Al~(3+)掺杂ScVO_4∶Eu~(3+),Bi~(3+)荧光粉的制备及发光性质

采用高温固相法在1 000℃下煅烧6 h合成了Sc VO4∶Eu3+,Bi3+,Al3+荧光粉。使用X射线粉末衍射仪和扫描电镜对样品的结构和形貌进行了表征,采用荧光分光光度计研究了样品的发光性质。用315 nm波长激发Sc VO4∶Eu3+,Bi3+,Al3+样品时,样品在590~620 nm范围内发射强烈的橙红光,最大发射峰位于615nm。少量Al3+的掺入可以增强Sc VO4∶Eu3+,Bi3+荧光粉的发光,而掺入过量Al3+时会使Sc VO4∶Eu3+,Bi3+荧光粉的发光变弱。当Al3+在Sc VO4∶Eu3+,Bi3+中的摩尔分数达到4%时,样品的发光最强且其发光强度较未掺杂Al3+的样品提高了约30%。     

Interband Stark effects in InxGa1−xAs/InyAl1−yAs coupled step quantum wells

The effects of an electric field on the interband transitions in In_xGa_1−xAs/In_yAl_1−yAs coupled step quantum wells have been investigated both experimentally and theoretically. A In_xGa_1−xAs/In_yAl_1−yAs coupled step quantum well sample consisted of the two sets of a 50 Å In_0.53Ga_0.47As shallow quantum well and a 50 Å In_0.65Ga_0.35As deep step quantum well bounded by two thick In_0.52Al_0.48As barriers separated by a 30 Å In_0.52Al_0.48As embedded potential barrier. The Stark shift of the interband transition energy in the In_xGa_1−xAs/In_yAl_1−yAs coupled step quantum well is larger than that of the single quantum well, and the oscillator strength in the In_xGa_1−xAs/In_yAl_1−yAs coupled step quantum well is larger than that in a coupled rectangular quantum well. These results indicate that In_xGa_1−xAs/In_yAl_1−yAs coupled step quantum wells hold promise for potential applications in optoelectron devices, such as tunable lasers.     

Preparation, characterization and oxide ion conductivity in U-substituted Bi4V2O11

A Bi₂V_{1 − x − y}U_xBi_yO_{5.5 + 0.5x − y} solid solution derived from Bi₄V₂O₁₁ has been prepared and characterized with x up to 0.125 for y = 0. Partial substitution of U⁶⁺ for V⁵⁺ in Bi₄V₂O₁₁ leads to the stabilization at room temperature of the high-oxide ion conducting γ-phase, in contrast with other M⁶⁺ dopants which stabilize the β-phase. The lower conductivity in U substituted system compared with BICUVOX.10 is attributed to its higher activation energy. Conductivity values and activation energies of the U substituted phases compare well with Bi₂UO₆.     

Effects of substitution of Ti for Fe in BiFeO3 films prepared by sol–gel process

Ti substituted BiFe_1−xTi_xO_3+δ films have been prepared on indium–tin oxide (ITO)/glass substrates by the sol–gel process. The films with x=0.00–0.20 were prepared at an annealing temperature of 600 °C. X-ray diffraction patterns indicate that all films adopt R3m structure and the films with x=0 and 0.10 show pure perovskite phase. Cross-section scanning shows the thickness of the films is about 300 nm. Through 0.05 Ti substitution, the 2P_r increases to 8.30 μC/cm² from 2.12 μC/cm² of the un-substituted BiFeO₃ film and show enhanced ferroelectricity at room temperature. The 2P_r values are 2.63 and 0.44 μC/cm² for the films with x=0.01 and 0.2, respectively. Moreover, the films with x=0.05 and 0.10 show enhanced dielectric property since the permittivity increases near 150 at the same measuring frequency. Through the substitution of Ti, the leakage conduction is reduced for the films with x=0.05–0.20.     

Magnetocaloric and magnetoresistance properties of La2/3Sr1/3Mn1−xCoxO3 compounds

Structural, magnetic, magnetoresistance and magnetocaloric studies on La_2/3Sr_1/3Mn_1−xCo_xO₃ compounds were reported. The samples were prepared by the conventional ceramic method. X-ray analysis showed the presence of one phase only, in all studied samples. From electrical resistance measurements it was found that the samples show large negative magnetoresistance behavior. The magnetic measurements were performed in a large temperature range, 4.2–750 K and external magnetic fields up to 5 T. The adiabatic magnetic entropy changes, |ΔS|, were determined from magnetization data. Large magnetocaloric effect (MCE) has been obtained in all studied samples.     

Phase composition-dependent physical and mechanical properties of YbxZr1−xO2−x/2 solid solutions

The paper represents a detailed insight into the correlation between changes of the phase composition of crystalline Yb_xZr_1−xO_2−x/2 solid solutions and their structural, electrical, mechanical and optical properties. Particularly, the effect of the crystal growth conditions and stabilizer amount in the range of 1.5–13.8 mol% of Yb₂O₃ are studied in terms of Rietveld analysis of powder X-ray diffraction data, electrical conductivity measured by impedance spectroscopy, absorption coefficient and refractive index measurements, Vickers microhardness (classical technique) as well as the plastic microhardness and effective elastic modulus (DSI—depth-sensing indentation technique). Potential applications of the investigated systems are discussed in view of the results obtained.     

Al~(3+)/Mo~(6+)双离子取代ZrV_2O_7中Zr~(4+)/V~(5+)实现近零膨胀

采用固相烧结法制备了Zri_(1-x)Al_(2-x)V_(2-x)Mo_xO_7(0≤x≤0.9),并通过调整Al~(3+)/Mo~(6+)对ZrV_2O_7中的Zr~(4+)/V~(5+)离子替代量来实现近零膨胀,对于较小的x值(x≤0.3),材料保持了与ZrV_2O_7相同的立方相结构.随着Al~(3+)/Mo~(6+)替代量的增加,(Al/Zr)~-和(Mo/V)~+之间的库仑相互作用逐渐加强,这种库仑相互作用导致材料中未发生畸变的立方相晶体结构逐渐减少.当x≥0.7时,材料中立方相晶体结构完全消失.在425-750 K温度区间内,Zr_(0.5)Al_(0.5)M_(0.6)O_7展示出近零膨胀性质(-0.39×l0~(-6)K~(-1)).Zr_(0.5)Al_(1.5)V_(1.5)Mo_(0.5)O_7的低热膨胀性能可能与Al~(3+)/Mo~(6+)对ZrV_2O_7中Zr~(4+)/V~(5+)部分替代引起部分晶体结构发生的畸变及其对未替代部分的晶格结构的影响有关.     

Dependence of the electronic parameters on the InyGa1−yAs quantum well width in modulation-doped AlxGa1−xAs/InyGa1−yAs/GaAs strained single quantum wells

The variation of the electronic parameters in the subband as a function of the In_yGa_1−yAs quantum well width in modulation-doped strained Al_xGa_1−xAs/In_yGa_1−yAs/GaAs single quantum wells were investigated by means of Shubnikov-de Haas (S-dH) and Van der Pauw Hall-effect measurements. The fast Fourier transform (FFT) of the S-dH oscillations and the Hall-effect data showed that the carrier density and the mobility of the two-dimensional electron gas (2DEG) occupied in the subband increased as the quantum well width increased. The increase in the 2DEG density with increasing the In_yGa_1−yAs well width originated from an increase in the energy difference between the energy level of the electronic subband and Fermi energy, and the increase in the 2DEG mobility is attributed to a decrease of the scattering source. The electronic subband energies, the corresponding wavefunctions, and the Fermi energies in the Al_xGa_1−xAs/In_yGa_1−yAs/GaAs single quantum wells were calculated by a self-consistent method taking into account the exchange-correlation effect together with the strain and nonparabolicity effects. These results indicate that the electronic parameters in Al_xGa_1−xAs/In_yGa_1−yAs/GaAs strained single quantum wells are significantly dependent on the quantum well width.     

Structure and composition of secondary phase particles in cobalt-doped TiO2 films

The microstructural properties of secondary phase particles formed in epitaxial Co_xTi_1−xO₂ anatase thin films grown on (0 0 1)LaAlO₃ by a reactive RF magnetron co-sputter deposition are examined. These films exhibit ferromagnetic behavior in magnetization measurements, showing a M–H loop at room temperature with a saturation magnetization on the order of 0.7 μ_B /Co. X-ray photoemission spectrometry indicates that the Co cations are in the Co²⁺ valence state. Cross-section electron microscopy reveals that a significant fraction of the cobalt segregates into Co–Ti–O secondary phase particles. Selected area electron diffraction shows that the secondary phase particles are cobalt-rich anatase. While the cobalt is concentrated in the segregated particles, local energy dispersive spectrometry indicates some Co throughout the film.     

Tuning the multiferroic properties of Pb(Fe1/2Nb1/2)O3 by cationic substitution

A series of substituted lead iron niobate compounds with the general formula Pb²⁺_(1−x)A^Z_x(Fe_{{(1−(2−Z)x)/2}}Nb_{{(1+(2−Z)x)/2}})O₃ (0<x<0.6 and A=La³⁺, K⁺ or Sr²⁺) were prepared by a modified solid-state synthesis. The relative concentrations of Fe³⁺ and Nb⁵⁺ were adjusted to compensate the charge imbalance due to the aliovalent substitution. The dielectric constant and magnetic susceptibilities were studied as a function of temperature. The temperature of the dielectric maximum, T_M, of the substituted compounds decreased linearly with increasing concentration of the substituent ions. The magnetic measurements showed an antiferromagnetic transition at temperatures T_N1 due to the superexchange interactions mediated by Fe–O–Fe and an additional antiferromagnetic-type transition at T_N2. T_N1 linearly increased with the increasing concentration of Fe³⁺ ion at the B-site of ABO₃-type substituted compounds. T_M is shown to be directly dependent on the concentration of the ferroactive Nb⁵⁺ ions at the B-site and Pb²⁺ ions at the A-site.     

红色荧光粉La2Mo2O9:Eu3+,W6+的制备及发光性能

采用高温固相法合成出La₂Mo₂O₉:Eu³⁺,W⁶⁺系列红色荧光粉,其结构为立方晶系的β- La₂Mo₂O₉。在395 nm光激发下,样品La_1.40Mo₂O₉:0.60Eu³⁺发射出很强的红光,最强发射峰位于616 nm处。适量地掺杂W⁶⁺离子可以提高样品的激发和发射强度,在395 nm光激发下,La_1.40Mo_1.84O₉:0.60Eu³⁺,0.16W⁶⁺荧光粉的Eu³⁺的⁵D₀→⁷F₂跃迁发射强度最大,是样品La_1.40Mo₂O₉:0.60Eu³⁺的1.23倍。最后,将La_1.40Eu_0.60Mo_1.84O₉:0.16W⁶⁺荧光粉与~395 nm发射的InGaN芯片一起制作成红光发光二极管(LED),该LED发射出很强的红光。     

The influence of different fabrication processes on characteristics of excess Bi2O3-doped 0.95 (Na0.5Bi0.5)TiO3–0.05 BaTiO3 ceramics

In this study, we will develop the influences of the excess x wt% (x=0, 1, 2, and 3) Bi₂O₃-doped and the different fabricating process on the sintering and dielectric characteristics of 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃ ferroelectric ceramics with the aid of SEM and X-ray diffraction patterns, and dielectric–temperature curves. The 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃+x wt% Bi₂O₃ ceramics are fabricated by two different processes. The first process is that (Na_0.5Bi_0.5)TiO₃ composition is calcined at 850 °C and BaTiO₃ composition is calcined at 1100 °C, then the calcined (Na_0.5Bi_0.5)TiO₃ and BaTiO₃ powders are mixed in according to 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃+x wt% Bi₂O₃ compositions. The second process is that the raw materials are mixed in accordance to the 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃+x wt% Bi₂O₃ compositions and then calcining at 900 °C. The sintering process is carried out in air for 2 h from 1120 to 1240 °C. After sintering, the effects of process parameters on the dielectric characteristics will be developed by the dielectric–temperature curves. Dielectric–temperature properties are also investigated at the temperatures of 30–350 °C and at the frequencies of 10 kHz–1 MHz.     

Lithium insertion into V6O13 studied by deformation electron density refinement of single-crystal X-ray data

Deformation electron density refinement of single-crystal X-ray data has been performed for V₆O₁₃ and for one of its electrochemically lithiated phases Li₂V₆O₁₃. The electron rearrangement associated with lithium insertion is extracted by subtracting the two derived electron deformation models from one another. The reduction (from nominally V⁵⁺ to V⁴⁺) of one of the three independent vanadium atoms (V2) in the asymmetric unit can be identified, along with significant changes in the effective charges on certain of the oxygens.     

The NaCrS2 cathode material. IV. Effect of vanadium substitution on its physical properties and electrochemical performance in secondary Li cells

The introduction of 0.10–0.15 eq/mol of V³⁺ into the layered structure of NaCrS₂ substantially raises its conductivity and lowers its magnetic susceptibility without changing its crystal lattice parameters or nucleating a new phase, this implying considerable changes in the electron band structure of the dichalcogenide. When used as a cathode in a Li cell the partially desodiated vanadium substituted thiochromite exhibits a considerable increase in the equilibrium potential as compared to that of the nonsubstituted compound. Chemical and X-ray analysis reveal that in single phase samples (V³⁺0.15 eq/mol) practically all the V³⁺ ions are incorporated into the disulfide slabs, replacing equivalent amounts of Cr³⁺. It is demonstrated that the partially desodiated host structure Na_0.2Cr_0.9V_0.1S₂ can reversibly intercalate up to 1 eq Li/mole. The energy density, power capability and cycle life of this layered compound make it an attractive cathode material for secondary Li cells.     

Nax/2Bi1−x/2MoxV1−xO4 and Bi1−x/3MoxV1−xO4 New Scheelite-related phases

New Scheelite-related solid solutions of the compositions Na_x/2Bi_1−x/2Mo_xV_1−xO₄ (0≤x≤1) and Bi_1−x/3 Mo_xV_1−xO₄(0≤x≤0.2) have been synthesised by the substitution of Na and Mo at the A and B sites respectively of the ABO₄ type ferroelastic BiVO₄. The phases were characterised using chemical analysis, powder X-ray diffraction, scanning electron microscopy, EDAX, and Raman spectroscopy. While almost a continuous solid solution is obtained for the series Na_x/2Bi_1−x/2Mo_xV_1−xO₄, the absence of Na at the A-site results only in a narrow stability region for the other series, Bi_1−x/3 Mo_xV_1−xO₄ where 0≤x≤0.2. Raman spectra of selected samples at room temperature also suggest that vanadium and molybdenum atoms are disordered at the tetrahedral sites.     

Valence and spin states in perovskites LaCo0.95M0.05O3 (M=Mg, Ga, Ti)

The samples LaCoO₃ with dilute substitutions on cobalt sites have been studied using the resistivity, thermopower and magnetic susceptibility measurements over the temperature range up to 900 K. The Co-site substitution does not affect the magnetic transition at 100 K and the onset of massive population of hole carriers at 500 K, characteristic for undoped LaCoO₃. On the other hand, the low-temperature transport and magnetism is markedly distinct for samples with extra charge on cobalt ions introduced by the heterovalent dopants (Mg²⁺, Ti⁴⁺) compared to samples with minor non-stoichiometry (LaCoO₃, Ga³⁺-doped sample). Magnetic properties suggest that these extra charges create thermally stable magnetic polarons of total S2–3. Common features of Co-site doped and La-site doped samples (La_1−xSr_xCoO₃) are discussed.     

Spectroscopic study of BixEu1−xVO4 and BiyGd1−yVO4 mixed oxides

The mixed oxides Bi_xEu_1−xVO₄ and Bi_yGd_1−yVO₄ crystallize in a zircon-type structure, for 0 <x < 0.6 and 0 < y < 0.64, and in a fergusonite-type structure, for 0.94 < x < 1 and 0.93 < y < 1. A process of competition between the dominant and the constrained effects of the lone-pair 6s² of Bi³⁺ is discussed. The diffuse reflectance spectroscopic studies of these mixed oxides are presented. The observed broad bands are attributed to charge transfer processes and the sharp peaks in the Bi_xEu_1−xVO₄ spectra are ascribed to intra-configurational 4f – 4ftransitions of the Eu³⁺ ion. The broad absorption shift in BiLnVO₄ (Ln : Eu and Gd) compounds to the longer wavelengths range, when Bi is introduced in the LnVO₄ lattice, is ascribed to charge transfer processes in a Bi-VO₄ center and are interpreted assuming a Jahn-Teller effect in the excited state of Bi³⁺. The concept of an internal pressure of Bi³⁺ ions is also used to explain the broad A-band shifts.     

Nb/Au/(1 1 0)YBa2Cu3O7−δ Josephson junctions: evidence against atomic scaled “corner junctions”

We report on I–V characteristics for in situ formed Nb/Au/(1 1 0)YBa₂Cu₃O_7−δ (YBCO) Josephson junction, where the homoepitaxial (1 1 0)YBCO film shows ultra-smooth surface morphology. The field dependence of critical supercurrent I_c shows anisotropic large junction behavior with normal Fraunhofer patterns expected from BCS model of d_x²−y² wave superconductors. This strongly suggests that the Nb/Au/(1 1 0)YBCO junctions cannot be regarded as atomic scaled corner junctions, in contrast with (0 0 1)/(1 1 0)YBCO grain boundary junctions to show “π-junction” with a pronounced dip near zero fields in field modulation of I_c.     

Oxygen transfer processes in (La,Sr)MnO3/Y2O3-stabilized ZrO2 cathodes: an impedance spectroscopy study

Impedance spectroscopy was used to study the oxygen reaction kinetics of La_0.8Sr_0.2MnO₃ (LSM)-based electrodes on Y₂O₃-stabilized ZrO₂ (YSZ) electrolytes. Three types of electrodes were studied: pure LSM, LSM–YSZ composites, and LSM/LSM–YSZ bilayers. The electrodes were formed by spin coating and sintering on single-crystal YSZ substrates. Measurements were taken at temperatures ranging from 550 to 850°C and oxygen partial pressures from 1×10⁻³ to 1 atm. An arc whose resistance R_el had a high activation energy, E_a=1.61±0.05 eV, and a weak oxygen partial pressure dependence, (P_O2)^−1/6, was observed for the LSM electrodes. A similar arc was observed for LSM–YSZ electrodes, where R_el(P_O2)^−0.29 and the activation energy was 1.49±0.02 eV. The combination of a high activation energy and a weak P_O2 dependence was attributed to oxygen dissociation and adsorption rate-limiting steps for both types of electrodes. LSM–YSZ composite cathodes showed substantially lower overall interfacial resistance values than LSM, but exhibited an additional arc attributed to the resistance of YSZ grain boundaries within the LSM–YSZ. At 850°C and low P_O2, an additional arc was observed with size varying as (P_O2)^−0.80 for LSM and (P_O2)^−0.57 for LSM–YSZ, suggesting that diffusion had become an additional rate limiting step. Bilayer LSM/LSM–YSZ electrodes yielded results intermediate between LSM and LSM–YSZ. The results showed that most of the improvement in electrode performance was achieved for a LSM–YSZ layer only ≈2 μm thick. However, a decrease in the grain-boundary resistance would produce much better performance in thicker LSM–YSZ electrodes.     

Magnetic properties of Lu2Co17−xSix single crystals

The Co-sublattice anisotropy in Lu₂Co₁₇ consists of four competitive contributions from Co atoms at crystallographically different sites in the Th₂Ni₁₇-type of crystal structure, which result in the appearance of a spontaneous spin-reorientation transition (SRT) from the easy plane to the easy axis at elevated temperatures. In order to investigate this SRT in detail and to study the influence of Si substitution for Co on the magnetic anisotropy, magnetization measurements were performed on single crystals of Lu₂Co_17−xSi_x (x=0−3.4) grown by the Czochralski method. The SRT in Lu₂Co₁₇ was found to consist of two second-order spin reorientations, “easy-plane”–“easy-cone” at T_SR1≈680 K and “easy-cone”–“easy-axis” at T_SR2≈730 K. Upon Si substitution for Co, both SRTs shift toward the lower temperatures in Lu₂Co₁₆Si (T_SR1≈75 K and T_SR2≈130 K) with the further onset of the uniaxial type of magnetic anisotropy in the whole range of magnetic ordering for Lu₂Co_17−xSi_x compounds with x>1 due to a weakening of the easy-plane contribution from the Co atoms at the 6g and 12k sites to the total anisotropy.