Structural and magnetic phase transformations in the BiFeO<Subscript>3</Subscript>-CaFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> system

The crystal structure and magnetic properties of the Bi_{1 ? x} Ca _x Fe_{1 ? x/2}Nb _x/2O₃ system were studied. It is shown that, at x ≤ 0.15, the unit-cell symmetry of solid solutions is rhombohedral (space group R3c). Solid solutions with x ≥ 0.3 have an orthorhombic unit cell (space group Pbnm). The rhombohedral compositions are antiferromagnetic, while the orthorhombic compositions exhibit a small spontaneous magnetization due to Dzyaloshinski?-Moriya interaction. In CaFe_0.5Nb_0.5O₃, the Fe³⁺ and Nb⁵⁺ ions are partially ordered and the unit cell is monoclinic (space group P2₁/n). In the concentration range 0.15 < x < 0.30, a two-phase state (R3c + Pbnm) is revealed.     

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.     

Isotropic positive magnetoresistance in Co-Al<Subscript>2</Subscript>O<Subscript>n</Subscript> nanocomposites

The magnetotransport properties of Co_x(Al₂O_n)_{100 ? x} nanocomposites were studied in a wide concentration range (34 ≤ x ≤ 74 at %). Negative tunnel magnetoresistance reaching 6.5% in a field of 10 kOe was established. In addition to the negative magnetoresistance, the Co_x(Al₂O_n)_{100 ? x} composites were found to exhibit positive magnetoresistance reaching 1.5% in fields of 10 kOe over the concentration range corresponding to the percolation threshold (54 ≤ x ≤ 67 at %). The positive magnetoresistance is assumed to be due to the simultaneous existence in the composite structure of clusters and individual nanoparticles characterized by different values of the magnetic anisotropy and due to the dipole-dipole interaction between the clusters and nearest neighbor particles.     

Positive magnetoresistance of La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript>/C Composites at room temperature

Two-phase composites xLa_0.7Sr_0.3MnO₃/(100–x)C (x = 5–85 mass %) have been synthesized. The magnetoresistive properties of these materials in magnetic fields from 0 to 15 kOe have been investigated. It has been shown that, at room temperature, the positive isotropic magnetoresistance for samples with x = 50–60 mass % reaches 15%.     

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.     

Crystal-structure and magnetic phase transformations in solid solutions of BiFeO<Subscript>3</Subscript>-AFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> (A = Ca,Sr, Ba,Pb)

Solid solutions of Bi_{1 ? x} A _x (Fe_{1 ? x/2}Nb _x/2)O₃, where A = Ca, Ba, and Pb, are obtained and their crystal structure and magnetic properties are investigated. It is shown that for A = Ca and x ≈ 0.15, the symmetry of the unit cell changes from rhombohedral (space group R3c) to orthorhombic (Pbnm). The transformation leads to the emergence of spontaneous magnetization due to the Dzyaloshinskii-Moriya interaction. Solid solutions with A = Pb remain rhombohedral up to a concentration of x = 0.3. Spontaneous magnetization sharply increases in the compound with x ≈ 1 at low temperatures and is due to the formation of the spin-glass component.     

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.     

Suppression of superconductivity in layered Bi<Subscript>4</Subscript>O<Subscript>4</Subscript>S<Subscript>3</Subscript> by Ag doping

We report X-ray diffraction, magnetization and transport measurements for polycrystalline samples of the new layered superconductor Bi_4?x Ag _x O₄S₃(0 ≤ x ≤ 0.2). The superconducting transition temperature (T _C) decreases gradually and finally suppressed when x < 0.10. Accordingly, the resistivity changes from a metallic behavior for x < 0.1 to a semiconductor-like behavior for x > 0.1. The analysis of Seebeck coefficient shows there are two types of electron-like carriers dominate at different temperature regions, indicative of a multiband effect responsible for the transport properties. The suppression of superconductivity and the increased resistivity can be attributed to a shift of the Fermi level to the lower-energy side upon doping, which reduces the density of states at E _F. Further, our result indicates the superconductivity in Bi₄O₄S₃ is intrinsic and the dopant Ag prefers to enter the BiS₂ layers, which may essentially modify the electronic structure.     

The influence of magnetic and structural heterogeneity on thermopower,magnetothermopower, electrical resistivity,and magnetoresistivity of Nd<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> manganite

The thermopower, S, magnetothermopower, ΔS/S, resistivity, ρ, and magnetoresistivity, Δρ/ρ, depending on the temperature T and magnetic field H, have been studied in an Nd_0.5Sr_0.5MnO₃ single crystal consisting of three types of clusters: an antiferromagnetic CE-type with charge-orbital ordering (below the Neel temperature T_NCE ~ 145 K) and an A-type with T_NA ~ 220 K; a ferromagnetic at 234 ≤ T ≤ 252 K, and a ferromagnetic metal phase below the Curie temperature T_C = 248 K. The thermopower was found to be negative, indicating the dominance of the electronic type of conductivity. In the S(T) curves, a sharp minimum is observed in the temperature range of 100 K ≤ T ≤ 133 K, close to T_NCE, where the absolute S value attains 53 μV/K. With a further increase in temperature, the absolute S value decreases rapidly; at 200 K it is equal to 7 μV/K. It then slightly increases, reaching its maximum value of 15 μV/K at a temperature of 254 K, which is close to T_C. The absolute thermopower decreased under the influence of the magnetic field; i.e., a negative magnetothermopower occurs. In {ΔS/S}(T) curves, a sharp minimum is observed at T = 130 K close to T_NCE, where the magnetothermopower reaches a huge value of ~45% at H = 13.23 kOe. A broad minimum in the {ΔS/S}(T) curves is observed near the Curie temperature and its value is also high, viz., ~15% in the maximum measuring magnetic field of 13.23 kOe. The extremely high magnetothermopower values mean that the charge-orbital ordered nanoclusters or ferron type make the main contribution to the thermopower of the entire sample. The behavior of the ρ(T) and {Δρ/ρ}(T) curves is similar to that of the S(T) and {ΔS/S}(T) dependencies, which is in agreement with this conclusion.     

Oxygen isotope effect in chromium-doped Pr<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> manganites

The effect of oxygen isotope substitution on the properties of Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x O₃ manganites (x = 0, 0.02, 0.05) have been studied. The introduction of chromium favors (i) the decomposition of a charge-ordered state and (ii) the appearance of a ferromagnetic metallic phase in Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x ^16–18O₃. The isotope substitution ¹⁶O → ¹⁸O leads to a decrease in the content of the ferromagnetic phase, an increase in the charge-ordering transition temperature (T _CO), and a decrease in the ferromagnetic transition temperature (T _FM). The isotope mass exponent is evaluated.     

Peculiarities of magnetic,galvanomagnetic, elastic,and magnetoelastic properties of Eu<Subscript>0.55</Subscript>Sr<Subscript>0.45</Subscript>MnO<Subscript>3</Subscript>

Magnetic, elastic, magnetoelastic, transport, and magnetotransport properties of the Eu_0.55Sr_0.45MnO₃ ceramics have been studied. A break was detected in the temperature dependence of electrical resistivity ρ(T) near the temperature of the magnetic phase transformation (41 K), with the material remaining an insulator down to the lowest measurement temperature reached (ρ=10⁶ Ω cm at 4.2 K). In the interval 4.2≤T≤50 K, the isotherms of the magnetization, volume magnetostriction, and ρ were observed to undergo jumps at the critical field H_C1, which decreases with increasing T. For 50≤T≤120 K, the jumps in the above curves persist, but the pattern of the curves changes and H_C1 grows with increasing T. The magnetoresistance Δρ/ρ = (ρ _H ?ρ_H=0)/ρ _H is positive for H<H_C1 and passes through a maximum at 41 K, where Δρ/ρ = 6%. For H>H_C1, the magnetoresistance is negative, passes through a minimum near 41 K, and reaches a colossal value of 3×10⁵ % at H=45 kOe. The volume magnetostriction is negative and attains a giant value of 4.5×10^?4atH=45 kOe. The observed properties are assigned to the existence of three phases in Eu_0.55Sr_0.45MnO₃, namely, a ferromagnetic (FM) phase, in which carriers are concentrated because of the gain in s-d exchange energy, and two antiferromagnetic (AFM) phases of the A and CE types. Their fractional volumes at low temperatures were estimated to be as follows: ～3% of the sample volume is occupied by the FM phase; ～67%, by the CE-type AFM phase; and ～30%, by the A-type AFM phase.     

Weak ferromagnetism in BiFeO<Subscript>3</Subscript>-based multiferroics

The magnetic properties of the Bi_{1 ? x} Ln _x FeO₃ (Ln is a rare-earth ion), Bi_{1 ? x} A _x FeO_{3 ? x/2} (A is an alkali earth ion), and BiFe_{1 ? x} Ti _x O_{3 + δ} solid solutions in magnetic fields up to 14 T have been studied. The concentration ranges of the existence of the ferroelectric phase described by the space group R3c have been determined. It is shown that the substitution of the rare-earth ions for the Bi³⁺ ions leads to a sharp decrease in the critical fields inducing the metamagnetic transition from a modulated antiferromagnetic state to a weakly ferromagnetic one; however, the modulated structure in the concentration range of the R3c phase is mainly retained. The substitution of the alkali earth ions (x ～ 0.1) for the bismuth ions leads to the total destruction of the modulated structure and to the implementation of the weakly ferromagnetic state within the R3c phase. A homogeneous weakly ferromagnetic state has been revealed when the Ti⁴⁺ ions (x = 0.1) are substituted for the Fe³⁺ ions in the ferroelectric R3c phase.     

Magnetic phase diagram of the Bi<Subscript>1-<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript>x</Subscript>MnO<Subscript>3</Subscript> manganites

The magnetic and elastic properties of the Bi_1-xCa_xMnO₃ manganites are studied. The phase transformations revealed are ferromagnet-spin glass (x≥0.15) and spin glass-charge-ordered antiferromagnet (x≥0.25). The ferromagnetic state is characterized by ordering of the Mn³⁺d _x ²-y orbitals. It is suggested that thespin glass state originates from local static Jahn-Teller distortions. The antiferromagnetic charge-ordered and the spin-glass disordered phases coexist in samples with 0.25<x<0.32, which may be due to the charge order-disorder phase transformation being martensitic in character. The magnetic phase diagram is constructed.     

Manifestation of pseudogap features in structurally inhomogeneous optimally doped HTSC YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6.92</Subscript>

Magnetization M(H,T) in magnetic fields H up to 90 kOe and at temperatures 2 K ≤ T < T _c (where Tc is the superconducting transition temperature), along with magnetic susceptibility χ(T) in the normal state T _c < T < 400 K for optimally oxygen-doped samples of YBa₂Cu₃O_6.92 with varying degrees of defects in the crystal structure, are studied to determine the influence of structural inhomogeneity on the electron systems characteristics of cuprate superconductors. It is shown that the existence of structural inhomogeneity of samples leads to the manifestation of peculiarities appropriate to pseudogap regime in their properties.     

Antisite defects and valence state of vanadium in Na<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

Electron paramagnetic resonance (EPR) studies have been performed with the aim of determining the valence state and local crystal structure of the nearest environment of vanadium ions in the initial, charged, and discharged samples of the cathode material Na_xV₂(PO₄)₃ (1 ≤ x ≤ 3). It has been found that the charged sample (x = 1) is characterized by an intense signal corresponding to V⁴⁺ ions located in a highly distorted octahedral crystal field. An EPR signal with the g-factor close to the g-factor of the V⁴⁺ ion has also been observed in the initial sample (x = 3), where the intensity of the resonance signal is one order of magnitude lower than that in the charged sample. It has been revealed that the resonance signal under consideration is associated with the formation of antisite defects when a part of vanadium ions are located in sites of sodium ions. It has also been found that the intensity of this signal increases after a complete charge–discharge cycle (x = 3).     

High-temperature complex impedance and modulus spectroscopic studies of doped Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-BaTiO<Subscript>3</Subscript> ferroelectric ceramics

Lead-free Na_0.5Bi_0.5TiO₃ (NBT) and (1 ? x)Na_0.5Bi_0.5TiO₃ + xBaTiO₃ with x = 0.1 and 0.2 (where x = 0.1 and 0.2 are named as NBT1 and NBT2, respectively), (1 ? y)Na_0.5Bi_0.5TiO₃ + yBa_0.925Nd_0.05TiO₃ with y = 0.1 and 0.2 (where y = 0.1 and 0.2 are named as NBT3 and NBT4, respectively)-based relaxor ferroelectric ceramics were prepared using the sol-gel method. The crystal structure was investigated by X-ray diffraction (XRD) at room temperature (RT). The XRD patterns confirmed the presence of the rhombohedral phase in all the samples. The electrical properties of the present NBT-based samples were investigated by complex impedance and the modulus spectroscopy technique in the temperature range of RT–600 °C. The AC conductivity was found to increase with the substitution of Ba²⁺ ions to the NBT sample whereas it significantly decreased with the addition of Nd³⁺ ions. The more anion vacancies in Ba-added samples and the lower anion vacancies in Nd-added samples were found to be responsible for higher and lower conductivities, respectively.     

Influence of Si substitution on structural,electronic and magnetic properties of Fe<Subscript>2</Subscript>MnGa Heusler compound

We investigate the electronic and magnetic properties of Fe₂MnGa_1?x Si _x alloy (x = 0, 0.25, 0.5, 0.75, and 1) using first-principles density functional theory within the generalized gradient approximation method. The lattice constant decreases linearly whereas bulk modulus increases with increasing Si content. The total magnetic moment varies linearly with increasing Si content, which follows the Slater-Pauling rule. Electronic band structure calculations indicate that the Fe₂MnGa_1?x Si _x exhibits half-metallic character for all the concentrations studied and the spin polarization and the spin-down band gap both increase with the Si content. Based on the magnetic properties calculations, the Heisenberg exchange coupling parameters give Fe-Mn ferromagnetic coupling and Mn-Mn antiferromagnetic coupling. The T _C first decreases and then increases with Si content, which is in well agreement with the experimental results.     

Electronic Structure and Magnetic Phase Transition in Helicoidal Fe<Subscript>1 - <Emphasis Type="Italic">x</Emphasis></Subscript>Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Si Ferromagnets

LSDA + U + SO calculations of the electronic structure of helicoidal Fe_{1 - x}Co _x Si ferromagnets within the virtual crystal approximation have been supplemented with the consideration of the Dzyaloshinski-Moriya interaction and ferromagnetic fluctuations of the spin density of collective d electrons with the Hubbard interactions at Fe and Co atoms randomly distributed over sites. The magnetic-state equation in the developed model describes helicoidal ferromagnetism and its disappearance accompanied by the occurrence of a maximum of uniform magnetic susceptibility at temperature T _C and chiral fluctuations of the local magnetization at T > T _C . The reasons why the magnetic contribution to the specific heat at the magnetic phase transition changes monotonically and the volume coefficient of thermal expansion (VCTE) at low temperatures is negative and has a wide minimum near T _C have been investigated. It is shown that the VCTE changes sign when passing to the paramagnetic state (at temperature T _S ).     

Nonstoichiometric high-pressure phase of Tm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>3</Subscript>V<Subscript>4</Subscript>O<Subscript>12</Subscript>

Tm _x Cu₃V₄O₁₂, a perovskite-like oxide (space group, Im-3; Z = 2; a = 7.279–7.293 Å) containing vacancies in its cationic sublattice, was obtained barothermally (P = 7.0–9.0 GPa, t = 1000–1100°C) for the first time. The temperature dependences on the electrical resistivity (10–300 K) and the magnetic susceptibility (0–300 K) were investigated. It was shown that the oxide Tm _x Cu₃V₄O₁₂ is characterized by metal-type conductivity and paramagnetic properties.     

Multicomponent <Emphasis Type="Italic">n</Emphasis>-(Bi,Sb)<Subscript>2</Subscript>(Te,Se,S)<Subscript>3</Subscript> solid solutions with different atomic substitutions in the Bi and Te sublattices

The thermoelectric properties of n-Bi_{2 ? x} Sb _x Te_{3 ? y ? z} Se _y S _z solid solutions are studied in the temperature range 300–550 K. It is shown that an increase in the parameter β determining the figure-of-merit Z of the material is observed in compositions with the optimally related effective mass of the density of states m/m ₀, the carrier mobility μ₀, and the lattice thermal conductivity κ _L . Within the temperature range 300–350 K, the parameter β and the figure-of-merit Z are found to increase in solid solutions with substitutions in both bismuth telluride sublattices Bi → Sb and Te → Se, S (x = 0.16, y = z = 0.12) for optimum electron concentrations. An increase in the electron concentration and substitutions of atoms only in the tellurium sublattice bring about an increase in the β parameter and the value of Z at higher temperatures. Within the range 350–450 K, the parameters β and Z are observed to increase in a solid solution with a low content of substituted atoms in the tellurium sublattice Te → Se, S for y = z = 0.09 and, at higher temperatures up to 550 K, in compositions with tellurium substituted by selenium only, with increasing content of substituted atoms.