Materials with long-range order like ferromagnetism or ferroelectricity exhibit uniform, yet differently oriented three-dimensional regions called domains that are separated by two-dimensional topological defects termed domain walls\cite{Tagantsev2010,AlexHubert1998}. A change of the ordered state across a domain wall can lead to local non-bulk properties such as enhanced conductance or the promotion of unusual phases\cite{Seidel2009,Meier2012,Farokhipoor2014}. Although highly desirable, controlled transfer of these exciting properties between the bulk and the walls is usually not possible. Here we demonstrate this crossover from three- to two-dimensions for confining multiferroic Dy$_{0.7}$Tb$_{0.3}$FeO$_3$ domains into multiferroic domain walls at a specified location within a non-multiferroic environment. This process is fully reversible; an applied magnetic or electric field controls the transformation. Aside from the aspect of magnetoelectric functionality, such interconversion can be key to tailoring elusive domain architectures such as in antiferromagnets.
Domain-wall-to-domain interconversion in a polar conducting oxide
University of Groningen（格罗宁根大学）；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）；Groningen Cognitive Systems and Materials Center (CogniGron), University of Groningen（格罗宁根认知系统与材料中心）；Faculty of Physics, University of Duisburg-Essen（杜伊斯堡-埃森大学物理学院）；Research Center Future Energy Materials and Systems (RC FEMS), Research Alliance Ruhr（鲁尔研究联盟未来能源材料与系统研究中心）；Institut des Molécules et Matériaux du Mans, UMR 6283 CNRS, Le Mans Université（勒芒大学CNRS 6283分子与材料研究所）；The European Synchrotron Radiation Facility (ESRF)（欧洲同步辐射装置）；Theoretical Materials Physics, Q-MAT, University of Liège（列日大学Q-MAT理论物质物理）
The antiferromagnetic domain structure of a multiferroic has been investigated in the presence of a ferroelectric domain structure. It has been demonstrated that an inhomogeneous magnetoelectric (flexomagnetoelectric) interaction leads to pinning of antiferromagnetic domain walls at the walls of the ferroelectric domains and to a change in the structure of antiferromagnetic domain walls.
Tweaking the properties of carbon nanotubes is a prerequisite for their practical applications. Here we demonstrate fine-tuning the electronic properties of single-wall carbon nanotubes via filling with ferrocene molecules. The evolution of the bonding and charge transfer within the tube is demonstrated via chemical reaction of the ferrocene filler ending up as secondary inner tube. The charge transfer nature is interpreted well within density functional theory. This work gives the first direct observation of a fine-tuned continuous amphoteric doping of single-wall carbon nanotubes.
The dynamics of a multiferroic domain wall in which an electric field can couple to the magnetization via inhomogeneous magnetoelectric interaction is investigated by the collective-coordinate framework. We show how the electric field is capable of delaying the onset of the Walker breakdown of the domain wall motion, leading to a significant enhancement of the maximum wall velocity. Moreover, we show that in the stationary regime the chirality of the domain wall can be efficiently reversed when the electric field is applied along the direction of the magnetic field. These characteristics sugge…
The transport properties of domain walls in oxygen deficient multiferroic YMnO3 single crystals have been probed using conductive atomic force microscopy and piezoresponse force microscopy. Domain walls exhibit significantly enhanced conductance after being poled in electric fields, possibly induced by oxygen vacancy ordering at domain walls. The electronic conduction can be understood by the Schottky emission and Fowler-Nordheim tunnelling mechanisms. Our results show that the domain wall conductance can be modulated through band structure engineering by manipulating ordered oxygen vacancies …
We demonstrate that the magnetization of a ferromagnet in contact with an antiferromagnetic multiferroic (LuMnO3) can be speedily reversed by electric field pulsing, and the sign of the magnetic exchange bias can switch and recover isothermally. As LuMnO3 is not ferroelastic, our data conclusively show that this switching is not mediated by strain effects but is a unique electric-field driven decoupling of the ferroelectric and ferromagnetic domains walls. Their distinct dynamics are essential for the observed magnetic switching.
The behavior of antiferromagnetic domain wall (ADW) against the background of a periodic ferroelectric domain structure has been investigated. It has been shown that the structure and the energy of ADW change due to the interaction with a ferroelectric domain structure. The ferroelectric domain boundaries play the role of pins for magnetic spins, the spin density changes in the vicinity of ferroelectric walls. The ADW energy becomes a periodical function on a coordinate which is the position of ADW relative to the ferroelectric domain structure. It has been shown that the energy of the magneti…
We show that switching in ferroelectric lead germanate and lead iron tantalate zirconate titanate (PZTFT) does not resemble the equilibrium domain structure evolution of the Landau-Lifshitz-Kittel model but is instead highly nonequilibrium and similar, respectively, to the Richtmyer-Meshkov instability in liquids and the Helfrich-Hursault sliding instability in liquid crystals. The resulting nano-domain structures in PZTFT are circular or parabolic and involving folding bifurcations. These may have an undesirable impact on ferroelectric thin-film memoriesthat are also ferroelastic.
In elastically coupled multiferroic heterostructures that exhibit full domain correlations between ferroelectric and ferromagnetic sub-systems, magnetic domain walls are firmly pinned on top of ferroelectric domain boundaries. In this work we investigate the influence of pinned magnetic domain walls on the magnetization reversal process in a Co40Fe40B20 wedge film that is coupled to a ferroelectric BaTiO3 substrate via interface strain transfer. We show that the magnetic field direction can be used to select between two distinct magnetization reversal mechanisms, namely (1) double switching ev…
Deterministic polarization reversal in ferroelectric and multiferroic films is critical for their exploitation in nanoelectronic devices. While ferroelectricity has been studied for nearly a century, major discrepancies in the reported values of coercive fields and saturation polarization persist in literature for many materials. This raises questions about the atomic-scale mechanisms behind polarization reversal. Unconventional ferroelectric switching in $ε$-Fe2O3 films, a material that combines ferrimagnetism and ferroelectricity at room temperature, is reported here. High-resolution in-situ…
Domain walls (DWs), the two-dimensional boundaries between symmetry equivalent ferroic domains, are actively investigated due to their promise for novel logic and memory devices. Moreover, they can be easily created, erased and reshaped at a low energy cost due to their high mobility and large electrical conductivity. Most work so far has been focused on DWs in proper ferroelectrics, where the primary order parameter, ferroelectric polarization, interpolates between the values in the domains by either reducing to zero (in Ising-type DW) or rotating (Bloch type DW). Here we present a new member…
We report the dielectric dispersion of the giant magnetocapacitance (GMC) in multiferroic DyMnO$_{3}$ over a wide frequency range. The GMC is found to be attributable not to the softened electromagnon but to the electric-field-driven motion of multiferroic domain wall (DW). In contrast to conventional ferroelectric DWs, the present multiferroic DW motion holds extremely high relaxation rate of $\sim$$10^{7}$ s$^{-1}$ even at low temperatures. This mobile nature as well as the model simulation suggests that the multiferroic DW is not atomically thin as in ferroelectrics but thick, reflecting it…
We report on domain pattern transfer from a ferroelectric BaTiO$_{\mathrm{3}}$ substrate with a $(111)$-orientation of the surface to an epitaxial Co film grown on a Pd buffer layer. Spatially modulated interfacial strain transfer from ferroelectric/ferroelastic domains and inverse magnetostriction in the ferromagnetic film induce stripe regions with a modulation of the in-plane uniaxial magnetic anisotropy direction. Using spin-polarized low energy electron microscopy, we observe the formation of two distinct anisotropy configurations between stripe regions. Moreover, through application of a…
Domains in BaTiO$_3$ induces a regular modulation of uniaxial magnetic anisotropy in CoFeB via an inverse magnetostriction effect. As a result, the domain structures of the CoFeB wedge film and BaTiO$_3$ substrate correlate fully and straight ferroelectric domain boundaries in BaTiO$_3$ pin magnetic domain walls in CoFeB. We use x-ray photoemission electron microscopy and magneto-optical Kerr effect microscopy to characterize the spin structure of the pinned domain walls. In a rotating magnetic field, abrupt and reversible transitions between two domain wall types occur, namely, narrow walls w…
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.
Inhomogeneous magnetoelectric effect in magnetization distribution heterogeneities (0-degree domain walls) appeared on crystal lattice defect of the multiferroic material has been investigated. Magnetic symmetry based predictions of kind of electrical polarization distribution in their volumes were used. It was found that magnetization distribution heterogeneity with any symmetry produces electrical polarization. Results were systemized in scope of micromagnetic structure chirality. It was shown that all 0-degree domain walls with time-noninvariant chirality have identical type of spatial dist…
We present a first-principles density functional study of the structural, electronic and magnetic properties of the ferroelectric domain walls in multiferroic BiFeO3. We find that domain walls in which the rotations of the oxygen octahedra do not change their phase when the polarization reorients are the most favorable, and of these the 109 degree domain wall centered around the BiO plane has the lowest energy. The 109 degree and 180 degree walls have a significant change in the component of their polarization perpendicular to the wall; the corresponding step in the electrostatic potential is …
We calculate the exact analytical solution to the domain wall properties in a multiferroic system with two order parameters that are coupled bi-quadratically. This is then adapted to the case of a magnetoelectric multiferroic material such as BiFeO3, with a view to examine critically whether the domain walls can account for the enhancement of magnetization reported for thin films fo this material, in view of the correlation between increasing magnetization and increasing volume fraction of domain walls as films become thinner. The present analysis can be generalized to describe a class of magn…
We construct ferroelectric (LuFeO3)m/(LuFe2O4) superlattices with varying index m to study the effect of confinement on topological defects. We observe a thickness-dependent transition from neutral to charged domain walls and the emergence of fractional vortices. In thin LuFeO3 layers, the volume fraction of domain walls grows, lowering the symmetry from P63cm to P3c1 before reaching the non-polar P63/mmc state, analogous to the high-temperature ferroelectric to paraelectric transition. Our study shows how dimensional confinement stabilizes textures beyond those in bulk ferroelectric systems.
We consider theoretically the effect of an inhomogeneous magnetoelectric coupling on the magnon-induced dynamics of a ferromagnet. The magnon-mediated magnetoelectric torque affects both the homogeneous magnetization and magnon-driven domain wall motion. In the domains, we predict a reorientation of the magnetization, controllable by the applied electric field, which is almost an order of magnitude larger than that observed in other physical systems via the same mechanism. The applied electric field can also be used to tune the domain wall speed and direction of motion in a linear fashion, pro…
The structure of domain walls determines to a large extent the properties of magnetic materials, in particular their hardness and switching behavior, it represents an essential ingredient of spintronics. Common domain walls are of Bloch and Neel types in which the magnetization rotates around a fixed axis, giving rise to a one-dimensional magnetization profile. Domain walls in helical magnets, most relevant in multiferroics, were never studied systematically. Here we show that domain walls in helical magnets are fundamentally different from Bloch and Neel walls. They are generically characteri…
Recent works have shown that the domain walls of room-temperature multiferroic BiFeO3 (BFO) thin films can display distinct and promising functionalities. It is thus important to understand the mechanisms underlying domain formation in these films. High-resolution x-ray diffraction and piezo-force microscopy, combined with first-principles simulations, have allowed us to characterize both the atomic and domain structure of BFO films grown under compressive strain on (001)-SrTiO3, as a function of thickness. We derive a twining model that describes the experimental observations and explains why…
Low-dimensional multiferroic materials hold great promises in miniaturized device applications such as nanoscale transducers, actuators, sensors, photovoltaics, and nonvolatile memories. Here, using first-principles theory we predict that two-dimensional (2D) monolayer Group IV monochalcogenides including GeS, GeSe, SnS, and SnSe are a class of 2D semiconducting multiferroics with strongly coupled giant in-plane spontaneous ferroelectric polarization and spontaneous ferroelastic lattice strain that are thermodynamically stable at room temperature and beyond, and can be effectively modulated by…
The coupling between antiferrodistortion (AFD) and ferroelectric (FE) polarization, universal for all tilted perovskite multiferroics, is known to strongly correlate with domain wall functionalities in the materials. The intrinsic mechanisms of domain wall phenomena, especially AFD-FE coupling-induced phenomena at the domain walls, have continued to intrigue the scientific and technological communities because of the need to develop the future nano-scale electronic devices. Over the past years, theoretical studies often show controversial results, owing to the fact that they are neither suffic…
Unusual domains with curved walls and failure to satisfy the Landau-Lifshitz-Kittel Law are modeled as folding catastrophes (saddle-node bifurcations). This description of ballistic motion in a viscous medium is based upon early work by Dawber et al., Appl. Phys. Lett. 82, 436 (2003). It suggests that ferroelectric films can exhibit folds or vortex patterns but not both.
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 …
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.
Spintronic devices currently rely on magnetic switching or controlled motion of domain walls by an external magnetic field or spin-polarized current. Achieving the same degree of magnetic controllability using an electric field has potential advantages including enhanced functionality and low power consumption. Here, we report on an approach to electrically control local magnetic properties, including the writing and erasure of regular ferromagnetic domain patterns and the motion of magnetic domain walls, in multiferroic CoFe-BaTiO3 heterostructures. Our method is based on recurrent strain tra…
We have analyzed the morphology of ferroelectric domains in very thin films of multiferroic BiFeO3. Unlike the more common stripe domains observed in thicker films BiFeO3 or in other ferroics, the domains tend not to be straight, but irregular in shape, with significant domain wall roughening leading to a fractal dimensionality. Also contrary to what is usually observed in other ferroics, the domain size appears not to scale as the square root of the film thickness. A model is proposed in which the observed domain size as a function of film thickness can be directly linked to the fractal dimen…
Magnetoelastic and magnetoelectric coupling in the artificial multiferroic heterostructures facilitate valuable features for device applications such as magnetic field sensors and electric write magnetic-read memory devices. In a ferromagnetic/ferroelectric heterostructures, the strain mediated coupling exploits piezoelectricity/electrostriction in ferroelectric phase and magnetostriction/piezomagnetism in ferromagnetic phase. Such verity of these combined effect can be manipulated by an external perturbation, such as electric field, temperature or magnetic field. Here, we demonstrate the remo…
Charge dipole moment and spin moment rarely coexist in single-phase bulk materials except in some multiferroics. Despite the progress in the past decade, for most multiferroics their magnetoelectric performance remains poor due to the intrinsic exclusion between charge dipole and spin moment. As an alternative approach, the oxide heterostructures may evade the intrinsic limits in bulk materials and provide more attractive potential to realize the magnetoelectric functions. Here we perform a first-principles study on LaAlO$_3$/PbTiO$_3$ superlattices. Although neither of the components is magne…
Multiferroicity can be induced in strontium titanate by applying biaxial strain, resulting in the coexistence of both ferroelectric and antiferrodistortive domains. The magnitude and sign of the strain imposed on the lattice by design can be used to tune the phase transitions and interactions between these two phenomena. Using optical second harmonic generation, we report a transition from centrosymmetric 4/mmm phase to ferroelectric mm2, followed by an antiferrodistortive transition to a coupled ferroelastic-ferroelectric mm2 phase in a strontium titanate thin film strained in biaxial tension…
Among the recent discoveries of domain wall functionalities, the observation of electrical conduction at ferroelectric domain walls in the multiferroic insulator BiFeO3 has opened exciting new possibilities. Here, we report evidence of electrical conduction also at 180° ferroelectric domain walls in the simpler tetragonal ferroelectric PZT thin films. The observed conduction shows nonlinear, asymmetric current-voltage characteristics, thermal activation at high temperatures and high stability. We relate this behavior to the microscopic structure of the domain walls, allowing local defects segr…
Recent interests towards novel functionalities arising at domain walls of ferroic materials naturally call for a microscopic understanding. To this end, first-principles calculations have been performed in order to provide solid evidence of ferroelectricity in the twin walls of nonpolar CaTiO3 and magnetic CaMnO3. We show that ferroelectricity arises from rotation/tilting octahedral distortions --- cooperatively acting at the twin wall in both considered systems --- rather than from a proper secondary ferroelectric instability, as often believed. Our results are in excellent agreement with exp…
Control of magnetic domain wall motion by electric fields has recently attracted scientific attention because of its potential for magnetic logic and memory devices. Here, we report on a new driving mechanism that allows for magnetic domain wall motion in an applied electric field without the concurrent use of a magnetic field or spin-polarized electric current. The mechanism is based on elastic coupling between magnetic and ferroelectric domain walls in multiferroic heterostructures. Pure electric-field driven magnetic domain wall motion is demonstrated for epitaxial Fe films on BaTiO$_3$ wit…
Multiferroic materials open up the possibility to design novel functionality in electronic devices, with low energy consumption. However, there are very few materials that show multiferroicity at room temperature, which is essential to be practically useful. AlxFe2-xO3 (x-AFO) thin films, belonging to the k-Al2O3 family are interesting because they show room temperature ferrimagnetism and have a polar crystal structure. However, it is difficult to realise its ferroelectric properties at room temperature, due to low resistivity of the films. In this work, we have deposited x-AFO (0.5 <= x <= 1)…
Ferroelectric domain nucleation and growth in multiferroic BiFeO3 films is observed directly by applying a local electric field with a conductive tip inside a scanning transmission electron microscope. The nucleation and growth of a ferroelastic domain and its interaction with pre-existing 71^{\circ} domain walls are observed and compared with the results of phase-field modeling. In particular, a preferential nucleation site and direction-dependent pinning of domain walls is observed due to slow kinetics of metastable switching in the sample without a bottom electrode. These in-situ spatially-…
Sizeable b and c components of the 4f moments and pronounced circular dichroism are observed in the ferroelectric phase of DyMnO_3 by soft X-ray diffraction at the Dy-M_5 resonance. This points to cycloidal order of the 4f moments and indicates that inversion-symmetry breaking in this material is not characteristic of the Mn spins alone. The circular dichroism allows to image chiral domains that are imprinted on the surface of a DyMnO$_3$ single crystal, exploiting the local charging by the X-ray beam via the photoelectric effect. These findings suggest a novel approach to control and image do…
The recently proposed dynamical multiferroic effect describes the generation of magnetization from temporally varying electric polarization. Here, we show that the effect can lead to a magnetic field at moving ferroelectric domain walls, where the rearrangement of ions corresponds to a rotation of ferroelectric polarization in time. We develop an expression for the dynamical magnetic field, and calculate the relevant parameters for the example of 90$^\circ$ and 180$^\circ$ domain walls in BaTiO$_3$ using a combination of density functional theory and phenomenological modeling. We find that the…
We report the nanoscale electrical imaging results in hexagonal $Lu_{0.6}Sc_{0.4}FeO_3$ single crystals using conductive atomic force microscopy (C-AFM) and scanning microwave impedance microscopy (MIM). While the dc and ac response of the ferroelectric domains can be explained by the surface band bending, the drastic enhancement of domain wall (DW) ac conductivity is clearly dominated by the dielectric loss due to DW vibration rather than mobile-carrier conduction. Our work provides a unified physical picture to describe the local conductivity of ferroelectric domains and domain walls, which …
Experimental observations suggest that nominally uncharged, as-grown domain walls in ferroelectric thin films can be conductive, yet comprehensive theoretical models to explain this behavior are lacking. Here, Landau theory is used to evolve an analytical treatment of the anisotropic carrier accumulation by nominally uncharged domain walls in multiferroic BiFeO3. Strong angular dependence of the carrier accumulation by 180-degree domain walls originates from local band bending via angle-dependent electrostriction and flexoelectric coupling mechanisms. Theoretical results are in qualitative agr…
Power dissipation is one of the most important factors limiting the future miniaturisation of integrated circuits. The capability of controlling magnetic states with a low voltage through magnetoelectric coupling in magnetostrictive/piezoelectric systems may pave the way toward ultra low-power electronics. Although the former effect has been demon-strated in several multiferroic heterostructures, the incorporation of such complex geometries into practical magnetic memory and logic nanodevices has been lacking. Here, we demonstrate the room temperature control of a domain wall gate with an elec…
Magnetoelectric coupling in ferromagnet/multiferroic systems is often manifested in the exchange bias effect, which may have combined contributions from multiple sources, such as domain walls, chemical defects or strain. In this study we magnetically "fingerprint" the coupling behavior of CoFe grown on epitaxial BiFeO3 (BFO) thin films by magnetometry and first-order-reversal-curves (FORC). The contribution to exchange bias from 71°, 109° and charged ferroelectric domain walls (DWs) was elucidated by the FORC distribution. CoFe samples grown on BFO with 71° DWs only exhibit an enhancement of t…
We study the structure of domain walls in multiferroic magnets with the conical spiral ordering. We formulate a simple spin model which has a conical spiral ground state in absence of magnetic anisotropies. We find a transition from the regime where ferromagnetic and ferroelectric domain walls are clamped to the regime where they are decoupled and derive a continuum model describing rotation of the spiral plane at the domain wall. The importance of these results for the switching phenomena observed in CoCr2O4 is discussed.
Using Landau-Ginzburg-Devonshire approach, we predict the intrinsic instability of the ferroelectric-ferroelastic domain walls in the multiferroic BiFeO3 emerging from the interplay between the gradient terms of the antiferrodistortive and ferroelectric order parameters at the walls. These instabilities are the interface analogue of the structural instabilities in the vicinity of phase coexistence in the bulk; and so they do not steam from incomplete polarization screening in thin films or its spatial confinement, electrostrictive or flexoelectric coupling. The effect of BiFeO3 material parame…
The interplay between the surface and domain wall phenomena in multiferroic LaxBi1-xFeO3 in the vicinity of morphotropic phase transition is explored on the atomic level. Scanning Transmission Electron Microscopy (STEM) has enabled mapping of atomic structures of the material with picometer-level precision, providing direct insight into the spatial distribution of the order parameters in this material and their behavior at surfaces and interfaces. Here, we use the thermodynamic Landau-Ginzburg-Devonshire (LGD) approach to explain the emergence of spatially modulated phases (SMP) in La0.22Bi0.7…
We investigate polarization memory effects in single-crystal CuFeO2, which has a magnetically-induced ferroelectric phase at low temperatures and applied B fields between 7.5 and 13 T. Following electrical poling of the ferroelectric phase, we find that the nonpolar collinear antiferromagnetic ground state at B = 0 T retains a strong memory of the polarization magnitude and direction, such that upon re-entering the ferroelectric phase a net polarization of comparable magnitude to the initial polarization is recovered in the absence of external bias. This memory effect is very robust: in pulsed…
We present a microscopic first-principles study of the neutral structural domain walls (DWs) in the multiferroic hexagonal manganites, which have been shown to exhibit cross-couplings between ferroelectricity and struc- tural antiphase. We find that, in contradiction with previously proposed models, the interlocked antiphase- ferroelectric domain walls have approximately zero width, and their energy is lower than that of antiphase-only or ferroelectric-only domain walls. Furthermore, we show that the ferroelectric-only and antiphase-only DWs are superpositions of interlocked antiphase ferroele…
