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%.     

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.     

Magnetization of La- and Ce-doped CaMnO<Subscript>3</Subscript> manganite single crystals in a strong magnetic field

Studies of the magnetization curves of electron-doped single-crystal manganites Ca_{1 ? x} Ln _x MnO₃ (Ln = La³⁺, Ce⁴⁺; x ≤ 0.12) in strong pulsed magnetic fields of up to 350 kOe have revealed a metamagnetic transition in Ca_0.9Ce_0.1MnO₃ in the temperature range 77–190 K. The critical transition fields increase to ～350 kOe with the temperature decreasing to 100 K. The spin polarization is ～50% of the theoretical value. These results are interpreted as due to “melting” of the orbital/charge ordering below the temperature T _OO/CO = 185 K = T _N (of the C type AFM phase); this entails a decrease in the volume of the ordered phase with localized carriers and an increase in the volume of the ferromagnetic phase with delocalized carriers. The temperature and field dependences of the magnetization are used to compare two manganite systems in the region of the two-phase magnetic state.     

The Nernst-Ettingshausen coefficient in the normal phase of doped HTSCs of the YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>y</Subscript> system

The temperature dependence of the Nernst-Ettingshausen coefficient Q(T) in the normal phase of doped HTSCs of the yttrium system was studied. The main features characterizing the behavior of this coefficient were revealed, and the character and mechanism of the effect that various nonisovalent substituents exert on the Q(T) dependence were analyzed. It is shown that the narrow-band model permits one not only to describe all the specific features observed in the Q(T) curves but also to perform a simultaneous quantitative analysis of the temperature dependences of four kinetic coefficients (the electrical resistivity and the Seebeck, Hall, and Nernst-Ettingshausen coefficients) with the use of a common set of model parameters characterizing the band structure and carrier system in the normal phase of an HTSC. This approach was employed to determine the carrier mobilities and the asymmetry of the dispersion curve in the systems studied (YBa₂Cu₃O_y, y = 6.37–6.91; YBa₂Cu_3?xCo_xO_y, x = 0–0.3; Y_1?xCa_xBa₂Cu₃O_y, x = 0–0.25; Y_1?xCa_xBa_2?xLa_xCu₃O_y, x = 0–0.5) and to analyze the effect of the substitutions involved on the variation of these parameters.     

Crystal structure and electronic states of Co and Gd ions in a Gd<Subscript>0.4</Subscript>Sr<Subscript>0.6</Subscript>CoO<Subscript>2.85</Subscript> single crystal

X-ray diffraction and X-ray absorption near edge structure (XANES) spectra have been measured at the Со K-edge and Gd L ₃-edge in GdCoO₃ and Gd_0.4Sr_0.6CoO_2.85 cobaltites. The effect of Sr substitution on the crystal structure and electronic and magnetic states of Co³⁺ ions in a Gd_0.4Sr_0.6CoO_2.85 single crystal has been analyzed. The XANES measurements at the Co K-edge have not showed a noticeable shift of the absorption edge with an increase in the concentration of Sr. This indicates that the effective valence of cobalt does not change. An increase in the intensity of absorption at the Gd L ₃-edge is due to an increase in the degree of hybridization of the Gd(5d) and O(2p) states. The effect of hole doping on the magnetic properties results in the appearance of the ferromagnetic component and in a significant increase in the magnetic moment.     

X-ray studies of the (La,Sr)MnO<Subscript>3</Subscript> perovskite manganite structure

X-ray studies of perovskite manganites (La_0.9Sr_0.1)_0.9MnO₃ and La_1?xSr_xMnO₃ (x = 0.1, 0.15, 0.2, 0.25) are reported. The atom positions and interatomic distances and angles are calculated as a function of Sr doping at room temperature using the FullProf software. The temperature dependences of the crystal lattice parameters and unit cell volume are investigated. The effects of structural and magnetic phase transitions on the crystal lattice parameters are studied in detail. The bulk magnetoelastic contribution to thermal expansion is studied experimentally and calculated.     

Microstructure and superconducting properties of the DyBaCuO ceramic doped with Na<Subscript>2</Subscript>CO<Subscript>3</Subscript>, NaCl,and KClO<Subscript>3</Subscript>

This paper reports on a study of the effect of doping with Na₂CO₃, NaCl, and KClO₃ salts on the microstructure and superconducting characteristics of ceramics with nominal compositions Dy_{1 ? x} M _x Ba₂Cu_{3 ? y} O_{7 ? δ} and DyBa₂Cu_{3 ? y} O_{7 ? δ} : M _x for M = Na, K; x = 0.2, 0.3, and y = 0, 0.2. The microstructure was characterized by transmission electron microscopy with local energy-dispersive x-ray in situ analysis (probe size ～1 nm). An analysis shows that none of the doping elements (Na, K, or Cl) enters into 123 grains in sizable amounts and that, as a result, the critical temperature of the superconducting transition remains practically constant in the range 90.0–93.5 K. Potassium and chlorine segregate at grain boundaries. It is shown that grain-boundary segregation of chlorine leads to a substantial increase in the superconducting critical current (by a factor 3–5 at 70 K) as compared to the undoped sample. The possible mechanisms accounting for the effect of Cl on intergrain critical current are discussed.     

Stabilization of Ferromagnetism in BiFeO<Subscript>3</Subscript>:Ho at Hydrostatic Pressure

The isothermal magnetization of the Bi_{1 – x}Ho _x FeO₃ (x = 0?0.2) multiferroic has been studied at a hydrostatic pressure up to 9 GPa in the range of room temperatures. A new anomaly at P_C ≈ 3.81 GPa related to intermediate phases between the structural transition R3c → Pnma has been found against the background of the pressure-induced antiferromagnetic ordering in BiFeO₃ (BFO) at P ≈ 2.59 GPa. It is established that the ferromagnetic behavior under pressure depends on the Ho impurity concentration: P_C decreases at 0.05 ≤ x ≤ 0.1 because of the decrease in R3c bond lengths in the structure, and the stabilization of ferromagnetism is implemented at 0.1 ≤ x ≤ 0.2 probably because of the coexistence of the R3c and Pnma phases. The results of studies indicate that, in Bi_{1 – x}Ho _x FeO₃ with x = 0.2, the transition pressure P_C = 3.7 GPa exceeds the values for BFO doped with other 4f elements (Eu, Y, Sm) in the region R3c → Pnma of the transition.     

Electron paramagnetic resonance in mixed crystals (BaF<Subscript>2</Subscript>)<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>(LaF<Subscript>3</Subscript>)<Subscript>x</Subscript> activated by Ce<Superscript>3+</Superscript> ions

The electron paramagnetic resonance (EPR) spectra of mixed crystals (BaF₂)_{1?x? y}(LaF₃)_x(CeF₃)_y (y = 0.001 = 0.1%, x = 0–0.02) are investigated in a magnetic field H‖C₄ at a frequency of 9.5 GHz. The angular dependence of the EPR spectrum is measured for the sample with x = 0.02. The lines attributed to Ce³⁺ impurity centers with tetragonal symmetry and g factors (g_‖ = 0.75, g_⊥ = 2.4) close to those measured for the KY₃F₁₀: Ce³⁺ compound are separated in the complex EPR spectrum. The assumption is made that the aforementioned impurity centers are cubooctahedral clusters of the La₆F₃₇ type in which one of the La³⁺ ions is replaced by the Ce³⁺ ion.     

Pressure-induced structural transformations,orbital order and antiferromagnetism in La<Subscript>0.75</Subscript>Ca<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript>

High pressure evolution of structural, vibrational and magnetic properties of La_0.75Ca_0.25MnO₃ was studied by means of X-ray diffraction and Raman spectroscopy up to 39 GPa, and neutron diffraction up to 7.5 GPa. The stability of different magnetic ground states, orbital configurations and structural modifications were investigated by LDA + U electronic structure calculations. A change of octahedral tilts corresponding to the transformation of orthorhombic crystal structure from the Pnma symmetry to the Immaone occurs above P ~ 6 GPa. At the same time, the evolution of the orthorhombic lattice distortion evidences an appearance of the e _g d _{x² ? z²} orbital polarization at high pressures. The magnetic order in La_0.75Ca_0.25MnO₃ undergoes a continuous transition from the ferromagnetic 3D metallic (FM) ground state to the A-type antiferromagnetic (AFM) state of assumedly 2D pseudo-metallic character under pressure, that starts at about 1 GPa and extends possibly to 20–30 GPa.     

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.     

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.     

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.     

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.     

X-Ray Spectral Studies of the Interface Interaction in CuO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/MWCNTs Nanocomposite

Results of a comprehensive study of the interface interaction of a nanostructured CuO_x and multiwalled carbon nanotubes (MWCNTs) in CuO_x/MWCNT nanocomposite by X-ray absorption spectroscopy (XANES, NEXAFS) and X-ray photoelectron spectroscopy (XPS) methods using a synchrotron radiation are presented. It is established that a nanostructured CuO_x in CuO_x/MWCNT nanocomposite is predominantly formed by CuO and has the form of flakelike particles 200–500 nm in size uniformly dispersed over an array of nanotubes. A chemical interaction of CuO_x and nanotubes with formation of covalent carbon–oxygen bonds, which does not lead to a significant destruction of the outer layers of carbon nanotubes, is observed at the interfaces of the nanocomposite.     

Effect of heterovalent substitution of rare-earth elements on the magnetic and transport properties of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7</Subscript>

The Y_{(1 ? x} Ce _x Ba₂Cu₃O₇ system with low cerium concentrations has been synthesized. The cerium solubility limit measured using x-ray powder diffraction analysis is about 2.4 at. %. The temperature dependences of the magnetization M(T) are measured for samples cooled in a magnetic field (FC) and in a zero field (ZFC). The difference between the magnetizations M _ZFC-M _FC at 77.4 K, which is proportional to the pinning potential, passes through a maximum at x = 0.0156. This concentration corresponds to the average distance (equal to eight lattice constants) between the impurity ions in the plane of the rare-earth elements, which is comparable to the diameter of Abrikosov vortices in YBa₂Cu₃O₇.     

Doping induced spin state transition in Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>CoO<Subscript>2</Subscript> as studied by the GGA + DMFT calculations

The magnetic properties of Li _x CoO₂ for x = 0.94, 0.75, 0.66, and 0.51 are investigated within the method combining the generalized gradient approximation with dynamical mean field theory (GGA + DMFT). A delicate interplay between Hund’s exchange energy and t _2g ?e _g crystal field splitting is found to be responsible for the high-spin to low-spin state transition for Co⁴⁺ ions. The GGA + DMFT calculations show that the Co⁴⁺ ions at a small doping level adopt the high-spin state, while delithiation leads to an increase in the crystal field splitting and low-spin state becomes preferable. The Co³⁺ ions are found to stay in the low-spin configuration for any x values.     

Phase separation of the spin system in the La<Subscript>0.93</Subscript>Sr<Subscript>0.07</Subscript>MnO<Subscript>3</Subscript> crystal

The magnetic state of the manganite La_0.93Sr_0.07MnO₃ in the range 4.2–290 K was studied using elastic neutron scattering. The magnetic state of this compound was found to occupy a particular place in the La_1?xSr_xMnO₃ solid-solution system, in which the antiferromagnetic type of order (LaMnO₃, T_N=139.5 K) switches to ferromagnetic ordering (La_0.9Sr_0.1MnO₃, T_C=152 K) with increasing x. In the transition state, this compound contains large-scale spin configurations of two types. A fractional crystal volume of about 10% is occupied by regions of the ferromagnetic phase with an average linear size of 200 Å, while the remainder of the crystal is a phase with a nonuniform canted magnetic structure. Arguments are presented for the phase separation of the La_0.93Sr_0.07MnO₃ spin system being accounted for by Mn⁴⁺ ion ordering.     

Effect of cation substitution on the lattice dynamics and ferroelectric instability of cubic BaTiO<Subscript>3</Subscript> and BaZrO<Subscript>3</Subscript> doped with Bi and La ions

The spectra of lattice vibration frequencies of solid solutions Ba_{1 ? x} Bi_2x/3? _x/3Ti(Zr)O₃ and Ba_{1 ? x} La _x Ti(Zr)_{1 ? x/4}? _x/4O₃ are calculated in terms of a generalized Gordon-Kim model with inclusion of the dipole and quadrupole polarizabilities. Over the entire concentration range, the calculated phonon spectra contain a ferroelectric soft mode. The effect of various interactions on the ferroelectric instability of these solid solutions is studied. It is shown that the character of ferroelectric instability is largely determined by the mechanism of charge compensation.     

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.