The low-temperature ferroelectric polarization of multiferroic $YMn_2O_5$ is completely reversed at a critical pressure of 10 kbar and the phase transition from the incommensurate to the commensurate magnetic phase is induced by pressures above 14 kbar. The high-pressure data correlate with thermal expansion measurements indicating a significant lattice strain at the low-temperature transition into the incommensurate phase. The results support the exchange striction model for the ferroelectricity in multiferroic $RMn_2O_5$ compounds and they show the importance of magnetic frustration as well as the spin-lattice coupling.
Based on temperature dependent far infrared transmission spectra of YMn2O5 and TbMn2O5 single crystals, we report the observation of electric dipole-active magnetic excitations, or electromagnons, in these multiferroics. Electromagnons are found to be directly responsible for the step-like anomaly of the static dielectric constant at the commensurate--incommensurate magnetic transition and are the origin of the colossal magneto-dielectric effect reported in these multiferroics.
We have determined the magnetic structure of the low-temperature incommensurate phase of multiferroic YMn2O5 using single-crystal neutron diffraction. By employing corepresentation analysis, we have ensured full compliance with both symmetry and physical constraints, so that the electrical polarization must lie along the b axis, as observed. The evolution of the spin components and propagation through the commensurate-incommensurate phase boundary points unambiguously at the exchange-striction mechanism as the primary driving force for ferroelectricity.
We studied magnetic excitations in a low-temperature ferroelectric phase of the multiferroic YMn2O5 using inelastic neutron scattering (INS). We identify low-energy magnon modes and establish a correspondence between the magnon peaks observed by INS and electromagnon peaks observed in optical absorption [1]. Furthermore, we explain the microscopic mechanism, which results in the lowest-energy electromagnon peak, by comparing the inelastic neutron spectral weight with the polarization in the commensurate ferroelectric phase.
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$0.5 in the temperature range investigated, which can be attributed solely to the dilution of magnetic interactio…
In this article, the collective response of the spins is explored through low field bulk magnetic measurement for the series YMn$_{2-x}$Cr$_x$O$_5$ (x= 0.0, 0.05). Low field ac susceptibility and dc magnetization of YMn$_2$O$_5$ shows multiple transition in analogy to those observed in electrical measurement of the compound. Using various time dependent magnetization protocols it has been observed that the behavior of spins in commensurate and incommensurate phase are drastically different. YMn$_{1.95}$Cr$_{0.05}$O$_5$ undergoes a ferrimagnetic ordering with an enhanced magnetic ordering tempe…
We investigated the magnetic structure of an orthorhombic YMnO3 thin film by resonant soft x-ray and hard x-ray diffraction. We observed a temperature-dependent incommensurate magnetic reflection below 45 K and a commensurate lattice-distortion reflection below 35 K. These results demonstrate that the ground state is composed of coexisting E-type and cycloidal states. Their different ordering temperatures clarify the origin of the large polarization to be caused by the E-type antiferromagnetic states in the orthorhombic YMnO3 thin film.
Hexagonal YMnO_3 with space group P63cm is one of the rare examples of multiferroic materials that exhibit co-dependence of a robust ferroelectric phase along with antiferromagnetic ordering. This is primarily ascribed to tilting of the MnO_5 polyhedra driven by magnetoelectric coupling. We report on the effect of magnetic field at the atomic level in YMnO_3 by utilizing magnetic field and temperature dependent neutron diffraction measurements. We show that near the Néel temperature the lattice parameters, effective magnetic moment per site, Mn-O bond lengths and O-Mn-O bond angles show large …
We report the observation of a magnetic polarization of the O\,$2p$-states in YMn$_2$O$_5$ through the use of soft X-ray resonant scattering at the oxygen $K$-edge. Remarkably, we find that the temperature dependence of the integrated intensity of this signal closely follows the macroscopic electric polarization, and hence is proportional to the ferroelectric order parameter. This is in contrast to the temperature dependence observed at the Mn\,$L_3$-edge, which reflects the Mn magnetic order parameter. First principle calculations provide a microscopic understanding of these results and show …
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 report on the structural and electronic properties of the interface between the multiferoic oxide YMnO$_3$ and wide band-gap semiconductor GaN studied with the Hubbard-corrected local spin density approximation (LSDA+U) to density-functional theory (DFT). We find that the band offsets at the interface between antiferromagnetically ordered YMnO$_3$ and GaN are different for spin-up and spin-down states. This behavior is due to the spin splitting of the valence band induced by the interface. The energy barrier depends on the relative orientation of the electric polarization with respect to th…
By combining neutron four-circle diffraction and polarized neutron diffraction techniques we have determined the complex spin structures of a multiferroic, YMn2O5, that exhibits two ferroelectric phases at low temperatures. The obtained magnetic structure has spiral components in both the low temperature ferroelectric phases that are magnetically commensurate and incommensurate, respectively. Among proposed microscopic theories for the magneto-electric coupling, our results are consistent with both the spin-current model that requires a magnetic transverse (cycloidal) spiral structure in order…
We uncover a new pathway towards multiferroicity, showing how magnetism can drive ferroelectricity without relying on inversion symmetry breaking of the magnetic ordering. Our free-energy analysis demonstrates that any commensurate spin-density-wave ordering with a phase dislocation, even if it is collinear, gives rise to an electric polarization. Due to the dislocation the electronic and magnetic and inversion centers do not coincide, which turns out to be a sufficient condition for multiferroic coupling. The novel mechanism explains the formation of multiferroic phases at the magnetic commen…
The magnetic and ferroelectric properties of the multiferroic system Mn$_{1-x}$Co$_x$WO$_4$ (x=0.135, 0.15, and 0.17) are studied in magnetic fields $H_c$ oriented along the monoclinic $c$-axis. Mn$_{0.85}$Co$_{0.15}$WO$_4$, which is right at the phase boundary between two helical spin structures, exhibits a spontaneous sign change of the ferroelectric polarization when cooled in fields $H_c>$ 25 kOe. The origin of the ferroelectric polarization is studied and two magnetic exchange interactions contributing to the polarization are identified. In Mn$_{0.85}$Co$_{0.15}$WO$_4$ domains of the char…
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…
By an electrical-pump--optical-probe technique we show that the electric-field-induced reversal of the magnetic order parameter in multiferroic MnWO$_4$ occurs on the time scale of milliseconds and maintains a rigid coupling of the magnetization to the magnetically induced electric polarization. The temporal progression of the spatially resolved domain structure was imaged with nanosecond resolution by optical second harmonic generation and compared to the quasi-static domain reversal. A qualitative model gives an estimate of why the magnetoelectric order-parameter reversal in the magnetically…
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…
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…
Frustration-induced multiferroicity in hauerite MnS2
Leibniz Institute for Solid State and Materials Research Dresden（德累斯顿莱布尼茨固体与材料研究所）；University of Salzburg（萨尔茨堡大学）；Zernike Institute for Advanced Materials, University of Groningen（格罗宁根大学泽尔尼克先进材料研究所）；Technische Universität Dresden（德累斯顿工业大学）
We present spin transport studies on a low-field, room-temperature magnetoelectric multiferroic polycrystalline $\text{Sr}_{3}\text{Co}_{2}\text{Fe}_{24}\text{O}_{41}$ (SCFO)|Pt heterostructure wherein a highly tunable transverse conical magnetic phase is responsible for static and dynamic magnetoelectric coupling. We measured angular dependence of spin Hall magnetoresistance (SMR) at constant magnetic fields ($H$) in the range of 50 to 100 kOe. Application of field below the critical value (2.5 kOe), yielded negative SMR and the $H$-evolution of normalized SMR exhibited a negative gradient. F…
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…
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 directly imaged reversible electrical switching of the cycloidal rotation direction (magnetic polarity) in a (111)-BiFeO3 epitaxial-film device at room temperature by non-resonant x-ray magnetic scattering. Consistent with previous reports, fully relaxed (111)-BiFeO3 epitaxial films consisting of a single ferroelectric domain were found to comprise a sub-micron-scale mosaic of magneto-elastic domains, all sharing a common direction of the magnetic polarity, which was found to switch reversibly upon reversal of the ferroelectric polarization without any measurable change of the magneto-…
The symmetry conditions for the development of a macroscopic electrical polarization as a secondary order parameter to a magnetic ordering transition, and the constraints on the direction of the polarization vector, are determined by a non-conventional application of the theory of irreducible co-representations. In our approach, which is suitable for both magnetic and structural modulations, anti-unitary operators are employed to describe symmetry operations that exchange the propagation vector $\textbf{k}$ with $\textbf{-k}$, rather than operations combined with time-reversal as in classical …
Mutual control of the electricity and magnetism in terms of magnetic (H) and electric (E) fields, the magnetoelectric (ME) effect, offers versatile low power-consumption alternatives to current data storage, logic gate, and spintronic devices. Despite its importance, E-field control over magnetization (M) with significant magnitude was observed only at low temperatures. Here we have successfully stabilized a simultaneously ferrimagnetic and ferroelectric phase in a Y-type hexaferrite single crystal up to T=450K and demonstrated the reversal of large non-volatile M by E field close to room temp…
We report on TmMnO3 far infrared emissivity and reflectivity spectra from 1910 K to 4 K. At the highest temperature the number of infrared bands is lower than that predicted for centrosymmetric P63/mmc (D6h4) (Z=2) space group due high temperature anharmonicity and possible defect induced bitetrahedra misalignments. On cooling, at ~1600 K TmMnO3 goes from non-polar to an antiferroelectric-ferroelectric polar phase reaching the ferroelectric onset at the ~700 K. The 300 K reflectivity is fitted using 19 oscillators and this number of phonons is maintained down to 4 K. A weak phonon anomaly in t…
We report a soft x-ray resonant magnetic scattering study of the spin configuration in multiferroic thin films of Co$_{0.975}$Ge$_{0.025}$Cr$_2$O$_4$ (Ge-CCO) and CoCr$_2$O$_4$ (CCO), under low- and high-magnetic fields, from 0.2 T up to 6.5 T. A characterization of Ge-CCO at a low magnetic field is performed and the results are compared to those of pure CCO. The ferrimagnetic phase transition temperature $T_C \approx 95$ K and the multiferroic transition temperature $T_S \approx 27$ K in Ge-CCO are comparable to those observed in CCO. In Ge-CCO, the ordering wave vector $\textit{(qq0)}$ obser…
