Crystal structure and properties of Bi1 ? x Ca x FeO3 and Bi1 ? x Ca x FeO1 ? x Ti x O3 solid solutions

Systems of solid solutions Bi_{1 − x} Ca _x FeO₃ (I) and Bi_{1 − x} CaxFeO_{1 − x} Ti _x O₃ (II) have been obtained and their properties have been studied using neutronography and M?ssbauer spectroscopy; magnetization and permittivity have been measured. It is shown that an increase in the concentration of calcium ions in system I for x > 0.2 changes rhombohedral distortions of a unit cell (space group R3c) to tetragonal distortions (space group I4/mcm), while rhombohedral distortions in system II for x > 0.2 are replaced by orthorhombic distortions (space group Pnma). Analysis of the crystal structure has revealed strong anisotropy in vibrations of Bi and O ions in system I compounds. Systems I and II are characterized by G-type antiferromagnetic ordering of magnetic moments. In system II, spontaneous magnetization associated with the Dzyaloshinskii-Moriya interaction has been detected. According to M?ssbauer spectroscopy data, iron ions in compounds I and II are in the trivalent state and charge compensation occurs due to the formation of oxygen vacancies. The permittivity increases with the calcium concentration. Original Russian Text ? I.O. Troyanchuk, D.V. Karpinsky, M.V. Bushinskii, O. Prokhnenko, M. Kopcevicz, R. Szymczak, J. Pietosa, 2008, published in Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2008, Vol. 134, No. 1, pp. 105–112.     

Optical properties of the HfO2 ? x N x and TiO2 ? x N x films prepared by ion beam sputtering

Optical characteristics of the HfO_{2 − x} N _x and TiO_{2 − x} N _x films obtained by reactive ion beam sputtering have been investigated by spectral ellipsometry. The chemical composition of the films was determined using X-ray photoelectron spectroscopy. The nitrogen content in the oxynitride films (determined by the N₂/O₂ ratio in the gas mixture during synthesis) reached ≈9 at % for TiO_{2 − x} N _x and ≈ 6 at % for HfO_{2 − x} N _x . It is found that the dispersion relations n(λ) and k(λ) for the TiO_{2 − x} N _x films change from those characteristic of titanium dioxide to those typical of titanium nitride with an increase in the nitrogen content from 0 to ≈9 at %. The optical parameters of the HfO_{2 − x} N _x films depend weakly on the nitrogen content in the range 0–6 at %. Original Russian Text ? V.V. Atuchin, V.N. Kruchinin, A.V. Kalinkin, V.Sh. Aliev, S.V. Rykhlitskiĭ, V.A. Shvets, E.V. Spesivtsev, 2009, published in Optika i Spektroskopiya, 2009, Vol. 106, No. 1, pp. 77–82.     

Magnetic, electrical, and optical properties of Ca1 ? x Ce x MnO3 ( x ≤ 0.12) single crystals

The magnetic, electrical, and optical properties of Ca_{1 − x} Ce _x MnO₃ (x≤0.12) manganite single crystals are investigated with the aim of revealing the specific features of the multiphase electronic and magnetic state as a function of the cerium concentration and the atmosphere used for growing single crystals. It is found that the concentration dependence of the low-temperature magnetization M(x) of the single crystals is shifted toward the high-concentration range as compared to the corresponding dependence of the polycrystals, which is explained by the predominant cation deficiency. The electrical resistivity and the reflection spectra of the single crystals in the infrared spectral range indicate that charge carriers exhibit a band nature at temperatures close to room temperature. The temperature dependence of the electrical resistivity of the single crystal with x = 0.08, which has the maximum magnetization in the studied series of Ca_{1 − x} Ce _x MnO₃ compounds, unlike polycrystals, exhibits a metallic behavior over the entire temperature range. The G-type antiferromagnetic phase with the Néel and Curie temperatures T _N(G) = T _C = 100 K is characterized by maxima of the electrical resistivity ρ and the magnetoresistance Δρ/ρ = |(ρ₀ − ρ _H )/ρ₀| = 38% in the magnetic field H = 90 kOe. The magnetoresistance Δρ/ρ of the single crystals at cerium concentrations x = 0.10 and 0.12 with variations in temperature exhibit three specific features: near the temperature of charge ordering T _co, near the temperature of the magnetic phase transition to the C-type antiferromagnetic phase T _N(C), and near the temperature of the phase transition to the magnetic charge-ordered phase T _N(MCO). An anomalous temperature dependence of the magnetization is revealed for a single crystal with x = 0.10 grown in oxygen at a pressure of 5 atm, which is explained by the presence of regions with hole conductivity due to cation deficiency. The inhomogeneous electronic and magnetic state is associated with the interrelation of the charge, orbital, and spin orderings. Original Russian Text ? N.N. Loshkareva, A.V. Korolev, N.I. Solin, E.V. Mostovshchikova, S.V. Naumov, N.V. Kostromitina, A.M. Balbashov, 2009, published in Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2009, Vol. 135, No. 1, pp. 98–107.     

Enhanced magnetization of nanoparticles of Mg x Fe(3? x )O4 (0.5≤ x ≤1.5) synthesized by combustion reaction

For the first time nanocrystalline magnetic particles of Mg _x Fe_(3−x)O₄ with x ranging from 0.5 to 1.5 have been synthesized by a combustion reaction method using iron nitrate Fe(NO₃)₃.9H₂O, magnesium nitrate Mg(NO₃)₂.6H₂O, and urea CO(NH₂)₂ as fuel without intermediate decomposition and/or calcining steps. X-ray diffraction patterns of all systems showed broad peaks consistent with cubic inverse spinel structure of MgFe₂O₄. The absence of extra reflections in the diffraction patterns of as-prepared materials ensures the phase purity. The mean crystallite sizes determined from the prominent (311) peak of the diffraction using Scherrer’s equation and transmission electron microscopy micrographs were c.a. 40 nm with spherical morphology. Fourier transform infrared spectra of the as-prepared material showed traces of organic and metallic salt by-products; however, these could be removed by washing with deionized water. Typical hysteresis curves were obtained for all specimens in magnetic field up to 14 T between 4 and 340 K. The saturation magnetization was 48.3 emu/g and 31.3 emu/g, 44.8 emu/g, and 28.4 emu/g for x=1.0 and 0.8 at 4 K and 340 K, respectively. The saturation magnetization, M _s , of nanoparticles of the MgFe₂O₄ specimen is about 50% higher when compared to the bulk. The enhanced magnetization measured in our nanoparticles MgFe₂O₄ specimens may be attributed to the uncompensated magnetic moment of iron ions between the A- and B-sites, i.e., changes in the inversion factor. Our magnetization results of MgFe₂O₄ specimens are comparable to the existing data for the same compound but with different particle size and prepared by different synthesis methods.     

Dispersion of the refractive index in β-Tl1 ? x Cu x InS2 crystals (0 ≤ x ≤ 0.015)

The refractive index dispersion in β-Tl_{1 − x} Cu _x InS₂ (0 ≤ x ≤ 0.015) crystals has been studied using intrinsic interference. It is shown that these crystals are characterized by anomalous-dispersion regions at wavelengths slightly exceeding those corresponding to exciton peaks. It is established that, using intrinsic interference, one can detect excitons in these crystals at room temperature. Modulation of interference patterns is revealed, and explanation of this phenomenon is proposed. Original Russian Text ? A.N. Georgobiani, A.Kh. Matiyev, S.V. Bulyarski, T.A. Matiyeva, 2008, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2008, Vol. 72, No. 10, pp. 1523–1525.     

Phase x-T diagram of actual solid solutions of the (1 ? x )PbZrO3- x PbTiO3 system (0.37 ≤ x ≤ 0.57)

Ceramics of PbZr_{1 − x} Ti _x O₃ solid solutions were systematically studied in the range 0.37 ≤ x ≤0.57. The x-T phase diagram of the system is constructed in the range 25°C ≤ T ≤ 650°C. The diagram has a region of an indefinite symmetry in the vicinity of the transition to the nonpolar cubic phase. It is established that solid solutions in this region are characterized by weak distortions and temperature-time instability of the crystal structure. Three concentration regions are separated differing in the value of the jump in the unit cell volume ΔV at the line of transitions from the rhombohedral (tetragonal) phase to the region of indefinite symmetry. It is revealed that there are three temperature ranges differing in the behavior of the temperature dependence of the inverse permittivity, which are due to the existence of two critical Curie points at the boundary separating the ferroelectric phases from the cubic phase. Original Russian Text ? L.A. Reznichenko, L.A. Shilkina, O.N. Razumovskaya, E.A. Yaroslavtseva, S.I. Dudkina, O.A. Demchenko, Yu.I. Yurasov, A.A. Esis, I.N. Andryushina, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 8, pp. 1469–1475.     

IR reflection and Raman spectra of β-Tl1 ? x Cu x InS2 (0 ≤ x ≤ 0.015) single crystals

The IR reflection and Raman spectra of β-Tl_{1 − x} Cu _x InS₂ (0 ≤ x ≤ 0.015) single crystals have been studied in the temperature range 84–300 K. It is shown that partial replacement of thallium by copper atoms leads to a decrease in the frequencies of the corresponding oscillations in the frequency range 40–500 cm⁻¹ and does not induce (at given concentrations) local oscillations. Analysis of the transformation of the IR reflection spectra at T ₂ ≈ 185 K revealed a ferroelectric phase transition. Original Russian Text ? A.N. Georgobiani, A.Kh. Matiyev, C.V. Bulyarski, T.A. Matiyeva, 2009, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2009, Vol. 73, No. 1, pp. 138–140.     

Low-temperature properties of magnetic Ni50 + x Mn25 ? x + y Ga25 ? y shape memory alloys

The effect of atomic disordering and deviation from the Ni₂MnGa stoichiometric composition on the low-temperature properties of alloys with magnetically controlled shape memory effect is studied. The specific features of the magnetic, galvanomagnetic, and electrical properties of alloys with magnetically controlled shape memory effect are discussed. The specific features of the magnetic, galvanomagnetic, and electrical properties of alloys Ni₅₀Mn₂₅Ga₂₅, Ni₅₄Mn₂₁Ga₂₅, and Ni₅₀Mn_28.5Ga_21.5 in the temperature range 2 ≤ T ≤ 80 K under magnetic fields H ≤ 12 MA/m are studied. Original Russian Text ? N.I. Kourov, V.V. Marchenkov, V.G. Pushin, A.V. Korolev, E.B. Marchenkova, H.W. Weber, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 11, pp. 2037–2042.     

Anomalies of the pyroelectric and dielectric properties of ferroelectric ceramics of the PbZr1- x Ti x O3 system with 0.06 ≤ x ≤ 0.35 at the R3 c ? R 3 m phase transition

The temperature dependences of the pyroelectric and dielectric properties of ferroelectric ceramics of the PbZr_{1 − x} Ti _x O₃ binary system with x = 0.06, 0.07, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, and 0.35 have been obtained synchronously for each sample in the range of the structural phase transition between the states with the symmetry space groups R3c ↔ R3m. It is established that the temperatures of this phase transition for unpolarized and polarized samples coincide in the range 0.06 ≤ x ≤ 0.15. In this case, the x−T phase diagram, constructed on the basis of the pyroelectric and dielectric data, is in excellent agreement with the X-ray diffraction data on single crystals in this concentration range. The effect of dc electric fields from 5 × 10⁵ V m⁻¹ did not lead to any temperature shifts of the R3c ↔ R3m phase transition for the compositions with 0.06 ≤ x ≤ 0.25. Original Russian Text ? Yu.N. Zakharov, A.G. Lutokhin, N.A. Korchagina, V.G. Kuznetsov, 2008, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2008, Vol. 72, No. 4, pp. 589–591.     

Growth of the magnetic semiconductor Fe2? x Ti x O3± δ thin films by pulsed laser deposition

The understanding and control of the ilmenite–hematite solid solutions (Fe_2−x Ti _x O_3±δ or IH) thin film structure and properties are crucial for spintronics applications. Good quality films of Fe_2−x Ti _x O_3±δ on Al₂O₃(0001) substrates were obtained by pulsed laser deposition. For the studied compositions (x=1, 0.7, 0.5) in a wide oxygen pressure range all the films were epitaxial, with flat interfaces, and without secondary phases. Unconventional lattice strain relaxation with the increase of in-plane lattice parameter above its relaxed bulk value was observed for different film compositions, oxygen pressures, substrate temperatures, and film growth rates. This phenomenon is most likely explained by the buckling of a few first film monolayers because of a significant compressive stress induced on the film by the sapphire substrate. The IH thin films with x=0.7 and 0.5 exhibited the properties of a room temperature magnetic semiconductor. The resistivity changed over three orders of magnitude in the studied pressure range, thus clearly demonstrating the important role of oxygen stoichiometry in the creation of carriers.     

Dielectric properties of perovskite ceramics of (1–x)BiFeO3 ? x(KBi)1/2TiO3 (0.40 < x < 0.85) solid solutions from impedance spectroscopy data

The dielectric properties of the ceramics of (1 − x)BiFeO₃ − x(KBi)_1/2TiO₃ (0.40 < x < 0.85) solid solutions with an orthorhombic structure have been studied using impedance spectroscopy in the frequency range 25–10⁶ Hz at different temperatures. It has been shown that these solid solutions undergo a diffuse ferroelectric phase transition. The Curie temperature is found to be in the range 620–640 K. The activation energies of dielectric polarization relaxation (δE _M ) and dc charge carriers (ΔE _dc) are determined. It has been established that, in the vicinity of 460 K, ΔE _dc increases jumpwise as the temperature increases.     

Structure and impedance spectroscopy of Pr1? x Sr x Fe0.8Co0.2O3? δ ( x =0.1, 0.2, 0.3) thin films grown by laser ablation

Polycrystalline samples of Pr_1−x Sr _x Fe_0.8Co_0.2 O_3−δ (x=0.1, 0.2, 0.3) (PSFC) were prepared by the combustion synthesis route at 1200°C. The structure of the polycrystalline powders was analysed with X-ray powder diffraction data. The X-ray diffraction (XRD) patterns were indexed as the orthoferrite similar to that of PrFeO₃ having a single-phase orthorhombic perovskite structure (Pbnm). Pr_1−x Sr _x Fe_0.8Co_0.2O_3−δ (x=0.1, 0.2, 0.3) films have been deposited on yttria-stabilized zirconia (YSZ) single-crystal substrates at 700°C by pulsed laser deposition (PLD) for application to thin film solid oxide fuel cell cathodes. The structure of the films was analysed by XRD, scanning electron microscopy (SEM) and atomic force microscopy (AFM). All films are polycrystalline with a marked texture and present pyramidal grains in the surface with different size distributions. Electrochemical impedance spectroscopy (EIS) measurements of PSFC/YSZ single crystal/PSFC test cells were conducted. The Pr_0.7Sr_0.3Fe_0.8Co_0.2O_3−δ film at 850°C presents a lower area specific resistance (ASR) value, 1.65 Ω cm², followed by the Pr_0.8Sr_0.2Fe_0.8Co_0.2O_3−δ (2.29 Ω cm² at 850°C) and the Pr_0.9Sr_0.1Fe_0.8Co_0.2O_3−δ films (5.45 Ω cm² at 850°C).     

Optical parameters of nanostructured thin films of?electromagnetite Pb1? x Sr x (Fe0.012Ti0.988)O3

Polycrystalline Pb_1−x Sr _x (Fe_0.012Ti_0.988)O₃ (0.2≤x≤0.4) (PSFT) thin films have been grown on fused quartz substrates by metallo-organic decomposition technique. The grown films were characterized using X-ray diffraction (XRD), atomic force microscopy (AFM), source meter and UV–Vis–NIR spectrophotometer to determine the structural, microstructural, dc resistivity and optical properties. The XRD pattern confirmed that the PSFT films has distorted tetragonal single phase, which close to cubic at higher Sr concentration. AFM analysis revealed that the grains size reduces with increasing Sr concentration and their average values lies in the range of 26–9 nm. The higher values of dc resistivity of PSFT nano grains indicate that the transmission of light occurs within these grains up to short wavelength. The refractive index and the extinction coefficient were determined from the optical transmission spectrum in the wavelength range of 200–1100 nm and compared with that theoretically calculated, when fitted to a single oscillator model. The values of optical band gap were determined from Tauc’s extrapolation fitting and suggests that the transformation of electrons during transmission of light through local states within Fermi gap.     

UV excitable Y2? x ? y Gd y SiO5:Ce x phosphors for cool white light emission

Cool white light was realized in Y_2−x−y Gd _x SiO₅: Ce _y phosphor under near UV excitation, due to the occupation Ce³⁺ in Y³⁺ 1st and 2nd site, synthesized using solid state carbothermal reduction route. SEM with elemental analysis show the existence of Gd in Y₂SiO₅:Ce enhances the particles size in comparison to Y₂SiO₅:Ce phosphors alone. Gd³⁺ (0.00≤x≤0.75) and Ce³⁺ (0.02≤y≤0.10) concentration was optimized to 0.50 and 0.08 in Y₂SiO₅, respectively. The CIE chromaticity color coordinates (0.24, 0.20) are close to cool white light value which could be useful for the fabrication of cool white LED.     

Structure and electromagnetic properties of hot-pressed La0.65Sr0.35Mn1 ? x Cr x O3 manganites under different synthesis conditions

The effect of hot pressing conditions on the characteristics of the crystalline and magnetic structures of Cr-doped lanthanum-strontium manganites has been investigated for the first time using X-ray diffraction, electron microscopy, magneto-optical visualization of magnetic flux, ferromagnetic resonance, and magnetic measurements. It is shown that application of pressure during sintering affects the concentration of differentvalence ions and structural vacancies and phase separation in the manganites studied. Original Russian Text ? N.A. Vybornov, F.D. Aliev, V.K. Karpasyuk, A.A. Pankratov, A.V. Saitov, V.V. Senin, S.G. Titova, L.S. Uspenskaya, 2008, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2008, Vol. 72, No. 10, pp. 1506–1509.     

Perpendicular magnetic anisotropy in Co50Pt50 and Co50Pt50 ? x Pd x films

Atomic ordering and its effect on the perpendicular magnetic anisotropy and coercive force in Co₅₀Pt₅₀ and Co₅₀Pt_{50 − x} Pd _x (x = 3–10 at %) alloy films are investigated. The dependence of the coercive force on the film thickness is studied. It is shown that thin films of the ordered alloys become magnetically uniaxial with the easy magnetic axis normal to the plane of the film. Such films can be used for magnetic and thermomagnetic data recording and storage.     

Influence of cobalt on the structural and magnetic Inhomogeneities, phase transitions, and magnetoresistive properties of La0.6Sr0.2Mn1.2 ? x Co x O3 ± δ

The structure and properties of magnetoresistive ceramics La_0.6Sr_0.2Mn_{1.2 − x} Co _x O3 ± δ (x = 0−0.3) sintered at a temperature of 1200°C are investigated using x-ray diffraction, resistance, and magnetic (χ _ac , M, ⁵⁵Mn NMR) measurements. It is shown that the samples contain the rhombohedral (R c) perovskite (90%) and tetragonal (I4₁/amd) hausmannite (10%) phases. The lattice parameters of these phases decrease with an increase in the cobalt content x. The real perovskite structure involves point defects (anion and cation vacancies) and nanostructured defects of the cluster type. An analysis of the asymmetrically broadened ⁵⁵Mn NMR spectra confirms the high-frequency electron-hole exchange between Mn³⁺ and Mn⁴⁺ ions and a local inhomogeneity of their environment by other ions and defects of the point and cluster types. An increase in the Co content leads to an increase in the electrical resistivity, an enhancement of the magnetoresistance (MR) effect, and a decrease in the magnetic susceptibility and the temperatures of the metal-semiconductor (T _ms ) and ferromagnetic-paramagnetic (T _C) phase transitions due to the suppression of the exchange interaction between Mn³⁺ and Mn⁴⁺ ions by vacancies and clusters. The introduction of cobalt results in a decrease in the ferromagnetic component and the activation energy. The magnetoresistance effect in the vicinity of the phase transition temperatures T _ms and T _C is associated with the scattering of charge carriers from intracrystallite inhomogeneities of the lattice, and the low-temperature magnetoresistance effect is governed by the tunneling at the intercrystalline boundaries. Original Russian Text ? A.V. Pashchenko, V.P. Pashchenko, A.A. Shemyakov, N.G. Kisel’, V.K. Prokopenko, Yu.F. Revenko, A.G. Sil’cheva, V.P. Dyakonov, H. Szymczak, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 7, pp. 1257–1262.     

Synthesis of Eu x Si6? z Al z O z N8? z green phosphor and?its?luminescent properties

Rare-earth-doped oxynitride or nitride compounds have been reported to be photoluminescent and may then serve as new phosphors because of their good thermal and chemical stabilities. In this work, Eu²⁺-doped β-SiAlON phosphor with a composition of Eu _x Si_6−z Al _z O _z N_8−z (x=0.018, z=0.23) was prepared by gas-pressured solid state reaction. The crystallinity and particle morphology of the prepared phosphor were characterized. The Stokes shift and zero-phonon line were calculated mathematically and estimated from the spectral data. The temperature dependence of photoluminescence was measured from 25 to 250°C. The prepared Eu²⁺-doped β-SiAlON green phosphor showed superior thermal quenching property compared to silicate (SrBaSiO₄:Eu²⁺) green phosphor. The white light-emitting diode (LED) back-lighting unit (BLU) using the prepared β-SiAlON:Eu²⁺ green phosphor exhibited higher color gamut than a commercial silicate phosphor.     

Magnetostriction and magnetization of the intermetallic compounds R Fe2 ? x Co x ( R = Tb, Dy, Er) with compensated magnetic anisotropy

The compounds Tb_0.35Dy_0.45Er_0.2Fe_{2 − x} Co _x (0 ≤ x ≤ 2) are synthesized in both polycrystalline and single-crystal states. The composition of the new multicomponent alloys with compensated magnetic anisotropy is calculated in the framework of the single-ion magnetic anisotropy model with allowance for the data on the temperature dependences of the magnetic anisotropy constants for RFe₂ single crystals. The synthesized compounds are characterized using metallographic, chemical, X-ray diffraction, and thermomagnetic methods. A combined analysis of the magnetic and magnetoelastic properties is also carried out. It is established that the high magnetostriction characteristics of the rare-earth intermetallic compounds Tb_0.35Dy_0.45Er_0.2Fe_{2 − x} Co _x with a structure of Laves phases are observed in the region of the spin-reorientational phase transition whose temperature can be varied by properly choosing the Co content. It is found that, in the room-temperature region, the magnetic susceptibility (dλ/dH) of the composition with x = 1.3 reaches levels in excess of the value of dλ/dH for terphenol D due to the compensation of magnetic anisotropy. Original Russian Text ? I.S. Tereshina, S.A. Nikitin, G.A. Politova, A.A. Opalenko, E.A. Tereshina, I.V. Telegina, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 1, pp. 85–90.