Effect of oxygen content on the magnetic state of La0.5Ca0.5MnO3−γ perovskites

The magnetization and magnetoresistance are studied in La_0.5Ca_0.5MnO_3−γ as a function of oxygen content. It is found that as the oxygen content is decreased, this compound undergoes a sequence of transitions from an antiferromagnetic to a ferromagnetic state (γ⩾0.04), from the ferromagnetic to a spin-glass state (γ ⩾0.14), and from the spin glass to an inhomogeneous ferromagnetic state (γ⩾0.25). Strongly reduced samples (γ⩾0.25) show a large magnetoresistance despite the absence of Mn³⁺–Mn⁴⁺ pairs. It is suggested that the oxygen vacancies in the strongly reduced samples (γ⩾0.25) are long-range ordered. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 9, 583–587 (10 November 1999) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Growth of Cu0.5Tl0.5Ba2Ca3Cu4−yZnyO12−δ superconductor with optimum carriers

We have tried to vary the carriers concentration in Cu_0.5Tl_0.5Ba₂Ca₃Cu_4?yZn_yO_12?δ (y = 0, 1, 1.5, 2, 2.5) superconductor with the help of post-annealing experiments carried out in nitrogen, oxygen and air and to investigate its effects on the superconductivity parameters. The zero resistivity critical temperature [T_c(R = 0)], the magnitude of diamagnetism and critical current [I_c(H = 0)] are found to increase in Zn free samples after post-annealing in oxygen and air, while these superconducting properties have been suppressed after post-annealing in nitrogen at 550 °C for 6 h. The post-annealing of Zn-doped samples in air has marginally increased the superconducting properties, while these properties have been suppressed after post-annealing in nitrogen and oxygen. These studies have led us to the definite conclusion that the Zn-doped material has grown with optimum carriers concentration.     

Influence of Bi3+ doping on electronic transport properties of La0.5−xBixCa0.5MnO3 manganites

Electronic transport properties of La_0.5?xBi_xCa_0.5MnO₃ (x=0, 1/16, 1/8, 1/4, 3/8 and 1/2) compounds have been studied systematically to investigate their charge ordering (CO) behaviors. The results show that the CO temperature increases with the substitution of Bi³⁺ ion for La³⁺ ion, suggesting that the charge ordering is enhanced. This is attributed to the special role of the 6s² lone pair of Bi³⁺. It is found that for all the samples the adiabatic small polaronic conduction mechanism is responsible for the transport behavior above CO transition, whereas Mott's variable range hopping mechanism dominates below the CO transition. In addition, the electronic transport behavior of La_0.5?xBi_xCa_0.5MnO₃ compounds is high sensitive to an external magnetic field, which could raise fresh opportunities for application in magnetic sensors.     

Structure evolution and microwave dielectric response of (Ca0.5+xSr0.5−x)[(Al0.5Nb0.5)0.5Ti0.5]O3 solid solutions

The phase assemblage, crystal structure evolution and microwave dielectric response of (Ca_0.5+xSr_0.5−x)[(Al_0.5Nb_0.5)_0.5Ti_0.5]O₃ ceramics (abbreviated as CSANT hereafter) are investigated. Single perovskite solid solution is formed in the CSANT ceramics in Sr-rich composition range of x < −0.05, however, Ca₄Ti₃O₁₀-type layered perovskite phase begins to segregate after x = −0.05. The CSANT perovskites crystallized in Fm3m cubic symmetry in the composition range of x ≤ −0.2, however, as the Ca²⁺ content in A-site increased, the oxygen octahedral began to be anti-phase tilted at x = −0.1 and the crystal structure transited to P2₁/n pseudo-orthorhombic space group thereafter. The microwave dielectric response of the CSANT ceramics is elaborately discussed in terms of their crystallographic structure and chemical composition. When sintered at 1500 °C for 4 h, a dielectric constant ɛ_r of 52.5, a Qf product of 28000 GHz and a τ_f of +25.4 ppm/°C microwave dielectric ceramic can be obtained in the CSANT ceramics at x = 0.3.     

Dielectric and piezoelectric properties of (Bi1−x−yNdxNa1−y)0.5BayTiO3 lead-free ceramics

New lead-free (Bi_1−x−yNd_xNa_1−y)_0.5Ba_yTiO₃ ceramics were prepared by a conventional ceramic technique and their dielectric and piezoelectric properties were studied. X-ray diffraction studies reveal that Nd³⁺ and Ba²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure, and a morphotropic phase boundary (MPB) of rhombohedral and tetragonal phases is formed at 0.04 < y < 0.10. The partial substitutions of Nd³⁺ and Ba²⁺ decrease effectively the coercive field E_c and increase significantly the remanent polarization P_r. Because of lower E_c, larger P_r and the formation of the MPB, the piezoelectric properties of the ceramics are significantly enhanced at x/y = 0.02/0.06: d₃₃ = 150 pC/N and k_p = 30.5%. The ceramics exhibit relaxor characteristic, which is probably resulted from the cation disordering in the 12-fold coordination sites. The depolarization temperature T_d shows a strong compositional dependence and reaches a minimum value at the MPB. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics may contain both the polar and non-polar regions near the depolarization temperature T_d, which cause the polarization hysteresis loop become deformed near/above T_d.     

Effect of K-doping to the weak link behaviour of (Cu0.5Tl0.5−xKx)Ba2Ca2Cu3O10−δ superconductors

A systematic study of the weak link behaviour for (Cu_0.5Tl_0.5?xK_x)Ba₂Ca₂Cu₃O_10?δ (x = 0, 0.25) superconductors samples has been carried out using electrical resistivity and AC-susceptibility techniques. The K-doped (Cu_0.5Tl_0.5?xK_x)Ba₂Ca₂Cu₃O_10?δ samples were synthesized by solid-state reaction method. In magnetic susceptibility measurements, the real (χ′) and imaginary (χ″) parts of the magnetic susceptibility of (Cu_0.5Tl_0.5?xK_x)Ba₂Ca₂Cu₃O_10?δ (x = 0, 0.25) samples were measured as a function of temperature under various DC-magnetic fields up to 172 Oe. It is observed from these studies that the magnitude of the diamagnetism is substantially enhanced by K-doping. The possible reasons for the enhanced magnitude of diamagnetism have been investigated. It is observed from in-field magnetic measurements that the inter-grain coupling is improved with the K-doping. It is concluded from these studies that potassium atoms appearing at the crystal boundaries enhance inter-grain coupling and pinning mechanism in K-doped (Cu_0.5Tl_0.25K_0.25)Ba₂Ca₂Cu₃O_10?δ superconductors.     

Dielectric response of Cu0.5Tl0.5Ba2(Ca2−yMgy)(Cu0.5Zn2.5)O10−δ bulk superconductor to frequency and temperature

The dielectric properties of Cu_0.5Tl_0.5Ba₂Ca_2?yMg_yCu_0.5Zn_2.5O_10?δ (y = 0, 0.5, 1.0, 1.5) superconductor samples were studied at 79 and 290 K by means of capacitance (C) and conductance (G) measurements with the test frequency (f) in the range of 10 KHz to 10 MHz. A negative capacitance (NC) phenomenon has been observed, which is most likely arising due to higher Fermi level of ceramic superconductor samples than metal electrodes. Also the NC may be due to the space charge located at the multiple insulator–superconductor interfaces (grain boundaries) in the materials. The negative dielectric constant (ε′) and loss factor (tan δ) show strong dispersion at low frequencies. The lower thermal agitation at 79 K may enhance the polarizability and hence the dielectric constants (ε′ and ε″).     

Suppression of charge ordering and thermal hysteresis of electronic transport and magnetisation in La0.5Ca0.5Mn1−xNixO3

A series of polycrystalline La_0.5Ca_0.5Mn_1?xNi_xO₃ (x = 0.00, 0.025, 0.050, 0.075, 0.100 and 0.125) was synthesised using solid state reaction. Measurements in a cooling and warming cycle between 300 and 80 K were carried out to study the Ni-doping effects on the electrical resistivity, thermopower and magnetisation of single-phase La_0.5Ca_0.5Mn_1?xNi_xO₃. Partial substitution of Ni for Mn leads to the suppression of charge ordering state, the evidence of which is shown by the dramatic decrease in electrical resistivity and thermal hysteresis width in electrical resistivity, thermopower and magnetisation. However, the magnitude of both electrical resistivity and thermopower increases with increasing Ni content. This can be attributed to an increase in the Mn⁴⁺ concentration, which favours the antiferromagnetic state and leads to a gradual disappearance of ferromagnetic double exchange interaction. Besides, the metal–nonmetal transition temperature decreases with increasing Ni content until x = 0.075, which might arise from increased electron–phonon coupling due to less ordered spins at temperatures above ferromagnetic transition. For samples with x greater than 0.075, no metal–nonmetal transition is observed due to the suppression of double exchange mechanism.     

Microwave properties of Nd0.5Sr0.5MnO3: a key role of the (x2−y2)-orbital effects

Transmittance of the colossal magnetoresistive compound Nd_0.5Sr_0.5MnO₃ showing metal–insulator phase transition has been studied by means of the submm- and mm-wavelength band spectroscopy. An unusually high transparency of the material provided direct evidence for the significant suppression of the coherent Drude-weight in the ferromagnetic metallic state. Melting of the A-type antiferromagnetic states has been found to be responsible for a considerable increase in the microwave transmission, which was observed at the transition from the insulating to the metallic phase induced by magnetic field or temperature. This investigation confirmed a dominant role of the (x²−y²)-orbital degree of freedom in the low-energy optical properties of Nd_0.5Sr_0.5MnO₃ and other doped manganites with planar (x²−y²)-orbital order, as predicted theoretically. The results are discussed in terms of the orbital-liquid concept.     

Luminescence of the compounds Y0.5 − x Li1.5PO4:Eu x

In this paper for the first time, the compounds Y_{0.5 ? x} Li_1.5PO₄:Eu _x (YLP:Eu) were synthesized by the simple method of solid state reaction. The technology takes much time dry low temperature and little time calcined to synthesize rare earth phosphates. Their structures were analyzed by X-ray powder diffraction experiment. The excitation and emission spectra were measured at room temperature. Y_{0.5 ? x} Li_1.5PO₄:Eu _x shows the characteristice emissions of Eu³⁺ (⁵ D ₀-⁷ F _{1, 2, 3, 4} transitions dominated by ⁵ D ₀-⁷ F ₄). Incorporation of Li⁺ ions in the phosphors promote the crystallinity, reduce the amount of Y₂O₃, and lower the cost of production, moreover, transition dominated by ⁵ D ₀-⁷ F ₄ is important for a number of practical applications.     

Luminescent properties of Sr2.5−3x/2Ba0.5SmxAlO4F oxyfluorides

Effective orange Sm³⁺-doped Sr_2.5Ba_0.5AlO₄F phosphors excited at 254 and 408 nm excitation were prepared by the solid-state method. The excitation and emission spectra of Sr_2.5?3x/2Ba_0.5Sm_xAlO₄F and Sr_2.5?3x/2Ba_0.5Sm_xAlO_4?αF_1?δ (x=0.001～0.1) based on photoluminescence spectroscopy are investigated. The defects in anion-deficient Sr_2.5?3x/2Ba_0.5Sm_xAlO_4?αF_1?δ (x=0.001, 0.01) are monitored by broad-band photoluminescence emission centered near 480 nm along with the orange emission transitions of Sm³⁺. CIE values and relative luminescent intensities of Sr_2.5?3x/2Ba_0.5Sm_xAlO₄F and Sr_2.5?3x/2Ba_0.5Sm_xAlO_4?αF_1?δ by changing the Sm³⁺ content (x=0.001～0.1) are discussed.     

Phase diagram of (1−x%)(0.89Bi0.5Na0.5TiO3–0.06BaTiO3–0.05K0.5Na0.5NbO3)–x%MnO2 lead-free anti-ferroelectric ceramics

A phase diagram for the lead-free ceramics in the (1?x%)(0.89Bi_0.5Na_0.5TiO₃–0.06BaTiO₃–0.05K_0.5Na_0.5NbO₃)–x%MnO₂ (BNBKN-x%Mn) binary system is constructed for the first time based on the ferroelectric and dielectric measurements. The ferroelectric behaviors under different temperatures suggest that the ceramics are basically of relaxor anti-ferroelectric nature near room temperature. The temperature dependent dielectric properties show that when the addition of MnO₂ increases, the relaxor anti-ferroelectric phase can be stabilized to be close to the Curie point, which corresponds to a relaxor anti-ferroelectric to paraelectric phase transition.     

Seebeck-effect in the mixed state of Y−Ba−Cu−O

We report on measurements of the Seebeck-effect, the Nernst-effect, and the magnetoresistance in the mixed state of ac-axis oriented expitaxial film of Y–Ba–Cu–O. In contrast to conventional superconductors we find a large Seebeck-coefficientS, which is comparable in magnitude to the Nernst-effect. The broadening of the super-conducting transitions of magnetoresistance and Seebeck-effect are rather similar with respect to (1) the temperature dependence, (2) the dependence on the direction between magnetic field and crystal axis and (3) the dependence on the direction between magnetic field and driving forces. The large Seebeck-effect has to be attributed to dissipation due to normal quasiparticle-excitations, since the vortex-contribution to the Seebeck-effect is by far too small to account for the observed magnitude ofS. It is argued that such a quasiparticle contribution to the dissipation is large in the high-T _c superconductors because of the small coherence lengths and thus the small vortex cores. Another possibility is that granularity leads to dissipation proportional to the normal state transport properties. The Seebeck-voltage depends on all dissipative processes other than vortex motion, whereas the Nernst-effect depends only on the vortex motion. Therefore by measurements of thermomagnetic effects the various dissipative properties may be separated.     

Magnetic properties of Nd0.5Pb0.5-xSrxMnO3 materials

The structure and magnetic properties of Nd0.5Pb0.5-xSrxMnO3 (0≤x≤0.4) manganites were systematically investigated. Significant changes in Curie temperature and metal-insulator (MI) transition temperature of the samples were observed. All samples exhibited a transition from paramagnetic semiconducting to ferromagnetic metallic state.Curie temperature Tc and the MI transition temperature Tp increased with increasing Sr content. We attributed these behaviours to the enhancing of both the double exchange mechanism and the Jahn-Teller electron-phonon coupling.     

Effect of cooling method on the electrochemical performance of 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2 cathodes

0.5Li₂MnO₃·0.5LiNi_0.5Mn_0.5O₂ powders were synthesized by coprecipitation, and high temperature sintered with different cooled methods, such as cooled with furnace material, water material, and in liquid nitrogen (N-material). The effect of cooling methods on physical and electrochemical properties are discussed through the characterizations of X-ray diffraction (XRD), scanning electron microscopy, electrochemical impedance spectroscopy (EIS), and discharge, cyclic, and rate tests. XRD results show that all samples exhibit layered characteristics. The electrochemical performance results indicate that the N-material has the best electrochemical performance. The discharge capacity at 0.1 and 5 C are 279 and 99 mAhg^?1, respectively. The coulomb efficiency is highest, 78.4 %. The capacity retention after 50 cycles at 0.2 C is 97.1 %. EIS results show that the charge transfer resistance of N-materials is lowest, which is responsible for higher rate capacity.