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.     

Equation of state and structural transition at high hydrostatic pressures in the BiFeO<Subscript>3</Subscript> crystal

Change in the crystal structure of the BiFeO₃ multiferroic at high pressures up to 70 GPa in a diamond anvil cell has been studied by the method of synchrotron x-ray diffraction at room temperature. The experiment has been carried out under hydrostatic conditions with helium as a pressure-transferring medium. An anomaly has been observed in the behavior of the structural parameters at pressures P _c ≈ 40?50 GPa. This anomaly correlates with the effect of the magnetic collapse of iron moments revealed in this pressure range. It has been found that the bulk compression modulus is equal to B ₀ = (75.5 ± 15.5) GPa in the interval 0 < P < P _c and is almost quadrupled to a value of B = (292 ± 9) GPa in the interval P > P _c. When the pressure decreases, the behavior of the structural parameters is completely reversible in correlation with the reversibility of the magnetic transition. The “diffuseness” of the structural transition in pressure is explained by thermal fluctuations between the high-and low-spin states of Fe³⁺ ions in the transition region.     

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)].     

Investigation of the field-tuned quantum critical point in CeCoIn<Subscript>5</Subscript>

The main properties and the type of the field-tuned quantum critical point in the heavy-fermion metal CeCoIn₅ that arise upon application of magnetic fields B are considered within a scenario based on fermion condensation quantum phase transition. We analyze the behavior of the effective mass, resistivity, specific heat, charge, and heat transport as functions of applied magnetic fields B and show that, in the Landau Fermi liquid regime, these quantities demonstrate critical behavior, which is scaled by the critical behavior of the effective mass. We show that, in the high-field non-Fermi liquid regime, the effective mass exhibits very specific behavior, M*～ T^{? 2/3}, and the resistivity demonstrates T^2/3 dependence. Finally, at elevated temperatures, it changes to M*～T^?1/2, while the resistivity becomes linear in T. In zero magnetic field, the effective mass is controlled by temperature T and the resistivity is also linear in T. The obtained results are in good agreement with recent experimental facts.     

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.     

High-frequency EPR of Cr<Superscript>2+</Superscript> ions in CdGa<Subscript>2</Subscript>S<Subscript>4</Subscript>

High-frequency broad-band (65–240 GHz) EPR is used to study impurity centers of bivalent chromium in a CdGa₂S₄ crystal. It is found that the EPR spectra correspond to tetragonal symmetry. The spin Hamiltonian H = βB · g · S + B ₂ ⁰ O ₂ ⁰ + B ₄ ⁰ O ₄ ⁰ + B ₄ ⁴ O ₄ ⁴ with the parameters B ₂ ⁰ =23659±2 MHz, B ₄ ⁰ =1.9±1 MHz, |B ₄ ⁴ |=54.2±2 MHz, g_‖=1.93±0.02, and g_⊥=1.99±0.02 is used to describe the observed spectra. It is concluded that chromium ions occupy one of the tetrahedrally coordinated cation positions.     

Magnetic ordering in Fe<Subscript>1.087</Subscript>Te under pressure

The crystal and magnetic structures of Fe_1.087Te have been studied by neutron powder diffraction in the temperature range from 1.7 to 80 K at pressures of  ≈0.4 and ≈1.2 GPa. No symmetry change of the tetragonal paramagnetic ambient pressure phase (space group P4/nmm) was observed for temperatures above 60 K and pressures up to  ≈1.2 GPa. A novel pressure-induced phase of Fe_1.087Te having orthorhombic symmetry (space group Pmmn) and incommensurate antiferromagneticbicollinear order was observed in the temperature range from 50 to 60 K at  ≈1.2 GPa. The known monoclinic ambient pressure phase of Fe_1.087Te (space group P2 ₁/n) with commensurate antiferromagnetic order was found to be stable up to at least  ≈1.2 GPa at low temperature.     

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).     

Transport and magnetic properties of a Zn<Subscript>0.1</Subscript>Cd<Subscript>0.9</Subscript>GeAs<Subscript>2</Subscript> + 10 wt % MnAs composite with magnetic clusters at high pressure

The temperature (T = 77–420 K) dependences of the electrical resistivity and the magnetization, the magnetic-field (H ≤ 5 kOe) and pressure (P ≤ 7 GPa) dependences of the resistivity, the Hall coefficient, and the magnetization have been measured in the Zn_0.1Cd_0.9GeAs₂ + 10 wt % MnAs composite with the Curie temperature T _C = 310 K. The magnetoresistive effect has been observed at high hydrostatic pressure to 7 GPa. At nearly room temperature, the pressure dependence of the magnetization demonstrated a transition from the ferromagnetic to paramagnetic state at P ~ 3.2 GPa that was accompanied by the semiconductor–metal phase transition.     

Thermodynamics of a Magnetic Transition in MnS<Subscript>2</Subscript> at High Pressures

The behavior of the specific heat of MnS₂ at high pressures has been studied. A significant increase in the transition temperature T_N to an antiferromagnetic state with the pressure from 48.2 K at atmospheric pressure to 76 K at a pressure of 5.3 GPa has been revealed. The initial pressure derivative is dT _N /dP = 4.83 K/GPa. It has been found that the parameter α = d(logT _N )/d(logV ) = ?6.6 ± 0.1 is significantly different from the value α = ?10/3 ≈ ?3.3 (Bloch relation), which is typical of numerous antiferromagnetic insulators—transition- metal oxides and fluorides. The volume jump at the magnetic transition point has been estimated. The necessity of direct dilatometric measurements of the volume has been justified.     

Superconductivity in Ti-doped iron-arsenide compound Sr<Subscript>4</Subscript>Cr<Subscript>0.8</Subscript>Ti<Subscript>1.2</Subscript>O<Subscript>6</Subscript>Fe<Subscript>2</Subscript>As<Subscript>2</Subscript>

Superconductivity was achieved in Ti-doped iron-arsenide compound Sr₄Cr_0.8Ti_1.2O₆Fe₂As₂ (abbreviated as Cr-FeAs-42622). The X-ray diffraction measurement shows that this material has a layered structure with the space group of P4/nmm, and with the lattice constants a = b = 3.9003 Å and c = 15.8376 Å. Clear diamagnetic signals in ac susceptibility data and zero-resistance in resistivity data were detected at about 6 K, confirming the occurrence of bulk superconductivity. Meanwhile we observed a superconducting transition in the resistive data with the onset transition temperature at 29.2 K, which may be induced by the nonuniform distribution of the Cr/Ti content in the FeAs-42622 phase.     

Fine structure and mechanical properties of the shape-memory Ni<Subscript>50</Subscript>Ti<Subscript>32</Subscript>Hf<Subscript>18</Subscript> alloy rapidly quenched by spinning

We have reported the results of investigations of the structure and chemical and phase compositions of the amorphous Ni₅₀Ti₃₂Hf₁₈ alloy prepared by rapid quenching from melt by spinning and subjected to heat treatments. The specific features of the fine polycrystalline alloy structure formation depending on the heat-treatment mode have been studied by transmission and scanning electron microscopy, chemical microanalysis, electron diffraction, and X-ray diffraction analysis. According to the data on the temperature behavior of electrical resistivity, critical temperatures of devitrification and subsequent thermoelastic martensitic transformation B2 → B19′ have been determined. The mechanical properties in different heat-treatment modes have been investigated.     

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.     

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.     

Thermodynamic and dilatometric properties of the dimerized phase of a C<Subscript>60</Subscript> fullerene

This paper reports on the results of complex investigations into the structural, thermodynamic, and dilatometric properties of the C₆₀ dimerized phase prepared under compression of a C₆₀ fullerite at a pressure up to 8 GPa and a temperature of 290 K. It is demonstrated that the dimerized phase has a face-centered cubic structure with a lattice parameter a=14.02±0.05 Å. The dimeric structure of the studied sample is confirmed by x-ray diffraction analysis. According to the dilatometric data, the volume jump observed in the vicinity of the orientational transition for the dimerized phase is estimated to be approximately 30 times less than that for the C₆₀ fullerite. The temperature dependence of the heat capacity of the (C₆₀)₂ crystalline dimer is examined using precision adiabatic vacuum calorimetry under normal pressure in the temperature range from T → 0 K to 340 K. The results obtained are used in the calculations of thermodynamic functions, namely, the heat capacity C _p ⁰ (T), the enthalpy H⁰(T)-H⁰(0), the entropy S⁰(T), and the Gibbs function G⁰(T)-H⁰(0). The fractal dimension D is determined as a function of the heat capacity. The standard entropy of the formation of the (C₆₀)₂ crystalline dimer from a simple compound (graphite) at T=298.15 K and normal pressure is calculated.     

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.     

Magnetoresistance of La<Subscript>0.67</Subscript>Sr<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> epitaxial films grown on a substrate with low lattice mismatch

The structure, electrical resistivity, and magnetoresistance of La_0.67Sr_0.33MnO₃ heteroepitaxial films (120-nm thick) practically unstrained by lattice mismatch with the substrate were studied. A strong maximum of negative magnetoresistance of ≈27% (for μ₀H = 4 T) was observed at T ≈360 K. While the magnetoresistance decreased monotonically in magnitude with decreasing temperature, it was still in excess of 2% at 150 K. For T < 250 K, the temperature dependence of the electrical resistivity ρ of La_0.67Sr_0.33MnO₃ films is fitted well by the relation ρ = ρ₀ + ρ ₁(H)T^2.3, where ρ₀ = 1.1×10^?4 Ω cm, ρ₁(H = 0) = 1.8×10^?9 Ω cm/K^2.3, and ρ₁(μ₀H = 4 T)/ρ₁(H = 0) ≈0.96. The temperature dependence of a parameter γ characterizing the extent to which the electrical resistivity of the ferromagnetic phase of La_0.67Sr_0.33MnO₃ films is suppressed by a magnetic field (μ ₀H = 5 T) was determined.     

Phase transition with suppression of magnetism in BiFeO<Subscript>3</Subscript> at high pressure

The magnetic behavior of a Bi⁵⁷FeO₃ powdered sample was studied at high pressures by the method of nuclear forward scattering (NFS) of synchrotron radiation. The NFS spectra from ⁵⁷Fe nuclei were recorded at room temperature under high pressures up to 61.4 GPa, which were created in a diamond anvil cell. In the pressure interval 0 < P < 47 GPa, the magnetic hyperfine field H^Fe at the ⁵⁷Fe nuclei increased reaching a value of ～52.5 T at 30 GPa, and then it slightly decreased to ～49.6 T at P = 47 GPa. As the pressure was increased further, the field H^Fe abruptly dropped to zero testifying a transition from the antiferromagnetic to a nonmagnetic state (magnetic collapse). In the pressure interval 47 < P < 61.4 GPa, the value of H^Fe remained zero. The field H^Fe recovered to the low-pressure values during decompression.     

Electrical instability of LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> crystals

The temperature behavior of I-U curves and the field and temperature dependences of the electrical resistivity and dielectric permittivity of crystals of the LiCu₂O₂ phase have been studied. It was established that the crystals belong to p-type semiconductors and that their static resistivity in the range 80–260 K follows the Mott law ρ=Aexp(T₀/T)^1/4 describing variable-range hopping over localized states. At comparatively low electric fields, the crystals exhibit threshold switching and characteristic S-shaped I-U curves containing a region of negative differential resistivity. In the critical voltage region, jumps in the conductivity and dielectric permittivity are observed. Possible mechanisms of the disorder and electrical instability in these crystals are discussed.