一种新的橙红色长余辉荧光材料Y2O2S∶Sm3+

铜激活的硫化锌(ZnS∶Cu)和铕激活的硫化钙(CaS∶Eu)是最早获得应用的蓝色和红色长余辉材料. 随后, 相继发现了铝酸盐体系和硅酸盐体系两大类长余辉荧光材料[1～3]. 这两类长余辉荧光材料在发光亮度、余辉时间、稳定性方面都较前述硫化物系列长余辉荧光材料有很大提高, 从而具有非常广阔的应用前景和应用范围[4～6]. 但这两类长余辉荧光材料的发光颜色一般为蓝紫、蓝或黄绿, 没有红色发光现象. 随着研究的深入, 人们发现了稀土元素激活的碱土钛酸盐红色长余辉荧光材料, 这种荧光材料在发光亮度及余辉上都有明显的提高[7,8], 而且解决了硫化物不稳定的缺点. 近年来才发展起来的以碱土金属氧化物为发光基质, 以Eu3+为激活剂的红色长余辉荧光材料进一步提高了余辉亮度及时间[9].     

Eu3+在La2O2S中的长余辉发光

The new Eu³⁺ doped lanthanum oxysulfide phosphors,which have the orange-red long afterg low emission,were synthesized by solid-state reaction method.The synthesized phosphors were characterized by X-ray diffraction.The excitation and emission spectra,afterglow spectra and afterglow decay curves were examined.XRD confirmed the phosphor as pure phase La₂O₂S.The phosphors showed typical transitions ⁵D_J(J=0,1) → ⁷J_J(J=0,1,2,3,4)of Eu³⁺.The photoluminescence spectra and afterglow spectra presented the regular alteration with various Eu³⁺ concentration, due to cross relaxation between energy levels of Eu³⁺. In addition, we studied the effects of activator concentration and dopants species on the afterglow property. The data showed afterglow result was the best with 2 % Eu³⁺ and doped with Mg²⁺ and Zr⁴⁺. A prominent phosphorescence can be seen in this phosphor after illuminated with UV light.     

Er3+，Ho3+和Tm3+在硫氧化钆中的余辉发光

The new Er^3 , Ho^3 and Tm^3 doped gadolinium oxysulfide phosphors with the long afterglow emission were synthesized by solid-state reaction method. The synthesized phosphors were characterized by X-ray diffraction. The excitation and photolumineseenee spectra, afterglow spectra and afterglow decay curve were examined by fluorescence spectroscopy. The afterglow spectra of Gd2O2S:Er^3 , Mg, Ti showed typical transitions of Er^3 at 528(2H11/2→4I15/2), 548 (^4S3/2 →^4I15/2) and 669 nm (^4F9/2→^4I15/2). In the afterglow spectra of Gd2O2S: Ho^3 , Mg, Ti,typical transitions of Ho^3 at 546 nm (^5S2→^5I8), 651 and 661 nm (^2F5→^5I8) were observed. In Gd2O2S:Tm^3 , Mg,Ti, the afterglow emission at 800 nm (^1G4→^3H5) of Tm^3 was seen. The meehnism and model of afterglow energy transfer were proposed.     

Er~(3 ),Ho~(3 )和Tm~(3 )在硫氧化钆中的余辉发光

非放射性长余辉磷光粉作为美化和清洁光源在发光陶瓷、交通安全标志、紧急突发事件的照明设施、工艺美术涂料等众多领域得到越来越广泛的应用,引起人们的重视.到目前为止,文献报道的稀土长余辉磷光体的激活离子主要有铕离子(Eu3+和Eu2+[1-4]、三价铈离子(Ce3+)[5]、三价铽离子(Tb3+)[6]、三价镨离子(Pr3+)[7]、三价钐离子(Sm3+)[8].Ho3+,Er3+,Tm3+等稀土离子作为红外上转换发光材料的激活离子[9～12],而关于它们的长余辉发光的报道极少.最近,雷炳富等在Tm3+离子[13]激活的硫氧化钇体系中发现了长余辉发光.在此,我们通过高温固相法合成了Er3+,Ho3+和Tm3+掺杂的硫氧化钆长余辉磷光粉,观察到该体系中迄今未见文献报道的Er3+,Ho3+和Tm3+离子的长余辉发光.     

新型长余辉发光材料SrMgSi2O6:Eu2+,Ln3+的制备及性质

采用凝胶-燃烧法合成了系列稀土离子掺杂的Sr0.94MgSi2O6:Eu0.022+,Ln0.043+(Ln=La,Ce,Nd,Sm,Gd,Dy)蓝色长余辉发光材料,用X射线粉末衍射(XRD)、扫描电镜(SEM)、荧光分光光度计等对合成产物进行了分析和表征.结果表明:掺杂了不同稀土离子的SrMgSi2O6:Eu2+,La3+的晶体结构均为网方品系结构;其激发、发射光谱的峰形、峰位基本无变化,激发光谱为一宽带,最大激发峰位于400 nm处,次激发峰佗于415 nm处,发射光谱也为一宽带,最大发射峰位于470 nm附近,是典型的Eu2+的4F5d_4f跃迁导致的,不同之处在于其激发光谱、发射光谱强度及余辉性质有所差别,其中Dy3+是最理想的共掺杂稀土离子,Sr0.94MgSi2O6:Eu0.022+Dy0.043+的余辉时间最长,可达4 h;而Sm3+最差,Sr0.94MgSi2O6:Eu0.022+,Sm0.043+的余辉亮度最低,余辉时间最短.     

长余辉发光材料研究进展

90年代发现和发展起来的铝酸盐体系长余辉发光材料是一类重要的新 型能源材料和节能材料。本文主要综述了最近几年来铝酸盐体系中长人科辉发光研究进展。指出了氧化物体系长余辉发光材料的特点和优势,总结了新型长余辉发光材料的基质和激活剂种类、性质及其对稀土 离子 长余辉发光性能的影响和作用,概括了长余辉发光模型,并提出了今后研究和应用的发展方向。     

ZnO-B2O3∶Tb3+长余辉玻璃的发光性质

通过还原方法制备了Tb3+离子掺杂的硼酸锌玻璃,并观察到在254 nm紫外光激发后有明亮的绿色长余辉发光现象,余辉时间达6 h.通过激发与发射光谱、余辉光谱、余辉衰减曲线、热释光谱、热释光释出速率衰减曲线等得到的信息,研究了Tb3+离子掺杂的硼酸锌玻璃的发光性质.     

水热法合成Sr4Al14O25:Eu2+,Dy3+长余辉发光材料及性能研究

采用水热法制备了均匀分散的前驱体,然后通过煅烧获得蓝绿色Sr4 Al14O25:Eu2+,Dy3+长余辉发光材料.在制备前躯体过程中,分别用NH3·H2O和NH4HCO3作为沉淀剂,研究了其对最终发光材料的结构和性能的影响.结果表明,用氨水做沉淀剂最终合成的发光粉为物相较纯的Sr4 Al14O25相,粒径小,分散性好,发光强度高,余辉衰减时间长.     

溶剂热合成纳米球状La2O2S:Eu3+荧光粉

Eu3+离子激活的硫氧化物荧光粉是目前国内外广泛使用的CRT红色发光材料[1]. 它具有色纯度高、色彩不失真、亮度-电流饱和度特性好和稳定性高等特性, 已成为CRT不可替代的红色荧光粉. 此外, 掺杂或不掺杂Eu3+的硫氧化镧是还原SO2有害气体为S单质的优良催化剂[2,3]. 近年来兴起的纳米材料是有可能在本世纪得到广泛应用的材料; 掺杂稀土离子的硫氧化物有望应用于各种显示技术及催化剂中. 最近, 吴长峰等[4]在Y2O3∶Eu3+纳米管中观察到发射峰展宽等特性. 因而, 研究Eu3+离子激活的硫氧化镧纳米荧光粉是很有意义的.     

A template-free solvothermal synthesis and photoluminescence properties of multicolor Gd2O2S:xTb3+, yEu3+ hollow spheres

The multicolor Gd₂O₂S:xTb³⁺, yEu³⁺ hollow spheres were successfully synthesized via a template-free solvothermal route without the use of surfactant from commercially available Ln (NO₃)₃·6H₂O (Ln = Gd, Tb and Eu), absolute ethanol, ethanediamine and sublimed sulfur as the starting materials. The phase, structure, particle morphology and photoluminescence (PL) properties of the as-obtained products were investigated by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM) and photoluminescence spectra. The influence of synthetic time on phase, structure and morphology was systematically investigated and discussed. The possible formation mechanism depending on synthetic time t for the Gd₂O₂S phase has been presented. These results demonstrate that the Gd₂O₂S hollow spheres could be obtained under optimal condition, namely solvothermal temperature T = 220 °C and synthetic time t = 16 h. The as-obtained Gd₂O₂S sample possesses hollow sphere structure, which has a typical size of about 2.5 μm in diameter and about 0.5 μm in shell thickness. PL spectroscopy reveals that the strongest emission peak for the Gd₂O₂S:xTb³⁺ and the Gd₂O₂S:yEu³⁺ samples is located at 545 nm and 628 nm, corresponding to ⁵D₄→⁷F₅ transitions of Tb³⁺ ions and ⁵D₀→⁷F₂ transitions of Eu³⁺ ions, respectively. The quenching concentration of Tb³⁺ ions and Eu³⁺ ions is 7%. In the case of Tb³⁺ and Eu³⁺ co-doped samples, when the concentration of Tb³⁺ or Eu³⁺ ions is 7%, the optimum concentration of Eu³⁺ or Tb³⁺ ions is determined to be 1%. Under 254 nm ultraviolet (UV) light excitation, the Gd₂O₂S:7%Tb³⁺, the Gd₂O₂S:7%Tb³⁺,1%Eu³⁺ and the Gd₂O₂S:7%Eu³⁺ samples give green, yellow and red light emissions, respectively. And the corresponding CIE coordinates vary from (0.3513, 0.5615), (0.4120, 0.4588) to (0.5868, 0.3023), which is also well consistent with their luminous photographs.     

Cd2Ge7O16中Tb的长余辉发光特性

本文研究了Cd₂Ge₇O₁₆∶Tb³⁺材料的发光及其长余辉性质。指出Tb³⁺的发光是该离子的 ⁵D₃- ⁷D_J、 ⁵D₄- ⁷D_J两种跃迁产生的；随着掺杂浓度的增加 ⁵D₄- ⁷D_J跃迁增强，发光颜色由蓝变绿。并把该材料的长余辉性质归结为基质结构中有电子陷阱和空穴陷阱。提出余辉机理模型。     

N263和TBP为协同流动载体的液膜体系分离钐(Ⅲ)和钆(Ⅲ)的研究

研究了N263和TBP为协同载体的液膜体系分离钐和钆的行为.考察了膜相添加剂、内水相反萃剂、外水相盐析剂和膜相中载体浓度对传质分离的影响.当用TBP作为膜相添加剂时,N263能很好地溶解在煤油中.N263-TBP-LMA-1-煤油和NH₄NO₃协同流动载体液膜体系在迁移稀土离子时表现出"倒序"特性,与单纯的N263体系相比,该体系对钐、钆具有较高的选择性.     

纳米棒状MAl2O4:Eu2+, Dy3+(M=Sr, Ba)长余辉发光材料的制备与性能

利用硝酸铝、硝酸锶/硝酸钡、尿素为原料,以一定比例H2O/正丁醇/CTAB的混合液作传递压力的介质进行反应,然后将得到的前驱体在还原气氛下高温煅烧,得到亮度高、余辉时间长的MAl2O4∶Eu^2＋,Dy^3＋纳米结构长余辉发光材料。TEM测试表明,高温煅烧后得到的MAl2O4∶Eu^2＋,Dy^3＋均为棒状结构,其激发光谱和发射光谱均为宽带,主发射峰分别为513和498 nm,是典型的Eu^2＋5d→4f跃迁。在对单掺Eu^2＋与双掺Eu^2＋,Dy^3＋比较的过程中,明显发现双掺Eu^2＋和Dy^3＋的强度增加,且余辉增强。材料的余辉强度随时间的变化由最初的快减过程和随后的慢减过程组成,符合I=t^-1.1双曲线规律。该方法操作简单,在不同的温度和时间下均合成出了棒状MAl2O4∶Eu^2＋,Dy^3＋,不需球磨,可直接应用。     

萃取色谱分离—原子发射光谱测定氧化钐,氧化铕,氧化钆中14个稀土杂质

用２－乙基己基膦酸单２－乙基己酯萃取色谱分离－原子发射光谱测定超高纯Ｓｍ２Ｏ３、Ｅｕ２Ｏ３、Ｇｄ２Ｏ３中痕量稀土杂质，可用于纯度为９９９９９９％～９９９９９９９％（不含非稀土杂质）Ｓｍ２Ｏ３、Ｅｕ２Ｏ３、Ｇｄ２Ｏ３的纯度分析，１４个稀土杂质的回收率在６７％～１３３％之间，相对标准偏差±６４％～±１８４％，分离周期１０～１４ｈ。     

共掺La3+对Sr2SnO4∶Sm3+的余辉增强

研究了以La3+离子为辅助激活剂,对Sm3+掺杂的发光材料Sr2SnO4:Sm3+余辉性能的影响。采用传统的高温固相法合成Sr2SnO4∶Sm3+,La3+红色长余辉发光材料。利用X射线粉末衍射仪、荧光光谱仪、热释光剂量仪等手段对粉末样品进行了表征。分析结果表明,在1400℃得到了单相Sr2SnO4,Sr2SnO4∶Sm3+,La3+发光粉末有563、599和646 nm 3个发射峰,与Sm3+单掺杂的Sr2SnO4∶Sm3+相比,其光谱发射峰位没有明显变化。余辉亮度衰减曲线表明适量的La3+掺杂可以延长Sr2SnO4∶Sm3+的余辉时间。通过对热释光谱的分析,解释了双掺杂发光粉余辉性能增强的原因,La3+掺杂增加了更多适宜深度的陷阱(VSr″),可以有效存储光能,增强余辉的时间和强度。