Spectra of transmission and reflection coefficients of single crystalline Y-type hexaferrite Ba_(2)Mg_(2)Fe_(12)O_(22) are measured at Terahertz and infrared frequencies, 3 - 4500 c--1, and at temperatures 10 to 300 K, for polarization E prp c. Oscillator parameters of nineteen phonon lines allowed by the R3m crystal lattice symmetry are determined. Absorption lines assignment to vibrational modes of the lattice structural fragments is performed. Below the temperatures of 195 K and 50 K, corresponding to the zero field phase transitions to the proper screw and to the longitudinal-conical spin states, respectively, new absorption lines are discovered whose origin is assigned to the electric-dipole active magnetic excitations.
BaFe12O19 is a popular M-type hexaferrite with T(Neel) = 720 K of enormous commercial value (3 billion dollars/year). It exhibits an incipient ferroelectric phase transition (in violation of the Spaldin-Hill rule) extrapolated to lie at 6.0 K Kelvin but suppressed due to quantum fluctuations (as in SrTiO3). The QCP theory of Khmelnitskii for such uniaxial ferroelectrics predicts that the inverse isothermal electric susceptibility varies as T cubed, in contrast to that for pseudo-cubic materials such as SrTiO3 or KTaO3, a hypothesis we verify.
Magnetoelectric (ME) properties under rotating magnetic field H are comparatively investigated in two representative hexaferrites Y-type Ba0.5Sr1.5Zn2(Fe0.92Al0.08)12O22 and Z-type Ba0.52Sr2.48Co2Fe24O41, both of which have exhibited a similar transverse conical spin structure and giant ME coupling near room temperature. When the external H is rotated clockwise by 2pi, in-plane P vector is rotated clockwise by 2pi in the Y-type hexaferrite and counterclockwise by 4pi in the Z-type hexaferrite. A symmetry-based analysis reveals that the faster and opposite rotation of P vector in the Z-type hex…
Strain-Induced Relaxor Multiferroicity at Room Temperature in Hexaferrite BaFe12O19 Thin Films
Cornell University（康奈尔大学）；The Pennsylvania State University（宾夕法尼亚州立大学）；Leibniz-Institut für Kristallzüchtung（莱布尼兹晶体生长研究所）；Oak Ridge National Laboratory（橡树岭国家实验室）；University of Tennessee（田纳西大学）；University of California, Berkeley（加州大学伯克利分校）；University of North Texas（北德克萨斯大学）；University of Southern California（南加州大学）；Kavli Institute at Cornell for Nanoscale Science（康奈尔纳米科学卡弗里研究所）
Magnetoelectric multiferroics in which ferroelectricity and magnetism coexist have attracted extensive attention because they provide great opportunities for the mutual control of electric polarization by magnetic fields and magnetization by electric fields. From a practical point view, the main challenge in this field is to find proper multiferroic materials with a high operating temperature and great magnetoelectric sensitivity. Here we report on the magnetically tunable ferroelectricity and the giant magnetoelectric sensitivity up to 250 K in a Y-type hexaferrite, BaSrCoZnFe11AlO22. Not onl…
We investigated static and dynamic magnetoelectric properties of single crystalline BaSrCoZnFe$_{11}$AlO$_{22}$ which is a room-temperature multiferroic with Y-type hexaferrite crystal structure. Below $300\,\rm K$, a purely electric-dipole-active electromagnon at $\approx 1.2\,\rm THz$ with the electric polarization oscillating along the hexagonal axis was observed by THz and Raman spectroscopies. We investigated the behavior of the electromagnon with applied DC magnetic field and linked its properties to static measurements of the magnetic structure. Our analytical calculations determined se…
Simultaneous occurrence of big ferroelectricity and strong ferromagnetism has been observed in Barium Hexaferrite ceramics. Barium hexaferrite (BaFe12O19) powders with hexagonal crystal structure have been successfully synthesized by polymer precursor method using barium acetate and ferric acetylacetonate as the precursor. The powders were pressed into pellets, which were sintered into ceramics at 1100^{\circ}C~1300^{\circ}C for 1 hour. The structure and morphology have been determined by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). Large spontaneous polariz…
Polycrystalline M-type hexagonal Strontium hexaferrite and its modified systems by Cobalt (Co) and Titanium (Ti) were successfully prepared by the solid state reaction method. The single phase formation of all the systems and well grain growth of micrometer range was confirmed by X-ray diffraction pattern and Scanning Electron Microscopic image respectively. The impedance spectroscopy and dielectric properties were investigated in a selected frequency & temperature range. The room temperature M-H loop study for Strontium hexaferrite and Cobalt modified Strontium hexaferrite was carried out by …
Single-phase multiferroic materials are usually considered useless because of the weak magnetoelectric effects, low operating temperature, and small electric polarization induced by magnetic orders. As a result, current studies on applications of the magnetoelectric effects are mainly focusing on multiferroic heterostructures and composites. Here we report a room-temperature giant effect in response to external magnetic fields in single-phase multiferroics. A low magnetic field of 1000 Oe applied on the spin-driven multiferroic hexaferrites BaSrCo2Fe11AlO22 and Ba0.9Sr1.1Co2Fe11AlO22 is able t…
Hexagonal ferrites (h-RFeO$_3$, R=Y, Dy-Lu) have recently been identified as a new family of multiferroic complex oxides. The coexisting spontaneous electric and magnetic polarizations make h-RFeO$_3$ rare-case ferroelectric ferromagnets at low temperature. Plus the room-temperature multiferroicity and predicted magnetoelectric effect, h-RFeO$_3$ are promising materials for multiferroic applications. Here we review the structural, ferroelectric, magnetic, and magnetoelectric properties of h-RFeO$_3$. The thin film growth is also discussed because it is critical in making high quality single cr…
The intrinsic ferroelectricity and related dielectric properties of M-type Barium Hexaferrite (BaFe12O19) with excellent magnetic performance are reported in this paper. A classic electric polarization (P-E) hysteresis loop with full saturation, together with two nonlinear reversal current peaks in the I-V curve and huge change of dielectric constant in the vicinity of Curie temperature, have all demonstrated themselves as sufficient experimental evidences to verify the ferroelectricity of BaFe12O19 ceramics. It holds a large remnant polarization at 108 uC/cm2 and a suitable coercive field at …
We report a study of magnetic dynamics in multiferroic hexagonal manganite HoMnO3 by far-infrared spectroscopy. Low-temperature magnetic excitation spectrum of HoMnO3 consists of magnetic-dipole transitions of Ho ions within the crystal-field split J=8 manifold and of the triangular antiferromagnetic resonance of Mn ions. We determine the effective spin Hamiltonian for the Ho ion ground state. The magnetic-field splitting of the Mn antiferromagnetic resonance allows us to measure the magnetic exchange coupling between the rare-earth and Mn ions.
The crystal and magnetic structures of single-crystalline hexagonal LuFeO$_3$ films have been studied using x-ray, electron and neutron diffraction methods. The polar structure of these films are found to persist up to 1050 K; and the switchability of the polar behavior is observed at room temperature, indicating ferroelectricity. An antiferromagnetic order was shown to occur below 440 K, followed by a spin reorientation resulting in a weak ferromagnetic order below 130 K. This observation of coexisting multiple ferroic orders demonstrates that hexagonal LuFeO$_3$ films are room-temperature mu…
Hexagonal RMnO3 manganites are improper ferroelectrics in which the electric polarization is a by-product of the tripling of the unit cell. In YMnO3, there is a second transition at ~ 920K whose nature remains unexplained. We argue that this transition can be seen as a sort of hidden order in which a residual symmetry displayed by the trimerization order parameter is spontaneously broken. This additional order gives rise to twelve structural domains instead of six, and structural domain boundaries that can be either ferroelectric or non-ferroelectric domain walls.
Numerous applications of hexagonal ferrites are related to their easy axis or easy plane magnetocrystalline anisotropy configurations. Certain W-type ferrites undergo spin reorientation transitions (SRT) between different anisotropy states on magnetic field or temperature variation. The transition point can be tuned by modifying the chemical composition, which suggests a potential application of hexaferrites in room temperature magnetic refrigeration. Here we present the results of structural and magnetic characterization of BaCo_xZn_{2-x}Fe_{16}O_{27} (0.7 \leq x \leq 2) doped barium ferrites…
Using first-principles calculations we examine the band structures of ferromagnetic hexagonal manganites $\mathrm{YXO_3}$ (X=V, Cr, Mn, Fe and Co) in the nonpolar nonsymmorphic $P6_3/mmc$ space group. For $\mathrm{YVO_3}$ and $\mathrm{YCrO_3}$ we find a band inversion near the Fermi energy that generates a nodal ring in the $k_z=0$ mirror plane. We perform a more detailed analysis for these compounds and predict the existence of the topological "drumhead" surface states. Finally, we briefly discuss the low-symmetry polar phases (space group $P6_3cm$) of these systems, and show they can undergo…
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 fabricated epitaxial thin films of hexagonal DyMnO3, which otherwise form in a bulk perovskite structure, via deposition on Pt(111)//Al2O3 (0001) and YSZ(111) substrates: each of which has in-plane hexagonal symmetry. The polarization hysteresis loop demonstrated the existence of ferroelectricity in our hexagonal DyMnO3 films at least below 70 K. The observed 2.2 uC/cm^2 remnant polarization at 25 K corresponded to a polarization enhancement by a factor of 10 compared to that of the bulk orthorhombic DyMnO3. Interestingly, this system showed an antiferroelectric-like feature in its hysteres…
The spontaneous transformations associated with symmetry-breaking phase transitions generate domain structures and defects that may be topological in nature. The formation of these defects can be described according to the Kibble-Zurek mechanism, which provides a generic relation that applies from cosmological to interatomic lengthscales. Its verification is challenging, however, in particular at the cosmological scale where experiments are impractical. While it has been demonstrated for selected condensed-matter systems, major questions remain regarding e.g. its degree of universality. Here w…
Hexagonal rare-earth ferrite RFeO$_3$ family represents a unique class of multiferroics exhibiting weak ferromagnetism, and a strong coupling between magnetism and structural trimerization is predicted. However, the hexagonal structure for RFeO$_3$ remains metastable in conventional condition. We have succeeded in stabilizing the hexagonal structure of polycrystalline YbFeO$_3$ by partial Sc substitution of Yb. Using bulk magnetometry and neutron diffraction, we find that Yb$_{0.42}$Sc$_{0.58}$FeO$_3$ orders into a canted antiferromagnetic state with the Neel temperature $T_N$ ~ 165 K, below w…
We use a combination of symmetry analysis, phenomenological modelling and first-principles density functional theory to explore the interplay between the magnetic ground state and the detailed atomic structure in the hexagonal rare-earth manganites. We find that the magnetic ordering is sensitive to a breathing mode distortion of the Mn and O ions in the $ab$ plane, which is described by the K\textsubscript{1} mode of the high-symmetry structure. Our density functional calculations of the magnetic interactions indicate that this mode particularly affects the single-ion anisotropy and the inter…
Structural changes in REMnO3 (RE= Y, Ho, Lu) under high pressure were examined by synchrotron x-ray diffraction methods at room temperature. Compression occurs more readily in the ab plane than along the c-axis. Under hydrostatic pressure (~11 GPa), the atoms hold their approximate ambient fractional positions in the unit cell and the spontaneous polarization shows no significant change. With increased pressure, a pressure-induced hexagonal to orthorhombic phase transition was observed starting at ~ 22GPa for Lu(Y)MnO3. A small volume fraction of Lu(Y)MnO3 is converted to the orthorhombic phas…
The magnetic interaction between rare-earth and Fe ions in hexagonal rare-earth ferrites (h-REFeO3), may amplify the weak ferromagnetic moment on Fe, making these materials more appealing as multiferroics. To elucidate the interaction strength between the rare-earth and Fe ions as well as the magnetic moment of the rare-earth ions, element specific magnetic characterization is needed. Using X-ray magnetic circular dichroism, we have studied the ferrimagnetism in h-YbFeO3 by measuring the magnetization of Fe and Yb separately. The results directly show anti-alignment of magnetization of Yb and …
Hexagonal LuFeO$_3$ has drawn a lot of research attention due to its contentious room-temperature multiferroicity. Due to the unstability of hexagonal phase in the bulk form, most experimental studies focused on LuFeO$_3$ thin films which can be stabilized by strain using proper substrates. Here we report on the hexagonal phase stabilization, magnetism, and magnetoelectric coupling of bulk LuFeO$_3$ by partial Sc-substitution of Lu. First, our first-principles calculations show that the hexagonal structure can be stabilized by partial Sc substitution, while the multiferroic properties includin…
We report an investigation of hexagonal Y_(1-x)Eu_xMnO_3 ceramics with x=0, 0.1 and 0.2 using infrared and THz spectroscopies in the temperature range between 5 and 900 K. The temperature dependence of the THz permittivity reveals a kink near the antiferromagnetic phase transition temperature T_N ~ 70 K giving evidence of a strong spin-lattice coupling. Below T_N two absorption peaks were revealed in the THz spectra close to 43 and 73 cm-1. While the first peak corresponds to a sharp antiferromagnetic resonance exhibiting softening on heating towards TN, the second one may be attributed to an …
We have 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…
PbFe12O19 (PFO) powders in hexagonal structure have been synthesized by sol-gel process using lead acetate, glycerin and ferric acetylacetonate as the precursor. PbFe12O19 ceramics were obtained by sintering the PbFe12O19 powders at 1000\degree C for 1 hour. Distorted flaky hexahedron grains are frequently observed in the SEM images of sintered PbFe12O19 ceramics. Large spontaneous polarization was observed in PbFe12O19 ceramic at room temperature, exhibiting a clear ferroelectric hysteresis loop. The remnant polarization of PbFe12O19 ceramic is estimated to be Pr~21μC/cm2. The distortion of h…
We show that the improper ferroelectric phase transition in the multiferroic hexagonal manganites displays the same symmetry-breaking characteristics as those proposed in early-universe theories. We present an analysis of the Kibble-Zurek theory of topological defect formation applied to the hexagonal manganites, discuss the conditions determining the range of cooling rates in which Kibble-Zurek behavior is expected, and show that recent literature data are consistent with our predictions. We explore experimentally for the first time to our knowledge the cross-over out of the Kibble-Zurek regi…
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 on the magnetic structure and ordering of hexagonal LuFeO3 films grown by molecular-beam epitaxy (MBE) on YSZ (111) and Al2O3 (0001) substrates. Using a set of complementary probes including neutron diffraction, we find that the system magnetically orders into a ferromagnetically-canted antiferromagnetic state via a single transition between 138-155 K, while a paraelectric to ferroelectric transition occurs above 1000 K. The symmetry of the magnetic structure in the ferroelectric state implies that this material is a strong candidate for linear magnetoelectric coupling and control of…
We report on optical studies of the thin films of multiferroic hexagonal (P.G. 6mm) rare-earth orthoferrites RFeO3 (R=Ho, Er, Lu) grown epitaxially on a (111)-surface of ZrO2(Y2O3) substrate. The optical absorption study in the range of 0.6-5.6 eV shows that the films are transparent below 1.9 eV; above this energy four broad intense absorption bands are distinguished. The absorption spectra are analyzed taking into account the unusual fivefold coordination of the Fe(3+) ion. Temperature dependence of the optical absorption at 4.9 eV shows anomaly at 124 K, which we attribute to magnetic order…
Multiferroic hexagonal RMnO3 (R=rare earths) crystals exhibit dense networks of vortex lines at which six domain walls merge. While the domain walls can be readily moved with an applied electric field, the vortex cores were so far impossible to control. Our experiments demonstrate that shear strain induces a Magnus-type force pulling vortices and antivortices in opposite directions and unfolding them into a topological stripe domain state. We discuss the analogy between this effect and the current-driven dynamics of vortices in superconductors and superfluids.
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 …
We deduce the intrinsic conductivity properties of the ferroelectric domain walls around the topologically protected domain vortex cores in multiferroic YMnO3. This is achieved by performing a careful equivalent-circuit analysis of dielectric spectra measured in single-crystalline samples with different vortex densities. The conductivity contrast between the bulk domains and the less conducting domain boundaries is revealed to reach up to a factor 500 at room temperature, depending on sample preparation. Tunneling of localized defect charge carriers is the dominant charge-transport process in …
Simultaneous co-existence of room-temperature(T) ferromagnetism and ferroelectricity in Fe doped BaTiO$_3$ (BTO) is intriguing, as such Fe doping into tetragonal BTO, a room-T ferroelectric (FE), results in the stabilization of its hexagonal polymorph which is FE only below $\sim$80K. Here, we investigate its origin and show that Fe-doped BTO has a mixed-phase room-temperature multiferroicity, where the ferromagnetism comes from the majority hexagonal phase and a minority tetragonal phase gives rise to the observed weak ferroelectricity. In order to achieve majority tetragonal phase (responsib…
Local structural measurements have been performed on hexagonal HoMnO3 in order to ascertain the specific changes in bond distances which accompany magnetic ordering transitions. The transition from paramagnetic to the antiferromagetic (noncollinear) phase near ~70 K is dominated by changes in the a-b plane Mn-Mn bond distances. The spin rotation transition near ~40 K involves both Mn-Mn and nearest neighbor Ho-Mn interactions while the low temperature transition below 10 K involves all interactions, Mn-Mn, Ho-Mn (nearest and next nearest) and Ho-Ho correlations. These changes in bond distances…
Hexagonal LuFe2O4 is a promising charge-order (CO) driven multiferroic material with high charge and spin ordering temperatures. The coexisting charge and spin orders on Fe3+/Fe2+ sites result in novel magnetoelectric behaviors, but the coupling mechanism between the charge and spin orders remains elusive. Here, by tuning external pressure, we reveal three correlated spin-charge ordered phases in LuFe2O4: i) a centrosymmetric incommensurate three-dimensional CO with ferrimagnetism, ii) a non-centrosymmetric incommensurate quasi-two-dimensional CO with ferrimagnetism, and iii) a centrosymmetric…
In this work, we report on the epitaxial growth of multiferroic YMnO3 on GaN. Both materials are hexagonal with a nominal lattice mismatch of 4%, yet x-ray diffraction reveals an unexpected 30 degree rotation between the unit cells of YMnO3 and GaN that results in a much larger lattice mismatch (10%) compared to the unrotated case. Estimates based on first principles calculations show that the bonding energy gained from the rotated atomic arrangement compensates for the increase in strain energy due to the larger lattice mismatch. Understanding the energy competition between chemical bonding e…
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…
To tune the magnetic properties of hexagonal ferrites, a family of magnetoelectric multiferroic materials, by atomic-scale structural engineering, we studied the effect of structural distortion on the magnetic ordering temperature (TN). Using the symmetry analysis, we show that unlike most antiferromagnetic rare-earth transition-metal perovskites, a larger structural distortion leads to a higher TN in hexagonal ferrites and manganites, because the K3 structural distortion induces the three-dimensional magnetic ordering, which is forbidden in the undistorted structure by symmetry. We also revea…
We have carried out temperature-dependent inelastic neutron scattering measurements of YMnO3 over the temperature range 50 - 1303 K, covering both the antiferromagnetic to paramagnetic transition (70 K), as well as the ferroelectric to paraelectric transition (1258 K). Measurements are accompanied by first principles calculations of phonon spectra for the sake of interpretation and analysis of the measured phonon spectra in the room temperature ferroelectric (P63cm) and high temperature paraelectric (P63/mmc) hexagonal phases of YMnO3. The comparison of the experimental and first-principles ca…
Magnetic structure evolution of multiferroic hexagonal $YMn_{1-x}Fe_{x}O_{3}$ (${x} = 0, 0.05,$ and $0.1$) has been studied by carrying out detailed temperature-dependent neutron diffraction at zero- and 5T-fields. Thermodynamic data confirm antiferromagnetic ordering at $T_{N}$ in all the compositions. Our sub-$T_{N}$ neutron diffraction results assign the magnetic structure of pure $YMnO_3$ to $Γ_{1}$ irreducible representation. Over the perturbative-doping range, the magnetic configuration changes via $Γ_{1}+Γ_{2}$ for $YMn_{0.95}Fe_{0.05}O_{3}$ on to $Γ_{2}$ for $YMn_{0.9}Fe_{0.1}O_{3}$, a…
We used Raman and terahertz spectroscopies to investigate lattice and magnetic excitations and their cross-coupling in the hexagonal YMnO3 multiferroic. Two phonon modes are strongly affected by the magnetic order. Magnon excitations have been identified thanks to comparison with neutron measurements and spin wave calculations but no electromagnon has been observed. In addition, we evidenced two additional Raman active peaks. We have compared this observation with the anti-crossing between magnon and acoustic phonon branches measured by neutron. These optical measurements underly the unusual s…
The improper ferroelectricity in YMnO$_3$ and other related multiferroic hexagonal manganites are known to cause topologically protected ferroelectric domains that give rise to rich and diverse physical phenomena. The local structure and structural coherence across the ferroelectric transition, however, were previously not well understood. Here we reveal the evolution of the local structure with temperature in YMnO$_3$ using neutron total scattering techniques, and interpret them with the help of first-principles calculations. The results show that, at room temperature, the local and average s…
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 investigate partially disordered antiferromagnetism in CoCl$_2$-2SC(NH$_2$)$_2$, in which a-b plane hexagonal layers are staggered along the c-axis, rather than stacked. A robust 1/3 state forms in applied magnetic fields which the spins are locked, varying neither as a function of temperature nor field. By contrast, in zero field, partial antiferromagnetic order occurs, in which free spins are available to create a Curie-like magnetic susceptibility. We report measurements of the crystallographic structure, and the specific heat, magnetization, and electric polarization down to $T$ = 50 mK…
