燃烧法合成Ln_2O_2S∶RE~(3+)(Ln=Gd,La;RE=Eu,Tb)X射线荧光粉及发光性能

采用燃烧合成法,以稀土硝酸盐和二硫代乙二酰胺为反应物,通过控制两者的摩尔比例,在点燃温度为300 ~350℃时,制备了掺杂不同浓度稀土激活剂离子的硫氧化物X射线荧光粉。分别以X射线衍射(XRD)、扫描电子显微镜(SEM)、光致发光(PL)光谱及X射线激发的发光(XEL)光谱对样品进行了表征。XRD分析表明,当热处理温度低于500℃时,可得到单一相的硫氧化物X射线荧光粉,这就避免了高温烧结的缺点;而当烧结温度较高时,开始有硫酸氧化物出现。从SEM图像中可以看到荧光粉粉末具有疏松和多孔连续的三维的网络块状结构,但其初级粒子尺寸较小,均小于50nm,这在一定程度上,可以提高成像系统的空间分辨率。PL光谱分析表明,所制备的荧光粉样品分别呈现出Eu3+,Tb3+离子的特征发射。XEL光谱结果表明,尽管它与光致发光的激发原理不一样,但同样呈现出Eu3+,Tb3+离子的特征发射;这些样品本身对X射线的吸收系数及掺杂浓度不一样,因此它们的光发射效率也有所差别。     

水热法合成ZnS∶Au,Cu超细X射线发光粉

报道了水热法合成的高强度ZnS∶Au,Cu超细X射线发光粉及其光致发光(PL)和X射线激发发光(XEL)的光谱特性。200℃水热处理12h直接合成样品的纳米晶粒约15nm,尺寸分布窄,分散性好,具有纯立方相的类球形结构。氩气保护下1000℃焙烧1h后的样品存在一定的团聚,但团聚后尺寸为1～2μm,为超细X射线发光粉,此时样品为纯六角相的类球形为主的结构。所有样品的PL和XEL光谱均为宽带谱,水热法直接合成样品的XEL强度最强时,样品的Cu/Zn,Au/Cu比值分别为3×10-5和2。在此比值条件下,1000℃焙烧1h样品的XEL发光最强,此时其2个峰值分别位于445和513nm,且与未焙烧前相比强度增强了10倍左右。另外通过比较PL光谱与XEL光谱特性,讨论了PL和XEL光谱的发光机理和其不同的激发机制。     

水热法合成ZnS:Au,Cu超细X射线发光粉

报道了水热法合成的高强度ZnS:Au,Cu超细X射线发光粉及其光致发光(PL)和X射线激发发光(XEL)的光谱特性.200℃水热处理12 h直接合成样品的纳米晶粒约15 nm,尺寸分布窄,分散性好,具有纯立方相的类球形结构.氩气保护下1000℃焙烧1 h后的样品存在一定的团聚,但团聚后尺寸为1～2μm,为超细X射线发光粉,此时样品为纯六角相的类球形为主的结构.所有样品的PL和XEL光谱均为宽带谱,水热法直接合成样品的XEL强度最强时,样品的Cu/Zn,Au/Cu比值分别为3×10-5和2.在此比值条件下,1000℃焙烧1h样品的XEL发光最强,此时其2个峰值分别位于445和513 nm,且与未焙烧前相比强度增强了10倍左右.另外通过比较PL光谱与XEL光谱特性,讨论了PL和XEL光谱的发光机理和其不同的激发机制.     

Eu^3+激活氟氧硼酸锗酸盐闪烁玻璃的发光性能

采用传统高温熔融法合成了玻璃组成为B2O3-GeO2-15GdF3-(40-x)Gd2O3-xEu2O3(0≤x≤10)的Eu^3+激活氟氧硼酸锗酸盐闪烁玻璃。在硼锗酸盐玻璃基质中,Gd2O3和GdF3稀土试剂的总含量高达55%,从而确保其密度高于6.4 g/cm^3。闪烁玻璃的光学性能通过光学透过光谱、光致发光光谱、X射线激发发射(XEL)光谱和荧光衰减曲线来表征。玻璃中Gd^3+→Eu^3+离子的能量传递通过激发光谱、发射光谱和Gd^3+-Eu^3+离子间距得到证明,同时也确定了在紫外线和X射线激发下Eu^3+激活氟氧硼酸锗酸盐闪烁玻璃的最佳浓度。Judd-Ofelt理论分析了玻璃中Eu―O键的共价性随Eu^3+掺杂浓度增加而显著增强。Eu^3+激活氟氧硼酸锗酸盐闪烁玻璃在80~470 K温度范围内荧光衰减曲线和发射光谱的温度依赖关系最终证实了其具有较好的发光稳定性。     

水热法制备ZnS:Cu,Tm超细X射线发光粉

研究了水热法合成的ZnS: Cu,Tm超细X射线发光粉及其光致发光(PL)和X射线激发发光(X-ray excited luminescence,XEL)光谱特性.200 ℃水热处理12 h直接合成样品的纳米晶粒径约15 nm,尺寸分布窄,分散性好,具有纯立方相的类球形结构.氩气保护下900 ℃退火1 h后的样品存在一定的团聚,但团聚后尺寸为200—600 nm,为超细X射线发光粉,此时样品为纯六方相的类球形为主的结构.所有样品的PL和XEL光谱均为宽带谱.水热法直接合成样品的XEL强度最强时,样品的Cu/Zn,Tm/Cu比值分别为3×10^-4和2.在此比值条件下,900 ℃退火1 h样品的XEL发光最强,此时其两个峰值分别位于453,525 nm.发光强度增强的同时粒径很小,对提高成像系统分辨率非常有意义.通过比较PL光谱与XEL光谱特性,讨论了PL和XEL光谱的发光机理和其不同的激发机理. 关键词： ZnS:Cu Tm 水热法 X射线激发发光     

稀土离子掺杂CaY_(1-x)AlO_4:xRE~(3+)(RE=Dy,Ho,Sm,Tm)荧光材料的发光性能

采用溶胶凝胶法合成稀土离子掺杂Ca Y_(1-x)Al O_4∶xRE~(3+)(RE=Dy,Ho,Sm,Tm)荧光粉。采用X射线粉末衍射仪(XRD)、高分辨率透射电镜(TEM)和荧光分光光度计(PL)分别对荧光粉的物相结构、形貌以及荧光性能进行表征。研究结果表明,所合成样品为四方晶系结构的纳米级材料,在紫外光激发下,掺杂离子均表现出特征的f-f电子跃迁发射,当Dy~(3+)、Ho~(3+)、Sm~(3+)和Tm~(3+)的掺杂摩尔分数分别为0.03,0.015,0.015,0.02时,样品发光强度最大,分别发射出白光、绿光、橙光和蓝光。     

Eu3+掺杂MMoO4(M=Ca,Sr)荧光粉的表征及发光性质

本文采用简易的Pechini方法制备了Eu3+掺杂MMoO4(M=Ca,Sr)红色荧光粉.产物的结构、形貌和性质分别通过X射线衍射(XRD)、扫描电子显微镜(SEM)、光致发光发射谱(PL)和激发谱(PLE)进行表征分析.XRD表明反应得到了纯相目标掺杂产物,SEM照片显示两种体系掺杂产物形貌均匀性不同,Eu3+掺杂C...     

稀土离子掺杂LaAlO3:RE3+(RE=Eu,Tb,Sm,Tm)荧光粉的发光性能

采用溶胶凝胶法合成La_1-xAlO₃：xRE³⁺（RE=Eu，Tb，Sm，Tm）荧光粉，对样品进行热重差热（TGA-DTA）、X射线粉末衍射（XRD）、透射电镜（TEM）以及荧光光谱（PL）等表征，探讨样品的合成温度及稀土离子掺杂浓度对样品发光性能的影响。研究结果表明，当煅烧温度为800~1 200℃时，所合成样品为三方晶体结构。在紫外光激发下，掺杂离子均表现出特征的f-f电子跃迁发射，在一定掺杂浓度范围内，当Eu³⁺、Tb³⁺、Sm³⁺和Tm³⁺的掺杂浓度x值分别为0.02，0.04，0.005和0.005时，样品发光强度最大，在一定波长激发下，样品分别发射出红光、绿光、橙黄光和蓝光，Eu³⁺-Tb³⁺、Eu³⁺-Sm³⁺和Eu³⁺-Tm³⁺共掺杂有可能获得白光。     

ZnO∶Eu3^＋纳米晶的制备及发光性质研究

为了探讨稀土Eu^3＋与纳米ZnO基质之间的能量传递,利用溶胶-凝胶法（Sol-Gel）制备了ZnO∶Eu^3＋纳米晶,测量了样品的X射线衍射谱（XRD）、光致发光谱（PL）和激发谱（PLE）。X射线衍射结果表明,ZnO∶Eu^3＋具有六角纤锌矿晶体结构。观察到稀土Eu^3＋强而窄的特征发射和ZnO基质弱而宽的可见发射。分析了稀土Eu^3＋激发态5^D0→7^F1,5^D0→7^F3和5^D0→7^F2特征发射机制。给出了Eu^3＋离子特征发射的峰值强度随掺Eu^3＋浓度增加而增强的变化关系,证实了纳米ZnO基质与稀土Eu^3＋离子之间存在能量传递。比较了Eu^3＋离子5^D0→7^F1磁偶极跃迁（MD）与5^D0→7^F2电偶极跃迁（ED）的相对强度,证实了在ZnO纳米晶基质中大多数Eu^3＋占据了对称性较低的格位。     

CaZrO_3∶Ln(Ln=Pr~(3+),Sm~(3+),Tb~(3+),Dy~(3+),Tm~(3+))荧光粉的制备与光谱调控

采用高温固相法合成了稀土离子Pr3+、Sm3+、Tb3+、Dy3+、Tm3+掺杂的正交相CaZrO3荧光粉。利用X射线粉末衍射(XRD)对样品的结构进行表征,并通过荧光光谱对其发光性质进行了研究。在适当近紫外或蓝光激发下,CaZrO3∶Pr3+产生很强的绿光发射,CaZrO3∶Sm3+可发射550~700 nm的红橙光,Tm3+在CaZrO3中可获得良好的蓝光发射。研究结果表明,通过改变CaZrO3中的掺杂离子可实现其发光颜色的调控,稀土离子掺杂CaZrO3荧光粉是很有潜力的新型发光材料。     

Thermoluminescent properties of Eu and RE co-doped phosphors CaGa2S4:Eu, RE (RE=Ln, excluding Pm, Eu and Lu)

The thermo-luminescence (TL) of rare earth ions RE³⁺ (RE=Ln, excluding Pm, Eu and Lu) co-doped phosphors CaGa₂S₄:Eu²⁺, RE³⁺ was studied between room temperature and 300 °C, and 3D thermo-luminescence of the phosphors were measured from room temperature to 400 °C. The basic material CaGa₂S₄:Eu²⁺, showed at least two bands in the TL glow curve. Changing the auxiliary activator RE³⁺ (rare earth ion), intensities and the positions of the TL glow curve peaks were affected significantly. For the phosphors with long afterglow, auxiliary activator such as Ce³⁺, Pr³⁺, Gd³⁺, Tb³⁺, Ho³⁺, or Y³⁺ created some new defects in these compounds at lower trap levels and enhanced their TL intensities. The Nd³⁺ or Er³⁺ auxiliary activator only enhanced TL intensities to a low extent, so these two phosphors have short persistent luminescence at room temperature. TL intensities of La³⁺, Sm³⁺, Tm³⁺ or Yb³⁺ co-doped phosphors were suppressed greatly and no afterglow was shown. The relationship between auxiliary activators and corresponding thermo-luminescence curves of phosphors CaGa₂S₄:Eu²⁺, RE³⁺ are discussed in detail. According to our results, suitable activation energy and enough high corresponding trap density are necessary for the phosphor with long afterglow.     

Influence of co-doping different rare earth ions on CaGa2S4: Eu, RE(RE=Ln) phosphors

Photoluminescent phosphors CaGa₂S₄: Eu²⁺, RE³⁺ (RE³⁺ including all rare earth ions except for Sc³⁺, Pm³⁺, Eu³⁺ and Lu³⁺) were prepared by sintering at high temperature in a reductive atmosphere, and their luminescent properties were studied intensively. The influences of co-doping rare earth ions on their luminescent properties were also investigated. No remarkable differences were found from excitation spectra of co-doped phosphors CaGa₂S₄: Eu²⁺, RE³⁺ in contrast with that of phosphor CaGa₂S₄: Eu²⁺, but there were a few differences in emission spectra of Ce³⁺, Pr³⁺ or Ho³⁺ co-doped phosphors. Phosphors CaGa₂S₄: Eu²⁺, RE³⁺ (RE=Ce, Pr, Gd, Tb, Ho and Y) had persistent afterglow, and very short afterglow was shown for Nd³⁺ or Er³⁺ co-doped phosphors, but no long afterglow appeared when auxiliary activator was La³⁺, Sm³⁺, Dy³⁺, Tm³⁺ or Yb³⁺. Among the phosphors with long-lasting phosphorescence, in our experiments, CaGa₂S₄: Eu²⁺, Ho³⁺ had the longest and the highest brightness long yellow afterglow. Thermo-luminescence of all co-doped phosphors was measured to find the answer of different influences from different rare earth auxiliary activators.     

Local Disorder in Ln2Ti2O7 (Ln = Gd,Tb, Dy) Pyrochlores

JETP Letters - The orientational dynamics in the isotropic phase of a comb-like nematic polymer with mesogenic and functional side groups is studied using the Kerr effect and dielectric...     

Heat capacity of Ln 2Cu2O5 (Ln = Tb-Lu) cuprates

The correlation between the heat capacity of heavy lanthanide cuprates and the specific features of their structure has been analyzed. It has been shown that the heat capacity regularly changes depending on the Ln ³⁺ ion radius and the global instability index (GII) within the limits of corresponding tetrads (Tb-Ho, Er-Lu).     

Heat capacity of Ln 2CuO4 (Ln = La-Gd) cuprates

The correlation between the heat capacity of light lanthanide cuprates and the specific features of their structure has been analyzed. It has been shown that the specific heat of La-Gd oxides and cuprates changes regularly depending on the Ln ³⁺ ionic radius within the first and second tetrads (La-Nd, Pm-Gd).     

High temperature perturbed angular correlation studies of Ln2NiO4 + δ Ln=La,Pr,Nd

High temperature measurements on Ln₂NiO_4?+?δ (Ln=La, Pr, Nd) have been performed indicating a complex behavior in PAC experiments which can be attributed to fluctuating electric field gradients caused by the high mobility of excess oxygen.     

Photocatalytic properties of lanthanide tungstates Ln2W2O9 (Ln=La,Pr, Nd,Sm, and Gd)

Lanthanide tungstates, Ln₂W₂O₉ (Ln=La, Pr, Nd, Sm, and Gd), were prepared via the polymerized complex method at 1273 K for 2 h, and their photocatalytic activities for hydrogen and oxygen evolution were investigated. Pt-loaded Gd₂W₂O₉ exhibited activity for H₂ evolution from an aqueous methanol solution under light irradiation (λ>300 nm). The remaining Ln₂W₂O₉ were inactive for H₂ evolution due to the influence of the Ln elements and their crystal structures. All Ln₂W₂O₉ were inactive for O₂ evolution from an aqueous AgNO₃ solution due to the lack of O₂ evolution sites on the surface.     

Mössbauer study of amorphous Fe2RE (RE=Ce,Er) alloys

Among amorphous Fe₂RE (RE=Er, Ce, Gd, La, Pr, Sm, Dy, Ho) alloys, Fe₂Ce exhibits a tendency toward short range order, while the other Fe₂RE compounds show clustering. However, we have almost no information about environments around Fe atoms. Using Mössbauer spectroscopy we have determined the quadrupole splitting distributionsP(QS) of two representative amorphous Fe₂RE (RE=Ce, Er) alloys, leading to local environments of Fe atoms. The analysis of the mixed magnetic dipole and quadrupole interactions in Fe₂Er shows two kinds of electrical field gradients (EFT) with the positive and negative signs in the sample, indicating a random packing of Fe atoms. Furthermore, the analyzed quadrupole splitting distributionP(QS) of Fe₂Er also supports random packing in this amorphous alloy. On the other hand, the amorphous Fe₂Ce alloy shows two kinds of distributions of quadrupole splitting; the major component indicating random packing and the minor component Ce-rich Ce-Fe clusters.     

RE2O3 (RE = Lu, Y, Sc)的氧空位第一性原理计算研究

本研究选择三个电子结构类似的稀土倍半氧化物RE₂O₃(RE=Lu, Y,Sc),建立适当的模型通过第一性原理计算,研究氧空位对体系的电子结构的影响.本研究以密度泛函理论(DFT)为基础,利用PBE泛函加U值修正计算了纯稀土倍半氧化物的能带结构.计算结果表明三种基体材料RE₂O₃的能带结构相似.在引入氧空位后,其增加的缺陷能级数目不同,依次为:Sc₂O₃2O₃2O₃.     

Synthesis,crystal structure,and luminescence properties of CaY2Ge3O10:Ln3+, Ln = Eu,Tb

The crystal structure and luminescence properties of CaY₂Ge₃O₁₀:Ln³⁺ (Ln = Eu, Tb) germanates synthesized via a conventional solid-state reaction and an ethylenediaminetetraacetic acid complexing process are studied. The CaY_{2 ? x} Ln _x Ge₃O₁₀ (Ln = Eu, Tb; x = 0–1.0, 2.0; Δx = 0.1) solid solutions have a monoclinic structure (space group P2₁/c, Z = 4), in which dopant ions occupy three nonequivalent noncentrosymmetric sites with different Ca²⁺/Ln³⁺ ratios. The effect of the synthesis methods, dopant concentrations, and excitation wavelengths on the luminescence properties of the compounds obtained is determined.