Magnetoelectric effects in gadolinium iron borate GdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Magnetoelectric interactions have been investigated in a single crystal of gadolinium iron borate GdFe₃(BO₃)₄, whose macroscopic symmetry is characterized by the crystal class 32. Using the results of this study, the interplay of magnetic and electric orderings occurring in the system has been experimentally revealed and theoretically substantiated. The electric polarization and magnetostriction of this material that arise in spin-reorientation transitions induced by a magnetic field have been investigated experimentally. For H ‖ c and H ⊥ c, H-T phase diagrams have been constructed, and a strict correlation between the changes in the magnetoelectric and magnetoelastic properties in the observed phase transitions has been ascertained. A mechanism of specific noncollinear antiferroelectric ordering at the structural phase transition point was proposed to interpret the magnetoelectric behavior of the system within the framework of the symmetry approach in the entire temperature range. This ordering provides the conservation of the crystal class of the system when the temperature decreases to the antiferroelectric ordering point. The expressions that have been obtained for the magnetoelectric and magnetoelastic energy describe reasonably well the behavior of gadolinium iron borate observed experimentally.     

Colossal magnetodielectric effect in SmFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> multiferroic

The colossal (more than threefold) decrease in the dielectric constant ɛ in the easy-plane SmFe₃(BO₃)₄ ferroborate in a magnetic field of ∼5 kOe applied in the basal ab plane of the crystal has been found. A close relation of this effect to anomalies in the field dependence of the electric polarization has been established. It has been shown that this magnetodielectric effect is due to the contribution to ɛ from the electric susceptibility, which is related to the rotation of spins in the ab plane, arises in the region of the antiferromagnetic ordering T < T _N = 33 K, and is suppressed by the magnetic field. A theoretical model describing the main features of the behavior of ɛ and electric polarization in the magnetic field has been proposed, taking into account the additional anisotropy in the basal plane induced by the magnetoelastic stresses.     

Metamagnetism near <Emphasis Type="Italic">T</Emphasis><Subscript>C</Subscript> in Mn-substituted chalcopyrite Cd<Subscript>0.90</Subscript>Mn<Subscript>0.10</Subscript>GeAs<Subscript>2</Subscript>

The magnetic and electric properties of a Cd_0.90Mn_0.10GeAs₂ solid solution with the chalcopyrite structure have been investigated in wide temperature and field ranges. It has been found that a metamagnetic transition from a low-magnetization state to a high-magnetization one is initiated in Cd_0.90Mn_0.10GeAs₂ near the magnetic ordering temperature. This transition is accompanied by the hysteresis of magnetic properties. An external magnetic field at temperatures above T _C also induces the metamagnetic transition. When the temperature increases above T _C, the magnetization jump decreases, whereas fields inducing the metamagnetic transition increase. The band character of magnetism and metamagnetism in the effective magnetic field is assumed on the basis of the behavior of magnetization in the metamagnetic transition and analysis of the band structure of the solid solution of cadmium-germanium diarsenide with manganese.     

Effect of the la concentration on the dielectric and optical properties of the transparent ferroelectric ceramics 75PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript>-25PbTiO<Subscript>3</Subscript>

The dielectric, optical, and electro-optical properties of transparent ferroelectric ceramics 75PbMg_1/3Nb_2/3O₃-25PbTiO₃ (75PMN-25PT) with different La concentrations (2, 3, and 4 at %) have been studied. It has been shown that all the samples under study undergo a diffuse phase transition, and the degree of diffuseness increases with an increase in the La concentration. The temperature dependences of the optical transmission in different regimes of applying an electric field and the quadratic electro-optical effect have been investigated. It has been found that, at room temperature, the maximum electro-optical effect is observed in the ceramics with a La concentration of 3 at %. This is explained by the fact that the measurement temperature is close to the Vogel-Fulcher temperature at which the minimum electric field is required to induce ferroelectric states from the relaxor phase.     

Cascade of phase transitions in GdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Cascade of phase transitions in GdFe₃(BO₃)₄ at 156, 37, and 9 K has been detected by specific heat measurements and further studied by Raman scattering and Nd³⁺ spectroscopic probe method. A weakly first-order structural phase transition at 156 K is followed by a second-order antiferromagnetic ordering phase transition at 37 K and a first-order spin-reorientational phase transition at 9 K.     

Dipole ordering and ionic conductivity in NASICON-Type Na<Subscript>3</Subscript>Cr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> structures

The aspects of structure, dipole ordering, and ionic conductivity of the Na₃Cr₂(PO₄)₃ crystal with the four polymorphic phases (α, α', β, and γ) have been investigated. The features of the α-Na₃Cr₂(PO₄)₃ crystal structure and its dipole ordering and relaxation polarization in the low-temperature α and α' phases have been refined. The occurrence of Na₃Cr₂(PO₄)₃ dipole ordering in the α and α' phases and high ionic conductivity in the β and γ phases is attributed to the structural changes in the rhombohedral [Me₂(PO₄)₃]^–3_3∞ crystal frame upon phase transformations α → α', α' → β, and β → γ. A model for explaining the dipole ordering and ionic conductivity phenomena in Na₃Cr₂(PO₄)₃ is proposed.     

Magnetism of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> manganite in structurally ordered and disordered states

The specific features of the crystal structure and the magnetic state of stoichiometric lithium manganite in the structurally ordered Li[Mn₂]O₄ and disordered Li_{1 − δ}Mn_δ[Mn_{2 − δ}Li_δ]O₄ (δ = 1/6) states have been investigated using neutron diffraction, X-ray diffraction, and magnetic methods. The structurally disordered state of the manganite was achieved under irradiation by fast neutrons (E _eff ≥ 1 MeV) with a fluence of 2 × 10²⁰ cm⁻² at a temperature of 340 K. It has been demonstrated that, in the initial sample, the charge ordering of manganese ions of different valences arises at room temperature, which is accompanied by orthorhombic distortions of the cubic spinel structure, and the long-range antiferromagnetic order with the wave vector k = 2π/c(0, 0, 0.44) is observed at low temperatures. It has been established that the structural disordering leads to radical changes in the structural and magnetic states of the LiMn₂O₄ manganite. The charge ordering is destroyed, and the structure retains the cubic symmetry even at a temperature of 5 K. The antiferromagnetic type of ordering transforms into ferrimagnetic ordering with local spin deviations in the octahedral sublattice due to the appearance of intersublattice exchange interactions.     

Response of the capacitance and dielectric loss of the SrRuO<Subscript>3</Subscript>/SrTiO<Subscript>3</Subscript>/SrRuO<Subscript>3</Subscript> film heterostructures to variations in temperature and electric field

Three-layer epitaxial heterostructures with a 750-nm-thick intermediate strontium titanate layer between two strontium ruthenate conductive thin-film electrodes have been grown by laser deposition. Photolithography and ion etching have been used to form film parallel-plate capacitors based on the grown heterostructures. The capacitance (C) and dielectric loss tangent (tanδ) of the parallel-plate capacitors have been measured in the temperature range T = 4.2–300 K at an applied bias voltage of up to ±2.5 V and without it. At T > 100 K, the temperature dependence of the dielectric permittivity (ε) of the SrTiO₃ intermediate layer is well approximated by the Curie–Weiss law taking into account the capacitance induced by the penetration of an electric field into the oxide electrodes. At T ≈ 20 K, the dielectric permittivity ε of the SrTiO₃ intermediate layer decreases by approximately 20% in an electric field of 25 kV/cm. The dielectric loss tangent of the film capacitor heterostructures decreases monotonically with a decrease in the temperature in the range from 300 to 80 K and almost does not depend on the electric field strength. However, in the range from 80 to 4.2 K, the dielectric loss tangent increases nonmonotonically (abruptly) with a decrease in the temperature and decreases significantly in an applied electric field.     

Phase transitions in the (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>NbOF<Subscript>5</Subscript> oxyfluoride

The thermal and dielectric properties of the (NH₄)₂NbOF₅ oxyfluoride have been investigated. It has been established that the structural phase transitions Cmc2₁ → C2 → Ia observed at the temperatures T ₁ = 258.0 K and T ₂ = 218.9 K exhibit a nonferroelectric nature. The hydrostatic pressure, which stabilizes the initial phase and destabilizes the low-temperature phase, hardly affects the temperature range of stability of the intermediate phase. The model of sequential ordering of the structural elements due to phase transitions has been analyzed using experimental data on the entropies of the phase transitions.     

Comparative Study of the Magnetoelectric Effect in HoAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> and HoGa<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> Single Crystals

The comparative study of the magnetoelectric properties and magnetostriction of HoGa₃(BO₃)₄ and HoAl₃(BO₃)₄ single crystals has been carried out. The investigated compounds exhibit qualitatively similar magnetodielectric and inverse magnetoelectric ME _E effects with the close absolute values, which is indicative of the weak effect of a nonmagnetic metal ion. On the contrary, the magnetostriction of the galloborate has been found to be threefold higher than that of the alumoborate. In addition, the difference between the qualitative behaviors of magnetostriction has been established: the magnetic-field dependence of magnetostriction for the alumoborate has the maximum near 70 kOe at T = 4.2 K, while the galloborate magnetostriction has no maximum and does not saturate in a field of 140 kOe.     

Magnetic-resonance and thermophysical studies of the magnetic phase diagram for a GdFe<Subscript>2.1</Subscript>Ga<Subscript>0.9</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> single crystal

The antiferromagnetic resonance, heat capacity, magnetic properties, and magnetic phase diagram of a GdFe₃(BO₃)₄ crystal in which some of the iron ions were substituted by diamagnetic gallium ions have been investigated. It has been found that the Neél temperature upon diamagnetic substitution decreased to 17 K compared to 38 K in the unsubstituted crystal. The effective exchange and anisotropy fields for GdFe_2.1Ga_0.9(BO₃)₄ have been estimated from the field dependences of magnetization and resonance measurements. The magnetic phase diagram of the crystal has been constructed from magnetic and resonance measurements. In GdFe_2.1Ga_0.9(BO₃)₄, there is no spontaneous reorientation and, in the absence of a magnetic field, the crystal remains an easy-axis one in the entire domain of magnetic ordering. The critical field of the reorientation transition to an induced easy-plane state in a magnetic field along the trigonal axis has been found to increase compared to that in the unsubstituted crystal.     

Superposition of M<Subscript>5</Subscript>X<Subscript>5</Subscript> superstructures and X-ray diffraction in TiO<Subscript>1.0</Subscript> titanium monoxide

The interpretation of diffraction spectra of ordered high-temperature phases of solid solutions and strongly nonstoichiometric compounds is discussed. It has been shown that variations of the intensities of superstructure reflections, which cannot be explained within simple ordering models, can be due to the superposition of superstructures with different symmetries in the matrix of the basis crystal structure. Using an example of atom–vacancy ordering in TiO_1.0 titanium monoxide, a model of the order–order transition state formed by the superposition of low-temperature monoclinic (space group A2/m (C2/m)) and high-temperature cubic (space group Pm3?m) M₅X₅ superstructures has been proposed. It has been shown that the transition state is thermodynamically equilibrium and should be implemented instead of the M₅X₅ cubic superstructure. The transition state model can be considered as an M_(5–i)X_(5–i) superstructure (i = 1, 14/18, 11/18) with the monoclinic symmetry (space group P1m1).     

Magnetic properties of a quasi-one-dimensional NaFeGe<Subscript>2</Subscript>O<Subscript>6</Subscript> polycrystal

The magnetic properties of a synthesized dielectric NaFeGe₂O₆. polycrystal have been studied. The antiferromagnetic ordering of this compound below 15 K has been established. The Mössbauer spectrum at 300 K is a quadrupole doublet; it is characterized by an isomeric shift typical of the high-spin Fe³⁺ ion in the octahedral coordination and quadrupole splitting, which indicates distortion of the oxygen octahedron around the iron cation. Quasi-one-dimensionality of the sample magnetic structure is proved.     

Vibrational spectra of disordered oxyfluoride (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>WO<Subscript>3</Subscript>F<Subscript>3</Subscript>

Comparative analysis of the IR absorption and Raman scattering spectra of a polycrystalline sample of perovskite-type oxyfluoride (NH₄)₃WO₃F₃ has been performed in the frequency range 370–4000 cm^?1 at temperatures from 92 to 303 K, including the transition between the orientationally disordered cubic and low-symmetry phases. The conformation of WO₃F₃ octahedral groups is established and transitional anomalies of the internal modes of these groups and ammonium ions are revealed. Comparative analysis of the IR and Raman spectra suggests that the phase transition under study is mainly related to the ordering of octahedral groups and formation of W-O…H-N hydrogen bonds.     

Impedance spectroscopy analysis of Li<Subscript>2</Subscript>SnO<Subscript>3</Subscript>

In this work, Li₂SnO₃ has been synthesized by the sol–gel method using acetates of lithium and tin. Thermogravimetric analysis (TGA) has been applied to the precursor of Li₂SnO₃ to determine the suitable calcination temperature. The formation of the compound calcined at 800 °C for 9 h has been confirmed by X-ray diffraction (XRD) analysis. The Li₂SnO₃ is then pelletized and electrically characterized by using electrochemical impedance spectroscopy (EIS) in the frequency range from 50 Hz to 1 MHz. The complex impedance spectra clearly show the dominating presence of the grain boundary effect on electrical properties whereas the complex modulus plots reveal two semicircles which are due to the grain (bulk) and grain boundary. The spectra of imaginary parts of both impedance and modulus versus frequency show the existence of peaks with the modulus plots exhibiting two peaks that are ascribed to the grain and grain boundary of the material. The peak maximum shifts to higher frequency with an increase in temperature and the broad nature of the peaks indicates the non-Debye nature of Li₂SnO₃. The activation energy associated with the dielectric relaxation obtained from the electrical impedance spectra is 0.67 eV. From the electric modulus spectra, the activation energies related to conductivity relaxation in the grain and grain boundary of Li₂SnO₃ are 0.59 and 0.69 eV, respectively. The conductivity–temperature relationship is thermally assisted and obeys the Arrhenius rule with the activation energy of 0.66 eV. The conduction mechanism of Li₂SnO₃ is via hopping.     

Statistical mechanics of cation ordering in PbSc<Subscript>1/2</Subscript>Ta<Subscript>1/2</Subscript>O<Subscript>3</Subscript> and PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> solid solutions

A model Hamiltonian for B cation ordering (Sc-Nb(Ta)) in PbSc_1/2Nb_1/2O₃ and PbSc_1/2Ta_1/2O₃ solid solutions is constructed. The parameters of the model Hamiltonian are determined from the ab initio calculation within the ionic crystal model with allowance made for the deformability and the dipole and quadrupole polarizabilities of the ions. The temperatures of the phase transition due to the ordering of the B cations are calculated by the Monte Carlo method in the mean-field and cluster approximations. The phase transition temperatures calculated by the Monte Carlo method (1920 K for PbSc_1/2Ta_1/2O₃ and 1810 K for PbSc_1/2Nb_1/2O₃) are consistent with the experimental data (1770 and 1450 K, respectively). The thermodynamic properties of the cation ordering are investigated using the Monte Carlo method.     

The giant dielectric tunability effect in bulk Y<Subscript>2</Subscript>NiMnO<Subscript>6</Subscript> around room temperature

The effect of applied dc bias electric field on dielectric permittivity in bulk Y₂NiMnO₆ is investigated in this paper. It is found that a small bias field of 40 V/cm can greatly reduce the dielectric permittivity around the room temperature, compared to the much larger electric field that is required for conventional ferroelectric materials. The observed giant dielectric tunability is retained over a broad range of around room temperature and is most likely related to the charge ordering of Ni²⁺ and Mn⁴⁺ ions. This may further confirm the existence of electronic ferroelectricity in Y₂NiMnO₆.     

Muon-spin-relaxation investigation of EuMn<Subscript>2</Subscript>O<Subscript>5</Subscript>

The magnetic properties of the EuMn₂O₅ multiferroic (samples consisting of single crystals and ceramic samples) have been investigated by the muon-spin-relaxation (μSR) method in the temperature range of 10–300 K. Below the magnetic ordering temperature T _N = 40 K, the loss of the polarization of muons and the effect of the external magnetic field have been observed. Both phenomena can be explained by an additional channel of the depolarization of muons owing to the appearance of muons in a medium with a low electron density due to the charge separation process (the redistribution of the electron density in the phase transition process). The “memory” phenomenon has been revealed in a sample in the external magnetic field; the memory relaxation time depends on the size of the structure units of the samples (single crystals or ceramic grains).     

Nature of the low-energy excitations of a charge-ordered phase of La<Subscript>0.25</Subscript>Ca<Subscript>0.75</Subscript>MnO<Subscript>3</Subscript> manganites

The nature of the low-energy excitations of polycrystalline and nanostructured La_0.25Ca_0.75MnO₃ samples has been analyzed in order to investigate the mechanisms of charge ordering in manganites. It has been found that the electrodynamic response spectra of La_0.25Ca_0.75MnO₃ in the energy range of 0.5 to 90 meV and the temperature range of 5 to 300 K have no resonance features that could be attributed to the collective excitations of the charge-ordered phase. It has been shown that the absorption lines observed at frequencies of 20–40 and 80–100 cm^–1 are attributed to usual acoustic phonons becoming optically active owing to the structure phase transition and the appearance of a fourfold superstructure with a quadruple period along the crystallographic a axis. The suppression of the superstructure has been revealed in samples with nanocrystallites (≤40 nm). This suppression indicates a relatively weak coupling of the charge and magnetic order parameters with the phonon subsystem.