BaFCl：Ce^3＋和BaFCl：Gd^3＋晶体中的发光中心

运用不同的固相反应条件制备或后处理了几种BaFCl:RE~(3+)(RE=Ce或Gd)晶体,测定了它们的荧光光谱,对照并分析光谱数据和不同条件下可能引入晶体缺陷的情况,推论出晶体中存在有2类发光中心,即由RE_(?)-F_(?)和RE_(?)-F_(?)缔合体构成的中心。     

Efficient X-ray generation of Sm2+ in nanocrystalline BaFCl/Sm3+: a photoluminescent X-ray storage phosphor

Efficient X-ray generation of relatively stable Sm2+ centers is observed in nanocrystalline Sm3+-activated BaFCl, as prepared by a one-step wet chemical reaction. The conversion efficiency is approximately 50,000 times higher than that in microcrystalline BaFCl/Sm3+ prepared at 900 degrees C. The Sm2+ centers, and hence the radiation dose, can be directly monitored by the narrow photoexcited 5DJ-7FJ f-f luminescence lines. The relatively high efficiency of Sm2+ generation appears to be directly linked to the particle size.     

X-Ray storage luminescence of BaFCl:Eu2+ single crystals

Temperature behaviors of X-ray luminescence (XL), photoluminescence (PL), photostimulated luminescence, and thermoluminescence (TL) were studied in BaFCl:Eu2+ single crystals from room temperature to liquid nitrogen temperature. Six emissions at 275, 315, 365, 385, 435, and 500 nm were observed in the XL spectra and are attributed to Cl excitons, V(k)(Cl2-), the 4f65d1 (2e(g)) --> 4f7 (8S(7/2)) transition of Eu2+, and oxygen vacancies, respectively. Three emission peaks at 315, 365, and 390 nm were observed in the PL and TL measurements. These three emissions are from the transitions of 4f7(6I(7/2)) --> 4f7(8S(7/2)), 4f7(6P(7/2)) --> 4f7(8S(7/2)), and 4f65d1 (2e(g)) --> 4f7(8S(7/2)) of Eu2+, respectively. In our measurements, we observed that the emission of Eu2+ increases in intensity upon beta-irradiation and did not see any signals related to Eu3+ ions, which indicates that Eu2+ ions might not be oxidized to Eu3+ upon X-ray or beta-irradiation. Instead, the color centers, Cl excitons, and oxygen defects are created and are stable at room temperature, and they might play a key role in the storage luminescence.     

Study on the PSL mechanism in BaFCl:Eu<Superscript>2+</Superscript> phosphors

In this paper, the ESR and photoluminescence (PL) of BaFCl and BaFCl:Eu²⁺ radiated or un-radiated by X-ray were observed. The single electron in the color center could be produced in BaFCl without Eu²⁺. A series of traps of different energy level in BaFCl lattice were formed, and some shallow traps of them could be bleached by Vis-light, and the other deep traps could not. The bleaching effects on ESR and photostimulated luminescence (PSL) were investigated. An F-H-Eu²⁺ complex (F color center, H color center and Eu²⁺ complex) in the lattice of BaFCl:Eu²⁺ was suggested when the phosphor was X-ray irradiated. The Eu²⁺ located in the complex has only contribution to the ESR signal, but has no contribution to PL spectrum. The excitation of both F-center and located Eu²⁺ could decompose the complex to induce bleaching. The 440 nm light could excite the F-centers and the 220 nm and 270 nm could excite the located Eu²⁺, and the excitation disturbed the F-H-Eu²⁺ complex and caused a decrease of the PSL.     

ChemInform Abstract: Thermal Effect on BaFCl: High-Temperature X-Ray Diffraction.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

V Centers and Hole-Photostimulated Luminescence of BaFCl Crystal

V centers (hole centers) and hole-photostimulated luminescence of BaFCl crystal are reported for the first time. The absorption bands of V1, V2 and V3 centers are peaking at 205, 238 and 355 nm respectively. V2 center creation by X-irradiation and decay during photostimulated luminescence process are synchronousl with that of F center. This indicates that V centers play the same roles as F centers in X-ray storage and photostimulated luminescence processes.     

X射线诱导BaFCl:Eu2+光激励发光过程的新观察

本文研究了ＢａＦＣｌ：Ｅｕ＾２＾＋光激励发光（ＰＳＬ）对Ｘ射线剂量的响应关系，光激励发光的衰减规律，以及色心的形成与转型。除了简单的Ｆ心之外，我们还发现了Ｆ心的缔合中心，它们的吸收带位于７００－９５０ｎｍ。连续光激励Ｆ心时，光激励发光呈指数型衰减，而光激励发光（ＴＳＬ）也显现类似的衰减规律。光激励Ｆ缔合中心时，伴随着光激励发光还可能有一些无辐射跃迁过程的产生，例如色心的分解，转型和解离电子的再捕获     

GdPO4:Eu3+和GdBO3:Eu3+中"Gd-Eu"间的能量传递

利用同步辐射光源(德国HASYLAB实验室的SUPERLUMI实验站)对高温固相法制备的GdPO4 Eu3+和GdBO3Eu3+的发射谱与激发谱进行了研究, 并从量子剪裁的角度对"Gd3+-Eu3+"之间的能量传递作了讨论. 在两种样品监测Eu3+红光发射的激发谱上, 都显著观察到了对应Gd3+离子4f-4f跃迁的谱线, 说明从基质中Gd3+离子向掺杂的Eu3+离子之间存在非常有效的能量传递, 这有利于量子剪裁的发生. 在激发谱上还观察到了对应Eu3+-O2-电荷迁移态的宽激发带(180～270 nm), 而对应Gd3+离子8S7/2→6GJ跃迁的谱线(196 nm, 203 nm)叠加在这个宽带之上, 微弱可辨, 这不利于Gd3+-Eu3+间交叉弛豫的能量传递过程, 从而不利于量子剪裁的发生. 结合Eu3+-O2-电荷迁移态位置变化的规律, 提出了如何避开其干扰以增强量子剪裁效应的材料设计方案.     

紫外线对BaFCl:Eu光激励发光的增强效应

对X射线辐照后的BaFCl:Eu样品,通过研究紫外线辐照对光激励发光的影响,发现在一定条件下紫外线对光激励发光有增强的作用,并且根据光谱研究提出了光激励发光的过程为Eu²⁺和陷阱争夺激发态电子的观点,从机理上对这一现象进行了解释.     

Defect models of the three trigonal Ti3+ centers in LiF:Ti3+ and LiF:Ti3+:Mg2+ crystals

The EPR g factors of the trigonal Ti3+ center A in LiF:Ti3+ and two additional trigonal Ti3+ centers B and C in LiF:Ti3+:Mg2+ crystals are calculated from the third-order perturbation formulas based on the cluster approach. From the calculations and by considering the Ti3+ displacement along 111 axis obtained by ENDOR experiment, the defect models for the three Ti3+ centers are suggested. For center A, there are two possible models: (i) [Ti3+F3-O3(2-)] cluster and (ii) [Ti3+F6-] cluster with the Ti3+ off-center caused by a neighboring Li+ vacancy (VLi+) at <111> axis. The latter seems the more likely. The defect models of centers B and C are the [Ti3+F3-O(3)2-] clusters associated with a neighboring: Mg2+ ion at the Li+ site along 111 axis in the vicinity of three F- ions and three O2- ions, respectively. The reasonableness of these models is discussed.     

Phosphine-catalyzed annulations of azomethine imines: allene-dependent [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] pathways

In this paper we describe the phosphine-catalyzed [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] annulations of azomethine imines and allenoates. These processes mark the first use of azomethine imines in nucleophilic phosphine catalysis, producing dinitrogen-fused heterocycles, including tetrahydropyrazolo-pyrazolones, -pyridazinones, -diazepinones, and -diazocinones. Counting the two different reaction modes in the [3 + 3] cyclizations, there are five distinct reaction pathways-the choice of which depends on the structure and chemical properties of the allenoate. All reactions are operationally simple and proceed smoothly under mild reaction conditions, affording a broad range of 1,2-dinitrogen-containing heterocycles in moderate to excellent yields. A zwitterionic intermediate formed from a phosphine and two molecules of ethyl 2,3-butadienoate acted as a 1,5-dipole in the annulations of azomethine imines, leading to the [3 + 2 + 3] tetrahydropyrazolo-diazocinone products. The incorporation of two molecules of an allenoate into an eight-membered-ring product represents a new application of this versatile class of molecules in nucleophilic phosphine catalysis. The salient features of this protocol--the facile access to a diverse range of nitrogen-containing heterocycles and the simple preparation of azomethine imine substrates--suggest that it might find extensive applications in heterocycle synthesis.     

Er~(3+)∶Yb~(3+)∶Tm~(3+)共掺硼硅酸盐玻璃光致发光温度特性和能级劈裂

高温固相烧结法制备了Er^3＋：Yb^3＋：Tm^3＋共掺硼硅酸盐玻璃．在978nm半导体激光器抽运下,测量了样品在300～573K下光致发光谱强度随温度的变化,讨论了室温时上转换绿光和红光等波段的光谱劈裂．分析了Er^3＋：Yb^3＋和Tm^3＋之间的能量传递机制．研究结果表明,当温度升高时,Er^3＋：Yb^3＋：Tm^3＋共掺硼硅酸盐玻璃的481nm蓝光、517和534nm绿光、以及657nm红光等光致发光强度单调下降,在490K时几乎消失．但900nm左右的近红外光谱则随温度的升高而持续增强,而且其中心波长向短波方向移动．在室温时,光谱劈裂明显,高温时劈裂逐渐消失．     

GdF3∶Er3+，Yb3+的合成和上转换发光特性

采用水热法制备了Er3 离子浓度为3%,yb3 离子浓度分别为10%,20%的GdF3:Er3 ,Yb3 .XRD结果表明:合成的样品均为正交结构的GdF3,Cd0.87Yb0.10Er0.03F3和Gd0.77Yb0.20Er0.03F3样品的晶粒尺寸分别为28和26 nm.研究了980 nm红外光激发的上转换发射光谱.结果表明:红光和绿光发射分别来自于Er3 离子的2H11/2,4S3/2→4I15/2和4F9/2→4I15/2跃迁.样品的绿光发射强度较红光发射强.但绿光和红光发射的相对强度比例与Yb3 离子浓度有关.对Gd0.87Yb0.10Er0.03F3和Gd0.77Yb0.20Er0.03F3样品中可能的上转换发光机制进行了讨论.     

Optical characterization of Sm3+ and Dy3+:ZnO-PbO-B2O3 glasses

Here, we present the results of the analysis of Sm(3+) or Dy(3+) (0.5 mol%) ions doped heavy metal oxide (HMO)-based zinc lead borate (ZLB) glasses. Optical measurements such as absorption, emission spectra, lifetimes, XRD, DSC profiles have been carried out. The emission spectrum of Sm(3+):ZLB has shown the emission transitions of (4)G(5/2)-->(6)H(5/2) (563 nm), (4)G(5/2)-->(6)H(7/2) (598 nm), (4)G(5/2)-->(6)H(9/2) (646 nm), (4)G(5/2)-->(6)H(11/2) (708 nm) with lambda(exc): 401 nm ((6)H(5/2)-->(4)F(7/2)). In the case of the Dy(3+):ZLB glass, emission transitions of (4)F(9/2)-->(6)H(15/2) (485 nm), (4)F(9/2)-->(6)H(13/2) (575 nm) and (4)F(9/2)-->(6)H(11/2) (664 nm) with lambda(exi): 447 nm ((6)H(15/2)-->(4)I(15/2)) have been identified. Energy level schemes relating to the emission mechanisms involved in Sm(3+) and Dy(3+) glasses have been given.     

LaF_3∶Yb~(3+),Er~(3+)纳米晶:溶剂热法合成及上转换发光性质

利用溶剂热合成方法,分别以油酸和油胺为表面有机配体,合成了具有六角结构,颗粒尺寸分别为19和23nm单分散的LaF3:Yb3+,Er3+纳米晶。在980nm红外激光照射下,LaF3:Yb3+,Er3+纳米晶发射出肉眼可观察的绿色和红色上转换荧光,而且其发光过程均符合双光子过程。结合红外光谱与上转换光谱分析了表面有机配体对LaF3:Yb3+,Er3+纳米晶上转换发光的影响,结果显示,以油酸分子为表面配体的纳米晶具有较高的上转换发射强度,但以油胺为表面配体的纳米晶的红光发射相对增强。     

The critical concentration for quenching of the Eu3+ luminescence in some Gd3+ : Eu3+ systems

The critical concentration for quenching of the Eu³⁺ luminescence is calculated theoretically for several Gd³⁺ : Eu³⁺ systems. A comparison is made with the experimental values. The results are discussed in terms of energy migration.     

Nd3+:LaCl3中的上转换发光研究

当用582.6 nm的黄色激光激发Nd3+:LaCl3的2G7/2+4G5/2能级时,观察到了4D3/2和2G9/2能级的兰光和紫外发射.研究表明,2D3/2上转换的机理是能量传递和激发态吸收,而2G9/2则是由于4G5/2+4Gs/2→2G9/2+4F7/2交叉驰豫过程.通过对12K下4D3/2→4I11/2荧光衰减曲线的分析,得出能量传递几率为wt1＝1468 s-1.测量和讨论了Nd3+:LaCl3和NdCl3主要发光能级室温和12K下的寿命.     

Tunable luminescence and energy transfer process between Tb3+ and Eu3+ in GYAG:Bi3+, Tb3+, Eu3+ phosphors

A series of Eu³⁺ ions co-doped (Gd_0.9Y_0.1)₃Al₅O₁₂:Bi³⁺, Tb³⁺ (GYAG) phosphors have been synthesized by means of solvothermal reaction method. The XRD pattern of GYAG phosphor sintered at 1500 °C confirms their garnet phase. The luminescence properties of these phosphors have been explored by analyzing their excitation and emission spectra along with their decay curves. The excitation spectra of the GYAG:Bi³⁺, Tb³⁺, Eu³⁺ phosphors consists of broad bands in the shorter wavelength region due to 4f⁸ → 4f⁷5d¹ transition of Tb³⁺ ions overlapped with 6s² → 6s¹6p¹ (¹S₀ → ³P₁) transition of Bi³⁺ ions and the charge transfer band of Eu³⁺–O^2?. The present phosphors exhibit green and red colors due to ⁵D₄ → ⁷F₅ transition of Tb³⁺ ions and ⁵D₀ → ⁷F₁ transition of Eu³⁺ ions, respectively. The emission was shifted from green to red color by co-doping with Eu³⁺ ions, which indicate that the energy transfer probability from Tb³⁺ to Eu³⁺ ions are dependent strongly on the concentration of Eu³⁺ ions.     

Optical-transition Probability of Tm^3＋ Ions in Tm^3＋／Er^3＋：YVO4 Crystal

1INTRODUCTIONThelasersoperatedataround2mmwavelengthhavegainedmuchinterestbecauseofvariousappli-cations,e.g.(1)groundorspaceremotesensingforLIDARandmetrology,(2)medicalapplicationssinceliquidwaterhasastrongabsorptionbandnear2mm,and(3)eyesafelaser[1,2].The2…     

KMgF3:Ce3+,Tb3+纳米粒子中Ce3+→Tb3+的发光及能量传递

利用微乳液方法,合成了铈、铽共掺杂的氟镁钾纳米粒子,研究了体系中Ce3+→Tb3+的发光特性以及它们之间的相互作用,结果表明KMgF3:Ce3+Tb3+纳米粒子中存在Ce3+→Tb3+的能量传递过程,即Ce3+可以将吸收的能量直接传递给Tb3+离子,使得Tb3+的绿色发光强度大为增加.