Ab initio study of cubic complex Bi2CrCuO6 perovskite

We report a detailed calculation of the structural and electronic properties for the cubic complex Bi₂CrCuO₆ perovskite material by density functional theory. The exchange-correlation potential was included through the generalized gradient approximation. From the adjusting of Murnaghan state equation to the energy as a function of volume data, we obtain an ideal lattice parameter of 7.763 Å. The density of states study was carried out considering the two spin polarizations. Results reveal that this material behaves as a conductor to the spin-down polarization and evidence a semiconductor tendency to the spin-up configuration. This tendency to the half-metallicity character is corroborated by the integer number of magnetic moment (3.0 μ_B), which is attributed to the Cr-spin-up orbital contribution.     

Effect of magnetic annealing on magnetization of BiFeO3 ceramics

The effect of magnetic annealing treatment on the magnetization of multiferroic BiFeO₃ was studied systematically. A series of pelletized nano-sized BiFeO₃ powders were annealed at high temperature under different magnetic fields. Typical ferromagnetic hysteresis loops were obtained at room temperature of the ceramics which were derived from ferromagnetic BiFeO₃ precursors. On the other hand, antiferromagnetic behaviors were observed in other samples synthesized from nonmagnetic precursors. The enhanced magnetic properties were ascribed to the magnetic anisotropy which was induced by the strong magnetic fields. This work indicates that the strong magnetic annealing method is an alternative approach to tuning the magnetic properties of high performance multiferroic materials with canted antiferromagnetic ordering.     

Magnetic properties of Ni-substituted BiFeO3

BiFe_1−xNi_xO₃ ceramic powders with x up to 0.10 have been prepared by the sol-gel technique. The band gap of BiFeO₃ is 2.23 eV, and decreases to 2.09 eV for BiFe_0.95Ni_0.05O₃ and BiFe_0.90Ni_0.10O₃. The Mössbauer spectra show sextet at room temperature, indicating the magnetic ordering and the presence of only Fe³⁺ ions. Superparamagnetism with blocking temperature of 31 K for BiFe_0.95Ni_0.05O₃ and 100 K for BiFe_0.90Ni_0.10O₃ was observed. Enhanced magnetization at room temperature have been observed (1.0 emu/g for BiFe_0.95Ni_0.05O₃ and 2.9 emu/g for BiFe_0.90Ni_0.10O₃ under magnetic field of 10,000 Oe), which is one order larger than that of BiFeO₃ (0.1 emu/g under magnetic field of 10,000 Oe). The enhanced magnetization was attributed to the suppression of the cycloidal spin structure by Ni³⁺ substitution and the ferrimagnetic interaction between Fe³⁺ and Ni³⁺ ions.     

Ferroelectric,magnetoelectric and photoelectric properties of BiFeO3 /LaNiO3 heterostructure

BiFeO₃/LaNiO₃ (BFO/LNO) heterostructure was fabricated on quartz substrate via RF sputtering method. The microstructure and surface morphology of the BFO/LNO heterostructure was demonstrated. BFO layer shows good ferroelectric and weak ferromagnetic characters at room temperature. The dielectric constants of the heterostructure under an applied magnetic field 1.2T and zero field are both decreased with increasing frequency at room temperature and the dielectric constant under the applied magnetic field is larger, which is attributed to the coupling between the electric and magnetic dipoles, and further demonstrated in the framework of the Ginzburg-Landau theory for second phase transition. Additionally, the photoconductivity of the heterostructure under blue-laser illumination was observed, and the photoconductivity increase with the enhanced power of the blue-laser.     

First-principles study of the （001） surface of cubic PbHfO3 and BaHfO3

Using first-principles techniques,we investigate the(001) surfaces of cubic PbHfO3(PHO) and BaHfO3(BHO) terminated with both AO(A=Pb and Ba) and HfO2.Surface structure,partial density of states,band structure,and surface energy are obtained.The BaO surface is found to be similar to its counterpart in BHO.For the HfO2-terminated surface of cubic PHO,the largest relaxation appears on the second-layer atoms but not on the first-layer ones.The analysis of the structure relaxation parameters reveals that the rumpling of the(001) surface for PHO is stronger than that for BHO.The surface thermodynamic stability is explored,and it is found that both the PbO-and the BaO-terminated surfaces are more stable than the HfO2-terminated surfaces for PHO and BHO,respectively.The surface energy calculations show that the(001) surface of PHO is more easily constructed than that of BHO.     

Structural and magnetic properties of double-perovskite Ba2MnMoO6 by density functional theory

Perovskite-like materials which include magnetic elements have relevance due to the technological perspectives in the spintronics industry. In this work, we report the studies of Ba₂MnMoO₆ material by using the density functional theory. The interchange-correlation potential was included through the generalized gradient approximation. Our structural calculations are in agreement with the experimental results which show that the material crystallizes in the 225 space group (Fm3¯m) and has a lattice parameter of about 8070 Å. The density of states study was carried out by considering the up and down spin orientations. Results show that Ba₂MnMoO₆ has a conductor behavior due to dominant Mn spin-up and Mo spin-down contributions. The magnetic moment was calculated to be 2.9 μ_B.     

Magnetoelectric properties of Mn-substituted BiFeO3 thin films with a TiO2 barrier

Multiferroic thin films with the general formula TiO₂/BiFe_1−xMn_xO₃ (x=0.00, 0.05, 0.10 and 0.15) (TiO₂/BFMO) were synthesized on Au/Ti/SiO₂/Si substrates using a chemical solution deposition (CSD) method assisted with magnetron sputtering. X-ray diffraction analysis shows the thin films contained perovskite structures with random orientations. Compared with BFMO films, the leakage current density of the TiO₂/BFMO thin films was found to be lower by nearly two orders of magnitude, and the remnant polarizations were increased by nearly ten times. The enhanced ferroelectric properties may be attributed to the lower leakage current caused by the introduction of the TiO₂ layer. The J-E characteristics indicated that the main conduction mechanism for the TiO₂/BFMO thin film was trap-free Ohmic conduction over a wide range of electric fields (0-500 kV/cm). In addition, ferromagnetism was observed in the Mn doped BFO thin films at room temperature. The origin of ferromagnetism is related to the competition between distortion of structure and decrease of grain size and decreasing net magnetic moment in films due to Mn doping.     

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.     

Electronic and thermal properties of B2-type AlRE intermetallic compounds: A first principles study

The ground state electronic structure and thermal properties of B₂-type intermetallic compounds AlRE (RE: Pm, Sm, Eu, Tb, Gd and Dy) have been studied using a self-consistent tight-binding linear muffin-tin orbital (TB-LMTO) method at ambient as well as at high pressure. These compounds show metallic behavior under ambient condition. The band structure, total energy, density of states and ground state properties like lattice parameter, bulk modulus are calculated in the present work. The Debye-Grüneisen model is used to calculate the Debye temperature and the Grüneisen constant. The calculated results are in good agreement with the reported experimental and other theoretical results. The variation in the Debye temperature with pressure has also been reported. We present a detailed analysis of the role of f electrons of RE in the AlRE system.     

Electrical behavior of high resistivity Ce-doped BiFeO3 multiferroic

Bi_1+xCe_xFeO₃ (Ce–BFO) for x=0, 0.05, 0.1, and 0.15 monophasic ceramic samples were successfully synthesized by conventional solid-state reaction routes. The influences of Ce doping on structural, dielectric, ferroelectric, leakage current and capacitive properties of BiFeO₃ ceramics were investigated intensively. At higher concentrations of x (x=0.1 and 0.15) the samples showed good crystallinity with almost impurity free phases. No structural phase transformation took place after partial doping of Ce ions and all ceramic bulk samples remain in their rhombohedral structure with space group R3c. The dielectric behavior of the samples improved significantly and the ferroelectric hysteresis loops changed their shape from rounded to a strongly nonlinear typical ferroelectric feature mainly originating from the domain switching and became enhanced with increase in doping concentration of cerium (Ce). Experimental results also suggested that partial doping of higher valence, smaller ionic radius Ce ions in BiFeO₃ forces the reduction of oxygen vacancies, resulting in a great suppression of leakage current. It is found that the sharp capacitance peak/discontinuity present in the C–V characteristics of Ce–BFO for different Ce doping concentrations is directly associated with the polarization reversal. Incorporation of excess bismuth in the presence of Ce in BiFeO₃ is expected to compensate Bi loss during high temperature sintering and caused structural distortion which also favors enhancement of ferroelectric properties in Ce-doped BFO.     

Effects of magnetic annealing on structure and multiferroic properties of pure and dysprosium substituted BiFeO3

In this work, the effects of magnetic annealing on crystal structure and multiferroic properties of BiFeO₃ and Bi_0.85Dy_0.15FeO₃ have been investigated. It is found that the X-ray diffraction patterns of pure BiFeO₃ samples are obviously broadened after magnetic annealing, whereas those of Bi_0.85Dy_0.15FeO₃ samples are almost unchanged. Magnetic field annealing did not affect the magnetic properties of these two kinds of samples much. However, ferroelectric properties of the two materials exhibited different behaviors after magnetic field annealing. For pure BiFeO₃ samples, the remnant polarizations (P_r) are suppressed; in contrast, for Bi_0.85Dy_0.15FeO₃ samples, P_r is greatly enhanced. Possible mechanisms for the effects of magnetic field annealing have been discussed.     

Magnetic,ferroelectric and magnetoelectric properties of Ba-doped BiFeO3

Bi_1–xBa_xFeO₃ (0.0≤x≤0.25) ceramics are prepared by chemical synthesis route. At room temperature, antiferromagnetic BiFeO₃ is converted to ferromagnetic on doping Ba. A large change in the magnetization is observed around 370 °C which is close to the Neel temperature (T_N) of parent compound. Another magnetic transition is also observed near 600 °C. Spin canting or impurity phase could be a probable reason for the origin of ferromagnetism in both cases. Ferroelectric and magnetic transitions of the compounds shift towards higher temperature with Ba-doping concentration. Anomaly in the dielectric constant is also observed near the T_N of BiFeO₃. The composition x=0.15 shows the maximum magnetic moment at room temperature while better fatigue resistance and maximum magnetoelectric coupling are observed for x=0.20 composition.     

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.     

Theoretical studies of structural and magnetic properties of cubic perovskites PrCoO3 and NdCoO3

The structural and magnetic properties of cubic perovskites, PrCoO₃ and NdCoO₃, are studied using the full potential linearized augmented plane wave (FP-LAPW) method within the frame work of density functional theory (DFT). The structural parameters are also investigated by analytical techniques. The calculated structural parameters are consistent with the experimental results. The strong hybridization of the O-2p, Co-3d and Pr/Nd-4 f states around the Fermi level reveals that these compounds are metallic. It is also found that the origin of ferromagnetism in these compounds is double-exchange interaction between Co-3d states via O-2p states (Co-O-Co).     

Defect driven multiferroicity in Gd doped BiFeO3 at room temperature

This paper reports that defect driven magnetism can be obtained at room temperature by optimizing metal ion concentration in bismuth ferrite (BFO) following our novel slow step solid state sintering route. We observed a clean signature of enhanced multiferroic behavior in Gd doped bismuth ferrite (Gd-BFO) bulk ceramics at room temperature (RT). Bismuth rich iron deficient Gd-BFO ceramics were prepared by solid state route through slow step sintering schedule at 850 °C. At particular composition, (Bi_1.2Gd_0.1Fe_0.8O₃), this materials completely transform from rhombohedral R3c to orthorhombic Pn2₁a space group. We emphasized that excess bismuth is expected to act as point defects and occupy interstitials positions, which in turn interact by oxygen vacancies. These defects are likely to promote defect driven ferromagnetism in BFO system. Incorporation of Gd in presence of excess bismuth in BFO enhanced both spin and electric polarization at room temperature. We also infer that Gd substitution in BFO is likely to suppress spiral spin modulation, which also favors ferromagnetism in Gd-BFO.     

Epitaxial thin films of (Bi0.9La0.1)2NiMnO6 obtained by pulsed laser deposition

Bulk Bi₂NiMnO₆ has been shown to be ferromagnetic and ferroelectric. Here, we report a systematic study of the influence of the deposition conditions on the growth of (Bi_0.9La_0.1)₂NiMnO₆ thin films onto (0 0 1) SrTiO₃ substrates by pulsed laser deposition. Oxygen pressure and substrate temperature have been varied from 0.3 to 0.6 mbar and 600 to 660 °C, respectively. Whereas it is found that single-phase and epitaxial films can be obtained in a relatively broad oxygen pressure range, the temperature window, centred on 620 °C, is extremely narrow. Films of low roughness, about 1 unit cell, have been obtained. It is found that the magnetisation of the films, which are ferromagnetic with Curie temperatures about 100 K, is lower than the expected theoretical value, which might be attributed to an incomplete Ni-O-Mn long-range ordering.     

Structural,thermal, electrical and magnetic properties of pure and 50% La doped BiFeO3 ceramics

Polycrystalline ceramic samples of pure and 50% La substituted BiFeO₃ have been prepared by standard solid state reaction method using high purity oxides and carbonates. The formation of the single phase compound as well as its chemical analysis has been checked by X-ray diffraction and energy dispersive X-ray microanalysis (EDAX) techniques. A better agreement between observed and calculated X-ray powder diffraction patterns was obtained by performing the Rietveld refinement with a structural model using the non-centrosymmetric space group R3c. The lattice parameters in both the cases have been refined but the over-all structure remains the same. The microstructural studies have been carried out using scanning electron microscopy (SEM). Modulated differential scanning calorimetry (MDSC) has been used to detect the Neel/transition temperature in the compounds. The activation energies calculated from log σ vs 1/T curve are 0.81 eV and 1.13 eV respectively. Vibrating sample magnetometer (VSM) has been used to study the magnetic behaviour of the compounds. It has been observed that by 50% La substitution the insulating behaviour of the material has been improved and showing the antiferromagnetic to weak ferromagnetic behaviour.     

A study of electronic structure and lattice dynamics of CoSb3 skutterudite

The novel filled skutterudite materials have attracted much interest in recent years and experimental studies have revealed that electrical properties (electrical conductivity and Seebeck coefficient) in these materials are dominated by their electronic structure while the effective suppression of thermal conductivity is mainly determined by their lattice dynamics. To clarify the relationship between microstructure and properties in further, we report a systematic study of electronic structures and lattice dynamics of CoSb₃ in this paper using linearized augmented plane waves based on the density functional theory of first principles. By calculating band structure and partial density of states (PDOS), effects of electronic structures of CoSb₃ on electrical properties were investigated. Based on the calculated results of phonon dispersions and phonon density of states of CoSb₃, lattice dynamics of CoSb₃ (heat capacity, Debye temperature, mean free path and lattice thermal conductivity) are discussed in detail. The calculated results are excellently consistent with other work and experimental data.     

First-principles calculations of electronic and magnetic properties of Ni3Pd and Pd3Ni

Results of first-principles calculations of the electronic structure for the ordered compounds Ni₃Pd and Pd₃Ni at the equilibrium volume with L1₂ structure reveal that the Ni atoms carry an enhanced moment and that an induced moment is found on the Pd atoms. The Ni moment is higher in Pd₃Ni, whereas the Pd moment differs only slightly for these compounds. Large bulk moduli are found (341.34 GPa for Ni₃Pd and 314.35 GPa for Pd₃Ni), and an abrupt collapse of the magnetic moment is observed in Pd₃Ni under lattice compression. The results indicate good conductivity for these compounds as well as half-metallicity for Ni₃Pd.     

Structural and optical properties of low temperature synthesized Nanostructured BiFeO3 thin films

Nanostructured bismuth ferrite (BiFeO₃) thin films were deposited on glass substrate by the sol-gel process. The as-fired film at 250 °C was found to be amorphous crystallizing to pure rhombohedral phase after annealing at 450 °C for 2 h in air. The XRD pattern shows that the sample is polycrystalline in nature. The average grain size of the film calculated from the XRD data was found to be 16 nm. The as-fired film show high transmittance that decreases after crystallization. The absorption edge of the films was found to be sharper and shifting towards the lower energy as the annealing temperature increases. The optical energy band gaps of the amorphous and crystalline films were found to be 2.63 and 2.31 eV, respectively. The refractive indices of the amorphous and crystalline films were 2.05 and 2.26, respectively.