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 the nontrivial behavior of the electric polarization. We also predict the noncollinear deformation of the E-type spin structure and a wide coexisting regime of the E and spiral states, which resolve several experimental puzzles.
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.
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…
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…
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…
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.
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, …
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 …
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…
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…
Spin-phonon coupling, the interaction of spins with surrounding lattice is a key parameter to understand the underlying physics of multiferroics and engineer their magnetization dynamics. Elementary excitations in multiferroic materials are strongly influenced by spin-phonon interaction, making Raman spectroscopy a unique tool to probe these coupling(s). Recently, it has been suggested that the dielectric and magnetic properties of 15R-type hexagonal BaMnO3 are correlated through the spin-lattice coupling. Here, we report the observation of an extensive renormalization of the Raman spectrum of…
Raman scattering measurements on BiFeO3 single crystals show an important coupling between the magnetic order and lattice vibrations. The temperature evolution of phonons shows that the lowest energy E and A1 phonon modes are coupled to the spin order up to the Neel temperature. Furthermore, low temperature anomalies associated with the spin re-orientation are observed simultaneously in both the E phonon and the magnon. These results suggest that magnetostriction plays an important role in BiFeO3.
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 …
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…
In this contribution to the special issue on multiferroics we focus on multiferroicity driven by different forms of charge ordering. We will present the generic mechanisms by which charge ordering can induce ferroelectricity in magnetic systems. There is a number of specific classes of materials for which this is relevant. We will discuss in some detail $(i)$ perovskite manganites of the type (PrCa)MnO$_3$, $(ii)$ the complex and interesting situation in magnetite Fe$_3$O$_4$, $(iii)$ strongly ferroelectric frustrated LuFe$_2$O$_4$, $(iv)$ an example of a quasi one-dimensional organic system. …
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…
Magnetic properties of an antiferromagnetic double perovskite oxide Ba2CaReO6, where Re6+ (5d1) ions with large spin-orbit coupling are arranged on the face-centered-cubic lattice, are investigated using pulsed high magnetic field up to 66 T. Magnetization and magnetostriction measurements have revealed a magnetic field induced phase transition at around 50 T. The phase transition accompanies a jump of magnetization and longitudinal magnetostriction of approximately 2 10^(-4) with the change of power law behavior, indicating sizable coupling between the electronic degrees of freedom and the la…
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…
The magnetoelastic coupling in multiferroic $DyMn_2O_5$ is investigated by magnetostriction measurements along the three crystallographic orientations. Strong lattice anomalies as a function of the magnetic field are detected at the low temperature magnetic and ferroelectric phase transitions. The sign and magnitude of the magnetostrictive coefficient as well as the lattice anomalies at the transitions are correlated with the Dy moment order and with the sharp changes of the dielectric constant and the ferroelectric polarization. With the magnetic field applied along the c-axis a new high-fiel…
Exploring new magnetic materials is essential for finding advantageous functional properties such as magnetoresistance, magnetocaloric effect, spintronic functionality, and multiferroicity. Versatile classes of double perovskite compounds have been recently investigated because of intriguing physical properties arising from the proper combination of several magnetic ions. In this study, it is observed that the dominant ferrimagnetic phase is coexisted with a minor multiferroic phase in single-crystalline double-perovskite Er2CoMnO6. The majority portion of the ferrimagnetic order is activated …
We investigate magnetoelectric coupling and low-energy magnetic excitations in multiferroic $α$-Cu$_2$V$_2$O$_7$ by detailed thermal expansion, magnetostriction, specific heat and magnetization measurements in magnetic fields up to 15~T and by high-field/high-frequency electron spin resonance studies. Our data show negative thermal expansion in the temperature range $\leq 200$~K under study. Well-developed anomalies associated with the onset of multiferroic order (canted antiferromagnetism with a significant magnetic moment and ferroelectricity) imply pronounced coupling to the structure. We d…
We present a detailed temperature-dependent spectroscopic study of DyMnO3 single crystals with distorted perovskite structure. Energies of 36 crystal-field levels of Dy3+ in paramagnetic DyMnO3 were determined. The Dy3+ ground Kramers doublet does not split at T_N^Mn = 39 K and splits below Tlock = 18 K. The splitting grows fast at temperatures near T_N^Dy = 6.5 K and reaches Δ0 = 11 cm-1 at 4 K. Using the experimental temperature dependence Δ0(T), we calculate the dysprosium magnetic moment mDy(T) and the dysprosium contribution into specific heat and magnetic susceptibility. Analysing all th…
A microscopic model for the room-temperature multiferroic BiFeO$_3$ that includes two Dzyaloshinskii-Moriya interactions and single-ion anisotropy along the ferroelectric polarization predicts both the zero-field spectroscopic modes as well as their splitting and evolution in a magnetic field. Due to simultaneously broken time-reversal and spatial-inversion symmetries, the absorption of light changes as the magnetic field or the direction of light propagation is reversed. We discuss three physical mechanisms that may contribute to this absorption asymmetry known as non-reciprocal directional d…
We have investigated electrically-active magnetic excitations (electromagnons) in perovskite manganites with the $E$-type (up-up-down-down) spin structure by terahertz spectroscopy. Eu$_{1-x}$Y$_x$MnO$_3$ (0.1$\le x\le$1) and Y$_{1-y}$Lu$_y$MnO$_3$ (0$\le y\le$1) without magnetic $f$-moments, which host collinear sinusoidal, $A$-type, cycloidal, and $E$-type spin orders, are used to examine the systematics of possible electromagnons. Three-peak structures (23, 35, 45 cm$^{-1}$) of magnetic origin show up in the $E$-type phase with little composition ($y$) dependence of frequencies, making a co…
Recent spectroscopic studies at terahertz frequencies for a variety of multiferroics endowed with both ferroelectric and magnetic orders have revealed the possible emergence of a new collective excitation, frequently referred to as electromagnon. It is magnetic origin, but becomes active in response to the electric field component of light. Here we give an overview on our recent advance in the terahertz time-domain spectroscopy of electromagnons or electric-dipole active magnetic resonances, focused on perovskite manganites--$R$MnO$_3$ ($R$ denotes rare-earth ions). The respective electric and…
LiCuVO$_4$ is a model system of a 1D spin-1/2 chain that enters a planar spin-spiral ground state below its Néel temperature of 2.4 K due to competing nearest and next nearest neighbor interactions. The spin-spiral state is multiferroic with an electric polarization along the a axis which has been proposed to be caused purely by the spin supercurrent mechanism. With external magnetic fields in c direction T$_N$ can be suppressed down to 0 K at 7.4 T. Here we report dynamical measurements of the polarization from P(E)-hysteresis loops, magnetic field dependent pyro-current and non-linear dielec…
We have performed dielectric measurements and neutron diffraction experiments on the double perovskite In2NiMnO6. A ferroelectric polarization, P ~ 30 μC/m2, is observed in a polycrystalline sample below TN = 26 K where a magnetic phase ransition occurs. The neutron diffraction experiment demonstrates that a complex noncollinear magnetic structure with "cycloidal" and "proper screw" components appears below TN, which has the incommensurate propagation vector k = (ka,0,ks; ka ~ 0.274, ks ~ -0.0893). The established magnetic point group 21' implies that the macroscopic ferroelectric polarization…
We show theoretically with an accurate spin Hamiltonian describing the multiferroic Mn perovskites that the application of the picosecond optical pulse with a terahertz frequency can switch the spin chirality through intensely exciting the electromagnons. There are four states with different spin chiralities, i.e. clockwise and counterclockwise ab/bc-plane spin spirals, and by tuning the strength, shape and length of the pulse, the switching among these states can be controlled at will. Dynamical pattern formation during the switching is also discussed.
The phase diagram of quarter-hole-doped perovskite manganites is investigated using the doubleexchange model. An exotic striped type-II multiferroic phase, where 25% of the nearest-neighbor spin couplings are orthogonal to each other, is found in the narrow-bandwidth region. Comparing with the spiral-spin ordering phase of undoped manganites, the multiferroic Curie temperature of the new phase is estimated to be ~4 times higher, while the ferroelectric polarization is similar in magnitude. Our study provides a path for noncollinear spin multiferroics based on electronic self-organization, diff…
Multiferroicity and magnetodielectric coupling in metal-organic-frameworks (MOFs) is rare and so far restricted mainly to formate-based systems with perovskite structure. In the course of this work we designed a tetragonal framework [Co(C16H15N5O2)], exhibiting spin-chains of Co2+ ions, which are bridged by an organic linker containing a dipolar nitrobenzene moiety. This compound shows relaxor-like ferroelectricity at 100 K, which is followed by the onset of complex magnetic order at 15 K, indicative of weak ferromagnetism. The clear anomaly of the dielectric constant at the magnetic ordering …
By studying the dielectric properties of the geometrically frustrated spinel CdV2O4, we observe ferroelectricity developing at the transition into the collinear antiferromagnetic ground state. In this multiferroic spinel, ferroelectricity is driven by local magnetostriction and not by the more common scenario of spiral magnetism. The experimental findings are corroborated by ab-initio calculations of the electric polarization and the underlying spin and orbital order. The results point towards a charge rearrangement due to dimerization, where electronic correlations and the proximity to the in…
We present a first principles study of the series of multiferroic barium fluorides with the composition BaMF4, where M is Mn, Fe, Co, or Ni. We discuss trends in the structural, electronic, and magnetic properties, and we show that the ferroelectricity in these systems results from the "freezing in" of a single unstable polar phonon mode. In contrast to the case of the standard perovskite ferroelectrics, this structural distortion is not accompanied by charge transfer between cations and anions. Thus, the ferroelectric instability in the multiferroic barium fluorides arises solely due to size …
In this work we explore the overall structural behaviour of the [(CH3)2NH2][Mn(HCOO)3] multiferroic compound across the temperature range where its ferroelectric transition takes place by means of calorimetry, thermal expansion measurements and variable temperature powder and single crystal X-ray diffraction. The results clearly proof the presence of structural phase transition at Tt ~187 K (temperature at which the dielectric transition occurs) that involves a symmetry change from R-3c to Cc, twinning of the crystals, a discontinuous variation of the unit cell parameters and unit cell volume,…
Two dimensional multiferroics inherit prominent physical properties from both low dimensional materials and magnetoelectric materials, and can go beyond their three dimensional counterparts for their unique structures. Here, based on density functional theory calculations, a MXene derivative, i.e., i-MXene (Ta$_{2/3}$Fe$_{1/3}$)$_2$CO$_2$, is predicted to be a type-I multiferroic material. Originated from the reliable $5d^0$ rule, its ferroelectricity is robust, with a moderate polarization up to $\sim12.33$ $μ$C/cm$^2$ along the a-axis, which can be easily switched and may persist above room …
CuFeO_2 is one of the multiferroic materials and is the first case that the electric polarization is not explained by the magnetostriction model or the spin-current model. We have studied this material using soft x-ray resonant diffraction and found that superlattice reflection 0, 1 - 2q, 0 appears in the ferroelectric and incommensurate magnetic ordered phase at the Fe L2,3 absorption edges and moreover that the rotation of the x-ray polarization such as from σ to π or from π to σ is allowed at this reflection. These findings definitely provide direct evidence that the 3d orbital state of Fe …
Multiferroics - materials which are simultaneously (ferro)magnetic and ferroelectric, and often also ferroelastic, attract now considerable attention, both because of the interesting physics involved and as they promise important practical applications. In this paper I give a survey of microscopic factors determining the coexistence of these properties, and discuss different possible routes to combine them in one material. In particular the role of the occupation of d-states in transition metal perovskites is discussed, possible role of spiral magnetic structures is stressed and the novel mech…
By means of single-crystal X-ray diffraction we have revealed the breaking of centrosymmetry when lowering the temperature under T$_s$ = 200 K concomitantly with the setting of a commensurate superstructure in the small A-site quadruple perovskite YMn$_3$Mn$_4$O$_{12}$. This results is in agreement with all data already reported for this compounds and solve the previous inconsistency about the Yttrium position. The superstructure is characterized by the appearing of satellite reflections in the single crystal pattern, consistent with an I-centered pseudo-orthorhombic commensurate supercell wit…
We show that the symmetry of the spin zigzag chain E phase of the orthorhombic perovskite manganites and nickelates allows for the existence of a finite ferroelectric polarization. The proposed microscopic mechanism is independent of spin-orbit coupling. We predict that the polarization induced by the E-type magnetic order can potentially be enhanced by up to two orders of magnitude with respect to that in the spiral magnetic phases of TbMnO3 and similar multiferroic compounds.
We present a study of the anisotropy of the dielectric, magnetic and magnetoelastic properties of the multiferroic clinopyroxene NaFeGe$_2$O$_6$. Pyroelectric currents, dielectric constants and magnetic susceptibilities as well as the thermal expansion and the magnetostriction were examined on large synthetic single crystals of NaFeGe$_2$O$_6$. The spontaneous electric polarization detected below $T_{\rm C}\simeq 11.6$ K in an antiferromagnetically ordered state ($T_{\rm N}\simeq 13$ K) is mainly lying within the $ac$ plane with a small component along $b$, indicating a triclinic symmetry of t…
Magnetic and/or dielectric behaviors have been studied for YBaCuFeO5, LuBaCuFeO5 and TmBaCuFeO5, which are known as members of oxygen-defect ordered perovskite systems RBaCuFeO5 (R=lanthanides Ln and other trivalent elements) and have two magnetic transitions: The magnetic structure of the high temperature(T) ordered phase is basically antiferromagnetic, and with decreasing T, a modulated magnetic component superposed on the antiferromagnetic moments appears at the second transition, where the ferroelectricity also appears (multiferroic). Here, we have found that all the systems studied here e…
We report on structural, magnetic, dielectric, and thermodynamic properties of (Eu:Y)MnO3 for Y doping levels 0 <= x < 1. This system resembles the multiferroic perovskite manganites RMnO3 (with R= Gd, Dy, Tb) but without the interference of magnetic contributions of the 4f-ions. In addition, it offers the possibility to continuously tune the influence of the A-site ionic radii. For small concentrations x <= 0.1 we find a canted antiferromagnetic and paraelectric groundstate. For higher concentrations x <= 0.3 ferroelectric polarization coexists with the features of a long wavelength incommens…
We present a microscopic theory that shows the importance of spin-orbit coupling in perovskite compounds with heavy ions. In BiFeO3 (BFO) the spin-orbit coupling at the bismuth ion sites results in a special kind of magnetic anisotropy that is linear in the applied E-field. This interaction can convert the cycloid ground state into a homogeneous antiferromagnet, with a weak ferromagnetic moment whose orientation can be controlled by the E-field direction. Remarkably, the E-field control of magnetism occurs without poling the ferroelectric moment, providing a pathway for reduced energy dissipat…
Muon spin relaxation measurements are reported on samples of dimethylammonium metal formates containing magnetic divalent nickel, cobalt, manganese, and copper ions. These hybrid organic-inorganic perovskites exhibit weak ferromagnetism and are, apart from the copper system, multiferroics with well separated magnetic and antiferroelectric transitions. We use muons to follow the sublattice magnetization, observing the effect of the spin reorientation transitions below TN and the criticality approaching TN. The multiferroic samples have three-dimensional antiferromagnetic interactions, but the c…
Exchange bias is usually rationalized invoking spin pinning effects caused by uncompensated antiferromagnetic interfaces. However, for compensated antiferromagnets other extrinsic factors, such as interface roughness or spin canting, have to be considered to produce a small uncompensation. As an alternative, here we propose two (related) possible mechanisms, driven by the intrinsic Dzyaloshinskii-Moriya interaction and ferroelectric polarization, for the explanation of exchange bias effects in perovskites with compensated G-type antiferromagnetism. One of the mechanisms is only active when a m…
Chirality, i.e., the right- and left-handedness of structure, is one of the key concepts in many fields of science including biology, chemistry and physics, and its manipulation is an issue of vital importance. The electron spins in solids can form chiral configurations. In perovskite manganites RMnO3 (R=Tb, Dy,...etc), the Mn-spins form a cycloidal structure, which induces ferroelectric polarization (P) through the relativistic spin-orbit interaction. This magnetism-induced ferroelectricity (multiferroics) and associated infrared-active spin waves (electromagnons) open a promising route to co…
(NH$_4$)$_2$[FeCl$_5$(H$_2$O)], a member of the family of antiferromagnetic $A_2$[Fe$X_5$(H$_2$O)] compounds ($X$ = halide ion, $A$ = alkali metal or ammonium ion) is classified as a new multiferroic material. We report the onset of ferroelectricity below ~6.9 K within an antiferromagnetically ordered state ($T_N \sim 7.25 K$). The corresponding electric polarization can drastically be influenced by applying magnetic fields. Based on measurements of pyroelectric currents, dielectric constants and magnetization we characterize the magnetoelectric, dielectric and magnetic properties of (NH$_4$)$…
We report a magnetostriction study of a perovskite $\rm{LaCoO}_{3}$ above 100 T using our state-of-the-art strain gauge to investigate an interplay between electron correlations and spin crossover. There has been a controversy regarding whether two novel phases in $\rm{LaCoO}_{3}$ at high magnetic fields result from crystallizations or Bose-Einstein condensation during spin crossover as manifestations of localization and delocalization in spin states, respectively. We show that both phases are crystallizations rather than condensations, and the two crystallizations are different, based on the …
We present high-resolution thermal expansion $α(T)$ and magnetostriction $ΔL(H)/L$ measurements of GdMnO$_3$, which develops an incommensurate antiferromagnetic order (ICAFM) below $T_{\rm N}\simeq$ 42 K and transforms into a canted A-type antiferromagnet (cAFM) below $T_{\rm c}\simeq 20 $K. In addition, a ferroelectric polarization ${\bf P}||a$ is observed below $T_{\rm FE} $ for finite magnetic fields applied along the $b$ direction. In zero magnetic field we find a strongly anisotropic thermal expansion with certain, rather broad anomalous features. In finite magnetic fields, however, very …
Magnetic structures and the relationship between spin and charge-orbital orderings of an A-site ordered double-perovskite manganite SmBaMn2O6, an anticipated multiferroic material, were investigated by means of neutron diffraction. The spin arrangement in MnO2 planes perpendicular to the c axis is revealed to be the same as that in the A-site disordered half-doped manganites CE-type but the stacking pattern is found to be different displaying a unique twofold period. The temperature dependence of the superlattice magnetic and nuclear reflections clarifies that the antiferromagnetic spin orderi…
We have performed synchrotron radiation X-ray and neutron diffraction measurements on magnetoelectric multiferroic CuFe1-xAlxO2 (x=0.0155), which has a proper helical magnetic structure with incommensurate propagation wave vector in the ferroelectric phase. The present measurements revealed that the ferroelectric phase is accompanied by lattice modulation with a wave number 2q, where q is the magnetic modulation wave number. We have calculated the Fourier spectrum of the spatial modulations in the local electric polarization using a microscopic model proposed by Arima [T. Arima, J. Phys. Soc. …
The magnetic phase diagrams of RMnO3 (R = Er, Yb, Tm, Ho) are investigated up to 14 Tesla via magnetic and dielectric measurements. The stability range of the AFM order below the Neel temperature of the studied RMnO3 extends to far higher magnetic fields than previously assumed. Magnetic irreversibility indicating the presence of a spontaneous magnetic moment is found near 50 K for R=Er, Yb, and Tm. At very low temperatures and low magnetic fields the phase boundary defined by the ordering of the rare earth moments is resolved. The sizable dielectric anomalies observed along all phase boundari…
Strain is a leading candidate for controlling magnetoelectric coupling in multiferroics. Here, we use x-ray diffraction to study the coupling between magnetic order and structural distortion in epitaxial films of the orthorhombic (o-) perovskite LuMnO$_3$. An antiferromagnetic spin canting in the E-type magnetic structure is shown to be related to the ferroelectrically induced structural distortion and to a change in the magnetic propagation vector. By comparing films of different orientations and thicknesses, these quantities are found to be controlled by b-axis strain. It is shown that compr…
