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.     

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.     

Electrical and magnetic properties of manganites La1 ? xAgxMnO3 (x = 0.05, 0.1, and 0.2) at 77 K < T < 300 K

The electrical conductivity, magnetization, and magnetoresistance of manganites La_{1 − x} Ag _x MnO₃ have been investigated in the temperature range 78–300 K. The samples have been synthesized by the sol-gel method. At room temperature, the magnetic field of 0.6 T has no effect on the electrical conductivity. As the temperature decreases, an abrupt jump is observed in the magnetization curve due to the semiconductor-metal phase transition. This transition hardly affects the temperature dependence of the resistance.     

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.     

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.     

Investigation on cation distribution and magnetic properties in self-doped manganites La0.6−xSr0.4MnO3−δ

Self-doped manganites with nominal composition La_0.6−xSr_0.4MnO_3−δ (0≤x≤0.175) have been prepared by the sol–gel method. The X-ray diffraction (XRD) patterns and magnetic measurements indicate that the samples have two phases with the ABO₃ perovskite structure being the dominant phase and Mn₃O₄ being the minor phase when the doping level x≥0.05. On the basis of the thermal equilibrium theory of crystal defects, the contents of various ions in the perovskite phases were estimated, in which there are Mn²⁺ ions and no vacancies at A sites. The ion contents have been corrected by Rietveld fitting of the powder samples' X-ray diffraction data. The change tendency of the Curie temperature T_C vs. the Mn⁴⁺ ion content ratio at the B sites of ABO₃ perovskite phase is in accord with the experimental result of the samples La_1−xSr_xMnO₃.     

Effects of vacancy and Na doping on the structural, magnetic and transport properties of La0.8Pb0.1(□/Na)0.1MnO3

Study of structural, magnetic and transport properties of the polycrystalline La_0.8Pb_0.1□_0.1MnO₃ (LPMO) and La_0.8Pb_0.1Na_0.1MnO₃ (LPNMO) samples has been carried out. The X-ray diffraction shows that both samples crystallize in a rhombohedral structure with the space group. Ferromagnetic and insulating states are found for the LPMO sample, whereas a ferromagnetic behavior below 247 K and insulator-metal transition at 180 K are observed for the LPNMO sample. The temperature dependence of magnetic susceptibility at higher temperature for both samples reveals the presence of the Griffiths phase above the Curie temperature. The thermal evolution of magnetization in the ferromagnetic phase at low temperature varies as T^3/2, in accordance with Bloch’s law. The magnetization does not reach complete saturation up to a field of 6 T. Moreover, analysis of cell parameters indicates that the structure of LPMO is more distorted than LPNMO whereas additional results from the unit cell volume and the Curie temperature combined with previous results point to a lower average radius 〈r_A〉 (the average ionic radius, related to the one-electron bandwidth) and higher variance (the variance, measuring the quenched disorder) for LPMO reference to LPNMO. This result is in agreement with the enhancement of Griffiths phase characteristics and the low value of the spin stiffness constant D for LPMO. Finally, we show that the magnitude of the magnetic inhomogeneity depends on the random substitution in the A-site cations.     

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.     

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.     

Effect of chemical modification on the structure and dielectric and magnetic properties of multiferroic (1 – x)BiFeO3-xDyFeO3 solid solution

The solid solution of (1-x)BiFeO₃-xDyFeO₃ was prepared by solid state reactions in the form of ceramics. The effects of chemical modification by means of aliovalent ionic substitution of Ti⁴⁺ for Fe³⁺ on the structure and dielectric properties were investigated. A morphotropic phase boundary bridging the perovskite rhombohedral phase and the orthoferrite orthorhombic phase was identified at x around 0.1. The chemical modification was found to stabilize the perovsite phase. The dielectric performance of the solid solution was improved by the substitution of Ti⁴⁺ for Fe³⁺, which decreased the electric conductivity by reducing oxygen vacancies, as evidenced by the decrease in loss tangent values. Magnetic hysteresis and large saturated magnetization (0.5 μ_B/f.u.) were realized in 0.92BiFeO₃-0.08DyFeO₃ with 2% substitution of Ti⁴⁺ for Fe³⁺, which is believed to arise from the disruption of the spiral spin modulation after structural modification, and the interaction between the spins of the Dy³⁺ and Fe³⁺ at low temperatures which decouples the antiferromagnetic order between the Fe³⁺ ions.     

Effect of the spin and valence states of cobalt ions on the kinetic properties of Ho1 ? xSrxCoO3 ? δ and Er1 ? xSrxCoO3 ? δ compounds

The electrical conductivity and Seebeck effect in ceramics based on cobaltites Ho_{1 − x} Sr _x CoO_{3 − δ} (x = 0.65, 0.75, 0.85, 0.95) and Er_{1 − x} Sr _x CoO_{3 − δ} (x = 0.75, 0.85, 0.95) with a perovskite-like structure have been investigated in the temperature range T > 77 K. All the compounds under study are characterized by the variable-range-hopping conductivity with the temperature dependence of the electrical resistivity corresponding to the Mott law. It has been found that, in the Ho_0.35Sr_0.65CoO_{3 − δ} compound, thermally excited Co³⁺ ions contribute to the electrical conductivity with an increase in temperature to 250 K. The Seebeck coefficient of the systems studied decreases as the strontium concentration and temperature increase. It has been shown that, for an adequate explanation of this behavior, proper allowance must be made for the splitting of the 3d levels, as well as for the charge disproportionation of the cobalt ions.     

Structural and magnetic properties in the self-doped perovskite manganites with nominal composition La0.7Sr0.3−xMnO3−δ

Perovskite manganites with nominal composition La_0.7Sr_0.3−xMnO_3−δ (0.00≤x≤0.20) have been prepared by the sol-gel method with the highest heat treatment temperature being 1073 K. The XRD patterns indicate that when the doping level is x≤0.10 the samples have only a single phase, with the R3?c perovskite structure, while for x>0.10, the samples have two phases with the R3?c perovskite being the dominant phase and Mn₃O₄ being the second phase. A quantitative analysis and Rietveld fitting of the X-ray powder diffraction data indicate that on the basis of the thermal equilibrium theory of crystal defects there are Mn²⁺ ions at the A sites and Mn³⁺ plus Mn⁴⁺ ions at the B sites in the ABO₃ perovskite phase. The curves of magnetization versus applied magnetic field at 10 K showed that the magnetic moments of the Mn²⁺ ions at the A sites are antiparallel to those of the Mn³⁺ and Mn⁴⁺ ions at the B sites.     

Effect of the phonon and magnetic anharmonicity on the thermal and elastic properties of nearly magnetic δ-plutonium

The temperature dependences of the total heat capacity and the lattice components of the bulk modulus, the volume thermal expansion coefficient, and the mean-square deviation of atoms from the equilibrium positions of nearly magnetic δ-plutonium (using the Pu_0.96Ga_0.04 alloy as an example) have been calculated within the framework of the self-consistent thermodynamic model. The electronic heat capacity has been calculated using the results obtained in terms of the self-consistent spin-fluctuation theory based on the inclusion of the strong magnetic anharmonicity, which leads to a splitting of the electronic spectra by fluctuating exchange fields. On this basis, the effect of phonon anharmonicity not only on the lattice heat capacity but also on other thermal and elastic properties has been considered.     

Effect of the sintering temperature of ceramic manganites La0.7Mn1.3O3 ± Δ on their grain sizes, magnetic and electrical properties

The effect of the sintering temperature from 1070 to 1670 K of ceramic samples of lanthanum manganite La_0.7Mn_1.3O₃ on their grain size, structure, magnetic and resistive properties has been studied. An increase in the sintering temperature to 1270 K is shown to lead to an insignificant increase in the grain size and an increase in the density, fraction of the ferromagnetic phase in a grain, and colossal magnetoresistance. The ceramics sintering at temperatures higher than 1470 K is found to sharply increase the grain size; simultaneously, the grain takes a layered structure. The grain growth at these temperatures is established to be accompanied by manganese precipitation at the grain boundaries and likely in the grain interior. The increase in the sintering temperature is accompanied by appearance of a magnetically phase heterogeneity and a decrease in the Curie temperature and magnitude of the colossal magnetoresistance effect.     

Transformation of the acoustic mode near the structural and magnetic phase transitions in La1–xSrxMnO3 (x = 0.175) crystal

The peculiarities of the phase transitions in La_0.825Sr_0.175MnO₃ single crystal have been investigated by acoustic methods at the frequency f = 770 MHz. Generation of a magnetoelastic wave near the phase transition at 305 K is revealed, which is assigned to quasi-transverse modes. The most likely cause of the phase transition near T = 305 K and the formation of the quasi-transverse mode is the suppression of local Jahn-Teller distortions.     

Effect of Sc substitution on the structure,electrical, and magnetic properties of multiferroic BiFeO3 thin films grown by a sol–gel process

Multiferroic BiFeO₃ (BFO), Bi_1−xSc_xFeO₃ (BSF), and BiFe_1−xSc_xO₃ (BFS) (x=0.3 mol%) thin films are prepared on Pt/Ti/SiO₂/Si substrates using a sol–gel technique. The effect of Sc substitution along with the annealing ambient (N₂ and O₂) on the structure, electrical, and magnetic properties of the films are reported. X-ray diffraction (XRD) analysis reveals that the films can be prepared with the single-phase perovskite structure by annealing at 700 °C for 10 min either in O₂ or N₂ ambient. The unit cell volume increases on the substitution of Sc, which are 61.39, 62.50, and 62.57 (Å)³ for BFO, BSF, and BFS, respectively. X-ray photoelectron spectroscopy (XPS) study reveals that the chemical environments of Bi and Fe are different in BFO, BSF, BFS films. Similarly, XPS spectra for Sc2p lines in BSF and BFS also have different peak positions; this indicates Sc doping has certain chemical impact on BSF and BFS films. Systematic studies of Sc substitution along with the effect of annealing ambient on the dielectric constant (ε) and dielectric loss (tan δ), leakage current, remnant polarization (P_r), coercive field (E_c), and magnetic properties of the films are carried out. The room temperature values of ε and tan δ at 1 kHz for BFO and BFS films annealed in N₂ ambient are (∼208; 0.035) and (∼235; 0.023), respectively. The comparative value of leakage current for the BFO and BFS films at an applied field strength of 50 kV/cm are 2.997×10⁻⁴ and 1.87×10⁻⁵ A/cm², respectively. Room temperature value of coercive magnetization for BFS films has one order small compared to that of the BFO films; this indicates BFS films are magnetically soft and more suitable for potential device applications. Finally, among the studied compositions, the BFS films annealed in N₂ ambient show the best property.     

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.