ centers were identified by the two lines from 5D0 --> 7F0 transition emission. The doping mechanism of C12A7:Eu3+ might be attributed to Eu3+ ions substitution for two types of Ca2+ lattice sites in C12A7. The temperature dependent PL spectra of Eu-doped C12A7 were measured in the range from 100 to 300 K under the excitation of 488 nm laser line. The PL intensities as a function of temperature were well fitted by using a unified theoretical model, considering thermal activation and nonradiative energy transfer processes.     

Photoluminescence of CaxSr(1-x) (NbO3)2:Pr3+ (0 < or = x < or = 1) nanophosphors

Nanoparticles of CaxSr(1-x) (NbO3)2 doped with Pr3+ have been synthesized by sol-gel method. Particles have sizes in the range of 50-70 nm. The CaxSr(1-x) (NbO3)2:Pr3+ phosphors showed a white emission under the near-ultraviolet excitation (254 nm). There is a large photoluminescence enhancement of the CaxSr(1-x) (NbO3)2:Pr3+ phosphor samples when added with 0.5% KCl. X-ray diffraction (XRD), transmission electron microscope (TEM), photo luminescent (PL) analysis were utilized to characterize the CaxSr(1-x) (NbO3)2:Pr+ particles. The concentration quenching of the samples was discussed as well. The optical concentration and the calcination temperature were 0.8 mol% of Ca2+ and 900 degrees C for these phosphors, respectively, the possible mechanism was discussed. CaxSr(1-x) (NbO3)2:Pr3+ is a promising white phosphor under near-ultraviolet excitation for various applications.     

Visible upconversion emission of Pr3+ doped gadolinium gallium garnet nanocrystals

The luminescence properties of a Pr3+-doped gadolinium gallium garnet (GGG, Gd3Ga5O12) nanocrystalline host were investigated. Dominant blue/green emission was observed emanating from the 3P0 --> 3H4 transition after excitation using a wavelength of 457.9 nm. Continuous wave excitation into the 1D2 level of the Pr3+ ion at 606.9 nm transition produced blue upconversion luminescence spectra, ascribed to emission from the 3P1 --> 3H4 and 3P0 --> 3H4 transitions. The increase in the decay times of the observed transitions following excitation with 606.9 nm is indicative of the dominance of an energy transfer upconversion (ETU) mechanism relative to excited state absorption (ESA). Furthermore, blue, green and red upconversion emission was observed from the 3P0, 3P1 and 1D2 states following excitation into the 1G4 energy level with 980 nm. No change in the decay times of the emitting states was observed following excitation with a wavelength of 980 or 457.9 nm; hence, upconversion was determined to primarily occur through ESA. The luminescence properties of the nanocrystals are compared to a single crystal of GGG:Pr3+ (bulk) with an identical Pr3+ concentration (1%).     

Pr3+摩尔浓度对CaTiO3:Pr3+红色长余辉材料的影响

制备了不同Pr^3 摩尔浓度下的CaTiOs：Pr^3 红色长余辉材料，测量了磷光体的的初始亮度、余辉曲线、激发光谱和发射光谱、热释光曲线。研究发现CaTiO3：Pr^3 合适的Pr^3 摩尔浓度为0．1％—0．2％，在该摩尔浓度下，材料具有较好初始亮度和余辉时间。     

X射线荧光粉Gd2O2S:Pr,Ce的固相合成及发光性能研究

采用草酸铵共沉淀法实现在Gd2O3中掺杂Pr和Ce,以此为原料,硫粉为硫化剂,无水Na2CO3为助熔剂,1000℃真空固相合成了Gd2O2S:Pr和Gd2O2S:Pr,Ce粉末。采用XRD确认了反应产物为目标产物,制备的Gd2O2S:Pr为六方晶系单一相,粉末粒度分布1~10μm,在313 nm的紫外光激发下,主发射峰位于511 nm,属于Pr3+的3P0→3H4跃迁。主发射光强度随Pr3+的含量变化而改变,当Pr3+的含量在0.80%时主发射光强度最大。添加Ce3+可以明显降低Gd2O2S:Pr的荧光余辉,但同时也降低了发射光强度,Ce3+的添加量要在余辉控制,荧光光强和闪烁体使用寿命三者间平衡选择。     

Eu2+、Dy3+、Li+共掺杂CaSi2O2N2荧光粉的发光性能

采用高温固相反应法制备了一系列白光LED用CaSi2O2N2:0.05Eu2+,xDy3+,xLi+(0≤x≤0.03)荧光粉.利用X射线衍射仪对样品的物相结构进行了分析,结果表明:Dy3+和Li+离子的掺入没有改变CaSi2O2N2:Eu2+荧光粉的主晶相.利用荧光光谱仪对样品的发光性能进行了测试,发现所有样品的激发光谱均覆盖了从近紫外到蓝光的较宽范围,400 nm激发下得到的发射光谱为宽波段的单峰,峰值位于545 nm左右,是Eu2+离子5d-4f电子跃迁引起的.Dy3+离子掺杂可以提高CaSi2O2N2:Eu2+荧光粉的发光强度,Dy3+与Li+共掺杂可进一步提高荧光粉的发光强度,当Dy3+和Li+的掺杂量为1mol%时,荧光粉的发光强度达到最大值,是单掺杂Eu2+的荧光粉发光强度的157%.     

Preparation and visible emission of Er-doped 12CaO x 7Al2O3 powder

Er(3+)-doped 12CaO x 7Al2O3 (C12A7:Er3+) powders were prepared using the sol-gel method. X-ray diffraction, micro-Raman spectra and absorption spectra showed that C12A7:Er3+ powder had been obtained. Sharp and intense Er(3+)-related emission from C12A7:Er3+ powder with different Er3+ concentrations in the visible region at room temperature was investigated by analyzing the local structure of Ca atoms in C12A7, and it revealed that cation sites with low symmetry of the host were beneficial to the photoluminescence of Er3+ ions. The emission lines were attributed to two types of Er3+ centers, isolated Er3+ ions and complex centers formed by aggregation of Er3+ ions. The PL intensity might be affected by free oxygen species relative to Er3+ ions formed by charge compensation. The inverse temperature dependent luminescence from the upper level of 2H11/2 state and that from the lower level of 4S3/2 state implied that the thermalization or thermal equilibrium of electrons between the two closely emission states occurred.