Phase x-T diagram of actual solid solutions of the (1 ? x )PbZrO3- x PbTiO3 system (0.37 ≤ x ≤ 0.57)

Ceramics of PbZr_{1 − x} Ti _x O₃ solid solutions were systematically studied in the range 0.37 ≤ x ≤0.57. The x-T phase diagram of the system is constructed in the range 25°C ≤ T ≤ 650°C. The diagram has a region of an indefinite symmetry in the vicinity of the transition to the nonpolar cubic phase. It is established that solid solutions in this region are characterized by weak distortions and temperature-time instability of the crystal structure. Three concentration regions are separated differing in the value of the jump in the unit cell volume ΔV at the line of transitions from the rhombohedral (tetragonal) phase to the region of indefinite symmetry. It is revealed that there are three temperature ranges differing in the behavior of the temperature dependence of the inverse permittivity, which are due to the existence of two critical Curie points at the boundary separating the ferroelectric phases from the cubic phase. Original Russian Text ? L.A. Reznichenko, L.A. Shilkina, O.N. Razumovskaya, E.A. Yaroslavtseva, S.I. Dudkina, O.A. Demchenko, Yu.I. Yurasov, A.A. Esis, I.N. Andryushina, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 8, pp. 1469–1475.     

Dispersion of the refractive index in β-Tl1 ? x Cu x InS2 crystals (0 ≤ x ≤ 0.015)

The refractive index dispersion in β-Tl_{1 − x} Cu _x InS₂ (0 ≤ x ≤ 0.015) crystals has been studied using intrinsic interference. It is shown that these crystals are characterized by anomalous-dispersion regions at wavelengths slightly exceeding those corresponding to exciton peaks. It is established that, using intrinsic interference, one can detect excitons in these crystals at room temperature. Modulation of interference patterns is revealed, and explanation of this phenomenon is proposed. Original Russian Text ? A.N. Georgobiani, A.Kh. Matiyev, S.V. Bulyarski, T.A. Matiyeva, 2008, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2008, Vol. 72, No. 10, pp. 1523–1525.     

Enhanced magnetization of nanoparticles of Mg x Fe(3? x )O4 (0.5≤ x ≤1.5) synthesized by combustion reaction

For the first time nanocrystalline magnetic particles of Mg _x Fe_(3−x)O₄ with x ranging from 0.5 to 1.5 have been synthesized by a combustion reaction method using iron nitrate Fe(NO₃)₃.9H₂O, magnesium nitrate Mg(NO₃)₂.6H₂O, and urea CO(NH₂)₂ as fuel without intermediate decomposition and/or calcining steps. X-ray diffraction patterns of all systems showed broad peaks consistent with cubic inverse spinel structure of MgFe₂O₄. The absence of extra reflections in the diffraction patterns of as-prepared materials ensures the phase purity. The mean crystallite sizes determined from the prominent (311) peak of the diffraction using Scherrer’s equation and transmission electron microscopy micrographs were c.a. 40 nm with spherical morphology. Fourier transform infrared spectra of the as-prepared material showed traces of organic and metallic salt by-products; however, these could be removed by washing with deionized water. Typical hysteresis curves were obtained for all specimens in magnetic field up to 14 T between 4 and 340 K. The saturation magnetization was 48.3 emu/g and 31.3 emu/g, 44.8 emu/g, and 28.4 emu/g for x=1.0 and 0.8 at 4 K and 340 K, respectively. The saturation magnetization, M _s , of nanoparticles of the MgFe₂O₄ specimen is about 50% higher when compared to the bulk. The enhanced magnetization measured in our nanoparticles MgFe₂O₄ specimens may be attributed to the uncompensated magnetic moment of iron ions between the A- and B-sites, i.e., changes in the inversion factor. Our magnetization results of MgFe₂O₄ specimens are comparable to the existing data for the same compound but with different particle size and prepared by different synthesis methods.     

IR reflection and Raman spectra of β-Tl1 ? x Cu x InS2 (0 ≤ x ≤ 0.015) single crystals

The IR reflection and Raman spectra of β-Tl_{1 − x} Cu _x InS₂ (0 ≤ x ≤ 0.015) single crystals have been studied in the temperature range 84–300 K. It is shown that partial replacement of thallium by copper atoms leads to a decrease in the frequencies of the corresponding oscillations in the frequency range 40–500 cm⁻¹ and does not induce (at given concentrations) local oscillations. Analysis of the transformation of the IR reflection spectra at T ₂ ≈ 185 K revealed a ferroelectric phase transition. Original Russian Text ? A.N. Georgobiani, A.Kh. Matiyev, C.V. Bulyarski, T.A. Matiyeva, 2009, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2009, Vol. 73, No. 1, pp. 138–140.     

Magnetic, electrical, and optical properties of Ca1 ? x Ce x MnO3 ( x ≤ 0.12) single crystals

The magnetic, electrical, and optical properties of Ca_{1 − x} Ce _x MnO₃ (x≤0.12) manganite single crystals are investigated with the aim of revealing the specific features of the multiphase electronic and magnetic state as a function of the cerium concentration and the atmosphere used for growing single crystals. It is found that the concentration dependence of the low-temperature magnetization M(x) of the single crystals is shifted toward the high-concentration range as compared to the corresponding dependence of the polycrystals, which is explained by the predominant cation deficiency. The electrical resistivity and the reflection spectra of the single crystals in the infrared spectral range indicate that charge carriers exhibit a band nature at temperatures close to room temperature. The temperature dependence of the electrical resistivity of the single crystal with x = 0.08, which has the maximum magnetization in the studied series of Ca_{1 − x} Ce _x MnO₃ compounds, unlike polycrystals, exhibits a metallic behavior over the entire temperature range. The G-type antiferromagnetic phase with the Néel and Curie temperatures T _N(G) = T _C = 100 K is characterized by maxima of the electrical resistivity ρ and the magnetoresistance Δρ/ρ = |(ρ₀ − ρ _H )/ρ₀| = 38% in the magnetic field H = 90 kOe. The magnetoresistance Δρ/ρ of the single crystals at cerium concentrations x = 0.10 and 0.12 with variations in temperature exhibit three specific features: near the temperature of charge ordering T _co, near the temperature of the magnetic phase transition to the C-type antiferromagnetic phase T _N(C), and near the temperature of the phase transition to the magnetic charge-ordered phase T _N(MCO). An anomalous temperature dependence of the magnetization is revealed for a single crystal with x = 0.10 grown in oxygen at a pressure of 5 atm, which is explained by the presence of regions with hole conductivity due to cation deficiency. The inhomogeneous electronic and magnetic state is associated with the interrelation of the charge, orbital, and spin orderings. Original Russian Text ? N.N. Loshkareva, A.V. Korolev, N.I. Solin, E.V. Mostovshchikova, S.V. Naumov, N.V. Kostromitina, A.M. Balbashov, 2009, published in Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2009, Vol. 135, No. 1, pp. 98–107.     

Crystal structure and properties of Bi1 ? x Ca x FeO3 and Bi1 ? x Ca x FeO1 ? x Ti x O3 solid solutions

Systems of solid solutions Bi_{1 − x} Ca _x FeO₃ (I) and Bi_{1 − x} CaxFeO_{1 − x} Ti _x O₃ (II) have been obtained and their properties have been studied using neutronography and M?ssbauer spectroscopy; magnetization and permittivity have been measured. It is shown that an increase in the concentration of calcium ions in system I for x > 0.2 changes rhombohedral distortions of a unit cell (space group R3c) to tetragonal distortions (space group I4/mcm), while rhombohedral distortions in system II for x > 0.2 are replaced by orthorhombic distortions (space group Pnma). Analysis of the crystal structure has revealed strong anisotropy in vibrations of Bi and O ions in system I compounds. Systems I and II are characterized by G-type antiferromagnetic ordering of magnetic moments. In system II, spontaneous magnetization associated with the Dzyaloshinskii-Moriya interaction has been detected. According to M?ssbauer spectroscopy data, iron ions in compounds I and II are in the trivalent state and charge compensation occurs due to the formation of oxygen vacancies. The permittivity increases with the calcium concentration. Original Russian Text ? I.O. Troyanchuk, D.V. Karpinsky, M.V. Bushinskii, O. Prokhnenko, M. Kopcevicz, R. Szymczak, J. Pietosa, 2008, published in Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2008, Vol. 134, No. 1, pp. 105–112.     

Dependences of the dielectric and pyroelectric properties of (1 ? x)PbFe1/2Nb1/2O3?xPbTiO3 ferroelectric ceramics solid solutions on the PbTiO3 content in a compositional range of 0 ≤ x ≤ 0.08

(1 − x)PbFe_1/2Nb_1/2O_3−x PbTiO₃ (PFN-xPT) ferroelectric ceramics with low dielectric loss and pronounced anomalies of dielectric and pyroelectric properties near the ferroelectric-ferroelectric phase transition was obtained by doping with lithium. The temperature dependence of the position of the morphotropic boundary between the rhombohedral (monoclinic) and tetragonal phases in the x-T phase diagram of the PFN-xPT system was determined for the first time.     

Optical properties of the HfO2 ? x N x and TiO2 ? x N x films prepared by ion beam sputtering

Optical characteristics of the HfO_{2 − x} N _x and TiO_{2 − x} N _x films obtained by reactive ion beam sputtering have been investigated by spectral ellipsometry. The chemical composition of the films was determined using X-ray photoelectron spectroscopy. The nitrogen content in the oxynitride films (determined by the N₂/O₂ ratio in the gas mixture during synthesis) reached ≈9 at % for TiO_{2 − x} N _x and ≈ 6 at % for HfO_{2 − x} N _x . It is found that the dispersion relations n(λ) and k(λ) for the TiO_{2 − x} N _x films change from those characteristic of titanium dioxide to those typical of titanium nitride with an increase in the nitrogen content from 0 to ≈9 at %. The optical parameters of the HfO_{2 − x} N _x films depend weakly on the nitrogen content in the range 0–6 at %. Original Russian Text ? V.V. Atuchin, V.N. Kruchinin, A.V. Kalinkin, V.Sh. Aliev, S.V. Rykhlitskiĭ, V.A. Shvets, E.V. Spesivtsev, 2009, published in Optika i Spektroskopiya, 2009, Vol. 106, No. 1, pp. 77–82.     

Irreversible increase in the temperature range of existence of the orthorhombic antiferroelectric phase in PbZr1 ? xTixO3 ceramics (0.02 ≤ x ≤ 0.05)

The influence of thermostating at 450°C on the dielectric and pyroelectric properties of PbZr_{1 − x} Ti _x O₃ polarized ferroelectric specimens the range 0.02 ≤ x ≤ 0.05 has been investigated. An irreversible increase in the temperature of the ferroelectric-antiferroelectric phase transition was observed in all specimens upon their cooling after exposure to an elevated temperature for more than 1 h. The original position of the phase-transition point on the temperature scale was not recovered as a result of afterpoling upon cooling through the Curie temperature. Heating of the same specimens in the bridged mode up to 650°C with subsequent abrupt immersion in silicone oil at room temperature (hardening) is accompanied by an additional increase in the range of existence of the antiferroelectric phase from 3 to 15°C with an increase in the x concentration.     

Growth of the magnetic semiconductor Fe2? x Ti x O3± δ thin films by pulsed laser deposition

The understanding and control of the ilmenite–hematite solid solutions (Fe_2−x Ti _x O_3±δ or IH) thin film structure and properties are crucial for spintronics applications. Good quality films of Fe_2−x Ti _x O_3±δ on Al₂O₃(0001) substrates were obtained by pulsed laser deposition. For the studied compositions (x=1, 0.7, 0.5) in a wide oxygen pressure range all the films were epitaxial, with flat interfaces, and without secondary phases. Unconventional lattice strain relaxation with the increase of in-plane lattice parameter above its relaxed bulk value was observed for different film compositions, oxygen pressures, substrate temperatures, and film growth rates. This phenomenon is most likely explained by the buckling of a few first film monolayers because of a significant compressive stress induced on the film by the sapphire substrate. The IH thin films with x=0.7 and 0.5 exhibited the properties of a room temperature magnetic semiconductor. The resistivity changed over three orders of magnitude in the studied pressure range, thus clearly demonstrating the important role of oxygen stoichiometry in the creation of carriers.     

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.     

Specific features of the structural and magnetic states of a Zn1 ? x Ni x Se crystal ( x = 0.0025) at low temperatures

The magnetic state and the structure of a Zn_{1 − x} Ni _x Se (x = 0.0025) bulk crystal were studied at low temperatures. It is revealed that the magnetic and crystal structures below T ≅ 15 K are dependent on the cooling rate of this dilute semiconductor. For example, on fast cooling to 4.2 K, about 10% hexagonal ferromagnetic phase is formed in the crystal. During heating, the phase disappears at T ≅ 15 K. The results obtained are discussed with allowance for the specific features of the Jahn-Teller distortions in this compound. Original Russian Text ? S.F. Dubinin, V.I. Sokolov, V.D. Parkhomenko, S.G. Teploukhov, N.B. Gruzdev, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 12, pp. 2188–2191.     

Effect of polarization on the intensity of anomalous electron emission in the (1 ? x)PbMg1/3Nb2/3O3 + xPbTiO3 system

Spectra of anomalous electron emission from the surface of solid solutions in the (1 − x)PbMg_1/3Nb_2/3O₃ + xPbTiO₃ system with x = 0.06, 0.10, 0.13, 0.20, and 0.25 have been studied. While the energy characteristics of the anomalous electron emission spectra vary monotonically with x, the behavior of integrated intensity was found to be nonmonotonic with a maximum occurring at x = 0.1. According to the proposed interpretation, the results obtained are explained by the effect of the potential barrier on the electron emission; the potential barrier depends, in turn, on the permittivity ε of the samples. Original Russian Text ? A.T. Kozakov, A.V. Nikol’skiĭ, V.P. Sakhnenko, A.N. Pavlov, V.G. Smotrakov, V.V. Eremkin, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 7, pp. 1310–1314.     

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.     

Effect of the nonstoichiometric disorder on the temperature dependence of the upper critical field in Nd2? x Ce x CuO4+δ electron superconductors

The temperature dependences of the resistance of the Nd_2−x Ce _x CuO_4+δ single crystal with x = 0.15 and various disorder parameters δ have been investigated in various magnetic fields (B ‖ c, J ‖ ab) in the temperature range T = 1.8–40 K. It has been shown that the slope of the upper critical field, (dB _c2/dT)|T _c, in the electron superconductor decreases with an increase in the disorder parameter. This dependence makes it possible to experimentally distinguish between d-pairing superconductors and s-pairing superconductors. The dependence of the superconducting transition temperature on the disorder parameter in the system is investigated in the model of the superconductors with anisotropic impurity scattering. Original Russian Text ? T.B. Charikova, N.G. Shelushinina, G.I. Kharus, A.A. Ivanov, 2008, published in Pis’ma v Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2008, Vol. 88, No. 2, pp. 132–136.     

Dielectric properties of perovskite ceramics of (1–x)BiFeO3 ? x(KBi)1/2TiO3 (0.40 < x < 0.85) solid solutions from impedance spectroscopy data

The dielectric properties of the ceramics of (1 − x)BiFeO₃ − x(KBi)_1/2TiO₃ (0.40 < x < 0.85) solid solutions with an orthorhombic structure have been studied using impedance spectroscopy in the frequency range 25–10⁶ Hz at different temperatures. It has been shown that these solid solutions undergo a diffuse ferroelectric phase transition. The Curie temperature is found to be in the range 620–640 K. The activation energies of dielectric polarization relaxation (δE _M ) and dc charge carriers (ΔE _dc) are determined. It has been established that, in the vicinity of 460 K, ΔE _dc increases jumpwise as the temperature increases.     

Effect of oxygen deficiency on the magnetic, electrical, magnetoelectric, and magnetoelastic properties of La1 ? x Sr x MnO3 ? δ manganites

This paper reports on a study of the effect of oxygen deficiency on the magnetic and electrical properties of the La_{1 − x} Sr _x MnO_{3 − δ} manganites (x = 0, 0.2, 0.4; δ = 0, 0.13, 0.2). In compositions with x = 0 and δ = 0.13 and 0.2, the temperature dependence of the magnetization M (T) can be approximated by the Langevin function with the moment of superparamagnetic clusters μ = 77μ_B (δ = 0.13) and 86μ_B (δ = 0.2) at temperatures of 25 K ≤ T ≤ 250 K, with the exception of a small temperature range near 132 K in which a maximum characteristic of the LaMnO₃ antiferromagnet is seen. These compositions, as well as Sr-doped compositions with δ ≠ 0, reveal a difference between the magnetizations of the sample cooled in a weak magnetic field and in zero field. At T = 6 K in a magnetic field of 16 kOe, the compositions with x = 0.2 and 0.4, δ = 0.13 possess a magnetic moment per formula unit lower than that with δ = 0, as well as reveal an anomalous relation between the Curie temperature T _C and the Curie paramagnetic point gJ, namely, T _C > gJ. The magnetization of compositions with x = 0.2 and 0.4, δ = 0.2 follows the Langevin function with μ = 40μ_B and 130μ_B, respectively. The electrical resistivity of samples with x = 0.4 and δ = 0.13 and 0.2 is one to two orders of magnitude larger than that of the composition with x = 0.4, δ = 0, which evidences partial or complete compensation of acceptor defects (Sr²⁺ ions) by donor defects (doubly charged O²⁻ vacancies). The above properties of oxygen-deficient compositions suggest that they contain an insulating ferro-antiferromagnetic magnetically double-phase state. The magnetoresistance and volume magnetostriction in samples with x = 0.4 and δ = 0, 0.13, and 0.2 are small; indeed, in a magnetic field of 8 kOe, they do not exceed 1.4% and 6 × 10⁻⁶, respectively. On this basis, it is concluded that the unbalanced doubly charged donors (O vacancies) are in the state with antiparallel spins and, thus, do not initiate the formation of ferron-type ferromagnetic clusters. The significance of both compensated and unbalanced doubly charged donors consists in that they give rise to the formation of fractured Mn-O-Mn bonds, which bring about lowering of the magnetic moment per formula unit in compositions with x = 0.2 and 0.4 and δ = 0.13 and the transition to superparamagnetism in compositions with x = 0.2 and 0.4, δ = 0.2. Original Russian Text ? L.I. Koroleva, D.M. Zashchirinskiĭ, T.M. Khapaeva, L.I. Gurskiĭ, N.A. Kalanda, V.M. Trukhan, R. Szymczak, B. Krzumanska, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 12, pp. 2201–2205.     

Calculations of electronic structure and density of states in?the?wurtzite structure of Zn1? x Mg x O alloys using sp3 semi-empirical tight-binding model

Calculating the electronic structure and the density of states in the wurtzite structure of Zn_1−x Mg _x O (ZMO) alloys using sp³ semi-empirical tight-binding model, we observed increases of both band gap and electron effective mass that agree with the experimental results as increasing Mg composition up to x=0.3. From the calculated total density of states, the increasing electron effective mass is a result of less orbital overlap of cation sites due to extra density of modes coming from Mg3s and Mg3p orbitals as introducing more Mg composition. Additionally, reducing electronegative characteristic of oxygen was caused by that the O2p was less localized around the oxygen atom.     

Kinetics of glass transition and thermal stability of?Se58Ge42?xPbx?(9≤x≤20) glasses

Se₅₈Ge_42−x Pb _x (9≤x≤20) glasses have been prepared using conventional melt quenching technique. Differential Scanning Calorimetric (DSC) measurements show single glass transition and double crystallization, which indicate the occurrence of phase separation in the samples. The phases present in the samples were identified using XRD. The kinetics of the glass transition has been studied in terms of the variation of glass transition temperature with composition and heating rate. In addition to this, activation energy of the glass transition (E _t ) has also been evaluated and its composition dependence is also investigated. The thermal stability of these glasses has been investigated using various stability criteria: Deiztal first glass criterion, ΔT, Saad and Poulain weighted thermal stability, H′ and the S-parameter. The values of these parameters were obtained using various characteristic temperatures such as the glass transition temperature, T _g , the onset temperature of crystallization, T _c , and the peak crystallization temperature, T _p . The values of stability parameters show that the phase corresponding to second crystallization is more stable than the phase corresponding to first one. The stability in terms of the lead (Pb) content has been determined considering the values of stability parameters of the phase corresponding to second peak. It was found that the stability increases with the lead content.