Charged Domain Walls Research Articles

Ferroelectric Domain Modulation with Tip-Poling Engineering in BiFeO3 Films

BiFeO3 (BFO) films with ferroelectricity are the most promising candidates regarding the next generation of storage devices and sensors. The comprehensive understanding of ferroelectric switchable properties is challenging and critical to robust domain wall nanoelectronics. Herein, the domain dynamic was explored in detail under external bias conditions using scanning probe microscopy, which is meaningful for the understanding of domain dynamics and the foundation of ferroelectric devices. The results show that domain reversal occurred under external electric fields with sufficient energy excitation, combined with the existence of a charged domain wall. These findings extend the domain dynamic and current paths in ferroelectric films and shed light on the potential applications for ferroelectric devices.

ProtonationDriven Polarization Retention Failure in Nano-Columnar Lead-Free Ferroelectric Thin Films.

Understanding microscopic mechanisms of polarization retention characteristics in ferroelectric thin films is of great significance for exploring unusual physical phenomena inaccessible in the bulk counterparts and for realizing thin-film-based functional electronic devices. Perovskite (K,Na)NbO3 is an excellent class of lead-free ferroelectric oxides attracting tremendous interest thanks to its potential applications to nonvolatile memory and eco-friendly energy harvester/storage. Nonetheless, in-depth investigation of ferroelectric properties of (K,Na)NbO3 films and the following developments of nano-devices are limited due to challenging thin-film fabrication associated with nonstoichiometry by volatile K and Na atoms. Herein, ferroelectric (K,Na)NbO3 films of which the atomic-level geometrical structures strongly depend on thickness-dependent strain relaxation are epitaxially grown. Nanopillar crystal structures are identified in fully relaxed (K,Na)NbO3 films to the bulk states representing a continuous reduction of switchable polarization under air environments, that is, polarization retention failures. Protonation by water dissociation is responsible for the humidity-induced retention loss in nano-columnar (K,Na)NbO3 films. The protonation-driven polarization retention failure originates from domain wall pinning by the accumulation of mobile hydrogen ions at charged domain walls for effective screening of polarization-bound charges. Conceptually, the results will be utilized for rational design to advanced energy materials such as photo-catalysts enabling ferroelectric tuning of water splitting.

Rotating AdS3× S3 and dyonic strings from 3-dimensions

We make a general Killing spinor analysis of a particular D = 3, N = 4 gauged supergravity that comes from a consistent S3 reduction of D = 6, N = (1, 0) supergravity coupled to a single chiral tensor multiplet. We then focus on its supersymmetric solutions with a null Killing vector and find three new ones. Two of these, namely the null warped AdS3 (also known as the Schrödinger spacetime) and the charged domain wall solutions, admit non-trivial gauge fields which give rise to rotating solutions in 6-dimensions. The uplift of the first one produces an interesting AdS3 × S3 background with a non-trivial rotation in the U(1) fiber direction of the S3 which retains the Schrödinger scale invariance that the seed solution has. The second one leads to the well-known rotating dyonic string solution. Finally, the uplift of the third one, which is a domain wall solution with no gauge fields, results in a distribution of dyonic strings.

Magnetoelectric Phase Control at Domain‐Wall‐Like Epitaxial Oxide Multilayers

AbstractFerroelectric domain walls are nanoscale objects that can be created, positioned, and erased on demand. They often embody functional properties that are distinct from the surrounding bulk material. Enhanced conductivity, for instance, is observed at charged ferroelectric domain walls. Regrettably, domain walls of this type are scarce because of the energetically unfavorable electrostatics. This hinders the current technological development of domain‐wall nanoelectronics. Here this constraint is overcome by creating robust domain‐wall‐like objects in epitaxial oxide heterostructures. Charged head‐to‐head (HH) and tail‐to‐tail (TT) junctions are designed with two ferroelectric layers (BaTiO3 and BiFeO3) that have opposing out‐of‐plane polarization. To test domain‐wall‐like functionalities, an ultrathin ferromagnetic La0.7Sr0.3MnO3 layer is inserted into the junctions. The interfacial electron or hole accumulation at the interfaces, set by the HH and TT polarization configurations, respectively, controls the LSMO conductivity and magnetization. Thus it is proposed that trilayers reminiscent of artificial domain walls provide magnetoelectric functionality and may constitute an important building block in the design of oxide‐based electronic devices.

Intrinsically Stable Charged Domain Walls in Molecular Ferroelectric Thin Films

AbstractCharged domain walls in ferroelectrics hold great promise for applications in ferroelectric random‐access memory (FeRAM), with advantages such as low energy consumption, high density, and non‐destructive operation. Due to the mechanical compatibility condition, the neutral domain walls are dominant in traditional ferroelectric thin films. Herein, using phase‐field simulations, the formation of intrinsically stable charged domain walls (CDWs) in the molecular ferroelectric films is demonstrated, which can be mainly attributed to the small mechanical stiffness. The switching kinetics are further investigated for the CDWs, showing a lower switching barrier as compared to the neutral counterparts. Moreover, it is indicated that increasing the compressive misfit strain can lead to prolonged switching time, with a significantly increased switching energy barrier. These findings pave the way for the potential applications of metal‐free organic ferroelectric materials in FeRAM devices.

Atomic-Scale Scanning of Domain Network in the Ferroelectric HfO2 Thin Film.

Ferroelectric HfO2-based thin films have attracted much interest in the utilization of ferroelectricity at the nanoscale for next-generation electronic devices. However, the structural origin and stabilization mechanism of the ferroelectric phase are not understood because the film is typically nanocrystalline with active yet stochastic ferroelectric domains. Here, electron microscopy is used to map the in-plane domain network structures of epitaxially grown ferroelectric Y:HfO2 films in atomic resolution. The ferroelectricity is confirmed in free-standing Y:HfO2 films, allowing for investigating the structural origin for their ferroelectricity by 4D-STEM, high-resolution STEM, and iDPC-STEM. At the grain boundaries of <111>-oriented Pca21 orthorhombic grains, a high-symmetry mixed-(R3m, Pnm21) phase is induced, exhibiting enhanced polarization due to in-plane compressive strain. Nanoscale Pca21 orthorhombic grains and their grain boundaries with mixed-(R3m, Pnm21) phases of higher symmetry cooperatively determine the ferroelectricity of the Y:HfO2 film. It is also found that such ferroelectric domain networks emerge when the film thickness is beyond a finite value. Furthermore, in-plane mapping of oxygen positions overlaid on ferroelectric domains discloses that polarization is suppressed at vertical domain walls, while it is active when domains are aligned horizontally with subangstrom domain walls. In addition, randomly distributed 180° charged domain walls are confined by spacer layers.

Intrinsic Conductance of Ferroelectric Charged Domain Walls

Intrinsic Conductance of Ferroelectric Charged Domain Walls

Antipolar 2D Metallicity with Tunable Valence Wx+ (5 ≤ x ≤ 5.6) in the Layered Monophosphate Tungsten Bronzes [Ba(PO4)2]WmO3m-3.

The newly discovered series of layered monophosphate tungsten bronzes (L-MPTB) [Ba(PO4)2]WmO3m-3 consist of m-layer-thick slabs of WO6 octahedra separated by barium-phosphate spacers. They display a 2D metallic behavior confined in the central part of the perovskite slabs. Here, we report the missing m = 2 member of this series, containing the rather uncommon W5+ oxidation state. We have analyzed its structure-property relationships in relation to the other members of the L-MPTB family. In particular, we have determined its crystal structure by means of single-crystal X-ray and electron diffraction and investigated its physical properties from resistivity, Seebeck-coefficient and heat-capacity measurements combined with first-principles calculations. All the L-MPTB compounds show metallic behavior down to 1.8 K without any clear charge-density-wave (CDW) order. The m = 2 member, however, displays an increased influence of the spacer that translates into anisotropic negative thermal expansion, reversed thermopower and reversed crystal-field splitting of the tungsten t2g orbitals. Our analysis of the full [Ba(PO4)2]WmO3m-3 series reveals a systematic and significant W off-centering in their octahedral coordination. We identify the resulting anti-polar character of these W displacements as the crucial aspect behind the 2D metallicity of these systems: It leads to the presence of bound charges whose screening determines the distribution of mobile charges, tending to accumulate at the center of the [WmO3-m] block. We argue that this mechanism is analogous to enhanced conductivity observed for charged domain walls in ferroelectrics, thus providing a general design rule to promote 2D metallicity in layered systems.

Multi-step switchable superdomain architecture with enhanced photoelectrical performance in epitaxial ferroelectrics

Ferroic domains and relevant topological defects, such as domain walls and vortices, have gained significant attention as functional units for potential advancements in nanoelectronics. Pb(ZrxTi1-x)O3 (PZT) is a tetragonal ferroelectric material at room-temperature, exhibiting remarkable piezoelectricity and intricate domain structures. In this work, we explore the ferroelectric properties, photoelectric reactions, and efficient manipulation pathways of the unconventional superstructures in epitaxial (101)-oriented PZT thin films. Employing piezoresponse force microscopy (PFM) and conductive atomic force microscopy (cAFM), we unveil the three-dimensional polarization configurations of the superdomain structures inherently featuring conductive charged domain walls. Our findings reveal an increase in photoactivity at the head-side charged domain walls, attributed to the band-bending mechanism. Additionally, we discover the enhanced photoelectrochemical (PEC) performance in the superdomain structures compared to the (101)-oriented PZT films with conventional c/a domains. Furthermore, time-dependent pulse voltages are utilized to dynamically assess local currents and realize direct conductivity modulation by manipulating distinct polarization states. The elucidation of the photoelectrical mechanism and delineation of diverse pathways for intermediate state control underscore the potential of ferroelectric superdomains in constructing functional photoelectronic nanodevices.

Exploring the Reconfigurable Memory Effect in Electroforming-Free YMnO3-Based Resistive Switches: Towards a Tunable Frequency Response.

Memristors, since their inception, have demonstrated remarkable characteristics, notably the exceptional reconfigurability of their memory. This study delves into electroforming-free YMnO3 (YMO)-based resistive switches, emphasizing the reconfigurable memory effect in multiferroic YMO thin films with metallically conducting electrodes and their pivotal role in achieving adaptable frequency responses in impedance circuits consisting of reconfigurable YMO-based resistive switches and no reconfigurable passive elements, e.g., inductors and capacitors. The multiferroic YMO possesses a network of charged domain walls which can be reconfigured by a time-dependent voltage applied between the metallically conducting electrodes. Through experimental demonstrations, this study scrutinizes the impedance response not only for individual switch devices but also for impedance circuitry based on YMO resistive switches in both low- and high-resistance states, interfacing with capacitors and inductors in parallel and series configurations. Scrutinized Nyquist plots visually capture the intricate dynamics of impedance circuitry, revealing the potential of electroforming-free YMO resistive switches in finely tuning frequency responses within impedance circuits. This adaptability, rooted in the unique properties of YMO, signifies a paradigm shift heralding the advent of advanced and flexible electronic technologies.

Unit‐Cell‐Thickness Electron Confinement by Geometrically Constrained Antipolar Ordering

AbstractAchieving precise electron or spin confinement is essential for the progress of oxide electronics and emerging quantum information processing. While 2D electron confinement is commonly achieved with bare surfaces, heteroepitaxial interfaces, and charged domain walls, its practical application poses challenges, notably by diverse confinement widths, limited material selection, and the lack of freedom of positioning to a desired location within a given material system. Here, with scrutinizing a novel defect structure, the study suggests a new strategy with compelling evidence to trigger electron confinement down to single unit‐cell‐thickness, through geometrically constrained antipolar ordering facilitated by superlattice‐like periodic planar faults in metallic SrFeO3. Employing atomic resolution electron microscopy and density functional theory, the results demonstrate that electrons are confined two‐dimensionally to screen the positive bound charges on head‐to‐head antipolar state boundary, meanwhile oxygen vacancies segregated in the planar faults compensate the negative bound charges on the tail‐to‐tail one, leading to the stabilization of the antipolar ordering. Additionally, distinguished from traditional methods, this approach offers a potential programing capability for achieving precise charge and spin control by regulating planar fault structure at atomic scale.

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.

Interface engineering for facile switching of bulk-strong polarization in Si-compatible vertical superlattices

Ferroelectric thin films incorporating different compositional layers have emerged as a promising approach for enhancing properties and performance of electronic devices. In recent years, superlattices utilizing various interactions between their constituent layers have been used to reveal unusual properties, such as improper ferroelectricity, charged domain walls, and negative capacitance in conventional ferroelectrics. Herein, we report a symmetry scheme based on the interface engineering in which the inherent cell-doubling symmetry allowed atomic distortions (phonons) in any vertically aligned superlattice activate novel interface couplings among atomic distortions of different symmetries and fundamentally improve the ferroelectric properties. In a materialized case, the ionic size difference between Hf4+ and Ce4+ in the HfO2/CeO2 (HCO) ferroelectric/paraelectric superlattice leads to these couplings. These couplings mitigate the phase boundary between polar and non-polar phases, and facilitate polarization switching with a remarkably low coercive field (Ec\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${E}_{c}$$\\end{document}) while preserving the original magnitude of the bulk HfO2 polarization and its scale-free ferroelectric characteristics. We show that the cell-doubled distortions present in any vertical superlattice have unique implications for designing low-voltage ferroelectric switching while retaining bulk-strong charge storing capacities in Si-compatible memory candidates.

Phase-field theory study on the modulation mechanism of oxygen vacancy concentration on charged domain wall in ferroelectric thin films

This study analyzes the regulatory mechanism of oxygen vacancy concentration on tail-to-tail charged domain walls (T–T CDWs), along with the writing time, conduction current magnitude, and retention performance of through-type T–T CDWs. The research results show that the highest density and length of T–T CDWs are achieved when the oxygen vacancy concentration is 1 × 1020 cm−3. Moreover, the successful writing of through-type T–T CDWs is limited to a certain electric field range, which is controlled by oxygen vacancy concentration. An increase in the oxygen vacancy concentration leads to a decrease in the maximum and minimum threshold electric fields required for writing through-type charged domain walls. The writing time and conductivity of through-type T–T CDWs determine the information writing speed and signal strength of domain wall memories, and the oxygen vacancy concentration also plays a regulatory role in both aspects. When the oxygen vacancy concentration is 1 × 1020 cm−3, the through-type T–T CDW exhibits the fastest writing speed, requiring only 8 ns. The magnitude of the conduction current of through-type T–T CDWs is directly proportional to the oxygen vacancy concentration. The through-type T–T CDWs formed by the aggregation of oxygen vacancies exhibit excellent retention performance, making them highly promising for applications in ferroelectric domain wall memories. Our research demonstrates that oxygen vacancies have a significant regulatory effect on the morphology and current response of charged domain walls, opening up new avenues for the study of domain wall memories.

Reversible charge injection in artificially created charged domain wall region

The impact of electric field application in the charged domain wall (DW) region on the performance of DW devices remains elusive. Here, we present our observations of substantial charge injection occurring in an artificially created charged DW region. Rapid charge injection coincides with polarization switching, contributing to the transient current collected for the integration of polarization-voltage hysteresis loops. Subsequently, a gradual injection of charges persists under externally applied voltages, diffusing into the thin film from the DW region to screen the space defect dipoles and effectively suppressing the imprint field. The process of charge injection proves reversible and is notably more pronounced in aged ferroelectric thin films, as evidenced in planar BiFeO3 nanodevices where the charge injection amount is five orders of magnitude higher than charges generated from polarization switching. This work constitutes a significant contribution to understanding the intricate process of charge injection and its influence on charged DW.

Influence of oxygen vacancies on the domain wall stability in BiFeO3

AbstractOxygen vacancy is the most common type of point defects in functional oxides, and it is known to have profound influence on their properties. This is particularly true for ferroelectric oxides since their interaction with ferroelectric polarization often dictates the ferroelectric responses. Here, we study the influence of the concentration of oxygen vacancies on the stability of ferroelectric domain walls (DWs) in BiFeO3, a material with a relatively narrow bandgap among all perovskite oxides, which enables strong interactions among electronic charge carriers, oxygen vacancies, and ferroelectric domains. It is found that the electronic charge carriers in the absence of oxygen vacancies have essentially no influence on the spatial polarization distribution of the DWs due to their low concentrations. Upon increasing the concentration of oxygen vacancies, charge‐neutral DWs with an originally symmetric polarization distribution symmetric around the center of the wall can develop a strong asymmetry of the polarization field, which is mediated by the electrostatic interaction between polarization and electrons from the ionization of oxygen vacancies. Strongly charged head‐to‐head DWs that are unstable without oxygen vacancies can be energetically stabilized in the off‐stoichiometric BiFeO3−δ with δ ∼ 0.02 where ionization of oxygen vacancies provides sufficient free electrons to compensate the bound charge at the wall. Our results delineate the electrostatic coupling of the ionic defects and the associated free electronic charge carriers with the bound charge in the vicinity of neutral and charged DWs in perovskite ferroelectrics.

In-bulk polarization reversal in lithium tantalate with single charged domain wall

This paper presents the results of the first experimental observation of polarization reversal in the bulk of ferroelectric with a charged domain wall (CDW) under the action of an electric field on the example of a single crystal LiTaO3 plate. A CDW was obtained in the sample bulk at the locus of points with a sign change of the composition gradient which results from sample annealing in lithium rich atmosphere. Imaging of the domain structure in the bulk and its evolution on the surface made it possible to detect anomalous domain kinetics, which represents the growth of ledges on the CDW toward the polar surface. The main stages of the domain structure evolution on the polar surface, including the growth of isolated domains, as well as the formation and decay of the maze domain structure, were revealed. An analysis is made for the time dependence of the area fraction occupied by growing domains. We used a kinetic approach based on the analogy between the growth of domains and crystals to explain the obtained results.

Theory of cuprate pseudogap as antiferromagnetic order with charged domain walls

Theory of cuprate pseudogap as antiferromagnetic order with charged domain walls

Oxygen vacancies stabilized 180° charged domain walls in ferroelectric hafnium oxide

Ferroelectric domain walls (DWs) are spatial interfaces separating domains with distinct polarization orientations. Among these DWs, some can carry bound charges and display metallic-like conductivity. The feature is highly of interest for future nanoelectronics. However, the inherent instability of charged domain walls (CDWs) has posed a critical challenge for their experimental exploration. This Letter reports the head-to-head (HH) and tail-to-tail (TT) 180° CDWs within the context of ferroelectric hafnium oxide. We proposed that oxygen vacancy is a crucial factor stabilizing the periodic CDWs. Through meticulous first-principles calculations, we elaborated on the intricate properties of these CDWs, including their polarization profiles, and potential and charge distributions. Furthermore, we calculated the energy barrier for layer-by-layer propagation of a HH wall and carefully discussed the migration of a TT wall with oxygen vacancy. Our study can shed more light onto the characteristics of CDWs and their implications to hafnia-based ferroelectric devices.