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 and up to $μ_{0}H$ = 60 T. The Co$^{2+}$ $S = 3/2$ spins are Ising-like and form distorted hexagonal layers. The Ising energy scale is well separated from the magnetic exchange, and both energy scales are accessible to the measurements allowing us to cleanly parameterize them. In transverse fields, a quantum Ising phase transition can be observed at 2 T. Finally we find that magnetic exchange striction induces changes in the electric polarization up to 3 $μ$C/m$^2$ and single-ion magnetic anisotropy effects induce a much a larger electric polarization change of 300 $μ$C/m$^2$.
Neutron diffraction measurements on multiferroic LuFe2O4 show changes in the antiferromagnetic (AFM) structure characterized by wavevector q = (1/3 1/3 1/2) as a function of electric field cooling procedures. The increase of intensity from all magnetic domains and the decrease in the 2D magnetic order observed below the Neel temperature are indicative of increased ferroelectric charge order. The AFM order changes the dynamics of the CO state, and stabilizes it. It is determined that the increase in electric polarization observed at the magnetic ordering temperature is due to a transition from …
The bulk magnetic properties of the new quasi-one-dimensional Heisenberg antiferromagnet, CuCrO$_4$, were characterized by magnetic susceptibility, heat capacity, optical spectroscopy, EPR and dielectric capacitance measurements and density functional evaluations of the intra- and interchain spin exchange interactions. We found type-II multiferroicity below the Néel temperature of 8.2(5) K, arising from competing antiferromagnetic nearest-neighbor ($J_{\rm nn}$) and next-nearest-neighbor ($J_{\rm nnn}$) intra-chain spin exchange interactions. Experimental and theoretical results indicate that …
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…
We report on spherical neutron polarimetry and unpolarized neutron diffraction in zero magnetic field as well as flipping ratio and static magnetization measurements in high magnetic fields on the multiferroic square lattice antiferromagnet Ba$_2$CoGe$_2$O$_7$. We found that in zero magnetic field the magnetic space group is $Cm'm2'$ with sublattice magnetization parallel to the [100] axis of this orthorhombic setting. The spin canting has been found to be smaller than $0.2^\circ$ in the ground state. This assignment is in agreement with the field-induced changes of the magnetic domain structu…
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 present the muon spin relaxation/rotation spectra in the multiferroic compound (Cu,Zn)$_{3}$Mo$_{2}$O$_{9}$. The parent material Cu$_{3}$Mo$_{2}$O$_{9}$ has a multiferroic phase below $T_{\rm N}$ = 8.0 K, where the canted antiferromagnetism and the ferroelectricity coexist. The asymmetry time spectra taken at RIKEN-RAL pulsed muon facility show a drastic change at $T_{\rm N}$. At low temperatures the weakly beating oscillation caused by the static internal magnetic fields in the antiferromagnetic phase was observed in Cu$_{3}$Mo$_{2}$O$_{9}$ and the lightly ($0.5\%$) Zn-doped sample. From t…
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…
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 …
We investigate the possibility of controlling the magnetic phase transition of the heterointerface between a half-doped manganite La$_{0.5}$Ca$_{0.5}$MnO$_{3}$ and a multiferroic BiFeO$_{3}$ through magnetoelectric coupling. Using macroscopic magnetometry and element-selective x-ray magnetic circular dichroism at the Mn and Fe \emph{L}-edges, we discover that the ferroelectric polarization of BFO controls simultaneously the magnetization of BFO and LCMO. X-ray absorption spectra at oxygen \emph{K}-edge and linear dichroism at Mn \emph{L}-edge suggest that the interfacial coupling is mainly der…
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…
Epitaxial thin films of hexagonal ErMnO3 fabricated on Pt(111)/Al2O3(0001) and YSZ(111) substrates exhibited both ferroelectric character and magnetic ordering at low temperatures. As the temperature was reduced, the ErMnO3 films first showed antiferromagnetism. At lower temperatures, the films deposited at lower oxygen partial pressures exhibited spin glass behavior. This re-entrant spin glass behavior was attributed to competition between an antiferromagnetic interaction in the hexagonal geometry and a ferromagnetic interaction caused by a change in Mn valence induced by excess electrons fro…
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…
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…
We report on the growth and functional characterization of epitaxial thin films of the multiferroic YMnO3. We show that using Pt as a seed layer on SrTiO3(111) substrates, epitaxial YMnO3 films (0001) textured are obtained. An atomic force microscope has been used to polarize electric domains revealing the ferroelectric nature of the film. When a Permalloy layer is grown on top of the YMnO3(0001) film, clear indications of exchange bias and enhanced coercivity are observed at low temperature. The observation of coexisting antiferromagnetism and electrical polarization suggests that the biferro…
The rare-earth perovskite TbScO$_3$ has been widely used as a substrate for the growth of epitaxial ferroelectric and multiferroic thin films, while its detailed low-temperature magnetic properties were rarely reported. In this paper, we performed detailed magnetization, specific heat and single crystal neutron scattering measurements, along with the crystalline electric field calculations to study the low-temperature magnetic properties of TbScO$_3$. All our results suggest the magnetic Tb$^{3+}$ has an Ising-like pseudo-doublet ground state at low temperatures. Due to the constrain of local …
Magnetic monopoles and toroidal order are compelling features that have long been theorized but remain elusive in real materials. Multiferroic hexagonal ferrites are an interesting realization of frustrated triangular lattice, where magnetic order is coupled to ferroelectricity and trimerization. Here we propose a mechanism, through which magnetic monopolar and toroidal orders emerge from the combination of 120$^\circ$ antiferromagnetism and trimerization, present in hexagonal manganites and ferrites. The experimentally observable signatures of magnetic monopolar and toroidal orders are identi…
Vector-chiral (VC) antiferromagnetism is a spiral-like ordering of spins which may allow ferroelectricity to occur due to loss of space inversion symmetry. In this paper we report direct experimental observation of ferroelectricity in the VC phase of $β$-TeVO$_4$, a frustrated spin chain system with pronounced magnetic anisotropy and a rich phase diagram. Saturation polarization is proportional to neutron scattering intensities that correspond to the VC magnetic reflection. This implies that inverse Dzyaloshinskii-Moriya mechanism is responsible for driving electric polarization. Linear magnet…
Hexagonal Dy(0.5)Y(0.5)MnO3, a multiferroic rare-earth manganite with geometrically frustrated antiferromagnetism, has been investigated with single-crystal neutron diffraction measurements. Below 3.4 K magnetic order is observed on both the Mn (antiferromagnetic) and Dy (ferrimagnetic) sublattices that is identical to that of undiluted hexagonal DyMnO3 at low temperature. The Mn moments undergo a spin reorientation transition between 3.4 K and 10 K, with antiferromagnetic order of the Mn sublattice persisting up to 70 K; the antiferromagnetic order in this phase is distinct from that observed…
