Magnetic anisotropy and magnetoelectric properties of Tb1 ? xErxFe3(BO3)4 ferroborates

Magnetic and magnetoelectric properties of ferroborate single crystals with complex composition (Tb_{1 − x} Er _x Fe₃(BO₃)₄, x = 0, 0.75) and with competing exchange Tb-Fe and Er-Fe interactions are investigated. Jumps in electric polarization, magnetostriction, and magnetization are observed as a result of spin-flop transitions, as well as a considerable decrease in the critical field upon an increase in the Er concentration, in a field H _c parallel to the c axis. The observed behavior of phase-transition fields is analyzed and explained using a simple model taking into account anisotropy in g factors and exchange splitting of funda-mental doublets of the easy-axis Tb³⁺ ion and easy-plane Er³⁺ ion. It is established that magnetoelectric and magnetostriction anomalies under spin-flop transitions are mainly controlled by the Tb subsystem. The Tb subsystem makes a nonmonotonic contribution ΔP _a (H _a , T) to polarization along the a axis: the value of ΔP _a reverses its sign and increases with temperature due to the contribution from the excited states of the Tb³⁺ ion. Original Russian Text ? A.K. Zvezdin, A.M. Kadomtseva, Yu.F. Popov, G.P. Vorob’ev, A.P. Pyatakov, V.Yu. Ivanov, A.M. Kuz’menko, A.A. Mukhin, L.N. Bezmaternykh, I.A. Gudim, 2009, published in Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2009, Vol. 136, No. 1, pp. 80–86.     

Magnetic phase transitions in Nd1 ? xDyxFe3(BO3)4 ferroborates

The magnetic properties of ferroborate single crystals with substituted compositions Nd_{1 − x} Dy _x Fe₃(BO₃)₄ (x = 0.15, 0.25) with competing exchange Nd-Fe and Dy-Fe interactions are investigated. For each composition, we observed a spontaneous spin-reorientation transition from the easy-axis to the easy-plane state and step anomalies on the magnetization curves for the spin-flop transition induced by a magnetic field B | c. The measured parameters and effects are interpreted using a unified theoretical approach based on the molecular field approximation and on calculations performed in the crystal-field model for the rare-earth ion. The experimental temperature dependences of the initial magnetic susceptibility from T = 2 K to T = 300 K, anomalies on the magnetization curves for B | c in fields up to 1.8 T, and their evolution with temperature, as well as temperature and field dependences of magnetization in fields up to 9 T are described. In the interpretation of experimental data, the crystal-field parameters in trigonal symmetry for the rare-earth subsystem are determined, as well as the parameters of Nd-Fe and Dy-Fe exchange interactions.     

Observation of spontaneous spin reorientation in Nd1 ? xDyxFe3(BO3)4 ferroborates with a competitive R-Fe exchange

The magnetic, magnetoelectric, and magnetoelastic properties of DyFe₃(BO₃)₄ single crystals and the Nd_0.75Dy_0.25Fe₃(BO₃)₄ substituted compound with the competitive Nd-Fe and Dy-Fe exchange interactions have been investigated in magnetic fields up to 210 kOe. It has been shown that the antiferromagnetic state in Nd_0.75Dy_0.25Fe₃(BO₃)₄ below the Néel temperature is easy-plane and a spontaneous spin-reorientation transition to a uniaxial state occurs near 25 K. Anomalies are observed in various physical characteristics in a spin-flop transition induced by the magnetic field along the trigonal axis. The H-T phase diagrams are constructed; they are in good agreement with a simple model taking into account the anisotropy of the exchange splitting and g factors of the ground doublets of the Dy³⁺ and Nd³⁺ ions. The features of the magnetoelectric effect in various magnetic phases have been studied. Spontaneous electric polarization has been revealed in the region of the existence of an easy-plane antiferromagnetic state in the substituted compound. A qualitative theoretical justification of the possibility of the appearance of the spontaneous spin-reorientation transition in the Nd_0.75Dy_0.25Fe₃(BO₃)₄ substituted compound is given. Original Russian Text ? Yu.F. Popov, A.M. Kadomtseva, G.P. Vorob’ev, A.A. Mukhin, V.Yu. Ivanov, A.M. Kuz’menko, A.S. Prokhorov, L.N. Bezmaternykh, V.L. Temerov, 2009, published in Pis’ma v Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2009, Vol. 89, No. 7, pp. 405–411.     

New nonlinear optical crystals of the M1 ? xSc3 ? yYx + y(BO3)4 (M = Ce, Pr, or Nd) family

New Y_0.57M_0.72Sc_2.71(BO₃)₄ (M = Pr or Nd) nonlinear optical crystals of the huntite structural type with sp. gr. R32 were grown by the high-temperature solution-melt method. The analogous phase with cerium was prepared by solid-state synthesis. Lattice parameters were established by X-ray diffraction patterns of the powder.     

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.     

Magnetic and band parameters of (3HgS)1–x(Al2S3)x (x = 0.5) crystals doped with manganese

Investigations of magnetic susceptibility (χ) of (3HgS)_1–x (Al₂S₃) _x (x = 0.5) crystals doped with manganese investigated by the Faraday method in the range of Т = 77–300 K and Н = 0.25–4 kOe demonstrate that peculiar magnetic properties can be due to the presence of clusters of the Mn–S–Mn–S type in these crystals. Based on the investigation of kinetic coefficients of the crystals performed for Т = 77–300 K and Н = 0.5–5 kOe, it is established that the crystals demonstrate conductivity of the n-type, and their electric conduction only very slightly depends on the temperature and shows a maximum, the Hall coefficient is independent of the temperature, while the temperature dependences of mobility exhibit a maximum. Using the concentration dependence of the effective electron mass at the Fermi level, the width of the forbidden band, the matrix element of interatomic interaction, and the effective mass on the conduction-band bottom are obtained. Based on investigations by optical methods, the presence of direct optical interband transitions in the crystals is established and the value of the optical forbidden band (at Т = 300 K) is determined.     

Magnetic and ferroelectric properties of exchange-frustrated multiferroics (Ni1 ? xTx)3V2O8 (T = Co, Mn, Zn)

The effect of the substitution of Co²⁺, Mn²⁺, and Zn²⁺ ions for Ni²⁺ ions on the magnetic, dielectric, and ferroelectric properties of vanadate single crystals (Ni_{1 − x} T _x )₃V₂O₈ has been analyzed. It has been found that the low-level (x ≤ 0.1) substitution of both magnetic and nonmagnetic ions stabilizes the ferroelectric state with a cycloidal magnetic structure. The existence region of this state is expanded to low temperatures down to 3 K for Zn²⁺ and below 1.8 K for Co²⁺ and Mn²⁺ owing to the suppression of a low-temperature weak ferromagnetic phase. At the same time, the ferroelectric phase disappears completely at large concentrations of Co and Mn. The effect of magnetic fields on the magnetic and ferroelectric states has been analyzed. It has been shown that the magnetic field along the c axis suppresses the ferroelectric state, whereas the magnetization along the antiferromagnetism axis (a axis) induces the reentrant phase transition from a paraelectric weak ferromagnetic structure to a ferroelectric structure. The corresponding H-T phase diagrams have been drawn.     

Structure and magnetism of semiconductor crystals of the (Ga1 ? xMnx)2Se3 (x = 0?0.04) compounds

Neutron diffraction and magnetic measurements have been used to study the effect of doping with Mn³⁺ ions on the fine crystal structure of the Ga₂Se₃ monoclinic compound. It has been established that the structural state of the crystals is changed even at a relatively low doping level (x = 0.04). Arguments in favor of the fact that local Jahn-Teller distortions are responsible for the formation of the fine structure and magnetism in compounds of this class are presented.     

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.     

Thermal expansion of (Ba1 ? xLax)Ti1 ? x/4O3 solid solutions

Deformation and the thermal expansion coefficient of ceramic samples of (Ba_{1 − x} La _x )Ti_{1 − x/4}O₃ solid solutions (x = 0, 0.026, 0.036, 0.054) were studied in the temperature range 120–700 K. Based on an analysis of the data obtained, the temperature-composition phase diagram is refined, and the temperature dependence of the polarization is calculated. The results are discussed in combination with the dielectric measurement data. Original Russian Text ? M.V. Gorev, I.N. Flerov, Ph. Sciau, S. Guillemet-Fritsch, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 4, pp. 746–752.     

Magnetic, magetostrictive properties, spin reorientation and M?ssbauer effect of Tb0.3Dy0.7?xPrx(Fe0.9Al0.1)1.95 alloys

The effect of Pr substitution for Dy on the magnetic and magnetostrictive properties, anisotropy, spin reorientation and M?ssbauer effect of a series of Tb_0.3Dy_0.7−x Pr _x (Fe_0.9Al_0.1)_1.95 (x=0, 0.1, 0.20, 0.25, 0.30, 0.35) alloys at room temperature have been investigated. It was found that a small amount of Pr substitution is beneficial to a decrease in the magnetocrystalline anisotropy for the Tb_0.3Dy_0.7−x Pr _x (Fe_0.9Al_0.1)_1.95 alloys. The magnetostriction decreases drastically with increasing x and the magnetostrictive effect disappears for x>0.2. However, the magnetostriction exhibits a slightly bigger value at x=0.1 than the free alloys and is saturated more easily with the magnetic field H. The saturation magnetization and Curie temperature decrease monotonously, but the spontaneous magnetostriction increases linearly with increasing x, whereas the spin reorientation temperature increases first, then decreases rapidly and reaches the maximum at x=0.1. The analysis of M?ssbauer spectra indicated that the easy magnetization direction in the {110} plane deviates slightly from the main axis of symmetry with the Pr concentration x, namely spin reorientation. Compared with Al substitution for Fe, the effect of Pr substitution for Dy on spin reorientation is relatively small. The hyperfine field increases with Pr concentration increasing, and the isomer shifts and the quadrupole splitting (QS) show weak concentration dependence. Supported by the National Natural Science Foundation of China (Grant No. 10574059), the Natural Science Foundation of Gansu Province (Grant No. 0710RJZA074), the Second Scientific Research Project of Bureau of Gansu Education and ‘Qing Lan’ Talent Engineering Funds of Lanzhou Jiaotong University     

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.     

Growth, optical parameters, and spectroscopic properties of crystals of disordered scheelite-like molybdates NaLaxGd1 ? x(MoO4)2 (x = 0–1) activated by Tm3+ ions

Polarized optical absorption spectra in the range of 450–2000 nm have been recorded for the Czochralski-grown concentration series of single crystals of mixed scheelite-like molybdates NaLa _x Gd_{1 − x} (MoO₄)₂(x = 0–1) activated by Tm³⁺ ions. The intensity parameters Ω _t (t = 2, 4, 6) of the crystals grown were determined by the Judd-Ofelt method, and the values found were used to estimate the probabilities and emission branching ratios for a number of radiative transitions of Tm³⁺ ions. The main optical constants of an Na_0.909La_0.490Gd_0.498Tm_0.035Mo_2.020O_8.048 crystal were found and the temperature dependences of the refractive index for the ordinary and extraordinary waves were investigated in the temperature range of 293–373 K. The spectral dependences of the emission cross section for the expected ³ F ₄ → ³ H ₆ laser transition of Tm³⁺ ions in an Na_0.908La_0.301Gd_0.676Tm_0.048Mo_2.019O_8.043 crystal were measured in the spectral range of 1500–2000 nm. The gain cross section of the active medium on the ³ F ₄ → ³ H ₆ laser transition of Tm³⁺ ions in this crystal was calculated using the spectral dependences of the absorption and emission cross sections.     

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.     

M?ssbauer study of compounds of Cu3 ? xFexSnS4 and Cu2Fe1 ?xZnxSnS4 systems

A M?ssbauer study of the structural and charge states of ⁵⁷Fe and ¹¹⁹Sn atoms in the compounds of Cu_{3 −x} Fe _x SnS₄ and Cu₂Fe_{1 − x} Zn _x SnS₄ systems was performed. It was shown that the iron atoms in the compounds of both systems were in the divalent and trivalent states occupying the tetrahedral positions of the structure. The character of the changes of the degree of covalency of the Fe²⁺-S, Fe³⁺-S and Sn⁴⁺-S bonds during the isomorphic substitution in the systems was established.     

Ferromagnetic resonance and magnetic microstructure in nanocomposite films of Cox(SiO2)1 ? x and (CoFeB)x(SiO2)1 ? x

This paper reports on the results of the investigation of the relation between the magnetic microstructure and ferromagnetic resonance (FMR) in ferromagnetic metal-insulator composites by using granular alloys (Co₄₁Fe₃₉B₂₀) _x (SiO₂)_{1 − x} and Co _x (SiO₂)_{1 − x} as an example. A comparative analysis of the properties of FMR spectra and parameters of random magnetic anisotropy leads to correlations between these quantities. It has been found that the main mechanism that determines the FMR line width in the films under investigation is the exchange narrowing mechanism.     

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.     

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.     

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.