Dielectric Properties of Nanoporous Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Films Filled with Ferroelectric SC(NH<Subscript>2</Subscript>)<Subscript>2</Subscript>

Temperature dependences of permittivity ε′ and third harmonic amplitude γ_3ω of nanocomposites obtained by embedding ferroelectric SC(NH₂)₂ in porous alumina films with pore sizes of 60 and 100 nm are studied. A substantial increase in the temperatures of ferroelectric phase transition T_c1 and T_c2 and that of phase transition T_i from incommensurate phase to paraphase are also observed. The temperatures of all phase transitions are found to rise as pore diameters shrink.     

X-ray study of [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> at low temperatures

The unit cell parameters a, b, and c of [N(CH₃)₄]₂ZnCl₄ have been measured by x-ray diffraction in the temperature range 80–293 K. Temperature dependences of the thermal expansion coefficients α_a, α_b, and α_c along the principal crystallographic axes and of the unit cell thermal expansion coefficient α_V were determined. It is shown that the a=f(T), b=f(T), and c=f(T) curves exhibit anomalies in the form of jumps at phase transition temperatures T₁=161 K and T₂=181 K and that the phase transition occurring at T₃=276 K manifests itself in the a=f(T) and b=f(T) curves as a break. A slight anisotropy in the coefficient of thermal expansion of the crystal was revealed. The phase transitions occurring at T₁=161 K and T₂=181 K in [N(CH₃)₄]₂ZnCl₄ were established to be first-order.     

Elastic properties of La<Subscript>0.82</Subscript>Ca<Subscript>0.18</Subscript>MnO<Subscript>3</Subscript> single crystal

The temperature dependences of the velocity of longitudinal sound waves and the internal friction in a La_0.82Ca_0.18MnO₃ single crystal with the Curie temperature T _C = 181 K have been studied. As temperature decreases, the single crystal is shown to undergo the transition from the pseudocubic O* to the Jahn–Teller O’ phase at T ~ 254 K and the reverse transition from O’ to O* phase at T ~ 84 K. The velocity of sound and the internal friction in the O’ phase are found to be significantly smaller than those in the O* phase.     

Pressure-induced superconductivity and structural transitions in Ba(Fe<Subscript>0.9</Subscript>Ru<Subscript>0.1</Subscript>)<Subscript>2</Subscript>As<Subscript>2</Subscript>

Electrical transport and structural characterizations of isoelectronically substituted Ba(Fe_0.9Ru_0.1)₂As₂ have been performed as a function of pressure up to ～ 30 GPa and temperature down to ～ 10 K using designer diamond anvil cell. Similar to undoped members of the AFe₂As₂ (A = Ca, Sr, Ba) family, Ba(Fe_0.9Ru_0.1)₂As₂ shows anomalous a-lattice parameter expansion with increasing pressure and a concurrent ThCr₂Si₂ type isostructural (I4/mmm) phase transition from tetragonal (T) phase to a collapsed tetragonal (cT) phase occurring between 12 and 17 GPa where the a is maximum. Above 17 GPa, the material remains in the cT phase up to 30 GPa at 200 K. The resistance measurements show evidence of pressure-induced zero resistance that may be indicative of high-temperature superconductivity for pressures above 3.9 GPa. The onset of the resistive transition temperature decreases gradually with increasing pressure before completely disappearing for pressures above ～ 10.6 GPa near the T-cT transition. We have determined the crystal structure of the high-T _c phase of Ru-doped BaFe₂As₂ to remain as tetragonal (I4/mmm) by analyzing the X-ray diffraction pattern obtained at 10 K and 9.7 ± 0.7 GPa, as opposed to inferring the structural transition from electrical resistance measurement, as in a previous report [S.K. Kim, M.S. Torikachvili, E. Colombier, A. Thaler, S.L. Bud’ko, P.C. Canfield, Phys. Rev. B 84, 134525 (2011)].     

Dielectric and optical properties of Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)<Subscript>0.8</Subscript>Ti<Subscript>0.2</Subscript>O<Subscript>3</Subscript> (PMNT-0.2) ferroelectric relaxor single crystals

The dielectric and optical (optical transmission, small-angle light scattering, birefringence) properties of PMNT-0.2 single crystals and their variation induced by a dc electric field have been studied. The birefringence was found to increase anomalously at the transition from the rhombohedral ferroelectric to the inhomogeneous relaxor phase (the spontaneous ferroelectric transition temperature T_sp). Below T_sp, the dielectric and optical properties were observed to exhibit anomalies originating from reorientation and growth of domains in size. Unlike ferroelectric relaxors of the type of PbB′_1/3B′_2/3O₃ and PbB′_1/2B′_1/2O₃, in PMNT-0.2 neither induction of the ferroelectric phase by an electric field nor thermally stimulated destruction of the ferroelectric state occurs through the percolation mechanism (i.e., they are not accompanied by anomalously narrow maxima in small-angle light scattering). This is attributed to the inhomogeneous structure of the relaxor phase, as a result of which the phase transition does not take place simultaneously in various regions of the crystal.     

EPR study of copper ions in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> crystals

The EPR spectra of Cu²⁺ ions (² D _5/2) located at two structurally nonequivalent positions Cu1 and Cu2 in crystals of lithium heptagermanate Li₂Ge₇O₁₅ are recorded. The angular dependences of the EPR spectrum are measured in the paraelectric phase of the Li₂Ge₇O₁₅ compound (T = 300 K). The components of the g factor and the hyperfine interaction tensor A are determined, and the orientation of the magnetic axes with respect to the crystallographic basis is established. The EPR spectra are recorded in the temperature range in the vicinity of the temperature T _C = 283 K of the transition from the paraelectric phase to the ferroelectric phase. The position symmetry of the Cu1 and Cu2 centers is determined at temperatures above and below the phase transition temperature T _C . The localization of paramagnetic centers in the structure is discussed, An analysis of the results obtained demonstrates that the Cu1 and Cu2 centers in the Li₂Ge₇O₁₅ crystal lattice replace lithium ions located at two structurally nonequivalent positions with the symmetries described at temperatures above T _C by the triclinic C _i and monoclinic C ₂ point groups, respectively.     

Adiabatic calorimetric study of the intense magnetocaloric effect and the heat capacity of (La<Subscript>0.4</Subscript>Eu<Subscript>0.6</Subscript>)<Subscript>0.7</Subscript>Pb<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript>

The temperature dependences of the intense magnetocaloric effect ΔT _AD(T, H) and the heat capacity C _p (T) of the (La_0.4Eu_0.6)_0.7Pb_0.3MnO₃ manganite are directly measured using adiabatic calorimetry. The experimental dependences ΔT _AD(T) are in satisfactory agreement with those calculated from the data on the behavior of the magnetization. The factors responsible for the absence of an anomaly in the experimental temperature dependence of the heat capacity C _p (T) in the range of the magnetic phase transition are discussed.     

The influence of phase transitions in the Rb<Subscript>2</Subscript>CdI<Subscript>4</Subscript> ferroelastic on the exciton absorption spectrum

The parameters of the long-wavelength exciton band for Rb₂CdI₄ films are investigated in the temperature range 90–410 K. It is found that the Rb₂CdI₄ films undergo a sequence of phase transitions at temperatures T_c1=380 K (paraphase → incommensurate phase), T_c2=290 K (incommensurate phase → ferroelastic phase I), and T_c3 = 210 K (ferroelastic phase I → ferroelastic phase II). The parameters of the exciton band (such as the spectral position and the half-width) measured during heating and cooling of the Rb₂CdI₄ film differ significantly. This is especially true for the incommensurate phase. Upon heating of the incommensurate phase, the domain boundaries become frozen, whereas the cooling of this phase is accompanied by the generation of solitons and their pinning, which, in turn, results in a first-order phase transition at the temperature T_c2. It is revealed that the oscillator strength of the exciton band anomalously increases in the range of existence of commensurate phase I (T_c3<-T<-T_c2) due to ordering of the Rb₂CdI₄ crystal lattice.     

Thermophysical study of structural phase transitions in Na<Subscript>0.95</Subscript>Li<Subscript>0.05</Subscript>NbO<Subscript>3</Subscript> solid solution

Temperature dependences of specific heat C_p(T) and coefficient of thermal expansion ;(T) for Na_0.95Li_0.05NbO₃ sodium-lithium niobate ceramic samples are investigated in the temperature range of 100–800 K. The C_p(T) and α(T) anomalies at T₃ = 310 ± 3 K, T₂ = 630 ± 8 K, and T₁ = 710 ± 10 K are observed, which correspond to the sequence of phase transitions N ? Q ? S(R) ? T2(S). The effect of heat treatment of the samples on the sequence of structural distortions was established. It is demonstrated that annealing of the samples at 603 K leads to splitting of the anomaly corresponding to the phase transition Q → R/S in two anomalies. After sample heating to 800 K, the only anomaly is observed in both the C_p(T) and ;(T) dependence. Possible mechanisms of the observed phenomena are discussed.     

The influence of chromium impurity centers on the critical properties of a weakly polar ferroelectric Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript>

The Cr³⁺ EPR spectra of Li₂Ge₇O₁₅ (LGO) crystals are analyzed in the temperature range of the ferroelectric phase transition. The temperature dependence of the local order parameter is determined from the measured splittings of the EPR lines in the polar phase. The experimental critical exponent of the order parameter β=0.31 in the range from the phase transition temperature T _C to (T _C -T) ～ 40 K corresponds to the critical exponent of the three-dimensional Ising model. Analysis of the available data demonstrates that, away from the phase transition temperature T _C , the macroscopic and local properties of LGO crystals are characterized by a crossover from the fluctuation behavior to the classical behavior described in terms of the mean-field theory. The temperature dependence of the local order parameter for LGO: Cr crystals does not exhibit a crossover from the Ising behavior (β=0.31) to the classical behavior (β=0.5). This is explained by the defect nature of Cr³⁺ impurity centers, which weaken the spatial correlations in the LGO host crystal. The specific features of the critical properties of LGO: Cr³⁺ crystals are discussed within a microscopic model of structural phase transitions.     

Optical studies of phase transitions in the (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>Ti(O<Subscript>2</Subscript>)F<Subscript>5</Subscript> crystal

Polarization-optical study of twinning and measurements of the Raman spectra and birefringence in oxyfluoride (NH₄)₃Ti(O₂)F₅ were carried out over the temperature range 90–350 K. Phase transitions were detected at temperatures T ₀₁ = 266 K (second-order transition) and T ₀₂ = 225 K (first order). It is assumed that the crystal symmetry is changed as follows: Fm3m ? I4/mmm ? I4/m. Anomalies of the spectral parameters are established in the frequency range of internal vibrations of ammonium ions and Ti(O₂)F₅ complexes. An analysis of the results shows that the transition at T ₀₁ is likely due to small shifts of the tetrahedral groups from their position on the triad axis and that the transition at T ₀₂ is due to fluorine-oxygen ordering of Ti(O₂)F₅ complexes.     

Phase transition in a KPb<Subscript>2</Subscript>Br<Subscript>5</Subscript> crystal

Crystals of the KPb₂Br₅compound are investigated using polarized light microscopy and calorimetry. The birefringence and the angle of rotation of the optical indicatrix are measured in the temperature range 270–620 K. It is found that the KPb₂Br₅ crystal undergoes a first-order ferroelastic phase transition at temperatures T_0↑ = 519.5 K and T_0↓ = 518.5 K with a change in the enthalpy ΔH = 1300 ± 200 J/mol. This transition is accompanied by both twinning and the symmetry change mmm ? P2₁/c. It is revealed that the angle of rotation of the optical indicatrix exhibits an unusual behavior under variations in the temperature due to a strong temperature dependence of the birefringence.     

High-resolution spectroscopy of HoFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystal: a study of phase transitions

The transmission spectra of HoFe₃(BO₃) multiferroic single crystals are studied by optical Fourier-transform spectroscopy at temperatures of 1.7–423 K in polarized light in the spectral range 500–10 000 cm^–1 with a resolution up to 0.1 cm^–1. A new first-order structural phase transition close to the second-order transition is recorded at T_c = 360 K by the appearance of a new phonon mode at 976 cm^–1. The reasons for considerable differences in T_c for different samples of holmium ferroborate are discussed. By temperature variations in the spectra of the f–f transitions in the Ho³⁺ ion, we studied two magnetic phase transitions, namely, magnetic ordering into an easy-plane structure as a second-order phase transition at T_N = 39 K and spin reorientation from the ab plane to the c axis as a first-order phase transition at T_SR = 4.7 ± 0.2 K. It is shown that erbium impurity in a concentration of 1 at % decreases the spin-reorientation transition temperature to T_SR = 4.0 K.     

Magnetic susceptibility of fine crystalline high-temperature YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6.93</Subscript> superconductors. The role of nanoscale structural disordering

Static magnetic susceptibility χ(T) in the normal state (T_c ≤ T ≤ 400 K) and specific heat C(T) near temperature T_c of the transition to the superconducting state are experimentally studied for a series of fine crystalline samples of high-temperature YBa₂Cu₃O_y superconductor, having y and T_c close to optimal but differing in the degree of nanoscale structural disordering. It is shown that under the influence of structural disordering, there is enhancement of anomalous pseudogap behavior of the studied characteristics and a significant increase in the width of the pseudogap.     

Crystallographic characteristics and phase transitions in the [N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>CdBr<Subscript>4</Subscript> crystal in the low-temperature range

The results of x-ray structural studies of the [N(C₂H₅)₄]₂CdBr₄ crystal at low temperatures are presented. The unit cell parameters and the thermal expansion coefficients along the main crystallographic directions are measured at temperatures in the range from 90 to 320 K. The integrated intensities of the diffraction reflections are investigated as a function of the temperature. It is shown that the curves a = f(T), c = f(T), I ₅₀₀ = f(T), and I ₀₀₆ = f(T) at temperatures T ₁ ≈ 174 K and T ₂ ≈ 226 K exhibit anomalies in the form of abrupt changes in the lattice parameters and the diffraction reflection intensities. This indicates that the [N(C₂H₅)₄]₂CdBr₄ crystal undergo phase transitions at these temperatures. Moreover, there is an anomaly in the form of a small maximum at the temperature T ₃ = 293 K.     

Pressure-induced antiferromagnetism in La<Subscript>0.75</Subscript>Ca<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript> manganite

The crystal and magnetic structures of La_0.75Ca_0.25MnO₃ manganite are studied under high pressures up to 4.5 GPa in the temperature range 12–300 K by the neutron diffraction method. At normal pressure and temperature T _C = 240 K, a ferromagnetic state is formed in La_0.75Ca_0.25MnO₃. At high pressures P ≥ 1.5 GPa and at temperatures T < T _N ≈ 150 K, a new A-type antiferromagnetic state appears. A further increase in pressure leads to an increase in the volume fraction of the antiferromagnetic phase, which coexists with the initial ferromagnetic phase. The effect of high pressure causes a considerable increase in T _C with the slope dT _C /dP ≈ 12 K/GPa. Calculations performed in the framework of the double exchange model with allowance for the electron-phonon interaction make it possible to explain this pressure dependence of T _C on the basis of experimental data.     

Structural transformations of K<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals with variations in temperature

Single crystals of the K₃H(SO₄)₂ compound are investigated using X-ray diffraction on Xcalibur S and Bruker diffractometers. The structure of the low-temperature monoclinic phase is refined (space group C2/c, z = 4, a = 14.698(1) Å, b = 5.683(1) Å, c = 9.783(1) Å, β = 103.01(1)°, T = 293 K, Bruker diffractometer), the structural phase transition is revealed, and the structure of the high-temperature trigonal phase is determined (space group R \(\bar 3\) m, z = 3, a = 5.73(1) Å,c = 21.51(1) Å,T = 458 K, Xcalibur diffractometer).     

Effect of a magnetic field on the thermal and kinetic properties of the Sm<Subscript>0.55</Subscript>Sr<Subscript>0.45</Subscript>MnO<Subscript>3.02</Subscript> manganite

The temperature and magnetic-field dependences of the heat capacity, thermal conductivity, thermopower, and electrical resistivity of the Sm_0.55Sr_0.45MnO_3.02 ceramic material are studied in the temperature range 77–300 K and in magnetic fields up to 26 kOe. It is revealed that the quantities under investigation exhibit anomalous behavior due to a magnetic phase transition at the Curie temperature T_C. An increase in the magnetic field strength H leads to an increase in the Curie temperature T_C and a jump in the heat capacity ΔC_p at T_C. The temperature dependences of the measured quantities are characterized by hystereses that are considerably suppressed in a magnetic field of 26 kOe and depend neither on the thermocycling range nor on the rate of change in the temperature. The thermal conductivity K at temperatures above T_C shows unusual behavior for crystalline solids (dK/dT>0) and, upon the transition to a ferromagnetic state, drastically increases as a result of a decrease in the phonon scattering by Jahn-Teller distortions. It is demonstrated that the hystereses of the studied properties of the Sm_0.55Sr_0.45MnO_3.02 manganite are caused by a jumpwise change in the critical temperature due to variations in the lattice parameters upon the magnetic phase transition.     

Mechanisms of interaction of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript> <Emphasis Type="Italic">y</Emphasis> </Subscript> with water vapor at low-temperature annealing

Abstract—The interaction of YBa₂Cu₃O_y (123) with water vapor at temperatures T ≤ 150° has been studied. It has been shown that, with an increase in temperature, the mechanism of its interaction with water changes. Near room temperature, the main process is hydrolytic decomposition. At T ~ 100°C, the absorption of water is significantly reduced, because the role of hydrolysis becomes less important and water penetrates the structure weakly and is incorporated into oxygen vacancies mainly in the form of OH–-groups, which leads to the transition of YBa₂Cu₃O_y from the tetragonal to orthorhombic phase. With an increase in temperature to 150°C, the absorption of water increases again. In this case, the main mechanism is the penetration of water to the 123 structure, which leads to splitting of Cu–O chains and a phase transition from the 123 to pseudo-124 structure. The role of different mechanisms of interaction with water essentially depends on the oxygen content in the 123 structure. At a low oxygen index (y = 6.3), the role of hydrolysis is more important, and, at y ≥ 6.5, the incorporation of water into the structure prevails. It has been revealed that, at T = 150°C, after absorption of water, YBa₂Cu₃O_6.96 becomes a proton conductor.     

Oxygen isotope effect in chromium-doped Pr<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> manganites

The effect of oxygen isotope substitution on the properties of Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x O₃ manganites (x = 0, 0.02, 0.05) have been studied. The introduction of chromium favors (i) the decomposition of a charge-ordered state and (ii) the appearance of a ferromagnetic metallic phase in Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x ^16–18O₃. The isotope substitution ¹⁶O → ¹⁸O leads to a decrease in the content of the ferromagnetic phase, an increase in the charge-ordering transition temperature (T _CO), and a decrease in the ferromagnetic transition temperature (T _FM). The isotope mass exponent is evaluated.