The polar magnet CaBaCo$_{4}$O$_{7}$ is known to exhibit the largest magnetic-field-driven electric polarization change ($ΔP$) associated with an antiferromagnetic (AFM)-ferrimagnetic (FIM) transition in a narrow temperature range between 62 and 69 K. In this work, we investigate the effect of Ni doping on its multiferroic properties, by means of magnetization, electric polarization, dielectric constant, and magnetostriction measurements on single crystals of CaBaCo$_{3.9}$Ni$_{0.1}$O$_{7}$ up to 50 T. In the doped material, two kinds of AFM phases appear below 78 K, accompanying negative $ΔP$. Upon the application of a magnetic field along any crystallographic axis, giant positive $ΔP$ of up to $11 \sim 12$ mC/m$^{2}$ is observed along with an AFM-FIM transition in the whole temperature range below 78 K. The giant magnetoelectric effect inherent in CaBaCo$_{4}$O$_{7}$ can be further enhanced just by a small amount of chemical substitution, in terms of (i) increasing the magnitude of $ΔP$ and (ii) expanding the temperature range in which giant $ΔP$ appears.
The single crystal study of CaBaCo4O7, a non collinear ferrimagnet (TC=64K), with a polar orthorhombic space group (Pbn21) between 4 K and 293 K, shows the appearance below TC of a large electric polarization along its c axis, reaching 17mC.m-2 at 10K. At 62.5K, a magnetic field driven giant variation of polarization, P(9T)-P(0T)=8mC.m-2, is observed. Moreover, the present magnetoelectric measurements, are fully consistent with the m'm2' magnetic point group, strongly supporting that this oxide is also ferrotoroidic. This ferrimagnetic oxide, which belongs to the '114' structural family, opens…
Distinctive effects of dopant valency is discussed using an impurity level 1% doping each of Cr$^{3+}$ and Ni$^{2+}$ in CaBaCo$_4$O$_7$. Through a comparative study of the magnetic and dielectric properties of multiferroic CaBaCo$_{3.96}$Cr$_{0.04}$O$_7$ and CaBaCo$_{3.96}$Ni$_{0.04}$O$_7$, we highlight that Cr doping does not significantly alter the properties in spite of differences in magnetic spin and ionic radius compared to Co$^{3+}$ and Co$^{2+}$ while Ni doping induces spectacular changes. Particularly, a manifold increase of electric polarization change up to 650 ${\rm μ}$C/m$^2$ at 5…
We report magnetization measurements and magnetic resonance data for SrTiO3 doped by manganese. We show that the recently reported coexistent spin and dipole glass (multiglass) behaviours are strongly affected by the distribution of Mn ions between the Sr and Ti sites. Motivated by this finding we calculate the magnetic interactions between Mn impurities of different kinds. Both LSDA+U and many-body perturbation theory evidence that magnetic and magnetoelectric interactions are mediated by Mn$_B^{4+}$ ions substituting for Ti. We propose two microscopic magnetoelectric coupling mechanisms, whi…
We investigate the possibility of controlling the magnetic phase transition of the heterointerface between a half-doped manganite La$_{0.5}$Ca$_{0.5}$MnO$_{3}$ and a multiferroic BiFeO$_{3}$ through magnetoelectric coupling. Using macroscopic magnetometry and element-selective x-ray magnetic circular dichroism at the Mn and Fe \emph{L}-edges, we discover that the ferroelectric polarization of BFO controls simultaneously the magnetization of BFO and LCMO. X-ray absorption spectra at oxygen \emph{K}-edge and linear dichroism at Mn \emph{L}-edge suggest that the interfacial coupling is mainly der…
We report magnetic and magnetoelectric studies on BiFeO3 and divalent cation (A) suvtitute Bi0.7A0.3FeO3 (A = Sr,Ba, and Sr0.5Ba0.5). It is shown that the rapid increase of magnetization at the Neel temperature (TN = 642 K) is suppressed in the co-doped compound A = Sr0.5Ba0.5. All the divalent subtituted compounds show enhanced magnetization and hysteresis loop. Both longitudinal and transverse magnetoelectric coefficients were measured using the dynamical lock-in technique. The co-doped compound shows the highest magnetoelectric coefficient at room temperature although it is not the compound…
The effect of Cr doping with nominal compositions Mn2-xCrxO3 (0 less than equal to x less than equal to 0.10) has been undertaken to investigate its effect on structural, magnetic, dielectric and magnetoelectric properties. The Cr doping transformed the room temperature crystal structure from orthorhombic to cubic symmetry. Similar to alpha-Mn2O3, two magnetic transitions have been observed in the Cr doped samples. The effect of Cr doping is significant on the low temperature transition i.e. the lower magnetic transition shifted towards higher temperature (25 K for pristine to 40 K for x=0.10)…
In a recent study Viskadourakis et al. discovered that extremely underdoped La_2CuO_(4+x) is a relaxor ferroelectric and a magnetoelectric material at low temperatures. It is further observed that the magnetoelectric response is anisotropic for different directions of electric polarization and applied magnetic field. By constructing an appropriate Landau theory, we show that a bi-quadratic magnetoelectric coupling can explain the experimentally observed polarization dependence on magnetic field. This coupling leads to several novel low-temperature effects including a feedback enhancement of th…
In this work, we report the growth and functional characterizations of multiferroic TbMnO3 thin films grown on Nb-doped SrTiO3 (001) substrates using pulsed laser deposition. By performing detailed magnetic and ferroelectric properties measurements, we demonstrate that the multiferroicity of spin origin known in the bulk crystals can be successfully transferred to TbMnO3 thin films. Meanwhile, anomalous magnetic transition and unusual magnetoelectric coupling related to Tb moments are observed, suggesting a modified magnetic configuration of Tb in the films as compared to the bulk counterpart.…
Coexistence of mutually influencing ferroelectric and magnetic ordering at low temperature in hexagonal phase of rare-earth manganites gives rise to interesting physical phenomena. Here, we report a detailed analysis of powder neutron diffraction (ND) studies on polycrystalline Y1-xDyxMnO3 (x = 0, 0.05) as a function of temperature. Our analysis shows that Dy doping at Y site leads to modification in lattice constants: unit cell shrinks in c direction, but expands in ab plane, unit cell volume increases and effective Mn magnetic moment also reduces. All the Mn-O bond lengths and O-Mn-O bond an…
We report the discovery of a ferroelectric ground state below 4.5 K in highly underdoped La_2CuO_(4+x) accompanied by slow charge dynamics which develop below T~40 K. An anisotropic magnetoelectric response has also been observed, indicating considerable spin-charge coupling in this lightly doped "parent" high temperature copper-oxide superconductor. The ferroelectric state is proposed to develop from polar nanoregions, in which spatial inversion symmetry is locally broken due to non-stoichiometric carrier doping.
Violation of time reversal and spatial inversion symmetries has profound consequences for elementary particles and cosmology. Spontaneous breaking of these symmetries at phase transitions gives rise to unconventional physical phenomena in condensed matter systems, such as ferroelectricity induced by magnetic spirals, electromagnons, non-reciprocal propagation of light and spin waves, and the linear magnetoelectric (ME) effect - the electric polarization proportional to the applied magnetic field and the magnetization induced by the electric field. Here, we report the experimental study of the …
Hexagonal RMnO3 is a multiferroic compound with a giant spin-lattice coupling at an antiferromagnetic transition temperature [1]. Despite extensive studies over the past two decades, however, the origin and underlying microscopic mechanism of the strong spin-lattice coupling remain still very much elusive. In this study, we have tried to address this problem by measuring the thermal expansion and dielectric constant of doped single crystals Y1-xLuxMnO3 with x = 0, 0.25, 0.5, 0.75, and 1.0. From these measurements, we confirm that there is a progressive change in the physical properties with do…
Dielectric permittivity spectra of yttrium-doped EuMnO$_3$ in the composition range 0 =< x =< 0.5 have been investigated in the terahertz frequency range. Magnetoelectric contributions to the permittivity were observed in all compositions for ac electric fields parallel to the crystallographic a-axis. Well defined electromagnons exist for x >= 0.2 close to ν~ 20 cm^{-1} and with dielectric strength strongly increasing on doping. In addition to electromagnons, a broad contribution of magnetoelectric origin is observed for all compositions. For Eu_{0.8}Y_{0.2}MnO_3 the electromagnons can be supp…
We have stabilized the α-Fe1.6Ga0.4O3 (Ga doped α-Fe2O3) system in rhombohedral structure. The system has shown magnetically canted ferromagnetic state and ferroelectric properties at room temperature. In first time, we confirm the existence of magneto-electric coupling and multiferro-electric properties at room temperature in the Ga doped α-Fe2O3 system based on the experimental observation of magnetic field controlled electric polarization and electric field controlled magnetization. The α-Fe2O3 system does not exhibit electric field controlled magnetic exchange bias effect, where as Ga dope…
We have developed a new magnetoelectric material based on Ga doped α-Fe2O3 in rhombohedral phase. The material is a canted ferromagnet at room temperature and showing magneto-electric properties. The experimental results of electric field controlled magnetic state provided a direct evidence of room temperature magnetoelectric coupling in Ga doped α-Fe2O3 system. Interestingly, (un-doped) α-Fe2O3 system does not exhibit any electric field controlled magnetic exchange bias shift, but Ga doped α-Fe2O3 system has shown an extremely high electric field induced magnetic exchange bias shift up to the…
We employ electron paramagnetic resonance (EPR) of the spin probe Mn2+ to study the paraelectric ferroelectric transition in DMAMnF and Mn2 doped DMZnF, which are considered to be model metal organic frameworks (MOF) with a Pb free perovskite architecture. In DMAMnF, we study the variation of the Mn2+ EPR line shape and intensity at the X-band (9.4 GHz) and over 80 to 300 K, and we show the absence of magnetoelectric coupling at the ferroelectric transition. At the antiferromagnetic transition in DMMnF, we detect a magnetoelectric coupling caused by weak ferromagnetism in the AFM phase. In DMZ…
Domain wall dynamics in a magnetoelectric antiferromagnet is analyzed, and its implications for magnetoelectric memory applications are discussed. Cr$_2$O$_3$ is used in the estimates of the materials parameters. It is found that the domain wall mobility has a maximum as a function of the electric field due to the gyrotropic coupling induced by it. In Cr$_2$O$_3$ the maximal mobility of 0.1 m/(s$\times$Oe) is reached at $E\approx0.06$ V/nm. Fields of this order may be too weak to overcome the intrinsic depinning field, which is estimated for B-doped Cr$_2$O$_3$. These major drawbacks for devic…
The recent discovery of relaxor ferroelectricity and magnetoelectric effect in lightly doped cuprate material La_2CuO_{4+x} has provided a number of questions concerning its theoretical description. It has been argued using a Ginzburg-Landau free energy approach that the magnetoelectric effect can be explained by the presence of bi-quadratic interaction terms in the free energy. Here, by using the same free energy functional, we study the variety of behavior which can emerge in the electric polarization under an external magnetic field. Subsequently, we discuss the role of Dzyaloshinskii-Moriy…
Based on first-principles calculations, we predict that the magnetic anisotropy energy (MAE) of Co-doped TiO$_2$ sensitively depends on carrier accumulation. This magnetoelectric phenomenon provides a promising route to directly manipulate the magnetization direction of diluted magnetic semiconductor by external electric-fields. We calculate the band structures and reveal the origin of carrier-dependent MAE in k-space. In fact, the carrier accumulation shifts the Fermi energy and regulates the competing contributions to MAE. The first-principles calculations provide a straightforward way to de…
The spin-wave excitations of the multiferroic $\rm MnWO_4$ have been measured in its low-temperature collinear commensurate phase using high-resolution inelastic neutron scattering. These excitations can be well described by a Heisenberg model with competing long-range exchange interactions and a single-ion anisotropy term. The magnetic interactions are strongly frustrated within the zigzag spin chain along c axis and between chains along the a axis, while the coupling between spin along the b axis is much weaker. The balance of these interactions results in the noncollinear incommensurate spi…
Realization of the quantum anomalous Hall effect and axion electrodynamics in topological materials are among the paradigmatic phenomena in condensed matter physics. Recently, signatures of both phases are observed to exist in thin films of MnBi$_2$Te$_4$, a stoichiometric antiferromagnetic topological insulator. Direct evidence of the bulk topological magnetoelectric response in an axion insulator requires an energy gap at its topological surface state (TSS). However, independent spectroscopic experiments revealed that such a surface gap is absent, or much smaller than previously thought, in …
The present work reports synthesis, as well as a detailed and careful characterization of structural, magnetic, and dielectric properties of differently tempered undoped and doped CaCu3Ti4O12 (CCTO) ceramics. For this purpose, neutron and x-ray powder diffraction, SQUID measurements, and dielectric spectroscopy have been performed. Mn-, Fe-, and Ni-doped CCTO ceramics were investigated in great detail to document the influence of low-level doping with 3d metals on the antiferromagnetic structure and dielectric properties. In the light of possible magnetoelectric coupling in these doped ceramic…
Terahertz optical activity near crystal field transitions of Tm3+ ions in magnetoelectric alumoborates
Prokhorov General Physics Institute of the Russian Academy of Sciences（俄罗斯科学院普尔科沃普通物理研究所）；Vienna University of Technology（维也纳工业大学）；Institute of Spectroscopy of the Russian Academy of Sciences（俄罗斯科学院光谱研究所）；Kirensky Institute of Physics, Siberian Branch of the Russian Academy of Sciences（俄罗斯科学院西伯利亚分院基连斯基物理研究所）
Exploration of novel electromagnetic phenomena is a subject of great interest in topological quantum materials. One of the unprecedented effects to be experimentally verified is topological magnetoelectric (TME) effect originating from an unusual coupling of electric and magnetic fields in materials. A magnetic heterostructure of topological insulator (TI) hosts such an exotic magnetoelectric coupling and can be expected to realize the TME effect as an axion insulator. Here we designed a magnetic TI with tricolor structure where a non-magnetic layer of (Bi, Sb)2Te3 is sandwiched by a soft ferr…
Breaking the time-reversal symmetry of a topological insulator (TI) by ferromagnetism can induce exotic magnetoelectric phenomena such as quantized anomalous Hall (QAH) effect. Experimental observation of QAH effect in a magnetically doped TI requires ferromagnetism not relying on the charge carriers. We have realized the ferromagnetism independent of both polarity and density of carriers in Cr-doped BixSb2-xTe3 thin films grown by molecular beam epitaxy. Meanwhile, the anomalous Hall effect is found significantly enhanced with decreasing carrier density, with the anomalous Hall angle reaching…
Multiferroics possess two or more switchable states such as polarization, magnetization, etc. Phonon excitations in multiferroic phase are strongly modified by magnetoelectric coupling, spin-phonon coupling, and anharmonic phonon-phonon interactions. Here, we have investigated the correlation between phonons and multiferroic order parameters in hexagonal BaMO3: M = Ti1-x(Mn/Fe)x systems using powder x-ray diffraction (PXRD), Raman spectroscopic, and magnetic measurements. The structural transformation from a polar tetragonal to a non-polar 6H-type hexagonal phase is observed as a function of d…
Empowering conventional materials with unexpected magnetoelectric properties is appealing to the multi-functionalization of existing devices and the exploration of future electronics. Recently, owing to its unique effect in modulating a matter's properties, ultra-small dopants, e.g. H, D, and Li, attract enormous attention in creating emergent functionalities, such as superconductivity, and metal-insulator transition. Here, we report an observation of bipolar conduction accompanied by a giant positive magnetoresistance in D-doped metallic Ti oxide (TiOxDy) films. To overcome the challenges in …
CoCr$_2$O$_4$ has attracted significant attention recently due to several interesting properties such as magnetostriction, magnetoelectricity etc.. More recent experiments on Fe substituted CoCr$_2$O$_4$ observed a variety of novel phenomena such as the magnetic compensation accompanied by the occurrence of exchange bias, which reverses its sign. Understanding of such phenomena may lead to control the properties of these material in an efficient way to enhance its potential for multifunctional applications. In this paper, we study the microscopic understanding of Fe doping in modifying the str…
Topological insulators (TI) are a new class of quantum materials with insulating bulk enclosed by topologically protected metallic boundaries. The surface states of three-dimensional TIs have spin helical Dirac structure, and are robust against time reversal invariant perturbations. This extraordinary property is notably exemplified by the absence of backscattering by nonmagnetic impurities and the weak antilocalization (WAL) of Dirac fermions. Breaking the time reversal symmetry (TRS) by magnetic element doping is predicted to create a variety of exotic topological magnetoelectric effects. He…
The layered perovskite YBaCuFeO5 (YBCFO) is considered one of the best candidates to high-temperature chiral multiferroics with strong magnetoelectric coupling. In RBaCuFeO5 perovskites (R: rare-earth or Y) A-site cations are fully ordered whereas their magnetic properties strongly depend on the preparation process. They exhibit partial cationic disorder at the B-site that generates a magnetic spiral stabilized through directionally assisted long range coupling between canted locally frustrated spins. Moreover the orientation of its magnetic spiral can be critical for the magnetoelectric respo…
The magnetic compensation and magnetostriction properties in Fe doped CoCr2O4 samples have been investigated. Structural and magnetic measurements imply that the doped Fe3+ ions initially occupy the B1(Cr) sites when x<0.1, and then mainly take the A(Co) sites. This behaviour results in a role conversion of magnetic contributors and a composition compensation between two competitively magnetic sublattices at x=0.1. Temperature dependence compensation has also been found in the samples with x=0.1~0.22, with the compensation temperature in the range of 40~104 K. The Fe3+ doping also modulates th…
Multiferroic BiFeO3 ceramics have been doped with Ca. The smaller ionic size of Ca compared with Bi means that doping acts as a proxy for hydrostatic pressure, at a rate of 1%Ca=0.3GPa. It is also found that the magnetic Neel temperature (TNeel) increases as Ca concentration increases, at a rate of 0.66K per 1%Ca (molar). Based on the effect of chemical pressure on TNeel, we argue that applying hydrostatic pressure to pure BiFeO3 can be expected to increase its magnetic transition temperature at a rate around ~2.2K/GPa. The results also suggest that pressure (chemical or hydrostatic) could be …
In topological insulators (TI), strong spin-orbit coupling results in non-trivial scattering processes of the surface states, whose effects include suppressed back scattering1, 2, 3, 4 weak anti-localization5, 6 and the possibility of an exotic Kondo effect that mimics graphene7. Introducing time reversal breaking perturbations and establishing long-range magnetic order has been theorized to lead to the formation of quantized magnetoelectric phenomena8, fractionalized charge excitations, and the appearance of quantum wire states9. A key, elusive, step in exploring these and other novel electro…
The strain dependence of electric and magnetic properties has been widely investigated, both from a fundamental science perspective and an applications point of view. Electromechanical coupling through field-induced polarization rotation (PRO) and polarization reorientation (PRE) in piezoelectric single crystals can provide an effective strain in film/substrate epitaxial heterostructures. However, the specific pathway of PRO and PRE is a complex thermodynamic process, depending on chemical composition, temperature, electric field and mechanical load. Here, systematic studies of the temperature…
How to electrically control magnetic properties of a magnetic material is promising towards spintronic applications, where the investigation of carrier doping effects on antiferromagnetic (AFM) materials remains challenging due to their zero net magnetization. In this work, we found electron doping dependent variation of magnetic orders of a two-dimensional (2D) AFM insulator NiPS3, where doping concentration is tuned by intercalating various organic cations into the van der Waals gaps of NiPS3 without introduction of defects and impurity phases. The doped NiPS3 shows an AFM-ferrimagnetic (FIM…
The effects of non-stoichiometric lattice structure and secondary phase α-Fe2O3 on modifying the magnetic, electrical, and magneto-electric properties of Eu doped BaFe12O19 hexaferrite
Pondicherry University（本地治里大学）；UGC – DAE Consortium for Scientific Research Mumbai Centre, Bhabha Atomic Research Centre（UGC-DAE科学研究联合体孟买中心，巴哈原子研究中心）
Strong electronic correlations can produce remarkable phenomena such as metal-insulator transitions and greatly enhance superconductivity, thermoelectricity, or optical non-linearity. In correlated systems, spatially varying charge textures also amplify magnetoelectric effects or electroresistance in mesostructures. However, how spatially varying spin textures may influence electron transport in the presence of correlations remains unclear. Here we demonstrate a very large topological Hall effect (THE) in thin films of a lightly electron-doped charge-transfer insulator, (Ca, Ce)MnO3. Magnetic …
Abundant phenomena in CoCr2-xMnxO4 (x = 0 ~ 2) samples such as magnetic compensation, magnetostriction and exchange bias effect have been observed and investigated in this work. A structure transition from cubic to tetragonal symmetry has been found in the samples with x around 1.4. It has shown that the doped Mn3+ ions initially occupy the A (Co) sites when x < 0.2, and then mainly take the B1 (Cr) sites. This behavior results in a role conversion of magnetic contributors, and thus a magnetic compensation between two competitively magnetic sublattices at the composition near x = 0.5. Furtherm…
Multiferroics is a class of functional materials that simultaneously exhibit ferroelectricity and ferromagnetism in a single structure. We report here the integration of anti-ferroelectricity and ferromagnetism in a new M-type hexaferrite compound, in which 0.3 Sr ions was substituted by 0.2 La3+ ions in SrFe12O19 so as to keep the charge balance. This doped compound is expressed as a molecular formula of La0.2Sr0.7Fe12O19, which was confirmed by XRD to have the same structure as SrFe12O19 with a lattice contraction of 0.59%. Surprisingly, the doping effect turns La0.2Sr0.7Fe12O19 from ferroel…
The intricate interplay between nontrivial topology and magnetism in two-dimensional (2D) materials has led to the emergence of many novel phenomena and functionalities. An outstanding example is the quantum anomalous Hall (QAH) effect, which was realized in magnetically doped topological insulators (TIs) in the absence of magnetic field. Recently, the layered van der Waals compound MnBi2Te4 has been theoretically predicted and experimentally verified to be a TI with interlayer antiferromagnetic (AFM) order. It is a rare stoichiometric material with coexisting topology and magnetism, thus repr…
