Theoretical study on the electronic and magnetic properties of double perovskite La<Subscript>2−x</Subscript>Sr<Subscript>x</Subscript>MnCoO<Subscript>6</Subscript> (x = 0,1,2)

In this paper, the electronic and magnetic properties of double perovskite La_2−x Sr _x MnCoO₆ (x = 0,1,2) have been studied using the local-spin-density approximation + U method. For the three compositions investigated, the low symmetry P2₁/n structure yields consistently lower energy than that of the high symmetry \hbox{Fm[`3]mFm\bar{3}m} Fm3̅m structure. The strong electronic correlation and the orbital polarization of Co-d electrons play crucial roles. In agreement with experiments, we find that La<sub>2</sub>MnCoO<sub>6</sub> is a ferromagnetic insulator with both Mn and Co ions in their high-spin states. The tilting of oxygen octahedrons is most significant in this case and is responsible for its insulating behavior; for LaSrMnCoO<sub>6</sub>, the ground state remains a ferromagnetic insulator with Mn and Co ions in their high-spin states. The optimized P2<sub>1</sub>/n and \hbox{Fm[`3]mFm\bar{3}m}Fm3̅m crystal structures are nearly the same, and the P2₁/n structure is stabilized by the spontaneous layer-wise antiferro-orbital ordering of Co-d electrons. We also predict that Sr₂MnCoO₆ is a ferromagnetic metal, and its electronic structure can be viewed as a rigid band shifting from that of LaSrMnCoO₆. Due to the strong covalency between transition metal and oxygen ions, the valences of Mn and Co ions differ considerably from those derived from purely ionic model. Also, doping induced holes mainly go to oxygen sites though the density of states near the Fermi energy has strong mixed character. This feature, together with the orbital ordering phenomenon, should be observable via the X-ray near-edge absorption spectroscopy and the polarized X-ray diffraction spectra.     

Magnetic moments and hyperfine magnetic fields in ordered and disordered quasi-binary Fe<Subscript>75</Subscript>(Si<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript>x</Subscript>)<Subscript>25</Subscript> alloys

Disordered and DO₃ type-ordered Fe₇₅(Si_1?xGe_x)₂₅ alloys are fabricated and investigated using x-ray diffraction, Mössbauer spectroscopy, and magnetic measurements. The variations in the magnetic and Mössbauer characteristics are interpreted using ab initio calculations of the electronic structure, magnetic moments, hyperfine magnetic fields, and isomer shifts. The main differences in the properties are related to the increase in the crystal lattice parameter when Si is replaced by Ge in ordered alloys and to a different behavior of the correlations in the Si and Ge positions in disordered alloys.     

Optical and magneto-optical properties of Fe<Subscript>4−x</Subscript>Co<Subscript>x</Subscript> (x = 1–3)

We report a systematic study of the electronic, optical, and magneto-optical properties of the Fe_4−xCo_x (x = 1–3) compounds using the full-potential linearized augmented plane waves (FPLAPW) method within the local spin density approximation (LSDA). Pure Fe (x = 0) and Co (x = 4) have also been studied, the latter in hcp as well as bcc structure, to offer a better comparison. A good agreement is obtained between calculated optical conductivity spectra and experimental data. We note that the magneto-optical properties of these compounds are found to be more akin to those of bcc Co (which has MOKE very similar to that of bcc Fe) than to those of hcp Co. This shows strong impact of the environment on the MOKE of these compounds. With respect to the elemental values, the magnetic moments at Fe sites are found to be larger in general, while those at Co sites are almost the same. However, interestingly, despite their larger magnetic moment, the Kerr rotation remains comparable to that of bcc Fe for most of the energy range. The origin of Kerr spectra has been explained in terms of optical transitions.     

AC and DC properties of M-type SrCo<Subscript>x</Subscript>Ti<Subscript>x</Subscript>Fe<Subscript>(12−2x)</Subscript>O<Subscript>19</Subscript> hexagonal ferrite

Microwave characterization of SrCo _x Ti _x Fe_(12?2x)O₁₉ (x = 0.0, 0.2, 0.3, 0.5, 0.6, 0.7, 1.0) ferrites has been studied as a function of frequency, substitution and thickness, and static electrical current density-electric field characteristics have been investigated as a function of substitution. Microwave characteristics have been measured using power meter in the rectangular slotted waveguide and current density is measured using electrometer. The microwave absorption is evaluated using the standard available model. The results depict ?11.57 dB reflection loss at 10.38 GHz in composition x = 0.6. The electrical current density decreases at lower substitution and increases at higher substitution. The substitution of Co²⁺ and Ti⁴⁺ ions causes enhancement of electromagnetic and static electrical properties.     

Magnetic and magnetoresistive properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sr<Subscript>2</Subscript>FeMoO<Subscript>6–δ</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoheterostructures

A method has been developed for fabricating nanoporous matrices based on anodic aluminum oxide for the deposition of ferromagnetic nanoparticles in them. The modes of deposition of strontium ferromolybdate thin films prepared by the ion-plasma method have been worked out, and the magnetic and magnetoresistive properties, structure, and composition of the films have been investigated. It has been revealed that the microstructure and properties of the strontium ferromolybdate films deposited by ionplasma sputtering depend on the deposition rate and the temperature of the substrate. Based on the measurement of the electrical resistivity of nanoheterostructures in a magnetic field, it has been found that the magnetoresistance reaches 14% at T = 15 K and B = 8 T, which is due to the manifestation of tunneling magnetoresistance.     

Microwave characterization of Pb<Subscript>1−x</Subscript>Ca<Subscript>x</Subscript>Fe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> multiferroics at X-band

The microwave characteristics of Pb_1?x Ca _x Fe_0.5Nb_0.5O₃ multiferroics (x = 0.0, 0.4, 0.45, 0.5, 0.55, 0.6), have been investigated as a function of frequency and substitution. The results depict ?13.99 dB reflection loss at 11.65 GHz in composition x = 0.6. Microwave absorption is enhanced with substitution of Ca²⁺ ions and undoped composition 0.0 behaves as electromagnetic shield. The model governing microwave absorption is discussed and different compositions for electromagnetic applications have been suggested.     

The two-phase crystal structure and magnetic properties of the LaCo<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript>x</Subscript>O<Subscript>3−<Emphasis Type="Italic">d</Emphasis></Subscript> system

The preparation conditions and magnetic properties of the La(Co_1?xFe_x)O3?d system of solid solutions were studied. Irrespective of synthesis conditions, the samples with x ≤ 0.15 were rhombohedral (space group \(R\bar 3c\)), and those with x ≥ 0.7, orthorhombic (space group Pnma). In the intermediate region of 0.15 < x < 0.7, the samples could be mixtures of rhombohedral and orthorhombic phases. Structural heterogeneity considerably decreased as the temperature of the synthesis increased or after annealing in a reducing medium. The samples containing more than 40% iron exhibited weak spontaneous magnetization, as is characteristic of weak ferromagnets. The magnetic properties and structure depend on the content of oxygen. A decrease in the concentration of oxygen sharply increases magnetic anisotropy; the coercive force is then close to 10 kOe, which is more than that known for other oxide systems. The magnetic properties are explained in terms of the model according to which Co³⁺ ions are in the low-spin state.     

Heat capacity study of double perovskite-like compounds BaTi<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Zr<Subscript>x</Subscript>O<Subscript>3</Subscript>

The temperature dependence of the heat capacity of two compositions in the solid solution system BaTi_1?xZr_xO₃ (x = 0.25, 0.35) was measured using adiabatic calorimetry. In the T-x phase diagram, these compounds occupy positions near the crossover from conventional ferroelectric behavior to the relaxor state. Both compounds reveal diffuse heat capacity anomalies: two anomalies in the temperature ranges 250–350 and 150–200 K at x = 0.35 and one anomaly within the range ～150–320 K at x = 0.25. The results obtained are discussed together with structural and dielectric measurements.     

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.     

Simulation of the structural,electronic, and magnetic properties of Fe<Subscript>3</Subscript>C<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>B<Subscript>x</Subscript> borocementites

The structural, electronic, and magnetic properties and the enthalpy of formation of iron borocementites Fe₃C_1?x B_x (x= 0, 0.25, 0.50, 0.75, 1.00) are analyzed using ab initio calculations in the framework of the electron density functional theory. It is found that the unit cell parameter a of the orthorhombic lattice increases linearly and the parameters b and c decrease as the boron concentration increases. The density of states at the Fermi level changes only slightly, and the main variations in the band structure occur in the region of the bottom of the valence bands. The magnetic moment of the iron atoms and the total magnetization and stability of the Fe₃C_1?x B_x phases increase linearly with an increase in the boron concentration.     

Thermal expansion of (Sr<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>La<Subscript>x</Subscript>)<Subscript>3</Subscript>Ru<Subscript>2</Subscript>O<Subscript>7</Subscript> single crystals at low temperatures

For single-crystal samples of the (Sr_1?xLa_x)₃Ru₂O₇ ruthenates, the temperature dependence of the thermal expansion coefficient α(T)) is measured in the range 4.2–80 K. The effect of magnetic fields H ≤ 3.5 T on thermal expansion is analyzed. It is found that the (Sr_1?xLa_x)₃Ru₂O₇ ruthenates exhibit an anomalous (negative) thermal expansion coefficient in the temperature range T ≤ 18 K. The position and width of the anomaly revealed in the temperature dependence of the thermal expansion coefficient α(T)) depend substantially on the magnetic field. The origin of the thermal expansion anomaly in ruthenates, the correlation of this anomaly with the stability of the crystal lattice, and the common nature of the anomalies in the thermal properties of ruthenates and high-temperature superconductors are discussed.     

Magnetocaloric properties of manganites La<Subscript>1−x</Subscript>(Ag,K)<Subscript>x</Subscript>MnO<Subscript>3</Subscript>

The temperature and magnetic-field dependences of the magnetocaloric effect in manganites La_1−x Ag _x MnO₃ (x = 0.1; 0.15; 0.2) and La_1−x K _x MnO₃ (x = 0.1; 0.11; 0.13; 0.15; 0.175) were studied by a direct method. Large changes in the sample temperature were detected as a magnetic field changed by ΔH = 10 kOe. Temperatures of the magnetocaloric effect maxima are near room temperatures. Field dependences of the magnetocaloric effect show no signs of saturation in fields to 30 kOe.     

Magnetic property and Mössbauer analysis of SrSn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript><Emphasis Type="Bold">x</Emphasis></Subscript>O<Subscript>3</Subscript> prepared by a sol-gel method

The dilute magnetic properties of SrSn_1?xFe_xO₃ (x = 0.01 ? 0.15) prepared by sol-gel and thermal decomposition methods were investigated by ⁵⁷Fe Mössbauer spectrometry, magnetometry, and X-ray diffractometry. It was found that SrSnO₃ doped with 2–8 % Fe show weak ferromagnetism although only paramagnetic doublets are observed in ⁵⁷Fe Mössbauer spectra at room temperature (RT), whereas SrSnO₃ doped with 10–15 % Fe show relatively strong ferromagnetism, and the sextets are additionally observed in the ⁵⁷Fe Mössbauer spectra at RT. The weak ferromagnetism by doping 2–8 % Fe is considered to be caused by the induced magnetic defects, and the ferromagnetism by doping 10–15 % Fe are considered mainly due to the magnetic coupling between dilute Fe ³⁺ partially substituted at Sn ⁴⁺ sites in the orthorhombic structure of SrSnO_3?δ accompanying the oxygen deficiencies. It is further remarkable that poor crystalline 8 % Fe doped SrSnO_3?δ obtained by annealing at 600 ^°C shows relatively high saturation magnetization and low coercivity.     

Geometric resonance in the optical properties of microinhomogeneous PdMn<Subscript>x</Subscript>Fe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> alloys

The optical properties of PdMn_xFe_1?x ternary alloys in the homogeneous ferromagnetic (F₁, for x ～ 0) and antiferromagnetic (A, for x ～ 1) states, as well as in the microinhomogeneous state (at x=0.7), are discussed. In the x=0.7 alloy, the presence of nuclei of the low-resistivity, PdFe-type F₁ phase in the high-resistivity, PdMn-type A matrix was shown to produce a narrow maximum on the optical-conductivity σ(ω) curve at E ～ 0.1 eV, which is due to a geometric resonance associated with light scattering from phase inhomogeneities of the sample. The behavior of σ(ω) in the interband transition region is dominated by parameters of the electronic spectrum of both the A and F₁ phases.     

Modifying the properties of lead titanate in PbTi<Subscript>1 − <Emphasis Type=Italic>x</Emphasis></Subscript>Mn<Subscript><Emphasis Type=Italic>x</Emphasis></Subscript>O<Subscript>3</Subscript> solid solutions

Spontaneous deformation in the PbTi_{1 − x} Mn _x O₃ system at room temperature is found to decrease as x increases, indicating a drop in the temperature of the ferroelectric phase transition.     

Peculiarities of the magnetic,galvanomagnetic, elastic,and magnetoelastic properties of Sm<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript>x</Subscript>MnO<Subscript>3</Subscript> manganites

Manganites of the Sm1?xSr_xMnO₃ system (x=0.33, 0.4, and 0.45) possess giant negative values of the magnetoresistance Δρ/ρ and the volume magnetostriction ω near the Curie temperature T_C. In the compound with x=0.33, the isotherms of Δρ/ρ, ω, and magnetization σ exhibit smooth variation and do not reach saturation up to maximum magnetic field strengths (120 kOe) studied (according to the neutron diffraction data, this substance comprises a ferromagnetic (FM) matrix with distributed clusters of a layered antiferromagnetic (AFM) structure of the A type). In the compounds with x=0.4 and 0.45 containing, besides the FM matrix and A-type AFM phase, a charge-ordered AFM phase of the CE type (thermally stable to higher temperatures as compared to the A-type AFM and the FM phases), the same isotherms measured at T ≥ T_C show a jumplike increase in the interval of field strengths between H_c1 and H_c2 and then reach saturation. In the interval H_c1 > H > H_c2, the σ, ω, and Δρ/ρ values exhibit a metastable behavior. At temperatures above T_C, the anisotropic magnetostriction changes sign, which is indicative of rearrangements in the crystal structure. The giant values of ω and Δρ/ρ observed at T ≥ T_C for all compounds, together with excess (relative to the linear) thermal expansion and a maximum on the ρ(T) curve, are explained by the phenomenon of electron phase separation caused by a strong s-d exchange. The giant values of magnetoresistance and volume magnetostriction (with ω reaching ～10^?3) are attributed to an increase in the volume of the FM phase induced by the applied magnetic field. In the compound with x=0.33, this increase proceeds smoothly as the FM phase grows through the FM layers in the A-type AFM phase. In the compounds with x=0.4 and 0.45, the FM phase volume increases at the expense of the charge-ordered CE-type AFM structure (in which spins of the neighboring manganese ions possess an AFM order). The jumps observed on the σ(H) curves, whereby the magnetization σ reaches ～70% of the value at T=1.5 K, are indicative of a threshold character of the charge-ordered phase transition to the FM state. Thus, the giant values of ω and Δρ/ρ are inherent in the FM state, appearing as a result of the magnetic-field-induced transition of the charge-ordered phase to the FM state, rather than being caused by melting of this phase.     

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.     

Hall effect in La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript>x</Subscript>MnO<Subscript>3</Subscript> crystals

A study of the temperature dependences of the ordinary and anomalous Hall coefficients and of the Hall mobility of carriers in single crystals of the ferromagnetic manganites La_1?xSr_xMnO₃ (x=0.15, 0.20, 0.25) was carried out in the temperature interval from 85 to 400 K. The nature of the carriers and the conduction mechanisms in these compounds are discussed.     

Magnetorefractive effect in (Co<Subscript>50</Subscript>Fe<Subscript>50</Subscript>)<Subscript>x</Subscript>(Al<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> granular films

The reflectivity spectra and the magnetorefractive effect (MRE) of (Co₅₀Fe₅₀)_x(Al₂O₃)_1?x metal-dielectric granular films (0.07<x<0.52) are analyzed in the IR spectral range λ=2.5–25 µm. It is revealed that the specific features observed in the spectra at λ≈8.5 and 20 µm are associated with the excitation of phonon modes in the dielectric matrix. The magnetorefractive effect in the films is observed below the percolation thresh-old only in p-polarized light and above the percolation threshold for both the p and s polarizations. It is demonstrated that the optical properties of (Co₅₀Fe₅₀)_x(Al₂O₃)_1?x films in the IR spectral range, to a first approximation, can be interpreted in the framework of the effective-medium theory and the magnetorefractive effect can be explained in terms of the modified Hagen-Rubens relation.     

Sol–gel electrophoretic deposition and optical properties of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowire arrays

Ordered Fe₂O₃ nanowire arrays embedded in anodic alumina membranes have been fabricated by Sol–gel electrophoretic deposition. After annealing at 600 °C, the Fe₂O₃ nanowire arrays were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED) and X-ray diffraction (XRD). SEM and TEM images show that these nanowires are dense, continuous and arranged roughly parallel to one another. XRD and SAED analysis together indicate that these Fe₂O₃ nanowires crystallize with a polycrystalline corundum structure. The optical absorption band edge of Fe₂O₃ nanowire arrays exhibits a blue shift with respect of that of the bulk Fe₂O₃ owing to the quantum size effect. PACS 78.67.Lt; 81.05.Je; 81.07.Vb