Susceptibility of the paraprocess in spinel ferrites with a frustrated magnetic structure

The temperature dependence of the susceptibility of the paraprocess χ_para (T) is investigated for samples in the CuGa_xAl_xFe_2?2xO₄ (x = 0.2, 0.3, 0.4, 0.5, 0.6, 0.7), CuGa_xAl_2xFe_2?3xO4 (x = 0.1, 0.2, 0.3, 0.4, 0.5), and Ga_xFe_{1? x}NiCrO₄ (x = 0.0, 0.2, 0.4, 0.6, 0.8) systems. It is found that long-range magnetic order arises in spinel ferrites at the temperature T_tran of the transition from a cluster spin-glass state to a frustrated magnetic structure with a maximum in the temperature dependence of the susceptibility of the paraprocess.     

Long-range magnetic order in Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Na<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>2</Subscript>O<Subscript>2</Subscript>

Single crystals of Li _x Na_{1 ? x} Cu₂O₂ solid solutions have been grown from the melt and crystal lattice parameters have been studied. It is found that the solid solution of this system exists in the region x ≤ 0.25. Specific heat and magnetic susceptibility are investigated on monocrystalline samples with x = 0.07, 0.14, and 0.21. Long-range magnetic order in these compounds is formed at T = 13.8, 4.1, and 14.8 K, respectively. It is found that the Néel temperature T _N in these compounds increases with Li content.     

Crystal structure and magnetic susceptibility of (CuInSe<Subscript>2</Subscript>)<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>(2MnSe)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

The crystal structure of samples in the (CuInSe₂)_{1 ? x} (2MnSe) _x system at room temperature and their magnetic susceptibility in the temperature range 77–1000 K are investigated. It is established that compositions with concentrations 0≤ x ≤ 0.2 form solid solutions with a tetragonal structure, space group I \(\bar 4\)2d (122). The specific magnetic susceptibility χ of samples with 0.1 ≤ x ≤ 0.4 at 77 K lies in the range 9 × 10^?4?1.6 × 10^t-3cm³/g. The temperature dependence of the inverse magnetic susceptibility of the sample with x = 0.4 suggests the presence of a component with antiferromagnetic ordering and a reliably measured Néel temperature that is characteristic of MnSe. The dependences χ = f(T) of the compositions with x = 0.1, 0.2, 0.3, and 0.4 indicate the occurrence of magnetic phase transitions with a change in the spin state.     

Neutron-diffraction study of the crystal structure of BaTiO<Subscript>3</Subscript> ferroelectric doped with iron

The crystal structure of iron-doped barium titanate BaTi_1–x Fe _x O₃ is studied by neutron diffraction in the range of 0 ≤ x ≤ 0.12. At low concentrations of iron, x < 0.01, and at room temperature, these compounds have a polar structure with tetragonal symmetry with space group P4mm. The temperature of the transition of the tetragonal ferroelectric phase into the cubic paraelectric phase with space group Pm \(\bar 3\) m for an iron concentration of x = 0.01 is 390 K (for pure BaTiO₃, it is 410 K). At an iron concentration of x = 0.07, the crystal structure of the studied compounds varies, and it is described by the centrosymmetric hexagonal space group P6₃/mmc. The structural parameters of various phases of compound BaTi_1–x Fe _x O₃ are determined from the experimental data.     

Synthesis,microstructure, the complex nature of the magnetic state of lanthanum manganite weakly doped by bismuth

Structural, magnetic, and resonance studies of Bi _x La_1–x MnO₃ are performed. Nanopowders of weakly doped compounds (x = 0.0–0.1) with particle sizes of ≤40 nm are prepared using the sol–gel technique. Nanopowder sintering under the same conditions leads to a sharp increase in the mean granule size with increasing Bi concentration. The 55Mn NMR signal of manganites prepared via solid synthesis corresponds to rapid exchange Mn⁴⁺ ? Mn³⁺. Measurements of the magnetic susceptibility reveal an inhomogeneity in the ferromagnetic state of the Bi _x La_1–x MnO₃ system.     

Electrical conductivity and thermopower in Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Mn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript> S sulfides

This paper reports on the results of investigations into the structural, electrical, and thermoelectrical properties of sulfides Co _x Mn_{1 ? x} S (0 ≤ x ≤ 0.4) in the temperature range 80–950 K. It is established that the thermopower coefficient α decreases significantly with an increase in the cobalt concentration in the lattice of the α-MnS compound. The Co _x Mn_{1 ? x} S compounds with cobalt concentrations in the range 0 ≤ x ≤ 0.3 are semiconductors with hole conduction (α > 0), whereas the compound with x = 0.4 exhibits metallic conduction (α < 0). It is found that the band gap E _g of the compounds under investigation varies in the range from 1.46 eV for α-MnS (x = 0) to 0.26 eV for Co _x Mn_{1 ? x} S (x = 0.4).     

Transport properties and ferromagnetism of Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>S sulfides

We have studied the resistivity and thermoelectromotive force (thermo emf) in a temperature range of T = 80–1000 K, the magnetic susceptibility and magnetization in a temperature range of T = 4.2–300 K at an external magnetic field of up to 70 kOe, and the structural characteristics of Co _x Mn_1?x S sulfides (0 ≤ x ≤ 0.4). Anomalies in the transport properties of these compounds have been found in the temperature intervals ΔT ₁ = 200–270 K and ΔT ₂ = 530–670 K and at T ₃ ～ T _N. The temperature dependences of the magnetic susceptibility, magnetization, and resistivity, as well as the current-voltage characteristics, exhibit hysteresis. In the domain of magnetic ordering at temperatures below the Néel temperature (T _N), the antiferromagnetic Co _x Mn_1?x S sulfides possess a spontaneous magnetic moment that is explained using a model of the orbital ordering of electrons in the t _2g bands. The influence of the cobalt-ion-induced charge ordering on the transport and magnetic properties of sulfides has been studied. The calculated values of the temperatures corresponding to the maxima of charge susceptibility, which are related to a competition between the on-site Coulomb interaction of holes in various subbands and their weak hybridization, agree well with the experimental data.     

Superconductivity and metal-insulator transition in Cu(Ir<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Rh<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>S<Subscript>4</Subscript>

A new thiospinel CuIr₂S₄ exhibits a metal-insulator (M-I) transition at 226 K, while CuRh₂S₄ shows a superconducting transition at 4.70 K. We present a systematic study of electrical and magnetic properties of Cu(Ir_1?x Rh _x )₂S₄. TheM-I transition of CuIr₂S₄ is accompanied by a structural phase transition from tetragonal symmetry in insulating phase to cubic symmetry in high temperature metallic phase. With increasing Rh contentx, the sharpM-I transition shifts to lower temperature forx≦0.10. The samples show semiconductive behavior for 0.10≦0.30 between 4.2 and 300 K, and recover the metallic state forx≧0.50. The superconducting transition may occur for very close tox=1.00. Magnetic susceptibility shows the jump at theM-I transition temperature and the variation ofx leads to a systematic change of the magnetic susceptibilities, which is consistent with the electrical characteristic feature.     

Structure and dielectric properties of solid solutions Bi7Ti4 + x W x Ta1–2x O21 (x = 0–0.5)

A number of solid solutions Bi₇Ti_{4 + x} W _x Ta_1–2x O₂₁ (x = 0–0.5) have been synthesized from oxides by solid-phase reaction. The crystal structure, the electrophysical characteristics, and the microstructure of the prepared ceramic samples have been studied. According to X-ray powder diffraction, all the compounds are single-phase with the structure of mixed-layer Aurivillius phases (m = 2.5) with the orthorhombic crystal lattice (space group I2cm, Z = 2). Temperature dependences of the relative permittivity ε(T) of the compound have been measured, from which it has been found that the Curie temperature T _C of perovskite-like oxides Bi₇Ti_{4 + x} W _x Ta_1–2x O₂₁ (x = 0–0.5) decreases linearly as substitution parameter x decreases. The activation energies of charge carriers have been found in different temperature ranges.     

Spin-dimerization in rare-earth substituted La<Subscript>2</Subscript>RuO<Subscript>5</Subscript>

The Ru-Ru spin-singlet formation in La_2 ? x L n _x RuO₅ (Ln = Pr, Nd, Sm, Gd, Dy) was investigated by measurements of the specific heat and magnetic susceptibility. After subtraction of the lattice contribution from the specific heat (C _p ), similar excess entropy values were obtained for all compounds. These entropies can be explained by the formation of antiferromagnetic Ru-spin dimers at low temperatures and provide a lower estimate for the intradimer exchange strength. Pronounced changes in the transition temperatures and a broadening of the corresponding peak in C _p were observed. These changes depend on the rare-earth element and are due to local structural changes and heterogeneities caused by the substitution. The magnetic susceptibilities can be described by the sum of a rare-earth paramagnetic moment and the susceptibility of the unsubstituted La₂RuO₅. Density functional theory (DFT) calculations were performed for various compounds to investigate the origin of the magnetic transition and the relationship between structural changes and the spin-dimerization temperature. The combination of the present results with previous structural investigations supports the model of a spin-pairing of the Ru moments which occurs as a reason of the structural phase transition in La_2 ? x L n _x RuO₅.     

The Vogel-Fulcher law as a criterion for identifying a mixed ferroelectric-glass phase in potassium tantalate doped with lithium

The dynamic dielectric response and the nonlinear dielectric susceptibility of K_1?xLi_xTaO₃ (x=0.010, 0.016, 0.030) compounds are measured in a dc electric field in the temperature range 4≤T≤150 K. It is found that the permittivity ?′ of K_1?xLi_xTaO₃ samples with two lower concentrations of lithium impurities decreases in an electric field E. For samples with a lithium concentration x=0.030, the permittivity ?′ decreases in electric fields E>1 kV/cm and increases in fields E<0.5 kV/cm. The observed dependences of the maximum of the permittivity on the temperature and the frequency of the measuring field obey the Arrhenius law for samples with lower concentrations of lithium impurities (x=0.010, 0.016) and the Vogel-Fulcher law for samples with a higher lithium concentration (x=0.030). The results of the theoretical treatment performed in the framework of the random-field theory are consistent with the experimental data. It is established that the Arrhenius law is valid for dipole glass phases, whereas the Vogel-Fulcher law holds true for a mixed ferroelectric-glass phase in which the short-range and long-range polar orders coexist. The inference is made that the results of measurements of the dielectric response can be used to identify a mixed ferroelectric-glass phase in any disordered ferroelectric material.     

Anomalous thermopower in heavy-fermion compounds CeB<Subscript>6</Subscript>, CeAl<Subscript>3</Subscript>, and CeCu<Subscript>6 − <Emphasis Type="Italic">x</Emphasis></Subscript>Au<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

High-precision measurements of thermopower have been performed in a wide temperature range (2–300 K) for a series of cerium-based heavy-fermion compounds, including CeB₆, CeAl₃, CeCu₆, and substitutional solid solutions of the CeCu_{6 ? x} Au _x system (x = 0.1, 0.2). All compounds exhibit an unusual (logarithmic) asymptotic behavior of the temperature dependence of the Seebeck coefficient: S ∝ ?lnT. In the case of cerium hexaboride, this anomalous behavior of S(T) is accompanied by the appearance of weak-carrier-localization-mode asymptotics in the conductivity (σ(T) ∝ T ^0.39), while the paramagnetic susceptibility χ(T) and the effective mass of charge carriers m _eff(T) vary according to a power law (χ(T), m _eff(T) ∝ T ^?0.8) in the temperature interval T = 10–80 K. This behavior corresponds to renormalization of the density of states at the Fermi level. The observed anomalous behavior of thermopower in CeB₆ and other cerium-based intermetallic compounds is attributed to the formation of heavy fermions (many-body states in the metal matrix) at low temperatures.     

Synthesis,structure, and optical and photocatalytic properties of quasi-one-dimensional ZnO doped with Со<Subscript>3</Subscript>O<Subscript>4</Subscript> and carbon

One-dimensional nanocomposites Zn_1–x Co _x O_1–y С _у :nCo₃O₄ and solid solutions Zn_1–x Co _x O_1–y С _у , which are promising photocatalysts for the oxidation of toxic organic compounds in visible light, are obtained via the thermolysis of Zn_1–x Co _x (HCOO)(OCH₂CH₂O)_1/2 (0.1 ≤ x ≤ 0.5) precursor in a controlled gaseous atmosphere.     

Effect of cation substitution in Cs<Subscript>1–2<Emphasis Type="Italic">x</Emphasis></Subscript>Ba<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>H<Subscript>2</Subscript>PO<Subscript>4</Subscript> on structural properties and proton conductivity

We synthesized compounds with partial substitution of Cs⁺ cations in CsH₂PO₄ by Ba²⁺ cations. The structural, electron transport and thermodynamic properties of Cs_1–2x Ba _x H₂PO₄ (x = 0–0.15) were studied for the first time with the help of a set of physicochemical methods: infrared and impedance spectroscopy, X-ray diffraction and synchronous thermal analysis. The proton conductivity of Cs_1–2x Ba _x H₂PO₄ at 50–230°C was investigated in detail by impedance measurements. The formation of solid substitution solutions isostructural with CsH₂PO₄ (P2₁/m) is observed in the range of substitution degrees of x = 0–0.1, with a slight decrease in the unit cell parameters and some salt amorphization. The conductivity of disordered Cs_1–2x Ba _x H₂PO₄ in the low-temperature region increases by two orders of magnitude at x = 0.02 and increases with an increasing fraction of barium cations by three or four orders of magnitude at x = 0.05–0.1; the superionic phase transition practically disappears. At x = 0.15, heterophase systems based on salts are formed, showing high conductivity and a further decrease in the activation energy of conductivity to 0.63 eV. The conductivity of the high-temperature phase of Cs_1–2x Ba _x H₂PO₄ does not change with increasing fraction of the substituent.     

On the Theory of Plasmon Dispersion in Electron-Doped Cuprates

An explicit expression for the dynamic charge susceptibility for electron-doped cuprates has been derived. This expression accurately reproduces the wave vector dependence of the plasmon frequency observed in inelastic X-ray scattering experiments for Nd_{2 – x}Ce_xCuO₄. The imaginary part of the charge susceptibility along the triangular path in the Brillouin zone is plotted. It is demonstrated that the spectral weight of the plasmon mode near q = 0 is negligibly low. The calculated frequencies of the plasmon mode for all wave vectors in the Brillouin zone turn out to lie outside the range of damping related to electron?hole excitations. A formula for the charge susceptibility is derived within the t?t′?t″?J model supplemented by the Coulomb interaction operator and three-site terms. The derivation is performed by the Green’s function technique employing the formalism of composite Hubbard operators and the Mori projection method, which have proved themselves in the analysis of collective spin excitations. The used Fourier transform of the Coulomb interaction corresponds to the monolayer model with a spatially periodic structure, which is embedded in a three-dimensional crystal lattice.     

Effect of phase transitions on the exciton absorption spectrum of Rb<Subscript>x</Subscript>K<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ag<Subscript>4</Subscript>I<Subscript>5</Subscript> superionic conductors

The absorption spectrum of thin films of solid solutions of Rb_xK_1?xAg₄I₅ superionic conductors is investigated in the energy range 3–6 eV at temperatures from 90 to 290 K upon heating and cooling. It is established that the temperature dependences of the spectral position E _m and the half-width Γ of the long-wavelength exciton band are determined by the exciton-phonon interaction and the generation of Frenkel defects at phase transitions to the superionic state. Fluctuations of the composition of solid solutions do not affect the behavior of the dependences E _m (x) and Γ(x) at 90 K, which is indicative of the localization of excitons in the AgI sublattice of these compounds. A difference in the dependences T _c 1(x) and T _c 2(x) (the γ → β and β → α phase transitions, respectively) is revealed: the curve T _c 1(x) has a minimum at x ≈ 0.5, whereas the curve T _c 2(x) shows a weak maximum.     

Mössbauer study of copper ferrite diluted by Ga<Superscript>3+</Superscript> and Al<Superscript>3+</Superscript> ions

Mössbauer spectra of the CuGa _x Al_2x Fe_{2 ? 3x} O₄ system (x = 0.1, 0.2, 0.3, 0.4, 0.5) have been studied at a temperature of 295 K. The results obtained are compared with Mössbauer data for the CuGa _x Al _x Fe_2?2x O₄ system. It is established that the hyperfine magnetic fields H _B (for octahedral sites) and H _A (for tetrahedral sites) for ferrites in both systems with ferrimagnetic ordering decrease linearly depending on the total number of nonmagnetic ions in octahedral and tetrahedral sites of the two systems.     

Proton conductivity and phase composition of mixed salts in the systems <Emphasis Type="Italic">M</Emphasis>H<Subscript>2</Subscript>PO<Subscript>4</Subscript>–CsHSO<Subscript>4</Subscript> (<Emphasis Type="Italic">M</Emphasis> = Cs,K)

Phase transformations, electrical transport and thermal properties of the systems K_1?xCs_x(H₂PO₄)_1–x(HSO₄)_x (x = 0.01–0.95) and Cs(H₂PO₄)_1–x(HSO₄)_x (x = 0.01–0.30) have been studied in detail. It has been shown that the mixed compounds Cs(H₂PO₄)_1–x(HSO₄)_x are characterized by an increase in the low-temperature electrical conductivity by one to five orders of magnitude depending on the composition, as well as by the disappearance of the superionic phase transition at x ≥ 0.15. The partial substitution of HSO₄^- ions for the anions in CsH₂PO₄ at x = 0.01–0.10 leads to the formation of Cs(H₂PO₄)_1?x(HSO₄)_x solid solutions isostructural with the CsH₂PO₄ (P2₁/m) phase. For Cs(H₂PO₄)_1–x(HSO₄)_x with x = 0.15–0.30 at room temperature, there is a stabilization of the high-temperature cubic phase isostructural with the CsH₂PO₄ (\(Pm\overline 3 m\)) phase existing in CsH₂PO₄ at temperatures above 230°C. The stability of the \(Pm\overline 3 m\) cubic phase at room temperature has been investigated using X-ray powder diffraction, ¹H NMR spectroscopy, and impedance spectroscopy. In the K_1–xCs_x(H₂PO₄)_1–x(HSO₄) system, there are two regions of compositions with x = 0.05–0.50 and 0.60–0.95, where the proton conductivity and thermal properties are determined respectively by the formation of the CsH₅(PO₄)₂ phase, which is stoichiometrically different from the initial salts, and the potassium-containing phase, which is isostructural with the superionic salt Cs₃(HSO₄)₂(H₂PO₄).     

Magnetic Structures and Magnetic Phase Transitions in Rare-Earth <Emphasis Type="Italic">R</Emphasis>Mn<Subscript>2</Subscript>Si<Subscript>2</Subscript> Intermetallic Compounds (<Emphasis Type="Italic">R</Emphasis> = Sm,Tb)

The magnetic structures that form in La_1–xR_xMn₂Si₂ (R = Sm, Tb) layered compounds with various concentrations x have been determined by magnetic neutron diffraction and magnetic measurements, and the magnetic phase diagrams have been built. It is shown that the formation of the magnetic structures is dependent not only on exchange interactions, but also on the type of the magnetic anisotropy of a rare-earth atom. It is found that, in La_1–xTb_xMn₂Si₂ compounds with 0.2 < x < 0.5, the competition of the Tb–Mn and Mn–Mn interlayer exchange interactions and the existence of a strong uniaxial magnetic anisotropy in the Mn and Tb sublattices leads to the frustrated magnetic state and prevents the formation of the long-range magnetic order in the Tb sublattice.     

A statistical model of a metallic inclusion in semiconducting media

The atomic dynamics of the binary Al_100–xCu_x system is simulated at a temperature T = 973 K, a pressure p = 1.0 bar, and various copper concentrations x. These conditions (temperature, pressure) make it possible to cover the equilibrium liquid Al_100–xCu_x phase at copper concentrations 0 ≤ x ≤ 40% and the supercooled melt in the concentration range 40% ≤ x ≤ 100%. The calculated spectral densities of the time correlation functions of the longitudinal \({\tilde C_L}\)(k, ω) and transverse \({\tilde C_T}\)(k, ω) currents in the Al_100–xCu_x melt at a temperature T = 973 K reveal propagating collective excitations of longitudinal and transverse polarizations in a wide wavenumber range. It is shown that the maximum sound velocity in the v_L(x) concentration dependence takes place for the equilibrium melt at an atomic copper concentration x = 10 ± 5%, whereas the supercooled Al_100–xCu_x melt saturated with copper atoms (x ≥ 40%) is characterized by the minimum sound velocity. In the case of the supercooled melt, the concentration dependence of the kinematic viscosity ν(x) is found to be interpolated by a linear dependence, and a deviation from the linear dependence is observed in the case of equilibrium melt at x < 40%. An insignificant shoulder in the ν(x) dependence is observed at low copper concentrations (x < 20%), and it is supported by the experimental data. This shoulder is caused by the specific features in the concentration dependence of the density ρ(x).