严懋勋实验室与长余辉荧光材料

美国乔治亚大学(University of Georgia,UGA)物理系严懋勋(W. M. Yen)教授在他的后期工作中,主要从事长余辉荧光材料的基础研究和实际应用研究.在这些工作中,他起着组织、领导和支持的作用.因为他的倡导,长余辉荧光材料的研究在美国佐治亚大学取得很多成果.尤其是在长余辉的基础研究中,对长余辉基理的阐述,为长余辉材料的开发奠定了指导思想.作者在本文中将以记述的方式仅对其中一些主要成果加以介绍,并以此文表达对严懋勋教授的怀念.     

稀土离子激活长余辉发光材料的最新研究进展

长余辉发光材料是一种新型储能材料。评述了基质组成和制备技术对长余辉发光材料发光特性的影响;介绍了黄绿光、蓝光和红光长余辉材料的最新研究进展和获得长余辉发光的关键因素,即结构缺陷形成的陷阱态和稀土掺杂的作用,并对长余辉发光材料今后的研究和应用做出了展望。     

热释光谱研究长余辉发光材料的陷阱能级

介绍了热释光剂量计和热释光的基本原理。通过测量长余辉发光材料的热释光谱,并采用一阶动力学近似,可以量化分析长余辉发光材料中的陷阱能级的深度、电荷密度等参数,并可以讨论陷阱能级与长余辉性能的关系,深入理解长余辉过程。     

长余辉发光玻璃研究进展

介绍了长余辉发光玻璃的研究历程与进展，从长余辉发光玻璃的发展过程、发光机理、制备方法和发展现状等方面进行了分析，并对长余辉发光玻璃研究中存在的一些问题和发展方向提出了一些见解。     

长余辉发光材料研究进展

自从20世纪初发现长余辉现象以来，长余辉材料的发展取得了长足进展。从长余辉现象的发现到20世纪90年代，性能最好的长余辉材料为金属硫化物体系长余辉材料。从1992年起，新型铝酸盐长余辉材料的发展十分迅速，它的发光强度、发光时间、化学稳定性都较第一代长余辉材料有很大改进，长余辉材料的发展进入了一个新的阶段。在铝酸盐体系实现了蓝紫、蓝绿、黄绿、黄橙色发光，其中的蓝绿、黄绿两种长余辉材料是目前发光性能最好的长余辉材料。在硅酸盐体系蓝色长余辉材料发光强度及发光时间大大超过铝酸盐体系蓝紫色长余辉材料，是另一类极有前途的新型长余辉材料。红色长余辉材料的发展也取得了很大进步，目前在多个体系实现了红色自发光。性能最好的红色长余辉材料发光亮度达到CaS类红色长余辉材料的6倍以上，余辉时间达6-8小时。长余辉材料的应用研究也进展迅速。     

用单光子计数系统测量长余辉材料的发光

本文介绍了单光子计数技术的基本原理,并通过对长余辉发光材料余辉衰减的测量,说明了单光子计数在精确测量弱光衰减过程中的优点。     

Pr3+掺杂红色长余辉发光材料研究进展

Pr3+掺杂长余辉发光材料因其稳定高效的红色持久性发光而备受关注.近年来,Pr3+掺杂红色长余辉发光材料的基础研究和应用探索均取得了长足的进步.本文总结了Pr3+离子发光特性与电荷迁移带位置的关系,概述了最近报道的发光材料体系,讨论了余辉性能的优化途径,介绍了相关材料在信息加密、交流发光二极管(AC-LED)、生物成像...     

光学材料 发光材料、荧光材料

O482.312006010707长余辉材料的研究进展=Research progress in long per-sistence phosphors[刊,中]/赵军武(西安交通大学理学院.陕西,西安(710049)),齐晓霞∥半导体光电.—2005,26(4).—267-273系统地介绍了长余辉材料的发展历史、发光机理及常规制备方法。结合作者所做的工作及对近几年研究状况的对比分析,展望了长余辉材料的研究趋势和可能的应用前景。图4参32(杨妹清)O482.312006010708退火处理对ZnS∶Cu,Mn电致发光材料亮度的影响=Effect of annealing on brightness of ZnS∶Cu,Mn ACELmaterial[刊,中]/董国义(河北大学物理科…     

氧空位对Eu2+, Dy3+掺杂的Ca5MgSi3O12发光及余辉性能的影响

利用高温固相法合成了稀土离子Eu²⁺, Dy³⁺掺杂的Ca₅MgSi₃O₁₂长余辉发光材料. 利用光谱学证明了在材料内部存在与氧空位有关的缺陷发光. 通过对比不同条件下合成样品的发光及余辉性能, 发现氧空位对材料的发光及余辉均起到促进作用. 同时发现氧空位发光可以向发光中心传递能量. 利用热释光曲线系统的分析了氧空位对余辉性能的影响. Ca₅MgSi₃O₁₂:Eu²⁺,Dy³⁺是一种潜在的长余辉发光材料. 关键词： 长余辉 氧空位 能量传递 热释光     

上转换充能的动力学研究——以Mn2+掺杂的长余辉材料为例

无机长余辉材料是一种储能释光材料,其储能特性源于材料内部的电子或空穴陷阱在外界激发光作用下的填充..通过上转换激发的方式对长余辉材料充能是学者们在近几年提出的一种新颖的激发充能机制.这种两步离化的激发设计使长余辉材料的充能摆脱了高能离化光的限制,将充能激发波长扩展至可见光甚至红外光区,为长余辉技术在生物成像等领域的应用提供了原位激发的选择.目前,学者们对上转换充能的研究主要集中在材料的开发和激发路径的设计等方面,而对充能本身的物理过程知之甚少.本文通过构建分析上转换充能的速率方程,预测了激发辐照光对陷阱的光排空影响.在此基础上,选择450 nm激光激发的LaMgGa₁₁O₁₉:Mn²⁺长余辉材料体系为模板,分析了激发光剂量与材料热释光强度的函数关系,揭示了光辐照陷阱填充与光排空之间的动力学竞争.此外,相似的充能动力学规律也适用于其他具有上转换充能性质的长余辉材料.     

基于长余辉材料的激光书写和显示

本文给出了长余辉材料一个新的用途,研制了一台以长余辉材料为屏幕的激光书写显示装置,可以人为控制激光笔在余辉材料上随意书写文字、画图并显示.该装置利用单片机和步进电机控制两组轴镜在不同方向的转动,从自己建立的开源矢量图库中调用相关图片,使激光光束在长余辉材料上进行二维矢量的扫描,完成文字书写和绘图显示.用VASP(Vienna abinitio simulation package)软件计算出长余辉材料Mn(H_2PO_4)_2的能级结构,测试了SrAl_2O_4:Eu~(2+),Dy~(3+)和Mn(H_2PO_4)_2的余辉强度衰减曲线,便于调整样机电机的书写速度,测试了Mn(H_2PO_4)_2的反射谱和拉曼谱,其拉曼峰值在625,769和1049 nm及远红外.通过理论和实验研究,掌握了与相应长余辉材料匹配的激发最佳激光波段.制作样机后得到英文、中文、图像的实时书写和显示结果.本装置犹如一只无形的"笔"在纸上挥舞,流畅书写绘画,书写过程配上音乐颇具观赏性,该装置可应用于商业广告显示、动态标语书写、教学投影辅助设备、舞台效果、新型艺术表现形式等领域.     

长余辉发光材料的紫外-可见反射光谱测定

用“湿法”制备了长余辉发光材料,原料通过水溶液液相分子水平上的均匀混合,利用金属硝酸盐和有机还原剂在较低的温度下发生氧化还原燃烧反应,一步快速生成产品。加热起燃温度低至500℃,反应时间短,所制得的产品成份均匀,晶粒小,外观呈蓬松状态,易研磨粉碎,粉体表观密度小。以紫外－可见分光光度计测定分析了所制备样品在蓄光前后的反射光谱特征并作了探讨。结果表明,除表观密度外,“显法”与“干法”制备的长余辉发光材料的主要性质相同,紫外－可见反射光谱可以准确描述长余辉发光材料的紫外－可见光谱性能特征。     

绿色长余辉材料MgAl_2O_4∶Mn~(2+)的合成及其发光特性

采用高温固相法在1350℃下合成了Mn2+掺杂的MgAl2O4发光材料,利用X射线衍射对所合成样品的结构进行了表征。用209nm的紫外灯照射样品后,观察到来自Mn2+的4T1-6A1跃迁的绿色长余辉发光。发光的激发光谱表明:Mn2+-3d组态内存在一系列强的激发峰,分别在279,361,386,427,451nm,同时还有209nm处的Mn-O电荷迁移带,激发该吸收带会产生很强的绿色余辉。测量了余辉的衰减曲线及热释光谱,分析了Mn2+掺杂浓度对样品余辉性质的影响,给出了余辉产生的可能模型。     

Optical properties of rare earth doped strontium aluminate (SAO) phosphors: A review

After the first news on rare earth (RE) doped strontium aluminate (SAO) phosphors in late 1990s, researchers all over the world geared up to develop stable and efficient persistent phosphors. Scientists studied various features of long lasting phosphors (LLP) and tried to earmark appropriate mechanism. However, about two decades after the discovery of SrAl₂O₄: Eu²⁺, Dy³⁺, the number of persistent luminescent materials is not significant. In this review, we present an overview of the optical characteristics of RE doped SAO phosphors in terms of photoluminescence (PL), thermoluminescence (TL) and afterglow spectra. Also, we refresh the work undertaken to study diverse factors like dopant concentration, temperature, surface energy, role of activator, etc. Simultaneously, some of our important findings on SAO are reported and discussed in the end.     

Emission curves vs charging conditions in phosphorescent pigments embedded in sintered glass: Is there a reciprocity law?

Applications of phosphorescent materials are derived from their light emission properties at short and long times since the end of stimulation. The enhancement of such properties affects its performance in safety signs systems. Light emission power is conditioned by the time of excitation and the illumination received by the phosphorescent material, so that the total incoming energy is the product of both. For a given spectral profile, there is at least one upper limit of storable energy, resulting in effects of saturation for high values of illumination and excitation times. This work examines the emission curves of phosphorescent pigments embedded in sintered glass, in experiments where the total incoming energy is kept constant for combinations of illumination and time, in order to analyze the existence and the degree of reciprocity between these pairs. In addition, using a simple model we simulate some of the results obtained experimentally.     

Blue and red long lasting phosphorescence (LLP) in β-Zn3(PO4)2:Mn,Zr

Multi-color long lasting phosphorescent (LLP) phenomenon in β-Zn₃(PO₄)₂:Mn²⁺,Zr⁴⁺ was systematically investigated. It is found that the red (λ_Em=616 nm) LLP performance of Mn²⁺ such as brightness and duration is largely improved, and that the blue (λ_Em=475 nm) LLP of Zr⁴⁺ with lower intensity appears when Zr⁴⁺ ions are co-doped into the matrix. The fluorescence, phosphorescence and thermoluminescence (TL) spectra show that Mn²⁺ ion is solely expected as a luminescent center, while Zr⁴⁺ ion not only acts as a luminescent center, but also induces an electron trap (Trap_Zr) associated with a TL peak at 344 K. The trap depth for Trap_Zr is 0.25 eV, while that for the intrinsic trap is 0.38 eV, associated with a dominant peak at 385 K for Zn₃(PO₄)₂:Mn²⁺. The Zr⁴⁺-induced trap with suitable depth is responsible for the improvement of the red LLP of Mn²⁺ ion and the appearance of the blue LLP of Zr⁴⁺ ion. The LLP mechanism is also investigated.     

High-efficiency red phosphorescent electroluminescence devices based on mixed p/n host matrices

In this Letter, we demonstrate a way to control the charge carrier transport mechanisms in phosphorescent organic light-emitting devices based on the mixing of two p and n host materials in the emissive layer (EML). The matrices have been selected in order to fulfill the requirements of the energy level mismatch with the transporting and emitting materials. By using the mixed-host approach in combination with a phosphorescent red emitter, namely (1-phenylisoquinoline) iridium (III) [Ir(piq)(3)], maximum external and power efficiencies of 14.3% and 10 lm/W, respectively, have been achieved, with an average external efficiency value of 12% in the luminance range 100-10,000 cd/m(2).     

双极性主体材料9-phenyl-3-(phenylsulfonyl)-6-(triphenylsilyl)-9H-carbazole的合成及其光电性质

设计开发了一种新的双极性蓝色磷光主体材料,将其搭配Firpic应用于简单器件结构,通过调整器件中载流子传输层的厚度得到了比较满意的结果:最大电流效率40 cd/A,最大亮度19 691 cd/m²,最大流明效率12 lm/W。这一结果说明所开发的主体材料能够很好的平衡载流子的注入与传输能力,具有适宜的三线态能量和良好的热稳定性,是一种优良的蓝色磷光主体材料。     

Study of different roles phosphorescent material played in different positions of organic light emitting diodes

Phosphorescent materials are crucial to improve the luminescence and efficiency of organic light emitting diodes (OLED), because its internal quantum efficiency can reach 100%. So the studying of optical and electrical properties of phosphorescent materials is propitious for the further development of phosphorescent OLED. Phosphorescent materials were generally doped into different host materials as emitting components, not only played an important role in emitting light but also had a profound influence on carrier transport properties. We studied the optical and electrical properties of the blue 4,4′-bis(2,2-diphenylvinyl)-1,1′-biphenyl (DPVBi)-based devices, adding a common yellow phosphorescent material bis[2-(4-tert-butylphenyl)benzothiazolato-N,C2′] iridium(acetylacetonate) [(t-bt)₂Ir(acac)] in different positions. The results showed (t-bt)₂Ir(acac) has remarkable hole-trapping ability. Especially the ultrathin structure device, compared to the device without (t-bt)₂Ir(acac), had increased the luminance by about 60%, and the efficiency by about 97%. Then introduced thin 4,4′-bis(carbazol-9-yl)biphenyl (CBP) host layer between DPVBi and (t-bt)₂Ir(acac), and got devices with stable white color.