Mixed conductivity in SrCe0.95Yb0.05O3 protonic conductors

The results of electrical conductivity measurements on SrCe_0.95Yb_0.05O₃ under controlled oxygen partial pressure and temperature are presented. A defect model consistent with experimental results is proposed which provides for P_O2^−1/4 dependent n-type, P_o2-independent oxygen ion and P_O2^+1/4 dependent p-type conductivity components. The band gap, reduction, oxidation and ion-migration energies are determined from an analysis of the data in terms of the proposed defect model. These results suggest that some earlier data interpreted in terms of protonic conduction may require re-evaluation.     

EPR of Mn2+ doping unannealed single crystal of (La2O3)0.95(CeO2)0.05

X-band room temperature EPR spectra have been recorded for Mn²⁺ ion doping unannealed (La₂O₃)_0.95(CeO₂)_0.05 host crystal. The data are analysed using a rigorous least-squares fitting procedure in which a large number of lines characterized by ΔM = ± 1, Δm = 0 transition, obtained for several orientations of the static magnetic field, are simultaneously fitted. Combined with the knowledge of the absolute sign of the hyperfine interaction parameter. A, the hyperfine Hamiltonian parameters A, B, Q as reported in this paper, are given with their correct signs. The information on the linewidth is used to deduce the deviation of the crystal-field axes of different Mn²⁺ ions from the c axis; on the basis of the model proposed here these deviations are found to be between 0 and 10°.     

微秒脉冲电场下Pb_(0.99)(Zr_(0.95)Ti_(0.05))_(0.98)Nb_(0.02)O_3陶瓷击穿过程电阻变化规律

陶瓷作为应用非常广泛的一种材料,其电击穿问题一直是研究的重点和热点.由于击穿过程涉及热、光、电多场耦合效应,目前还没有一个普适的模型能够解释陶瓷击穿问题.针对此问题进行分析,实验中采用脉冲高压发生装置击穿陶瓷,通过对陶瓷击穿过程中等效电阻的研究,揭示了PZT95/5陶瓷样品体击穿和沿面闪络形成过程的异同.结果显示,在两种击穿模式下,陶瓷样品内部均会在40 ns左右形成导电通道,陶瓷等效电阻急剧下降至10~5?量级;然后体击穿与沿面闪络的导电通道以不同的速率继续扩展;电阻减小速率与导电通道上载流子的浓度有关,二者的等效电阻以不同速率减小,直至导电通道达到稳定.     

High-performance langasite (La3Ga5SiO14) electro-optic Q-switch

By cone-light interference method, the best langasite ( La₃Ga₅SiO₁₄, LGS) crystal is chosen to make an electro-optic Q-switch. When the input energy is 28 J, the Q-switched output is 360 mJ. The stability is 0.45%; the dynamic–static ratio is 80.05%; and the total electric-optical conversion efficiency is 1.3%.     

Dielectric and piezoelectric properties of Fe2O3-doped (Na0.5K0.5)0.96Li0.04Nb0.86Ta0.1Sb0.04O3 lead-free ceramics

The effect of a small amount Fe₂O₃ (0.1-2 mol%) doping on the electrical properties of (Na_0.5K_0.5)_0.96Li_0.04Nb_0.86Ta_0.1Sb_0.04O₃ (NKLNTS) ceramics was investigated. It was found that the B-site substitution of Fe³⁺ does not change the crystal structure within the studied doping level and all modified ceramics have a pure tetragonal perovskite structure at room temperature. The addition of Fe₂O₃ can promote the sintering of NKLNTS ceramics, and simultaneously cause the grain growth so that Fe³⁺-doped NKLNTS compositions show degraded densification at higher doping level. Furthermore, the dielectric properties of the NKLNTS ceramics do not show a significant change by Fe₂O₃ doping. However, the addition of Fe₂O₃ was found to have a significant influence on the electric fatigue resistance and the durability against water. The presence of oxygen vacancies caused by the replacement of Fe³⁺ for B-site ions makes the NKLNTS ceramics harder.     

A polarized micro-Raman study of a 0.65PbMg1/3Nb2/3O3 - 0.35PbTiO3 single crystal

Polarized micro-Raman spectra of a 0.65PbMg_1/3Nb_2/3O₃-0.35PbTiO₃ (0.65PMN-0.35PT) single crystal poled in the [001] direction are obtained in a wide frequency range (50-2000 cm^-1) at different temperatures. The best fit to the Raman spectrum at 77 K is achieved using 17 Lorenzians to convolute into it, and this is proved to be a reasonable fit. According to the group theory and selection rules of overtone and combinational modes, apart from the seven Raman modes that are from first-order Raman scattering, the remaining ones are attributed to being from second-order Raman scattering. A comparison between the experimental results and theoretical predictions shows that they are in satisfactory agreement with each other. Our results indicate that at 77 K the sample belongs to the rhombohedral symmetry with the C_3v⁵ (R3m) space group (Z=1). In our study, on heating, the 0.65PMN-0.35PT single crystal undergoes a rhombohedral to tetragonal to cubic phase transition sequence. The two phase transitions occur at 340 and 440 K, which correspond to the disappearance of the soft mode near 106 cm^-1 recorded in VV polarization and the vanishing of the band around 780 cm^-1 in VH polarization, respectively.     

Electrical and mechanical properties of proton conducting SrCe0.95Yb0.05O3 − α

Yb³⁺-doped ceramic strontium cerate of exactly the composition SrCe_0.95Yb_0.05O_{3 − α} was prepared, having a relative density of 99.0 (± 0.3%). Great care was taken to obtain homogeneous, carbonate free material. Analysis are made of the X-ray powder diffraction pattern of the as-prepared dense ceramic, resulting in the orthorhombic unit cell parameters a = 6.997(2) Å, b = 12.296(3) Å, c = 8.588(2) Å, Z = 8 and d_x = 5.806(2) g cm⁻³. Bending strength values of the ceramic in non-proton and proton conducting state are found to be 177 and 194 MPa respectively. The ceramic kept under proton conducting conditions for 500 h at 300 °C to 800 °C in a N₂ flow containing 155 mbar water vapour and 245 mbar H₂, have shown to remain chemically and structurally stable. Impedance spectroscopy measurements of the bulk conductivity of the proton conducting ceramic revealed an activation energy of 53.2 kJ mol⁻¹ and a preexponential factor of 359.1 (Ω cm)⁻¹ K. In the non-proton conducting state the ceramic is mainly oxygen ion vacancy conducting, which indicates that charge compensation on substituting Yb⁺³ in SrCeO₃ takes place by oxygen ion vacancies.     

Magnetotransport properties and magnetocaloric effects of Mn1.95Cr0.05Sb0.95Ga0.05 compound

The magnetotransport properties and magnetocaloric effects of the compound Mn_{1.95}Cr_{0.05}Sb_{0.95}Ga_{0.05} have been studied. With decreasing temperature, a spontaneous first-order magnetic phase transition from ferrimagnetic (FI) to antiferromagnetic (AF) state takes place at T_s=200K. A metamagnetic transition from the AF to FI state can be induced by an external field, accompanied by a giant magnetoresistance effect of 57%. The magnetic entropy changes are determined from the temperature and field dependence of the magnetization using the thermodynamic Maxwell relation. Mn_{1.95}Cr_{0.05}Sb_{0.95}Ga_{0.05} exhibits a negative magnetocaloric effect, and the absolute values of ΔS_M^{max}(T,ΔH) are 4.4, 4.1, 3.6, 2.8 and 1.5 J/(kg·K) for magnetic field changes of 0－5T, 0－4T, 0－3T, 0－2T and 0－1T, respectively.     

Temperature Raman scattering study of CaAl0.5Ta0.5O3 perovskite crystal

Temperature Raman scattering studies were performed for CaAl_0.5Ta_0.5O₃ crystal. This material features NaCl-type ordering of Al³⁺ and Ta⁵⁺ ions at the B-site superimposed onto b⁻b⁻c⁺ octahedral tilting. Because of the existing twin-related domains in crystal structure, the micro-Raman measurements were carried out at room temperature. Some differences in Raman spectra obtained using macro- and micro-Raman system were revealed. Most of the Raman modes show monotonous red-shift with the increase in temperature. Only the cubic-like fully symmetric A_1g mode slightly increases its frequency with an increase in temperature. There are no uncontinuous changes of mode frequency in the temperature range studied. It indicates the stable character of static distortions of crystal structure relying on changes of octahedra tilt angle.     

Theory of 2×2 switch based on electro-optic and piezoelectric effects in photorefractive LiNbO3 crystal

Based on the electro-optic and piezoelectric effects, the principle of a 2×2 bypass-exchange switch in photorefractive LiNbO₃ crystal is discussed. In photorefractive volume grating, the Bragg condition can be changed by applying a field during readout. That is, by applying a specific field E_s or zero, the diffraction efficiency will be 0 or 1, respectively and this property can be used to realize the bypass or exchange operation of the switch. In this paper, considering both the piezoelectric and electro-optic effects caused by the applied electric field, we analyzed relations of both the specific field and the incident intensity ratio with respect to the writing angles and polarizations of writing beams.     

Dramatic effects of excess oxygen on physical properties and crystal structure of La0.95Sr0.05MnOy single crystal

We have examined the effects of excess oxygen on the magnetization, electrical transport properties and crystal structure of La_0.95Sr_0.05MnO_y. An antiferromagnetic insulator phase confirmed in the as-grown crystal at low temperatures changed to a ferromagnetic insulator phase after the introduction of excess oxygen. The ferromagnetic transition temperature, T_C, systematically increased with increasing oxygen content, y, due to an increase in the mean valence of manganese. However, the T_C of crystals with excess oxygen was lower than that of the La_1−xSr_xMnO_3.00 having identical manganese valence. This is considered to be a result of the competition among the mean valence of manganese, the concentration of cation vacancies, and the mean ionic radius of cations at the A-site.     

基于PbMg_(1/3)Nb_(2/3)O_3-PbTiO_3压电单晶的磁电复合薄膜材料研究进展

电子信息技术的迅速发展对磁电功能器件的微型化、智能化、多功能化以及灵敏度、可靠性、低功耗等都提出了更高的需求,传统的块体磁电功能材料已日渐不能满足上述需求,而层状磁电复合薄膜材料同时具有铁电性、铁磁性和磁电耦合等多种特性,因此能满足上述需求且有望应用于新一代磁电功能器件.层状磁电复合材料不仅具有非常丰富的物理现象和效应,而且在弱磁探测器、多态存储器、电写磁读存储器、电场可调低功耗滤波器、移相器、天线等微波器件中也具有广阔的应用前景,因而受到材料科学家和物理学家广泛的关注和研究.在层状磁电复合材料中,功能薄膜/铁电单晶异质结因其制备简单、结构设计和材料选择灵活以及电场调控方便和有效,最近十余年引起了越来越多的研究人员的兴趣.目前,以具有优异铁电和压电性能的(1-x)PbMg_(1/3)Nb_(2/3)O_3-PbTiO_3(PMN-PT)单晶作为衬底,构建功能薄膜/PMN-PT异质结已成为国内外多铁性复合薄膜材料研究领域的重要方向之一.相比于其他国家,我国科学家无论在发表的文章数量还是在文章被引用次数方面都处于领先地位,表明我国在功能薄膜/PMN-PT单晶异质结方面的研究卓有成效.迄今为止,研究人员已构建了锰氧化合物/PMN-PT、铁氧体/PMN-PT、铁磁金属/PMN-PT、稀磁半导体/PMN-PT、发光材料/PMN-PT、二维材料/PMN-PT、多层薄膜/PMN-PT、超导薄膜/PMN-PT等多种类型的异质结,在理论研究和实验方面都取得了丰富的研究成果.本文对基于PMN-PT压电单晶的磁电复合薄膜材料的研究进展进行了总结:简要介绍了与功能薄膜/PMN-PT异质结相关的研究论文发表现状;介绍了PMN-PT单晶在准同型相界附近的相图和应变特性;按照功能薄膜材料所属的体系对异质结进行了分类,并选取部分代表性的研究成果,介绍了材料的磁电性能和内涵的物理机制;最后就目前有待解决的问题和未来可能的应用方向进行了总结和展望.     

Oxygen-vacancy-related high-temperature dielectric relaxation and electrical conduction in 0.95K0.5Na0.5NbO3-0.05BaZrO3 ceramic

The crystal structure and dielectric properties of 0.95K_0.5Na_0.5NbO₃-0.05BaZrO₃ (KNN-BZ) ceramic have been investigated by X-ray diffraction and dielectric measurement. A rhombohedral distortion was caused and the dielectric permittivity near Curie temperature was significantly enhanced by introducing BZ into KNN. The dielectric and conductivity properties of the sample were studied by using AC impedance spectroscopy and universal dielectric relaxation law in detail. The typical high-temperature dielectric relaxation process was confirmed to be related to the oxygen vacancies inside the ceramic. The effect of lattice distortion on the activation energy for oxygen vacancy migration in KNN-BZ was discussed by comparing with KNN and KNN-BaTiO₃.     

Voltage-decreased electro-optical Q-switch of La3Ga5SiO14 crystal

We present a novel method to achieve voltage-decreased electro-optical Q-switch with three different blocks of optically active crystal. The dynamic/static energy rate can be up to 82%. We also find a theory function to explain the achievement of Q-switch and find the requirement of the achievement of voltage-decreased Q-switch with optically active crystal. The theory coincides with the experiment result well.     

Magnetic study of Mg0.95Mn0.05Fe2O4 ferrite nanoparticles

The magnetic properties of Mg_0.95Mn_0.05Fe₂O₄ ferrite samples with an average particle size of ∼6.0±0.6 nm have been studied using X-ray diffraction, Mössbauer spectroscopy, dc magnetization and frequency dependent real χ^′(T) and imaginary χ^″(T) parts of ac susceptibility measurements. A magnetic transition to an ordered state is observed at about 195 K from Mössbauer measurements. The zero-field-cooled (ZFC) and field-cooled (FC) magnetization have been recorded at low field and show the typical behavior of a small particle system. The ZFC curve displays a broad maximum at , a temperature which depends upon the distribution of particle volumes in the sample. The FC curve was nearly flat below , as compared with monotonically increasing characteristics of non-interacting superparamagnetic systems indicating the existence of strong interactions among the nanoparticles. A frequency-dependent peak observed in χ^′(T) is well described by Vogel-Fulcher law, yielding a relaxation time and an interaction parameter . Such values show the strong interactions and rule out the possibility of spin-glass (SG) features among the nanoparticle system. On the other hand fitting with the Néel-Brown model and the power law yields an unphysical large value of τ₀ (∼6×10⁻⁶⁹ and 1.2×10⁻²² s respectively).     

Effect of different annealing methods on ferroelectric properties of 0.95Pb(Sc0.5Ta0.5)O3-0.05PbTiO3 thin films

0.95Pb(Sc_0.5Ta_0.5)O₃-0.05PbTiO₃ thin films were prepared on LaNiO₃/SiO₂/Si substrate by radio frequency magnetron sputtering, and the films were annealed subsequently with repeated many times by two approaches: normal one-step rapid thermal annealing and innovative two-steps rapid thermal annealing. X-ray diffraction demonstrates that all the films were preferred (1 0 0) oriented and an appropriate repeat of annealing process can enhance perovskite phase of the films. Scanning electron microscopy suggests that the films treated by two-steps rapid thermal annealing show crack-free, uniform size grains and dense microstructure. Measurement of remnant polarization and leakage current dependence of electric field confirms that the films treated by two-steps rapid thermal annealing exhibit better ferroelectric properties than the films treated by one-steps rapid thermal annealing. The results reveal that microstructure plays an important role in enhanced ferroelectric properties of the 0.95Pb(Sc_0.5Ta_0.5)O₃-0.05PbTiO₃ thin films.     

Molecular dynamics simulation comparison of atomic scale intermixing at the amorphous Al2O3/semiconductor interface for a-Al2O3/Ge, a-Al2O3/InGaAs, and a-Al2O3/InAlAs/InGaAs

The structural properties of a-Al₂O₃/Ge, a-Al₂O₃/In_0.5Ga_0.5As and a-Al₂O₃/In_0.5Al_0.5As/InGaAs interfaces were investigated by density-functional theory (DFT) molecular dynamics (MD) simulations. Realistic a-Al₂O₃ samples were generated using a hybrid classical-DFT MD “melt and quench” approach. The interfaces were formed by annealing at 700 K/800 K and 1100 K with subsequent cooling and relaxation. The a-Al₂O₃/Ge interface demonstrates pronounced interface intermixing and interface bonding exclusively through Al–O–Ge bonds generating high interface polarity. In contrast, the a-Al₂O₃/InGaAs interface has no intermixing, Al–As and O–In/Ga bonding, low interface polarity due to nearly compensating interface dipoles, and low substrate deformation. The a-Al₂O₃/InAlAs interface demonstrated mild intermixing with some substrate Al atoms being adsorbed into the oxide, mixed Al–As/O and O–Al/In bonding, medium interface polarity, and medium substrate deformation. The simulated results demonstrate strong correlation to experimental measurements and illustrate the role of weak bonding in generating an unpinned interface for metal oxide/semiconductor interfaces.     

Anisotropic dielectric properties of PbYb1/2Ta1/2O3 single crystals

PbYb_1/2Ta_1/2O₃ single crystals were obtained for the first time. They were grown by the flux method. The PbOPbF₂B₂O₃ system was used as a solvent. Dielectric investigations were carried out in 1 0 0_c, 1 1 0_c and 1 1 1_c pseudocubic directions. These studies pointed to anisotropy of dielectric properties. Frequency-independent ε′(T) and ε″(T) maxima related to the antiferroelectric–paraelectric (AFE—PE) phase transition are observed for all directions at 562 K. The frequency-dependent ε′(T) and ε″(T) maxima near 400 K related to the ferroelectric (FE)–AFE phase transition are observed only in 1 1 1_c direction. The hysteresis loops were observed in this direction only. These results point that ferroelectric relaxor properties appear only in 1 1 1_c direction. We propose to consider the ferroelectric phase as ferrielectric one.     

Magnetic properties of RE0.7Ca0.3Mn0.95Fe0.05O3 (RE=Sm and Gd) manganites at low temperature

The magnetic properties of RE_0.7Ca_0.3Mn_0.95Fe_0.05O₃ perovskite with rare-earth cations (RE=Sm and Gd) were investigated by means of X-ray diffraction, Mössbauer spectroscopy, and low temperature (4.2-266 K) magnetization measurements. Structural characterization of these compounds shows that they both have orthorhombic (Pbnm) structure. The Mössbauer spectra show clear evidence of local structural distortion of the Mn(Fe)O₆ octahedron, which is based on the non-zero nuclear quadrupole interactions for high-spin Fe³⁺ ions. It was found that the local structural distortion increases significantly when Sm³⁺ is replaced by Gd³⁺. This distortion is attributed to the Jahn-Teller coupling strength as estimated from the Mössbauer effect results. The magnetic results indicate that the Curie temperature decreases as a result of replacing Sm by Gd. This is due to the decrease of the average A-site cationic radius 〈r_A〉. The rapid increase of magnetization at low temperature indicates the magnetic ordering of rare earth ions at the A-site.     

Physical properties of BaMg1/3Nb2/3O3-BaCo1/3Nb2/3O3 solid solutions

Structural, electric and magnetic properties of Ba₃Mg_1−xCo_xNb₂O₉ based dielectric ceramic compounds have been studied. The samples, prepared by a solid state reaction method, were characterised by X-ray powder diffraction (XRPD), electron microscopy (SEM), dielectric (ε(T)) and magnetic measurements (χ⁻¹(T)). The XRPD analyses showed that the crystal structure of these compounds does change by the increase of substitution degree, passing from a superstructure hexagonal-type, (no. 164), space group (SG) to a simple structure cubic-type, (no. 221), SG. However, the evolution of the elementary unit cell lattice parameter can be followed and it exhibit a linear increasing tendency with increase in the substitution, indicating the existence of a solid solution through out the investigated range of substitution (0-1). The microstructure analysis shows a variation in the grain size and also the porosity of the samples with the degree of substitution. The results are in good agreement with that of dielectric measurements, which also showed that the dielectric constant (ε) increases with the increase of cobalt content. The magnetic characterization of cobalt substituted samples showed an antiferromagnetic type super-exchange interaction between these magnetic ions. At the same time, the values of effective magnetic momentum (μ_eff) are close to the value that corresponds to Co²⁺ free ions. The study highlights the possibility of modelling these materials by substitutions, in order to improve properties of negative-positive-zero (NPO) type dielectric applications.