We have employed resonant x-ray magnetic scattering to specifically probe the magnetic order of the rare-earth ions in multiferroic $\mathrm{TbMn_2O_5}$. Two energy resonances were observed, one originated from the E1-E1 dipolar transition and the other from the E2-E2 quadrupolar transition. These resonances directly probe the valence 5d band and the partially occupied 4f band, respectively. First, full polarization analysis, which is a measurement of the scattered polarization as a function of incident polarization, confirmed a spin polarization of the terbium valence states (probed by the E1-E1 transition) by the $\mathrm{Mn^{4+}}$ spin density in the commensurate phase. Second, full polarization analysis data were collected in the low-temperature incommensurate and commensurate phases when tuned to the E2-E2 resonance. By employing a least-squares fitting procedure, the spin orientations of the terbium ion sublattice were refined.
We report on resonant magnetic x-ray scattering and absorption spectroscopy studies of exchange-coupled antiferromagnetic ordering of Eu$^{3+}$ magnetic moments in multiferroic Eu$_{1-x}$Y$_{x}$MnO$_3$ in the absence of an external magnetic field. The observed resonant spectrum is characteristic of a magnetically ordered $^7F_1$ state that mirrors the Mn magnetic ordering, due to exchange coupling between the Eu $4f$ and Mn $3d$ spins. This is the first observation of long range magnetic order generated by exchange coupling of magnetic moments of formally non-magnetic Van Vleck ions, which is …
The rare earth nickelates RNiO3 are metallic at high temperatures and insulating and magnetically ordered at low temperatures. The low temperature phase has been predicted to be type II multiferroic, i.e. ferroelectric and magnetic order are coupled and occur simultaneously. Confirmation of those ideas has been inhibited by the absence of experimental data on single crystals. Here we report on Raman spectroscopic data of RNiO3 single crystals (R = Y, Er, Ho, Dy, Sm, Nd) for temperatures between 10 K and 1000 K. Entering the magnetically ordered phase we observe the appearance of a large number…
Three independent contributions to the magnetically induced spontaneous polarization of multiferroic TbMn2O5 are uniquely separated by optical second harmonic generation and an analysis in terms of Landau theory. Two of them are related to the magnetic Mn3+/4+ order and are independent of applied fields of up to 7 T. The third contribution is related to the long-range antiferromagnetic Tb3+ order. It shows a drastic decrease upon the application of a magnetic field and mediates the change of sign of the spontaneous electric polarization in TbMn2O5. The close relationship between the rare-earth…
Raman and infrared spectroscopies are used as local probes to study the dynamics of the Nd-O bonds in the weakly multiferroic NdMn2O5 system. The temperature dependence of selected Raman excitations reveals the splitting of the Nd-O bonds in NdMn2O5. The Nd3+ ion crystal field (CF) excitations in NdMn2O5 single crystals are studied by infrared transmission as a function of temperature, in the 1800-8000 cm-1 range, and under an applied magnetic field up to 11 T. The frequencies of all 4Ij crystal-field levels of Nd3+ are determined. We find that the degeneracy of the ground-state Kramers double…
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…
Experimental techniques using Bragg diffraction may elucidate electronic and magnetic properties of ferric ions in multiferroic ScFeO3 that are puzzling. A collinear magnetic motif of dipole moments is not expected for s-state ions with an acentric parent (paramagnetic) structure, because single-site anisotropy is negligible and antisymmetric exchange interactions promote an inhomogeneous magnetic motif. However, current indications are that ScFeO3 supports G-type antiferromagnetism, with an unknown moment direction, which implies that ferric ions are not in the high-spin 6S state. It is argue…
We report the results of our investigations on the influence of partial substitution of Er and Gd for Dy on the magnetic and magnetoelectric properties of DyFe0.5Cr0.5O3, which is known to be a multiferroic system. Magnetic susceptibility and heat capacity data, apart from confirming the occurrence of magnetic transitions at ~ 121 and 13 K in DyFe0.5Cr0.5O3, bring out that the lower transition temperature only is suppressed by rare-earth substitution. Multiferroic behavior is found to persist in Dy0.4Ln0.6Fe0.5Cr0.5O3 (Ln= Er and Gd). There is an evidence for magnetoelectric coupling in all th…
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…
Charge-ordered rare earth manganites Nd0.5Ca0.5MnO3, La0.25Nd0.25Ca0.5MnO3, Pr0.7Ca0.3MnO3 and Pr0.6Ca0.4MnO3 are found to exhibit dielectric constant anomalies around the charge-ordering or the magnetic transition temperatures. Magnetic fields have a marked effect on the dielectric properties, indicating the presence of coupling between the magnetic and electrical order parameters. The observation of magnetoferroelectricity in these manganites is in accord with the recent theoretical predictions of Khomskii and coworkers.
We show that charge ordered rare-earth nickelates of the type RNiO3 (R= Ho, Lu, Pr and Nd) are multiferroic with very large magnetically induced ferroelectric (FE) polarizations. This we determine from first principles electronic structure calculations. The emerging FE polarization is directly tied to the long-standing puzzle of which kind of magnetic ordering is present in this class of materials: its direction and size indicate the type of ground-state spin configuration that is realized. Vice versa, the small energy differences between the different magnetic orderings suggest that a chosen …
Multiferroic rare earth manganites attracted recent attention because of the coexistence of different types of magnetic and ferroelectric orders resulting in complex phase diagrams and a wealth of physical phenomena. The coupling and mutual interference of the different orders and the large magnetoelectric effect observed in several compounds are of fundamental interest and bear the potential for future applications in which the dielectric (magnetic) properties can be modified by the onset of a magnetic (dielectric) transition or the application of a magnetic (electric) field. The physical mec…
We investigated the static and dynamic magnetic properties of the polar ferrimagnet Mn$_2$Mo$_3$O$_8$ in three magnetically ordered phases via magnetization, magnetic torque, and THz absorption spectroscopy measurements. The observed magnetic field dependence of the spin-wave resonances, including Brillouin zone-center and zone-boundary excitations, magnetization, and torque, are well described by an extended two-sublattice antiferromagnetic classical mean-field model. In this orbitally quenched system, the competing weak easy-plane and easy-axis single-ion anisotropies of the two crystallogra…
Lattice and spin excitations have been studied by Raman scattering in hexagonal YbMnO3 single crystals. The temperature dependences of the phonon modes show that the E2 mode at 256 cm-1 related to the displacement of Mn and O ions in a-b plane is coupled to the spin order. The A1 phonon mode at 678 cm-1 presents a soft mode behavior at the Neel temperature. Connected to the motion of the apical oxygen ions along the c direction, this mode controls directly the Mn-Mn interactions between adjacent Mn planes and the superexchange path. Crystal field and magnon mode excitations have been identifie…
The breakdown of magnons, the quasiparticles of magnetic systems, has rarely been seen. By using an inelastic neutron scattering technique we report the observation of spontaneous magnon decay in multiferroic LuMnO$_3$, a simple two-dimensional Heisenberg triangular lattice antiferromagnet, with large spin, S = 2. The origin of this rare phenomenon lies in the non-vanishing cubic interaction between magnons in the spin Hamiltonian arising from the noncollinear 120$^o$ spin structure. We observed all three key features of the nonlinear effects as theoretically predicted: a roton-like minimum, a…
The effects of substituting nonmagnetic Mg2+ and Zn2+ ions for the Mn2+ (S = 5/2) ions on the structural, magnetic and dielectric properties of the multiferroic frustrated antiferromagnet MnWO4 were investigated. Polycrystalline samples of Mn1-xMgxWO4 and Mn1-xZnxWO4 (0<x<0.3) solid solutions were prepared by a solid-state route and characterized via X-ray and neutron diffraction, magnetization, and dielectric permittivity measurements. Mg and Zn substitutions give rise to very similar effects. The Neel temperature TN, the AF3-to-AF2 magnetic phase transition temperature T2, and the critical f…
Soft x-ray absorption experiments on the transition metal L2,3 edge of multiferroic MnWO4 and antiferromagnetic CoWO4 are presented. The observed linear polarization dependence, analyzed by full-multiplet calculations, is used to determine the ground state wave function of the magnetic Mn2+ and Co2+ ions. The impact of the local structure and the spin-orbit coupling on the orbital moment is discussed in terms of the single-ion anisotropy. It is shown that the orbital moment in CoWO4 is responsible for the collinear antiferromagnetism, while the small size of spin-orbit coupling effects make sp…
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. …
Magnetic order of the manganese and rare-earth lattices according to different symmetry representations is observed in multiferroic hexagonal (h-) DyMnO$_3$ by optical second harmonic generation and neutron diffraction. The incompatibility reveals that the 3d-4f coupling in the h-$R$MnO$_3$ system ($R$ = Sc, Y, In, Dy - Lu) is substantially less developed than commonly expected. As a consequence, magnetoelectric coupling effects in this type of split-order parameter multiferroic that were previously assigned to a pronounced 3d-4f coupling have now to be scrutinized with respect to their origin…
X-ray resonant scattering has been used to measure the magnetic order of the Dy ions below 40K in multiferroic DyMn$_{2}$O$_{5}$. The magnetic order has a complex behaviour. There are several different ordering wavevectors, both incommensurate and commensurate, as the temperature is varied. In addition a non-magnetic signal at twice the wavevector of one of the commensurate signals is observed, the maximum intensity of which occurs at the same temperature as a local maximum in the ferroelectric polarisation. Some of the results, which bear resemblence to the behaviour of other members of the R…
We developed numerical calculations to simulate the magnetoelectric coupling in multiferroic compounds, using the Monte Carlo technique. Two simple models were used to simulate the compounds. In the first one, the magnetic ions are represented by a spin 1/2 2D Ising lattice of ions, and the electric lattice by classical moments, coupled one to one with the magnetic moments. The coupling between both lattices allows to the leading lattice, that is, the magnetic one, to change the orientation of the electrical dipoles in one direction perpendicular to the magnetic dipoles. This direction was cho…
We present a neutron diffraction study of FeV2O4, which is rare in exhibiting spin and orbital degrees of freedom on both cation sublattices of the spinel structure. Our data confirm the existence of three structural phase transitions previously identified with x-ray powder diffraction, and reveal that the lower two transitions are associated with sequential collinear and canted ferrimagnetic transitions involving both cation sites. Through consideration of local crystal and spin symmetry, we further conclude that Fe2+ cations are ferro-orbitally ordered below 135K and V3+ orbitals order at 60…
We have established detailed magnetoelectric phase diagrams of (Eu$_{0.595}$Y$_{0.405}$)$_{1-x}$Tb$_x$MnO$_3$ ($0 \le x \le 1$) and (Eu,Y)$_{1-x}$Gd$_x$MnO$_3$ ($0 \le x \le 0.69$), whose average ionic radii of $R$-site ($R$: rare earth) cations are equal to that of Tb$^{3+}$, in order to reveal the effect of rare earth 4$f$ magnetic moments on the magnetoelectric properties. In spite of the same $R$-site ionic radii, the magnetoelectric properties of the two systems are remarkably different from each other. A small amount of Tb substitution on $R$ sites ($x \sim 0.2$) totally destroys ferroel…
Matter-light interaction is at the center of diverse research fields from quantum optics to condensed matter physics, opening new fields like laser physics. A magnetic exciton is one such rare example found in magnetic insulators. However, it is relatively rare to observe that external variables control matter-light interaction. Here, we report that the broken inversion symmetry of multiferroicity can act as an external knob enabling the magnetic exciton in van der Waals antiferromagnet NiI2. We further discover that this magnetic exciton arises from a transition between Zhang-Rice-triplet and…
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 …
In multiferroic BiFeO$_3$ a cycloidal antiferromagnetic structure is coupled to a large electric polarization at room temperature, giving rise to magnetoelectric functionality that may be exploited in novel multiferroic-based devices. In this paper, we demonstrate that by substituting samarium for 10% of the bismuth ions the periodicity of the room temperature cycloid is increased, and by cooling below $\sim15$ K the magnetic structure tends towards a simple G-type antiferromagnet, which is fully established at 1.5 K. We show that this transition results from $f-d$ exchange coupling, which ind…
Geometrical frustration of the Fe ions in LuFe2O4 leads to intricate charge and magnetic order and a strong magnetoelectric coupling. Using resonant x-ray diffraction at the Fe K edge, the anomalous scattering factors of both Fe sites are deduced from the (h/3 k/3 l/2) reflections. The chemical shift between the two types of Fe ions equals 4.0(1) eV corresponding to full charge separation into Fe2+ and Fe3+. Polarization and azimuthal angle dependence of the superlattice reflections demonstrates the absence of anisotropic scattering revealing random orientations of the Fe2+ orbitals characteri…
We used Raman scattering to study the lattice and magnetic excitations in the hexagonal HoMnO3 single crystals. The E2 phonon mode at 237 cm-1 is affected by the magnetic order. This mode is related to the displacement of Mn and O ions in a-b plane and modulates the Mn-O-Mn bond angles in a-b plane and the in-plane Mn-Mn superexchange interaction. The mode at 269 cm-1 associated to the displacement of the apical Ho3+ ions along the c direction presents an abrupt change of slope at TN showing that the role of the rare earth ions can not be neglected in the magnetic transition. We have identifie…
We argue for a recently observed puzzling multiferroic behavior in s=1/2 1D chain cuprate LiCu2O2 with edge-shared arrangement of CuO4 plaquettes and incommensurate spiral spin ordering can be consistently explained if one takes into account the nonrelativistic exchange-induced electric polarization on the Cu2+ centers substituting for the positions native for the Cu1+ ions. These substituent centers are proved to be an effective probe of the spin incommensurability and magnetic field effects.
In multiferroic TbMn$_2$O$_5$, the behavior of the terbium ions forms a crucial part of the magneto-electric coupling. The result is a magnetically induced reversal of the electric polarization at 2 T. In this article we present the first direct measurement of the terbium magnetic structure under applied magnetic fields. Contrary to the current interpretation of the magnetic properties of \tmo, we show that upon the electric polarization reversal the terbium sub-lattice adopts a canted antiferromagnetic structure with a large component of magnetic moment parallel to the \textit{a}-axis. Furthe…
We present a unique example of giant magnetoelectric effect in a conventional multiferroic HoMnO3, where polarization is very large (~56 mC/m2) and the ferroelectric transition temperature is higher than the magnetic ordering temperature by an order. We attribute the uniqueness of the giant magnetoelectric effect to the ferroelectricity induced entirely by the off-center displacement of rare earth ions with large magnetic moments. This finding suggests a new avenue to design multiferroics with large polarization and higher ferroelectric transition temperature as well as large magnetoelectric e…
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 …
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…
Multiferroics, showing simultaneous ordering of electrical and magnetic degrees of freedom, are remarkable materials as seen from both the academic and technological points of view. A prominent mechanism of multiferroicity is the spin-driven ferroelectricity, often found in frustrated antiferromagnets with helical spin order. There, similar to conventional ferroelectrics, the electrical dipoles arise from an off-centre displacement of ions. However, recently a different mechanism, namely purely electronic ferroelectricity, where charge order breaks inversion symmetry, has attracted considerabl…
Electric polarization in conventional ferroelectric oxides usually involves nonmagnetic transition-metal ions with an empty d shell (the d$^0$ rule). Here we unravel a new mechanism for local electric dipoles based on magnetic Fe$^{3+}$ (3d$^5$) ion violating the d$^0$ rule. The competition between the long-range Coulomb interaction and short-range Pauli repulsion in a FeO$_5$ bipyramid with proper lattice parameters would favor an off-center displacement of Fe$^{3+}$ that induces a local electric dipole. The manipulation of this kind of non-d$^0$ electric dipoles opens up a new route for gene…
The recently observed multiferroic behavior in the s=1/2 chain cuprate LiVCuO_4 (LiCuVO_4) with edge-shared CuO_4 plaquettes and helical spin ordering does not agree with the existing theories such as a spin-current scenario. We argue that the effect can be consistently explained, if the exchange-induced electric polarization on the out-of-chain Cu^2+ centers substituting for Li-ions in LiVCuO_4 is taken into account. These substituent centers are proved to be an effective probe of the spin incommensurability and the magnetic field effects.
The orthovanadate DyVO3 crystal, known to exhibit multiple structural, spin and orbital ordering transitions, is presently investigated on the basis of magnetization, heat capacity, resistivity, dielectric and polarization measurements. Our main result is experimental evidence for the existence of multiferroicity below a high TC of 108 K over a wide temperature range including different spin-orbital ordered states. The onset of ferroelectricity is found to coincide with the antiferromagnetic C-type spin ordering transition taking place at 108 K, which indicates that DyVO3 belongs to type II mu…
The structural, magnetic, electrical and transport properties of FeV2O4, by doping Li and Cr ions respectively in A and B sites, have been studied. Dilution of A-site by Li doping increases the ferri-magnetic ordering temperature and decreases the ferroelectric transition temperature. This also decreases the V-V distances which in effect increases the A-V coupling. This increased A-V coupling dominates over the decrease in A-V coupling due to doping of non-magnetic Li. On the other hand, Cr doping increases the ferri-magnetic ordering temperature but does not alter the ferroelectric transition…
Magnetic rare earths R have been proven to have a significant effect on the multiferroic properties of the orthorhombic manganites RMnO3. A re-examination of previous results from synchrotron based x-ray scattering experiments suggests that symmetric exchange striction between neighboring R and Mn ions may account for the enhancement of the ferroelectric polarization in DyMnO3 as well as the magnetic-field induced ferroelectricity in GdMnO3. In general, adding a second magnetic species to a multiferroic material may be a route to enhance its ferroelectric properties.
Ab-initio spin-polarized Density Functional Theory plus U is used to study the electronic and magnetic properties of tetragonal doped barium titanate (Ba$_{1-x}$Eu$_x$O$_3$) system for different europium (Eu$^{3+}$) concentrations. For this study, the Projector Augmented Wave (PAW) method and a Perdew-Zunger (LSDA) approximation, which has been used for the exchange correlation energy, have been considered taking into account a supercell model. In this model, the spin polarization as well as the Hubbard's potential have been used for the correction of the electron-electron Coulomb interactions…
Despite remarkable progress in developing multifunctional materials, spin-driven ferroelectrics featuring both spontaneous magnetization and electric polarization are still rare. Among such ferromagnetic ferroelectrics are conical spin spiral magnets with a simultaneous reversal of magnetization and electric polarization that is still little understood. Such materials can feature various multiferroic domains that complicates their study. Here we study the multiferroic domains in ferromagnetic ferroelectric Mn$_{2}$GeO$_{4}$ using neutron diffraction, and show that it features a double-Q conica…
We have performed high resolution neutron diffraction and inelastic neutron scattering experiments in the frustrated multiferroic hexagonal compounds RMnO3 (R=Ho, Yb, Sc, Y), which provide evidence of a strong magneto-elastic coupling in the the whole family. We can correlate the atomic positions, the type of magnetic structure and the nature of the spin waves whatever the R ion and temperature. The key parameter is the position of the Mn ions in the unit cell with respect to a critical threshold of 1/3, which determines the sign of the coupling between Mn triangular planes.
Intriguing Magnetocaloric Effect in Multiferroic Ba3RRu2O9 (R=Ho, Gd, Tb, Nd) with Strong 4d-4f Correlations
Rajiv Gandhi Institute of Petroleum Technology（拉吉夫·甘地石油技术学院）；Laboratoire CRISMAT, Universite´ de Caen Normandie, ENSICAEN, CNRS UMR 6508, Normandie Univ.（卡昂诺曼底大学CRISMAT实验室）；School of Physical Science, Indian Association for the Cultivation of Science（印度科学促进协会物理科学学院）
We report high-resolution optical absorption spectra for NdFe3(BO3)4 trigonal single crystal which is known to exhibit a giant magnetoelectric effect below the temperature of magnetic ordering TN = 33 K. The analysis of the temperature-dependent polarized spectra reveals the energies and, in some cases, symmetries and exchange splittings of Nd3+ 84 Kramers doublets. We perform crystal-field calculations starting from the exchange-charge model, obtain a set of six real crystal-field parameters, and calculate wave functions and magnetic g-factors. In particular, the values g(perpendicular) = 2.3…
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…
The spin reorientation (SR) phenomenon of the square-lattice antiferromagnets RMnAsO (R = Ce, Nd) was investigated by analyzing the spin exchange interactions between the rare-earth and transition-metal ions (R3+ and Mn2+, respectively) on the basis of density functional calculations. It is found that the symmetry and strength of the Dzyaloshinskii-Moriya (DM) interaction are determined primarily by the partially filled 4f states of the R3+ ions, and that the DM and biquadratic (BQ) exchanges between the R3+ and Mn2+ ions are unusually strong and control the observed spin reorientation phenome…
Ca_3Co_{2-x}Mn_xO_6 (x ~ 0.96) is a multiferroic with spin-chains of alternating Co(2+) and Mn(4+) ions. The spin state of Co(2+) remains unresolved, due to a discrepancy between high temperature X-ray absorption (S=3/2) and low temperature neutron (S=1/2) measurements. Using a combination of magnetic modeling and crystal-field analysis, we show that the existing low temperature data cannot be reconciled within a high spin scenario by invoking spin-orbit or Jahn-Teller distortions. To unify the experimental results, we propose a spin-state crossover with specific experimental predictions.
The complex interplay between the 3d and 4f moments in hexagonal ErMnO3 is investigated by magnetization, optical second harmonic generation, and neutron-diffraction measurements. We revise the phase diagram and provide a microscopic model for the emergent spin structures with a special focus on the intermediary phase transitions. Our measurements reveal that the 3d exchange between Mn^{3+} ions dominates the magnetic symmetry at 10 K < T < T_N with Mn^3+ order according to the Gamma_4 representation triggering 4f ordering according to the same representation on the Er^{3+}(4b) site. Below 10 …
Multiferroic TbMnO3 is investigated using x-ray diffraction in high magnetic fields. Measurements on first and second harmonic structural reflections due to modulations induced by the Mn and Tb magnetic order are presented as function of temperature and field oriented along the a and b-directions of the crystal. The relation to changes in ordering of the rare earth moments in applied field is discussed. Observations below T_N(Tb) without and with applied magnetic field point to a strong interaction of the rare earth order, the Mn moments and the lattice. Also, the incommensurate to commensurat…
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$0.5 in the temperature range investigated, which can be attributed solely to the dilution of magnetic interactio…
The electric field effect on magnetism was examined in the multiferroic conical magnet Mn$_2$GeO$_4$, which shows a strong coupling between ferromagnetic and ferroelectric order parameters. The systematic evaluation of the electric polarization in the multiferroic phase below 5.5 K under various field cooling conditions reveals that small magnetic fields of 0.1 T significantly reduce the required electric fields needed to reach saturation. By applying electric fields during magnetic field dependent hysteresis measurements of magnetization M and polarization P an electrically controllable excha…
We show that electronic correlations decimate the intrinsic ferroelectric polarization of the recently discovered class of multiferroic manganites RMn$_2$O$_5$, where R is a rare earth element. Such is manifest from {\it ab initio} bandstructure computations that account for the strong local Coulomb interactions between the manganese 3d electrons --the root of magnetism in these materials. When including these the computed electronic, magnetic and lattice structure of multiferroic HoMn$_2$O$_5$ results in an amplitude and direction of polarization that is in accordance with experiment. The mic…
We study magnetic and multiferroic behavior in Ca$_3$Co$_{2-x}$Mn$_{x}$O$_6$ ($x \sim$0.97) by high-field measurements of magnetization ($M$), magnetostriction ($L$($H$)/$L$), electric polarization ($P$), and magnetocaloric effect. This study also gives insight into the zero and low magnetic field magnetic structure and magnetoelectric coupling mechanisms. We measured $M$ and $Δ$$L$/$L$ up to pulsed magnetic fields of 92 T, and determined the saturation moment and field. On the controversial topic of the spin states of Co$^{2+}$ and Mn$^{4+}$ ions, we find evidence for $S$ = 3/2 spins for both…
We have successfully synthesized three quasi-2D geometrically frustrated magnetic compounds (α-MCr_2O_4, M=Ca, Sr, Ba) using the spark-plasma-sintering technique. All these members of the α-MCr_2O_4 family consist of the stacking planar triangular lattices of Cr$^{3+}$ spins (${\rm S}=3/2$), separated by non-magnetic alkaline earth ions. Their corresponding magnetic susceptibility, specific heat, dielectric permittivity and ferroelectric polarization are systematically investigated. A long-range magnetic ordering arises below the Néel temperature (around 40K) in each member of the α-MCr_2O_4 f…
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…
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.
Density-functional calculations are carried out to investigate incommensurate magnetic structures and ferroelectric polarization in newly discovered multiferroic material MnI$_2$. The exchange interactions among local moments on Mn are parameterized by mapping the mean-field Heisenberg model on to total energy difference of several magnetic ordering states. The experimentally observed noncollinear magnetic states are well reproduced by using this model and exchange interaction parameters. The direction of polarization experimentally measured is also consistent with the result derived from the …
A series of manganites Tb1-xHoxMnO3 (0<=x<=0.6) with orthorhombic structure are synthesized and detailed investigations on their multiferroicity are performed. Successive magnetic transitions upon temperature variation are evidenced for all samples, and both the Mn3+ spiral spin ordering and rare-earth spin ordering are suppressed with increasing x. Significant enhancement of both the polarization and magnetoelectric response within 0.2<x<0.4 is observed, which may be ascribed to the competition possibly existing between spiral and E-type spin orders. Theoretical calculation is given based on …
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…
