Phase transitions in solid solutions (1 ? x)BaTiO3-xBaMg1/3B2/3O3 (B = Nb, Ta)

The dielectric properties of ceramic samples of (1 − x)BaTiO₃-xBaMg_1/3Nb_2/3O₃ and (1 − x)BaTio₃-xBaMg_1/3Ta_2/3O₃ solid solutions (x = 0–0.25) are investigated in the frequency range from 10 Hz to 100 kHz at temperatures of 77–450 K. It is shown that the (x−T) phase diagrams of these solid solutions at x = 0.05 have a multiphase point at which the lines of all three phase transitions of BaTiO₃ converge. Original Russian Text ? V.G. Zalesskiĭ, V.V. Lemanov, E.P. Smirnova, A.V. Sotnikov, N. V. Zaĭtseva, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 1, pp. 108–112.     

The effect of bias field on the value and temperature dependence of the piezoelectric coefficient d 31 in (1 ? x )Pb(Mg1/3Nb2/3)O3? x PbTiO3 ( x = 0.06, 0.13) single crystals

It is established that, as a result of application of even a small (∼0.5 kV cm⁻¹) bias field E, the maximum of the piezoelectric coefficient d ₃₁ in (1 − x)Pb(Mg_1/3Nb_2/3)O₃ − xPbTiO₃(x = 0.06, 0.13) crystals shifts from the Vogel-Fulcher temperature to the critical point in the E-T phase diagram of a given composition. The field dependence of the d ₃₁(T) peak magnitude has a maximum near the E values corresponding to the critical point. Original Russian Text ? A.S. Emelyanov, S.I. Raevskaya, F.I. Savenko, I.P. Raevski, M.A. Malitskaya, E.I. Sitalo, 2009, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2009, Vol. 73, No. 1, pp. 132–133.     

Lithium ion conductivity of Li5+xBaxLa3?xTa2O12 (x?=?0–2) with garnet-related structure in dependence of the barium content

The stoichiometry range and lithium ion conductivity of Li_5+x Ba _x La_3−x Ta₂O₁₂ (x = 0, 0.25, 0.50, 1.00, 1.25, 1.50, 1.75, 2.00) with garnet-like structure were studied. The powder X-ray diffraction data of Li_5+x Ba _x La_3−x Ta₂O₁₂ indicated that single phase oxides with garnet-like structure exist over the compositional range 0 ≤ x ≤ 1.25; while for x = 1.5, 1.75 and 2.00, the presence of second phase in addition to the major garnet like phase was observed. The cubic lattice parameter increases with increasing x and reaches a maximum at x = 1.25 then decreases slightly with further increase in x in Li_5+x Ba _x La_3−x Ta₂O₁₂. The impedance plots of Li_5+x Ba _x La_3−x Ta₂O₁₂ samples obtained at 33 °C indicated a minimum grain-boundary resistance (R _gb) contribution to the total resistance (R _b + R _gb) at x = 1.0. The total (bulk + grain boundary) ionic conductivity increases with increasing lithium and barium content and reaches a maximum at x = 1.25 and then decreases with further increase in x in Li_5+x Ba _x La_3−x Ta₂O₁₂. Scanning electron microscope investigations revealed that Li_6.25Ba_1.25La_1.75Ta₂O₁₂ is much more dense, and the grains are more regular in shape. Among the investigated compounds, Li_6.25Ba_1.25La_1.75Ta₂O₁₂ exhibits the highest total (bulk + grain boundary) and bulk ionic conductivity of 5.0 × 10⁻⁵ and 7.4 × 10⁻⁵ S/cm at 33 °C, respectively.     

Photoluminescent properties of Eu 3 +(Dy 3 +)-activated YNb x Ta 1 - x O 4 and REVTa 2 O 9 (RE?=?Y, La, Gd) phosphors from the hybrid precursors

In the context, Eu³⁺ (Dy³⁺)-doped YNb_xTa_1-xO₄ and REVTa₂O₉ (RE=Y, La, Gd) phosphors have been synthesized from the hybrid precursors. Both XRD and SEM indicated the particles present good crystalline state, whose crystalline grain sizes were in the range of 0.5 to 1 μm. Besides, XRD patterns of YNb_xTa_1-xO₄ (x=0.1, 0.2, 0.3, 0.5, 0.9) have shown that the phase has been changed from M^′-type YTaO₄ to M-type YNbO₄ with increasing niobium content. Furthermore, from the luminescent spectra of Eu³⁺-doped YNb_xTa_1-xO₄, it was observed that the ⁵ D ₀–⁷ F ₂ transition of Eu³⁺ was predominated and its intensity increases with increasing niobium content, as well as the intensity ratio of ⁵ D ₀–⁷ F ₂ transition to ⁵ D ₀–⁷ F ₁ transition for Eu³⁺. The optimum concentrations of Eu³⁺ and Dy³⁺ in YNb_0.5Ta_0.5O₄ have been found to be 6 and 5 mol %, respectively. At the same time, the luminescent properties of Eu³⁺ and Dy³⁺ in REVTa₂O₉ (RE=Y, La, Gd) have also been investigated that GdVTa₂O₉:Eu³⁺ (Dy³⁺) presents high luminescence, while LaVTa₂O₉:Eu³⁺ (Dy³⁺) shows weak luminescence. PACS 78.20.-e; 78.55.-m; 61.72.Ss; 32.50.+d; 81.40 Tv     

Electrical properties of amorphous (Co45Fe45Zr10)x(Al2O3)1?x nanocomposites

The electrical properties of (Co₄₅Fe₄₅Zr₁₀)_x(Al₂O₃)_1−x granular nanocomposites have been studied. The concentration dependences of electrical resistivity are S-shaped (in accordance with the percolation theory of conduction) with a threshold at a metallic component concentration of ∼41 at. %. An analysis of the temperature behavior carried out in the range 300–973 K revealed that structural relaxation and crystallization of the amorphous phase are accompanied by a decrease in the electrical resistivity of the composites above the percolation threshold and by its increase below the percolation threshold. For metallic phase concentrations x<41 at. %, variable range hopping conduction over localized states near the Fermi level was found to be dominant at low temperatures (77–180 K). A further increase in temperature brings about a crossover of the conduction mechanism from Mott’s law ln(σ) ∝ (1/T)^1/4 to ln(σ) ∝ (1/T)^1/2. A model of inelastic resonance tunneling over a chain of localized states of the dielectric matrix was used to find the average number of localized states involved in the charge transport between metallic grains. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 11, 2004, pp. 2076–2082. Original Russian Text Copyright ? 2004 by Kalinin, Remizov, Sitnikov.     

Kinetic properties of p-Mg2SixSn1 ? x solid solutions for x < 0.4

The results of a study of Mg₂Si _x Sn_{1 − x} solid solutions (x = 0.25, 0.3, 0.35, 0.4) are reported. The measurements performed cover the Seebeck coefficient, electrical conductivity and the Hall coefficient over broad ranges of temperatures (80–700 K) and carrier concentrations (10¹⁸ to 6 × 10²⁰ cm⁻³). These measurements were used to derive the band structure parameters (band gap, hole mobility, hole effective mass). The effective mass of holes was found to grow strongly with an increase in their concentration.     

The study of lithium fast ion conductors of Li3xLa0.67−xScyTi1−2yNbyO3 system

Perovskite-type lithium fast ion conductors of Li_3xLa_0.67−xSc_yTi_1−2yNb_yO₃ system were prepared by solid state reaction. X-Ray powder diffraction shows that perovskite solid solution form in the ranges of x=0.10, y≤0.10. AC impedance measurements indicate that the bulk conductivities and the total conductivities are of the order of 10⁻⁴ S·cm⁻¹ and 10⁻⁵ S·cm⁻¹ at 25 °C respectively. The compositions have low bulk activation energies of about 17 kJ/mol in the temperature ranges of 298 – 523 K and total activation energies of about 37 kJ/mol in the temperature ranges of 298 – 523 K.     

Optical properties of Nb doped SrTiO3 from first principles study

The electronic and optical properties of Nb doped SrTiO₃ are studied by ab initio linear muffin-tin orbital method in the atomic sphere approximation. The equilibrium lattice constants of SrTi_1−xNb_xO₃ with x=0.0, 0.25 and 0.5 are found by minimization of the total energy curves. The computated lattice constants are in good agreement with experimental data. Our electronic band calculation shows that the Fermi level of SrTi_1−xNb_xO₃ with x≥0.125 moves into the conduction bands and the system shows metallic behavior. The numerical results indicate that the Nb impurity atoms would lead to the distortion of the band edges. The complex dielectric function of SrTiO₃ and Nb doped SrTiO₃ are calculated using the random-phase approximation. The doping effect on the optical properties of SrTi_1−xNb_xO₃ is discussed.     

Magnetooptical properties and FMR in granular nanocomposites (Co84Nb14Ta2) x (SiO2)100? x

For nanodimensional magnetically inhomogeneous amorphous granular films of the system (Co₈₄Nb₁₄Ta₂) _x (SiO₂)_100−x , 30≤x≤60 at.% the concentration dependences of the magnetooptical Kerr effect (MOKE) spectra and FMR have been investigated. The observed changes in the MOKE and FMR spectra are associated with transformations of microstructure and topology of the nanocomposites. For the compositions within the percolation region the transversal Kerr effect increases by an order of magnitude.     

The structure of mixed fluorides Ca1?xSrxF2 and Sr1?xBaxF2 and the luminescence of Eu2+ in these crystals

The structure of the mixed fluorites Ca_1−x Sr_xF₂ and Sr_1−x Ba_xF₂, as well as the structure of the Eu²⁺ impurity center in these crystals, is calculated within the framework of the virtual-crystal method realized in the shell model and pair-potential approximation. The phenomenological dependence of the position of the lower level of the 4f ⁶5d configuration of the Eu²⁺ ion on distance to the Eu²⁺-ligand is derived. The dependences of the Stokes shift and the Huang-Rhys factor on x are calculated for the yellow luminescence in Sr_1−x Ba_xF₂:Eu²⁺. The value of x at which the lower level of the 4f ⁶5d configuration of the Eu²⁺ ion in Sr_1−x Ba_xF₂:Eu²⁺ falls within the conduction band is found. __________ Translated from Fizika Tverdogo Tela, Vol. 45, No. 5, 2003, pp. 823–826. Original Russian Text Copyright ? 2003 by Nikiforov, Zakharov, Chernyshev, Ugryumov, Kotomanov.     

Refractive indices of SrTiO3 in the infrared region

We measured transmittance and reflectance spectra of SrTiO₃ crystals in the infrared region, at 200 and 100 K. These data and our previous 300 and 20 K data are analyzed in order to derive frequency and temperature dependence of the refractive indices n and k. We thus provide detailed n(v) and k(v) data at 300, 200, 100, and 20 K, in the frequency range 25–16000 cm⁻¹.     

High resistance modulation by the electric field based on La0.9Sr0.1MnO3/SrTiO3/Si structure

A field-effect configuration based on La_0.9Sr_0.1MnO₃/SrTiO₃/Si structure is fabricated on Si substrate by laser molecular-beam epitaxy. The resistance modulation by electric field of the La_0.9Sr_0.1MnO₃/SrTiO₃/Si structure is investigated in detail. An evident resistance modulation effect is observed at 80 K. The channel resistance modulation by field effect reaches 1.4×10⁷% and 2.6×10⁶% when V _DS are −2 and −6.5 V, respectively. The ON/OFF ratio of approximately 4000 is obtained. The present results are worthy of further investigations for potential applications of resistance modulation by electrostatic field in the heterostructures consisting of perovskite oxides and Si. Supported by the National Natural Science Foundation of China (Grant No. 50672120) and the National Basic Research Program of China (Grant No. 2004CB619004)     

Identification of the La6F37 cubooctahedral clusters in mixed crystals (BaF2)1 ? x(LaF3)x by the electron paramagnetic resonance method

The electron paramagnetic resonance (EPR) spectra of mixed crystals (BaF₂)_{1 − x} (LaF₃) _x (x = 0, 0.001, 0.002, 0.005, 0.010, 0.020) doped with Ce³⁺ ions (0.1%) are investigated at a frequency v ≈ 9.5 GHz in magnetic fields up to 1.45 T at temperatures T = 10 and 15 K. The EPR spectrum of “pure” barium fluoride BaF₂ (x = 0) is characterized by a single Ce³⁺-F⁻ center with tetragonal symmetry (i.e., the O center with g _‖ = 2.601 and g _⊥ = 1.555). For a lanthanum trifluoride concentration x ≠ 0, the spectrum exhibits new lines due to the presence of the clusters containing Ce³⁺ and La³⁺ ions. The intensity of EPR signals from the O centers decreases rapidly as the lanthanum trifluoride concentration x increases. The lines attributed to a paramagnetic center with tetragonal symmetry and strongly anisotropic g factors (i.e., the K center with g _‖ = 0.725 and g _⊥ = 2.52) are separated in the complex EPR spectrum with the use of the angular dependence of the EPR signal intensity measured for the samples with x ≥ 0.002. This center is identified as a cubooctahedral cluster of the La₆F₃₇ type in which one of the La³⁺ ions is replaced by the Ce³⁺ ion. Original Russian Text ? L.K. Aminov, I.N. Kurkin, S.P. Kurzin, I.A. Gromov, G.V. Mamin, R.M. Rakhmatullin, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 11, pp. 1990–1993.     

Magnetic properties of electron-irradiated quasi-layered manganites La2?2xSr1+2xMn2O7 (x=0.3, 0.35, 0.4)

The magnetic properties of La_2−2x Sr_1+2x Mn₂O₇ polycrystals (x=0.3–0.4) are studied over a broad temperature range 80–600 K. Quasi-two-dimensional manganites have a complex magnetic structure that undergoes several transitions from one type of magnetic ordering to another. A specific feature of these manganites is a hyperbolic dependence of inverse susceptibility in the transition region from the magnetically ordered to paramagnetic state for T>360 K. This suggests the onset of ferrimagnetism. Electron irradiation to a fluence Φ=1×10¹⁸ electrons/cm² is shown to have no effect on the long-range magnetic order while favoring the formation of paramagnetic polarons and of an inhomogeneous paramagnetic state. __________ Translated from Fizika Tverdogo Tela, Vol. 45, No. 8, 2003, pp. 1440–1445. Original Russian Text Copyright ? 2003 by Arbuzova, Naumov, Arbuzov.     

119Sn and 57Fe M?ssbauer study of the local structure of perovskite-type ferrites CaFe2 ? x N x O5 ( N = Sc, Al) and manganite CaMn7O12

Anion-deficient substituted ferrites Ca₂Fe_{2 − x} N _x O₅ (N = Sc³⁺, Al³⁺) and mixed manganite CaMn₇O₁₂ have been investigated by ¹¹⁹Sn and ⁵⁷Fe probe M?ssbauer spectroscopy. The mechanism of charge compensation for heterovalent impurity Sn⁴⁺ ions in the structure of the ferrite Ca₂Fe₂O₅ has been established. The presence of nonequivalent crystallographic positions of manganese cations, caused by their charge ordering in the structure of the manganite CaMn₇O₁₂, is shown. Magnetic ordering of Mn³⁺ and Mn⁴⁺ cations in the octahedral sublattice of CaMn₇O₁₂ at T < T _M2 ≈ 90 K is established. Original Russian Text ? A.V. Sobolev, I.A. Presnyakov, K.V. Pokholok, V.S. Rusakov, T.V. Gubaidulina, A.V. Baranov, G. Demazeau, 2007, published in Izvestiya Rossiiskoi Akademii Nauk Seriya Fizicheskaya, 2007, Vol. 71, No. 9, pp. 1347–1354.     

Emission features of Ho ion in Nb2O5, Ta2O5 and La2O3 mixed Li2O-ZrO2-SiO2 glasses

Li₂O-ZrO₂-SiO₂: Ho³⁺ glasses mixed with three interesting d-block elemental oxides, viz., Nb₂O₅, Ta₂O₅ and La₂O₃, were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature. The luminescence spectra of Nb₂O₅ and Ta₂O₅ mixed Li₂O-ZrO₂-SiO₂ glasses (free of Ho³⁺ ions) have also exhibited broad emission band in the blue region. This band is attributed to radiative recombination of self-trapped excitons (STEs) localized on substitutionally positioned octahedral Ta⁵⁺ and Nb⁵⁺ ions in the glass network. The Judd-Ofelt theory was successfully applied to characterize Ho³⁺ spectra of all the three glasses. From this theory various radiative properties, like transition probability A, branching ratio β_r and the radiative lifetime τ_r, for ⁵S₂ emission levels in the spectra of these glasses have been evaluated. The radiative lifetime for ⁵S₂ level of Ho³⁺ ions has also been measured and quantum efficiencies were estimated. Among the three glasses studied the La₂O₃ mixed glass exhibited the highest quantum efficiency. The reasons for such higher value have been discussed based on the relationship between the structural modifications taking place around the Ho³⁺ ions.     

Evolution of the ferroelectric phase in ?001?-oriented (100 ? x )PbMg1/3Nb2/3O3- x PbTiO3 single crystals

The effect of a dc electric field on the nucleation and evolution of the phase with long-range order in a cubic nonpolar matrix in 〈001〉-oriented (100 − x)PbMg_1/3Nb_2/3O₃-xPbTiO₃ single-crystal relaxors as the content of PbTiO₃ is gradually increased (6 ≤ x ≤ 20, where x is the PbTiO₃ content given in molecular percent) is investigated. The optical properties of these solid solutions are studied in different modes of application of an electric field. It is shown that an applied electric field with a strength above a threshold value induces a first-order ferroelectric phase transition with a temperature hysteresis occurring between measurements performed under cooling and heating of the crystal in the electric field. As the PbTiO₃ content or electric field strength increases, the hysteresis becomes less pronounced and the first-order phase transition is suppressed. At x ∼ 20, the induced transition resembles a second-order rather than first-order transformation. It is assumed that, for compositions with x > 10 in electric fields higher than 4 kV/cm, the formation of the rhombohedral phase is accompanied by the appearance of another (possibly, monoclinic) phase associated with the rotation of the polarization vector from the [111] direction of the rhombohedral phase to the [001] direction of the tetragonal phase. Original Russian Text ? L.S. Kamzina, E.V. Snetkova, I.P. Raevskiĭ, A.S. Emel’yanov, Jiayue Xu, Weidong Xiang, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 4, pp. 725–730.     

Investigating the structure and dielectric properties of ceramic solid solutions of the SrTiO3-BiScO3 system

Ceramic samples of (1 − x)SrTiO₃-(x)BiScO₃ system with x = 0, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5 were synthesized. Neither of the end members of this system are ferroelectric materials. X-ray diffraction analysis reveals that at room temperature, the samples with x = 0.2, 0.3, 0.4, and 0.5 consisted of a mixture of two phases: a cubic center-symmetric Pm3m phase and a tetragonal polar P4mm phase. Dielectric permittivity and dielectric losses measurements of these compositions showed anomalies associated with the diffuse phase transition characteristic of ferroelectrics.     

Dielectric property of CaCu3Ti4O12 thin film grown on Nb-doped SrTiO3(100) single crystal

Thin film of CaCu₃Ti₄O₁₂ (CCTO) has been deposited on Nb-doped SrTiO₃(100) single crystal using pulsed laser deposition. The dielectric constant and AC conductivity of CCTO film in the metal–insulator–metal capacitor configuration over a wide temperature (80 to 500 K) and frequency (100 Hz to 1 MHz) range have been measured. The small dielectric dispersion with frequency observed in the lower temperature region (<300 K) indicates the presence of small defects in the deposited CCTO thin film. The frequency-dependent AC conductivity at lower temperature indicates the hopping conduction. The dielectric dispersion data has been analyzed in the light of both conductivity relaxation and Debye type relaxation with a distribution of relaxation times. Origin of dielectric dispersion is attributed to the distribution of barrier heights such that some charge carriers are confined between long-range potential wells associated with defects and give rise to dipolar polarization, while those carriers which do not encounter long-range potential well give rise to DC conductivity.     

Phase transformation behavior and dielectric characteristics of BaTi1−x(Al1/2Nb1/2)xO3 (0.01≤x≤0.40) ceramics

Microstructure, phase transformation behavior and dielectric properties of BaTi_1−x(Al_1/2Nb_1/2)_xO₃ (0.01≤x≤0.40) ceramics were investigated. A high level of (Al_1/2Nb_1/2)⁴⁺ substitution for Ti⁴⁺ ions was not conducive to the stability of the perovskite structure and resulted in the formation of BaAl₂O₄. As x was increased, lattice constants and unit cell volume decreased, reached a minimum at x=0.10 and then increased. The BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics at room temperature experienced a transformation from ferroelectric to paraelectric phase with increasing (Al_1/2Nb_1/2)⁴⁺ concentration. Meanwhile, permittivity of the BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics was markedly reduced, while Q value was slightly increased. Frequency dispersion of dielectric peak was obviously increased as x was increased from 0.01 to 0.10. It is of great interest that a dielectric abnormity represented by a broad dielectric peak at 200-400 K was observed for the composition with x=0.40.