X-ray spectra and electronic band structure of nitrogen in Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>N solid solid solutions

The electronic energy structure of the valence band and the x-ray absorption near edge structure (XANES) region of nitrogen in Al _x Ga_1?x N solid solutions and binary crystals of gallium nitride GaN and aluminum nitride AlN are calculated using the local coherent potential method and the cluster version of the muffin-tin approximation within the framework of the multiple scattering theory. It is demonstrated that the calculated electron densities of states correlate with the nitrogen K x-ray emission and nitrogen K x-ray absorption spectra. The electronic energy structure of the top of the valence band and the XANES region in Al _x Ga_1?x N solid solutions are compared with those in the binary crystals of the GaN and AlN nitrides, and an interpretation of their specific features is proposed. An analogy is drawn between the evolution of the electronic energy structure of the valence band and the XANES region in the alloys under investigation and the evolution of the electronic band structure in the Al _x B_1?x N and B _x Ga_1?x N alloys. General trends in the transformation of the structure and variations in properties of these alloys are discussed.     

Magnetocaloric properties of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>K<Emphasis Type="Italic">x</Emphasis>MnO<Subscript>3</Subscript> manganites

A technology for obtaining single-phase ceramic samples of La_{1 − x} K _x MnO₃ manganites, as well as the dependence of their structure parameters on the potassium content, is described. The magnetocaloric effect in the samples has been measured by two direct methods, the classical method and the magnetic field modulation method, and has been calculated from the specific heat data. The values of the magnetocaloric effect obtained by these methods are significantly different. The observed discrepancies have been explained. Correlation between the doping level and the value of the effect has been found. It has been shown that the magnetic-field dependence of variation of the magnetic entropy near T _C in weak fields corresponds to theoretical calculations and that the value of the magnetocaloric effect in high magnetic fields can be predicted using this dependence.     

The magnetic properties of nanosized La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> (0.5 ≤ <Emphasis Type="Italic">x</Emphasis> ≤ 0.8)

Magnetic properties of La_1−x Ca _x MnO₃ (0.5 ≤ x ≤ 0.8) samples with an equivalent average particle size ~50 nm prepared by a sol–gel method were investigated. The charge ordering (CO) transition that is observed in the bulks disappears and the ferromagnetic (FM) transition occurs in all the prepared samples. For all the samples, the spontaneous magnetization (M _S) value is much lower than the corresponding theoretic value, which shows that the majority of the sample is antiferromagnetic (AFM). However, the M _S value is much larger than the corresponding value reported by some other groups. The invisible of CO transition and the large M _S value can be attributed to the good connection among the adjacent particles. Moreover, the exchange bias (EB) phenomenon is observed except the x = 0.5 sample. With x increasing, the M _S value decreases and the EB field increases, which can be understood by considering the coexistence of FM phase with Mn³⁺–Mn⁴⁺ spin clusters in the shell and the AFM phase in the core of the nanoparticles.     

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.     

Structural study of CuCr<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>V<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>2</Subscript> substitutional solid solutions

The local structure and charged state of metal atoms in the CuCrS₂ matrix and CuCr_{1 − x} V _x S₂ solid solutions of substitution of vanadium for chromium (0 < x < 0.25) are studied by x-ray absorption spectroscopy (XAFS) using synchrotron radiation. According to XANES spectra (near-edge fine structures), introducing vanadium does not change the charged state of matrix elements and they exist as Cu(1+), Cr(3+), V(3+), and S(2−) in the solid solution. According to EXAFS spectra (extended fine structures), introducing vanadium slightly distorts the local structures of both Cr and Cu atoms (to a greater extent for copper than for chromium). The XAFS analysis data show that vanadium only partially filled vacant positions (specified by the composition of the initial mixture) in the chromium sublattice, the majority of them being located in irregular positions of slightly distorted octahedrons consisting of sulphur atoms. It is shown that the substitution effect leads to deformation (compression) of the lattices of CuCr_{1 − x} V _x S₂ samples without changing their crystallochemical structures and symmetries, but changes their magnetic structures.     

Structure and magnetic properties of La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript>x</Subscript>MnO<Subscript>3+δ</Subscript> compounds

The structural and magnetic properties of La_1?x Ca_xMnO_3+δ (x = 0.01–0.10) compounds with a high superstoichiometric oxygen content (0.01 < δ < 0.07) are investigated. It is demonstrated that all the studied compounds are characterized by a magnetically inhomogeneous state at temperatures below 280 K. It is found that the compound with the calcium content x = 0.05 differs substantially in structure and superstoichiometric oxygen content from the other compounds in the system under investigation. The revealed difference in properties of the compounds can be associated with the fact that a specific state or a specific phase is formed in this system at the calcium content x = 0.05.     

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.     

Elasticity moduli of Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Hg<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Te solid solutions

Results of investigations into the temperature dependences (4.2–300 K) of the low-frequency ultrasound velocity in Cd _x Hg_1–x Te single crystals are presented. The elastic moduli and the Debye temperatures are calculated for different solid solution compositions. Based on the data obtained, possible stresses are estimated on the heteroboundary of the materials with a number of substrates.     

Spin-glass like behaviors in La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Tb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> perovskite

A series of samples of La_1−x Tb _x MnO₃ (0⩽x⩽0.15) are prepared. The static and dynamic magnetizations of La_1−x Tb _x MnO₃ have been investigated. The results indicate that the spins with the short-range order are frozen into random direction at low enough temperatures which leads to the samples exhibiting the spin-glass like behavior. It is considered that the spin-glass like behavior originates from the competition between ferromagnetic double exchange among Mn³⁺ and Mn²⁺ and antiferromagnetic superexchange among Mn³⁺ and Mn³⁺, as well as Tb³⁺ and Tb³⁺.     

Effect of the oxygen excess on the properties of weakly doped La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> lanthanum manganites

The effect of an oxygen excess δ on the magnetic and electrical properties of La_1−x Ca _x MnO_3+δ (x=0.10–0.15) has been studied over wide ranges of temperatures and magnetic fields. As δ increases, the magnetic ordering temperature T_cdecreases by 70–90 K, the magnetoresistance increases (the electrical resistivity decreases by a factor of up to 10⁴ in a field of 9 T), and the effective moment μ_eff of the paramagnetic susceptibility substantially exceeds the theoretical value at temperatures two to four times higher than T _c and undergoes a jump, just as the activation energy of electrical resistivity, at T∼270 K. These results are attributed to the formation of cation vacancies, the localization of electrons in their vicinity with the subsequent formation of magnetic clusters, tunneling (or hopping) of carriers among them, changes in the sizes of clusters with variations in the temperature and magnetic field strength, the onset of frustrations initiated by the competition among different types of exchange interaction, and the dependence of the cluster parameters on the annealing conditions. Annealing of the oxygen-excess samples at high temperatures in vacuum (above 1100°C) restores the samples to a nearly initial state with the magnetic and magnetotransport properties characteristic of weakly doped manganites, as a result of the removal of cation vacancies.     

Abrupt changes in the temperature dependence of the ESR linewidth of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript> Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> MnO<Subscript>3</Subscript> single crystals

The temperature dependence of the ESR linewidth in La_{1 ? x} Ca _x MnO₃ single crystals with various dopant concentrations (x = 0.18, 0.2, 0.22, 0.25, and 0.3) has been studied. An abrupt decrease in the ESR linewidth has been observed in the samples with a dopant concentration of x = 0.18 and 0.2 near the respective temperatures T _OO′ ≈ 260 and 240 K of the orthorhombic to pseudocubic structural phase transition. The abrupt decrease in the ESR linewidth by approximately 180 Oe has been also observed in the whole temperature range when the concentration is increased from x = 0.2 to x = 0.22. The formula for the fourth moment of the ESR line has been derived including both crystal fields and isotropic exchange interactions and taking into account the difference between the exchange coupling of a spin to its nearest in-plane and out-of-plane neighbors. The formula has been used to estimate the parameter D of the crystalline field on Mn³⁺ ions.     

Phase states in the Y<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> solid solution system

The room-temperature stability region of the tetragonal phase in the Y_{1 − x} Ca _x MnO₃ solid solution system has been found for the first time. The concentration boundaries between this phase and the orthorhombic (x > 0.5) and hexagonal (x < 0.25) phases are sensitive to the sample preparation conditions. The coexistence of the hexagonal and tetragonal phases in the range 0.15 < x < 0.25 indicates that these phases undergo a first-order reconstructive phase transition. Preliminary measurements of magnetic ordering effects for compositions with x = 0.3, 0.5, and 0.7 have been performed.     

Studying the electronic structure of Cr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ti<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript>2</Subscript> by X-ray resonance and absorption spectroscopy

Cr _x Ti_{1 − x} Se₂ (x = 0–0.83) solid solutions have been synthesized. Single crystals have been grown in the range of concentrations x = 0–0.83. Structural studies of samples have revealed that chromium atoms substitute titanium in the TiSe₂ matrix. The X-ray photoelectron spectra of the core levels, the resonance spectra of the valence bands in 1T-Cr _x Ti_{1 − x} Se₂, and the X-ray absorption spectra of titanium and chromium are studied. The titanium and chromium atoms are shown to have oxidation numbers of +4 and +3, respectively, in an identical octahedral environment. The local density of chromium states has been calculated. The results of the calculation agree well with the experimental data and indicate that the electronic 3d states of chromium substituting titanium in the matrix are spin-polarized and the density of chromium states is halfmetal magnet in behavior.     

Rubidium-cation conductivity of Rb<Subscript>3–2<Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript> solid solutions

New Rb₃PO₄-based ceramic materials with high rubidium-cation conductivity in the Rb_3–2x Pb _x PO₄ system have been synthesized and studied. Introduction of Pb²⁺ cations leads to a sharp increase in the conductivity of rubidium orthophosphate due to formation of cation vacancies and, at temperatures 350–550°C, also due to the stabilization of high-temperature cubic modification Rb₃PO₄. At high temperatures, the electrolytes prepared have very high ion conductivity higher than 10^–1 S cm^–1 at 700°C, which is higher than the values previously obtained in similar systems with additions of tin and cadmium ions. The factors influencing the transport properties of the materials under study are discussed.     

Spin glass effects in Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>S solid solutions

The magnetization, resistance, permittivity, and thermal expansion coefficient of cation-substituted sulfides Co _x Mn_{1 ? x} S have been measured. The relationship between the magnetic, electric, and elastic subsystems of Co _x Mn_{1 ? x} S solid solutions is established and the features of physical properties characteristic of multiferroics, induced by orbital-charge ordering, are found.     

Synthesis and magnetic and electrical study of Tm<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript>Mn<Subscript>1–<Emphasis Type="Italic">x</Emphasis> </Subscript>S solid solutions

New antiferromagnetic semiconductor compounds Tm_xMn_1–xS (0 ≤ x ≤ 0.15) with an NaCl-type FCC lattice are synthesized, and their structural, magnetic, and electrical properties are investigated at temperatures of 80–1100 K in magnetic fields of up to 10 kOe. Anomalies in the temperature dependence of resistivity in the region of magnetic transition are observed. The activation energy of the synthesized compounds is found and shown to grow along with the concentration of a substitute.     

Heat capacity and magnetocaloric properties of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>K<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> manganites

The magnetocaloric effect and the heat capacity of La_{1 − x} K _x MnO₃ (x = 0.1, 0.15, 0.175) ceramic samples have been studied at temperatures in the range 77–350 K and in magnetic fields of up to 27 kOe. The technique for preparing the samples has been described. The heat capacity anomalies related to the ferromagnetic-paramagnetic magnetic phase transition have been revealed and interpreted. It has been demonstrated that the change in the magnetic entropy ΔS calculated from the data on the heat capacity C _p and direct measurements of the magnetocaloric effect ΔT reaches values that are of practical interest.     

Magnetocaloric effect in sandwich structures of La<Subscript>1–<Emphasis Type="Italic">x</Emphasis> </Subscript>K<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript>MnO<Subscript>3</Subscript> manganites

This paper reports on the results of the investigation into the magnetocaloric properties of sandwich structures of La_1–xK_xMnO₃ manganites with x = 0.11 (LKM11), 0.13 (LKM13), and 0.15 (LKM15) in magnetic fields of up to 18 kOe. The results of the analysis of the field and temperature dependences of the magnetocaloric effect in the structures LKM11 + LKM13 and LKM13 + LKM15 have demonstrated that the use of sandwich structures increases the efficiency of magnetic cooling in a magnetic field of 18 kOe by 45%.     

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.