Effect of excess oxygen on the electrical and magnetic properties of La1 ? xAgxMnO3 (x = 0.05, 0.1, 0.2) at 77 K < T < 300 K

A study has been made of the magnetic and electrical properties of oxygen-enriched La_{1 − x} Ag _x MnO_3.1 manganites at 77 K < T < 300 K. The samples have been produced by the sol-gel technique. The study has revealed an increase of the Curie temperature and a shift of the maximum in magnetoresistance toward high temperatures.     

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.     

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.     

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.     

Synthesis and study of photocatalytic activity of nanoscale quasi-one-dimensional Ti1 ? xVxO2 (0 ≤ x ≤ 0.13) and Zn1 ? xCoxO (0 ≤ x ≤ 0.3) oxides

A original method of synthesis of quasi-one-dimensional Ti_{1 − x} V _x (OCH₂CH₂O)₂ (0 ≤ x ≤ 0.13) and Zn_{1 − x} Co _x (HCOO)(HOCH₂CH₂O) (0 ≤ x ≤ 0.3) has been developed. The synthesis products were used as a basis for nanoscale extended Ti_{1 − x} V _x O₂ and Zn_{1 − x} Co _x O oxides. The compounds obtained and products of their thermolysis were investigated by X-ray diffraction, microscopy, IR spectroscopy, thermogravimetry, and chemical analysis; the shape and size of particles were determined by scanning electron microscopy. The good prospects of Ti_{1 − x} V _x O₂ and Zn_{1 − x} Co _x O solid solutions as photocatalysts for hydroquinone oxidation are shown.     

Morphotropic phase boundary, weak ferromagnetism, and strong piezoelectric effect in Bi1 ? xCaxFeO3 ? x/2 compounds

The crystal structure and magnetic and piezoelectric properties of the Bi_{1 − x} Ca _x FeO_{3 − x/2} system (x ≤ 0.2) are studied. The crystal-structure transformations occur in the following sequence: rhombohedral (R3c) polar phase (x ≤ 0.06) → modulated polar phase (0.07 ≤ x ≤ 0.1) → modulated antipolar phase (0.11 ≤ x ≤ 0.14). The modulated polar and antipolar phases are weakly ferromagnetic with a spontaneous magnetization of 0.25 G cm³/g (x = 0.09). In the polar weak ferromagnet with x = 0.09, a uniform piezoelec- tric response 2.5 times stronger than in the initial BiFeO₃ compound is detected by the piezoelectric force microscopy.     

Electrical conductivity and magnetic properties of La1 ? xCaxMn1 ? yFeyO3 ceramic samples (x = 0.67, y = 0, 0.05)

The temperature dependences of the magnetic susceptibility χ(T) and the electrical resistivity ρ(T) of ceramic samples of La_{1 − x} Ca _x MnO₃ with x = 0.67 (LCMO) and La_{1 − x} Ca _x Mn_{1 − y} Fe _y O₃ with x = 0.67 and y = 0.05 (LCMFO) are investigated in magnetic fields B = 50–10⁵ G and the temperature range T = 4.2–400 K. Both samples undergo a transition from the paramagnetic state to a state with charge (orbital) ordering (CO) at temperatures T _CO ≈ 272 K for LCMO and T _CO ≈ 222 K for LCMFO. The behavior of the paramagnetic phase in the temperature range 320–400 K for LCMO and 260–400 K for LCMFO is described by the Curie-Weiss law with effective Bohr magneton numbers p _eff = 4.83 μ_B (LCMO) and 4.77 μ_B (LCMFO), respectively. The disagreement between the observed positive Weiss temperatures (θ ≈ 175 K (LCMO) and θ ≈ 134 K (LCMFO)) and negative Weiss temperatures required for the antiferromagnetic ground state can be explained by the phase separation and transition to the charge-ordered state. The magnetic irreversibility for T < T _CO is accounted for by the existence of a mixture of the ferromagnetic and antiferromagnetic phases, as well as the cluster glass phase. At low temperatures, doping with iron enhances the frustration of the system, which manifests itself in a more regular behavior of the decay rate of the remanent magnetization with time. The temperature dependence of the electrical resistivity in the range of the charge-ordered phase conforms to the variable-range hopping model. The behavior of the electrical resistivity is governed by the complex structure of the density of localized states near the Fermi level, which includes a soft Coulomb gap Δ = 0.464 eV for LCMO and 0.446 eV for LCMFO. It is established that the ratio between the localization radii of charge carriers a for LCMFO and a _und for LCMO is a/a _und = 0.88. Original Russian Text ? V.S. Zakhvalinskiĭ, R. Laiho, T.S. Orlova, A.V. Khokhulin, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 1, pp. 61–68.     

Micro-Raman response and phonon oscillator parameters in solid solutions Pb1 ? xCaxTiO3 (0.40 < x < 0.62)

The temperature (295 K < T < 650 K) investigations of the polarized Raman spectra measured for a single-crystal sample of the Pb_0.54Ca_0.46TiO₃ solid solution in the frequency range 10 < ν < 1200 cm⁻¹ have established the existence of at least one specific temperature (T _c ≈ 392 K) at which the oscillator parameters of phonon modes exhibit noticeable anomalies. Similar phenomena are observed in solutions with 0.4 < x < 0.5. A sharp increase in the intensity of the spectral lines corresponding to polarization waves at temperatures immediately below T _c suggests a transformation of Pb_{1 −x} Ca _x TiO₃ (0.4 < x < 0.5) into a polar state, which does not exist for x > 0.5. Original Russian Text ? A.N. Chabanyuk, V.I. Torgashev, Yu.I. Yuzyuk, V.V. Lemanov, P. Simon, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 1, pp. 155–163.     

Emission centers in Ca1–xPrxF2+x (x = 0.35) solid solutions

Luminescence spectra of Ca_0.65Pr_0.35F_2.35 solid solutions are studied. It is found that, depending on the excitation energy, different kinds of emission centers appear in these spectra. An interconfigurational 4f ¹5d¹ →4f² luminescence is typical for single Pr³⁺ ions in tetragonal sites. Data on the structure of the solid solutions show that the emission centers involved in ¹S₀ → 4f² transitions can be attributed to Pr³⁺ ions contained in clusters.     

Thermal conductivity of single crystals of Ca1 ? xErxF2 + x and Ca1 ? xTmxF2 + x solid solutions

The thermal conductivity of single crystals of Ca_{1 − x} Er _x F_{2 + x} (x = 0.01, 0.05, 0.07, and 0.10) and Ca_{1 − x} Tm _x F_{2 + x} (x = 0.02, 0.04, and 0.06) solid solutions is studied in the temperature ranges 50–300 and 298–673 K. With increasing content of rare-earth elements, the behavior of thermal conductivity in these solid solutions changes from the characteristic of defect single crystals to glasslike. The concentration dependences of thermal conductivity for the two systems differ insignificantly.     

Sulfide compounds Me x Mn1 ? x S ( Me = Cr, Fe, V, Co): Technology, transport properties, and magnetic ordering

Electronic transitions of the metal-insulator type and magnetic transitions of the antiferromagnetic semiconductor-ferromagnetic metal type are established in cation-substituted manganese sulfides Me _x Mn_{1 − x} S (Me = Cr, Fe, V, Co), synthesized on the basis of MnS. The effect of negative colossal magnetoresistance is found and the regularities of change in the conductivity type and magnetic order are analyzed. Original Russian Text ? L.I. Ryabinkina, O.B. Romanova, S.S. Aplesnin, 2008, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2008, Vol. 72, No. 8, pp. 1115–1117.     

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).     

Low-field magnetization of ludwigites Co3O2BO3 and Co3 ? xFexO2BO3 (x ≈ 0.14)

Ludwigite single crystals of compositions Co₃O₂BO₃ and Co_{3 − x} Fe _x O₂BO₃ (x ≈ 0.14) have been synthesized. The crystal structure is investigated at room temperature, and the magnetization is studied in the temperature range T = 4.2–100 K in magnetic fields of up to 600 Oe. The orthorhombic symmetry is revealed, and the unit cell parameters are determined. A number of features are established for the temperature dependence of the magnetization. In unsubstituted Co₃O₂BO₃, two magnetic transitions are found at T _C1 = 43 K and T _C2 = 15 K. At temperatures below 40 K, spin-glass state is revealed. Substitution of iron ions for cobalt ions leads to a noticeable shift in the magnetic transitions toward the high-temperature range: T _C1 = 83 K and T _C2 = 74 K. A ferromagnetic ordering of the P type is found in the Co_{3 − x} Fe _x O₂BO₃ (x ≈ 0.14) compound. Original Russian Text ? N.V. Kazak, N.B. Ivanova, V.V. Rudenko, A.D. Vasil’ev, D.A. Velikanov, S.G. Ovchinnikov, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 5, pp. 916–919.     

Novel synthesis of NixZn1?xFe2O4 (0?≤?x?≤?1) nanoparticles and their dielectric properties

Nanocrystalline Ni _x Zn_1−x Fe₂O₄ (0 ≤ x ≤ 1) ferrite powders with average particle size 15–20 nm have been successfully prepared at a very low temperature (180 °C) by a novel auto combustion process using citric acid and ethylenediamine as a coordinating agent and bridging ligand, respectively. Phase purity of the solid solutions has been confirmed by X-ray diffraction. Morphological characterizations of the prepared samples were performed by high resolution transmission electron and field emission scanning electron microscopy. Extensive Fourier transformed infrared spectroscopic characterization has been carried out to identify the plausible mechanism of the synthesis process. Composition-dependent electrical properties (resistivity and dielectric constant) of the synthesized solid solution have been investigated. Interestingly, a non-linear variation of dielectric permittivity with respect to composition has been observed. The room temperature electrical resistivity as well as the dielectric permittivity of Ni_0.5Zn_0.5Fe₂O₄ was found to decrease with the decrease of particle size.     

La1－xSrxMnO3/TiO2 (x=0.2, 0.15, 0.04)异质pn结的整流特性

采用磁控溅射法制备的La_1-xSr_xMnO₃ (LSMO)/TiO₂异质pn结表现出很好的整流特性.室温电流电压特性曲线显示随着Sr掺杂的增加，扩散电压增大，这可能由于Sr掺杂的增加导致载流子浓度增大所致.电流电压变温特性曲线显示随着测量温度的降低，扩散电压增大，这可能由于随着测量温度的变化导致界面电子结构的变化所致.值得提出的，异质pn结电阻随温度变化曲线表现出单层LSMO的金属绝缘相变特性，并且在低测量温度时表现出随着测量温度的降低结电阻增大，这可能是由于宽带隙的TiO₂的引入导致. 关键词： 异质结 整流特性 庞磁阻     

Structure, ferroelectric and piezoelectric properties of?(Bi0.98?xLa0.02Na1?x)0.5BaxTiO3 lead-free ceramics

Lead-free (Bi_0.98−x La_0.02Na_1−x )_0.5Ba _x TiO₃ ceramics have been prepared by an ordinary sintering technique and their structure, ferroelectric and piezoelectric properties have been studied. The results of X-ray diffraction show that La²⁺ 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) exists at 0.04<x<0.10. Compared with pure Bi_0.5Na_0.5TiO₃ ceramics, the (Bi_0.98−x La_0.02Na_1−x )_0.5Ba _x TiO₃ ceramics possess much smaller coercive field E _c and larger remanent polarization P _r. Because of the low E _c (3.38 kV/mm), large P _r (46.2 μC/cm²) and the formation of the MPB of rhombohedral and tetragonal phases, the piezoelectric properties of the ceramics are significantly enhanced at x=0.06: d ₃₃=181 pC/N and k _p=36.3%. The depolarization temperature T _d reaches a minimum value near the MPB. The ceramics exhibit relaxor characteristic, which is probably a result from the cation disordering in the 12-fold coordination sites. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics may contain both polar and non-polar regions at the temperatures above T _d.     

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.     

Crystal structure and electrical properties of GdxMn1 ? xS and TixMn1 ? xSe solid solutions

Regions of the existence of sulfide Gd _x Mn_{1 − x} S and selenide Ti _x Mn_{1 − x} Se solid solutions have been identified. Their electrical and thermoelectric properties have been studied in the temperature range 80–900 K. It has been established that the substitution of Gd²⁺ and Ti²⁺ ions for Mn²⁺ cations initiates reversal of the type of charge carrier with respect to the starting compounds MnS and MnSe. The cation substitution in solid solutions brings about a change from the hole conduction (α > 0) characteristic of the manganese monosulfide and monoselenide to the electronic conduction (α < 0).     

Magnetic phases in Pr0.5Sr0.5Mn1 ? xCoxO3 (x ≤ 0.5) solid solutions

The magnetic and magnetotransport properties of Pr_0.5Sr_0.5Mn_{1 − x} Co _x O₃ (x ≤ 0.5) solid solutions have been investigated using neutron diffraction methods. The magnetization and electrical conductivity have been measured in magnetic fields up to 140 kOe. It has been established that, during cooling in the temperature range from 160 to 110 K, the compounds of compositions with a cobalt content x ≤ 0.07 undergo a structural phase transition from the high-temperature ferromagnetic phase to the antiferromagnetic phase. A further substitution of cobalt for manganese leads to a stabilization of the inhomogeneous dielectric ferromagnetic state, whereas a state of the cluster spin-glass type has been revealed in compositions with x = 0.15 and 0.20. At x ≥ 0.25, a new magnetic phase with a Curie temperature up to 210 K is formed as a result of the magnetic interaction between manganese and cobalt ions. A magnetic phase diagram of the system under investigation has been constructed.