Soft-mode driven tetragonal-to-monoclinic phase transition in multiferroic BiFeO3

The phase transition of BiFeO₃ (BFO) from tetragonal to monoclinic induced by pressure was investigated by first-principles method. The sequential monoclinic phase, _Ma$M_{\mathrm{a}}$, which is favorable during low compression with respect to the tetragonal phase, was characterized. The order parameters were calculated in the vicinity of the phase transition, showing that phase transition has a second-order character. The results demonstrated that the pressure-induced tetragonal-to-monoclinic phase transition in BFO is related to the softening behavior of the E mode, which are very helpful in further investigations of the morphotropic phase boundary (MPB) in lead-free materials.     

Effect of Fe substitution on multiferroic hexagonal YMnO3

Polycrystalline YMn_1−xFe_xO₃ (x=0.02-0.20) powders were synthesized by means of modified citrate method. Powder X-ray diffraction gives evidence that all the samples are single phase and exhibit hexagonal structure with P6₃cm space group as observed for YMnO₃. The solubility limit of Fe was determined as about 6 wt.%. Cell parameter values were found to increase with Fe content, since Fe³⁺ and Mn³⁺ have the same ionic radii. This can be attributed to the increase of the tilting of MnO₅ bipyramid and the buckling of Y atoms. In addition, ⁵⁷Fe Mössbauer spectrometry provides evidence of two Fe³⁺ sites attributed to two different nearest atomic neighbours. Magnetic properties reveal a paramagnetic-to-antiferromagnetic transition, a possible increase of the magnetic anisotropy, and a competition between ferromagnetic and antiferromagnetic interactions.     

Anomalous field dependence of the inverse magnetocaloric effect in Ce(Fe0.93Ru0.07)2

A summary of detailed isothermal magnetization along with the ac susceptibility measurements on Ce(Fe_0.93Ru_0.07)₂ is presented. Near the first-order transition, i.e. near 110 K, Ce(Fe_0.93Ru_0.07)₂ displays a large positive magnetic entropy change, ΔSm, of 7.8 J/kg K in fields of only 2 T, i.e. it displays a strong inverse magnetocaloric (MCE) effect, as expected, on entering an antiferromagnetic (AF) state. However, the variation of the magnitude and width of this entropy change with field are anomalous when compared with model predictions, the former increasing with applied field below 2 T, while the latter exceeds 60 K in a field of 8 T.     

Synthesis and characterization of MnFe2O4-BiFeO3 multiferroic composites

The mixed spinel-perovskite composites of xMnFe₂O₄-(1-x)BiFeO₃ with x=0, 0.1, 0.2, 0.3 and 0.4 were prepared by solid state reaction method. The structure and grain size were examined by means of X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM), respectively. The XRD results showed that the composites consisted of spinel MnFe₂O₄ and perovskite BiFeO₃ phases after being calcined at the temperature 950 °C for 2 h. The grain size ranged from 0.8 to 1 μm. Magnetization was found to increase with increasing concentration of ferrite content. The variation of dielectric constant and dielectric loss with frequency showed dispersion in the low frequency range. Magnetocapacitance was also observed in the prepared composites, which may be the sign of magnetoelectric coupling in the synthesized composites at room temperature.     

Electrophoretic deposition of BaTiO3/CoFe2O4 multiferroic composite films

Electrophoretic deposition was utilized for preparation of BaTiO₃/CoFe₂O₄ multiferroic composite thick films on indium-tin oxide substrates. The suspensions for electrophoretic experiments were prepared by dispersing BaTiO₃ and CoFe₂O₄ nanoparticles with different molar ratios into solvents composed of ethanol and acetylacetone. Polyvinyl butyral was added to the suspensions in order to enhance the adhesion and strength of deposit and prevent cracking. The zeta potential values of BaTiO₃/CoFe₂O₄ suspensions were measured to be 26.4-36.9 mV. The experiment results showed that deposited films were obtained only when the applied electric field was larger than a certain critical value. XRD and SEM analysis depicted the presence of constituent phases in composite films. The percolation threshold of composite films was improved through dispersing ferromagnetic phase into ferroelectric phase. Therefore, the ferroelectric properties of composite thick films were maintained when the ferromagnetic properties were enhanced significantly with increasing CFO content.     

Magnetic structure and physical properties of the multiferroic compound PrMn2O5

RMn₂O₅ (R=lanthanide, Bi, Y) multiferroic compounds are intensively studied for their potential application in the spintronic field. In these systems, the key issue is to understand the origin of the strong coupling between the ferroelectric and magnetic orders and to investigate the influence of the nature of the R ions in this coupling. While the phase diagram of RMn₂O₅ compounds with small R size is well established, this of large R size compounds is missing due to the lack of samples originating with difficulties of synthesis. We present in this paper the first investigation of the thermodynamic, structural and magnetic properties of high quality polycrystalline PrMn₂O₅ samples. Our work shows that PrMn₂O₅ presents two magnetic transitions corresponding to commensurate magnetic orderings. We also evidence a weak lattice effect coupled to the magnetic order. Our results point out that the physical properties of PrMn₂O₅ differ from those of the parent compounds with magnetic R ions.     

The multiferroic properties of Bi(Fe0.95Co0.05)O3 films

Bi(Fe_0.95Co_0.05)O₃ films were prepared on conductive indium tin oxide (ITO)/glass substrates by chemical solution deposition. Well saturated polarization hysteresis loop has been observed with a remnant polarization value of about 22 μC/cm² at room temperature. Weak ferromagnetism with saturation magnetization of about 3 emu/cm³ was observed at room temperature. The clear observation of both room temperature ferroelectric and ferromagnetic properties suggests the potential multiferroic applications of Bi(Fe_0.95Co_0.05)O₃.     

Ferromagnetism in epitaxial orthorhombic YMnO3 thin films

Epitaxial orthorhombic YMnO₃ thin films, (0 0 1) oriented, have been grown by pulsed laser deposition on (0 0 1)SrTiO₃ substrates. Their crystal structure and magnetic response have been studied in detail. Although bulk o-YMnO₃ is antiferromagnetic, our magnetic measurements reveal intriguing thermal hysteresis between the zero-field-cooled and field-cooled curves below the onset of the antiferromagnetic ordering temperature, thus signaling a more complex magnetic structure with net ferromagnetic moments. We discuss on the possible origin of this net magnetization and we have found a correlation of the magnetic response with the strain state of the films. We propose that substrate-induced strain modifies the subtle competition of magnetic interactions and leads to a non-collinear magnetic state that can thus be tuned by strain engineering.     

Exchange bias effect in multiferroic Eu0.75Y0.25MnO3

The exchange bias phenomenon has been investigated in multiferroic Eu_0.75Y_0.25MnO₃. The material shows a weak ferromagnetism with cone spin configuration induced by external magnetic field below 30 K. Consequently, the electric polarization coming from the cycloid spin order below 30 K can be suppressed by external magnetic fields. The magnetic hysteresis loops after cooling in a magnetic field exhibit characteristics of exchange bias below the spin glassy freezing temperature (T_g)∼16 K. The exchange bias field, coercivity field, and remanent magnetization increase with increasing cooling magnetic field. The exchange bias effect is ascribed to the frozen uncompensated spins at the antiferromagnetism/weak ferromagnetism interfaces in the spin-glass like phase.     

Phase transitions and electrical properties of CsH(SO4)0.76(SeO4)0.24 mixed crystals

The study by X-ray diffraction, calorimetry, vibrational and impedance spectroscopy of CsH(SO₄)_0.76(SeO₄)_0.24 new solid solution is presented. Crystals of this composition undergo two phase transitions at T = 333 and 408 K. The last one at 408 K is a superionic-protonic transition (SPT) related to a rapid [HS(Se)O₄⁻] reorientation and fast H⁺ diffusion. A sudden jump in the conductivity plot confirms the presence of this transition. Above 408 K, this high temperature phase is characterized by high electrical conductivity (7 × 10^t-3 Ω⁻ cm⁻¹) and low activation energy (E_a < 0.3 eV).     

Phase transition, structural and electrical properties of Pb(Zn1/3Nb2/3)O3-doped Pb(Ni1/3Nb2/3)O3-PbTiO3 ceramics prepared by solid-state reaction method

Phase pure perovskite (1−x−y)Pb(Ni_1/3Nb_2/3)O₃-xPb(Zn_1/3Nb_2/3)O₃-yPbTiO₃ (PNN-PZN-PT) ferroelectric ceramics were prepared by conventional solid-state reaction method via a B-site oxide mixing route. The PNN-PZN-PT ceramics sintered at the optimized condition of 1185 °C for 2 h exhibit high relative density and rather homogenous microstructure. With the increase of PbTiO₃ (PT) content, crystal structure and electrical properties of the synthesized PNN-PZN-PT ceramics exhibit successive phase transformation. A morphotropic phase boundary (MPB) is supposed to form in (0.9−x)PNN-0.1PZN-xPT at a region of x=32-36 mol% confirmed by X-ray diffraction (XRD) measurement and dielectric measurement. The MPB composition can be pictured as providing a “bridge” connecting rhombohedral ferroelectric (FE) phase and tetragonal one since crystal structure of the MPB composition is similar to both the rhombohedral and tetragonal lattices. Dielectric response of the sintered PNN-PZN-PT ceramics also exhibits successive phase-transition character. 0.64PNN-0.1PZN-0.26PT exhibits broad, diffused and frequency dependent dielectric peaks indicating a character of diffused FE-paraelectric (PE) phase transition of relaxor ferroelectrics and 0.40PNN-0.1PZN-0.50PT exhibits narrow, sharp and frequency independent dielectric peaks indicating a character of first-order FE-PE phase transition of normal ferroelectrics. The FE-PE phase transition of 0.56PNN-0.1PZN-0.34PT is nearly first-order with some diffused character, which also exhibits the largest value of piezoelectric constant d₃₃ of 462pC/N.     

Phase transition and superconductivity of (Ba,Sr,La)2YCu3Oz (z>6.9)

A series of (Ba,Sr,La)₂YCu₃O_z (z>6.9) samples is studied to elucidate the relationship between structure, cation composition and oxygen content. The concentration of La plays an important role in the orthorhombic to tetragonal phase transition. The tetragonal structure is stabilized by increasing oxygen content and decreasing average ionic radius of cations on the Ba site. The phase transition is explained in terms of the random distribution of CuO₅ pyramids in the BaO–CuO_x slab. Superconductivity does not depend significantly on the phase transition.     

Crystallographic study of the phase transition in (Me4P)2ZnBr4

The compound (Me₄P)₂ZnBr₄, a member of the β-K₂SO₄ structure class, undergoes a phase transition at 84°C from the room temperature space group P12₁/c1 to the parent Pmcn structure. The room temperature structure corresponds to a ferrodistortive transition of B_1g symmetry at the zone center. At room temperature, the compound has lattice constants a=9.501(1), b=16.055(2), c=13.127(2) Å and β=90.43(1)°. For the high temperature phase, the orthorhombic cell has dimensions a=9.466(2), b=16.351(3) and c=13.284(2) Å. The structures consist of two crystallographically independent Me₄P⁺ cations and the ZnBr₄²⁻ anions. In the room temperature phase, all three ionic species show substantial displacement from the mirror plane perpendicular to the a-axis that exists in the high temperature phase, as well as rotations out of that plane. The thermal parameters of the cations are indicative of substantial librational motion. Measurements of lattice parameters have been made at 2-5°C intervals over the temperature range 40-140°C. The changes in the lattice constants appear continuous at T_c (within experimental limits) indicating that the phase transition is likely second-order. The a lattice constant shows an anomalous shortening as T_c is approached. Thermal expansion coefficients are calculated from this data. An application of Landau theory is used to derive the temperature dependencies of spontaneous shear strain and corresponding elastic stiffness constants associated with the primary order parameter.     

The bulk modulus of SmFeAs(O0.93F0.07)

The crystal structure of SmFeAs(O_0.93F_0.07) has been investigated under high pressure (up to ∼9 GPa) by means of synchrotron powder diffraction analysis followed by Rietveld refinement. The bulk modulus was calculated (K₀ = 103 GPa) using a 3rd order Birch–Murnaghan equation of state and resulted in quite good agreement with theoretical calculations reported for LaFeAsO. The linear compressibilities β_a and β_c are 2.11(4) and 4.56(7) × 10⁻³ GPa⁻¹, respectively.     

Properties of the solid solution (1−x)Na0.5Bi0.5TiO3-(x)BiFeO3

This study shows that remarkable electric and magnetic properties are encountered within the (1−x)Na_0.5Bi_0.5TiO₃ (NBT)-(x)BiFeO₃ (BF) solid solution. Dual ferroelectric and magnetic properties are observed in the BF-rich part of the solid solution implying intrinsic multiferroic character of the compounds. In addition, a relaxation phenomenon is evidenced within the overall compositional domain of the solid solution. This study emphasizes that in the NBT-rich part, the relaxor behaviour is very similar to that of NBT, while beyond x=0.5, it turns to a different mechanism of relaxation probably induced by the presence of oxygen vacancies resulting from the mixed valence of the iron cations.     

Electronic structure, magnetic and electrical properties of multiferroic PbFe1/2Ta1/2O3

Structural analysis of the synthesized lead iron tantalate, PbFe_1/2Ta_1/2O₃ (PFT) is performed by the refinement of the X-ray diffraction data at room temperature using the GSAS code. Energy dispersive X-ray spectrometry analysis is done to find out the chemical composition. The electronic structure of PFT is calculated by the first principles full potential linearized augmented plane wave method. The spin polarized density of states shows the insulating nature. The magnetic moment of 4.3 μB per Fe ion is obtained from the electronic structure calculation using the GGA+U method and compared with the available experimental data. The electronic structure of the PFT is verified by X-ray photoemission spectroscopy. The dielectric spectroscopy is applied to investigate the electrical properties of PFT in the frequency range from 100 Hz to 1 MHz and in the temperature range from 183 to 253 K. The frequency dependent electrical data are analyzed by conductivity formalism. The relaxation mechanism is explained using the Cole-Cole approach.     

Structural transition and enhanced magnetization in Bi1−xYxFeO3

Bi_1−xY_xFeO₃ (x=0-0.2) powders were prepared to study the effect of Y substitution on their structural and magnetic properties. A structural symmetric breaking from the rhombohedral R3c to orthorhombic Pnma at around x=0.10 was identified across a ferroelectric-paraelectric phase. A parabolic dependence of the magnetization upon substitution was obtained with a maximum at the phase transition boundary and a switching behavior for x=0.20. The composition-driven magnetic structure evolution was proposed to account for the magnetic properties in Bi_1−xY_xFeO₃.     

Improvement of multiferroic and leakage property in monophasic BiFeO3

This paper aims to report that impurity phase free single phase multiferroic BiFeO₃ ceramic can be prepared by critically optimizing the metal ion concentration using slow step sintering schedule at 850 °C for 24 h. Antiferromagnetic character of pure BiFeO₃ is completely changed and ferromagnetic behavior observed with increase of Bi as well as decrease of Fe concentration. It is found that Bi rich (Bi: 1.2) Fe deficient (Fe: 0.8) composition produces single phase rhombohedral structure with space group R3c along with enhanced ferroelectric and ferromagnetic properties. Incorporation of excess bismuth caused structural distortion and expected to compensate Bi loss during high temperature sintering. On the other hand, iron deficient helps the formation of Fe³⁺ state, which hinders the creation of oxygen vacancies and also favors the reduction of leakage current. Structural distortion in BiFeO₃ changes Fe-O-Fe bond angle or spin order, destructs the spin cycloid and releases a locked magnetization.     

Metal-like to insulator transition in Lu3Fe5O12

Polycrystalline Lu₃Fe₅O₁₂, prepared using the solid state reaction method, has Fe in the mixed valence state as inferred from the X-ray photoelectron spectroscopy. A spectral change in the impedance plot at 343 K is attributed to metal-like to insulator transition (MIT), which is analyzed in terms of localized and delocalized _eg$e_g$ electrons. The change in the slope at 343 K in the DC conductivity plot also proves the MIT. The dependence of Z^′${\mathrm{Z}}^{\prime }$ on temperature and Z^″${\mathrm{Z}}^{″}$ on frequency clearly substantiates the presence of localized electrons up to 343 K and delocalized electrons above 343 K.     

Weak field magnetic transition in Tb3Fe5O12

A jump like magnetic transition is observed at relatively weak field in Tb₃Fe₅O₁₂ when the magnetic field is applied along the hard axis and no transition is observed with the field applied along the easy axis. We believe that this evolution is related to the ”Umbrella” type magnetic structure known to exist in Tb₃Fe₅O₁₂ at low temperatures.