Charged Domain Walls In Ferroelectrics Research Articles

Concomitant Light-Reversible Magnetic Response in Multiferroic Oxide Heterostructures for Multiphysics Applications.

The concept of multiphysics, where materials respond to diverse external stimuli, such as magnetic fields, electric fields, light irradiation, stress, heat, and chemical reactions, plays a fundamental role in the development of innovative devices. Nanomanufacturing, especially in low-dimensional systems, enhances the synergistic interactions taking place on the nanoscale. Light-matter interaction, rather than electric fields, holds great promise for achieving low-power, wireless control over magnetism, solving two major technological problems: the feasibility of electrical contacts at smaller scales and the undesired heating of the devices. Here, we shed light on the remarkable reversible modulation of magnetism using visible light in epitaxial Fe3O4/BaTiO3 heterostructure. This achievement is underpinned by the convergence of two distinct mechanisms. First, the magnetoelastic effect, triggered by ferroelectric domain switching, induces a proportional change in coercivity and remanence upon laser illumination. Second, light-matter interaction induces charged ferroelectric domain walls' electrostatic decompensations, acting intimately on the magnetization of the epitaxial Fe3O4 film by magnetoelectric coupling. Crucially, our experimental results vividly illustrate the capability to manipulate magnetic properties using visible light. This concomitant mechanism provides a promising avenue for low-intensity visible-light manipulation of magnetism, offering potential applications in multiferroic devices.

Curvature conservation and conduction modulation for symmetric charged ferroelectric domain walls

Curvature conservation is a common feature for the physical properties with topological constraints, from the macroscopic cosmic string loops to the microscopic quantized vortex rings in the superfluid. Interestingly, ferroelectric domain-wall curvature is important to determine its conduction, which is the key parameter for designing domain-wall nanoelectronic devices. Here, we demonstrate the curvature conservation of the charged domain walls confined in ferroelectric topological structures with specific domain symmetry by combining piezoelectric force microscopy, conducting atomic force microscopy, and phase-field simulations. Significantly, the intrinsic conductivity of the charged domain walls exhibits an inverse functional relationship with the local domain-wall curvature in the ferroelectric BiFeO3 nano-islands, which can also be precisely and continuously modulated by applying an electric field. This work provides us with an insightful understanding of the conduction mechanism of charged domain walls confined in ferroelectric topological structures with a high degree of spatial symmetry, which paves the way for the application of charged domain walls as flexible conducting channels with continuously changing resistance states to be used for ferroelectric domain-wall memristors.

Electrophysical properties, memristive and resistive switching of charged domain walls in lithium niobate

Charged domain walls (CDWs) in ferroelectric materials raise both fundamental and practical interest due to their electrophysical properties differing from bulk ones. On a microstructure level, CDWs in ferroelectrics are 2D defects separating regions with different spontaneous polarization vector directions. Screening of electric field of the CDW's bound ionic charges by mobile carriers leads to the formation of elongated narrow channels with an elevated conductivity in initially dielectric materials. Controlling the position and inclination angle of CDW relative to the spontaneous polarization direction, one can change its conductivity over a wide range thus providing good opportunities for developing memory devices, including neuromorphic systems. This review describes the state of art in the formation and application of CDWs in single crystal uniaxial ferroelectric lithium niobate (LiNbO3, LN), as resistive and memristive switching devices. The main CDWs formation methods in single crystal and thin-film LN have been described, and modern data have been presented on the electrophysical properties and electrical conductivity control methods of CDWs. Prospects of CDWs application in resistive and memristive switching memory devices have been discussed.

Electrophysical properties, memristive and resistive switching in charged domain walls in lithium niobate

Charged domain walls (CDW) in ferroelectric materials are interesting from fundamental and applied points of view, since they have electrical properties different from bulk ones. At the microstructural level, CDW in ferroelectrics are two-dimensional defects that separate regions of the material with different directions of spontaneous polarization vectors. Compensation of the electric field of the bound ionic charge of the CDW by mobile carriers leads to the formation of extended narrow channels with increased conductivity in the original dielectric material. By controlling the position and angle of inclination of the CDW relative to the direction of spontaneous polarization, it is possible to change its conductivity in a wide range, which opens up broad prospects for creating memory devices, including for neuromorphic systems. The review presents the current state of research in the field of formation and application of CDW formed in single crystals of uniaxial ferroelectric lithium niobate (LiNbO3, LN) as resistive and memristive switching devices. The main methods for forming CDW in single crystals and thin films of LN are considered, and modern data on the electrophysical properties and methods for controlling the electrical conductivity of CDW are presented. The prospects for using CDW in memory devices with resistive and memristive switching are discussed.

Electromechanics of Domain Walls in Uniaxial Ferroelectrics

AbstractPiezoresponse force microscopy (PFM) is used for investigation of the electromechanical behavior of the head‐to‐head (H‐H) and tail‐to‐tail (T‐T) domain walls on the non‐polar surfaces of three uniaxial ferroelectric materials with different crystal structures: LiNbO3, Pb5Ge3O11, and ErMnO3. It is shown that, contrary to the common expectation that the domain walls should not exhibit any PFM response on the non‐polar surface, an out‐of‐plane deformation of the crystal at the H‐H and T‐T domain walls occurs even in the absence of the out‐of‐plane polarization component due to a specific form of the piezoelectric tensor. In spite of their different symmetry, in all studied materials, the dominant contribution comes from the counteracting shear strains on both sides of the H‐H and T‐T domain walls. The finite element analysis approach that takes into account a contribution of all elements in the piezoelectric tensor, is applicable to any ferroelectric material and can be instrumental for getting a new insight into the coupling between the electromechanical and electronic properties of the charged ferroelectric domain walls.

Charged Ferroelectric Domain Walls for Deterministic ac Signal Control at the Nanoscale.

The direct current (dc) conductivity and emergent functionalities at ferroelectric domain walls are closely linked to the local polarization charges. Depending on the charge state, the walls can exhibit unusual dc conduction ranging from insulating to metallic-like, which is leveraged in domain-wall-based memory, multilevel data storage, and synaptic devices. In contrast to the functional dc behaviors at charged walls, their response to alternating currents (ac) remains to be resolved. Here, we reveal ac characteristics at positively and negatively charged walls in ErMnO3, distinctly different from the response of the surrounding domains. By combining voltage-dependent spectroscopic measurements on macroscopic and local scales, we demonstrate a pronounced nonlinear response at the electrode-wall junction, which correlates with the domain-wall charge state. The dependence on the ac drive voltage enables reversible switching between uni- and bipolar output signals, providing conceptually new opportunities for the application of charged walls as functional nanoelements in ac circuitry.

Oxygen Vacancies Nucleate Charged Domain Walls in Ferroelectrics.

We study the influence of oxygen vacancies on the formation of charged 180° domain walls in ferroelectric BaTiO_{3} using first principles calculations. We show that it is favorable for vacancies to assemble in crystallographic planes, and that such clustering is accompanied by the formation of a charged domain wall. The domain wall has negative bound charge, which compensates the nominal positive charge of the vacancies and leads to a vanishing density of free charge at the wall. This is in contrast to the positively charged domain walls, which are nearly completely compensated by free charge from the bulk. The results thus explain the experimentally observed difference in electronic conductivity of the two types of domain walls, as well as the generic prevalence of charged domain walls in ferroelectrics. Moreover, the explicit demonstration of vacancy driven domain wall formation implies that specific charged domain wall configurations may be realized by bottom-up design for use in domain wall based information processing.

Vortex Domain Walls in Ferroelectrics.

Controlling the domain formation in ferroelectric materials at the nanoscale is a fertile ground to explore emergent phenomena and their technological prospects. For example, charged ferroelectric domain walls in BiFeO3 and ErMnO3 exhibit significantly enhanced conductivity which could serve as the foundation for next-generation circuits (Estévez and Laurson, Phys. Rev. B 2015, 91, 054407). Here, we describe a concept in which polar vortices perform the same role as a ferroelectric domain wall in classical domain structures with the key difference being that the polar vortices can accommodate charged (i.e., head-to-head and tail-to-tail) domains, for example, in ferroelectric PbTiO3/dielectric SrTiO3 superlattices. Such a vortex domain wall structure can be manipulated in a reversible fashion under an external applied field.

Engineering of multiferroic BiFeO3 grain boundaries with head-to-head polarization configurations

Confined low dimensional charges with high density such as two-dimensional electron gas (2DEG) at interfaces and charged domain walls in ferroelectrics show great potential to serve as functional elements in future nanoelectronics. However, stabilization and control of low dimensional charges is challenging, as they are usually subject to enormous depolarization fields. Here, we demonstrate a method to fabricate tunable charged interfaces with ~77°, 86° and 94° head-to-head polarization configurations in multiferroic BiFeO3 thin films by grain boundary engineering. The adjacent grains are cohesively bonded and the boundary is about 1 nm in width and devoid of any amorphous region. Remarkably, the polarization remains almost unchanged near the grain boundaries, indicating the polarization charges are well compensated, i.e., there should be two-dimensional charge gas confined at grain boundaries. Adjusting the tilt angle of the grain boundaries enables tuning the angle of polarization configurations from 71° to 109°, which in turn allows the control of charge density at the grain boundaries. This general and feasible method opens new doors for the application of charged interfaces in next generation nanoelectronics.

Giant thermoelectric power factor in charged ferroelectric domain walls of GeTe with Van Hove singularities

Increasing the Seebeck coefficient S in thermoelectric materials usually drastically decreases the electrical conductivity σ, making significant enhancement of the thermoelectric power factor σS2 extremelly challenging. Here we predict, using first-principles calculations, that the extraordinary properties of charged ferroelectric domain walls (DWs) in GeTe enable a five-fold increase of σS2 in the DW plane compared to bulk. The key reasons for this enhancement are the confinement of free charge carriers at the DWs and Van Hove singularities in the DW electronic band structure near the Fermi level. These effects lead to an increased energy dependence of the DW electronic transport properties, resulting in more than a two-fold increase of S with respect to bulk, without considerably degrading the in-plane σ. We propose a design of a nano-thermoelectric device that utilizes the exceptional thermoelectric properties of charged ferroelectric DWs. Our findings should inspire further investigation of ferroelectric DWs as efficient thermoelectric materials.

Application of a long short-term memory for deconvoluting conductance contributions at charged ferroelectric domain walls

Ferroelectric domain walls are promising quasi-2D structures that can be leveraged for miniaturization of electronics components and new mechanisms to control electronic signals at the nanoscale. Despite the significant progress in experiment and theory, however, most investigations on ferroelectric domain walls are still on a fundamental level, and reliable characterization of emergent transport phenomena remains a challenging task. Here, we apply a neural-network-based approach to regularize local I(V)-spectroscopy measurements and improve the information extraction, using data recorded at charged domain walls in hexagonal (Er0.99,Zr0.01)MnO3 as an instructive example. Using a sparse long short-term memory autoencoder, we disentangle competing conductivity signals both spatially and as a function of voltage, facilitating a less biased, unconstrained and more accurate analysis compared to a standard evaluation of conductance maps. The neural-network-based analysis allows us to isolate extrinsic signals that relate to the tip-sample contact and separating them from the intrinsic transport behavior associated with the ferroelectric domain walls in (Er0.99,Zr0.01)MnO3. Our work expands machine-learning-assisted scanning probe microscopy studies into the realm of local conductance measurements, improving the extraction of physical conduction mechanisms and separation of interfering current signals.

Probing the Dynamics of Topologically Protected Charged Ferroelectric Domain Walls with the Electron Beam at the Atomic Scale

Probing the Dynamics of Topologically Protected Charged Ferroelectric Domain Walls with the Electron Beam at the Atomic Scale

Tailoring properties of hybrid perovskites by domain-width engineering with charged walls

Charged ferroelectric domain walls are fascinating electrical topological defects that can exhibit unusual properties. Here, in the search for novel phenomena, we perform and analyze first-principles calculations to investigate the effect of domain width on properties of domains with charged walls in the photovoltaic material consisting of methylammonium lead iodide hybrid perovskite. We report that such domains are stable and have rather low domain wall energy for any investigated width (that is, up to 13 lattice constants). Increasing the domain width first linearly decreases the electronic band gap from ≃1.4 eV to about zero (which therefore provides an efficient band-gap engineering), before the system undergoes an insulator-to-metal transition and then remains metallic (with both the tail-to-tail and head-to-head domain walls being conductive) for the largest widths. All these results can be understood in terms of: (i) components of polarization along the normal of the domain walls being small in magnitude; (ii) an internal electric field that is basically independent of the domain width; and (iii) rather negligible charge transfer between walls. These findings deepen the knowledge of charged ferroelectric domain walls and can further broaden their potential for applications, particularly in the context of halide perovskites for photovoltaics.

Controllable conductive readout in self-assembled, topologically confined ferroelectric domain walls.

Charged domain walls in ferroelectrics exhibit a quasi-two-dimensional conduction path coupled to the surrounding polarization. They have been proposed for use as non-volatile memory with non-destructive operation and ultralow energy consumption. Yet the evolution of domain walls during polarization switching makes it challenging to control their location and conductance precisely, a prerequisite for controlled read-write schemes and for integration in scalable memory devices. Here, we explore and reversibly switch the polarization of square BiFeO3 nanoislands in a self-assembled array. Each island confines cross-shaped, charged domain walls in a centre-type domain. Electrostatic and geometric boundary conditions induce two stable domain configurations: centre-convergent and centre-divergent. We switch the polarization deterministically back and forth between these two states, which alters the domain wall conductance by three orders of magnitude, while the position of the domain wall remains static because of its confinement within the BiFeO3 islands.

Interactions of charged domain walls and oxygen vacancies in BaTiO3: a first-principles study

Ferroelectric domain walls have been promised for some potential applications due to their unique properties. In particular, the electrical conductivity of charged domain walls (DWs) allows a new dimension to ferroelectric functionalities. In this work, we construct two representative types of charged DWs, i.e. head-to-head (HH) wall and tail-to-tail (TT) wall, and employ the first-principles method to study the electronic structure of these charged walls in BaTiO3 and the interactions between them and oxygen vacancies. It is revealed that the HH walls show the n-type conductivity, but the TT walls show the p-type conductivity. While embedded oxygen vacancies attract the TT wall and repel the HH wall, the interaction between the walls and oxygen vacancies depends on the vacancy occupation. This interaction enhances the conductivity of HH walls and reduces the conductivity of TT walls, and in particular a TT wall in binding with oxygen vacancies will drive the transition of p-type wall conductivity into n-type wall conductivity. The interaction of these walls with oxygen vacancies is discussed using the electrostatic model. This work represents a comprehensive understanding of electrical transport of charged DWs in ferroelectrics and possible roadmaps for manipulation.

Ion and mixed electron-ion screening of charged domain walls in ferroelectrics

We consider theoretically the properties of charged domain walls (CDWs) in proper ferroelectrics for the ion and mixed electron-ion charge screening mechanisms. This includes an analysis of the spatial profiles of the polarization and electrostatic potential in the one-dimensional case, determination of the characteristic spatial widths, estimates of the CDW formation energies, and comparison with the CDW characteristics relevant to the electron-hole screening regime. Also we consider restrictions on the ion-related screening scenarios caused by slowness of the ion migration at ambient conditions.

As-grown domain structure in lithium tantalate with spatially nonuniform composition

ABSTRACTWe investigated the as-grown domain structure in LiTaO3 with different nonuniform spatial distributions of deviation from stoichiometry. The as-grown structure formed due to cooling below Curie temperature after vapor transport equilibration (VTE) process. The formation of wide charged domain boundary consisting of smooth head-to-head and zig-zag tail-to-tail charged domain walls and flat neutral domain walls was observed. The mechanisms of domain structure formation due to phase transition and subsequent cooling were explained. The different type of charged domain walls in ferroelectrics attracts interest due to possibilities of its applications.

Polarization driven conductance variations at charged ferroelectric domain walls.

Conducting domain walls (CDWs) in ferroelectric materials are promising candidates for applications in a manifold of nanoscale, optoelectronic devices. Characterization of their microscopic properties, however, remains challenging due to their small dimension and highly insulating environment. Here, we inspect individual CDWs in single-crystalline LiNbO3 by the combination of photoemission electron microscopy (PEEM) and second harmonic generation (SHG) microscopy. While SHG unveils the overall domain wall inclination angle α, PEEM is sensitive to local conductance variations, both at and away from the domain wall. Thus, the two imaging techniques deliver complementary information over a large field of view. In agreement with earlier theoretical predictions we find that the local conductance is dictated by α and reveal a quantitative connection between them. Our results help to elucidate the electronic structure of CDWs and underline the value of PEEM as a non-contact characterization tool for mapping local conductance variations in highly resistive environments.

Free‐Carrier‐Compensated Charged Domain Walls Produced with Super‐Bandgap Illumination in Insulating Ferroelectrics

Charged domain walls in ferroelectrics are movable and electronically conducting interfaces inside insulating materials. A simple and reliable method for their artificial production with ultraviolet (UV) light is described. The UV illumination produces free carriers in ferroelectric bulk, which simultaneously promotes the formation of charged domain walls and provides charge for their compensation.

Magnetic fingerprint of interfacial coupling between CoFe and nanoscale ferroelectric domain walls

Magnetoelectric coupling in ferromagnetic/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 the 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 the coercivity, but little exchange bias. Samples grown on BFO with 109° DWs and mosaic DWs exhibit a much larger exchange bias, with the main enhancement attributed to 109° and charged DWs. Based on the Malozemoff random field model, a varying-anisotropy model is proposed to account for the exchange bias enhancement. This work sheds light on the relationship between the exchange bias effect of the CoFe/BFO heterointerface and the ferroelectric DWs, and provides a path for multiferroic device analysis and design.