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.     

Luminescence centers in bismuth-containing oxytungstate ceramics

We have studied the photoexcitation and luminescence spectra of Bi₂WO₆, Y₂WO₆ and Y₂WO₆:Bi ceramics. We used the Alentsev-Fock method to decompose the spectra into elementary components. The emission bands with maximum at 2.93 eV in the luminescence spectrum of Bi₂WO₆, 3.02 eV in the luminescence spectrum of Y₂WO₆, and 2.95 eV in the luminescence spectrum of Y₂WO₆:Bi are assigned to luminescence of self-localized Frenkel excitons. The bands with maxima at 2.35 eV and 1.90 eV in the spectrum of Bi₂WO₆, 2.25 eV and 1.75 eV in the spectrum of Y₂WO₆, and 2.35 eV and 1.85 eV in the spectrum of Y₂WO₆:Bi are connected with oxygen vacancies. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 688–691, September–October, 2007.     

有机材料激子发光的温度特性

基于实验和理论模拟研究了12~320 K温度范围内八羟基喹啉铝[tris-(8-hydroxyquinoline)aluminum,Alq]和一种高效红光染料甲基2叔丁基6(1,1,7,7四甲基久咯呢定基9烯基)4H 1吡喃[4-(dicyanomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran,DCJTB]的光致发光(photoluminescence,PL)随温度的变化,提出三种不同电荷分离程度的激子参与的Alq的稳态光致发光过程,通过拟合参量得到了三种激子的能量差值和辐射复合几率之比,观察并解释了DCJTB发光光谱从200 K以下到室温的升温过程中发生的蓝移。认为变温光致发光有可能用于评估材料的发光和导电性能,比较并讨论了有机和无机发光材料激子发光的温度特性,认为低温下小分子发光材料倾向于分子态,随温度升高逐渐向半导体态转变,Alq在150~190K之间开始发生这种转变,而DCJTB则从300~320 K开始。     

Luminescence centers in ceramics of yttrium, scandium, and bismuth oxytungstates

An investigation is made of the luminescence spectra of Me₂WO₆ ceramics (Me=Y, Sc, Bi). The spectra were decomposed into elementary components by the Alentsev—Fock method. Radiation hands with a maximum at 3.02 eV in the Y₂WO₆ luminescence spectrum, at 2.8 eV in the ScWO₆ spectrum, and at 2.93 eV in the Bi₂WO₆ spectrum are assigned to the light emission of self-localized Frenkel excitons. The bands with maxima at 2.25 and 1.75 eV in the Y₂WO₆ spectrum, at 2.36 and 1.9 eV in the Sc₂WO₆ spectrum, and at 2.35 and 1.9 eV in the Bi₂WO₆ spectrum are related to oxygen vacancies. Translated from Zhurnal Prikladnoi Spektroskopii, Vol 67, No. 2, pp. 273–275, March–April, 2000.     

Luminescence of ytterbium complexes with octaphenyltetraazaporphyrins

We have synthesized outer complexes of ytterbium with octaphenyl-and octa(para-tert-butylphenyl)tetraazaporphyrins, in which for the first time we have detected luminescence of ytterbium with maximum at 980 nm. We have shown that the 4f-luminescence quantum yield in the complexes depends primarily on the nature of the outer ligand. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 5, pp. 693–696, September–October, 2006.     

Luminescence of CaWO4:Pr3+ and CaWO4:Tb3+ at ambient and high hydrostatic pressures

Photoluminescence spectra of CaWO₄ doped with Pr³⁺ and Tb³⁺ obtained at high hydrostatic pressures up to 315 kbar applied in a diamond anvil cell (DAC) are presented. The intensities of the luminescence from the ³P₀ state of Pr³⁺ and from the ⁵D₃ state of Tb³⁺ decreased with increasing pressure. At pressures greater than 50 kbar, the ¹D₂ → ³H_J transitions in Pr³⁺ and the ⁵D₄ → ⁷F_J transitions in Tb³⁺ dominated the spectra. At pressures greater than 100 kbar, only emissions from the lower excited states were observed. At pressures greater than 150 kbar, luminescence from the ¹D₂ and ⁵D₄ states also decreased with increasing pressure, and at a pressure of 315 kbar for CaWO₄:Pr³⁺ and 190 kbar for CaWO₄:Tb³⁺, the emissions related to the Pr³⁺ and Tb³⁺ were quenched. These effects were related to the influence of impurity trapped excitons (ITEs) on the efficiency of the f–f emission in the Pr³⁺ and Tb³⁺ ions. Analysis of the emission spectra collected at different pressures allowed the energies of the ground states of the Pr³⁺ and Tb³⁺ ions with respect to the band edges of the CaWO₄ host to be estimated.     

Mechanism of Crystal Phosphor Luminescence

An experimental method has been developed for determining the mechanism of luminescence of crystals by the changes arising in the intensity of a burst of their luminescence under the action of a constant electric field. An example of determining the mechanism of luminescence of AgBr crystals and AgBr_0.95 and AgBr_0.60Cl_0.40 solid solutions by the method proposed is presented. We were the first to establish that the low-temperature photoluminescence of AgBr_0.95I_0.05 in the band with _max = 540 nm proceeds by the Schone–Klasens recombination mechanism. It has also been established that the longwave luminescence of AgBr, AgBr_0.95I_0.05, and AgBr_0.60Cl_0.40 in the band with _max = 630 nm arises as a result of the recombination of electrons localized on a luminescence center with free holes.     

(Sr,Ca)4Si3O8Cl4基质中Eu2+的发光特性研究

采用高温固相法合成Sr4-xCaxSi3O8Cl4：Eu^2＋荧光材料,利用Van Uitert公式讨论Sr4-xCaxSi3O8Cl4：Eu^2＋中yEu^2＋的晶格环境和发光特性,确定晶体中有蓝色和黄绿色两种发光中心,并讨论了它们与光谱结构的对应关系。当0〈x〈0．5,Ca^2＋固溶入Sr4Si3O8Cl4基质晶格,Eu^2＋占据八配位Si^2＋格位,晶体主要产生蓝色中心的蓝绿色发射;当0．5〈x〈2,较大的Ca^2＋掺杂使晶胞参数变小,品格中的杂质束缚激子态的束缚增强,Eu^2＋处于杂质束缚激子中心所形成的激发态能量进一步降低,发射位于长波段方向并具有较大的Stokes位移,Sr4-xCaxSi3O8Cl4：yEu^2＋主要产生黄绿色中心的黄绿色发射光。     

Surface analysis of Hg2Cl2

A surface composition of (110) face of Hg₂Cl₂ in high vacuum is studied for the room temperature. The impact of primary electrons with energy of 2·5 keV causes a decomposition of the surface layer which is described in detail.The single crystals of Hg₂Cl₂ used in this work were prepared by Dr. Barta in Institute of Solid State Physics of Czechosl. Acad. Sci., Prague.     

Luminescence of complex organic molecules upon electron excitation

Pesults of investigation of the luminescence of complex organic compounds upon excitation with electrons of various energies are reported. Data on spectra of energy losses of electrons, fluorescence excitation cross sections and functions, fluorescence emission spectra, fluorescence kinetics, polarization, and energy yield, effects of impurity gases, and theoretical analysis of the processes taking place in the system are presented. Results of investigation of the luminescence of complex molecules in electric discharges (dc, pulsed, high-frequency, non-self-maintained, and plasma-beam) and in a condensed state (solutions, molecular crystals, and thin solid films) are discussed. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk 220072, Belarus. Transtated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 5, pp. 694–708, September–October, 1998.     

Luminescence centers in thin films of lead and bismuth tungstates

Luminescence spectra of thin films of PbWO₄ and Bi₂WO₆ are invesigated. The Alentsev-Fock method is used to separate the spectra into elementary components. The emission bands with maxima at 2.8 eV in PbWO₄ and at 2.93 eV in Bi₂WO₆ luminescence spectra are interpreted as the emission of self-localized Frenkel excitons. The bands with maxima at 2.35 and 1.75 eV in PbWO₄ and at 2.35 and 1.9 eV in Bi₂WO₆ are related to oxygen vacancies. L’vov State University, 50, Dragomanov St., L'vov, 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 1, pp. 143–145, January–February, 1998.     

Synthesis and Luminescence of a Novel Conjugated Europium Complex with 6-Aniline Carbonyl 2-Pyridine Carboxylic Acid

A novel organic ligand, 6-aniline carbonyl 2-pyridine carboxylic acid (HAP), and the corresponding europium complex, tris(6-aniline carbonyl 2-pyridine carboxylato) europium (III) (Eu-AP) have been designed and synthesized. The results showed that Eu-AP was a conjugated complex, emitting strong red luminescence. The lifetimes of ⁵D₀ of Eu³⁺ in the complex were examined using time-resolved spectroscopic analysis, and the lifetime value was 0.55 ± 0.01 ms for solid Eu(AP)₃. Thermogravimetric analysis showed that the europium complex had good thermal stability.     

稀土发光和光谱理论的研究进展

简述了近20多年以来我们在稀土发光和光谱理论方面所做的主要工作、取得的进展和成果。包括:(1)关于(4f)^N组态内单光子跃迁强度:推广Judd-Ofelt三参量公式,在其中计入"J混合"(偶宇称晶场成分造成的)导致的修正;澄清了国际上关于Judd-Ofelt全参量公式中"静力学项"和"动力学项"相对正负号的争论(仍为负号)。(2)关于(4f)^N组态内双光子过程强度:提出直接计算强度方法(放弃缔合近似,利用Ce³⁺的5d和左邻RE³⁺的(4f)^N能级-波函资料,近似模拟出最重要的虚中间组态(4f)^N-15d的能级-波函结构)来讨论和改进Judd-Ofelt缔合近似。(3)固体中声子辅助的稀土离子间能量传输理论:发现HLO理论关于单声子过程中的"干涉相消"实际只适合于对角过程,而非对角过程则是"干涉相加",因而,后者首要的是单声子而非双声子过程;同时,用"晶体格波模"取代"Debye模"描述能量传输中的声子,给出了新模型下计算对角和非对角过程速率等物理量的整套公式。并由之看出:波矢q=0和对应色散曲线扁平段的光学声子对单声子非对角过程速率有完全不能忽略的贡献,这些都不同于或超出于HLO理论。(4)提出和发展了分析指认4f-5d跃迁光谱的简单理论模型,用能量和跃迁强度同时进行近似拟合,成功地分析指认了从(4f)³到(4f)¹³离子在几种基质中的4f→5d吸收(激发)谱,也成功用于若干5d→4f辐射谱。(5)对跃迁的初末晶场态同时引用有效自旋哈密顿描述稀土离子间超交换作用,成功地解释了低温10 K时立方结构的纯稀土冰晶石晶体Cs₂NaLnCl₆(Ln=Er,Yb)等的吸收谱中0声子线(量级为几个cm^-1)的精细分裂。     

Clusters in the model ferroelastic Hg2Cl2

The critical fluctuations induced by a ferroelastic phase transition and corresponding to the soft TA mode at the X point at Brillouin zone boundary have been studied in the model crystal Hg₂Cl₂ within a broad temperature and wave-vector range. Anisotropic diffuse x-ray scattering maxima associated with order-parameter fluctuations and nucleation of low-temperature orthorhombic clusters in the high-temperature tetragonal matrix have been found to exist at these points. New information has been obtained on the temperature dependence of the susceptibility and correlation length, cluster shape and anisotropy, and the critical exponents. Fiz. Tverd. Tela (St. Petersburg) 41, 148–152 (January 1999)     

带-NH2的嘧啶环对钌配合物与DNA相互作用的瞬态发光特性的影响

采用时间分辨的发光光谱技术,分别测量了两种新合成的钌配合物[Ru(bpy)2 (dpbpd(NH2)2)]2 和[Ru(phen)2(dpbpd(NH2)2)]2 与小牛胸腺脱氧核糖核酸(ctDNA)相互作用时的瞬态发光动力学过程,并与以往对[Ru(phen)2dppz]2 等的研究结果进行对比,从而研究带-NH2的嘧啶环对配合物与DNA作用动力学过程的影响.结果表明:这两种含有带-NH2的嘧啶环的钌配合物与DNA相互作用时的发光按双指数规律衰减,发光寿命为几十纳秒,比dppz类钌配合物与DNA作用时的发光衰变寿命(几百纳秒)小一个数量级.归因于嘧啶环上的N和-NH2可能与水分子、DNA的碱基对或磷酸骨架形成氢键,从而加快激发态的无辐射弛豫,削弱发射光强,缩短发光寿命.该结论为进一步研究配合物分子与DNA的相互作用的机理提供了一定的依据.     

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.     

稀土/高分子杂化发光材料的研究

用SiO2为无机组份和以与SiO2具有相似折射率和优良力学性能的丙烯酸类如甲基丙烯酸甲酯（MMA）和甲基丙烯酸羟乙酯（HEMA），在交联剂3－（三甲氧基硅）丙基甲基丙烯酸酯（MSMA）存在下，快速制备了两种杂化基质材料SiO2/P(MMA-MSMA)和SiO2/P(HEMA-MSMA)。分别以盐酸和六次甲基四胺作为酸性催化剂和碱性催化剂，建立了快速制备透明凝胶的两步溶胶－凝胶法，大大缩短了溶胶的成胶时间，所得杂化材料具有良好的光学透明性，利用此方法制备了掺杂稀土配合物的多种发光杂化材料。采用组装的方法，得到了稀土配合物与层次化合物α－磷酸氢锆（α－ZrP)及中孔分子筛材料MCM－41的组装体，并对所制备的杂化材料进行了表征。另外，将稀土配合物通过共价键嫁接于无机SiO2基质中，得到了含有稀土配合物的分子杂化材料。     

X-Ray Luminescence of Defects in Spinel Single Crystals

The flareup of x-ray luminescence in spinel single crystals (MgAl₂O₄) depending on the time of x-ray irradiation and the decay of fluorescence depending on the time elapsed after the termination of irradiation have been investigated. These dependences were measured at different powers of the irradiation dose (power of the x-ray tube) and at different temperatures of the samples. The experimental results suggest the existence of large-size complexes of defects, which include antisite defects and impurity ions, the exchange of charge carriers between which during and after irradiation leads to luminescence of the impurity ions. Transfer of charge carriers between isolated elements of the pairs of antisite defects (not interacting with the impurity ions) leads to the formation of a competing channel of recombination luminescence in the UV region of the spectra. The decay of fluorescence attributable to transitions in the Mn²⁺ and Cr³⁺ ions depending on the time elapsed after the termination of x-ray irradiation points to the existence of various combinations of antisite defects in the surroundings of these ions.     

35Cl nuclear quadrupole resonance and the macroscopic superstructure in Hg2Cl2 crystal

A study has been made of the temperature dependences of the chlorine NQR frequency and linewidth in calomel crystals. These dependences show clearly pronounced anomalies in the region of the ferroelastic phase transition. The dynamic and static factors influencing the pattern of these dependences are discussed. A fine structure in the spin echo in the form of beats has been revealed within a narrow temperature interval near the phase transition. This effect is shown to be connected with the formation of a macroscopic heterophase superstructure in the crystal. Fiz. Tverd. Tela (St. Petersburg) 39, 1287–1290 (July 1997)