ABO3 perovskite multiferroic La0.5Bi0.5Mn0.5Fe0.5O3.09 where the B-site cations is responsible for the magnetic properties and the A-site cation with lone pair electron is responsible for the ferroelectric properties was synthesized at normal conditions. This oxide exhibits a ferromagnetic transition around 240 K with a well defined hysteresis loop, and a significant reversible remnant polarization below 67K similar to ferroelectric behavior. The magnetic interaction is interpreted by the ferromagnetic Fe3+-O-Mn3+ and antiferromagnetic Fe3+(Mn3+)-O-Fe3+(Mn3+) interactions competed each other, whereas the ferroelectricity is predominantly due to the polar nature introduced by the 6s2 lone pair of Bi3+ cations
Magnetic phase transitions in multiferroic bismuth ferrite (BiFeO3) induced by magnetic field, epitaxial strain, and composition modification are considered. These transitions from a spatially modulated spin spiral state to a homogenous antiferromagnetic one are accompanied by the release of latent magnetization and a linear magnetoelectric effect that makes BiFeO3-based materials efficient room-temperature single phase multiferroics.
Many multiferroic materials, with various chemical compositions and crystal structures, have been discovered in the past years. Among these multiferroics, some perovskite manganites with ferroelectricity driven by magnetic orders are of particular interest. In these multiferroic perovskite manganites, not only their multiferroic properties are quite prominent, but also the involved physical mechanisms are very plenty and representative. In this Brief Review, we will introduce some recent theoretical and experimental progress on multiferroic manganites.
We have investigated the effects of substituting In for Mn on the antiferromagnetic phase transition in YMnO3 using magnetic, dielectric, and specific heat measurements. We prepared a set of isostructural phase pure hexagonal YMn$_{1-x}$In$_{x}$O$_{3}$ samples having x=0 to x=0.9, which exhibit a systematic decrease of the antiferromagnetic ordering temperature with increasing In content. The multiferroic phase, which develops below TN, appears to be completely suppressed for x$\geq$0.5 in the temperature range investigated, which can be attributed solely to the dilution of magnetic interactio…
We show that the type-II multiferroic properties of bulk MnWO4 are kept in nanostructured ceramics of 50 nm grain size prepared via spark plasma sintering (SPS). This means that ferroelectric polarization is robust against downsizing, which is at variance with standard ferroelectrics like BaTiO3. We ascribe this stability to the spin-driven nature of the ferroe-lectric correlations in type-II multiferroics while it is resulting from lattice distortion in other cases. This may open the way for persistent type-II multiferroicity with no need for external stabilization like substrate-generated st…
PbFe12O19 (PFO) powders in hexagonal structure have been synthesized by sol-gel process using lead acetate, glycerin and ferric acetylacetonate as the precursor. PbFe12O19 ceramics were obtained by sintering the PbFe12O19 powders at 1000\degree C for 1 hour. Distorted flaky hexahedron grains are frequently observed in the SEM images of sintered PbFe12O19 ceramics. Large spontaneous polarization was observed in PbFe12O19 ceramic at room temperature, exhibiting a clear ferroelectric hysteresis loop. The remnant polarization of PbFe12O19 ceramic is estimated to be Pr~21μC/cm2. The distortion of h…
With the perovskite multiferroic RMnO3 (R = Gd, Tb, Dy) as guidance, we argue that the Dzyaloshinskii-Moriya interaction (DMI) provides the microscopic mechanism for the coexistence and strong coupling between ferroelectricity and incommensurate magnetism. We use Monte-Carlo simulations and zero temperature exact calculations to study a model incorporating the double-exchange, superexchange, Jahn-Teller and DMI terms. The phase diagram contains a multiferroic phase between A and E antiferromagnetic phases, in excellent agreement with experiments.
In this work multiferroic thin films of Bi containing perovskite oxides are discussed, where the driving force for ferroelectricity are the Bi3+ lone-pair electrons. First, a brief introduction of Bi containing multiferroic perovskite oxides will be presented to describe the mechanisms for establishing magnetic and ferroelectric order in these compounds and some recent developments in this field of research are reported. The second section addresses experimental aspects of epitaxial thin film growth of BiMnO3, (Bi0.9La0.1)2NiMnO6 (BLNMO) and BiFeO3 thin films by pulsed laser deposition. The th…
We report here the realization of ferroelectricity, ferromagnetism and magnetocapacitance effect in SrFe12O19 ceramics at room temperature. The ceramics demonstrate a saturated polarization hysteresis loop, two I-V peaks and large anomaly of dielectric constant near Curie temperature. These evidences confirmed the ferroelectricity of SrFe12O19 ceramics after annealing in O2 atmosphere. The remnant polarization of the SrFe12O19 ceramic is 103 μC/cm2. The material also exhibits strong ferromagnetic characterization, the coercive field and remnant magnetic moment are 6192Oe and 35.8emu/g, respect…
Simultaneous occurrence of big ferroelectricity and strong ferromagnetism has been observed in Barium Hexaferrite ceramics. Barium hexaferrite (BaFe12O19) powders with hexagonal crystal structure have been successfully synthesized by polymer precursor method using barium acetate and ferric acetylacetonate as the precursor. The powders were pressed into pellets, which were sintered into ceramics at 1100^{\circ}C~1300^{\circ}C for 1 hour. The structure and morphology have been determined by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). Large spontaneous polariz…
Multiferroics with coupling between ferroelectricity and magnetism have been pursued for decades. However, their magnetoelectric performances remain limited due to the common trade-off between ferroelectricity and magnetism. Here, a family of nitride perovskites is proposed as multiferroics with prominent physical properties and nontrivial mechanisms. Taking GdWN$_3$ as a prototype, our first-principles calculations found that its perovskite phases own large polarizations (e.g. $111.3$ $μ$C/cm$^2$ for the $R3c$ phase) and a magnetic moment $7$ $μ_{\rm B}$/Gd$^{3+}$. More interestingly, its fer…
We theoretically study origins of the ferroelectricity in the multiferroic phases of the rare-earth (R) Mn perovskites, RMnO3, by constructing a realistic spin model including the spin-phonon coupling, which reproduces the entire experimental phase diagram in the plane of temperature and Mn-O-Mn bond angle for the first time. Surprisingly we reveal a significant contribution of the symmetric (S.S)-type magnetostriction to the ferroelectricity even in a spin-spiral-based multiferroic phase, which can be larger than the usually expected antisymmetric (SxS)-type contribution. This explains well t…
We report observation of magneto-electric and magneto-dielectric couplings in ceramic Co3TeO6. Temperature dependent DC magnetization and dielectric constant measurements together indicate coupling between magnetic order and electronic polarization. Strong anomaly in dielectric constant at ~ 18K in zero magnetic field indicates presence of spontaneous polarization. Observations like weak ferromagnetic order at lower temperature, field and temperature dependences of the ferroelectric transition provide experimental verification of the recent theoretical proposal by P. Toledano et al., Phys. Rev…
Effect of an internal chemical pressure on structural, optical, magnetic and electrical properties in Bi0.9RE0.1FeO3 Ceramics (RE =Gd3+,Tb3+,Dy3+)has been studied extensively. Some of the highlights are as follows; 1. Coexistence of orthorhombic Bragg reflections along with the R3c phase.(Structural Phase separation revealed from XRD and Raman spectroscopy) 2. Selective softening of phonon mode corresponding to oxygen motion suggests a significant destabilization in the FeO6 octahedra. 3. Three Charge transfer transitions (Fe1 3d\rightarrow Fe2 3d, Op \rightarrow Fed,Op \rightarrow Bip) and a …
Complete magnetoelectric (ME) phase diagrams of orthorhombic $R$MnO$_{3}$ with and without magnetic moments on the $R$ ions have been established. Three kinds of multiferroic ground states, the $ab$-cycloidal, the $bc$-cycloidal, and the collinear $E$-type phases, have been identified by the distinct ME responses. The electric polarization of the $E$-type phase dominated by the symmetric spin exchange ($bm{S}_{i} cdot bm{S}_{j}$) is more than 10 times as large as that of the $bc$-cycloidal phase dominated by the antisymmetric one ($bm{S}_{i} times bm{S}_{j}$), and the ME response is enhanced n…
We study theoretically the electromagnon and its optical spectrum (OS) of the terahertz-frequency regime in the magnetic-spiral-induced multiferroic phases of the rare-earth (R) Mn perovskites, RMnO3, taking into account the elliptical deformation or the higher harmonics of the spiral spin configuration, which has been missed so far. A realistic spin Hamiltonian, which gives phase diagrams in agreement with experiments, resolves a long standing puzzle, i.e., the double-peak structure of the OS with a larger low-energy peak originating from magnon modes hybridized with the zone-edge state. We a…
The origin of the spiral spin-order in perovskite multiferroic manganites $R$MnO$_{3}$ ($RE=$ Tb or Dy) is here investigated using a two $e_{\rm g}$-orbitals double-exchange model. Our main result is that the experimentally observed spiral phase can be stabilized by introducing a relatively weak next-nearest-neighbor superexchange coupling ($\sim10%$ of the nearest-neighbor superexchange). Moreover, the Jahn-Teller lattice distortion is also shown to be essential to obtain a realistic spiral period. Supporting our conclusions, the generic phase diagram of undoped perovskite manganites is obtai…
Magnetic and dielectric properties on a polycrystalline La0.7Bi0.3CrO3 have been investigated. A canted antiferromagnetic (CAF) phase transition giving weak ferromagnetism at TN = 230K has been observed. M-H at 10K shows non-saturating trend, even up to 5T, confirms the CAF ordering. The permittivity (ε')-vs-temperature (T) variation shows a relaxor ferroelectric (RFE) nature accompanied by a pronounced anomaly in ε'-T at TN. The anomaly in ε'-T at TN indicates the presence of magentoelectric (ME) coupling in this material.
First-principles electronic structure calculations have been performed for the double perovskite Bi$_2$CoMnO$_6$ in its non-centrosymmetric polar state using generalized gradient approximation plus Hubbard U approach. We find that while Co is in a high spin state, Mn is in an intermediate spin state. The calculated dynamical charge tensors are anisotropic reflecting a low-symmetry structure of the compound. Magnetic structure dependent phonon frequencies indicate the presence of spin-phonon coupling. Using Berry phase method, we obtain a spontaneous electronic polarization of 5.88 $μC/cm^2$ wh…
The synthesis and structural studies on the polycrystalline La1-xBixCrO3 (x =0, 0.2, 0.25, 0.3, 0.35) have been done using XRD and TEM. The results of the Reitveld refinement of XRD data shows that these compounds crystallize in an orthorhombic structure with Pnma space group. With increasing Bi content, the unit cell volume and lattice parameters undergo non monotonous changes within the tolerance factor from 0.84092 to 0.84072. This has been attributed to the anisotropy induced by lone pair of Bi3+, which may distorted the lattice.
Magnetoelectric phase diagrams of the perovskite manganites, Eu1-xYxMnO3 and Gd1-xTbxMnO3, are theoretically studied. We first construct a microscopic model, and then analyze the model using the Monte-Carlo method. We reproduce the diagrams, which contain two different multiferroic states, i.e., the ab-plane spin cycloid with electric polarization P//a and the bc-plane spin cycloid with P//c. We reveal that their competition originates from a conflict between the single-ion anisotropy and the Dzyaloshinsky-Moriya interaction, which is controlled by the second-neighbor spin exchanges enhanced b…
We report the structural and magnetoelectrical properties of La$_{0.7}$Ca$_{0.3}$MnO$_3$/BaTiO$_3$ perovskite superlattices grown on (001)-oriented SrTiO$_3$ by the pulsed laser deposition technique. Magnetic hysteresis loops together with temperature dependent magnetic properties exhibit well-defined coercivity and magnetic transition temperature (T$_C$) \symbol{126}140 K. $DC$ electrical studies of films show that the magnetoresistance (MR) is dependent on the BaTiO$_3$ thickness and negative $MR$ as high as 30% at 100K are observed. The $AC$ electrical studies reveal that the impedance and …
A dielectric anomaly has been found near the incommensurate to commensurate antiferromagnetic phase transition (TN2=230 K) in YBaCuFeO5 ceramics, a compound which crystallizes in an ordered perovskite structure. The existence of electric polarization below TN2 suggests the magnetism induced charge polarization effect that is also confirmed by its strong magnetic field dependence below TN2. Accordingly, the peak near TN2 of the magnetodielectric effect indicates a maximum of magnetodielectric susceptibility near the spin reorientation transition. Considering the abundance of magnetic compounds …
This review devoted to multiferroic properties of Bismuth-based perovskites falls into two parts. The first part focuses on BiFeO3 and summarizes the recent progress made in the studies of its pressure-temperature phase diagram and magnetoelectric coupling phenomena. The second part discusses in a more general way the issue of polar - and multiferroic - phases in BiBO3 perovskites and the competition between ferroelectricity and other structural instabilities, from an inventory of recently synthetized compounds.
YBaCuFeO5 is one of the interesting multiferroic compounds, which exhibits magnetic ordering and dielectric anomaly above 200 K. Partial substitution of Fe with other magnetic and non-magnetic ion affects the magnetic and the structural properties of the system. We report detailed investigation of structural, magnetic and dielectric properties of YBaCuFe0.85M0.15O5 (M=Co, Ni and Ga). We observed that the partial replacement of Ni and Co in place of Fe, results in magnetic dilution and broadening of the magnetic transition and shifting towards lower temperature. The replacement of Fe with non-m…
A two step solid state reaction route has been presented to synthesize monophasic cobalt tellurate (Co3TeO6, CTO) using Co3O4 and TeO2 as starting reagents. During synthesis, initial ingredient Co3O4 is found better than CoO in circumventing the intermediate Co5TeO8 or CoTeO3 phases. High resolution Synchrotron X-ray Diffraction has been used to probe different phases present in synthesized CTO and to achieve its single phase. Further, XANES studies near Co K and Te L-edge reveal mixed oxidation states of Co (i.e. Co2+ and Co3+) and +VI valence state of Te respectively, which is also confirmed…
Dielectric study over a broadband was carried out from 10 to 70 K on ceramic Gd1-xYxMnO3 (x= 0.2, 0.3, and 0.4). For all the compositions, a prominent sharp peak about ~18K was observed in the temperature dependence of both ε'(T) and ε"(T) at all frequencies, indicating a long-range ferroelectric (FE) transition. Using Cole-Cole fit to the permittivity data, the relaxation time τ and the dielectric strength Δε were estimated. Temperature variation of τ(T) in the Arrhenius representation is found to be nonlinear (non-Debyean relaxation), with increasing barrier-activation energy over successive…
Multiferroic composites with the composition (1-x) BaTi0.8Sn0.2O3 - (x) La0.5Ca0.5MnO3 (x =0, 0.3, 0.5, 0.7, 0.9 and 1) were prepared by sol-gel techniques. Rietveld refinements of the composites with 0-3 and 3-0 type connectivities exhibit the formation of pure phases and confirm the fraction of the composite samples. It was found that the composites grain size decreases slightly with increasing the La0.5Ca0.5MnO3 content. Magnetic measurements of the composite ceramics exhibit a gradual increase in saturation and remanent magnetization with increasing La0.5Ca0.5MnO3 content. Dielectric data …
The combination of antiferroelectricity (AFE) and ferromagnetism (FM) in one structure would allow the development of new type of multiferroic candidates, which be applicable not only in magnetoelectric memories but also in novel energy storage devices. Here we propose a novel type of multiferroic candidate LaxSr1-xFe12O19, whose room temperature state could betuned from ferroelectrics (FE) to antiferroelectrics by changing x from 0 to 0.5. The emphasis of this paper will be focused on the La0.5Sr0.5Fe12O19 system, in which full AFE and FM coexist. The pure antiferroelectric behavior in La0.5S…
Structural, electrical and magnetic properties of Bi0.9-xLa0.1ErxFeO3 (BLEFOx) (x = 0.05, 0.07, 0.1) polycrystalline ceramics prepared by solid solution route were studied. A phase transition from rhombohedral phase to monoclinic phase was observed for x=0.05-0.1 in (BLEFOx). We have measured phase transition temperatures both alpha-beta transition and low-Temperature (low-T) transitions in doped BiFeO3. The transition peak near to 835C corresponds to alpha to beta-phase transition of BiFeO3 were measured using diffential thermal analysis (DTA). Dielectric measurements shows the low-T transiti…
We report cooperative magnetic orderings in a 6H-perovskite multiferroic system, Ba3HoRu2O9, via comprehensive neutron powder diffraction measurements. This system undergoes long-range antiferromagnetic ordering at TN1 ~ 50 K with a propagation wave vector of K1 = (0.5 0 0), a transition temperature much higher than the previously reported one at ~10 K (TN2). Both Ru and Ho-moments order simultaneously below TN1, followed by spin-reorientations at lower temperatures, demonstrating strong Ru(4d)-Ho(4f) magnetic correlation. Below TN1 another magnetic phase with a propagation wave vector K2 = (0…
The perovskite (1-x)YMnO$_3$-xBiFeO$_3$ binary system is very promising because of its multiferroic end members. Nanocrystalline phases have been recently obtained by mechanosynthesis across the system, and the perovskite structural evolution has been described. Two continuous solid solutions with orthorhombic Pnma and rhombohedral R3c symmetries were found, which coexist within a broad compositional interval of 0.5 < x < 0.9. This might be a polar-nonpolar morphotropic phase boundary region, at which strong phase-change magnetoelectric responses can be expected. A major issue is phase decompo…
Orthorhombically distorted perovskite manganites, RMnO3 with R being a trivalent rare-earth ion, exhibit a variety of magnetic and electric phases including multiferroic (i.e. concurrently magnetic and ferroelectric) phases and fascinating magnetoelectric phenomena. We theoretically study the phase diagram of RMnO3 by constructing a microscopic spin model, which includes not only the superexchange interaction but also the single-ion anisotropy (SIA) and the Dzyaloshinsky-Moriya interaction (DMI). Analysis of this model using the Monte-Carlo method reproduces the experimental phase diagrams as …
Multiferroic bismuth ferrite Bi_2Fe_4O_9 (BFO) ceramic was synthesized by conventional solid state reaction route. X-ray diffraction and Rietveld refinement show formation of single phase ceramic with orthorhombic crystal structure (space group Pbam). The morphological study depicted a well-defined grain of size $\simeq$2μm. The optical studies were carried out by using UV-Vis spectrophotometer which shows a band gap of 1.53 eV and a green emission spectrum at 537 is observed in the Photoluminescence study. The frequency dependent dielectric study at various temperature revealed that the diele…
AFe$_{1 / 2}$B$_{1 / 2}$O$_{3}$(A- Ba, Sr, Ca; B-Nb, Ta, Sb) ceramics were synthesized and temperature dependencies of the dielectric permittivity were measured at different frequencies. The experimental data obtained show very high values of the dielectric permittivity in a wide temperature interval that is inherent to so-called high-k materials. The analyses of these data establish a Maxwell-Wagner mechanism as a main source for the phenomenon observed.
We show that a superstructure of antiferromagnetically interacting Fe$^{3+}$ ($S=5/2$) ions in double perovskites AFe$_{1/2}$M$_{1/2}$O$_{3}$ exhibits a ferrimagnetic ordering below $T_{fe} \approx 5.6J_1$ ($J_1/k_B \sim 50$~K), which is close to room temperature. Small clusters of the same structure exhibit a superparamagnetic behavior at $T \lesssim T_{fe}$. The possibility of formation of such clusters explains the room-temperature (superpara)magnetism in 3$d$-metal based oxides.
In this proceeding, recent theoretical investigations by the authors on the multiferroic $R$MnO$_3$ perovskites are briefly reviewed at first. Using the double-exchange model, the realistic spiral spin order in undoped manganites such as TbMnO$_3$ and DyMnO$_3$ is well reproduced by incorporating a weak next-nearest neighbor superexchange ($\sim10%$ of nearest neighbor superexchange) and moderate Jahn-Teller distortion. The phase transitions from the A-type antiferromagnet (as in LaMnO$_3$), to the spiral phase (as in TbMnO$_3$), and finally to the E-type antiferromagnet (as in HoMnO$_3$), wit…
We present a detailed dielectric study of the relaxation effects that occur in several perovskite rare-earth manganites, including the multiferroics TbMnO3 and DyMnO3. We demonstrate that the strong magnetocapacitive effects, observed for electrical fields E||c, are nearly completely governed by magnetic-state induced changes of the relaxation parameters. The multiferroic materials, which undergo a transition into a spiral magnetic state, show qualitatively different relaxation behavior than those compounds transferring into an A-type antiferromagnetic state. We ascribe the relaxations in both…
Dielectric and magnetic properties of Eu0.5Ba0.25Sr0.25TiO3 are investigated between 10 K and 300 K in the frequency range from 10 Hz to 100 THz. A peak in permittivity revealed near 130 K and observed ferroelectric hysteresis loops prove the ferroelectric order below thistemperature. The peak in permittivity is given mainly by softening of the lowest frequency polar phonon (soft mode revealed in THz and IR spectra) that demonstrates displacive character of the phase transition. Room-temperature X-ray diffraction analysis reveals cubic structure, but the IR reflectivity spectra give evidence o…
We use a group theoretical approach to enumerate the possible couplings between magnetism and ferroelectric polarisation in the parent $Pm\bar{3}m$ perovskite structure. We show that third order magnetoelectric coupling terms must always involve magnetic ordering at the A and B-site which either transforms both as R-point or both as X-point time odd irreducible representations (irreps). For fourth order couplings we demonstrate that this criterion may be relaxed allowing couplings involving irreps at X, M and R-points which collectively conserve crystal momentum, producing a magnetoelectric ef…
We report an investigation of hexagonal Y_(1-x)Eu_xMnO_3 ceramics with x=0, 0.1 and 0.2 using infrared and THz spectroscopies in the temperature range between 5 and 900 K. The temperature dependence of the THz permittivity reveals a kink near the antiferromagnetic phase transition temperature T_N ~ 70 K giving evidence of a strong spin-lattice coupling. Below T_N two absorption peaks were revealed in the THz spectra close to 43 and 73 cm-1. While the first peak corresponds to a sharp antiferromagnetic resonance exhibiting softening on heating towards TN, the second one may be attributed to an …
We have used a shell model to study the phonon dynamics of multiferroic manganites RMnO3 (R= Tb, Dy, Ho). The calculated phonon dynamical properties, crystal structure, Raman frequencies and specific heat are found to be in good agreement with the available experimental data. Besides, the phonon density of states, elastic constants and phonon dispersion curves along high symmetry directions (sigma, delta and lambda) have also been computed. A zone-center imaginary Au mode is revealed in these phonon dispersion curves, which indicates the occurrence of metastability of the perovskite phase. The…
We propose experimental verification and theoretical explanation of magnetic anomalies in the complex Fe-contained double perovskite multiferroics like PbFe$_{1/2}$Nb$_{1/2}$O$_3$. The theoretical part is based on our model of coexistence of long-range magnetic order and spin glass in the above substances. In our model, the exchange interaction is anisotropic, coupling antiferromagnetically $z$ spin components of Fe$^{3+}$ ions. At the same time, the $xy$ components are coupled by much weaker exchange interaction of ferromagnetic sign. In the system with spatial disorder (half of corresponding…
The oxygen octahedral tilted domains in 0.90(Bi1/2Na1/2)TiO3-0.5(Bi1/2K1/2)TiO3-0.5BaTiO3 lead-free perovskite piezoelectric ceramic have been studied by transmission electron microscopy (TEM). Selected-area electron diffraction patterns shows the 1/2ooo and 1/2ooe reflections, indicating the presence of antiphase (a-a-a-) and in-phase (aoaoc+) octahedral tilting, respectively. The morphology and distributions of these tilted domains are shown in the centered dark-field images. Further, the Bragg-filtered high-resolution TEM image reveals that the size of the in-phase tilted domains varies fro…
Structural, impedance, ferroelectric and magnetic properties were examined in multiferroic Bi_{2}Fe_{4(1-x)}Co_{4x}O_{9} (0$\leq$x$\leq$0.02) ceramics synthesized via solid-state reaction method. X-ray diffraction analysis and Rietveld refinement showed secondary phase formation (for x$\geq$0.01) which was subsequently confirmed from room temperature Raman spectroscopy study. The frequency dependence of impedance and electric modulus of the material showed the presence of non-Debye type relaxation in all the samples. The values of the activation energies calculated from imaginary impedance and…
The study of grain size effects in ferroelectric ceramics has attracted great research interest over the last 50 years. Although different theoretical models have been proposed to account for the variation in structure and properties with grain size, the underlying mechanisms are still under debate, creating a significant level of uncertainty in the field. Here, we report the results of a study on the influence of grain size on the structural and physical properties of Ba(Ti0.96Sn0.04)O3, which represents a model perovskite system, where the effects of point defects, stoichiometry imbalance an…
BFO3 ceramics were investigated by means of infrared reflectivity and time domain THz transmission spectroscopy at temperatures 20 - 950 K, and the magnetodielectric effect was studied at 10 - 300 K, with the magnetic field up to 9 T. Below 175 K, the sum of polar phonon contributions into the permittivity corresponds to the value of measured permittivity below 1 MHz. At higher temperatures, a giant low-frequency permittivity was observed, obviously due to the enhanced conductivity and possible Maxwell-Wagner contribution. Above 200 K the observed magnetodielectric effect is caused essentially…
Despite the great technological and scientific importance, a well-controlled coupled behavior in magnetoelectric multiferroic materials at room temperature remains challenging. We demonstrate that the self-ordered A2BBO6 (e.g., A = La, B = Mn, and B = Ni) double perovskites provide a unique alternative opportunity to control and/or to induce such behavior in oxides. In this paper, we outline and discuss the various challenges and bottleneck issues related to this class of materials using La2NiMnO6 as a prototype. Details of the synthesis strategies, using pulsed laser deposition as a central t…
In this paper we investigated the influence of the rare-earth ionic radii on the spin-phonon coupling in RE2NiMnO6 double perovskites by Raman spectroscopy. Spin-phonon in dense Nd2NiMnO6 and Gd2NiMnO6 ceramics were investigated by Raman spectroscopy at low temperatures. The magnitude of the coupling observed in comparison with other isostructural compounds shows that it is not influenced by the rare-earth ionic radius, as well as the deviation of the position of the stretching phonon in the ferromagnetic phase with relation to the anharmonic contributions follows a power law.
PbTiO3 has the highest tetragonal distortion (c/a=1.064) and highest spontaneous polarization among perovskite titanates. But, it is hazardous and hence one needs to reduce Pb content by substituting or reducing Pb content for use in applications. Pb(1-x)(K0.5Sm0.5)xTiO3 (0&x&0.5) perovskite powders were synthesized by sol-gel process, where Pb2+ was replaced by a combination of K+10.5Sm+30.5 (equivalent charge and comparable ionic radius) providing an excellent substitution model to study changes in structural and electrical properties. Vibrational properties and dielectric properties are mod…
Double perovskites provide a unique opportunity to induce and control multiferroic behaviors in oxide systems. The appealing possibility to design materials with a strong coupling between the magnetization and the polarization fields may be achieved in this family since these magnetic insulators can present structural self-ordering in the appropriate growth conditions. We have studied the functional properties of La2CoMnO6 and Bi2CoMnO6 epitaxial thin films grown by pulsed laser deposition. Cation-ordered La2CoMnO6 films display a magnetic Curie temperature of 250 K while cation-disordered Bi2…
We investigate a magnetic hysteresis loop with a remanent moment that couples to electric polarization to create coupled hysteretic multiferroic behavior in Lu2MnCoO6. Measurements of elastic neutron diffraction, muon spin relaxation, and micro-Hall magnetometry demonstrate an unusual mechanism for the magnetic hysteresis, namely the hysteretic evolution of a microscopic magnetic order, and not classic ferromagnetic domain effects. We show how the frustrated spin system evolves from antiferromagnetism with an incommensurate long-wavelength modulation and strong fluctuations towards a net magne…
Magnetoelectric phase diagrams of the rare-earth (R) Mn perovskites RMnO3 are theoretically studied by focusing on crucial roles of the symmetric magnetostriction or the Peierls-type spin-phonon coupling through extending our previous work [M. Mochizuki et al., Phys. Rev. Lett. 105, 037205 (2010)]. We first construct a microscopic classical Heisenberg model for RMnO3 including the frustrated spin exchanges, single-ion anisotropy, and Dzyaloshinskii-Moriya interaction. We also incorporate the lattice degree of freedom coupled to the Mn spins via the Peierls-type magnetostriction. By analyzing t…
In this article, we perform the symmetry analysis of perovskite-based multiferroics: bismuth ferrite (BiFeO3)-like, orthochromites (RCrO3), and Ruddlesden-Popper perovskites (Ca3Mn2O7-like), being the typical representatives of multiferroics of the trigonal, rhombic, and tetragonal crystal families and explore the effect of crystallographic distortions on magnetoelectric properties. We determine the principal order parameters for each of the considered structures and obtain their invariant combinations consistent with the particular symmetry. This approach allowed us to analyze the features of…
We investigate the electronic, ferroelectric and magnetic properties of KTaO3/PbTiO3 interfaces by using conventional density functional theory (DFT) and advanced DFT such as hybrid functional HSE06. We show that doped holes in valence bands or electrons in conduction bands give rise to ferromagnetism at the interfaces. The ferromagnetic states are ground states for both hole-doped (p-type) and electron-doped (n-type) interfaces by comparison with their corresponding nonmagnetic and antiferromagnetic states. Carriers (holes or electrons) concentrate near the interface to screen the polarizatio…
We investigate the crystal structure in multiferroic tetragonal perovskite Sr$_{1/2}$Ba$_{1/2}$MnO$_3$ with high accuracy of the order of 10$^{-3}$ Angstrom for an atomic displacement. The large atomic displacement for Mn ion from the centerosymmetric position, comparable with the off-centering distortion in the tetragonal ferroelectric BaTiO$_3$, is observed in the ferroelectric phase ($T_\mathrm{N}$ $\leq$ $T$ $\leq$ $T_\mathrm{C}$). In stark contrast, in the multiferroic phase ($T$ $\leq$ $T_\mathrm{N}$), the atomic displacement for Mn ion is suppressed, but those for O ions are enlarged. T…
The structural phase transition in hexagonal BaMnO$_3$ occurring at $T_c$=130 K was studied in ceramic samples using electron and X-ray diffraction, second harmonic generation as well as by dielectric and lattice dynamic spectroscopies. The low-temperature phase (space group $P6_{3}cm$) is ferroelectric with a triplicated unit cell. The phase transition is driven by an optical soft mode from the Brillouin-zone boundary [$q = (\frac{1}{3},\frac{1}{3},0)$]; this mode activates in infrared and Raman spectra below $T_c$ and it hardens according to the Cochran law. Upon cooling below $T_c$, the per…
