High-temperature study of SrFe<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Mo<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3−<Emphasis Type="Italic">z</Emphasis></Subscript> perovskites

The structure of high-temperature SrFe_{1 − x} Mo _x O_{3 − z} (0 ≤ x ≤ 0.5) phases was studied. Such studies are necessary to understand the mechanism of oxygen transport in membrane materials used for high-temperature oxygen separation.     

Mössbauer studies of multiferroics BiFe<Subscript>1 – <Emphasis Type="Italic">x</Emphasis></Subscript>Cr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3</Subscript> (<Emphasis Type="Italic">x</Emphasis> = 0–0.20)

The Mössbauer studies on ⁵⁷Fe nuclei in multiferroics BiFe_{1 – x} Cr _x O₃ (x = 0.05, 0.10, and 0.20) have been performed at room temperature. The multiferroics BiFe_{1 – x} Cr _x O₃ (x = 0.05, 0.10, and 0.20) with the rhombohedral R3c structure have been prepared by solid-state synthesis under high pressures. The effect of substitution of Cr cations for Fe cations on the spatial spin-modulated structure, and also hyperfine electrical and magnetic interactions of ⁵⁷Fe nuclei has been studied. The substituted ferrites demonstrate an anharmonic modulated spin structure of cycloid type, in which iron atoms with different cation environments take part. The anharmonism parameter of the cycloid linearly increases from m = 0.10 at x = 0 to m = 0.78 ± 0.02 at x = 0.20. The constants of magnetic uniaxial anisotropy K _u are estimated at room temperature: K _u ≈ 0.36 × 10⁶ erg/cm³ at x = 0 and K _u ≈ 4.22 × 10⁶ erg/cm³ at x = 0.20.     

Magnetic phase transitions in Nd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Emphasis Type="Italic">x</Emphasis>MnO<Subscript>3</Subscript> manganites

The magnetic properties of manganites of the Nd_1?xCa_xMnO₃ system with x≤0.15 have been studied. It is shown that, in the 0.06≤x≤0.1 interval, the results can be interpreted using a model according to which the concentrational transition from a weakly ferromagnetic (WFM) state (x=0) to a ferromagnetic (FM) state (x>0.15) proceeds via a mixture of the exchange-coupled FM and WFM phases. In the vicinity of T=9 K, samples with 0.06≤x≤0.1 exhibit a spontaneous magnetic phase transition involving reorientation of the magnetization vectors of the WFM and the exchange-coupled FM phases. In the temperature interval between 5 and 20 K, a sample with the composition Nd^0.92Ca^0.08MnO^2.98 exhibits metamagnetic behavior. Magnetic phase diagrams in the H?T and T?x coordinates are presented. The appearance of the spin-reorientation transitions is explained in terms of the magnetic analog of the Jahn-Teller effect with allowance for the fact that, according to the neutron diffraction data, the magnetic moments of neodymium ions in the FM phase are parallel to the magnetic moments of manganese ions.     

Phase transitions and dielectric relaxation in (1 − <Emphasis Type="Italic">x</Emphasis>)SrTiO<Subscript>3</Subscript>-<Emphasis Type="Italic">x</Emphasis>BiFeO<Subscript>3</Subscript> (0 ≤ <Emphasis Type="Italic">x</Emphasis> ≤ 0.04)

The dielectric and acoustic properties of (1 − x)SrTiO₃-xBiFeO₃ (0 ≤ x ≤ 0.04) solid solutions have been studied in the temperature range 10–300 K. The polar state exhibiting permittivity dispersion and dielectric hysteresis loops has been revealed at temperatures of 40–100 K. At 20–40 K, we have observed one more dielectric relaxation, which is not associated with the polar state and vanishes at a concentration of the second solid-solution component x = 0.04. The antiferrodistorsive transition has been found to vary with increasing concentration x. At temperatures below the antiferrodistorsive transition point, the polar (relaxor) state has been shown to persist in all the measured solid solutions.     

Anomalous magnetotransport in LaMn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3</Subscript>

The LaMn_1−x Te _x O_3+δ (x=0.1, 0.2, 0.3) were synthesized using solid-state reaction method for the first time. X-ray photoemission spectrum (XPS) shows that in the samples the Te ions have a valence of Te⁴⁺, and Mn³⁺ ions are partly converted into Mn²⁺ and Mn⁴⁺ due to the excess oxygen and Te doping. The magnetotransport associated with Mn²⁺, Mn³⁺ and Mn⁴⁺ was investigated. The experimental results show that the samples are insulator at 0 T when the amount of Mn³⁺ is much larger or less than the sum of Mn²⁺ and Mn⁴⁺; by contrast, the samples display metal to insulator transition with increasing temperature when the amount of Mn³⁺ is close to the sum of Mn²⁺ and Mn⁴⁺. These anomalous magnetotransport behaviors were analyzed in the frame of the double-exchange (DE) mechanism. Supported by the National Major Fundamental Research Program of China (Grant No. G1998061412) and the Foundation for Fostering Elitists of Beijing, China (Grant No. 20071D1100500379)     

X-Ray Diffraction and Mössbauer Studies of the Structural Features of BiFe<Subscript>1 ‒ <Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3</Subscript> Multiferroics

The structure of ceramic BiFe_1?xZn_xO₃ multiferroic samples is investigated using the X-ray diffraction method and Mössbauer spectroscopy. X-ray diffraction analysis of the samples indicates the existence of the Bi₁₂(Bi_0.5Fe_0.5)O_19.5 impurity phase. High-temperature heating of the samples generates additional phases. The parameters of the Mössbauer spectra depend on the zinc concentration. In this case, for pure bismuth ferrite, the spectrum is a superposition between two Zeeman sextets and two paramagnetic doublets arising from two nonequivalent magnetic and electrical positions occupied by iron ions at the crystallattice sites of a sample. The replacement of iron ions with zinc ions substantially affects the spectrum parameters. This is probably related to changes in the spin-cycloid structure typical of multiferroics, the destruction of which stimulates the appearance of significant magnetoelectric interactions.     

Magnetic and dielectric properties of orthorhombic and hexagonal multiferroics Tb<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Y<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript>

The transition from a stable orthorhombic structure to a hexagonal structure has been revealed in Tb_1−x Y _x MnO₃ multiferroics at x = 0.2–0.4. It has been shown that almost single-phase crystals with an orthorhombic or hexagonal structure can be obtained by choosing the growth conditions. It has been found that the magnetic and dielectric properties of orthorhombic single crystals with x = 0.2–0.3 are similar to the properties of pure TbMnO₃ and are characterized by a strong anisotropy of the magnetic susceptibility at low temperatures and by the presence of a number of magnetic phase transitions, including those to the ferroelectric state. New spontaneous (T ≤ 15 K) and magnetic-field induced (H | C ₆) phase transitions accompanied by the appearance of an uncompensated rare-earth magnetic moment ∼1 μ_B/mole have been observed in hexagonal single crystals with x = 0.3–0.5.     

Knight shift in superconducting oxides BaPb<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Bi<Subscript>x</Subscript>O<Subscript>3</Subscript> (<Emphasis Type="Italic">x</Emphasis> < 0.35)

The Knight shift ²⁰⁷K_s for the ²⁰⁷Pb nuclei in the metal phase of the oxides BaPb_1?xBi_xO₃ (x < 0.35) has been analyzed as a function of the concentration. The shift, which is proportional to the density of states near the Fermi energy: ²⁰⁷K_s ～ N(E_F), reaches a maximum for an oxide with the maximum superconducting transition temperature T_c(x ≈ 0.25) = 12 K. A significant increase in the width of the shift distribution with the Bi concentration testifies to the formation of a nonuniform state of the electronic system in the conduction band of superconducting oxides, which is accompanied by an increase in short-wavelength contributions to the spin susceptibility. To detect the ²⁰⁷Pb NMR spectra in superconducting oxides with x > 0.2, the ¹⁷O-²⁰⁷Pb spin-echo double-resonance method is used, which provides successful detection of the ²⁰⁷Pb NMR signal with an anomalously high rate of spin-spin relaxation T ₂ ^?1 > 500 ms^?1. Thus, fundamental restrictions arising in investigations of rapidly relaxing ²⁰⁷Pb nuclei, which are “unobservable” in superconducting oxides BaPb_1?xBi_xO₃ when they are studied by traditional single-resonance methods of pulse NMR spectroscopy, have been overcome.     

Magnetic state of a Zn<Subscript>1 −<Emphasis Type="Italic">x</Emphasis></Subscript>Cr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se bulk crystal

The spin system of a Zn_{1 ?x} Cr _x Se bulk crystal (x = 0.045) was studied using thermal-neutron diffraction and magnetic measurements. Previously, it was reported in the literature that thin films (～200 nm thick) of this type of semiconductors exhibit a ferromagnetic order. In this study, the ferromagnetic order is found to be absent in the bulk crystal.     

Metal-insulator transition in Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>S crystals

Results of an experimental study of MnS, FeS, and Fe _x Mn_1?x S single crystals are presented. The phase composition, the lattice parameters, and the state of paramagnetic ions in Fe _x Mn_1?x S have been determined by x-ray diffraction analysis and Mössbauer spectroscopy. A sequence of transitions have been found in iron manganese sulfide with x = 0.29 at temperatures T ₁ ≈ 25–50 K, T ₂ ≈ 125 K, and T ₃ ≈ 190 K with a change in kinetic properties and the formation of a metallic state at low temperatures T ≈ 2 K. The possibility of a Mott-Hubbard transition in Fe _x Mn_1?x S sulfides with variation of the composition and the temperature is discussed.     

Mn<Superscript>2+</Superscript> 3<Emphasis Type="Italic">d</Emphasis> luminescence kinetics in Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>x</Subscript>Se

Intracenter luminescence (IL) of Mn²⁺ in Zn_1?xMn_xSe (x=0.07, 0.02) was studied under pulsed excitation by the neodymium laser second harmonic. At 4 K, the IL saturation originates from the nonlinearity of the system only at the instant of excitation, the IL decay kinetics after the exciting pulse termination depending only weakly on the pumping level. At 77 K, the decay kinetics in Zn_0.93Mn_0.07Se depends substantially on the pumping level, because the migration of intracenter excitation over the manganese ions initiates up-conversion, which is a slow nonlinear process. As shown by IL decay measurements in Zn_0.98Mn_0.02Se (x=0.02), excitation migration over the Mn²⁺ ions is insignificant even at a high temperature and under strong optical pumping.     

Electronic structure and ground state parameters of Ru<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript><Emphasis Type="Italic">Me</Emphasis><Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Al refractory alloys

The electronic structure and ground state parameters of B2 RuAl-based refractory alloys have been investigated in the framework of the density functional theory using the exact muffin-tin orbital method in combination with the coherent potential approximation. It has been demonstrated that the number of states at the Fermi level for the Ru_{1 − x} Me _x Al alloys as a function of the alloying metal content has a minimum, which indicates a change in the Fermi surface topology and the presence of specific features in the behavior of elastic constants. It has been concluded that the electronic structure of the alloys can be described in terms of the rigid band model. The nonlinear variations of the lattice parameters of the alloys has been explained.     

Ordered phases of lithium nickelite Li<Subscript>1−<Emphasis Type="Italic">x</Emphasis>−<Emphasis Type="Italic">z</Emphasis></Subscript>Ni<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>2</Subscript>

A symmetry analysis of ordering in lithium nickelite Li_1?x?zNi_1+xO₂ (Li_1?x?z□_yNi_1+xO₂) was performed with regard to the substitution of Li and Ni atoms and the occurrence of structural vacancies □ in the metal sublattice. For all the ordered phases, the k ₉ ⁽³⁾ ray of the Lifshitz {k₉} star is present in the order-disorder transition channel. This ray determines the consecutive alternation of atomic planes filled with only Ni atoms or only Li atoms and vacancies in the \([1\bar 11]_{B1} \) direction. It was shown that the rhombohedral ordered LiNiO₂ phase is formed in the defect-free lithium nickelite, whereas a family of three monoclinic Li₃□Ni₄O₈ (C2/m space group) and Li₂□Ni₃O₆ (C2/m and C2 space groups) superstructures arises as the concentration of structural vacancies increases. For all the superstructures, the order-disorder phase-transition channels were determined and the distribution functions of Li and Ni atoms have been calculated. The long-range order parameters describing each superstructure were found as functions of the Li_{1?x? z}Ni_1+xO₂ composition.     

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).     

Magnetic ordering in La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript>x</Subscript>MnO<Subscript>3−<Emphasis Type="Italic">x</Emphasis>/2</Subscript> anion-deficient manganites

The structural, magnetic, and electrotransport properties of La_1?xSr_xMnO_{3? x/2}(0≤x≤0.30) manganites with perovskite structure are investigated experimentally as a function of oxygen deficiency. In the solid solutions La_1?xSr_xMnO₃, a change in the type of symmetry of the unit cell is observed at x=0.125. Samples with x≤0.125 are characterized by an O′-orthorhombic unit cell, whereas samples with x>0.125 are characterized by a rhombohedral unit cell. The structural properties of the anion-deficient solid solutions La_1?xSr_xMnO_3?x/2 are analogous to those of the stoichiometric system. It is assumed that, as the oxygen content decreases, La_{1? x}Sr_xMnO_3?x/2 anion-deficient solid solutions experience a series of successive magnetic phase transformations in the ground state: from an A-type (x=0) antiferromagnet to a cluster spin-glass-type inhomogeneous magnetic state (0.175>x≤0.30) through a two-phase (antiferromagnetic and ferromagnetic) state (0>x≤0.175). The anion-deficient solid solution with x=0.175 has the maximal value of the ferromagnetic component. As the oxygen deficiency increases, the resistivity of La_{1? x}Sr_xMnO_3?x/2 samples first decreases (up to a value of x=0.175), acquiring an activation character, and then increases (up to a value of x=0.30). In this case, none of the anion-deficient solid solutions exhibits a metal-semiconductor transition in the whole range of concentrations considered. A peak of magnetoresistance at a temperature below the point of magnetic ordering is observed only in the sample with x=0.175. The results of experiments carried out with a series of La_1?xSr_xMnO_3?x/2 anion-deficient solid solutions are summarized in the concentration diagrams of the spontaneous magnetic moment and the critical temperature of magnetic phase transitions. Hypothetical magnetic phase states are pointed out. The experimental results obtained can be interpreted in terms of the phase-separation model and the competition between ferromagnetic and antiferromagnetic indirect superex-change interactions. It is assumed that Mn³⁺-O-Mn³⁺ indirect superexchange interactions in the orbitally disordered phase are positive in the case of octahedral coordination of manganese ions and are negative when the coordination of at least one Mn³⁺ ion is pentahedral.     

Magnetostriction of Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>S (<Emphasis Type="Italic">x</Emphasis> = 0.27) crystals

The magnetostriction of Fe _x Mn_{1 − x} S (x = 0.27) single crystals in strong magnetic fields up to 120 kOe has been investigated. It has been found that the magnetostriction reaches colossal values (±3 × 10⁻⁴) atypical of compounds of 3d elements. It has been found that the magnetostriction changes sign when varying temperature and magnetic field; this behavior indicates an important role of the spin-phonon interactions in the formation of the magnetic order in solid solutions of iron-manganese sulfides.     

Electrical conductivity of Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O ferromagnetic films at low temperatures

The results of experiments on electrical conductivity and magnetic properties of thin cobalt-doped zinc oxide films are reported. The results indicate the predominance of the hoping conduction mechanism at low temperatures and the band mechanism at high temperatures. An increase in the cobalt concentration from 1.5 to 6.3 at % leads to the reduction of the electrical conductivity of the films. The contribution of hopping conduction to the conductivity increases due to a decrease in the crystallinity of the films and localization of a part of electron states upon an increase in the cobalt concentration. For cobalt-containing films, a hysteresis of the magnetic moment as a function of the magnetic field is observed. The dependence of the shape of the magnetization curves on the cobalt concentration is irregular. The paramagnetic contribution to the magnetic susceptibility increases with the cobalt concentration.     

Theory of the giant magnetoresistance in La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>A<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript>

To clarify the origin of the giant magnetoresistance (GMR) observed in La_1?x A _x MnO₃ (A²⁺=Sr²⁺, Pb²⁺, Ba²⁺ and Ca²⁺), we have investigated theoretically the electrical resistivity ρ of carriers in the background of Mn spins which interact with each other through the double exchange interaction. It has been found that extraordinarily large pin fluctuations caused by the instability of the ferromagnetic state are responsible for the transport anomalies including the GMR.     

Thermal and magnetic properties of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript>

The thermodynamic and magnetic properties of the La_{1 − x} Pb _x MnO₃ (0.24 ≤ x ≤ 0.40) solid solution system were investigated in the temperature range of 4.2–340 K. All objects were ferromagnetics with Curie temperature T _C ≈ 320–340 K, which slowly increased with x. The M(T) behavior in the magnetic ordering region indicated a nonuniform ground state, due possibly to the competition of ferromagnetic and antiferromagnetic interactions. The increase in the saturation magnetic moment with x can be described by a simple model of the binary bonds in La_{1 − x} Pb _x MnO₃.     

Dual structures and transition regions in <Emphasis Type="Italic">x</Emphasis>PbTiO<Subscript>3</Subscript>-(1−<Emphasis Type="Italic">x</Emphasis>)Pb(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> crystals

Model concepts of dual structures are developed as applied to crystals of xPbTiO₃-(1?x)Pb(Zn_1/3Nb_2/3)O₃ solid solutions in the range 0 ≤ x ≤ 0.08. The conditions of the formation of dual structures upon partial and complete relaxation of internal mechanical stresses are considered. A new model of transition regions is proposed for analyzing several variants of changing the unit cell parameters that satisfy the condition of complete stress relaxation inside the transition regions in crystals at concentrations x = 0.045 and 0.08. The influence of the intermediate phase P4mm and stability of its 90° domain structure on the formation of dual structures at x ≥ 0.045 is discussed.