We present the microscopic theory of improper multiferroicity in BiMnO3, which can be summarized as follows: (1) the ferroelectric polarization is driven by the hidden antiferromagnetic order in the otherwise centrosymmetric C2/c structure; (2) the relativistic spin-orbit interaction is responsible for the canted spin ferromagnetism. Our analysis is supported by numerical calculations of electronic polarization using Berry's phase formalism, which was applied to the low-energy model of BiMnO3 derived from the first-principles calculations. We explicitly show how the electric polarization can be controlled by the magnetic field and argue that BiMnO3 is a rare and potentially interesting material where ferroelectricity can indeed coexist and interplay with the ferromagnetism.
Using a first-principles-based effective Hamiltonians within molecular dynamics simulations, we discover that applying an electric field that is opposite to the initial direction of the polarization results in a switching of both the polarization and the magnetic chirality vector of multiferroic BiFeO3 at an ultrafast pace (namely of the order of picoseconds). We discuss the origin of such a double ultrafast switching, which is found to involve original intermediate magnetic states and may hold promise for designing various devices.
Electrically driven adiabatic changes of temperature are identified in the archetypal electrocaloric material PbSc0.5Ta0.5O3 by comparing isothermal changes of electrical polarization due to slow variation of electric field, and adiabatic changes of electrical polarization due to fast variation of electric field. By obtaining isothermal (adiabatic) electrical polarization data at measurement (starting) temperatures separated by <0.4 K, we identify a maximum temperature change of ~2 K due to a maximum field change of 26 kV cm-1, for starting temperatures in the range 300 - 315 K. These quasi in…
Electric polarization loops are measured at room temperature on highly pure BiFeO3 single crystals synthesized by a flux growth method. Because the crystals have a high electrical resistivity, the resulting low leakage currents allow us to measure a large spontaneous polarization reaching 100 microC.cm^{-2}, a value never reported in the bulk. During electric cycling, the slow degradation of the material leads to an evolution of the hysteresis curves eventually preventing full saturation of the crystals.
We report electric polarization and magnetization measurements in single crystals of double perovskite Lu2MnCoO6 using pulsed magnetic fields and optical second harmonic generation (SHG) in DC magnetic fields. we observe well-resolved magnetic field-induced changes in the electric polarization in single crystals and thereby resolve the question about whether multiferroic behavior is intrinsic to these materials or an extrinsic feature of polycrystals. We find electric polarization along the crystalline b-axis, that is suppressed by applying a magnetic fields along c-axis and advance a model fo…
This work presents the results for the Faraday rotation in pure and Cr-doped lead germanate crystals studied in the course of proper ferroelectric phase transition. We show that the increment of the Faraday rotation appearing at the phase transition is caused by a combined magneto-electrooptic effect induced by spontaneous polarization. It is proportional to the square of spontaneous polarization. The phenomenon revealed by us corresponds to combined effects of crystal optics, which appear due to common action of different fields.
Electric polarization in ErCrO3 single crystals has been investigated in the temperature range of 5_370 K. Ferroelectric ordering has not been found in any of the directions. However, electric polarization induced by restricted polar domains of structural origin has been observed. These domains are formed in the crystal matrix near impurity Bi^{3+} ions partially substituting Er^{3+} ions during the growth of single crystals by the method of spontaneous crystallization using solvent Bi_2O_3. The restricted polar domains form the superparaelectric state. Hysteresis loops with remanent polarizat…
The relationship between the applied elastic strain gradient and the induced electric polarization in the alpha-phase polyvinylidene fluoride (PVDF) films under bending conditions has been investigated. Our experimental studies have shown that the flexoelectric polarization is linearly proportional to the strain gradient and the corresponding direct flexoelectric response is strong. It is reasonable to believe that the physical mechanisms behind the flexoelectric effects in polymers and solid dielectrics are different.
The Landau theory of phase transitions of Ba0.8Sr0.2TiO3 thin film under external electric field applied in the planar geometry is developed. The interfacial van-der-Waals field Ez=1.1x10^8 V/m oriented normal to the film-substrate interface was introduced in to the model calculation to explain experimentally observed behavior of the polarization as a function of planar electric field. The Ez - misfit strain phase diagram of the film is constructed and discussed.
The electric polarization induced by local polar domains of two types (phase separation domains of magnetic nature and structure-distorted domains) has been observed in YCrO3 single crystals. These domains form a superparaelectric state. Below some temperatures, in the frozen superparaelectric state, the pyrocurrent maxima and the hysteresis loops with remanent polarization are observed as along axis c so in directions [110]. The polarization exists to the temperatures depending on the orientation of electric field with respect to the crystal axes. The sources of formation of such local domain…
Hidden spin polarization (HSP) emerges in centrosymmetric crystals where visible spin splittings in the real space can be observed because of the lack of inversion symmetry in each local sector. Starting from tight-binding models, we introduce nonsymmorphic antiferroelectric (AFE) crystals as a new class of functional materials that can exhibit strong local spin polarization. Such AFE crystals can be basically classified as in-plane and out-of-plane AFE configurations, and can be reversibly switched to the ferroelectric phase by an electric field to manifest global spin splittings, enabling a …
The three-fold symmetry of planar boron nitride, the III-V analog to graphene, prohibits an electric polarization in its ground state, but this symmetry is broken when the sheet is wrapped to form a BN nanotube. We show that this leads to an electric polarization along the nanotube axis which is controlled by the quantum mechanical boundary conditions on its electronic states around the tube circumference. Thus the macroscopic dipole moment has an {\it intrinsically nonlocal quantum} mechanical origin from the wrapped dimension. We formulate this novel phenomenon using the Berry's phase approa…
Ferroelectric field-effect transistors (FE-FETs) consisting of tunable dielectric layers are utilized to investigate interfacial transport processes. Large changes in the dielectric constant as a function of temperature are observed in FE-FETs in conjunction with the ferroelectric to paraelectric transition. The devices offer a test bed to evaluate specific effects of polarization on the electrical processes. FE-FETs have dominant contributions from polarization-fluctuation rather than static dipolar disorder prevalent in high k paraelectric dielectric-based FETs. Additionally, photo-excitatio…
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 report observation of magneto-electric and magneto-dielectric couplings in ceramic Co3TeO6. Temperature dependent DC magnetization and dielectric constant measurements together indicate coupling between magnetic order and electronic polarization. Strong anomaly in dielectric constant at ~ 18K in zero magnetic field indicates presence of spontaneous polarization. Observations like weak ferromagnetic order at lower temperature, field and temperature dependences of the ferroelectric transition provide experimental verification of the recent theoretical proposal by P. Toledano et al., Phys. Rev…
Ultrafast optical control of ferroelectricity using intense terahertz fields has attracted significant interest. Here we show that the nonlinear interactions between two optical phonons in SnTe, a two-dimensional in-plane ferroelectric material, enables a dynamical amplification of the electric polarization within subpicoseconds time domain. Our first principles time dependent simulations show that the infrared-active out-of-plane phonon mode, pumped to nonlinear regimes, spontaneously generates in-plane motions, leading to rectified oscillations in the in-plane electric polarization. We sugge…
A pseudospin model for description of the influence of the electric field, confined to the plane of sublattice polarization, on the two-dimensional squaric acid antiferroelectrics is developed. The system behavior is analyzed in terms of the parameters of ferroelectric and antiferroelectric ordering, as well as the non-collinearity angle $θ$, which is the angle between sublattice polarizations. The temperature-electric field $T-E_1$ phase diagram is constructed. Most of the field-induced transitions are found to be associated with polarization rotation. The observed phases include the collinea…
Electric-field control of spin-dependent properties has become one of the most attractive phenomena in modern materials research due the promise of new device functionalities. One of the paradigms in this approach is to electrically toggle the spin polarization of carriers injected into a semiconductor using ferroelectric polarization as a control parameter. Using first-principles density functional calculations, we explore the effect of ferroelectric polarization of electron-doped BaTiO3 (n-BaTiO3) on the spin-polarized transmission across the SrRuO3/n-BaTiO3 (001) interface. Our study reveal…
We describe ferroelectric thin films with circular electrodes and develop a thermodynamic theory that explains previously mysterious experiments. It is found to be especially useful for restricted geometries such as microstructures for which boundary conditions are well known to play an important role in ferroelectric properties. We have explored a new switching mechanism, which consists of an inhomogeneous rotational motion of the polarization and leads to an extended vortex state. The vortex appearance exhibits characteristic properties of a first-order field-induced phase transition: three …
Polyvinylidenefluoride (PVDF) a semicrystalline pieozoelectric polymer was synthesized with varying process conditions and its ferroelectric domain orientations were studied using piezoresponse force microscope (PFM). PVDF thin films fabricated using tape casting technique with precursor solutions of varying viscosities reveal that the polarization components transform from a dominant planar component to an out-of-plane polarization components with increase in viscosity. Interestingly the planar components possessed a head to head or tail to tail kind of paired domains separated by a distance …
Valleytronics has been widely investigated for providing new degrees of freedom to future information coding and processing. Here, it is proposed that valley polarization can be achieved by electric field induced magnetic anisotropy (MA) transformation. Through the first-principle calculations, our idea is illustrated by a concrete example of $\mathrm{VSi_2P_4}$ monolayer. The increasing electric field can induce a transition of MA from in-plane to out-of-plane by changing magnetic anisotropy energy (MAE) from negative to positive value, which is mainly due to increasing magnetocrystalline ani…
Electric polarization driven by non-collinear spin alignment investigated by first principles calculations
Institute of Materials Science, TU Darmstadt（达姆施塔特工业大学材料科学研究所）；Department of Chemistry/Phys. Chemistry, LMU Munich（慕尼黑大学化学/物理化学系）；New Technologies Research Center, University of West Bohemia（西波希米亚大学新技术研究中心）
We show that the propagation of spin polarized carriers may be dramatically affected by {\em inhomogeneous} electric fields. Surprisingly, the spin diffusion length is found to strongly depend on the sign and magnitude of electric field \emph{gradients}, in addition to the previously reported dependence on the sign and magnitude of the electric field [Yu & Flatté, Phys. Rev. B {\bf 66}, 201202(R) 2002; {\em ibid.} {\bf 66}, 235302 (2002)]. This indicates that purely electrical effects may play a crucial role in spin polarized injection, transport and detection in semiconductor spintronics. A g…
From an experimental point of view, room temperature ferroelectricity in BiFeO3 is raising many questions. Electric measurements made a long time ago on solid-solutions of BiFeO3 with Pb(Ti,Zr)O3 indicate that a spontaneous electric polarization exists in BiFeO3 below the Curie temperature TC=1143K. Yet in most reported works, the synthesised samples are too conductive at room temperature to get a clear polarization loop in the bulk without any effects of extrinsic physical or chemical parameters. Surprisingly, up to now there has been no report of a P(E) (polarization versus electric field) l…
Electrical control of magnetization is of crucial importance for integrated spintronics devices. Spin-orbit torques (SOT) in heavy-metal/ferromagnetic heterostructures have emerged as promising tool to achieve efficiently current-induced magnetization reversal. However, the microscopic origin of the SOT is being debated,with the spin Hall effect (SHE) due to nonlocal spin currents and the spin Rashba-Edelstein effect (SREE) due to local spin polarization at the interface being the primary candidates. We investigate the electrically induced out-of-equilibrium spin and orbital polarizations in p…
A stochastic model for polarization switching in tetragonal ferroelectric ceramics is introduced, which includes sequential 90°- and parallel 180°-switching processes and accounts for the dispersion of characteristic switching times due to a nonuniform spatial distribution of the applied field. It presents merging of the recent multistep stochastic mechanism (MSM) with the earlier nucleation limited switching (NLS) and inhomogeneous field mechanism (IFM) models. The new model provides a much better description of simultaneous polarization and strain responses over a wide time window and a deep…
Using the previously developed model we revisit the problem of the electric field induced polarization rotation in antiferroelectric crystals of squaric acid. We test an alternative set of the model parameters, according to which the dipole moments associated with the H$_2$C$_4$O$_4$ groups are assumed to be parallel to the diagonals of the $ac$ plane. The $T$-$E$ phase diagrams and the polarization curves $P(E)$ for the fields directed along the $a$ axis and along one of the diagonals are considered. Comparison of the theoretical results with the newly published experimental data confirm the …
In the presence of a (time-dependent) macroscopic electric field the electron dynamics of dielectrics cannot be described by the time-dependent density only. We present a real-time formalism that has the density and the macroscopic polarization P as key quantities. We show that a simple local function of P already captures long-range correlation in linear and nonlinear optical response functions. Specifically, after detailing the numerical implementation, we examine the optical absorption, the second- and third-harmonic generation of bulk Si, GaAs, AlAs and CdTe at different level of approxima…
The effect of the Fe-Ga ratio on the magnetic and electric properties of the multiferroic Ga2-xFexO3 compound has been studied in order to determine the composition range exhibiting magnetic and electric orders coexistence and their critical temperatures. A magnetoelectric phase diagram, showing the evolution of both the Neel magnetic ordering temperature and the electric ordering temperature, versus the iron content has been established for x values between 0.9 and 1.4. While the ferrimagnetic Neel temperature increases with the iron content, the electric ordering temperature shows an opposit…
We consider the flow of polarization current J(t)=dP/dt produced by a homogeneous electric field E(t) or by rapidly varying some other parameter in the Hamiltonian of a solid. For an initially insulating system and a collisionless time evolution, the dynamic polarization P(t) is given by a nonadiabatic version of the King-Smith--Vanderbilt geometric-phase formula. This leads to a computationally convenient form for the Schroedinger equation where the electric field is described by a linear scalar potential handled on a discrete mesh in reciprocal space. Stationary solutions in sufficiently wea…
The effect of rare-earth ions (R = Er^{3+}, Tb^{3+}) with strong spin-orbit coupling on the dielectric properties and the electric polarization induced by local polar phase separation domains in RMn_2O_5 multiferroics has been studied. These parameters were found to be qualitatively distinguished from those studied before in GdMn_2O_5, in which Gd^{3+} ion in the ground ^8S_{7/2} state is weakly bounded with the lattice. It is shown that the properties of the polar phase separation domains, which form in the subsystem of Mn^{3+} and Mn^{4+} ions, are substantially dependent on the values of cr…
Spin-polarized electrical transport is investigated in $ Al_{2}O_{3}/Ni_{80}Fe_{20}/Al_{2}O_{3}$ thin films for permalloy thickness between 6 and 20nm. The degree of spin-polarization of the current flowing in the plane of the film is measured through the current induced spin wave Doppler shift. We find that it decreases as the film thickness decreases, from 0.72 at 20nm to 0.46 at 6nm. This decrease is attributed to a spin depolarization induced by the film surfaces. A model is proposed which takes into account the contributions of the different sources of electron scattering (alloy disorder,…
The impact of flexoelectric coupling on polarization reversal kinetics and space charge dynamics in thin films of ferroelectric-semiconductors has been theoretically studied. The relaxation-type Landau-Khalatnikov equation together with the Poisson equation and the theory of elasticity equations have been used to calculate in a self-consistent way the spatial-temporal development of ferroelectric polarization, electric potential and space charge, elastic stresses, strains and their gradients. The analysis of the obtained results reveals a moderate increase of the flexocoupling influence on the…
We present Maxwell equations with source terms for the electromagnetic field interacting with a moving electron in a spin-orbit coupled semiconductor heterostructure. We start with the eight--band ${\bm k}{\bm p}$ model and derive the electric and magnetic polarization vectors using the Gordon--like decomposition method. Next, we present the ${\bm k}{\bm p}$ effective Lagrangian for the nonparabolic conduction band electrons interacting with electromagnetic field in semiconductor heterostructures with abrupt interfaces. This Lagrangian gives rise to the Maxwell equations with source terms and …
The hyperfine interaction between the quadrupole moment of atomic nuclei and the electric field gradient (EFG) provides information on the electronic charge distribution close to a given atomic site. In ferroelectric materials, the loss of inversion symmetry of the electronic charge distribution is necessary for the appearance of the electric polarization. We present first-principles density functional theory calculations of ferroelectrics such as BaTiO3, KNbO3, PbTiO3 and other oxides with perovskite structures, by focusing on both EFG tensors and polarization. We analyze the EFG tensor prope…
We present a short critical overview of different microscopic models for nonrelativistic and relativistic magnetoelectric coupling including the so-called "spin current scenario", ab-initio calculations, and several recent microscopic approaches to a spin-dependent electric polarization in 3d oxides.
We clarify that the antiferromagnetic order in the distorted tetrahedral quasi-one dimensional spin system induces electric polarizations. In this system, the effects of the low dimensionality and the magnetic frustration are expected to appear simultaneously. We obtain the magnetic-field-temperature phase diagram in Cu3Mo2O9 by studying the dielectric constant and the spontaneous electric polarization. Around the tricritical point at 10 T and 8 K, the change of the direction in the electric polarization causes a colossal magnetocapacitance. We calculate the charge redistribution in the small …
We consider a disordered two-dimensional electron gas with spin-orbit coupling placed in a perpendicular magnetic field and calculate the magnitude and direction of the electric-field-induced spin polarization. We find that in strong magnetic fields the polarization becomes an oscillatory function of the magnetic field and that the amplitude of these oscillations is parametrically larger than the polarization at zero magnetic field. We show that the enhanced amplitude of the polarization is a consequence of strong electron-hole asymmetry in a quantizing magnetic field.
The response of an infinite, periodic, insulating, solid to an infinitesimally small electric field is investigated in the framework of Density Functional Theory. We find that the applied perturbing potential is not a unique functional of the periodic density change~: it depends also on the change in the macroscopic {\em polarization}. Moreover, the dependence of the exchange-correlation energy on polarization induces an exchange-correlation electric field. These effects are exhibited for a model semiconductor. We also show that the scissor-operator technique is an approximate way of bypassing…
Two prominent magnetoelectrics MnWO$_4$ and CuO possess low-temperature commensurate paraelectric magnetically ordered phase. Here using Monte Carlo simulations we show that the walls between the domains of this phase are ferroelectric with the same electric polarization direction and value as that in the magnetoelectric phases of these compounds. We also suggest that experimental observation of electric polarization of domain walls in MnWO$_4$ should help to determine the macroscopic interactions responsible for its magnetoelectric properties.
We show that electric field can induce spin polarization and dichroism effects in angle resolved photoemission spectroscopy (ARPES) in spin orbit coupling systems. The physical origin behind the effects essentially is the same as the spin Hall effect induced by the electric field. Since the ARPES experiments have both energy and momentum resolutions, the spin Hall effect can be directly verified by the ARPES experiments for individual band even if there is no net spin current.
We theoretically show that an interlayer bias voltage in the AB-stacked bilayer graphene nanoribbons with armchair edges induces an electric polarization along the ribbon. Both tight-binding and ab initio calculations consistently indicate that when the bias voltage is weak, the polarization shows opposite signs depending on the ribbon width modulo three. This nontrivial dependence is explained using a two-band effective model. A strong limit of the bias voltage in the tight-binding model shows either one-third or zero polarization, which agrees with topological argument.
We examine theoretically a possibility of ferroelectricity caused by electronic charge order without inversion symmetry, motivated by layered iron oxides. Quantum electronic models in a paired-triangular lattice are analyzed by utilizing the variational Monte Carlo simulation. Our calculation demonstrates that combined effects of electron transfer between the layers, corresponding to quantum fluctuation between the potential minima, and geometrical frustration promote appearance of an electric polarization. Present results are in contrast to the conventional manner of quantum fluctuation in fe…
The magnetic and electrical properties of Co$_3$TeO$_6$ single-crystals with corundum related structure reveal a magnetic-field induced polarization below 21 K. A sharp peak in the specific heat at \approx 18 K indicates a reconstructive-type first-order phase transition. From second-harmonic generation (SHG) measurements breaking of inversion symmetry is evident and the point-group symmetry was determined as m. The temperature and magnetic-field dependence of the magnetic and electrical polarizations are discussed in the light of the SHG results.
We derive and discuss expressions for the temperature-dependent electrostatic polarizabilities of off-center ions holding good under various experimental conditions. At low temperatures and electric-field strengths, all of them reasonably reduce to values characteristic of phonon-coupled two-level systems. Prospects for further studies of the dispersive coupling are also considered.
We investigate tunable electric polarization and electronic structure of quasi-two-dimensional (quasi-2D) allotropes of selenium, which are formed from their constituent one-dimensional (1D) structures through an inter-chain interaction facilitated by the multi-valence nature of Se. Our em ab initio calculations reveal that different quasi-2D Se allotropes display different types of electric polarization, including ferroelectric (FE) polarization normal to the chain direction in alpha and delta allotropes, non-collinear ferrielectric (FiE) polarization along the chain axis in tau-Se, and anti-…
We address a systematic microscopic theory of spin-dependent electric polarization in 3d oxides starting with a generic three-site two-hole cluster. A perturbation scheme realistic for 3d oxides is applied which implies the quenching of orbital moments by low-symmetry crystal field, strong intra-atomic correlations, the dp-transfer effects, and rather small spin-orbital coupling. An effective spin operator of the electric dipole moment is deduced incorporating both nonrelativistic and relativistic terms. The nonrelativistic electronic polarization mechanism related with the effects of the redi…
We investigate electric polarizations emergent perpendicular to an applied thermal gradient in insulating systems. The thermally-induced electric polarization, known as thermopolarization, has been studied conventionally in the case that an electric polarization appears along the thermal gradient. Here, we focus on the antisymmetric component of the thermopolarization tensor and reveal that it becomes nonzero owing to the ferro-type order for electric-toroidal dipole moments. To describe local electric polarizations originating from the disproportionation of localized electronic clouds, we int…
Synthesis and extensive structural, pyroelectric, magnetic, dielectric and magneto-electric characterizations are reported for polycrystalline Co4Nb2O9 towards unraveling the multiferroic state especially in reference to the magnetic spin flop transition. Magnetic measurements confirm the Co4Nb2O9 becomes antiferromagnetic (AFM) at around 28 K but no clear evidence for spin-flop effect was found. Associated with the magnetic phase transition, a sharp peak in pyroelectric current indicates the appearance of the strong magneto-electric coupling below Neel temperature (TN) with a large coupling c…
A common scenario of magnetoelectric coupling in multiferroics is the electric polarization induced by spatially modulated spin structures. It is shown in this paper that the same mechanism works in magnetic dielectrics with inhomogeneous magnetization distribution: the domain walls and magnetic vortexes can be the sources of electric polarization. The electric field driven magnetic domain wall motion is observed in iron garnet films. The electric field induced nucleation of vortex state of magnetic nanodots is theoretically predicted and numerically simulated. From the practical point of view…
A layered iron oxide \rfeo ($R$: rare-earth elements) is an exotic dielectric material with charge-order (CO) driven electric polarization and magnetoelectric effect caused by spin-charge coupling. In this paper, a theory of electronic structure and dielectric property in \rfeo is presented. Charge frustration in paired-triangular lattices allows a charge imbalance without inversion symmetry. Spin frustration induces reinforcement of this polar CO by a magnetic ordering. We also analyze an orbital model for the Fe ion which does not show a conventional long-range order.
We detected the spin polarization due to charge flow in the spin non-degenerate surface state of a three dimensional topological insulator by means of an all-electrical method. The charge current in the bulk-insulating topological insulator Bi1.5Sb0.5Te1.7Se1.3 (BSTS) was injected/extracted through a ferromagnetic electrode made of Ni80Fe20, and an unusual current-direction-dependent magnetoresistance gives evidence for the appearance of spin polarization which leads to a spin-dependent resistance at the BSTS/Ni80Fe20 interface. In contrast, our control experiment on Bi2Se3 gave null result. T…
