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.     

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)].     

Statistical mechanics of cation ordering in PbSc<Subscript>1/2</Subscript>Ta<Subscript>1/2</Subscript>O<Subscript>3</Subscript> and PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> solid solutions

A model Hamiltonian for B cation ordering (Sc-Nb(Ta)) in PbSc_1/2Nb_1/2O₃ and PbSc_1/2Ta_1/2O₃ solid solutions is constructed. The parameters of the model Hamiltonian are determined from the ab initio calculation within the ionic crystal model with allowance made for the deformability and the dipole and quadrupole polarizabilities of the ions. The temperatures of the phase transition due to the ordering of the B cations are calculated by the Monte Carlo method in the mean-field and cluster approximations. The phase transition temperatures calculated by the Monte Carlo method (1920 K for PbSc_1/2Ta_1/2O₃ and 1810 K for PbSc_1/2Nb_1/2O₃) are consistent with the experimental data (1770 and 1450 K, respectively). The thermodynamic properties of the cation ordering are investigated using the Monte Carlo method.     

Electronic Structure,Optical Properties,and Pressure Behavior of the CdB<Subscript>4</Subscript>O<Subscript>7</Subscript> and HgB<Subscript>4</Subscript>O<Subscript>7</Subscript> Compounds

Ab initio calculations of the structural, electronic, and optical properties of the CdB₄O₇ and HgB₄O₇ tetraborate compounds in three structural modifications with the Pbca, Cmcm, and Pmn2₁ symmetry have been performed in the framework of the density functional theory using the VASP package. The calculations of the electronic band structure showed that these compounds in all the investigated modifications are dielectrics with a band gap of 2–4 eV. The calculation of the structural properties of the tetraborates under pressure showed that the phase transition between the Pbca and Pmn2₁ structures in cadmium and mercury tetraborates occurs under pressures of 4.8 and 4.7 GPa, respectively.     

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.     

<Emphasis Type="Italic">In situ</Emphasis> study of the mechanism of formation of pressure-densified Sio<Subscript>2</Subscript> glasses

The volume of glassy a-SiO₂ upon compression to 9 GPa was measured in situ at high temperatures up to 730 K and at both pressure buildup and release. It was established that the residual densification of a-SiO₂ glass after high-pressure treatment was due to the irreversible transformation accompanied by a small change in volume directly under pressure. The bulk modulus of the new amorphous modification was appreciably higher (80% more than its original value), giving rise to residual densification as high as 18% under normal conditions. It was shown that the transformation pressure shifted to a lower pressure of about 4 GPa with a rise in temperature. A conclusion was drawn about the existence of at least two pressure-induced phase transitions accompanied by structure rearrangement in a-SiO₂. A nonequilibrium phase diagram is suggested for glassy SiO₂. It accounts for all the presently available experimental data and is confirmed by the existing modeling data.     

Phase transitions of SC(NH<Subscript>2</Subscript>)<Subscript>2</Subscript> ferroelectrics in Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-based nanoporous matrices

Temperature dependences of the linear permittivity ε' and the third harmonic amplitude γ_3ω of composites prepared by introducing ferroelectrics SC(NH₂)₂ into matrices of porous aluminum oxide Al₂O₃ with pore sizes 60 and 100 nm are determined. It is found that temperature T _c of the ferroelectric phase transition and the temperature T _i of the phase transition from incommensurable phase to the paraphrase increase significantly. The transition shifts increase as pore diameters decrease.     

Equation of state and electrical resistivity of the heavy fermion superconductor CeCoIn<Subscript>5</Subscript> to 51 GPa

We have used X-ray diffraction to study the structural phase of CeCoIn₅ in external pressure. Using high-pressure X-ray diffraction, we find that the crystalline phase is stable in the P4/mmm phase for pressures ≤51.2 GPa. From our measured equation of state, we find a bulk modulus given by B ₀ = 72.8 ± 2.9 GPa and a first pressure derivative of B ^′ = 5.1 ± 0.3. Measurement of the electrical resistivity of CeCoIn₅ to pressures as high as 34.4 GPa shows the existence of a peak in resistivity at p ^? = 8.2 ± 0.2 GPa.     

Investigation of polyamorphism in compressed B<Subscript>2</Subscript>O<Subscript>3</Subscript> glass by the direct measurement of the density

Precise measurements of the relative volume change of vitreous B₂O₃ have been performed by the strain-gauge technique at hydrostatic pressures up to 9 GPa. The features of the strain-gauge technique are analyzed and the specificity of the measurements of “relaxed” and “unrelaxed” bulk moduli is discussed. Smeared anomalies of compressibility (at P > 0.5 GPa and P > 5 GPa) and logarithmic relaxation of the glass density are observed. A significant (by several times!) difference has been revealed between the relaxed bulk modulus of glass obtained from the volume measurements and the unrelaxed modulus estimated from the Brillouin spectroscopic data. The measurements of the relative volume change under compression together with the previous structure investigations and computer simulation results reveal the basic features of the phase transitions in B₂O₃ glass. Both direct and reverse transitions are smeared in pressure. The residual densification in glass is not associated with change in the short-range order.     

Heat capacity,structure, and <Emphasis Type="Italic">p-T</Emphasis> phase diagram of elpasolite (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>KMoO<Subscript>3</Subscript>F<Subscript>3</Subscript>

Thermophysical and structural studies of an (NH₄)₂KMoO₃F₃ crystal show that this crystal belongs to the family of elpasolites (space group \(Fm\bar 3m\)) and undergoes an order-disorder phase transition at T ₀ = 241.5 K. Under hydrostatic pressure, this phase transition splits into two consecutive transitions at the tricritical point with parameters T _tr = 232.5 K and p _tr=0.21 GPa. It was found that anomalous hysteresis and relaxation phenomena accompany the transitions from the cubic to both distorted phases. The results are analyzed taking into account the data on the phase transition in the related elpasolite (NH₄)₂KWO₃F₃.     

Study of the compressibility of FeSi,MnSi, and CoS<Subscript>2</Subscript> transition-metal compounds at high pressures

Silicides and sulfides of transition metals attract great attention of researchers because of a wide spectrum of interesting magnetic, electronic, and optical properties. The crystal structure of FeSi, MnSi, and CoSi silicides is P2₁3(B20), whereas FeS₂, CoS₂, and MnS₂ sulfides have a structure of pyrite Pa3. Despite the great interest in these systems and the cubic symmetry of crystals, the structure and compressibility of these compounds at high pressures are still insufficiently studied. There is a significant spread (more than a factor of two!) in the bulk modulus and its pressure derivative for a single compound. Most studies were performed under nonhydrostatic conditions. In this work, the compressibility of FeSi and MnSi silicides (at pressures up to 35 GPa) and CoS₂ sulfide (up to 22 GPa) has been studied by the X-ray diffraction method in a diamond anvil cell with the use of helium as the softest pressure-transmitting medium. The values obtained for the bulk modulus and its derivative—B = 178 ±3 GPa and B_p = 5.6 ± 0.5 for FeSi, B = 167 ± 3 GPa and B_p^' = 4.6 ± 0.5 for MnSi, and B = 94 ± 2 GPa and B_p^' = 6.9 ± 0.5 for CoS₂—can be considered as the most reliable and can be used to test numerous theoretical models. The results for the compressibility of FeSi are important for the verification of models of the Earth’s core.     

Pressure-induced structural transformations,orbital order and antiferromagnetism in La<Subscript>0.75</Subscript>Ca<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript>

High pressure evolution of structural, vibrational and magnetic properties of La_0.75Ca_0.25MnO₃ was studied by means of X-ray diffraction and Raman spectroscopy up to 39 GPa, and neutron diffraction up to 7.5 GPa. The stability of different magnetic ground states, orbital configurations and structural modifications were investigated by LDA + U electronic structure calculations. A change of octahedral tilts corresponding to the transformation of orthorhombic crystal structure from the Pnma symmetry to the Immaone occurs above P ~ 6 GPa. At the same time, the evolution of the orthorhombic lattice distortion evidences an appearance of the e _g d _{x² ? z²} orbital polarization at high pressures. The magnetic order in La_0.75Ca_0.25MnO₃ undergoes a continuous transition from the ferromagnetic 3D metallic (FM) ground state to the A-type antiferromagnetic (AFM) state of assumedly 2D pseudo-metallic character under pressure, that starts at about 1 GPa and extends possibly to 20–30 GPa.     

Nature of low-temperature phase transitions in CaMn<Subscript>7</Subscript>O<Subscript>12</Subscript>

New data on the specific heat, thermal expansion, and magnetization of the CaMn₇O₁₂ phase require a revision of the current concepts of the sequence of phase transitions in this compound. It is found that a spin-glass phase transition occurs in CaMn₇O₁₂ at T _M = 49 K, whereas the transition at T _S = 89 K exhibits the features of a first-order phase transition and thereby is apparently of structural origin. In the range T _M < T< T _S , the CaMn₇O₁₂ compound exhibits negative thermal expansion, which is also indicative of structural changes.     

Thermophysical studies of the phase transitions in (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>NbOF<Subscript>6</Subscript> crystals

The thermophysical properties of oxyfluoride (NH₄)₃NbOF₆ were studied in detail over wide ranges of temperatures and pressures. At atmospheric pressure, a sequence of four structural phase transitions was established with the following changes in entropy: ΔS ₁ = Rln 2.7, δS ₂ = Rln38.3, ΔS ₃ = 0.08R, and ΔS ₄ = 0.17R. An external hydrostatic pressure was found to narrow the region of existence of the initial cubic phase. A triple point was detected in the p-T diagram; at a pressure above 0.07 GPa, the transition between the tetragonal and monoclinic phases occurs through a distorted high-pressure phase.     

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.     

Nonstoichiometric high-pressure phase of Tm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>3</Subscript>V<Subscript>4</Subscript>O<Subscript>12</Subscript>

Tm _x Cu₃V₄O₁₂, a perovskite-like oxide (space group, Im-3; Z = 2; a = 7.279–7.293 Å) containing vacancies in its cationic sublattice, was obtained barothermally (P = 7.0–9.0 GPa, t = 1000–1100°C) for the first time. The temperature dependences on the electrical resistivity (10–300 K) and the magnetic susceptibility (0–300 K) were investigated. It was shown that the oxide Tm _x Cu₃V₄O₁₂ is characterized by metal-type conductivity and paramagnetic properties.     

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.     

Synthesis and properties of high-pressure phase [Er<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>3</Subscript>](V<Subscript>4</Subscript>)O<Subscript>12</Subscript>

A new perovskite-like compound Er_0.73Cu₃V₄O₁₂ (space group Im \(\bar 3\), Z = 2, a = 7.266 Å) has been synthesized barothermally (P = 8.0 GPa, t = 1000°C). Its electrical and magnetic properties have been studied. It is found that the temperature dependence of the electrical conductivity (in the range 78–300 K) has of semiconductor type. The behavior of the impedance and admittance has been analyzed at 290 K and frequencies of 200 Hz to 200 kHz under atmospheric pressure and at high (15–42 GPa) pressures.     

Electrospun Dy-doped SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript> nanofibers: microstructure and magnetic properties

SrDy _x Fe_12?x O₁₉ (x ≤ 0.08) nanofibers have been synthesized by the electrospinning method followed by calcinations process. The partial substitution of rare earth ions Dy³⁺ (10.5 μ _B of magnetic moments) mainly occupying 12k sublattice sites in the SrFe₁₂O₁₉ crystal structure is investigated and discussed in this work. An enhanced coercivity of 7155 Oe has been obtained when the doped content reached to 0.08 at a relative low calcination temperature of 800 °C. As a result, we believe the synthesized SrDy _x Fe_12?x O₁₉ nanofibers can potentially be useful in high-density recording media as well as permanent magnets.     

Dimerization in Honeycomb Na<Subscript>2</Subscript>RuO<Subscript>3</Subscript> under Pressure: a DFT Study

The structural properties of Na₂RuO₃ under pressure are studied using density functional theory within the nonmagnetic generalized gradient approximation (GGA). We found that one may expect a structural transition at ～3 GPa. This structure at the high-pressure phase is exactly the same as the low-temperature structure of Li₂RuO₃ (at ambient pressure) and is characterized by the P2₁/m space group. Ru ions form dimers in this phase and one may expect strong modification of the electronic and magnetic properties in Na₂RuO₃ at pressure higher than 3 GPa.