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.     

Phase transitions and the dielectric and piezoelectric properties of ceramic solid solutions based on BiScO<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript>

The ferroelectric and piezoelectric properties of ceramic solid solutions having a composition of (1−x)(Bi_0.9Nd_0.1)(Sc_0.9 B _0.1)O_{3 − x} PbTiO₃ (x = 0.60–0.66; B = Lu, Yb, Er, Y) and obtained by solid state reaction were studied. An increase in the Curie temperature was found upon an increase in the concentration of lead titanate, while a drop occured upon the doping of the A and B sublattices. It was shown that at high temperatures, MnO₂ and Bi₂O₃ additives lead to a reduction in the total conductivity and a dielectric loss of less than one order of magnitude. In modified ceramics, an increase in the d ₃₃ and k _t piezoelectric coefficients was observed as well. The effects of dielectric relaxation that are determined by the composition of the ceramics were revealed.     

Effect of Sr<Superscript>2+</Superscript> ion substitution with trivalent ions (Sc<Superscript>3+</Superscript>, In<Superscript>3+</Superscript>, La<Superscript>3+</Superscript>, Bi<Superscript>3+</Superscript>) on its ferroelectric instability in SrTiO<Subscript>3</Subscript>

The vibration frequencies of unstable ferroelectric and antiferrodistortion modes and the dependences of the energy on the ion displacement amplitude have been calculated within the generalized Gordon-Kim model for distortions along eigenvectors of these modes in the mixed compounds Sr_{1 − x} A _x Ti_{1 − x} /₄□ _x/4O₃ and Sr_{1 − y} A _2y /₃□ _y/3TiO₃ (A = Sc³⁺, In³⁺, La³⁺, Bi³⁺; □ is the vacancy). To compensate an excess positive charge, vacancies are introduced into the Ti⁴⁺ or Sr²⁺ site. Calculations have been performed in the “daverage” crystal approximation for impurity concentrations of 0.25 and 0.50. To this end, a set of 40 atomic superlattices with various orderings of heterovalent ions Sr²⁺ and impurity A ³⁺ has been considered. It has been found that each impurity type, independently of charge balance, induces ferroelectric instabilities in doped compounds. In the case of doping with In³⁺ and La³⁺ for concentration x = 0.25, the possibility of rotating the polarization vector has been shown.     

Effect of Ba-substitution on the structure and properties of Pb<Subscript>0.8</Subscript>Ba<Subscript>0.2</Subscript>[(In<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)<Subscript>1-x</Subscript>Ti<Subscript>x</Subscript>]O<Subscript>3</Subscript> ceramics

Ferroelectric ceramics with formula Pb_0.8Ba_0.2[(In_1/2Nb_1/2)_1-xTi_x]O₃ (PBINT) (x=0.0,0.1,0.2,0.3,0.4 and 0.5) were prepared via a two-step solid state reaction method. It was found that ceramics with compositions in the range of x=0.0∼0.3 showed a pseudo-cubic structure, whereas the ceramic with x=0.5 displayed a tetragonal structure. All compositions showed significant frequency dispersion in their dielectric properties. The remanent polarization P_r as well as the coercive field E_c, measured at room temperature, increases with the Ti content. The experimental results obtained in this system are summarized into a phase diagram, with the morphotropic phase boundary (MPB) located at x=0.4. Compared with the Pb[(In_1/2Nb_1/2)_1-xTi_x]O₃ solid solution system, incorporating Ba in the A-site leads to a significant decrease in the dielectric maximum temperature T_max, a suppression of the dielectric relaxation parameter γ, and a shift of the MPB composition to a higher Ti content. PACS 77.84.Dy; 77.80.Bh; 77.22.Ch     

Photoluminescence of nanoparticles of (Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>)<Subscript>0.95</Subscript>(Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>0.05</Subscript> solid solution

We have ground bulk samples to obtain nanoparticles of (Ga₂S₃)_1–x (Eu₂O₃) _x solid solutions, the sizes of which were determined using an atomic force microscope. The photoluminescence spectra of the nanoparticles were studied in the temperature interval 77–300 K. We have established the mechanisms for emission and transfer of energy from the matrix to the rare-earth ion, and we determined the Stokes shift (ΔS = 0.7 eV), the Huang–Rhys parameter (S = 16), and the optical phonon energy (ħ−ω = 23 meV).     

Fundamental band edge optical absorption in Bi<Subscript>0.5</Subscript>Sb<Subscript>1.5</Subscript>Te<Subscript>3</Subscript>

Spectra of optical absorption in Bi_0.5Sb_1.5Te₃ films grown on mica and KBr substrates have been investigated for T = 145 and 300 K. The data obtained have been analyzed together with the data of investigations on the fundamental absorption edge for Bi₂Te₃ available in the scientific literature. It has been revealed that the interband absorption spectra for both Bi_0.5Sb_1.5Te₃ and Bi₂Te₃ represent a superposition of two components corresponding to direct and indirect allowed optical transitions. In this case, the least energy gap separating the valence band and the conduction band is direct for Bi_2−xSb_xTe₃ (x ≤ 1.5, T = 300 K). For Bi_0.5Sb_1.5Te₃ the temperature variation rates have been estimated for the thresholds of direct and indirect interband transitions. It has been shown that this solid solution is direct gap solution at T ≥ 145 K. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 50–52, July, 2008.     

Correlation between the dynamics of oxygen atoms and oxidation kinetics of solid solutions based on Bi<Subscript>2</Subscript>Sr<Subscript>2</Subscript>CaCu<Subscript>2</Subscript>O<Subscript>8</Subscript>

The oxidation kinetics of Bi_1.3Pb_0.8Sr₂Ca_0.8Y_0.2Cu₂O_8+δ solid solutions at different temperatures and \(p_{O_2 } = 0.21\) atm is investigated by thermogravimetry. The results obtained are compared with the previously studied oxidation kinetics of Bi_1.3Pb_0.8Sr₂Ca_0.8Y_0.2Cu₂O_8+δ solid solutions. It is found that the substitution of yttrium for calcium leads to an appreciable retardation of the initial oxidation stage associated with the oxygen diffusion. The phonon spectra of the solid solutions are examined using inelastic neutron scattering on a DIN-2PI direct-geometry spectrometer. The high-frequency (>50 meV) phonon densities of states for yttrium-containing and yttrium-free solid solutions are analyzed. The possible model is proposed for a correlation between the differences observed in the high-frequency phonon densities of states attributed to the vibrations of oxygen atoms and the differences in the oxidation kinetics of the solid solutions under consideration.     

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.     

Thermal stability and electrical conductivity of multiferroics BiFeO<Subscript>3</Subscript>/REEs

Ceramic samples of bismuth ferrite and solid solutions of Bi_{1 − x} A _x FeO₃ type (where A = Lu, Yb, Tm, Er, Ho, Dy, Tb, Gb, Eu, Sm, Nd, Pr, La; 0.05 ≤ x ≤ 0.20; Δx = 0.05) were prepared. Spectra of the real part of electrical conductivity were studied within the range 10⁻⁴–10⁻⁶ Hz. The dependence of the samples’ thermal stability and electrical conductivity on the size of the substituting ions was established.     

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.     

High-temperature complex impedance and modulus spectroscopic studies of doped Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-BaTiO<Subscript>3</Subscript> ferroelectric ceramics

Lead-free Na_0.5Bi_0.5TiO₃ (NBT) and (1 ? x)Na_0.5Bi_0.5TiO₃ + xBaTiO₃ with x = 0.1 and 0.2 (where x = 0.1 and 0.2 are named as NBT1 and NBT2, respectively), (1 ? y)Na_0.5Bi_0.5TiO₃ + yBa_0.925Nd_0.05TiO₃ with y = 0.1 and 0.2 (where y = 0.1 and 0.2 are named as NBT3 and NBT4, respectively)-based relaxor ferroelectric ceramics were prepared using the sol-gel method. The crystal structure was investigated by X-ray diffraction (XRD) at room temperature (RT). The XRD patterns confirmed the presence of the rhombohedral phase in all the samples. The electrical properties of the present NBT-based samples were investigated by complex impedance and the modulus spectroscopy technique in the temperature range of RT–600 °C. The AC conductivity was found to increase with the substitution of Ba²⁺ ions to the NBT sample whereas it significantly decreased with the addition of Nd³⁺ ions. The more anion vacancies in Ba-added samples and the lower anion vacancies in Nd-added samples were found to be responsible for higher and lower conductivities, respectively.     

<Superscript>29</Superscript>Si MAS-NMR study of oxide conductors derived from the apatite-type La<Subscript>9.33</Subscript>Si<Subscript>6</Subscript>O<Subscript>26</Subscript> compound

The preparation of (La_9.33−2x/3Sr _x □_0.67−x/3)Si₆O₂₄O₂ (0 ≤ x ≤ 2) samples with different amounts of cation vacancies is reported. Structure and unit-cell parameters were deduced by Rietveld analysis of XRD patterns. Structural features that enhance oxygen conductivity in Sr-doped apatites are discussed. Up to three components were detected in ²⁹Si MAS-NMR spectra which change with the amount and distribution of cation vacancies. In general, oxygen conductivity increases with the amount of vacancies at La1 (6h) sites, passing through a maximum for x = 0.4. In the case of activation energy, a minimum is detected near x = 1.2, indicating that entropic and enthalpic change in different ways. The presence of cation vacancies should enhance oxygen hopping along c-axis; however, the analysis of the frequency dependence of conductivity suggests that oxygen motions are produced along three axes.     

Magnetic properties of the ordered and disordered double perovskite Sr<Subscript>2</Subscript>Fe<Subscript>1+x</Subscript>Mo<Subscript>1−x</Subscript>O<Subscript>6</Subscript> (−1 ≤ x ≤ 1/3)

We have studied the effect of cationic disorder on the spin polarization of the double perovskite system Sr₂Fe_1+x Mo_1−x O₆ with  −1 ≤ x ≤ 1/3. The composition x = 0 corresponds to the well-known double-perovskite Sr₂FeMoO₆, which is expected to have complete spin polarization, however all samples present some degree of Fe/Mo disorder which reduces the tunneling magnetoresistance in granular samples. We consider an electronic model within the renormalized perturbation expansion Green’s functions, consisting in a correlated electron picture with localized Fe-ions and itinerant electrons interacting with the local spins via a double-exchange type mechanism. Our results show the influence of disorder on the density of states and the ground-state properties, particularly on the spin polarization over the whole range of x.     

Characterizing the insulator adjacent to the superconductor in Bi<Subscript>2</Subscript>Sr<Subscript>2-x</Subscript>La<Subscript>x</Subscript>CuO<Subscript>6+δ</Subscript> (x = 0.3)

The time-averaged and low-frequency noise transport properties were investigated in the vicinity of the superconductor-insulator transition for a Bi₂Sr_2-x La _x CuO_6+δ (x = 0.3) thin film. The results are consistent with a superconductor (metal) embedded in a strong insulator, the latter showing two-dimensional variable range hopping properties. The weak insulator behavior - if any - is attributed to the metallic inclusions only.     

Magnetic and electric properties of Eu<Subscript>0.62</Subscript>Bi<Subscript>0.38</Subscript>MnO<Subscript>3</Subscript> and Eu<Subscript>0.53</Subscript>Bi<Subscript>0.32</Subscript>Sr<Subscript>0.15</Subscript>MnO<Subscript>3</Subscript> crystals

Single crystals of Eu_0.62Bi_0.38MnO₃ and Eu_0.53Bi_0.32Sr_0.15MnO₃ solid solutions crystallizing in an orthorhombically distorted perovskite structure were prepared. At temperatures above 120 K, Eu_0.62Bi_0.38MnO₃ exhibits the properties of structural glass while remaining a dielectric at all temperatures. There is no long-range magnetic order in this compound. Eu_0.53Bi_0.32Sr_0.15MnO₃ behaves as a semiconductor above 120 K and exhibits a jump in conductivity at T = 175 K associated with a metal-insulator transition occurring within limited regions of the crystal. In these regions, there appears a ferromagnetic moment (due to double exchange mediated by charge carriers) and local electric polarization.     

Giant positive magnetoresistance in heterostructure (La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript>) coated with YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7</Subscript> composites

(La_0.7Sr_0.3MnO₃) _x /(YBa₂Cu₃O₇) _y composites were prepared by mixing La_0.7Sr_0.3MnO₃ powders and the sol–gel-derived YBa₂Cu₃O₇ matrix, followed by high-temperature calcinations. Their structural, magnetic properties and magnetoresistance effect have been investigated systematically. A giant positive magnetoresistance (PMR) at low magnetic field is observed at low temperatures. In the case of (La_0.7Sr_0.3MnO₃)₁/(YBa₂Cu₃O₇)₉ composite, the PMR achieves 260% under a magnetic field of 5800 Oe. However, the PMR value sharply decreases with increasing temperature and no magnetoresistance effects are found above metal-insulator transition temperature. The enhancement of spin-dependent scattering at the grain boundaries should be responsible for the observed PMR. In addition, the temperature dependence of resistance under magnetic field could be explained by the competition between diamagnetism and paramagnetism in YBCO phase. At low temperature, the diamagnetism is predominant over paramagnetism and the interface scattering between LSMO grains is enhanced correspondingly. As a result, the low-temperature resistance increases and large PMR appears.     

Dielectric and polar order behaviors of BaTiO<Subscript>3</Subscript>-Bi(Mg<Subscript>1/2</Subscript>Ti<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> ceramics

New perovskite solid solution ceramics of (1−x)BaTiO₃-xBi(Mg_1/2Ti_1/2)O₃ ((1−x)BT-xBMT, x≤0.09) were synthesized by the solid-state reaction technique. X-ray diffraction studies have revealed a stable single perovskite structure for all samples. Dielectric measurements were carried out at different frequencies and temperatures. The polarization evolutions with temperatures were measured to investigate the ferroelectric properties. All the compositions show features of ferroelectrics with diffuse phase transition, though the temperature T _m of their dielectric constant maximum ε _m is frequency dependent. The dielectric constant peak ε(T) of (1−x)BT-xBMT ceramics become broad with increasing BMT content. During the temperature range of ε(T) peak summit, (1−x)BT-xBMT ceramics present quasi-linear dielectric phenomenon under high electric field with very high dielectric constant.     

Investigating the structure and dielectric properties of ceramic solid solutions of the SrTiO3-BiScO3 system

Ceramic samples of (1 − x)SrTiO₃-(x)BiScO₃ system with x = 0, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5 were synthesized. Neither of the end members of this system are ferroelectric materials. X-ray diffraction analysis reveals that at room temperature, the samples with x = 0.2, 0.3, 0.4, and 0.5 consisted of a mixture of two phases: a cubic center-symmetric Pm3m phase and a tetragonal polar P4mm phase. Dielectric permittivity and dielectric losses measurements of these compositions showed anomalies associated with the diffuse phase transition characteristic of ferroelectrics.     

Thermal expansion and thermal conductivity of CuGa<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>In<Subscript>x</Subscript>Te<Subscript>2</Subscript> solid solutions

The thermal expansion coefficients and the thermal conductivity of Bridgman-grown crystals of CuGa_1−x In_xTe₂ solid solutions are investigated. It is found that the thermal expansion coefficient varies with x linearly, while the thermal conductivity is minimal when x=0.5. The Debye temperature and the rms dynamic atomic displacements are calculated from experimental data. It is shown that the Debye temperature decreases and the rms displacements in the crystal lattice sharply increase as the In content in the solid solutions grows.     

Effect of high pressure on the crystal and magnetic structures of La<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>CoO<Subscript>3</Subscript> cobaltite

The atomic and magnetic structures of La_0.5Ca_0.5CoO₃ cobaltite have been studied by the neutron diffraction technique at high pressures of up to 4 GPa in the 10- to 300-K temperature range. The pressure dependences of the structural parameters have been obtained. The Curie temperature increases with the pressure with the coefficient dT _C/dP = 1 K/GPa, demonstrating the stability of the ground ferromagnetic (FM) state. The pressure dependence of the ground FM state in La_0.5Ca_0.5CoO₃ is in drastic contrast with that for La_{1 − x} Ca _x CoO₃ at a lower calcium content (x < 0.3). For the latter compound, the pressure suppressed the ground FM state and a large negative pressure coefficient of the Curie temperature (dT _C/dP ∼ −10 K/GPa) was observed. The nature of such a phenomenon is analyzed in the framework of the double exchange model also taking into account the changes in the electron configuration of Co³⁺ ions.