Co-existence of tetragonal and monoclinic phases and multiferroic properties for x <= 0.30 in the (1-x)Pb(Zr0.52Ti0.48)O-3-(x)BiFeO3 system

Compositions with x <= 0.30 in the system (1- x)Pb(Zro(0.52)Ti(0.48))O-3-(x)BiFeO3 were synthesized by sol-gel method. Rietveld analysis of X-ray diffraction data reveals tetragonal structure (P4mm) for x <= 0.05 and monoclinic (Cm) phase along with the existence of tetragonal phase for 0.10 <= x <= 0.25 and monoclinic phase for x = 0.30. Transformation of E(2TO) and E + B1 vibrational modes in the range 210-250 cm(-1) (present for x <= 0.25) into A' + A `' modes at similar to 236 cm(-1) for x = 0.30, and occurrence of new vibrational modes A' and A `' in Raman spectra for x >= 0.10 unambiguously support the presence of monoclinic phase. Occurrence of remnant polarisation and enhanced magnetization with concentration of BiFeO3 indicates superior multiferroic properties. Variation of magneto-capacitance with applied magnetic field is a strong evidence of magneto-electric multiferroic coupling in these materials. (C) 2014 Elsevier B.V. All rights reserved.

Large magnetoelectric coupling in nanoscale BiFeO3 from direct electrical measurements

We report the results of direct measurement of remanent hysteresis loops on nanochains of BiFeO3 at room temperature under zero and ∼20 kOe magnetic field. We noticed a suppression of remanent polarization by nearly ∼40% under the magnetic field. The powder neutron diffraction data reveal significant ion displacements under a magnetic field which seems to be the origin of the suppression of polarization. The isolated nanoparticles, comprising the chains, exhibit evolution of ferroelectric domains under dc electric field and complete 180 switching in switching-spectroscopy piezoresponse force microscopy. They also exhibit stronger ferromagnetism with nearly an order of magnitude higher saturation magnetization than that of the bulk sample. These results show that the nanoscale BiFeO3 exhibits coexistence of ferroelectric and ferromagnetic order and a strong magnetoelectric multiferroic coupling at room temperature comparable to what some of the type-II multiferroics show at a very low temperature.

Temperature-dependent infrared reflectivity studies of multiferroic TbMnO3: Evidence for spin-phonon coupling

We have measured near normal incidence far-infrared (FIR) reflectivity spectra of a single crystal of TbMnO3 from 10 K to 300 K in the spectral range of 50 cm(-1)-700 cm(-1). Fifteen transverse optic (TO) and longitudinal optic (LO) modes are identified in the imaginary part of the dielectric function epsilon(2)(omega) and energy loss function Im(-1/epsilon(omega)), respectively. Some of the observed phonon modes show anomalous softening below the magnetic transition temperature T-N (similar to 46 K). We attribute this anomalous softening to the spin-phonon coupling caused by phonon modulation of the superexchange integral between the Mn3+ spins. The effective charge of oxygen (Z(O)) calculated using the measured LO-TO splitting increases below TN.

Hybrid Multiferroic Nanostructure with Magnetic−Dielectric Coupling

The development of methods to economically synthesize single wire structured multiferroic systems with room temperature spin−charge coupling is expected to be important for building next-generation multifunctional devices with ultralow power consumption. We demonstrate the fabrication of a single nanowire multiferroic system, a new geometry, exhibiting room temperature magnetodielectric coupling. A coaxial nanotube/nanowire heterostructure of barium titanate (BaTiO3, BTO) and cobalt (Co) has been synthesized using a template-assisted method. Room temperature ferromagnetism and ferroelectricity were exhibited by this coaxial system, indicating the coexistence of more than one ferroic interaction in this composite system

Coupling of magnetic, strain and electric polarization fields in the structure of multiferroic material

The comprehensive study on the coupling of magnetism, electrical polarization and the crystalline lattice with the off-stoichiometric effects in self-doped multiferroic hexagonal h-LuMnxO3±δ (0.92≤x≤1.12) ceramic oxides was carried out for the PhD work. There is a complex coupling of the three ferroic degrees. The cancelation of the magnetic moments of ions in the antiferromagnetic order, electric polarization with specific vortex/antivortex topology and lattice properties have pushed researchers to find out ways to disclose the underlying physics and chemistry of magneto-electric and magneto-elastic couplings of h-RMnO3 multiferroic materials. In this research work, self-doping of Lu-sites or Mn-sites of h-LuMnxO3±δ ceramics prepared via solid state route was done to pave a way for deeper understanding of the antiferromagnetic transition, the weak ferromagnetism often reported in the same crystalline lattices and the ferroelectric properties coupled to the imposed lattice changes. Accordingly to the aim of the PhD thesis, the objectives set for the sintering study in the first chapter on experimental results were two. First, study of sintering off-stoichiometric samples within conditions reported in the bibliography and also extracted from the phase diagrams of the LuMnxO3±δ, with a multiple firings ending with a last high temperature step at 1300ºC for 24 hours. Second, explore longer annealing times of up to 240 hours at the fixed temperature of 1300 ºC in a search for improving the properties of the solid solution under study. All series of LuMnxO3±δ ceramics for each annealing time were characterized to tentatively build a framework enabling comparison of measured properties with results of others available in literature. XRD and Rietveld refinement of data give the evolution the lattice parameters as a function to x. Shrinkage of the lattice parameters with increasing x values was observed, the stability limit of the solid solution being determined by analysis of lattice parameters. The evolution of grain size and presence of secondary phases have been investigated by means of TEM, SEM, EDS and EBSD techniques. The dependencies of grain growth and regression of secondary phases on composition x and time were further characterized. Magnetic susceptibility of samples and magnetic irreversibility were extensively examined in the present work. The dependency of magnetic susceptibility, Neel ordering transition and important magnetic parameters are determined and compared to observation in other multiferroics in the following chapter of the thesis. As a tool of high sensitivity to detect minor traces of the secondary phase hausmannite, magnetic measurements are suggested for cross-checking of phase diagrams. Difficulty of previous studies on interpreting the magnetic anomaly below 43 K in h-RMnO3 oxides was discussed and assigned to the Mn3O4 phase, with supported of the electron microscopy. Magneto-electric coupling where AFM ordering is coupled to dielectric polarization is investigated as a function of x and of sintering condition via frequency and temperature dependent complex dielectric constant measurements in the final chapter of the thesis. Within the limits of solid solubility, the crystalline lattice of off-stoichiometric ceramics was shown to preserve the magneto-electric coupling at TN. It represents the first research work on magneto-electric coupling modified by vacancy doping to author’s knowledge. Studied lattices would reveal distortions at the atomic scale imposed by local changes of x dependent on sintering conditions which were widely inspected by using TEM/STEM methods, complemented with EDS and EELS spectroscopy all together to provide comprehensive information on cross coupling of distortions, inhomogeneity and electronic structure assembled and discussed in a specific chapter. Internal interfaces inside crystalline grains were examined. Qualitative explanations of the measured magnetic and ferroelectric properties were established in relation to observed nanoscale features of h-LuMnxO3±δ ceramics. Ferroelectric domains and topological defects are displayed both in TEM and AFM/PFM images, the later technique being used to look at size, distribution and switching of ferroelectric domains influenced by vacancy doping at the micron scale bridging to complementary TEM studies on the atomic structure of ferroelectric domains. In support to experimental study, DFT simulations using Wien2K code have been carried out in order to interpret the results of EELS spectra of O K-edge and to obtain information on the cation hybridization to oxygen ions. The L3,2 edges of Mn is used to access the oxidation state of the Mn ions inside crystalline grains. In addition, rehybridization driven ferroelectricity is also evaluated by comparing the partial density of states of the orbitals of all ions of the samples, also the polarization was calculated and correlated to the off-stoichiometric effect.

A Raman study of multiferroic LuMnO3

Magnetic and dielectric measurements confirm the multiferroic nature of LuMnO3. Raman spectra of LuMnO3 have been recorded in the 77-800 K range covering both the antiferromagnetic transition at 90 K and the ferroelectric-paraelectric transition at 750 K. The changes in the phonon modes frequencies and band-widths indicate the presence of phonon-spin coupling in the antiferromagnetically ordered phase. The ferroelectric-paraelectric transition is accompanied by the broadening and disappearance of many of the phonon modes. Some of the phonon modes also show anomalies at the ferroelectric transition.

Raman evidence for orbiton-mediated multiphonon scattering in multiferroic TbMnO3

Temperature-dependent Raman spectra of TbMnO3 from 5 to 300 K in the spectral range of 200-1525 cm(-1) show five first-order Raman allowed modes and two high frequency modes. The intensity ratio of the high frequency Raman band to the corresponding first-order Raman mode is nearly constant and high (similar to 0.6) at all temperatures, suggesting an orbiton-phonon mixed nature of the high frequency mode. One of the first-order phonon modes shows anomalous softening below T-N (similar to 46 K), suggesting a strong spin-phonon coupling.

Charge-order driven multiferroic and magneto-dielectric properties of rare earth manganates

Charge-order driven magnetic ferroelectricity is shown to occur in several rare earth manganates of the general formula, Ln(1-x)A(x)MnO(3) (In = rare earth, A = alkaline earth). Charge-ordered manganates exhibit dielectric constant anomalies around the charge-ordering or the antiferromagnetic transition temperature. Magnetic fields have a marked effect on the dielectric properties of these compounds, indicating the presence of coupling between the magnetic and electrical order parameters. Magneto-dielectric properties are retained in small particles of the manganates. The observation of magneto-ferroelectricity in these manganates is in accordance with theoretical predictions.

Charge-order driven multiferroic and magneto-dielectric properties of rare earth manganates

Charge-order driven magnetic ferroelectricity is shown to occur in several rare earth manganates of the general formula, Ln(1-x)A(x)MnO(3) (In = rare earth, A = alkaline earth). Charge-ordered manganates exhibit dielectric constant anomalies around the charge-ordering or the antiferromagnetic transition temperature. Magnetic fields have a marked effect on the dielectric properties of these compounds, indicating the presence of coupling between the magnetic and electrical order parameters. Magneto-dielectric properties are retained in small particles of the manganates. The observation of magneto-ferroelectricity in these manganates is in accordance with theoretical predictions.

Magneto-structural study of the multiferroic BiFeo(3)-SrTiO3

The structural and magnetic study of the pseudo-binary multiferroic (1 x)BiFeO3 (x)SrTiO3 has been investigated as a function of composition and temperature. In contrary to the previous studies, detailed examination revealed that the reported anomaly in the magnetization at x-0.30 does not occur at the composition induced rhombohedral-cubic phase boundary, but within the rhombohedral phase itself. The rhombohedral to cubic transition occurs at x > 0.4. Evidence of magneto-elastic coupling near the Neel temperature and nucleation-growth mode of the rhombohedral-cubic transformation, with both the phases coexisting over a range of temperature was found. (C) 2014 Elsevier B.V. All rights reserved.

Enhanced electric field tunable magnetic properties of lead-free Na0.5Bi0.5TiO3-MnFe2O4 multiferroic composites

Strong magnetoelectric (ME) interaction was exhibited at both dc and microwave frequencies in a lead-free multiferroic particulate composites of Na0.5Bi0.5TiO3 (NBT) and MnFe2O4 (MFO) multiferroic, which were prepared by sol-gel route. The room temperature permeability measurements were carried out in the frequency range of 1 MHz-1 GHz. A systematic study of structural, magnetic and ME properties were undertaken. The room temperature ferromagnetic resonance (FMR) was studied. Strong ME coupling is demonstrated in 70NBT-30MFO composite by an electrostatically tunable FMR field shift up to 428 Oe (at E = 4 kV/cm), which increases to a large value of 640 Oe at E = 8 kV/cm. Furthermore, these lead-free multiferroic composites exhibiting electrostatically induced magnetic resonance field at microwave frequencies provide great opportunities for electric field tunable microwave devices.

Magnetic switching of ferroelectric domains at room temperature in multiferroic PZTFT

Single-phase magnetoelectric multiferroics are ferroelectric materials that display some form of magnetism. In addition, magnetic and ferroelectric order parameters are not independent of one another. Thus, the application of either an electric or magnetic field simultaneously alters both the electrical dipole configuration and the magnetic state of the material. The technological possibilities that could arise from magnetoelectric multiferroics are considerable and a range of functional devices has already been envisioned. Realising these devices, however, requires coupling effects to be significant and to occur at room temperature. Although such characteristics can be created in piezoelectric-magnetostrictive composites, to date they have only been weakly evident in single-phase multiferroics. Here in a newly discovered room temperature multiferroic, we demonstrate significant room temperature coupling by monitoring changes in ferroelectric domain patterns induced by magnetic fields. An order of magnitude estimate of the effective coupling coefficient suggests a value of ~1 × 10-7 sm-1.

Controlling magnetoelectric coupling by nanoscale phase transformation in strain engineered bismuth ferrite

The magnetoelectric coupling in multiferroic materials is promising for a wide range of applications, yet manipulating magnetic ordering by electric field proves elusive to obtain and difficult to control. In this paper, we explore the prospect of controlling magnetic ordering in misfit strained bismuth ferrite (BiFeO3, BFO) films, combining theoretical analysis, numerical simulations, and experimental characterizations. Electric field induced transformation from a tetragonal phase to a distorted rhombohedral one in strain engineered BFO films has been identified by thermodynamic analysis, and realized by scanning probe microscopy (SPM) experiment. By breaking the rotational symmetry of a tip-induced electric field as suggested by phase field simulation, the morphology of distorted rhombohedral variants has been delicately controlled and regulated. Such capabilities enable nanoscale control of magnetoelectric coupling in strain engineered BFO films that is difficult to achieve otherwise, as demonstrated by phase field simulations.