Can the ferroelectric soft mode trigger an antiferromagnetic phase transition?

Type-II multiferroics, where spin interactions induce a ferroelectric polarization, are interesting for new device functionalities due to large magnetoelectric coupling. We report on a new type of multiferroicity in the quadruple-perovskite BiMn₃Cr₄O₁₂, where an antiferromagnetic phase is induced by the structural change at the ferroelectric phase transition. The displacive nature of the ferroelectric phase transition at 125 K, with a crossover to an order-disorder mechanism, is evidenced by a polar soft phonon in the THz range and a central mode. Dielectric and pyroelectric studies show that the ferroelectric critical temperature corresponds to the previously reported Néel temperature of the Cr³⁺ spins. An increase in ferroelectric polarization is observed below 48 K, coinciding with the Néel temperature of the Mn³⁺ spins. This increase in polarization is attributed to an enhanced magnetoelectric coupling, as no change in the crystal symmetry below 48 K is detected from infrared and Raman spectra.     

Synthesis and thermodynamic stability of multiferroic BiFeO3

Ceramic BiFeO₃ samples were prepared by the sol gel combustion method using urea as fuel. The obtain powders were thermal treated at different temperatures (300-840  °C) and times (1-64  h) to investigate the best synthesis conditions of the material. The resulting materials were analysed by TGA, FTIR, SEM/EDS and XRD. Rietveld analysis was applied to the diffraction data. The temperature and time of the heat treatment are critical for a high BiFeO₃ phase content. Thermal treatment of 1  h at 600  °C yielded 99% molar of the BiFeO₃ phase with a mean particle size of 120  nm. Upper or lower calcinations temperatures yielded higher content of the secondary phases Bi₂Fe₄O₉ and Bi₂₅FeO₃₉. Further heat treatment in air or in argon, up to 64  h, induces a decomposition of the BiFeO₃ phase according to the reaction 49 BiFeO₃ BiFeO₃ → 12 Bi₂Fe₄O₉ + Bi₂₅FeO₃₉ pointing out that BiFeO₃ is not thermodynamically stable at 600  °C. The BiFeO₃ decomposition follows Avrami-Erofeev law with a slope of 1 indicating a one-dimensional kinetics.     

Exploring multiferroicity in BiFeO3 - NaNbO3 thermistor electroceramics

The BiFeO₃ –NaNbO₃ electroceramics, synthesized by the ceramic method, are studied aiming to obtain materials with a well-defined thermistor response coexisting with a relevant magnetic response. XRD data and Raman analysis reveal a structural transition as a function of composition. Compositional features explored from ICP, XPS and EDS measurements, suggest compositional heterogeneity leading to a cluster-type scenario implying NNO-rich and BFO-rich regions in the samples. Impedance spectroscopy data reveal the development of a PTCR thermistor response for x ≥ 0.5 near room temperature. The x = 0.9 ceramic shows resistivity changes of about six orders of magnitude in the first thermal cycle and maximum permittivity values of ∼ 10⁵, much higher than those previously reported for BFO-doped ceramics. Magnetization data are interpreted in terms of the stabilization of superparamagnetic clusters. The response displayed by the x = 0.9 ceramic makes it a promising multifunctional material for device applications.     

Structural properties of multiferroic 0.5BiFeO3–0.5Pb(Fe0.5Nb0.5)O3 solid solution

Magnetoelectric multiferroics are very promising materials because of their practical applications and fundamental interests. The most widely studied magnetoelectric oxides are ABO₃ perovskites. In the paper structural properties of BiFeO₃ and Pb(Fe_0.5Nb_0.5)O₃ solid solution are described. The material crystallizes in rhombohedral R3c crystal structure which parameters are presented. Mössbauer spectroscopy was used to study local changes in an iron environment due to Fe/Nb substitution and hyperfine interaction parameters of different local surroundings of iron atoms are presented. The random distribution of B-site sublattice cations was confirmed. Ab initio calculations of the studied solid solution were conducted and theoretical crystal structure parameters were compared with the experimental data. The theoretical magnetic and electric properties are discussed. The local iron magnetic moments were estimated and their dependence on the local surrounding changes is shown. The calculated electrons densities and Bader's topological analysis were used to describe chemical bonding properties.     

Correlation between structure,dielectric and multiferroic properties of lead free Ni modified BaTiO3 solid solution

Present study highlights the influence of Ni doping on the structural, optical, dielectric, ferroelectric and magnetic properties of nanocrystalline BaTi_1-xNi_xO₃ (0 ≤ x ≤ 0.06) ceramics synthesized by sol-gel auto combustion process. Phase identification and crystal structure are examined through Rietveld refinement analysis that ensures mono-phase nature with tetragonal crystal structure in P4mm space group. The observed variation in the structural parameters viz. lattice constants, unit cell volume, bond lengths (Ti-O) and bond angles (Ti-O-Ti) are the direct evidence of distortion produce in the unit cell under the effect of Ni doping. The FTIR studies confirm perovskite structure and presence of stretching/bending vibrations of the various bands present in the samples. The optical properties divulge a minor alteration in optical bandgap under the influence of Ni content. Dielectric studies reveal higher value of the dielectric constant for pristine sample in the low frequency region, but its value decreases on Ni doping. The dielectric response, analyzed through UDR model, exhibits deviation from linear behavior at higher frequencies. Ferroelectric measurements demonstrate that the pristine sample has higher values of remnant polarization (P_r) and maximum polarization (P_m) which decrease linearly with the increase in Ni doping. Magnetic hysteresis loops at room temperature establish a weak ferromagnetic nature of the samples that arises due to the carrier-mediated exchange interactions with smaller values of magnetic parameters. These investigations ensure that the ferromagnetism can be induced in BaTiO₃ by appropriate doping of Ni ions, which may find their potential use in the field of multiferroics.     

Role of Ni–Co co-substitution in improving electrical and dielectric properties of La-based multiferroics nanomaterials

The synthesis of a material having ferroelectric and ferromagnetic properties in the same phase is a challenging task. In the present work, lanthanum based multiferroic materials, with composition La_1−xCo_xFe_1−yNi_yO₃ (where, x=0.0–0.5 and y=0.0–1.0), have been synthesized via sol–gel auto-combustion method. The phase of the synthesized materials was confirmed by the X-ray diffraction (XRD) analysis, while the surface morphology and particle size were determined by the scanning electron microscopy (SEM) analysis. The DC electrical resistivity and activation energy were observed to increase from 2.14×10⁷ to 3.04×10¹⁰ Ω cm and 0.64 to 0.77 eV, respectively with the increase in concentration of substituents. The drift mobility decreases from 3.27×10⁻¹³ to 2.80×10⁻¹⁶ cm² V⁻¹ S⁻¹. The dielectric constant, dielectric loss and dielectric loss factor decrease with the increase in frequency (1 MHz to 3 GHz) and Ni–Co content as well. The electrical and dielectric results are in good agreement with each other. The increase in electrical resistivity and decrease in dielectric parameters make these materials suitable for applications in microwave devices.     

Investigation of structural,optical, dielectric and magnetic studies of Mn substituted BiFeO3 multiferroics

A series of Mn doped BiFeO₃ with composition BiMn_xFe_1−xO₃ (x = 0.0, 0.025, 0.05, 0.075, 0.1) was synthesized via a citrate precursor method. Structural, morphological, optical, electrical and magnetic properties were investigated by using various measurement techniques. XRD patterns confirmed that the materials possess distorted rhombohedral structure with space group R3c. Average crystallite size was found to be in the range 18–36 nm. A decrease in the value of lattice parameters has been observed due to contraction of unit cell volume with Mn doping. Higher tensile strain for the prepared nanoparticles was observed in Hall-Williamson Plot. Field Emission Scanning Microscopy (FESEM) showed the spherical, uniform, dense nanoparticles in the range 80–200 nm. Reduction in grain size was observed which may be due to suppression of grain growth with Mn doping. FTIR studies reported two strong peaks at 552 cm⁻¹ and 449 cm^-1 which confirmed the pervoskite structure. Dielectric properties were studied by measuring the dielectric constant and loss in the frequency range 1 kHz to 1 MHz. Magnetic hysteresis loop showed the retentivity (M_r) increasing from 0.0514 emu/g of BFO to 0.0931 emu/g of 10% Mn doping. Coercivity was found to increase upto 0.0582 T for 5% Mn doping and then reduced to 0.0344 T for 7.5% Mn doping. Saturation magnetization was observed to increase from 0.6791 emu/g for BFO to 0.8025 emu/g for 7.5% and then reduced to 0.6725 emu/g for 10% Mn doping in BFO. Improvement in dielectric and magnetic properties makes this material as a promising candidate for multifunctional device applications.     

Structural transformation and multiferroic properties of Sm and Ti co-doped BiFeO3 ceramics with Fe vacancies

Sm and Ti co-doped BiFeO₃ (BFO) ceramics with Fe vacancies—Bi_0.86Sm_0.14FeO₃, Bi_0.86Sm_0.14Fe_0.99Ti_0.01O₃, and Bi_0.86Sm_0.14Fe_0.9Ti_0.05O₃—were prepared by a solid-state method using a rapid liquid process. X-ray diffraction indicated that all samples exhibited a rhombohedral structure with a minor secondary phase. The structural transformation from a rhombohedral (space group: R3c) to orthorhombic structure (space group: Pnma) was observed in the sample of Bi_0.86Sm_0.14Fe_0.9Ti_0.05O₃, which was also confirmed by Raman scattering spectra. Microstructural investigations with scanning electron microscopy showed a reduction in grain size with doping of BFO. The dielectric loss of Bi_0.86Sm_0.14Fe_0.9Ti_0.05O₃ reaches 0.05 (at 100 Hz) owing to the introduction of Ti and Fe vacancies. Ferroelectromagnetic measurements revealed the existence of ferroelectricity with a remanent polarization of 0.24 µC/cm² in Bi_0.86Sm_0.14FeO₃, paraelectricity in Bi_0.86Sm_0.14Fe_0.9Ti_0.05O₃, and weak ferromagnetism with a remanent magnetization of 0.2 emu/g in Bi_0.86Sm_0.14Fe_0.99Ti_0.01O₃. The two composition-driven phases exist simultaneously and the different coercive field might be related to the jumps in the ferromagnetic hysteresis loops. Both the ferroelectric and magnetic properties were shown to correlate with the composition-driven structural evolution.     

Magnetic and electrical properties of single-phase multiferroic (1-x)Pb(Zr0.52Ti0.48)O3–xPb(Fe0.5Nb0.5)O3 thin films prepared by sol-gel route

Single-phase multiferroic (1-x)Pb(Zr_0.52Ti_0.48)O₃-xPb(Fe_0.5Nb_0.5)O₃ (0≤x≤0.5) thin films were synthesized by sol-gel route and characterized to understand their structural, electrical, and magnetic properties. The films were thermally treated by conventional furnace (CFA) and rapid thermal annealing (RTA). A pyrochlore-free perovskite phase is stabilized only by RTA in samples with high Fe³⁺/Nb⁵⁺ content. The films displayed excellent dielectric and ferroelectric properties in the whole concentration range, with saturated hysteresis loops and remanent polarization values of ～15μC/cm². Films with x>0.3 showed ferromagnetic behavior at room temperature. Consequently, the multiferroic behavior in the films occurs in a different concentration range than that observed in bulk ceramics. The origin of the weak ferromagnetism is discussed.     

Multiferroic composite for combined detection of static and alternating magnetic fields

Magneto-electric (ME) effects in bi-layer multiferroics consisting of single crystal hexagonal SrAl_xFe_12 − xO₁₉ ferrites (hexaferrites, where x = 0, 0.8, 1.2) and PbZrTiO₃ (PZT) have been studied. The main objective of the study was to determine the effect of the Al doping concentration on the ME coupling. We experimentally demonstrate that the Al doping improves dramatically the magnetically induced ME voltage. Moreover, our data indicate that the ME response is a linear function of both ac and dc applied magnetic fields. This is in contrast to previously reported multiferroic laminates that show a non-linear magneto-electric induced voltage as a function of the applied dc magnetic field. The multiferroic structures reported in this work have therefore enhanced functionality because they can linearly operate as a dual ac/dc magnetic field sensors.