Thermal conductivity of single crystals of Ca1 ? xErxF2 + x and Ca1 ? xTmxF2 + x solid solutions

The thermal conductivity of single crystals of Ca_{1 − x} Er _x F_{2 + x} (x = 0.01, 0.05, 0.07, and 0.10) and Ca_{1 − x} Tm _x F_{2 + x} (x = 0.02, 0.04, and 0.06) solid solutions is studied in the temperature ranges 50–300 and 298–673 K. With increasing content of rare-earth elements, the behavior of thermal conductivity in these solid solutions changes from the characteristic of defect single crystals to glasslike. The concentration dependences of thermal conductivity for the two systems differ insignificantly.     

Synthesis and characterization of ZnxHg1?xSeyS1?y quantum dots

This article describes the synthesis of highly water-soluble Zn _x Hg_1−x Se _y S_1−y quantum dots (QDs) in aqueous solution through a simple photo-assisted reaction between ZnSe QDs and mercury(I) nitrate dihydrate [Hg₂(NO₃)₂·2H₂O]. In order to deduce the optimal synthesis conditions, we varied several parameters, including the concentrations of mercaptosuccinic acid (MSA) and Hg₂(NO₃)₂·2H₂O, the illumination time, and the reaction temperature. When irradiated at temperatures below 80 °C, the ZnSe QDs reacted with the S²⁻ ions formed rapidly from MSA and the Hg²⁺ ions formed from Hg₂ ²⁺ ions to form Zn _x Hg_1−x Se _y S_1−y QDs through a process of photo-etching and surface combination. Under different conditions, we prepared a series of Zn _x Hg_1−x Se _y S_1−y QDs that emit fluorescence at the maximum wavelengths ranging from 405 to 760 nm. Inductively coupled plasma-mass spectrometry and transmission electron microscopy/energy dispersive spectrometry revealed that the content of Hg in the Zn _x Hg_1−x Se _y S_1−y QDs was greater when the synthesis was conducted at higher temperature. The Zn_0.88Hg_0.12Se_0.44S_0.56 QDs exhibit improved photostability than crude ZnSe QDs and possess long lifetimes (τ₁ ~ 38 ns and τ₂ ~ 158 ns).     

Noncentrosymmetric cubic helical ferromagnets Mn1 ? yFeySi and Fe1 ? xCoxSi

Two systems of noncentrosymmetric cubic helical magnets Mn_{1 − y} Fe _y Si (y = 0.06, 0.08, 0.10) and Fe_{1 − x} Co _x Si (x = 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.50) have been compared. The concentration dependences of the critical temperature and magnetic field have been obtained using small-angle polarized-neutron scattering and analyzed in the framework of the Bak-Jensen model. It has been established that, among the two interactions that play the main role in these systems, i.e., the isotropic symmetric ferromagnetic exchange and the Dzyaloshinskii-Moriya isotropic antisymmetric interaction, the former interaction determines the critical temperature in the Mn_{1 − y} Fe _y Si system and the latter interaction determines this temperature in the Fe_{1 − x} Co _x Si system.     

Electrical conductivity and magnetic properties of La1 ? xCaxMn1 ? yFeyO3 ceramic samples (x = 0.67, y = 0, 0.05)

The temperature dependences of the magnetic susceptibility χ(T) and the electrical resistivity ρ(T) of ceramic samples of La_{1 − x} Ca _x MnO₃ with x = 0.67 (LCMO) and La_{1 − x} Ca _x Mn_{1 − y} Fe _y O₃ with x = 0.67 and y = 0.05 (LCMFO) are investigated in magnetic fields B = 50–10⁵ G and the temperature range T = 4.2–400 K. Both samples undergo a transition from the paramagnetic state to a state with charge (orbital) ordering (CO) at temperatures T _CO ≈ 272 K for LCMO and T _CO ≈ 222 K for LCMFO. The behavior of the paramagnetic phase in the temperature range 320–400 K for LCMO and 260–400 K for LCMFO is described by the Curie-Weiss law with effective Bohr magneton numbers p _eff = 4.83 μ_B (LCMO) and 4.77 μ_B (LCMFO), respectively. The disagreement between the observed positive Weiss temperatures (θ ≈ 175 K (LCMO) and θ ≈ 134 K (LCMFO)) and negative Weiss temperatures required for the antiferromagnetic ground state can be explained by the phase separation and transition to the charge-ordered state. The magnetic irreversibility for T < T _CO is accounted for by the existence of a mixture of the ferromagnetic and antiferromagnetic phases, as well as the cluster glass phase. At low temperatures, doping with iron enhances the frustration of the system, which manifests itself in a more regular behavior of the decay rate of the remanent magnetization with time. The temperature dependence of the electrical resistivity in the range of the charge-ordered phase conforms to the variable-range hopping model. The behavior of the electrical resistivity is governed by the complex structure of the density of localized states near the Fermi level, which includes a soft Coulomb gap Δ = 0.464 eV for LCMO and 0.446 eV for LCMFO. It is established that the ratio between the localization radii of charge carriers a for LCMFO and a _und for LCMO is a/a _und = 0.88. Original Russian Text ? V.S. Zakhvalinskiĭ, R. Laiho, T.S. Orlova, A.V. Khokhulin, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 1, pp. 61–68.     

Ternary alloys CdyZn1 ? yO and MgxZn1 ? xO as materials for optoelectronics

Thin films of Cd _y Zn_{1 − y} O and Mg _x Zn_{1 − x} O (y = 0−0.35, x = 0−0.45) ternary alloys have been grown by pulsed laser deposition onto sapphire substrates. The record solubility limits of Cd (y = 0.3) and Mg (x = 0.35) have been achieved in hexagonal zinc oxide. The mismatch of the lattice parameters a of Cd_0.2Zn_0.8O and Mg_0.35Zn_0.65O does not exceed 1%; in this case, the band gap discontinuity is 1.3 eV. The surface roughness of the films does not exceed 2.5 nm at x = 0−0.27 and y = 0−0.20.     

Synthesis and study of photocatalytic activity of nanoscale quasi-one-dimensional Ti1 ? xVxO2 (0 ≤ x ≤ 0.13) and Zn1 ? xCoxO (0 ≤ x ≤ 0.3) oxides

A original method of synthesis of quasi-one-dimensional Ti_{1 − x} V _x (OCH₂CH₂O)₂ (0 ≤ x ≤ 0.13) and Zn_{1 − x} Co _x (HCOO)(HOCH₂CH₂O) (0 ≤ x ≤ 0.3) has been developed. The synthesis products were used as a basis for nanoscale extended Ti_{1 − x} V _x O₂ and Zn_{1 − x} Co _x O oxides. The compounds obtained and products of their thermolysis were investigated by X-ray diffraction, microscopy, IR spectroscopy, thermogravimetry, and chemical analysis; the shape and size of particles were determined by scanning electron microscopy. The good prospects of Ti_{1 − x} V _x O₂ and Zn_{1 − x} Co _x O solid solutions as photocatalysts for hydroquinone oxidation are shown.     

Structure and M?ssbauer studies of manganese monosulfide solid solutions MxMn1 ? xS (M = Cr, Fe)

This paper reports on the results of the synthesis and study of the diffraction patterns and M?ssbauer spectra of single crystals of homogeneous M xMn_{1 − x} S solid solutions with a cubic NaCl structure prepared by the cation substitution of 3d elements for divalent manganese ions in manganese monosulfide. It has been shown that, similarly to the hydrostatic pressure, the substitution of 3d ions with a smaller ionic radius is accompanied by the contraction of the MnS cubic cell. The calculated lattice parameters agree with the experimental data. The homogeneous region of the formation of homogeneous solid solutions is limited in composition x, which depends on the choice of a substitutional cation.     

Effect of the spin and valence states of cobalt ions on the kinetic properties of Ho1 ? xSrxCoO3 ? δ and Er1 ? xSrxCoO3 ? δ compounds

The electrical conductivity and Seebeck effect in ceramics based on cobaltites Ho_{1 − x} Sr _x CoO_{3 − δ} (x = 0.65, 0.75, 0.85, 0.95) and Er_{1 − x} Sr _x CoO_{3 − δ} (x = 0.75, 0.85, 0.95) with a perovskite-like structure have been investigated in the temperature range T > 77 K. All the compounds under study are characterized by the variable-range-hopping conductivity with the temperature dependence of the electrical resistivity corresponding to the Mott law. It has been found that, in the Ho_0.35Sr_0.65CoO_{3 − δ} compound, thermally excited Co³⁺ ions contribute to the electrical conductivity with an increase in temperature to 250 K. The Seebeck coefficient of the systems studied decreases as the strontium concentration and temperature increase. It has been shown that, for an adequate explanation of this behavior, proper allowance must be made for the splitting of the 3d levels, as well as for the charge disproportionation of the cobalt ions.     

M?ssbauer study of compounds of Cu3 ? xFexSnS4 and Cu2Fe1 ?xZnxSnS4 systems

A M?ssbauer study of the structural and charge states of ⁵⁷Fe and ¹¹⁹Sn atoms in the compounds of Cu_{3 −x} Fe _x SnS₄ and Cu₂Fe_{1 − x} Zn _x SnS₄ systems was performed. It was shown that the iron atoms in the compounds of both systems were in the divalent and trivalent states occupying the tetrahedral positions of the structure. The character of the changes of the degree of covalency of the Fe²⁺-S, Fe³⁺-S and Sn⁴⁺-S bonds during the isomorphic substitution in the systems was established.     

Magnetic properties and magnetic entropy change in Heusler alloys Ni50Mn35?xCuxSn15

The influence of Cu substitution for Mn on magnetic properties and magnetic entropy change has been investigated in Heusler alloys, Ni₅₀Mn_35−x Cu _x Sn₁₅ (x=2,5 and 10). With increasing Cu content from x=2 to x=5, the martensitic transition temperature, T _M , decreases from 220 K to 120 K. Further increasing Cu up to x=10 results in the disappearance of T _M . For samples Ni₅₀Mn₃₃Cu₂Sn₁₅ and Ni₅₀Mn₃₀Cu₅Sn₁₅, both martensitic and austenitic states exhibit ferromagnetic characteristics, but the magnetization of martensitic phase is notably lower than that of austenitic phase. The magnetization difference, ΔM, across the martensitic transition leads to a considerably large Zeeman energy, μ ₀ΔM⋅H, which drives a field-induced metamagnetic transition. Associated with the metamagnetic behavior, a large positive magnetic entropy change ΔS takes place around T _M . For the sample Ni₅₀Mn₃₃Cu₂Sn₁₅,ΔS reaches 13.5 J/kg⋅K under a magnetic field change from 0 to 5 T.     

The equilibrium states of A1?xB1+x binary alloys in the hard-sphere and pair-binding model

The equilibrium ordering states of A _1−x B _1+x alloys are investigated analytically and by computer simulation with the hard-sphere and pair-binding model. The alloy energies are calculated for the case where an excess of the B component forms a solid solution or precipitates as pure phase particles. Criteria for pair-binding energies are obtained that define the type of the resulting alloy. The analytical results are presented for an alloy of arbitrary dimensionality and for any number of coordination spheres involved in interatomic interactions. Illustrating examples are given for B2 and L1₀ superstructures and for a two-dimensional square lattice in view of the atomic interaction in the first two coordination spheres.     

Magnetic phases in Pr0.5Sr0.5Mn1 ? xCoxO3 (x ≤ 0.5) solid solutions

The magnetic and magnetotransport properties of Pr_0.5Sr_0.5Mn_{1 − x} Co _x O₃ (x ≤ 0.5) solid solutions have been investigated using neutron diffraction methods. The magnetization and electrical conductivity have been measured in magnetic fields up to 140 kOe. It has been established that, during cooling in the temperature range from 160 to 110 K, the compounds of compositions with a cobalt content x ≤ 0.07 undergo a structural phase transition from the high-temperature ferromagnetic phase to the antiferromagnetic phase. A further substitution of cobalt for manganese leads to a stabilization of the inhomogeneous dielectric ferromagnetic state, whereas a state of the cluster spin-glass type has been revealed in compositions with x = 0.15 and 0.20. At x ≥ 0.25, a new magnetic phase with a Curie temperature up to 210 K is formed as a result of the magnetic interaction between manganese and cobalt ions. A magnetic phase diagram of the system under investigation has been constructed.     

Ion-electron transfer in solid solutions Rb2 ? 2xFe2 ? xPxO4

The rubidium monoferrite RbFeO₂-based solid solutions with the composition Rb_{2 − 2x} Fe_{2 − x} P _x O₄ have been synthesized, and their crystal structure and the temperature and concentration dependences of the total and electron conductivities have been studied. The introduction of P⁵⁺ ions has been found to sharply decrease the electron conductivity that prevails in pure rubidium monoferrite and, at the same time, to increase the ionic conductivity. The latter becomes dominant as the phosphorus concentration increases. The maximum rubidium-cation conductivity of the materials under study is ∼3 × 10⁻² S/cm at 300°C and ∼3 × 10⁻¹ S/cm at 700°C. The results have been compared with the previously obtained data for similar solid solutions based on rubidium monogallate and monoaluminate.     

M?ssbauer and X-ray studies of the structural phase transformations and suppression of polymorphism in La1 ? xSrxMn0.98Fe0.02O3 + δ (x = 0.05?0.30)

The specific features of the structural transformations in La_{1 − x} Sr _x Mn_0.98Fe_0.02O_{3 + δ} (x = 0.05−0.30) as functions of the Sr content have been investigated using M?ssbauer spectroscopy and X-ray diffraction. It has been shown that, when the Sr content is lower than 10%, three phases are formed: PnmaII, PnmaI, and R-3c. In the Sr concentration range from 10 to 20%, the PnmaI and R-3c phases are formed. At a strontium content of 20%, the rhombohedral phase is formed. When the strontium content increases to 30%, the presumably monoclinic (distorted cubic) phase is formed in addition to the rhombohedral phase. The specific features of the formation and suppression of the phases in the LaMn_0.98Fe_0.02O_{3 + δ} compound are compared with those observed in the strontium-doped La_{1 − x} Sr _x Mn_0.98Fe_0.02O_{3 + δ} compound. The general regularities of the structural transformations and substantial differences between them have been revealed.     

Emission centers in Ca1–xPrxF2+x (x = 0.35) solid solutions

Luminescence spectra of Ca_0.65Pr_0.35F_2.35 solid solutions are studied. It is found that, depending on the excitation energy, different kinds of emission centers appear in these spectra. An interconfigurational 4f ¹5d¹ →4f² luminescence is typical for single Pr³⁺ ions in tetragonal sites. Data on the structure of the solid solutions show that the emission centers involved in ¹S₀ → 4f² transitions can be attributed to Pr³⁺ ions contained in clusters.     

Ferromagnetic resonance and magnetic microstructure in nanocomposite films of Cox(SiO2)1 ? x and (CoFeB)x(SiO2)1 ? x

This paper reports on the results of the investigation of the relation between the magnetic microstructure and ferromagnetic resonance (FMR) in ferromagnetic metal-insulator composites by using granular alloys (Co₄₁Fe₃₉B₂₀) _x (SiO₂)_{1 − x} and Co _x (SiO₂)_{1 − x} as an example. A comparative analysis of the properties of FMR spectra and parameters of random magnetic anisotropy leads to correlations between these quantities. It has been found that the main mechanism that determines the FMR line width in the films under investigation is the exchange narrowing mechanism.     

Morphotropic phase boundary, weak ferromagnetism, and strong piezoelectric effect in Bi1 ? xCaxFeO3 ? x/2 compounds

The crystal structure and magnetic and piezoelectric properties of the Bi_{1 − x} Ca _x FeO_{3 − x/2} system (x ≤ 0.2) are studied. The crystal-structure transformations occur in the following sequence: rhombohedral (R3c) polar phase (x ≤ 0.06) → modulated polar phase (0.07 ≤ x ≤ 0.1) → modulated antipolar phase (0.11 ≤ x ≤ 0.14). The modulated polar and antipolar phases are weakly ferromagnetic with a spontaneous magnetization of 0.25 G cm³/g (x = 0.09). In the polar weak ferromagnet with x = 0.09, a uniform piezoelec- tric response 2.5 times stronger than in the initial BiFeO₃ compound is detected by the piezoelectric force microscopy.     

Influence of the illumination on the subband structure and?occupation in AlxGa1?xN/GaN heterostructures

The subband structure and occupation in the triangular quantum well at Al _x Ga_1−x N/GaN heterointerfaces have been investigated by means of temperature dependent Shubnikov–de Haas (SdH) measurements at low temperatures and high magnetic fields under illumination. After the illumination of the heterostructures, the total two-dimensional electron gas concentration increases, and the SdH oscillation amplitudes are enhanced when there is no additional subband occupation. It is also found that the energy separation between the subbands decreases after the illumination. We suggest that the illumination decreases the electric field and thus weakens the quantum confinement of the triangular quantum well at Al _x Ga_1−x N/GaN heterointerfaces. The GaN layer is thought to be the primary contributor of the excited electrons by the illumination.     

Charge state of manganese ions and the nonstoichiometry of Ca1 ? xLayMnO3 ? δ single crystals

The charge states and effective spins of manganese ions in nonstoichiometric single crystals of Ca_{1 − x} La _y MnO_{3 − δ} (x = 0, 0.05, 1) manganites have been determined from the exchange splitting of Mn 3s X-ray photoelectron spectra. The chemical composition of the manganite samples under investigation, including the concentration of oxygen, has been determined using the data of the X-ray microanalysis of cations. It has been found that the manganite single crystals under investigation have large defectiveness in both the cation and oxygen sublattices. The efficiency of the complex use of 3s photoelectron spectroscopy and X-ray microanalysis in the determination of the charge state of manganese ions and violations of stoichiometry in doped and defected manganites has been demonstrated.     

Mechanism of NdSr2 ? xCaxMn2O7 (0 ≤ x ≤ 2.0) solid solution formation

The mechanisms of formation of NdSr_{2− x} Ca _x Mn₂O₇ (0 ≤ x ≤ 2.0) solid solution have been studied. The dependence of its volume magnetic susceptibility on the calcium concentration is obtained. The stability of this solid solution is compared with that of similar solid solutions in lanthanum-containing systems.