Optical absorption of isotopically enriched Li2B4O7 single crystals irradiated by thermal neutrons

Induced absorption spectra in the range 200–900 nm at 77 and 290 K for Li₂B₄O₇ single crystals, isotopically Li and B enriched are presented after irradiation of these crystals by thermal neutrons with fluence 1.8×10¹⁶ cm⁻². The dependence of induced absorption spectra on the isotope composition was revealed: for ⁶Li₂¹⁰B₄O₇ and ⁷Li₂¹⁰B₄O₇ crystals intensive band in the region of 280–294 nm was observed. Under substitution of ⁷Li isotope by ⁶Li in the lithium tetraborate lattice no changes in the absorption spectra were observed. The nuclear reaction ¹⁰B(n,)⁷Li is proposed to be the main mechanism of formation of the radiation defects.     

Study of the interfacial structure and chemistry of CVD κ-Al2O3/TiC multilayer coatings

This article describes the interfacial regions in CVD grown TiC/κ-Al₂O₃ multilayers. A number of microanalytical techniques were used including HREM, EDX and EELS. Occasionally, the first 50 nm of the alumina layers deposited on the intermediate TiC layers grew as a cubic alumina, heavily faulted, containing small amounts of sulphur (S), maybe as a stabiliser. The presence of slightly rounded TiC (111) facets may act as preferred nucleation sites for the cubic Al₂O₃ phase, with a ‘cube on cube’ orientation relationship. In this way the nucleation of κ-Al₂O₃ is less favourable. After some tens of nanometres the cubic phase cannot be stabilised any longer and the layer continues to grow as κ-Al₂O₃. A number of observations point towards the reaction zone (RZ) being η- and/or γ-Al₂O₃. The diffraction work and the FFT analysis of the HREM images show that the RZ is an fcc phase with a=7.9 Å, which matches with η- and γ-Al₂O₃. The EELS Al fine structure indicate more tetrahedral Al ions than in κ-Al₂O₃, as in η- and γ-Al₂O₃. The RZ contains small amounts of S, as has been reported for γ-Al₂O₃. Due to the structural similarities between η- and γ-Al₂O₃ it was not possible to determine which of these cubic phases is present in the RZ.     

Fabrication and growth rate estimation of PrBa2Cu3O7−δ single crystal by the modified top seeded crystal pulling method

Recently, we succeeded in fabricating single crystals of PrBa₂Cu₃O_7−δ by a modified top seeded crystal pulling method called the SRL-CP (Solute Rich Liquid-Crystal Pulling) method. Y₂O₃ and MgO polycrystalline crucibles and a MgO single crystal crucible were used to grow the single crystals. The crystal growth temperature was set in the range of 968°C to 972°C. The grown crystals were identified as PrBa₂Cu₃O_7−δ by X-ray diffraction. In the case of using Y₂O₃ crucibles the composition of the grown crystals was Y_xPr_1−xBa₂Cu₃O_7−δ (0.48 < x < 0.57) and in the case of using MgO crucibles a relatively small amount of Mg contamination to the grown crystals occurred at a typical concentration of approximately 1 at.% of the sum of cations. According to the crystal growth model of the SRL-CP method [1–5], a maximum growth rate of 1.7 × 10⁻⁵ cm/s was calculated with the aid of the phase diagram studies we reported earlier [6]. This value is reasonably in agreement with the experimental results.     

Kinetics of the transient optical absorption in Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript> and LiB<Subscript>3</Subscript>O<Subscript>5</Subscript> lithium borate crystals

This paper reports on a study of the kinetics of electron tunneling transport between electron and hole centers in Li₂B₄O₇ and LiB₃O₅ lithium borate crystals under the conditions where the mobility of one of the partners in the recombination process is thermally stimulated. A mathematical model has been proposed to describe all specific features in the relaxation kinetics of the induced optical density observed in Li₂B₄O₇ (LTB) and LiB₃O₅ (LBO) nonlinear optical crystals within a broad time interval of 10⁻⁸−1 s after a radiation pulse. The results of calculations have been compared with experimental data on transient optical absorption (TOA) of LTB and LBO crystals in the visible and ultraviolet spectral regions. The nature of the radiation defects responsible for TOA and the dependence of the TOA decay kinetics on temperature, excitation power, and other experimental conditions have been discussed.     

Luminescence of excitons and antisite defects in the phosphors based on garnet compounds

Intrinsic emission (excitons, anti-site defects (AD)) of oxides with garnet structure has been analysed by means of investigation of the time resolved luminescence and decay kinetic spectra under excitation by the synchrotron and X-ray radiation at 10–300 K of the model objects: undoped single crystals and single crystalline films of Y₃Al₅O₁₂ and Lu₃Al₅O₁₂ garnets which are characterised by the significant differences in concentrations of AD Y_Al³⁺ and Lu_Al³⁺-types as analogs of cation isoelectronic impurities.     

INS investigation on disaccharide/H2O mixtures

New Inelastic Neutron Scattering findings on homologues disaccharides (C₁₂H₂₂O₁₁)/H₂O mixtures are presented. The comparison among the spectra of trehalose, maltose and sucrose/H₂O mixtures, besides evidencing a different destructuring effectiveness on the H₂O hydrogen bond network, and hence different cryoprotectant properties, shows a higher ‘crystallinity’ degree for the trehalose/H₂O system which accounts for its higher ‘rigidity’. This result justifies the better cryptobiotic action of trehalose in respect to maltose and sucrose.     

Growth and luminescent properties of Yb—doped oxide single crystals for scintillator application

Rod-shaped (Lu_1−xYb_x)₃Al₅O₁₂ with x=0.05, 0.15, 0.30 and (Y_1−xYb_x)AlO₃ with x=0.05, 0.10, 0.30 single crystals were grown by the micro-pulling-down method. Edge-defined film-fed growth method was used to prepare (Y_0.9Yb_0.1)VO₄ crystal, while Ca₈(La_1.98Yb_0.02)(PO₄)₆O₂ crystal was grown by the Czochralski method. Luminescence of these crystals was studied with main attention paid to the charge transfer emission of Yb³⁺. Temperature tuned decay times in the time scale of units—tens of nanosecond was measured as a feature possibly interesting for an application in scintillation detectors in positron emission tomography.     

Field-induced pinning effect of Nd(Ba1−xNdx)2Cu3O7−δ single crystals grown by the traveling-solvent floating-zone method

We have studied the superconducting properties of Nd(Ba_1−xNd_x)₂Cu₃O_7−δ (Nd123, x ≈ 0.1) single crystals grown by the traveling-solvent floating-zone method under 0.1% O₂ in Ar atmosphere. The enhancement of the magnetization with increasing field is observed in the hysteresis (M-H) loop in fields both parallel and perpendicular to the c-axis of the Nd123 single crystals as well as in the bulk crystals prepared by the oxygen-controlled-melt-growth (OCMG) method. The composition variation of Ba/Nd is observed in the matrix of Nd123 crystals by an analytical TEM equipped with a cold field-emission gun. It turns out that the enhancement is due to the field-induced pinning effect ascribed to the weak superconducting Nd---Ba substitution regions in the Nd123 matrix.     

Radiation resistance property of barium gallo-germanate glass doped by Nb2O5

Effects of Nb₂O₅dopant on the radiation response of barium gallo-germanate(BGG)glass are studied mainly by electron paramagnetic resonance and absorption spectroscopy.Owing to the Nb⁵⁺$Nb³⁺interconversion in doped samples,formations of Ge-related non-bridging oxygen hole center and Ge-related electron center defects after g-ray irradiation are inhibited.Thereby,Nb₂O₅dopant can enhance radiation resistance of BGG glass,and 1.0%Nb2O5 concentration is the best.     

Eu3+激活K2CaP2O7荧光粉的制备和发光性质

采用高温固相法制备了系列不同浓度Eu³⁺离子掺杂的K₂CaP₂O₇红色荧光粉。通过X射线衍射、扫描电子显微镜、荧光光谱和荧光寿命曲线等手段对荧光粉的物相结构、形貌以及发光性质进行了研究。结果表明所制备的荧光粉均属于单斜结构,Eu³⁺离子掺杂没有引起晶体结构明显变化,荧光粉形貌不规则,颗粒为微米量级且部分发生团聚。在393 nm紫外光激发下,荧光粉显示出红光发射,最强发射峰位于613 nm。Eu³⁺离子掺杂浓度对发光强度有显著影响,最佳掺杂摩尔分数为0.08,由此计算能量传递临界距离为1.61 nm。荧光寿命受掺杂浓度影响较小,当Eu³⁺掺杂摩尔分数为0.005~0.10时,荧光寿命在2.45~2.58 ms范围内。变温发射光谱显示,测试温度为150℃时,荧光粉的发光强度为室温的73%。研究表明,Eu³⁺离子掺杂的K₂CaP₂O₇是性能较好的红色荧光粉。     

Recombination kinetics in nonlinear defective LiB3O5 crystals

A study of recombination kinetics in LiB₃O₅ (LBO) crystals by time-resolved luminescence and absorption spectroscopy is reported. An investigation of the kinetics of transient optical absorption (TOA) and luminescence under ns-scale electron-beam excitation performed within a broad temperature range of 77–500 K and a 1.2–5-eV spectral interval has established that the specific features in the recombination kinetics observed in LBO involve electronic, B²⁺, and hole, O⁻, trapping centers. The TOA and luminescence kinetics, as well as their temperature dependence, are interpreted by a model of competing hole centers. Relations connecting the kinetics parameters and the temperature dependence to the parameters of the main LBO point defects are presented. Fiz. Tverd. Tela (St. Petersburg) 40, 2008–2014 (November 1998)     

掺杂晶体材料ZnGa_2O_4:Fe~(3+)局域结构畸变及其微观自旋哈密顿参量研究

基于Newman的晶场叠模型与微观自旋哈密顿理论,建立了ZnGa2O4:Fe3+晶体材料中磁性离子Fe3+局域结构与其自旋哈密顿(spin-Hamiltonian,SH)参量(包括二阶零场分裂(zero-field splitting,ZFS)参量D,四阶ZFS参量(a-F),Zeeman g因子:g//,g⊥,△g(=g//-g⊥))之间的定量关系.采用以全组态完全对角化方法为理论背景的CFA/MSH(Crystal Filed Analysis/Microscopic Spin Hamiltonian)研究软件,研究了ZnGa2O4:Fe3+材料中磁性离子Fe3+的SH参量与其局域结构的依赖关系.研究表明:对于ZnGa2O4:Fe3+晶体材料,当磁性离子Fe3+的局域结构畸变参数△R=0.0487 nm,△θ=0.192°时,其基态SH参量理论计算结果与实验测量符合很好,进一步表明Fe3+掺入晶体材料后将引起磁性Fe3+离子局域结构的微小畸变,但其仍然保持D3d点群对称局域结构.在此基础上研究分析了SH参量的微观起源,结果表明:ZnGa2O4:Fe3+晶体材料的SH参量主要来源于SO(spin-orbit)磁相互作用机理,来自其他磁相互作用机理(包括SS(spin-spin),SOO(spin-other-orbit),OO(orbit-orbit),SO-SS-SOO-OO)的贡献比较小.     

Scintillation properties of PbWO4 crystals doped with the rare-earth ions

In PbWO₄(PWO) crystals grown by Czochralski method the influence of atmosphere of the growth (O₂, air) and doping with the rare-earth ions of different types (A³⁺=Lu³⁺, Gd³⁺,Tb³⁺,Eu³⁺ as well as doubly doped A³⁺–Li⁺) on light yield and luminescence decay were analyzed. PWO scintillator with the ultra-fast (τ=0.5 ns) main component of luminescence decay (87% of total light yield) was obtained using the O₂-growth atmosphere and doping by Eu₂O₃ at a concentration of 5000 ppm. It is concluded that the decrease of decay constant of the main scintillation component is the result of the resonant energy transfer between the centers of “blue” PWO luminescence (λ_max=420 nm) and the 4f–4f-transitions of Eu³⁺ ions in this spectral region.     

n(Zn)：n(Ga)比值对合成ZnGa2O4结构及光致发光性能的影响

以ZnO和HGaO₂为原料,用不同配比合成出系列ZnGa₂O₄,并对其晶体结构和发光性能进行了研究。用荧光分光光度计检测了ZnGa₂O₄的激发和发射光谱,用X射线衍射仪检测了ZnGa₂O₄的衍射图谱,用热重差热仪绘制了TGA-DAT曲线。对检测结果分析认为:1.ZnGa₂O₄属于尖晶石结构,稍过量的Zn或Ga能进入ZnGa₂O₄结构中,并对ZnGa₂O₄的晶格常数产生一定影响。2.ZnGa₂O₄存在两个自激发光中心,当Ga稍过量时,自激发光中心是四面体镓氧键[T_d(Ga-O)],最大激发波长约248nm,最大发射波长约367nm;当Zn稍过量时,自激发光中心是八面体镓氧键[O_h(Ga-O)],最大激发波长约270nm,最大发射波长约441nm。当n(Zn):n(Ga)在理论值附近,激发和发射光强度最大,而且光谱峰位发生了红移。3.ZnGa₂O₄的热稳定性能非常好。上述结论对研究ZnGa₂O₄基质或掺杂的发光材料具有一定意义。     

蓝色长余辉材料Sr2MgSi2O7：Eu2+,Dy3+及其基质的VUV-UV激发特性

Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺是一种有效的蓝色长余辉材料,采用高温固相法合成了Sr₂MgSi₂O₇,Sr₂MgSi₂O₇:Dy³⁺,Sr₂MgSi₂O₇:Eu²⁺及Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺,利用同步辐射研究了它们的VUV-UV激发特性.在真空紫外光激发下,在基质中发现了稍弱的位于385nm的发射带,在双掺杂的样品中,除了Eu²⁺的4f5d→4f发射带(465nm)外,还观察到了575nm处的发射峰;通过和Dy³⁺单掺杂样品的发射谱比较,发现它是来自于Dy³⁺的4f-4f(⁴F_9/2→6H_13/2)跃迁.在它们的激发谱上可以看出Dy³⁺与基质发射的有效激发均处于真空紫外区,在近紫外及可见区激发下未见到它们发光.另外在Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺中观察到Dy³⁺的发射也说明了Dy³⁺在该类长余辉材料中不仅作为陷阱用来延长余辉,而且也以发光中心形式存在于基质中.     

(1-x)Sr_3Sn_2O_7+xCa_3Mn_2O_7陶瓷合成及其光电性能

为了寻求新的非常规多铁性材料,采用固相合成方法制备具有Ruddlesden-Popper结构的(1-x)Sr_3Sn_2O_7+x Ca_3Mn_2O_7(SSO+CMO)(x=0,0.05,0.10,0.15,0.20)系列陶瓷.通过X射线衍射、紫外可见光谱和磁性测量,发现SSO+CMO陶瓷为单一正交相结构,空间群为A21am.随着掺杂量x的增加,样品的晶胞参数和体积相应地减小;在室温不同频率下,样品的介电常数和介电损耗随着频率增加而减小,且在x=0.1时有弱的铁磁性.     

Nd~(3+):SrY_2O_4粉体的制备、结构与光谱性能研究

为探索新型激光晶体,采用固相法合成了(3 at.%)Nd~(3+):SrY_2O_4多晶,对其结构和发光性质进行了研究.对样品的X射线衍射谱进行Rietveld精修得到了样品的晶胞参数、原子位置等.在353 nm激发下,Nd~(3+):SrY_2O_4在可见波段的最强荧光峰位于419 nm,对应Nd3+的2D15/2→4I9/2跃迁.在824 nm激发下,Nd3+的4F3/2→4I11/2跃迁的荧光谱带宽约为90 nm,最强峰为1083 nm,荧光寿命为281.7μs.宽发射光谱和长的能级寿命表明,Nd~(3+):SrY_2O_4是一种很有希望的新波长激光二极管抽运超短脉冲激光材料.     

Effects of processing variables on the magnetic properties of melt-processed YBa2Cu3Ox

Samples of YBa₂Cu₃O_x (Y123) with excess Y₂BaCuO₅ (Y211) in the molar ratio of 5:1 (Y123/Y211) were processed using the SLMG (‘solid-liquid melt growth’) technique. The effects of precursor particle size, thermal pretreatment, and substrate choice were examined. Particle size was shown to accelerate degradation of the BaCuO₂ precursor. Thermal pretreatment resulted in reduction of porosity in the samples and hence improved magnetic properties. Contamination by carbon and magnesium from the substrates was also examined and eliminated by using BaZrO₃ substrates.     

Optical and electrical properties of binary WO3–Pb3O4 glasses

A glass system of the composition xWO₃+(100−x)Pb₃O₄, with x=5, 10, 20 and 30 mol.% was prepared. The optical absorption, ac and dc conductivities are the subject of the present work. The optical absorption indicates that the electronic transition is indirect and is associated with phonon assisted transition. The exponential dependence of the absorption coefficient as a function of the incident photon energy suggests that the Urbach rule is obeyed, and indicates the formation of a band tail. On the other hand, ac conductivity measurements are performed in the frequency range 0.1–100 kHz, and in the temperature range 300–600 K. The results of the electrical conductivity are discussed on the basis of electronic glass conduction models. Correlated narrow-band limit for random sites and single polaron hopping model are found to describe the experimental results effectively. The dielectric constant was correlated to the optical band gap and a satisfactory relation was found. It was also possible to calculate the thermochromic properties from independent ac and dc measurements, and it was possible to evaluate the optical gap at 0 K by extrapolation.     

Exciton–dopant and exciton–charge interactions in electronically doped OLEDs

The electronic dopants, like tetrafluorocyanoquinodimethane (F₄–TCNQ) molecules, used for p-doping of hole transport layers in organic light-emitting diodes (OLEDs) are found to quench the electroluminescence (EL) if they diffuse into the emissive layer. We observed EL quenching in OLED with F₄-TCNQ doped N,N′-diphenyl-N′N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine hole transport layer at large dopant concentrations, >5%. To separate the effects of exciton–dopant quenching, from exciton–polaron quenching we have intentionally doped the emissive layer of (8-tris-hydroxyquinoline) with three acceptors (A) of different electron affinities: F₄-TCNQ, TCNQ, and C₆₀, and found that C₆₀ is the strongest EL-quencher, while F₄-TCNQ is the weakest, contrary to intuitive expectations. The new effects of charge transfer and usually considered energy transfer from exciton to neutral (A) and charged acceptors (A⁻) are compared as channels for non-radiative Ex–A decay. At high current loads the EL quenching is observed, which is due to decay of Ex on free charge carriers, hole polarons P⁺. We consider contributions to Ex–P⁺ interaction by short-range charge transfer and describe the structure of microscopic charge transfer (CT)-processes responsible for it. The formation of metastable states of ‘charged excitons’ (predicted and studied by Agranovich et al. Chem. Phys. 272 (2001) 159) by electron transfer from a P to an Ex is pointed out, and ways to suppress non-radiative Ex–P decay are suggested.