Ferroic Materials Research Articles

Composite quadrupole order in ferroic and multiferroic materials

The formalism of composite and intertwined orders has been remarkably successful in discussing the complex phase diagrams of strongly correlated materials and high-$T_c$ superconductors. Here, we propose that composite orders are also realized in ferroelectric and ferromagnetic materials when lattice anisotropy is taken into account. This composite order emerges above the ferroic phase transition, and its type is determined by the easy axis of magnetization or polarization, respectively. In multiferroic materials, where polarization and magnetization are coupled, composites of both orders are possible. This formalism of composite orders naturally accounts for magnetoelectric monopole, toroidal, and quadrupole orders. More broadly, composite orders may explain precursor phenomena in incipient (multi)ferroic materials, arising at temperatures above the ferroic phase transition and potentially contributing to the characterization of currently hidden orders.

Individual domain characteristics determined by second-harmonic generation diffractometer for multi-domain multiferroics

We investigated the multi-domain states of a multiferroic La-doped BiFeO3 (BLFO) thin film by examining diffraction patterns in optical second-harmonic generation (SHG) measurement. By directing a laser onto the domain wall within the domain-patterned sample, we observed clear diffraction signatures of SHG waves generated from two ferroelectric domains. We explained the experimental results of the diffraction patterns, including the intensity distribution and the polarization characteristics, using Fresnel propagation of SHG waves. From this, we could determine the amplitude and phase of the SHG waves generated from each domain, and figure out not only the polarization direction of each ferroelectric domain but also the phase related to the complex-valued second-order susceptibility tensor. Consequently, we could present SHG diffractometry as an effective measurement method to reveal the phase details of electric polarization of the multi-domain states of ferroic materials.

Progress and challenges in the synthesis of two-dimensional Van der Waals ferroic materials and heterostructures

Abstract Two-dimensional ferroelectric and magnetic van der Waals materials are emergent platforms for the discovery of novel cooperative quantum phenomena and development of energy-efficient logic and memory applications as well as neuromorphic and topological computing. This review presents a comprehensive survey of the rapidly growing 2D ferroic family from the synthesis perspective, including brief introductions to the top-down and bottom-up approaches for fabricating 2D ferroic flakes, thin films, and heterostructures as well as the important characterization techniques for assessing the sample properties. We also discuss the key challenges and future directions of the field, including scalable growth, property control, sample stability, and integration with other functional materials.

On-demand nanoengineering of in-plane ferroelectric topologies.

Hierarchical assemblies of ferroelectric nanodomains, so-called super-domains, can exhibit exotic morphologies that lead to distinct behaviours. Controlling these super-domains reliably is critical for realizing states with desired functional properties. Here we reveal the super-switching mechanism by using a biased atomic force microscopy tip, that is, the switching of the in-plane super-domains, of a model ferroelectric Pb0.6Sr0.4TiO3. We demonstrate that the writing process is dominated by a super-domain nucleation and stabilization process. A complex scanning-probe trajectory enables on-demand formation of intricate centre-divergent, centre-convergent and flux-closure polar structures. Correlative piezoresponse force microscopy and optical spectroscopy confirm the topological nature and tunability of the emergent structures. The precise and versatile nanolithography in a ferroic material and the stability of the generated structures, also validated by phase-field modelling, suggests potential for reliable multi-state nanodevice architectures and, thereby, an alternative route for the creation of tunable topological structures for applications in neuromorphic circuits.

(Invited) Functional Complex Oxides for Next-Generation Logic, Memory, Sensing, and Beyond

Complex-oxide materials possess a range of interesting properties and phenomena that make them candidates for next-generation devices and applications. But before these materials can be integrated into state-of-the-art devices, it is important to understand how to control and engineer their response in a deterministic manner. In this talk, we will discuss some of the state-of-the-art science, engineering, and utilization of complex ferroic materials and their potential for emergent order and phenomena that can enable new device function. We will explore the role of the epitaxial thin-film growth process and the use of epitaxial constraints to engineer a range of systems with special attention to ferroelectric (i.e., materials with robust spontaneous polarization that can be switched with an electric field thereby producing a ferroelectric hysteresis loop), antiferroelectric (i.e., materials which have an antiparallel alignment of polarization (or are non-polar) in the ground state but can be switched to a polar (parallel) order by an external electric field producing a reversible antiferroelectric-to-ferroelectric phase transition and a characteristic double polarization-electric-field hysteresis loop), and relaxor (i.e., chemically complex materials that exhibit a competition between short- and long-range interactions such that it produces a complex, dynamic polarization structure and exotic properties) materials.In recent years, the use of epitaxial constraints has enabled the production of model versions of these complicated materials and the subsequent deterministic study of an array of physical phenomena that are now being widely considered for next-generation applications. Specifically, we will investigate the potential of ferroelectric materials for non-volatile, ultra-low voltage memory and logic applications including their use in ferroelectric-field-effect transistors, the realization of multi-state/neuromorphic function, and more. In turn, we will explore how antiferroelectric and relaxor thin-film materials can open the door to a new generation of thin-film based electromechanical, sensing, high-frequency, and capacitive-energy-storage devices. Along the way we will leverage advanced thin-film growth techniques to control the materials and to solicit new insights about their function, apply state-of-the-art characterization methods, including unique in operando studies under applied stimuli, to understand how materials function, and explore how such materials can be integrated and utilized in realistic device structures. We will try to introduce the listener to these complex materials and their potential for new applications – in effect working to motivate engineers to explore these materials. The discussion will range from the development of fundamental understanding of the physics that lies at the heart of the observed effects, to an illustration of routes to manipulate and control these effects, to the demonstration of rudimentary solid-state devices based on these materials.

Hybrid magnon-phonon localization enhances function near ferroic glassy states.

Ferroic materials on the verge of forming ferroic glasses exhibit heightened functionality that is often attributed to competing long- and short-range correlations. However, the physics underlying these enhancements is not well understood. The Ni45Co5Mn36.6In13.4 Heusler alloy is on the edge of forming both spin and strain glasses and exhibits magnetic field-induced shape memory and large magnetocaloric effects, making it a candidate for multicaloric cooling applications. We show using neutron scattering that localized magnon-phonon hybrid modes, which are inherently spread across reciprocal space, act as a bridge between phonons and magnons and result in substantial magnetic field-induced shifts in the phonons, triple the caloric response, and alter phase stability. We attribute these modes to the localization of phonons and magnons by antiphase boundaries coupled to magnetic domains. Because the interplay between short- and long-range correlations is common near ferroic glassy states, our work provides general insights on how glassiness enhances function.

Realization of 2D multiferroic with strong magnetoelectric coupling by intercalation: a first-principles high-throughput prediction

The discovery of novel two-dimensional (2D) multiferroic materials is attractive due to their potential for the realization of information storage and logic devices. Although many approaches have been explored to simultaneously introduce ferromagnetic (FM) and ferroelectric (FE) orders into a 2D material, the resulting systems are often plagued by weak magnetoelectric (ME) coupling or limited room-temperature stability. Here, we present a superlattice strategy to construct non-centrosymmetric AM2X4 multiferroic monolayers, i.e., intercalating transition metal ions (A) into the tetragonal-like vacancies of transition metal dichalcogenide bilayers (MX2). Starting from 960 intercalated AM2X4 compounds, our high-throughput calculations have identified 21 multiferroics with robust magnetic order, large FE polarization, low transition barrier, high FE/FM transition temperature, and strong ME coupling. According to the origin of magnetism, we have classified them into twelve type-a, seven type-b, and two type-c multiferroics, which exhibit different ME coupling behavior. During the switching of polarization, the reversal of skyrmions chirality, the transition of the magnetic ground state from FM to antiferromagnetic, and the changes in spin-polarized electron distribution were observed in type-a, type-b, and type-c 2D multiferroic materials, respectively. These results substantially expand the family of 2D ferroic materials and pave an avenue for designing and implementing nonvolatile logic and memory devices.

An Emergent Quadruple Phase Ensemble in Doped Bismuth Ferrite Thin Films Through Site and Strain Engineering

AbstractIn ferroic materials, giant susceptibilities can be realized at artificially constructed phase boundaries through deterministic manipulation of the order parameter. Here, emergent ferroelectric structural phase evolution behavior is demonstrated through a synergistic combination of A‐site doping and strain engineering. Using chemical solution deposition derived (001)‐oriented Sm‐substituted bismuth ferrite (Bi1‐xSmxFeO3) films as a prototypical system, a morphotropic phase boundary comprising a coexistence of four distinct crystallographic phases is uncovered. These ferroelectric, polar, and nonpolar phases form a nanoscale mixture without the presence of crystallographically hard boundaries. The system thus possesses the ability to show both polarization rotation and extension, effectively releasing the polarization from its crystallographic constraint. Consequently, both robust ferroelectric properties and giant electromechanical responses are obtained. For instance, the optimized composition with x = 0.14 has a remnant polarization of 2Pr = 103 µC cm−2 and electromechanical response 175% that of undoped BFO. These findings showcase the tremendous potential of synthetic phase boundaries, particularly in the context of lead‐free functional multiferroics.

Electronic Properties of W’ Twin Walls in Ferroelastic BiVO4

AbstractTopological defects in ferroic materials can exhibit intrinsic properties that differ from the bulk. Here， structural and electronic variations of non‐prominent (W’) ferroelastic twin domain walls are investigated in BiVO4, a widely investigated photocatalytic material. Using aberration‐corrected scanning transmission electron microscopy (STEM), a kink configuration of the sharp ferroelastic twin wall with an altered electronic structure is revealed. Nanoscale conductivity measurements by conductive atomic force microscopy (c‐AFM) show higher conductivity at twin walls compared to non‐conductive bulk domains. Electronic structure investigation by electron energy loss spectroscopy (EELS) shows a higher density of oxygen vacancies and possible polaron accumulation at the wall. These findings reveal the electronic properties of BiVO4 domain walls, which are interesting for nanoscale‐engineered catalytic concepts of BiVO4 and materials design for photochemistry‐relevant applications.

Domains with Varying Conductance in Tensile Strained SrMnO3 Thin Films Using Out‐of‐Plane Electric Fields

AbstractDomains and domain wall engineering have been extensively explored in ferroic materials for a wide range of applications in nanoelectronics and spintronics. Complex oxides exhibiting strongly correlated properties are model platforms for such studies where response to strain or external stimuli such as electric field, temperature and light can be probed. Here, domains in strained SrMnO3 films, grown on a degenerate semiconductor, allowing for conduction in an out‐of‐plane geometry, are studied using a combination of microscopy probes. Using conductive atomic force microscopy, electrically isolated domains with varying conductance are found and their temporal evolution is investigated. Further, their formation and microstructure are studied using scanning transmission electron microscopy and secondary electron contrast in scanning electron microscopy. An important contribution is establishing that the observed domains are formed by cracks, driven by inhomogeneous strain relaxation throughout the film, resulting in significantly high strain planes. The potential of secondary electrons to detect domain dependent contrast over a large area, ensuing due to the use of a degenerate semiconductor correlates with the conductive properties of the domains and serves as a new direction to probe domains and domain walls in ferroic materials.

Nanoscale mechanical probing of ferroic materials

Nanoscale mechanical probing of ferroic materials

2D Ferroic Materials for Nonvolatile Memory Applications.

The emerging nonvolatile memory technologies based on ferroic materials are promising for producing high-speed, low-power, and high-density memory in the field ofintegrated circuits. Long-range ferroic orders observed in 2D materials have triggered extensive research interest in 2D magnets, 2D ferroelectrics, 2D multiferroics, and their device applications. Devices based on 2D ferroic materials and heterostructures with an atomically smooth interface and ultrathin thickness have exhibited impressive properties and significant potential for developing advanced nonvolatile memory. In this context, a systematic review of emergent 2D ferroic materials is conducted here, emphasizing their recent research on nonvolatile memory applications, with a view to proposing brighter prospects for 2D magnetic materials, 2D ferroelectric materials, 2D multiferroic materials, and their relevant devices.

Robust Ferroelasticity and Carrier Dynamics Across the Domain Wall in Perovskite‐Like van der Waals WO2I2

AbstractAs a new group of van der Waals (vdWs) ferroic materials, transition metal dioxydihalides MO2X2 (M: Mo, W; X: halogen) with a perovskite‐like structure are theoretically predicted to exhibit intriguing physics and versatile ferroic characteristics, which is not achieved experimentally as far as it is known. In this work, the robust ferroelasticity in vdWs WO2I2 with the switching strain as low as ≈0.3%, accompanied with the striped optical contrast between adjacent domains, spot splitting of selected area electron diffraction (SAED) patterns at domain wall, and 90° domain wall is demonstrated. With the aid of ab‐initio calculations, the origin of ferroelasticity in WO2I2 is unveiled, where the imaginary phonon mode in the high‐symmetry paraelastic phase leads to the spontaneous displacement of W atom away from the center of the [WO4I2] octahedron, resulting in the switchable spontaneous strain under an external strain field. Moreover, transient absorption microscopy (TAM) measurements demonstrate that the diffusion of photogenerated carriers is significantly hindered by the ferroelastic domain walls. This study provides deep insights into the ferroic order and domain wall in perovskite‐like vdWs MO2X2 for new physics and functionalities.

Nanoscopic spin-wave channeling along programmable magnetic domain walls in a CoFeB/BaTiO3 multiferroic heterostructure

We report a micromagnetic study on spin-wave propagation along magnetic domain walls in a ferromagnetic/ferroelectric bilayer. In our system, strain coupling between the two ferroic materials and inverse magnetostriction produce a fully correlated domain pattern wherein straight and narrow ferroelectric domain walls pin the magnetic domain walls. Consequently, an external magnetic field does tailor the spin structure of the magnetic domain walls instead of moving them. We use experimental parameters from a previously studied CoFeB/BaTiO3 material system to investigate the potential of artificial multiferroics for programmable nanoscopic spin-wave channeling. We show that spin waves are transported along the pinned magnetic domain walls at zero magnetic field and low frequency due to a local demagnetizing field. Further, switching of the domain wall spin structure from a head-to-tail to a head-to-head configuration abruptly changes the propagating spin-wave mode. We study the effect of magnetic field strength on the localized modes and discuss reversible control of spin-wave channeling via electric-field-driven magnetic domain wall motion. Nanoscopic guiding of propagating spin waves by an electric field, in combination with positional robustness to and mode programming by an external magnetic field, offers prospects for low-power and reconfigurable domain-wall-based magnonic devices.

Observation of stabilized negative capacitance effect in hafnium-based ferroic films

A negative capacitance (NC) effect has been proposed as a critical pathway to overcome the ‘Boltzmann tyranny’ of electrons, achieve the steep slope operation of transistors and reduce the power dissipation of current semiconductor devices. In particular, the ferroic property in hafnium-based films with fluorite structure provides an opportunity for the application of the NC effect in electronic devices. However, to date, only a transient NC effect has been confirmed in hafnium-based ferroic materials, which is usually accompanied by hysteresis and is detrimental to low-power transistor operations. The stabilized NC effect enables hysteresis-free and low-power transistors but is difficult to observe and demonstrate in hafnium-based films. This difficulty is closely related to the polycrystalline and multi-phase structure of hafnium-based films fabricated by atomic layer deposition or chemical solution deposition. Here, we prepare epitaxial ferroelectric Hf0.5Zr0.5O2 and antiferroelectric ZrO2 films with single-phase structure and observe the capacitance enhancement effect of Hf0.5Zr0.5O2/Al2O3 and ZrO2/Al2O3 capacitors compared to that of the isolated Al2O3 capacitor, verifying the stabilized NC effect. The capacitance of Hf0.5Zr0.5O2 and ZrO2 is evaluated as −17.41 and −27.64 pF, respectively. The observation of the stabilized NC effect in hafnium-based films sheds light on NC studies and paves the way for low-power transistors.

Optical properties of ferroic Fe2O(SeO3)2 and Fe2(SeO3)3·3H2O.

Ferroic compounds Fe2O(SeO3)2 (FSO) and Fe2(SeO3)3·3H2O (FSOH) prepared by the hydrothermal method are characterized and their optical properties are investigated by combining with first-principles calculations. The results show that (i) FSO is antiferromagnetic below ∼110 K and becomes ferromagnetic at elevated temperatures, while FSOH is antiferromagnetic at low temperatures probably due to a change in the spin state from Fe3+ (S = 5/2) to Fe2+ (S = 2); (ii) the optical bandgap is determined to be ∼2.83 eV for FSO and ∼2.15 eV for FSOH, consistent with the theoretical calculation; and (iii) the angle-resolved polarized Raman spectroscopy results of both crystals demonstrate the strong anisotropic light absorption and birefringence effects, and the unconventional symmetricity of some Raman modes is observed, which can be interpreted from the variation of Raman scattering elements. This work can provide not only an understanding of the structure and physical properties of iron selenites, but also a strategy for exploring the anomalous Raman behaviors in anisotropic crystals, facilitating the design and engineering of novel functional devices with low-symmetry ferroic materials.

Steric Effect Induced Modulation on Crystallographic Symmetry: Implementing Ferroelasticity in Molecular Ferroelectric

Ferroelastic materials, as a significant category within the primary ferroic materials, have paved the way for the development of shape memory, superelasticity, tunable electronics, MEMS and actuators. The ferroic phase...

Kibble–Zurek scaling of nonequilibrium phase transition in barium titanate

Far-from-equilibrium phase transition dynamics is one of the grand challenges in modern materials science. A theoretical landmark is the Kibble–Zurek (KZ) scaling to describe the relationship between the temperature quenching rate and the resulting defect density in the vicinity of symmetry-breaking phase transformations. Despite the confirmation of the KZ scaling in ferroic perovskite materials and macroscopic simulations, its atomistic mechanisms remain elusive. Here, we demonstrate the KZ scaling using all-atom molecular dynamics simulations for a prototypical ferroelectric perovskite, barium titanate, with the scaling exponent corresponding to the theoretical prediction for rapid quenching. Simulated diffuse neutron scattering data are presented to guide future experiments.

In-Plane Ferrielectric Order in van der Waals β'-In2Se3.

van der Waals ferroic materials exhibit rich potential for implementing future generation functional devices. Among these, layered β'-In2Se3 has fascinated researchers with its complex superlattice and domain structures. As opposed to ferroelectric α-In2Se3, the understanding of β'-In2Se3 ferroic properties remains unclear because ferroelectric, antiferroelectric, and ferroelastic characteristics have been separately reported in this material. To develop useful applications, it is necessary to understand the microscopic structural properties and their correlation with macroscopic device characteristics. Herein, using scanning transmission electron microscopy (STEM), we observed that the arrangement of dipoles deviates from the ideal double antiparallel antiferroelectric character due to competition between antiferroelectric and ferroelectric structural ordering. By virtue of second-harmonic generation, four-dimensional STEM, and in-plane piezoresponse force microscopy, the long-range inversion-breaking symmetry, uncompensated local polarization, and net polarization domains are unambiguously verified, revealing β'-In2Se3 as an in-plane ferrielectric layered material. Additionally, our device study reveals analogous resistive switching behaviors of different types owing to polarization switching, defect migration, and defect-induced charge trapping/detrapping processes.

Low voltage–driven high-performance thermal switching in antiferroelectric PbZrO 3 thin films

Effective control of heat transfer is vital for energy saving and carbon emission reduction. In contrast to achievements in electrical conduction, active control of heat transfer is much more challenging. Ferroelectrics are promising candidates for thermal switching as a result of their tunable domain structures. However, switching ratios in ferroelectrics are low (<1.2). We report that high-quality antiferroelectric PbZrO 3 epitaxial thin films exhibit high-contrast (>2.2), fast-speed (<150 nanoseconds), and long-lifetime (>10 7 ) thermal switching under a small voltage (<10 V). In situ reciprocal space mapping and atomistic modelings reveal that the field-driven antiferroelectric-ferroelectric phase transition induces a substantial change of primitive cell size, which modulates phonon-phonon scattering phase space drastically and results in high switching ratio. These results advance the concept of thermal transport control in ferroic materials.