Tm3+掺杂SrAl2O4:Eu2+的光激励和热释光性能

通过高温固相法制备出Sr_{0.98-xAl2O4:0.02Eu²⁺,xTm³⁺(x=0,0.01,0.02,0.03,0.04,0.05)系列样品,并对其光激励和热释光性能进行了研究。在SrAl2O4:Eu²⁺原有陷阱能级结构的基础上,通过Tm³⁺的掺杂引入了更深的陷阱TB,并增加原有陷阱TA浓度,进而优化了材料的光存储容量及光激励特性。对比研究了系列样品的初始光激励发光强度和热释光强度随着Tm³⁺掺杂量的变化规律,证实陷阱TB为光激励发光提供了有效俘获中心。当Tm³⁺的掺杂摩尔分数x=0.03时,材料中的陷阱TB的浓度达到最高值,同时光激励发光强度最大。对比Tm³⁺共掺前后热释光图谱,通过Chen's半宽法计算出了引入陷阱TB的陷阱深度。实验结果证实材料中TB的浓度对其光激励发光性能起着决定性的作用。在980 nm激发下,由深陷阱TB释放出来的电子可以再次被浅陷阱TA俘获,这种浅陷阱TA的再俘获效应在光激励发光过程中表现为光激励余辉现象。}     

Luminescence centers in Sc2O3

Sc₂O₃ luminescence spectra are studied. The spectra are separated into elementary bands by the Alentsev–Fock method. It is established that the luminescence spectra consist of a number of overlapping bands with maxima at 3.5; 3.05; 2.65; 2.35, and 2.05 eV. The band at 3.5 eV is interpreted as emission of self-localized excitons, and the other bands, as defect-center recombination. L’vov State University, 50, Dragomanov St., L’vov, 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 776–778, November–December, 1997.     

Nonlinear Luminescence Quenching in Eu2O3

We report a laser spectroscopic investigation of saturation effects in the spectra and dynamics of Eu₂O₃. The saturation effects occur at high laser intensity and appear as dips in the center of the fluorescence excitation lines and as a shortening of the ⁵D₀ excited‐state decay curve. The saturation effects are observed in nanoparticles, micrometer‐sized particles, and a fused crystal of monoclinic‐phase Eu₂O₃ and in micrometer‐sized particles of cubic‐phase Eu₂O₃. We attribute the mechanism of the nonlinear luminescence quenching to upconversion by energy transfer.     

纳米Gd2O3中两种格位Eu3+的电荷迁移态激发跃迁

观测了粒径分别为15,23,135m的立方相Gd2O3：Eu^3 的选择激发光谱、发射光谱和激发光谱。受强量子限域效应的影响,纳米Gd2O3：Eu^3 的激发光谱的强度表现出对颗粒尺寸的明显依赖性。用Jorgensen公式计算电荷迁移带的位置,与实验测得激发光谱中位置相一致。通过电荷迁移带不同位置的选择激发光谱可以分辨出立方相Gd2O3：Eu^3 中C2和S6格位Eu^3 的发光,从选择激发的发射光谱和激发光谱结果计算出C2和S6格位电荷迁移带的激发光谱,与实验结果相符合。     

Luminescence spectroscopy and energy transfer in Eu2+/Mn2+-doped KCaPO4 phosphors

Eu²⁺/Mn²⁺-doped KCaPO₄ phosphors were prepared by conventional solid-state reaction. X-ray powder diffraction (XRD), SEM, photoluminescence excitation, and emission spectra, and the luminescence decay curves were measured. Mn²⁺ singly doped KCaPO₄ shows the weak origin-red luminescence band peaked at about 590 nm. The Eu²⁺/Mn²⁺ co-doped phosphors emit two distinctive luminescence bands: a blue one centered at 480 nm originating from Eu²⁺ ions and a broad red-emitting one peaked at 590 nm from Mn²⁺ ions. The luminescence intensity from Mn²⁺ ions can be greatly enhanced with the co-doping of Eu²⁺ ions. The efficient energy transfer from Eu²⁺ to Mn²⁺ was verified by the photoluminescence spectra together with the luminescence decay curves. The resonance-type energy transfer via a dipole–quadrupole interaction mechanism was supported by the decay lifetimes. The emission colors could be tuned by changing the Mn²⁺-doping concentration.     

Eu2+掺杂CaSi2O2N2荧光粉发光性能

采用固相反应法合成了组成为Ca_1-xEu_xSi₂O₂N₂的Eu²⁺掺杂CaSi₂O₂N₂荧光粉.通过荧光光谱对样品的发光性能进行了研究,发现Eu²⁺掺杂CaSi₂O₂N₂荧光粉发射光谱为宽波段的单峰结构,主要包含绿光和黄光区,发射峰在556~568 nm.从发射光谱的宽带特征来看,CaSi₂O₂N₂:Eu²⁺的发射主要对应着Eu²⁺离子4f⁶5d→4f⁷跃迁.从激发光谱所覆盖的范围还可以看到,样品可以有效的被UV蓝-光激发,这意味着该类荧光粉在白光LED方面有可能得到广泛的应用.另外,样品的发光性能与激发离子的浓度有着很大关系.激发离子浓度增大时,发射光谱会发生明显红移.利用这一性质,可以通过改变Eu²⁺浓度来调节荧光粉的发光范围,从而满足不同场合的需要.同时,Eu²⁺浓度提高,样品发射光谱的强度也会随之增强,在x=0.06时发射强度达到最大值,之后继续增加Eu²⁺浓度,强度不仅没有增加反而降低,即出现浓度猝灭现象.     

Eu2+在磷酸镧中的发光及Ce3+→Eu2+的能量传递

采用高温固相反应合成了LaPO₄:Eu²⁺和LaPO₄:Ce³⁺,Eu²⁺样品,报道了Eu²⁺在LaPO₄中的发光性质和Ce³⁺→Eu²⁺的能量传递现象。文中探讨了Ce³⁺→Eu²⁺的能量传递机理,根据Dexter电多极相互作用的理论证明其为偶极子偶极子相互作用的共振能量传递。     

Cd3Al2Ge3O12:Mn2+锗酸盐石榴石光谱性质

本文报道室温下Cd₃Al₂Ge₃O₁₂:Mn²⁺(简称CAGG:Mn²⁺)锗酸盐石榴石的漫反射光谱、激发和发射光谱.在UV光激发下,在CAGG中Mn²⁺离子发射强黄光,这是基质到Mn²⁺离子无辐射能量传递的结果.Mn²⁺的黄发射带是由一个弱的红带和一个强的绿带所组成.讨论了这两个Mn²⁺发射带的起因.     

Luminescence of Ln3+ and WO 2 2+ ions in wolframylphosphate glasses

We investigate the luminescent properties of potassium wolframylphosphate glasses doped with Eu³⁺, Tb³⁺, and Dy³⁺ ions whose luminescence is excited by donor-acceptor interaction between the active WO ₂ ²⁺ and Ln³⁺ ions, as well as the migration of energy in the subsystems of each type of the active ions. Comparison of the obtained data with the results of investigation of the spectroscopic properties of Ln³⁺ in uranylphosphate materials shows that a sufficiently high degree of the ionicity of bonds of Ln³⁺ with the atoms of its first coordination sphere is preserved in wolframylphosphate matrices. We show that three stages of the decomposition of electron excitations are typical of the WO ₂ ²⁺ ions in wolframylphosphate glasses doped with Ln³⁺ and two stages in nonactivated glasses. The electron excitation energy transfer in the WO ₂ ²⁺ −Ln³⁺ system occurs due to induction-resonance interaction. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 620–625, September–October, 1997.     

电子俘获光存储材料BaLiF3:Eu2+的光激励发光及光存储性质研究

利用高温固相反应法制备了混晶状的BaLiF3:Eu2 样品.其紫外光激发的发射峰与光激励发光峰均在410 nm处,属于Eu2 的5d-4f跃迁发光.光激励峰位于660 nm,因而可以配用简单廉价的氦氖激光器.根据光谱特征给出了光激励发光的简单机理.测量了该材料光激励发光衰减性能,结果表明BaLiF3:Eu2 存储的信息可以方便地擦除掉.该材料具有优良的光激励发光特性,是一类很有发展前途的电子俘获光存储材料.     

柠檬酸-凝胶法合成ZnGa2O4:Mn2+/Eu3+及其发光性能的研究

采用柠檬酸－凝胶法合成了纯的ZnGa2O4粉末以及ZnGa2O4:Mn^2 /Eu^3 粉末,利用X射线衍射（XRD）、热重及差热分析（TG－DTA）、发光光谱等测试手段对ZnGa2O4和ZnGa2O4:Mn^2 /Eu^3 的结晶过程、发光性质进行了研究。XRD结果表明,柠檬酸－凝胶法合成的样品在500℃。发光光谱测试表明ZnGa2O4:Mn^2 在450nm和506nm处出现两个发射带,前者属于ZnGa2O4基质的发射,后者属于Mn^2 的^4T1→^6A1的跃迁发射。ZnGa2O4:Eu^3 则呈现Eu^3 的特征红光发射,最强峰位于613nm,属于Eu^3 的^5D0→^7F2超灵敏跃迁。通过光谱分析进一步证实了ZnGa2O4:Mn^2 /Eu^3 的发光机理是基质敏化,吸收能量并向激活离子传递能量。     

SrGa2O4:Eu的合成及其发光性能

采用固相反应法合成了掺杂Eu3 离子的SrGa2O4,用X射线粉末衍射对其结构进行了表征。XRD数据经计算机处理表明:SrGa2O4属单斜晶系,晶胞参数a=0.943nm,b=0.900nm,c=0.839nm,β=89.06°,属P21/c(No.14)空间群。测定了激发光谱和发射光谱,光谱数据表明:SrGa2O4:Eu3 荧光粉的发射主峰在610nm,证明Eu3 离子占据了非反演对称中心的位置。在掺杂Eu3 离子摩尔分数大于1%时,由于晶体场的影响,位于590,610nm附近的2个发射峰均出现劈裂现象,即有2个5D0→7F1(586,597nm)和2个5D0→7F2(609,615nm)发射峰,7F2劈裂出两个分支的强度比例随Eu3 浓度的变化而变化。     

SrAl2O4：Eu2+的长余辉发光特性的研究

本文研究了SrAl2O4:Eu2+材料的发光及长余辉特性.首次得到了这一材料的发光衰减由初始的快衰减和后期的慢衰减过程所组成,以及热释发光光谱出现两个热释发光峰值的实验结果.对所得结果进行了分析讨论,提出了这一材料的发光衰减是由两个足够深的电子陷阱所引起.     

Luminescence properties of the Eu-doped porous glass and spontaneous reduction of Eu to Eu

The luminescent properties of Eu³⁺-doped porous glass were investigated and reduction of Eu³⁺ to Eu²⁺ was observed when the Eu³⁺-doped porous glasses were heat treated in air. The absorption, emission and excitation spectra of Eu³⁺-doped porous glasses were measured and the results significantly depended on the treating temperature. The integral intensity of Eu³⁺ and Eu²⁺ ions at different temperatures was also investigated to investigate this reduction process. Electron spin resonance (ESR) spectra of the samples were also measured, which also confirmed the reduction effect. A possible mechanism was discussed to explain this process.     

Eu2+,Mn2+在BaZnP2O7中的发光及Eu2+→Mn2+能量传递

采用高温固相法合成了BaZnP2 01:Eu2 ,Mn2 荧光粉,并对其发光性质及Eu2 对Mn2 的能量传递机理进行了研究.Eu2 和Mn2 在380 am和670 nm的发射峰分别由Eu2 的5d-14f跃迁和Mn2 的4T1(4G)-6A1(6S)跃迁产生.Eu2 对Mn2 的发光有很强的敏化作用,根据Dexter电多极相互作用的能量传递概率公式,判断出BaZnP2O7中Eu2 对Mn2 的能量传递属于电偶极-电四极相互作用引起的共振能量传递.     

纳米GdPO4：Eu3+的合成和光谱特性

采用EDTA二钠盐参加的共沉淀方法制备出纳米GdPO₄:Eu³⁺,利用X射线衍射,荧光光谱和电镜等测试手段对GdPO₄:Eu³⁺的相结构和发光性质进行了研究。XRD图谱结果表明700℃合成了纯的具有单斜晶系、独居石结构的纳米GdPO₄:Eu³⁺。根据Scherrer公式计算,700,800℃热处理后样品的一次颗粒度分别为18,40nm左右。激发光谱和发射光谱的研究表明,电荷迁移态和Eu³⁺的特征发射峰的强度随GdPO₄:Eu³⁺纳米粒子的增大而增强。在较小的纳米粒子中,存在结构扭曲的现象,315nm激发下的发射光谱研究表明,Gd³⁺和Eu³⁺具有较好的能量传递。     

Eu3+摩尔浓度对Y2O2S:Eu3+,Mg2+,Ti4+红色长余辉材料光谱的影响

用高温固相法制备了Y2O2S：Eu^3 ,Mg^2 ,Ti^4 红色长余辉材料。测量了该材料的余辉曲线,余辉时间为1h以上;由X射线衍射得到晶体结构为Y2O2S.测量了不同Eu^3 摩尔浓度下的激发光谱和发射光谱,得到从^5DJ(J=0,1,2,3)^-7FJ(J=0,1,2,3,4,5)的发射谱线,并得到位于260,345,468和540nm激发峰。由于激活剂饱和效应,Y2O2S：Eu^3 ,Mg^2 ,Ti^4 发射光谱中513．6,540．1,556．4,587．3和589．3nm属于从^5D2,^5D1到^7FJ(J=0,1,2,3,4)跃迁的发射峰随Eu^3 摩尔浓度的增加相对削弱;激发谱包括位于350nm左右属于电荷转移态吸收(Eu^3 -O^2-,Eu^3 -S^2 )的激发主峰和在可见光区位于468,520和540nm属于Eu^3 离子4f-4厂吸收的激发峰。随着Eu^3 摩尔浓度的增加,位于468,520和540nm的激发峰相对增强。     

Optical spectroscopy of Mn2+ ions in CaCl2 single crystals

Abstract

In the present investigation the excitation and fluorescence spectra and lifetimes of Mn²⁺ ions in calcium chloride, for various manganese concentrations and sample temperatures have been studied for the first time. The fluorescence spectrum consists of an asymmetric broad band, which upon lowering the sample temperature, shifts its maximum from 580 nm at 300 K to 596 nm at 11 K. This luminescence band was associated with the ⁴T_lg(⁴G)→⁶A_lg(⁶S) spin-forbidden transition in the manganese ions occupying Ca-sites in the lattice of CaCl₂. The excitation spectrum of the Mn²⁺ fluorescence revealed the features of manganese ions in octahedral coordination and consisted of nine excitation peaks which were associated with Mn²⁺-crystal-field-sensitive transitions. A crystal field analysis of the wavelength positions of these transitions by means of the model developed by Curie et al. allowed us to determine the magnitude of the cubic field splitting 10Dq, the reduced Racah parameter B', the Koide-Pryce covalency parameter ε and the spin transfer coefficients f _[sgrave] and f _σ. From the measurement of the temperature dependence of the Mn²⁺ fluorescence lifetime, we have also obtained information about the different mechanisms which are involved in the relaxation of excited Mn²⁺ ions in this host crystal in the temperature range (11–300 K).     

CaSO4掺Eu和Ag,Mn的热释发光谱

用三维发光谱方法,研究了掺Eu和Ag,Mn的CaSO4热释光材料的发光特性。测定了CaSO4：Eu(0．1％,摩尔分数)经1kGy的^60Co的γ射线照射后的热释发光谱,观察到Eu^2 离子的波长为385nm,温度为120,154℃的两个发光峰,Eu^3 离子在波长590,620,700nm处有多个发光峰。测量样品经不同温度热处理后的热释发光谱,发现Eu^2 和Eu^3 离子的发光强度随热处理温度变化规律极不相同,可见,Eu^2 和Eu^3 浓度比可通过热处理来改变,从而得到需要的Eu^2 和Eu^3 相对发光强度。通过CaSO4：Mn(0．5％)和CaSO4：Eu,Mn(0．1％,0．1％)热释发光谱的比较,观察到Mn^2 不仅是发光中心,而且能起能量转移的作用。实验得到的CaSO4：Eu,Mn磷光体有很高的发光效率。实验结果表明Eu^2 取代CaSO4中的Ca^2 ,不需要电荷补偿,有比较稳定和简单的结构,其热释光峰基本符合以一陷阱和一发光中心为前提的一级动力学模型,Ag和Mn的掺入不产生Eu^2 的高温发光峰。当Eu^3 在CaSO4中取代Ca^2 离子时,因其价态不同,则需电荷补偿,可能产生缺陷复合体和局部跃迁发光,它的热释光发光机制不能用一级动力学方程表示,而Ag的掺入起电荷补偿作用,从而改变了Eu^3 发光峰温,而对Eu^2 的发光峰温影响极小。     

Unlocking The Inherent Luminescence of Eu2+/Eu3+ by Light-Induced Oxidation for Invisible Optical Storage

Color-tunable luminescent materials are increasingly recognized for their potential applications in high-security anticounterfeiting and optical storage technologies. However, luminescent materials with high-contrast photoswitching behavior that change their luminescence properties in response to external stimuli are extremely scarce. In this study, a time-dependent color-tunable luminescent material, Na₂BaSiO₄:Eu²⁺ (NBSO:Eu), is introduced. This material leverages the inherent luminescence of Eu²⁺/Eu³⁺ through a light stimulus. Under 365 nm irradiation, the blue luminescence of Eu²⁺ gradually degraded over time, reaching a luminescence contrast of up to 88%. This degradation is accompanied by a color change of the emitted light from blue to red (Eu³⁺). These color changes can be reversibly tuned by alternating light or thermal stimuli. Experimental investigations revealed that the photogenerated Eu³⁺ ions and defects, acting as killer centers, induced multicolor luminescent switching behavior. Owing to their unique optical properties, NBSO:Eu offers exciting opportunities for designing advanced dynamic anticounterfeiting and invisible optical storage.