Optical and dielectric studies of phase transitions in single crystals of NaNbO<Subscript>3</Subscript>-Gd<Subscript>1/3</Subscript>NbO<Subscript>3</Subscript> solid solutions

The temperature dependences of the permittivity ? and the false-color image patterns obtained by the rotating polarizer method for single crystals of (1 ? x)NaNbO_3?x Gd_1/3NbO₃ (x = 0.003, 0.090) solid solutions with different degrees of diffuseness of the phase transition are investigated. A multifractal analysis of the false-color images has revealed anomalies in the temperature dependences of the parameter ?_∞ of the multifractal spectrum. For a sample with a sharp phase transition (x ≈ 0.003), the temperature of this anomaly is in good agreement with the temperature of the jumps in the permittivity ?(T) and birefringence. For an NNG crystal with x ≈ 0.09, which exhibits a diffuse maximum of ?(T), the temperatures of the anomalies of ?_∞(T) differ in the central and peripheral regions, which correlates with the distribution of Gd over the crystal.     

Structure and dynamics of the pure and mixed fluorites <Emphasis Type="Italic">Me</Emphasis>F<Subscript>2</Subscript> (<Emphasis Type="Italic">Me</Emphasis> = Ca,Sr, Ba,and Pb)

The structure and dynamics of the crystal lattice of MeF₂ fluorites (Me = Ca, Sr, Ba, and Pb) under external hydrostatic compression (0–3.5 GPa) are calculated within the shell model in the pair potential approximation. The first-order structural phase transition from the cubic to the orthorhombic phase in these crystals under pressure is investigated. The effect of chemical pressure on the BaF₂ crystal is analyzed by the simulation of mixed crystals, namely, Ba_1?xCa_xF₂ and Ba_1?xSr_xF₂. It is demonstrated that the supercell method, as applied to the simulation of mixed crystals, results in a lower lattice energy per formula unit as compared to the lattice energy obtained by the virtual-crystal method.     

Dielectric and magnetic properties of the multiferroic Tb<Subscript>(1−<Emphasis Type="Italic">x</Emphasis>)</Subscript>Bi<Subscript>x</Subscript>MnO<Subscript>3</Subscript>: Electric dipole glass and self-organization of charge carriers

Single crystals of the new multiferroic Tb_(1?x)Bi_xMnO₃ have been grown and studied. A semiconductor compound with x = 0.05 is investigated in most detail. At temperatures T ≥ 165 K, the electric dipole glass state is realized in the crystal. Localized charge carriers form conducting drops of electrons and holes, which are located predominantly in thin layers at the boundaries of polar domains. When drops escape as the temperature increases, jumps in conductance and capacitance are observed. The state of drops is controlled by low bias voltage. The long-range magnetic order arises at temperatures T ≤ 90 K. Negative magnetoresistance is observed at temperatures of the existence of localized charge carriers.     

Crystallographic and dynamic characteristics of K<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Rb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>TiOPO<Subscript>4</Subscript> solid solutions in the low-temperature ranges

The unit cell parameters a and c of K_{1 ? x} Rb _x TiOPO₄ (x= 0, 0.3, and 0.5) crystals are investigated using x-ray diffraction in the temperature range 90–320 K. The thermal expansion coefficients along the principal crystallographic axes of the crystals are determined from the obtained temperature dependences of the unit cell parameters. It is found that the parameter a increases with increasing temperature, while the parameter c decreases. For the crystals under investigation, the elastic moduli c ₁₁ and c ₃₃ along the [100] and [001] directions are determined by the ultrasonic pulse-echo technique in the temperature range 100–350 K. It is shown that c ₃₃ > c ₁₁. The anomalies revealed in the temperature dependences of the crystallographic and dynamic characteristics of the samples at a temperature T ≈ 280 K indicate the occurrence of a phase transition. The temperature of the phase transition is found to increase with increasing rubidium content x.     

Symmetry and lattice parameters of SrTiO<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> solid solutions

The lattice parameters of ceramic samples of (1 ? x)SrTiO₃-xPbTiO₃ solid solutions are measured at room temperature. It is found that the samples have cubic symmetry in the concentration range x = 0?0.3 and tetragonal symmetry for x > 0.3. The lattice parameter a is virtually independent of temperature for x < 0.8 and slightly decreases in the range x = 0.8?1.0, while the lattice parameter c increases with increasing x. The reduced cubic parameter varies nonlinearly and deviates from Vegard’s linear law as the concentration x increases.     

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.     

Relation between giant volume magnetostriction,colossal magnetoresistance,and crystal lattice softening in manganites La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>A<Subscript>y</Subscript>MnO<Subscript>3</Subscript> (A = Ca,Ag, Ba,Sr)

Giant volume magnetostriction (GVM) is detected near the Curie temperature T _C in La_1?x A_xMnO₃ single crystals (A = Ca, Sr, Ba, 0.1 ≤ x ≤ 0.3) and above T _C in La_1?x Ag_yMnO₃ (x = y = 0.15, 0.2 and x = 0.2, y = 0.1) ceramics (in the latter system, giant volume magnetostriction attains a value of 6.5 × 10^?4 in a magnetic field of 8.2 kOe). The behavior of GVM and colossal magnetoresistance (CMR) is found to be the same: both quantities have negative values, the temperature dependences of their absolute values pass through a peak, and the isotherms do not exhibit saturation up to the maximal measuring fields of 130 kOe. In compounds with compositions La_0.7Ba_0.3MnO₃ and La_0.85Ag_0.15MnO₃, GVM and CMR were observed at room temperatures (in a magnetic field of 8.2 kOe, GVM attains values of 2.54 × 10^?4 and 2 × 10^?4 and CMR is equal to 11.6 and 11.2%, respectively). Both phenomena are attributed to the presence of a magnetic (ferromagnetic-antiferromagnetic) two-phase state in these systems, which is associated with a strong s-d exchange. It is found that the maximum value of the GVM in single crystals of La_1?x A_xMnO₃ (A = Ba, Sr, Ca, Ag) depends on the radius R _A of cation A (it is the higher, the larger the difference \(|R_A - R_{LA^{3 + } } |\)). The only exception is the compound with A = Ag, in which the pattern is complicated by additional defectiveness. Local disorder in the La_1?x A_x sublattice, which is associated with the presence of cations with different radii, leads to a displacement of oxygen ions and to crystal lattice softening. The exchange s-d interactions in La_1?x A_xMnO₃ (A = Ca, Sr, Ba, Ag) are found to be comparable with electrostatic interactions ensuring the existence of the crystal; this facilitates manifestation of the GVM.     

Long-range magnetic order in Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Na<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>2</Subscript>O<Subscript>2</Subscript>

Single crystals of Li _x Na_{1 ? x} Cu₂O₂ solid solutions have been grown from the melt and crystal lattice parameters have been studied. It is found that the solid solution of this system exists in the region x ≤ 0.25. Specific heat and magnetic susceptibility are investigated on monocrystalline samples with x = 0.07, 0.14, and 0.21. Long-range magnetic order in these compounds is formed at T = 13.8, 4.1, and 14.8 K, respectively. It is found that the Néel temperature T _N in these compounds increases with Li content.     

Lattice IR spectroscopy of Zn<Subscript>1 −<Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se epitaxial layers grown on a GaAs substrate by molecular-beam epitaxy

Based on the results from comparison of the data on lattice reflection for Zn_{1 ?x} Cd _x Se bulk crystals (x = 0.08, 0.22) and Zn_{1 ?x} Cd _x Se thin layers of the same compositions grown on GaAs, a more adequate interpretation is given to the lattice IR reflection spectra of Zn_{1 ?x} Cd _x Se alloy films (x = 0–0.55) grown on a GaAs substrate by molecular-beam epitaxy. In this composition region, two ZnSe-and CdSe-like lattice modes are observed corresponding to a double-mode type of rearrangement of the vibration spectrum with varying x. A weak (with oscillator strength smaller than 0.25) high-frequency mode (with respect to the dominant modes) at 220 cm^?1 is also observed.     

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.     

Electronic energy structure and x-ray spectra of wide-gap AlN and BN crystals and B<Subscript>x</Subscript>Al<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>N solid solutions

The electronic energy structure of 2H and 3C AlN and BN crystals and B_xAl_1?xN solid solutions is calculated on the basis of the local coherent potential method using the cluster version of the MT approximation and the theory of multiple scattering. The features of the electronic structure of 2H-AlN crystals are compared with x-ray K and L absorption and emission spectra of aluminum and nitrogen. An interpretation of these features is given. The concentration dependences of the width of the upper subband of the valence band and the band gap in B_xAl_1?xN solid solutions (x = 0.25, 0.5, 0.75) are investigated. Charge transfer from aluminum to nitrogen atoms is shown to occur and increase with boron doping in both crystallographic modifications.     

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.     

Crystal-structure and magnetic phase transformations in solid solutions of BiFeO<Subscript>3</Subscript>-AFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> (A = Ca,Sr, Ba,Pb)

Solid solutions of Bi_{1 ? x} A _x (Fe_{1 ? x/2}Nb _x/2)O₃, where A = Ca, Ba, and Pb, are obtained and their crystal structure and magnetic properties are investigated. It is shown that for A = Ca and x ≈ 0.15, the symmetry of the unit cell changes from rhombohedral (space group R3c) to orthorhombic (Pbnm). The transformation leads to the emergence of spontaneous magnetization due to the Dzyaloshinskii-Moriya interaction. Solid solutions with A = Pb remain rhombohedral up to a concentration of x = 0.3. Spontaneous magnetization sharply increases in the compound with x ≈ 1 at low temperatures and is due to the formation of the spin-glass component.     

Existence of two types of perfect Bi<Subscript>2</Subscript>Sr<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>La<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>CuO<Subscript>6+δ</Subscript> single crystals

It is found that perfect Bi₂Sr_2?x La _x CuO_6+δ single crystals with the same concentrations of lanthanum x = 0.64 and excess oxygen δ = 0.237 exist in two types. Single crystals of the first type are obtained by slow cooling (the synthesis time is 90–105 h). They have a monoclinic superlattice and exhibit no superconducting transition down to 2 K. Crystals of the second type are obtained by rapid cooling (the synthesis time is 30–40 h) and are characterized by a orthorhombic superlattice and T _c = 18 K. Thus, the superconducting transition temperature is determined not only by the concentration of carriers but also by the configuration of defects. A rhombic superlattice prevails in single crystals obtained by slow cooling in the lanthanum concentration range x = 0.3–0.5, while a monoclinic superlattice dominates in the range x = 0.75–0.85. This fact explains the high values of T _c at optimal doping (x = 0.4) and the absence of high-T _c superconductivity at p < 0.10.     

Effect of electron irradiation on the galvanomagnetic properties of In<Subscript>x</Subscript>Bi<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript>3</Subscript> semiconductor single crystals

The effect of 5-MeV electron irradiation of p-In_xBi_2?xTe₃ single crystals (x=0, 0.04, 0.07), performed at 250 K, on the galvanomagnetic properties of the crystals was studied. The irradiation was shown to change the conduction from the p to the n type. Annealing at temperatures of 310–390 K restores the conduction to the p type. The reversal of the conduction type and variation of the carrier concentration can be accounted for by an increase in the concentration of charged point radiation defects produced in In_xBi_2?xTe₃ by irradiation. Electron irradiation of p-type Te single crystals reduces the electrical resistivity without reversing the conduction type. Annealing restores the original properties almost completely.     

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.     

Ferromagnetism in a new dilute magnetic semiconductor Sb<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>Cr<Subscript>x</Subscript>Te<Subscript>3</Subscript>

Magnetic and galvanomagnetic properties of single crystals of a new dilute magnetic semiconductor p-Sb_2?xCr_xTe₃ (x = 0, 0.0115, 0.0215) are investigated in a temperature range of 1.7–300 K. A ferromagnetic phase with a Curie temperature of T_C ≈ 5.8 (x = 0.0215) and 2.0 K (x = 0.0115) is detected. The easy magnetization axis is parallel to the C₃ crystallographic axis. Analysis of the Shubnikov-de Haas effect observed in these crystals in strong magnetic fields leads to the conclusion that the hole concentration decreases as a result of doping with Cr. Negative magnetoresistance and the anomalous Hall effect are observed in Cr-doped samples at liquid helium temperature.     

Structure and dielectric properties of solid solutions Bi7Ti4 + x W x Ta1–2x O21 (x = 0–0.5)

A number of solid solutions Bi₇Ti_{4 + x} W _x Ta_1–2x O₂₁ (x = 0–0.5) have been synthesized from oxides by solid-phase reaction. The crystal structure, the electrophysical characteristics, and the microstructure of the prepared ceramic samples have been studied. According to X-ray powder diffraction, all the compounds are single-phase with the structure of mixed-layer Aurivillius phases (m = 2.5) with the orthorhombic crystal lattice (space group I2cm, Z = 2). Temperature dependences of the relative permittivity ε(T) of the compound have been measured, from which it has been found that the Curie temperature T _C of perovskite-like oxides Bi₇Ti_{4 + x} W _x Ta_1–2x O₂₁ (x = 0–0.5) decreases linearly as substitution parameter x decreases. The activation energies of charge carriers have been found in different temperature ranges.     

Dielectric properties of betaine phosphite-betaine phosphate solid-solution crystals in the improper ferroelastic phase

Temperature dependences of dielectric permittivity in the improper ferroelastic phase, including the region of the improper ferroelastic phase transition occurring at T=T_c1, were studied in the betaine phosphite-betaine phosphate solid-solution crystals. At a betaine phosphate (BP) concentration of 10%, the phase transition temperature T_c1 was found to shift toward higher temperatures by about 5 K compared to betaine phosphite (BPI) crystals, where T_c1=355 K. The phase transition remains in the vicinity of the tricritical point. As the BP concentration in BPI is increased, the dielectric anomaly at T=T_c1 weakens substantially compared to pure BPI. The nonlinear temperature dependence of reciprocal dielectric permittivity in the improper ferroelastic phase of BPI_xBP_1?x crystals is described in the concentration region 0.9≤x≤1 in terms of a thermodynamic model taking into account the biquadratic relation of the nonpolar order parameter of the improper ferroelastic phase transition to polarization. The decrease in the ferroelectric phase transition temperature T_c1 (or in the temperature of loss of improper ferroelastic phase stability) with increasing BP concentration in the above limits is due to the decreasing effect of the nonpolar mode on the polar instability, which is accompanied by a weakening of the dielectric anomaly at T=T_c1     

Structural and magnetic phase transformations in the BiFeO<Subscript>3</Subscript>-CaFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> system

The crystal structure and magnetic properties of the Bi_{1 ? x} Ca _x Fe_{1 ? x/2}Nb _x/2O₃ system were studied. It is shown that, at x ≤ 0.15, the unit-cell symmetry of solid solutions is rhombohedral (space group R3c). Solid solutions with x ≥ 0.3 have an orthorhombic unit cell (space group Pbnm). The rhombohedral compositions are antiferromagnetic, while the orthorhombic compositions exhibit a small spontaneous magnetization due to Dzyaloshinski?-Moriya interaction. In CaFe_0.5Nb_0.5O₃, the Fe³⁺ and Nb⁵⁺ ions are partially ordered and the unit cell is monoclinic (space group P2₁/n). In the concentration range 0.15 < x < 0.30, a two-phase state (R3c + Pbnm) is revealed.