Electronic transition and the metallization effect in the BiFeO<Subscript>3</Subscript> crystal at high pressures

The optical absorption spectra from bismuth ferrite (BiFeO₃) have been studied at high pressures up to 60 GPa in diamond anvil cells. An electronic transition at which the energy of the optical absorption edge decreases sharply from ～1.5 eV to zero has been observed at room temperature in a pressure range of 45–55 GPa. This indirectly indicates a insulator-metal transition. The observed electronic transition correlates with the recently revealed structural and magnetic transitions induced by high pressures in this crystal. The behavior of the optical absorption edge with decreasing the pressure is completely reversible in correlation with the reversibility of the magnetic transition. The “smearing” of the structural transition in pressure is caused by thermal fluctuations between the high-spin state and low-spin state of the Fe³⁺ ions near the transition.     

High-spin-low-spin transition and the sequence of the phase transformations in the BiFeO<Subscript>3</Subscript> crystal at high pressures

The transition of Fe³⁺ ions from the high-spin (HS) state (S = 5/2) to the low-spin (LS) state (S = 1/2) has been observed in the BiFeO₃ multiferroic crystal at high pressures in the range 45–55 GPa. This effect has been studied in high-pressure diamond-anvil cells by means of two experimental methods using synchrotron radiation: nuclear resonant forward scattering (NFS or synchrotron Mössbauer spectroscopy) and FeK _β high-resolution X-ray emission spectroscopy (XES). The HS-LS transition correlates with anomalies in the magnetic, optical, transport, and structural properties of the crystal. At room temperature, the transition is not stepwise, but is extended in a pressure range of about 10 GPa due to thermal fluctuations between the high-spin and low-spin states. It has been found that the transition of the BiFeO₃ insulator to the metal occurs only in the low-spin phase and the cause of all phase transitions is the HS-LS crossover.     

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.     

Electronic transitions in the VBO<Subscript>3</Subscript> single crystal at high pressures

Optical absorption spectra of single crystals of the ferromagnetic semiconductor VBO₃ are studied at high pressures up to 70 GPa achieved in a diamond-anvil cell. An electronic transition accompanied by sharp changes in the optical parameters and a decrease in the optical gap from E ₀ = 3.02 eV to 2.25 eV is found at the pressure P _C ～ 30 GPa. The gap does not disappear in the high-pressure phase and its value becomes typical of semiconductors. This is indicative of a semiconductor-semiconductor transition. The transition to the metallic state may occur at the critical pressure P _met ≈ 290 GPa.     

Lattice dynamics of BiFeO<Subscript>3</Subscript> under hydrostatic pressure

The vibrational frequencies of the BiFeO₃ crystal lattice in the cubic phase (Pm3m) and the rhombohedral paraelectric phase (R3c) are calculated in terms of the ab initio model of an ionic crystal with the inclusion of the dipole and quadrupole polarizabilities. In the ferroelectric phase with the symmetry R3c, the calculated spontaneous polarization of 136 μC cm^?2 agrees well with the experimental data. The dependences of the unit cell volume, the elastic modulus, and the vibrational frequencies on the pressure are calculated. It is found that the frequency of an unstable ferroelectric mode in both the cubic (Pm3m) and rhombohedral (R3c) phases are almost independent of the applied pressure, in contrast to classical ferroelectrics with a perovskite structure, where the ferroelectric instability is very sensitive to a variation in the pressure.     

Specific features of structural states in the BiFeO<Subscript>3</Subscript>-YMnO<Subscript>3</Subscript> solid solutions

The (1 − x)BiFeO_3−x YMnO₃ solid solutions have been found to undergo the following sequence of phase transformations with increasing x: R3c → Pbnm → C2 → Pnma → P6₃ cm. It has been established that the Pbnm and Pnma phases have different orientations of atomic displacements and can exhibit antiferroelectric properties.     

Electronic and structural transitions in NdFeO<Subscript>3</Subscript> orthoferrite under high pressures

The effect of high pressure up to 65 GPa on the crystal structure and optical absorption spectra of NdFeO₃ orthoferrite single crystals is studied in diamond anvil cells. At P～37.5 GPa, an electronic transition at which the optical absorption edge jumps from ～2.2 to ～0.75 eV is observed. The equation of state V(P) is studied on the basis of the X-ray diffraction data obtained under pressure. This study reveals a first-order structural phase transition at P～37 GPa with a jump of ～4% in the unit cell volume. It is shown that the phase transition observed in rare-earth orthoferrites at 30–40 GPa is a transition of the insulator-to-semiconductor type.     

Lattice dynamics and baric behavior of phonons in Hg<Subscript>2</Subscript>Cl<Subscript>2</Subscript> crystals at high hydrostatic pressures

A theoretical model based on long-range dispersion corrections of the charge density functional is proposed for model Hg₂Cl₂ calomel crystals, typical representatives of molecular inorganic compounds where the intermolecular interaction is found to play an important role. This model successfully describes the electronic state and the phonon spectrum of the above crystal, predicts the earlier unstudied phase transition at high hydrostatic pressure. Study of the baric behavior of the phonon spectrum with Raman spectroscopy observes the soft mode in the low-symmetry orthorhombic phase with the frequency softening as the pressure rises. Pressures above 9 GPa considerably transform the Raman spectra, indicating a structural phase transition.     

Effect of KNbO<Subscript>3</Subscript> modification on structural,electrical and magnetic properties of BiFeO<Subscript>3</Subscript>

The polycrystalline samples of (Bi_1?x K _x ) (Fe_1?x Nb _x ) O₃ (BKFN) for x = 0.0, 0.1, 0.2 and 0.3 were synthesized by a solid-state reaction method. The X-ray diffraction patterns of BKFN exhibit that the addition of KNbO₃ in BiFeO₃ gradually changes its structure from rhombohedral to pseudocubic. The analysis of scanning electron micrograph clearly showed that the sintered samples have well-defined and uniformly distributed grains. Addition of KNbO₃ to BiFeO₃ enhances the dielectric, ferroelectric and ferromagnetic properties of BiFeO₃. Detailed studies of impedance and related parameters of BKFN using the complex impedance spectroscopic technique exhibit the significant contributions of grain and grain boundaries in the resistive and transport properties of the materials. Some oxygen vacancies created in the ceramic samples during high-temperature processing play an important role in the conduction mechanism. The leakage current or tangent loss of BiFeO₃ is greatly reduced on addition of KNbO₃ to the parent compound BiFeO₃. Preliminary studies of ferroelectric and magnetic characteristics of the samples reveal the existence of ferroelectric, and weak ferromagnetic ordered ceramics.     

Frustrated exchange interactions formation at low temperatures and high hydrostatic pressures in La<Subscript>0.70</Subscript>Sr<Subscript>0.30</Subscript>Mn<Subscript>O2.85</Subscript>

The magnetic and thermal properties of the anion-deficient La_0.70Sr_0.30MnO_2.85 manganite are investigated in wide temperature (4–350 K) range, including under hydrostatic pressure (0–1.1 GPa). Throughout the pressure range investigated, the sample is spin glass with diffused phase transition into paramagnetic state. It is established, that spin glass state is a consequence of exchange interaction frustration of the ferromagnetic clusters embeded into antiferromagnetic clusters. The magnetic moment freezing temperature T _f of ferromagnetic clusters increases under pressure, freezing temperature dependence on pressure is characterized by derivative value ∼4.5 K/GPa, while the magnetic ordering T _MO temperature dependence is characterized by derivative value ∼13 K/GPa. The volume fraction of sample having ferromagnetic state is V _fer ∼ 13% and it increases under a pressure of 1.1 GPa by ΔV _fer ≈ 6%. Intensification of ferromagnetic properties of the anion-deficient La_0.70Sr_0.30MnO_2.85 manganite under hydrostatic pressure is a consequence of oxygen vacancies redistribution and unit cell parameters decrease. The most likely mechanism of frustrated exchange interactions formation is discussed.     

Contactless density measurement of high-temperature BiFeO<Subscript>3</Subscript> and BaTiO<Subscript>3</Subscript>

The density of liquid and undercooled BiFeO₃ and high-temperature solid, liquid, and undercooled BaTiO₃ was measured with an electrostatic levitation furnace. The density was obtained with an ultraviolet-based imaging technique that allowed excellent sample contrast throughout all phases of processing, including at elevated temperatures. Over the 1250- to 1490-K temperature range, the density of liquid BiFeO₃ can be expressed as _L(T)=6.70×10³–1.31(T-T_m)(kgm^-3) (±2 per cent) with T_m=1423 K, yielding a volume coefficient of thermal expansion _L(T)=1.9×10^-4 K^-1. For BaTiO₃, the density of the solid can be expressed as _S(T)=5.04×10³–0.21(T-T_m) (T_m=1893 K) over the 1220- to 1893-K range, yielding a volume coefficient of thermal expansion _S(T)=4.2×10^-5 K^-1, whereas that of the liquid can be expressed as _L(T)=4.04×10³-0.34(T-T_m) over the 1300- to 2025-K range with _L(T)=8.4×10^-5 K^-1. PACS 77.84.-s; 81.05.Je; 81.20.n     

Conditions favoring the polar weak ferromagnetic state in BiFeO<Subscript>3</Subscript>-type multiferroics

The crystal structure and magnetic properties of Bi_{1 − x} A _x FeO_{3 − x/2} (A = Ca, Sr, Pb, Ba), Bi_{1 − x} A _x (Fe_{1 − x} Ti _x )O₃, and Bi_{1 − x} A _x (Fe_{1 − x/2}Nb _x/2)O₃ solid solutions have been studied. It is shown that the homogeneous polar weak ferromagnetic state occurs in the vicinity of a morphotropic phase boundary in the systems where dopant ions lead to the reduction of the unit cell volume in the polar phase. In the case of A = Ca, the non-polar phase also exhibits weak ferromagnetism and the spontaneous magnetizations in the polar and nonpolar phases differ only slightly.     

Weak ferromagnetism in BiFeO<Subscript>3</Subscript>-based multiferroics

The magnetic properties of the Bi_{1 ? x} Ln _x FeO₃ (Ln is a rare-earth ion), Bi_{1 ? x} A _x FeO_{3 ? x/2} (A is an alkali earth ion), and BiFe_{1 ? x} Ti _x O_{3 + δ} solid solutions in magnetic fields up to 14 T have been studied. The concentration ranges of the existence of the ferroelectric phase described by the space group R3c have been determined. It is shown that the substitution of the rare-earth ions for the Bi³⁺ ions leads to a sharp decrease in the critical fields inducing the metamagnetic transition from a modulated antiferromagnetic state to a weakly ferromagnetic one; however, the modulated structure in the concentration range of the R3c phase is mainly retained. The substitution of the alkali earth ions (x ～ 0.1) for the bismuth ions leads to the total destruction of the modulated structure and to the implementation of the weakly ferromagnetic state within the R3c phase. A homogeneous weakly ferromagnetic state has been revealed when the Ti⁴⁺ ions (x = 0.1) are substituted for the Fe³⁺ ions in the ferroelectric R3c phase.     

Structural and magnetic phase transitions in Pr<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> at high pressures

The crystal structure and Raman spectra of Pr_0.7Ca_0.3MnO₃ manganite at high pressures of up to 30 GPa and the magnetic structure at pressures of up to 1 GPa have been studied. A structural phase transition from the orthorhombic phase of the Pnma symmetry to the high-pressure orthorhombic phase of the Imma symmetry has been observed at P ∼ 15 GPa and room temperature. Anomalies of the pressure dependences of the bending and stretching vibrational modes have been observed in the region of the phase transition. A magnetic phase transition from the initial ferromagnetic ground state (T _C = 120 K) to the A-type antiferromagnetic state (T _N = 140 K) takes place at a relatively low pressure of P = 1 GPa in the low-temperature region. The structural mechanisms of the change of the character of the magnetic ordering have been discussed.     

High-frequency ultrasonic studies of the structural phase transition in an La<Subscript>0.875</Subscript>Sr<Subscript>0.125</Subscript>MnO<Subscript>3</Subscript> single crystal

The specific features of a phase transition from a disordered orbital state to an ordered orbital state in an La_0.875Sr_0.125MnO₃ single crystal are investigated using acoustic methods at a frequency f = 500 MHz. The phase transition is accompanied by a distortion of MnO₆ octahedra due to the cooperative Jahn-Teller effect and is a first-order phase transition, as judged from the sharp change observed in the damping of acoustic pulses, the acoustic wave velocity, and the temperature hysteresis. It is revealed that the parameters of the acoustic waves change significantly throughout the temperature range of existence of the cooperatively distorted structure. In an external magnetic field, the structural phase transition is shifted toward lower temperatures.     

Lattice dynamics of BiFeO<Subscript>3</Subscript>: The untypical behavior of the ferroelectric instability under hydrostatic pressure

Within a nonempirical model of an ionic crystal with the inclusion of the dipole and quadrupole ion polarizations, the lattice vibrational frequencies, high-frequency dielectric constant, Born dynamic charges, and the elasticity moduli of the BiFeO₃ crystal have been calculated and their dependencies on the hydrostatic pressure in the cubic, rhombic, and rhombohedral phases have been determined. The results indicate the presence of the ferroelectric instability, which depends weakly on the pressure in all of the phases investigated. The dependence of the crystal lattice dynamics on the applied pressure for the cubic phases of BiAlO₃, BaTiO₃, and PbTiO₃ has been calculated for comparison.     

Pressure-induced phase transition in the cubic ScF<Subscript>3</Subscript> crystal

Pressure-induced phase transitions in the ScF₃ crystal were studied using synchrotron radiation diffraction, polarization microscopy, and Raman spectroscopy. The phase existing in the range 0.6–3.0 GPa is optically anisotropic; its structure is described by space group R ₃ c (Z = 2), and the transition is due to rotation of ScF₆ octahedra around a threefold axis. The pressure dependence of the structural parameters and angle of rotation are determined. The number of Raman spectral lines corresponds to that expected for this structure; above the phase transition point, a recovery of soft modes takes place. At a pressure of 3.0 GPa, a transition occurs to a new phase, which remains metastable as the pressure decreases. The results are interpreted using an ab initio method based on the Gordon-Kim approach.     

Nonlinear properties and paramagnet-to-ferromagnet transition in Nd<Subscript>0.7</Subscript>Ba<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> single crystal with metallic ground state

We present the results from studying the magnetic properties (linear and nonlinear susceptibilities and the depolarization of polarized neutrons) of Nd_{1 − x} Ba _x MnO₃ manganite, x = 0.3, with Curie temperature T _C ≈ 140 K and dielectric-to-metal transition temperature T _DM ≈ 129 K. Its critical behavior corresponds to that of an isotropic 3-D ferromagnet at temperatures above T*≈ 144 K, but a strong nonlinear response in weak magnetic fields and depolarization are observed at temperatures below T*. It is shown that this nontraditional behavior is related to the generation of ferromagnetic clusters in the paramagnetic matrix that form a conducting percolative network at temperatures near T _DM.     

Stabilization of Ferromagnetism in BiFeO<Subscript>3</Subscript>:Ho at Hydrostatic Pressure

The isothermal magnetization of the Bi_{1 – x}Ho _x FeO₃ (x = 0?0.2) multiferroic has been studied at a hydrostatic pressure up to 9 GPa in the range of room temperatures. A new anomaly at P_C ≈ 3.81 GPa related to intermediate phases between the structural transition R3c → Pnma has been found against the background of the pressure-induced antiferromagnetic ordering in BiFeO₃ (BFO) at P ≈ 2.59 GPa. It is established that the ferromagnetic behavior under pressure depends on the Ho impurity concentration: P_C decreases at 0.05 ≤ x ≤ 0.1 because of the decrease in R3c bond lengths in the structure, and the stabilization of ferromagnetism is implemented at 0.1 ≤ x ≤ 0.2 probably because of the coexistence of the R3c and Pnma phases. The results of studies indicate that, in Bi_{1 – x}Ho _x FeO₃ with x = 0.2, the transition pressure P_C = 3.7 GPa exceeds the values for BFO doped with other 4f elements (Eu, Y, Sm) in the region R3c → Pnma of the transition.     

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.