By combining single crystal x-ray and neutron diffraction, and the magnetodielectric measurements on single crystal Fe4Nb2O9, we present the magnetic structure and the symmetry-allowed magnetoelectric coupling in Fe4Nb2O9. It undergoes an antiferromagnetic transition at TN=93 K, followed by a displacive transition at TS=70 K. The temperature-dependent dielectric constant of Fe4Nb2O9 is strongly anisotropic with the first anomaly at 93 K due to the exchange striction as a result of the long range spin order, and the second one at 70 K emanating from the structural phase transition primarily driven by the O atomic displacements. Magneticfield induced magnetoelectric coupling was observed in single crystal Fe4Nb2O9 and is compatible with the solved magnetic structure that is characteristic of antiferromagnetically arranged ferromagnetic chains in the honeycomb plane. We propose that such magnetic symmetry should be immune to external magnetic fields to some extent favored by the freedom of rotation of moments in the honeycomb plane, laying out a promising system to control the magnetoelectric properties by magnetic fields.
Magnetoelectric effects in honeycomb antiferromagnet Co4Nb2O9 are investigated on the basis of symmetry analyses of Co ions in trigonal P-3c1 space group. For each Co ion, the possible spin dependence is classified by C3 point-group symmetry. This accounts for the observed main effect that an electric polarization rotates in the opposite direction at the twice speed relative to the rotation of the external magnetic field applied in the ab-plane. Inversion centers and twofold axes in the unit cell restrict the active spin-dependence of the electric polarization, which well explains the observed…
The honeycomb antiferromagnet Co4Nb2O9 is known to exhibit an interesting magnetoelectric effect that the electric polarization rotates at the twice speed in the opposite direction relative to the rotation of the external magnetic field applied in the basal ab-plane. The spin-dependent electric dipole can be an origin of the magnetoelectric effect. It is described by the product of spin operators at different sites (type-I theory) or at the same site (type-II theory). We examine the electric polarization for the two cases on the basis of the symmetry analysis of the crystal structure of Co4Nb2…
Through analysis of single crystal neutron diffraction data, we present the magnetic structures of magnetoelectric Co4Nb2O9 under various magnetic fields. In zero-field, neutron diffraction experiments below TN=27 K reveal that the Co2+ moments order primarily along the a* direction without any spin canting along the c axis, manifested by the magnetic symmetry C2/c'. The moments of nearest neighbor Co atoms order ferromagnetically with a small cant away from the next nearest neighbor Co moments along the c axis. In the applied magnetic field H//a, three magnetic domains were aligned with their…
Magnetoelectric phenomena are intimately linked to relativistic effects and also require the material to break spatial inversion symmetry and time reversal invariance. Magnetoelectric coupling can substantially affect light-matter interaction and lead to non-reciprocal light propagation. Here, we confirm on a fully experimental basis, without invoking either symmetry-based or material-specific assumptions, that the optical magnetoelectric effect in materials with non-parallel magnetization ($\boldsymbol{M}$) and electric polarization ($\boldsymbol{P}$) generates a trilinear term in the refract…
We study the effects of static magnetic and electric fields on Kitaev's honeycomb model. Using the electric polarization operator appropriate for Kitaev materials, we derive the effective Hamiltonian for the emergent Majorana fermions to second-order in both the electric and magnetic fields. We find that while individually each perturbation does not qualitatively alter Kitaev spin liquid, the cross-term induces a finite chemical potential at each Dirac node, giving rise to a Majorana-Fermi surface. We argue this gapless phase is stable and exhibits typical metallic phenomenology, such as linea…
Co4Ta2O9 exhibits a three-dimensional magnetic lattice based on the buckled honeycomb motif. It shows unusual magnetoelectric effects, including the sign change and non-linearity. These effects cannot be understood without the detailed knowledge of the magnetic structure. Herein, we report neutron diffraction and direction-dependent magnetic susceptibility measurements on Co4Ta2O9 single crystals. Below 20.3 K, we find a long-range antiferromagnetic order in the alternating buckled and flat honeycomb layers of Co2+ ions stacked along the c axis. Within experimental accuracy, the magnetic momen…
We report the discovery of a metamagnetic phase transition in a polar antiferromagnet Ni$_3$TeO$_6$ that occurs at 52 T. The new phase transition accompanies a colossal magnetoelectric effect, with a magnetic-field-induced polarization change of 0.3 $μ$C/cm$^2$, a value that is 4 times larger than for the spin-flop transition at 9 T in the same material, and also comparable to the largest magnetically-induced polarization changes observed to date. Via density-functional calculations we construct a full microscopic model that describes the data. We model the spin structures in all fields and cl…
We have carried out high magnetic field studies of single-crystalline Li$_2$MnO$_3$, a honeycomb lattice antiferromagnet. Its magnetic phase diagram was mapped out using magnetization measurements at applied fields up to 35 T. Our results show that it undergoes two successive meta-magnetic transitions around 9 T fields applied perpendicular to the ab-plane (along the c*-axis). These phase transitions are completely absent in the magnetization measured with field applied along the ab-plane. In order to understand this magnetic phase diagram, we developed a mean-field model starting from the cor…
Recent experiments for linear magnetoelectric (ME) response in honeycomb antiferromagnet Co$_4$Nb$_2$O$_9$ revealed that the electric polarization can be manipulated by the in-plane rotating magnetic field in a systematic way. We propose the minimal model by extracting essential ingredients of Co$_4$Nb$_2$O$_9$ to exhibit such ME response. It is the three-orbital model with $xy$-type atomic spin-orbit coupling (SOC) on the single-layer honeycomb structure, and it is shown to reproduce qualitatively the observed field-angle dependence of the electric polarization. The obtained results can be un…
Strongly correlated materials with multiple order parameters provide unique insights into the fundamental interactions in condensed matter systems and present opportunities for innovative technological applications. A class of antiferromagnetic honeycomb lattices compounds, A4B2O9 (A = Co, Fe, Mn; B = Nb, Ta), have been explored owing to the occurrence of linear magnetoelectricity. We observe a highly nonlinear magnetoelectric effect on single crystals of Co4Ta2O9 (CTO), distinctive from the linear behavior in the isostructural Co4Nb2O9. Ferroelectricity emerges primarily along the [110] direc…
The majority of magnetoelectric crystals show complex temperature-magnetic field or temperature-pressure phase diagrams with alternating antiferromagnetic incommensurate, magnetoelectric, and commensurate phases. Such phase diagrams occur as a result of successive magnetic instabilities with respect to different order parameters, which usually transform according to different irreducible representations (IR) of the space group of the crystal. Therefore, in order to build a phenomenological theory of phase transitions in such magnetoelectrics one has to employ several order parameters and assum…
The layered compound $α$-RuCl$_3$ is composed of a honeycomb lattice of magnetic Ru$^{3+}$ ions with the $4d^5$ electronic state. We have investigated the magnetic properties of $α$-RuCl$_3$ via magnetization and specific heat measurements using single crystals. It was observed that $α$-RuCl$_3$ undergoes a structural phase transition at $T_{t}\,{\simeq}\,150$ K accompanied by fairly large hysteresis. This structural phase transition is expected to be similar to that observed in closely related CrCl$_3$. The magnetizations and magnetic susceptibilities are strongly anisotropic, which mainly ar…
Magnetic and dielectric properties of åkermanite Ca$_2$CoSi$_2$O$_7$ single crystals were investigated in pulsed high magnetic fields. In magnetic fields along the $c$ axis, this material shows a magnetization plateau in a wide range of field below the saturation. Magnetization processes for fields along the $a$ and $b$ axes show multiple anomalies but different traces to each other, indicating the breaking of four-fold symmetry. Measurements of the magnetoelectric effects exhibit the changes in electric polarization according to the changes in the spin system. The experimentally determined qu…
We report the results of various measurements, namely magnetization, complex dielectric permittivity and electric polarization (P) on Dy2BaNiO5 as a function of temperature (T) and magnetic-field (H), apart from heat-capacity (C), with the primary motivation of exploring the existence of magnetoelectric (ME) coupling among Haldane spin-chain systems. The M(T) and C(T) data establish long range magnetic ordering at 58K. The most noteworthy observations are: (i) Distinct anomalies are observed in dielectric constant (ε') vs T and loss (tanδ) vs T at different temperatures, i.e. 12.5, 30, 50 and …
Magnetization measurements under direct electric currents were performed for toroidal magnetic ordered state of UNi$_4$B to test a recent theoretical prediction of current-induced magnetization in a metallic system lacking local inversion symmetry.We found that each of the electric currents parallel to [$2\bar{1}\bar{1}0$] and [$0001$] in the hexagonal 4-index notation induces uniform magnetization in the direction of [$01\bar{1}0$].The observed behavior of the induced magnetization is essentially consistent with the theoretical prediction; however it also shows an inconsistency suggesting tha…
We have studied the magnetic properties of Na$_2$Co$_2$TeO$_6$, which features a honeycomb lattice of magnetic Co$^{2+}$ ions, through macroscopic characterization and neutron diffraction on a powder sample. We have shown that this material orders in a zig-zag antiferromagnetic structure. In addition to allowing a linear magnetoelectric coupling, this magnetic arrangement displays very peculiar spatial magnetic correlations, larger in the honeycomb planes than between the planes, which do not evolve with the temperature. We have investigated this behavior by Monte Carlo calculations using the …
We have synthesized single crystalline sample of Mn$_2$V$_2$O$_7$ using floating zone technique and investigated the ground state using magnetic susceptibility, heat capacity and neutron diffraction. Our magnetic susceptibility and heat capacity reveal two successive magnetic transitions at $T_{N1} =$ 19 K and $T_{N2} =$ 11.8 K indicating two distinct magnetically ordered phases. The single crystal neutron diffraction study shows that in the temperature ($T$) range 11.8 K $\le T \le$ 19 K the magnetic structure is commensurate with propagation vector $k_1 = (0, 0.5, 0)$, while upon lowering te…
Antiferromagnetic and ferro/ferrimagnetic orders are typically exclusive in nature, thus, their co-existence in atomic-scale proximity is expected only in heterostructures. Breaking this paradigm and broadening the range of unconventional magnetic states, we report here on an atomic-scale hybrid spin state, which is stabilized in three-dimensional crystals of the polar antiferromagnet Co$_2$Mo$_3$O$_8$ by magnetic fields applied perpendicular to the \emph{Co} honeycomb layers and possesses a spontaneous in-plane ferromagnetic moment. Our microscopic spin model, capturing the observed field dep…
Hexagonal alpha-Ru trichloride single crystals exhibit a strong magnetic anisotropy and we show that upon applying fields up to 14 T in the honeycomb plane the successive magnetic order at T1 = 14 K and T2 = 8 K could be completely suppressed whereas in the perpendicular direction the magnetic order is robust. Furthermore the field dependence of chi(T) implies coexisting ferro- and antiferromagnetic exchange between in-plane components of Ru^3+-spins, whereas for out-of-plane components a strong antiferromagnetic exchange becomes evident. 101^Ru zero-field nuclear magnetic resonance in the ord…
We study quantum phase transitions in the honeycomb Kitaev model under a magnetic field, focusing on the topological nature of Majorana fermion excitations. We find a gapless phase between the low-field gapless quantum spin liquid and the high-field gapped forced-ferromagnetic state for the antiferromagnetic Kitaev model in the [001] field by using the Majorana mean-field theory, in conjunction with the exact diagonalization and the spin-wave theory supporting the validity of this approach. The transition between the two gapless phases is driven by a topological change of the Majorana spectrum…
Toroidal order, given by a composite of electric and magnetic orders, manifests itself not only in the peculiar magnetism but also in anomalous transport and magnetoelectric effect. We report our theoretical results on the influence and stability of a toroidal order in metals on the basis of a microscopic model. We consider an effective single-band Hubbard-type model with a site-dependent antisymmetric spin-orbit coupling, which is derived from a four-band tight-binding model including the atomic spin-orbit coupling, off-site hybridizations between orbitals with different parities, and odd-par…
We report a muon spin rotation/relaxation ($μ$SR) study of single-crystalline samples of the $α$-RuCl$_3$ honeycomb magnet, which is presumed to be a model compound for the Kitaev-Heisenberg interaction. It is inferred from magnetic susceptibility and specific-heat measurements that the present samples exhibit successive magnetic transitions at different critical temperatures $T_{\rm N}$ with decreasing temperature, eventually falling into the $T_{\rm N}=7$ K antiferromagnetic (7 K) phase that has been observed in only single-crystalline specimens with the least stacking fault. Via $μ$SR measu…
We report the results of magnetization and specific heat measurements of Ba$_2$CoTeO$_6$ composed of two subsystems A and B, which are magnetically described as an $S\,{=}\,1/2$ triangular-lattice Heisenberg-like antiferromagnet and a $J_1-J_2$ honeycomb-lattice Ising-like antiferromagnet, respectively. These two subsystems were found to be approximately decoupled. Ba$_2$CoTeO$_6$ undergoes magnetic phase transitions at $T_{\rm N1}\,{=}\,12.0$ K and $T_{\rm N2}\,{=}\,3.0$ K, which can be interpreted as the orderings of subsystems B and A, respectively. Subsystem A exhibits a magnetization plat…
The magnetism of magnetoelectric $S$ = 3/2 pyroxenes LiCrSi$_2$O$_6$ and LiCrGe$_2$O$_6$ is studied by density functional theory (DFT) calculations, quantum Monte Carlo (QMC) simulations, neutron diffraction, as well as low-field and high-field magnetization measurements. In contrast with earlier reports, we find that the two compounds feature remarkably different, albeit non-frustrated magnetic models. In LiCrSi$_2$O$_6$, two relevant exchange integrals, $J_1 \simeq$ 9 K along the structural chains and $J_{\text{ic1}}$ $\simeq$ 2 K between the chains, form a 2D anisotropic honeycomb lattice. …
The spin-orbit coupling in the absence of spatial inversion symmetry plays an important role in realizing intriguing electronic states in solids, such as topological insulators and unconventional superconductivity. Usually, the inversion symmetry breaking is inherent in the lattice structures, and hence, it is not easy to control these interesting properties by external parameters. We here theoretically investigate the possibility of generating the spin-orbital entanglement by spontaneous electronic ordering caused by electron correlations. In particular, we focus on the centrosymmetric lattic…
We study the lead rhenium oxide PbRe2O6 as a candidate spin-orbit-coupled metal (SOCM), which has attracted much attention as a testing ground for studying unconventional Fermi liquid instability associated with a large spin-orbit interaction. The compound comprises a stack of modulated honeycomb lattices made of Re5+ (5d2) ions in a centrosymmetric R-3m structure at room temperature. Resistivity, magnetic susceptibility, and heat capacity measurements using single crystals reveal two successive first-order phase transitions at Ts1 = 265 K and Ts2 = 123 K. At Ts1, the magnetic susceptibility i…
We report a neutron diffraction study of the multiferroic mechanism in (ND4)2FeCl5D2O, a molecular compound that exhibits magnetically induced ferroelectricity. This material exhibits two successive magnetic transitions on cooling: a long-range order transition to an incommensurate (IC) collinear sinusoidal spin state at TN=7.3 K, followed by a second transition to an IC cycloidal spin state at TFE=6.8 K, the later of which is accompanied by spontaneous ferroelectric polarization. The cycloid structure is strongly distorted by spin-lattice coupling as evidenced by the observations of both odd …
The crystal growth and the structural, transport and magnetic properties of the magnetically frustrated YbMn$_2$Sb$_2$ single crystals are reported. The crystals show a trigonal symmetry (space group $P\bar{3}m1$), where corrugated honeycomb layers of MnSb are separated by Yb atoms. No structural phase transition was observed down to 22~K. The resistivity measurements show a predominantly insulating behavior. The combined resistivity, dc susceptibility and heat capacity measurements confirm successive transitions at 230~K, 116~K and 27~K, being the transition at $T_N$=116~K due to the Mn$^{+2}…
