Intrinsic excitons in 12CaO·7Al2O3

Unusual crystal structure of 12CaO·7Al₂O₃ is composed by a framework of positively charged nanocages, which enable accommodation of various negative ions (and even electrons) inside these cages. Different filling of cages leads to significant changes in electronic structure and as the result in luminescence properties, as well. Luminescence was studied using time-resolved spectroscopy in VUV in the temperature range from 6 to 300 K. Electron loaded samples exhibit UV luminescence band peaked at ～5 eV. The excitation spectrum of this emission has the onset at the energy gap value of 6.8 eV, and its decay is well described with the sum of two exponential functions with life-times of τ₁ = 3.7 ns and τ₂ = 29 ns, respectively. Its thermal quenching is well approximated by the sum of two Mott-Seitz type curves with the activation energies of 34 meV and 70 meV. Experimental results indicate that this luminescence is possibly due to radiative decay of two singlet self-trapped exciton states, which hole components are localized on two non-equivalent framework oxygens.     

Field-assisted sustainable O− ion emission from fluorine-substituted 12CaO·7Al2O3 with improved thermal stability

We examined the electric field-assisted thermionic emission of atomic oxygen radical anion (O^?) in a vacuum from fluorine-substituted derivatives of 12CaO·7Al₂O₃ (C12A7) with a composition of (12 ? x)CaO·7Al₂O₃·xCaF₂ (0 ≤ x ≤ 0.8). Unsubstituted C12A7 easily decomposed into 5CaO?3Al₂O₃ (C5A3) and 3CaO?Al₂O₃ (C3A) above 830 °C during the emission experiment in a vacuum. The decomposition temperature range became narrower as the amount of F^? ion substitution increased, e.g. the sample with x = 0.4 kept a single phase after the emission experiment at 900 °C. The emitted anionic species from the x = 0.4 sample were dominated by O^? ions (～ 92%) together with a small amount of O₂^? ions (～ 4%) and F^? ions (～ 4%). The absence of an O₂ gas supply to the opposite side of the emission surface led to a nearly steady co-emission of O^? ions and electrons with a ratio of < 1/1. The O₂ gas supply markedly enhanced the O^? ion emission, and suppressed the electron emission. A sustainable and high-purity O^? ion emission with a current density of 11 nA cm^? 2 was achieved at 830 °C with the supply of 40 Pa O₂ gas. The similarity in these emission features to the unsubstituted C12A7, together with the improved thermal stability demonstrates that the F^? ion-substituted C12A7 is a promising material for higher intensity O^? ion emission at higher temperatures.     

Sr-doping enhanced electrical transport and thermionic emission of single crystal 12CaO·7Al2O3 electride

Sr-doped single crystals (C_1-xS_x)12A7:e⁻ (x = 0, 0.01, 0.02, 0.03) were successfully fabricated by floating zone method. It is found that Sr-doping decreases the reduction time from 30 h to 20 h. The maximum emission current of (C_1-xS_x)12A7:e⁻ is greatly improved by 50% than that of the un-doped. The DFT calculations show Sr-doping in C12A7 contributed to the free O²⁻ in the cages spread out, leading to a short reduction time; increase the “window” between two adjacent cages that is conducive to the electrons in cages to escape. And the work function of the (C_1-xS_x)12A7:e⁻ is lower than that of C12A7:e⁻.     

双波长Pr3+掺杂12CaO·7Al2O3的光存储特性

采用化学共沉淀法制备了Pr3+掺杂的12CaO·7Al2O3(C12A7:Pr3+)材料.通过X射线衍射(XRD)、发射光谱、激发光谱、余辉衰减曲线、热释发光及光激励发光等测试手段系统研究了C12A7:Pr3+材料的微观结构和光学性质.结果表明,C12A7是一种理想的适合Pr3+掺杂的基质材料,C12A7:Pr3+具有...     

Blue upconversion luminescence in 12 CaO·7 Al2O3:Tm3 +/Yb3 + polycrystals

The effect of Yb^3 + concentration on the fluorescence of 12 CaO·7 Al₂O₃:Tm^3 +/Yb^3 + polycrystals is investigated. Under the excitation of 980 nm laser, the strong blue (477 nm) emission band is observed and attributed to ¹G₄ → ³H₆ of Tm^3 +. The ratio of blue to red emission increases with the increasing of Yb^3 + and remains constant at 10 mol% Yb^3 +. The pump dependence and upconversion mechanisms show that the two-photon cooperative upconversion process is responsible for the enhancement of the blue upconversion emission. The Commission Internationale de l'eclairage chromaticity coordinates (x, y) illustrate that the 12 CaO·7 Al₂O₃:1 mol% Tm^3 +/10 mol% Yb^3 + can emit high-purity blue light.     

Oxygen ordering in YBa2Cu3O7−y in terms of the Landau theory

Oxygen ordering in nonstoichiometric compositions of YBa₂Cu₃O_7?y is considered in terms of the Landau theory of second-order phase transitions. It is shown that there can only be ten types of homogeneous long-range order, of which two types correspond to the OI and OII phases. The Landau theory predicts that the filling of vacant positions 2(f)D _4h ¹ by oxygen must follow a scenario that is far from forming chains but compatible with known facts. Such a scenario of filling vacancies with oxygen was not considered earlier. It is demonstrated that the predicted structures can be experimentally identified from the spectra of copper ions. In the course of identification of diffraction patterns, the symmetry-allowed displacement of copper ions from centrosymmetric positions in a Cu(1)(O_x□_1?x )₂ layer should be taken into account.     

Luminescence and absorption of Tb3+in mo·Al2O3·B2O3·Tb2O3 glasses

Quantum yields of the green Tb luminescence for 254 nm excitation of glass compositions in the system MO·Al₂O₃· B₂O₃·Tb₂O₃ (M = Mg, Ca, Sr, Ba and Zn) were studied in relation to absorption and excitation spectra. Yields as high as 80% were observed. The Tb 4f-5d absorption maximum ranges from 218 to 232 nm, always at a longer wavelength than the glass matrix absorption. The yield strongly depends on the spectral position of the 4f-5d absorption, due to competing impurity absorption at 254 nm.     

Simple identification of Al2O3 and MgO·Al2O3 spinel inclusions in steel using X-ray-excited optical luminescence

Nonmetallic inclusions in steel cause problems in steel products and steel production. In particular, an analysis of Al₂O₃ and MgO·Al₂O₃ spinel inclusions is important since they are one of the most harmful inclusions. A rapid and simple analysis of nonmetallic inclusions is required as the conventional analytical methods for nonmetallic inclusions are time-consuming. In this study, we propose a simple method to identify Al₂O₃ and MgO·Al₂O₃ spinel inclusions in steels. X-ray-excited optical luminescence (XEOL) analysis was selected as a promising method because it can rapidly identify sizes, shapes, and compositions of nonmetallic inclusions and can be performed in air. A model steel sample prepared by heating a mixture of Fe, Al, and MgO powders at 1550°C in argon atmosphere was used. XEOL images of the model steel sample showed that Al₂O₃ inclusions emitted blue and red luminescences. Using a filter attached to the camera, blocking light in the wavelength region above 650 nm, only the blue luminescence of the Al₂O₃ inclusions was observed. This was implemented as the luminescences of the Al₂O₃ inclusions appeared in both blue and red regions at wavelengths of 350, 485, 695, and 750 nm; consequently, the luminescences at 695 nm and 750 nm were blocked by the filter. In contrast, MgO·Al₂O₃ spinel inclusions emitted green luminescence (peak at 520 nm), unaffected by the filter. This indicates that we can simply identify Al₂O₃ and MgO·Al₂O₃ spinel inclusions by an XEOL image in the wavelength range of 420–650 nm.     

Oxygen diffusion in YBa2Cu3O7−x; An impedance spectroscopy study

The ionic conductivity of YBa₂Cu₃O_7−x has been studied in the temperature range of 650 to 1085 K, using Pt(O_z)/YSZ electrodes, which are ionically reversible, and blocking for electronic charge carriers. A.c. and d.c. polarization studies in air reveal an ionic conductivity activation enthalpy of 1.51 eV. In the range of 775 to 890 K ionic transference numbers range from 2×10⁻⁷ to 8×10⁻⁸. The enthalpy value is related to ionic conduction via oxide ion vacancies V_Ö, and oxygen loss.     

Study of YBa2Cu3O7−δ ceramics/Al interface

Properties of oxide layers at the interface between Al metal and YBa₂Cu₃O_7−δ ceramics were investigated using X-ray diffraction (XRD), X-ray photoelectron spectra (XPS) and impedance measurements. There have been found the oriented grains having their c-plane parallel to the surface of YBa₂Cu₃O_7−δ. When Al metal was evaporated onto the ceramics sample, the aluminum oxide layer was produced at the interface between Al and YBa₂Cu₃O_7−δ because Al metal oxidizes more easily. The oxygen-deficiency was observed at the ceramics side of the interface as examined by X-ray photoelectron spectra. This oxygen-deficiency can be partly replenished by post annealing whereas it can be fully replenished for the sample to which the mechanical polishing is applied beforehand in order to remove the oriented grains. The thickness of aluminum oxide layer was evaluated by means of the impedance measurements using the alternating current three-terminal method.     

Ionic conduction in BaxCe0.8Er0.2O3−α

Ba_xCe_0.8Er_0.2O_3−α (x=0.98–1.03) solid electrolytes were synthesized by high temperature solid-state reaction. X-ray diffraction (XRD) patterns showed that the specimens were a single perovskite-type orthorhombic phase. The conduction properties of the specimens were studied electrochemically in the temperature range of 600–1000 °C. The influence of nonstoichiometry in the specimens with x≠1 on conduction properties was investigated and compared with that in the specimen with x=1. These three specimens showed a good protonic conduction under wet hydrogen, a mixed conduction of oxide-ion and electronic hole under dry higher oxygen partial pressure, and a mixed conduction of proton, oxide-ion and electronic hole under wet higher oxygen partial pressure. Both of the protonic and oxide-ionic conductivities increased with increasing barium content in the specimens under wet hydrogen and dry air, respectively.     

A computational study of the electron detachment energies of Al2As2 − and Al3As3 −

Ab initio and density functional theory calculations are reported for the low-lying electronic states of Al₂As₂ ^?, Al₂As₂, Al₃As₃ ^?, and Al₃As₃. The ²B_2g ground electronic state of Al₂As₂ ^? has a rhombic structure with the Al atoms occupying the shorter diagonal. In contrast, the As atoms occupy the shorter diagonal of the ground state rhombic structure of Al₂As₂. Electron detachment energies computed for Al₂As₂ ^? are presented and discussed. The adiabatic electron affinity of Al₂As₂ ^? is calculated to be 2.1 eV at the CCSD(T) level, using B3LYP and MP2 optimized geometries. The ground states of both Al₃As₃ ^? (²A₁′) and Al₃As₃ (¹A₁′) have planar hexagonal D_3h geometry. Electron detachment energies computed for the anion are reported. At the CCSD(T)//B3LYP level, the electron affinity of Al₃As₃ is calculated to be 2.47 eV.     

Al,F-doped new perovskite lithium fast ion conductor Li3x La2/3−x□1/3−2x Ti1−y Al y O3−y F y (x=0.11)

Al, F-doped new perovskite lithium ion conductors (x=0.11) have been prepared by solid state reaction. It is found that a pure perovskite-structured phase with space group of P4mm(99) exits in the composition range of 0<y≤0.10. The sample with y=0.02 possesses the highest ionic conductivity of 1.06×10⁻³ S/cm at room temperature, and its decomposing voltage is 2.3 V. The factors affecting the conductivity of this system are discussed.     

K2O·CaO·4B2O3·12H2O∶Nd3+的合成及发光性能

以CaCl2、K2B4O7和Nd2O3为原料,采用易于工业化、无污染的水溶液法反应合成碱-碱土金属硼酸盐K2O·CaO·4B2O3·12H2O∶Nd3+晶体,利用X射线衍射、红外光谱、扫描电镜、荧光分光度计等现代分析测试手段,对所合成晶体进行了分析和表征.结果表明,所制备的K2O·CaO·4B2O3·12H2O∶Nd3...     

K2O·CaO·4B2O3·12H2O∶Nd3+的合成及发光性能

以CaCl2、K2B4O7和Nd2O3为原料,采用易于工业化、无污染的水溶液法反应合成碱-碱土金属硼酸盐K2O·CaO·4B2O3·12H2O∶Nd3+晶体,利用X射线衍射、红外光谱、扫描电镜、荧光分光度计等现代分析测试手段,对所合成晶体进行了分析和表征.结果表明,所制备的K2O·CaO·4B2O3·12H2O∶Nd3+晶型发育良好、形貌规整.基质本身具有上转换发光特性,K2O·CaO·4B2O3·12H2O∶Nd3+的发光强度较基质弱.当激发源为828 nm时,材料呈橙红色光.     

Effect of Li2O on the structure,electrical and dielectric properties of xLi2O·(20−x)CaO·30P2O5·30V2O5·20Fe2O3 glasses

Glasses of the general formula xLi₂O·(20?x)CaO·30P₂O₅·30V₂O₅·20Fe₂O₃ with x=0, 5, 10, 15 and 20 mol% were prepared; IR, density, electrical and dielectric properties have been investigated. Lithia-containing glasses revealed more (P₂O₇)^4?, FeO₆, V–O^? and PO^? groups and mostly have lower densities than those of lithia-free ones. The electrical properties showed random behavior by replacing Li₂O for CaO, which has been assigned to the change of the glass structure. The results of activation energy and frequency-dependent conductivity indicate that the conduction proceeds via electronic and ionic mechanisms, the former being dominant. The mechanism responsible for the electronic conduction is mostly thermally activated hopping of electrons from Fe(II) ions to neighboring Fe(III) sites and/or from V⁴⁺ to V⁵⁺. The dielectric constant (ε′) showed values that depend on the structure of glass according to its content of Li₂O. The (ε′) values are ranging between 3 and 41 at room temperature for 1 kHz, yet at high temperatures, glass with 20 mol Li₂O exhibits values of 110 and 3600 when measurement was carried out in the range 0.1–1 kHz, and at 5 MHz, respectively.     

Infrared spectra of superconducting La2−xSrxCuO4 and YBa2Cu3O7−δ

Abstract

Abstract Infrared spectra of La_2?xSr_xCuO₄ and YBa₂Cu₃O_7?δ are discussed, specially with respect to the disappearance of the high-frequency (～650 cm) band of the superconducting compositions at 300K. Some of the bands persist at 300K eventhough the materials are fairly conducting. YBa₂Cu₃O_7?δ does not show evidence in the far IR spectrum for the presence of an optical gap.     

Relaxation phenomena in Cr3+ doped Al2O3−Fe 2 57 O3 systems

Mössbauer absorption spectra have been measured for Cr³⁺ doped Al₂O₃?Fe ₂ ⁵⁷ O₃ systems for different values of the Cr³⁺ concentration at room temperature. The cross relaxation between Fe³⁺ and Cr³⁺ ions, which destroys the paramagnetic hyperfine structure of Fe⁵⁷ observed in undoped Al₂O₃?Fe ₂ ⁵⁷ O₃, is thoroughly studied. The experimental results suggest a new kind of cross-relaxation process involving three spins, i.e. two Fe³⁺.ions and one Cr³⁺. The process, though it is a higher-order one, is highly effective because it is energy-conserving.     

Magnetic properties of GdBa2Cu3O7−x in the normal and superconducting states

The magnetic properties of superconducting GdBa₂Cu₃O_7–x withT _c95 K are measured. In the normal state, its susceptibility closely follows the Curie law with an effective moment of 7.77 _B .H _c1 is determined to be 650 Oe. No superconducting fluctuation can be delineated. Flux pinning indicated behavior of type II superconductors. A 25–405 diamagnetic state indicating bulk superconductivity in GdBa₂Cu₃O_7–x .     

Model of current and optical conductivity switching in YBa2Cu3O7−x films

A model is proposed for the thermal and electrical responses of films of the high-T _c superconducting material YBa₂Cu₃O7_7−x to current and optical pulses. Numerical calculations are compared with experimental data for current pulses of duration 100 μs and laser pulses of duration 0.1 ns; this yields improved data on the thermal conductivity of thin YBa₂Cu₃O7_7−x films (1.5–2 W/m·K) and thermal resistance of the film-substrate contact (5×10⁻⁸m²·K/W) in the neighborhood of the superconducting transition. This model can be used for optimizing the film structure parameters and control regimes for switching elements for pulses lasting longer than 0.1 ns. Zh. Tekh. Fiz. 69, 77–82 (October 1999)