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At least 199 records · Page 11

A Graph Dynamical neural network approach for decoding dynamical states in ferroelectrics.

Ferroelectric materials such as BaTiO 3 show tremendous potential for emerging advances in memory devices, particular neuromorphic type devices. High density of memory can be obtained by stabilising polar domain walls at the nanoscale, regions of discontinuity between the well-defined polarization order parameter, but little is known about what controls their structure and dynamics in real nanoscale materials. Indeed, chiral polar domain walls have been observed in heterogeneous ferroelectrics, such as oxygen-deficient BaTiO 3 , but very little is known about how such polar-domains walls interact with defects. Indeed, a critical understanding of how dynamics of domain-walls depend on point-defects is crucial to create engineered ferroelectric memory devices. For this work, we perform large-scale simulations of nansocale domain-wall dynamics in pristine and defective BaTiO 3 using reactive force-field developed by us earlier (Phys. Chem. Chem. Phys., 2019, 21, 18240–18249), and capture their dynamical dependence on point defects using a graph dynamical neural-network approach, which we adapted to interrogate solids with well-defined order-parameters, and implemented using Pytorch based libraries. Our machine learning (ML) approach goes beyond the traditional post-processing methods to capture both spatial and temporal heterogeneities of large-scale molecular dynamics simulations of complex defective ferroelectric oxide materials. We crucially find that isolated oxygen vacancies introduce very localized spatial regions (~1–2 unit-cell in length) that show slow dipole relaxation due to formation of defect-dipoles, and that these defect-dipoles in turn slow the intrinsic dynamics of domain walls. Further, the roughness of domain walls, also influenced by vacancies, introduce dynamic heterogeneity along the domain-wall. As such we find a novel mechanism by which quenched disorder due to defects introduce dynamic heterogeneity thereby influencing response to external fields (particularly time varying fields) in a ferroelectric. Our study also emphasizes the need for creating digital twins of dynamical quantities to achieve autonomous in operando control of nanoscale switching.

42 ENGINEERING↗

Nanoengineering room temperature ferroelectricity into orthorhombic SmMnO 3 films

Orthorhombic R MnO 3 ( R = rare-earth cation) compounds are type-II multiferroics induced by inversion-symmetry-breaking of spin order. They hold promise for magneto-electric devices. However, no spontaneous room-temperature ferroic property has been observed to date in orthorhombic R MnO 3 . Here, using 3D straining in nanocomposite films of (SmMnO 3 ) 0.5 ((Bi,Sm) 2 O 3 ) 0.5 , we demonstrate room temperature ferroelectricity and ferromagnetism with T C,FM ~ 90 K, matching exactly with theoretical predictions for the induced strain levels. Large in-plane compressive and out-of-plane tensile strains (-3.6% and +4.9%, respectively) were induced by the stiff (Bi,Sm) 2 O 3 nanopillars embedded. The room temperature electric polarization is comparable to other spin-driven ferroelectric R MnO 3 films. Also, while bulk SmMnO 3 is antiferromagnetic, ferromagnetism was induced in the composite films. The Mn-O bond angles and lengths determined from density functional theory explain the origin of the ferroelectricity, i.e. modification of the exchange coupling. Our structural tuning method gives a route to designing multiferroics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ordered hexagonal columnar liquid crystalline self-assembly of mesogen-free sulfonylated side-chain chiral polyethers and their high dielectric property

To achieve large spontaneous polarization for ferroelectric liquid crystalline polymers, we have designed a series of mesogen-free isotactic polyethers with sulfonylated side chains. Different from prior studies using linear alkyl side chains, in this work a methyl branch was implemented in the alkyl side chains of the chiral polyethers. As a result of the continuous twist from the methyl branches and strong dipole-dipole interactions among neighboring sulfonyl groups, a helical chain conformation with tilted side chains was achieved. When the branched side chains were short (e.g., C5) and double chirality existed in both the main chain and side chains, a crystalline structure was obtained. When the branched side chains were long (e.g., ≥ C8) and single chirality existed in the main chain, an ordered hexagonal columnar liquid crystalline phase was induced. Their high-field dielectric property was studied by electric displacement-electric field (D-E) loop tests; however, no ferroelectric behavior was observed up to 200 MV/m. It was considered that the dipole-dipole interaction among neighboring sulfonyl groups in the helical chains was too strong to allow easy ferroelectric flipping.

36 MATERIALS SCIENCE↗

Reversible control over the distribution of chemical inhomogeneities in multiferroic BiFeO3

Abstract Despite the appeal of flawless order, semiconductor technology has demonstrated that implanting inhomogeneities into single-crystalline materials is pivotal for modern electronics. However, the influence of the local arrangement of chemical inhomogeneities on the material’s functionalities is underexplored. In this work, we control the distribution of chemical inhomogeneities in La 3+ -substituted ferroelectric BiFeO 3 thin films. By means of a stress- and composition-driven phase transition, we trigger the formation of a lattice of La 3+ -rich and La 3+ -poor layers. This ordering correlates with the emergence of an antipolar phase. An electric field restores the original ferroelectric phase and re-randomizes the distribution of the La 3+ inhomogeneities. Leveraging these insights, we tune the polar/antipolar phase coexistence to set the net polarization of La 0.15 Bi 0.85 FeO 3 to any desired value between its saturation limits. Finally, we control the net polarization response in device-compliant capacitor heterostructures to show that inhomogeneity-distribution control is a valuable tool in the design of functional oxide electronics.

Science & Technology - Other Topics↗

Terahertz-field activation of polar skyrons

Unraveling collective modes arising from coupled degrees of freedom is crucial for understanding complex interactions in solids and developing new functionalities. Unique collective behaviors emerge when two degrees of freedom, ordered on distinct length scales, interact. Polar skyrmions, three-dimensional electric polarization textures in ferroelectric superlattices, disrupt the lattice continuity at the nanometer scale with nontrivial topology, leading to previously unexplored collective modes. Here, using terahertz-field excitation and femtosecond x-ray diffraction, we discover subterahertz collective modes, dubbed “skyrons”, which appear as swirling patterns of atomic displacements functioning as atomic-scale gearsets. The key to activating skyrons is the use of the THz field that couples primarily to skyrmion domain walls. Momentum-resolved time-domain measurements of diffuse scattering reveal an avoided crossing in the dispersion relation of skyrons. Atomistic simulations and dynamical phase-field modeling provide microscopic insights into the three-dimensional crystallographic and polarization dynamics. The amplitude and dispersion of skyrons are demonstrated to be controlled by sample temperature and electric-field bias. The discovery of skyrons and their coupling with terahertz fields opens avenues for ultrafast control of topological polar structures.

ferroelectrics↗

Atomistic theories and Simulations of Multiferroics

The goal of this award was to build a research program aimed at investigating puzzling complex phenomena in multiferroics, that are systems possessing electric and magnetic dipoles. We first emphasized the study of multiferroic nanostructures, that are 0D, 1D, 2D systems as well as superlattices and then also study multiferroics as a whole, i.e., bulks as well. In order to fully understand such complex systems, we also decided to study magnetic systems and ferroelectrics, both in their nanostructure and bulk forms. For that and in addition to use standard Density Functional Theory codes, we developed and used ab-initio tools that are able to model properties of large supercells (about a million atoms nowadays) at finite temperature and for any mechanical and boundary conditions. We also collaborated with experimentalists to fully understand the systems under study. The whole program resulted in 108 publications that are listed at the end of this report. In the following, I will put an emphasis on some publications before the last award period and also indicate a description of the last award period.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polarization-dependent photoemission electron microscopy for domain imaging of inorganic and molecular materials

Polarization-dependent photoemission electron microscopy (PD-PEEM) exploits spatial variation in the optical selection rules of materials to image domain formation and material organization on the nanoscale. In this Perspective, we discuss the mechanism of PD-PEEM that results in the observed image contrast in experiments and provide examples of a wide range of material domain structures that PD-PEEM has been able to elucidate, including molecular and polymer domains, local electronic structure and defect symmetry, (anti)ferroelectricity, and ferromagnetism. As a result, we discuss challenges and new directions that are possible with this tool for probing domain structure in materials, including investigating the formation of transient ordered states, multiferroics, and the influence of molecular and polymer order and disorder on excited state dynamics and charge transport.

36 MATERIALS SCIENCE↗

Interlayer Coupling Controlled Ordering and Phases in Polar Vortex Superlattices

The recent discovery of polar topological structures has opened the door for exciting physics and emergent properties. There is, however, little methodology to engineer stability and ordering in these systems, properties of interest for engineering emergent functionalities. Notably, when the surface area is extended to arbitrary thicknesses, the topological polar texture becomes unstable. Here we show that this instability of the phase is due to electrical coupling between successive layers. We demonstrate that this electrical coupling is indicative of an effective screening length in the dielectric, similar to the conductor–ferroelectric interface. Controlling the electrostatics of the superlattice interfaces, the system can be tuned between a pure topological vortex state and a mixed classical-topological phase. This coupling also enables engineering coherency among the vortices, not only tuning the bulk phase diagram but also enabling the emergence of a 3D lattice of polar textures.

3D ordering↗

Electronic structures, charge transfer, and charge order in twisted transition metal dichalcogenide bilayers

Moiré superlattices of transition metal dichalcogenide (TMD) bilayers have been shown to host correlated electronic states, which arise from the interplay of long wavelength moiré potential and long-range Coulomb interaction. Here, we theoretically investigate structural relaxation and single-particle electronic structure of twisted TMD homobilayer. From the large-scale density functional theory calculation and continuum model with layer degrees of freedom, we find that the out-of-plane gating field creates a tunable charge transfer gap at the Dirac point between the first and second moiré valence bands. We further study the charge orders at the fractional band fillings. In the flat band limit, we find from Monte Carlo simulations a series of charge-ordered insulating states at various fillings $n = \frac{1}{4}, \frac{1}{3}, \frac{1}{2}, \frac{2}{3}, 1$. Further, we predict that gating field induces a phase transition between different electron crystals at fixed filling $n = \frac{1}{2}$ or $\frac{2}{3}$. At half-filling $\textit{n} = 1$, the ground state is a Mott insulator with electronically driven ferroelectricity. This work demonstrates that TMD homobilayer provides a powerful platform for the investigation of tunable charge transfer insulator and charge orders.

36 MATERIALS SCIENCE↗

Stacking-engineered ferroelectricity in bilayer boron nitride

Stacking a ferroelectric Properties of layered van der Waals structures can depend sensitively on the stacking arrangement of constituent layers. This phenomenon has been exploited to engineer superconducting, correlated insulator, and magnetic states. Two groups now show that ferroelectricity can also be engineered through stacking: Parallel-stacked bilayers of hexagonal boron nitride exhibit ferroelectric switching even though the bulk material is not ferroelectric (see the Perspective by Tsymbal). To explore these phenomena, Yasuda et al. used transport measurements, whereas Vizner Stern et al. focused on atomic force microscopy. Science , abd3230 and abe8177, this issue p. 1458 and p. 1462 ; see also abi7296, p. 1389

Science & Technology - Other Topics↗

Quenched lattice fluctuations in optically driven SrTiO3

Abstract Crystal lattice fluctuations, which are known to influence phase transitions of quantum materials in equilibrium, are also expected to determine the dynamics of light-induced phase changes. However, they have only rarely been explored in these dynamical settings. Here we study the time evolution of lattice fluctuations in the quantum paraelectric SrTiO 3 , in which mid-infrared drives have been shown to induce a metastable ferroelectric state. Crucial in these physics is the competition between polar instabilities and antiferrodistortive rotations, which in equilibrium frustrate the formation of long-range ferroelectricity. We make use of high-intensity mid-infrared optical pulses to resonantly drive the Ti–O-stretching mode at 17 THz, and we measure the resulting change in lattice fluctuations using time-resolved X-ray diffuse scattering at a free-electron laser. After a prompt increase, we observe a long-lived quench in R-point antiferrodistortive lattice fluctuations. Their enhancement and reduction are theoretically explained by considering the fourth-order nonlinear phononic interactions to the driven optical phonon and third-order coupling to lattice strain, respectively. These observations provide a number of testable hypotheses for the physics of light-induced ferroelectricity.

36 MATERIALS SCIENCE↗

Ultrafast Neuromorphic Dynamics Using Hidden Phases in the Prototype of Relaxor Ferroelectrics

Materials possessing multiple states are promising to emulate synaptic and neuronic behaviors. Their operation frequency, typically in or below the GHz range, however, limits the speed of neuromorphic computing. Ultrafast THz electric field excitation has been employed to induce nonequilibrium states of matter, called hidden phases in oxides. One may wonder if there are systems for which THz pulses can generate neuronic and synaptic behavior, via the creation of hidden phases. Using atomistic simulations, we discover that relaxor ferroelectrics can emulate all the key neuronic and memristive synaptic features. Their occurrence originates from the activation of many hidden phases of polarization order, resulting from the response of nanoregions to THz pulses. We find such phases further possess different dielectric constants, which is also promising for memcapacitor devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Giant electric field-induced second harmonic generation in polar skyrmions

Electric field-induced second harmonic generation allows electrically controlling nonlinear light-matter interactions crucial for emerging integrated photonics applications. Despite its wide presence in materials, the figures-of-merit of electric field-induced second harmonic generation are yet to be elevated to enable novel device functionalities. Here, we show that the polar skyrmions, a topological phase spontaneously formed in PbTiO3/SrTiO3 ferroelectric superlattices, exhibit a high comprehensive electric field-induced second harmonic generation performance. The second-order nonlinear susceptibility and modulation depth, measured under non-resonant 800 nm excitation, reach ~54.2 pm V −1 and ~664% V −1 , respectively, and high response bandwidth (higher than 10 MHz), wide operating temperature range (up to ~400 K) and good fatigue resistance (>10 10 cycles) are also demonstrated. Through combined in-situ experiments and phase-field simulations, we establish the microscopic links between the exotic polarization configuration and field-induced transition paths of the skyrmions and their electric field-induced second harmonic generation response. Our study not only presents a highly competitive thin-film material ready for constructing on-chip devices, but opens up new avenues of utilizing topological polar structures in the fields of photonics and optoelectronics.

Nonlinear optics↗

Towards a Deeper Fundamental Understanding of (Al,Sc)N Ferroelectric Nitrides

Density functional theory (DFT) calculations, within the virtual crystal alloy approximation, are performed, along with the development of a Landau-type model employing a symmetry-allowed analytical expression of the internal energy and having parameters determined from first principles, to investigate properties and energetics of Al1-xScxN ferroelectric nitrides in their hexagonal forms. These DFT computations and this model predict the existence of two different types of minima, namely, the fourfold-coordinated wurtzite (WZ) polar structure and a five-fold coordinated paraelectric hexagonal phase (denoted as H5), for any Sc composition up to 40%. The H5 minimum progressively becomes the lowest-energy state within hexagonal symmetry as the Sc concentration increases from 0 to 0.4. Furthermore, the model points to several key findings. Examples include the crucial role of the coupling between polarization and strains to create the WZ minimum, in addition to polar and elastic energies, and that the origin of the H5 state overcoming the WZ phase as the global minimum within hexagonal symmetry when increasing the Sc composition mostly lies in the compositional dependency of only two parameters-one linked to the polarization and another one being purely elastic in nature. Other examples are that forcing Al1-xScxN systems to have no or a weak change in lattice parameters when heating them allows us to reproduce their finite-temperature polar properties well and that a value of the axial ratio close to that of the ideal WZ structure implies a large polarization at low temperatures but not necessarily at high temperatures because of the ordered-disordered character of the temperature-induced formation of the WZ state. Such findings should allow for a better fundamental understanding of (Al,Sc)N ferroelectric nitrides, which may be used to design efficient devices having, e.g., low operating voltages.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Large Polarization and Susceptibilities in Artificial Morphotropic Phase Boundary PbZr 1– x Ti x O 3 Superlattices

The ability to produce atomically precise, artificial oxide heterostructures allows for the possibility of producing exotic phases and enhanced susceptibilities not found in parent materials. Typical ferroelectric materials either exhibit large saturation polarization away from a phase boundary or large dielectric susceptibility near a phase boundary. Both large ferroelectric polarization and dielectric permittivity are attained wherein fully epitaxial (PbZr 0.8 Ti 0.2 O 3 ) n /(PbZr 0.4 Ti 0.6 O 3 ) 2 n ( n = 2, 4, 6, 8, 16 unit cells) superlattices are produced such that the overall film chemistry is at the morphotropic phase boundary, but constitutive layers are not. Here, long- ( n ≥ 6) and short-period ( n = 2) superlattices reveal large ferroelectric saturation polarization ( P s = 64 µC cm –2 ) and small dielectric permittivity (ε r ≈ 400 at 10 kHz). Intermediate-period ( n = 4) superlattices, however, exhibit both large ferroelectric saturation polarization ( P s = 64 µC cm –2 ) and dielectric permittivity (ε r = 776 at 10 kHz). First-order reversal curve analysis reveals the presence of switching distributions for each parent layer and a third, interfacial layer wherein superlattice periodicity modulates the volume fraction of each switching distribution and thus the overall material response. This reveals that deterministic creation of artificial superlattices is an effective pathway for designing materials with enhanced responses to applied bias.

36 MATERIALS SCIENCE↗

Structural mode coupling in perovskite oxides using hypothesis-driven active learning

Abstract Finding the ground-state structure with minimum energy is paramount to designing any material. In ABO 3 -type perovskite oxides with Pnma symmetry, the lowest energy phase is driven by an inherent trilinear coupling between the two primary order parameters such as rotation and tilt with antiferroelectric displacement of the A-site cations as established via hybrid improper ferroelectric mechanism. Conventionally, finding the relevant mode coupling driving phase transition requires performing first-principles calculations which is computationally time-consuming as well as expensive. It involves following an intuitive iterative hit and trial method of (a) adding two or multiple mode vectors, followed by (b) evaluating which combination would lead to the ground-state energy. In this study, we show how a hypothesis-driven active learning framework can identify suitable mode couplings within the Landau free energy expansion with minimal information on amplitudes of modes for a series of double perovskite oxides with A-site layered, columnar and rocksalt ordering. This scheme is expected to be applicable universally for understanding atomistic mechanisms derived from various structural mode couplings behind functionalities, for e.g. polarization, magnetization and metal–insulator transitions.

36 MATERIALS SCIENCE↗

High Velocity, Low‐Voltage Collective In‐Plane Switching in (100) BaTiO 3 Thin Films

Abstract Ferroelectrics are being increasingly called upon for electronic devices in extreme environments. Device performance and energy efficiency is highly correlated to clock frequency, operational voltage, and resistive loss. To increase performance it is common to engineer ferroelectric domain structure with highly‐correlated electrical and elastic coupling that elicit fast and efficient collective switching. Designing domain structures with advantageous properties is difficult because the mechanisms involved in collective switching are poorly understood and difficult to investigate. Collective switching is a hierarchical process where the nano‐ and mesoscale responses control the macroscopic properties. Using chemical solution synthesis, epitaxially nearly‐relaxed (100) BaTiO 3 films are synthesized. Thermal strain induces a strongly‐correlated domain structure with alternating domains of polarization along the [010] and [001] in‐plane axes and 90° domain walls along the [011] or [01] directions. Simultaneous capacitance–voltage measurements and band‐excitation piezoresponse force microscopy revealed strong collective switching behavior. Using a deep convolutional autoencoder, hierarchical switching is automatically tracked and the switching pathway is identified. The collective switching velocities are calculated to be ≈500 cm s −1 at 5 V (7 kV cm −1 ), orders‐of‐magnitude faster than expected. These combinations of properties are promising for high‐speed tunable dielectrics and low‐voltage ferroelectric memories and logic.

36 MATERIALS SCIENCE↗

Thermal disorder and phonon softening in the ferroelectric phase transition of lead titanate

We report a molecular dynamics study of ab initio quality of the ferroelectric phase transition in crystalline PbTi⁢O3. We model anharmonicity accurately in terms of potential energy and polarization surfaces trained on density functional theory data with modern machine learning techniques. Our simulations demonstrate that the transition has a strong order-disorder character, in agreement with diffraction experiments, and provide fresh insight into the approach to equilibrium across the phase transition. We find that the emergence and disappearance of the macroscopic polarization is driven by dipolar switching at the nanometer scale. We also computed the infrared optical absorption spectra in both the ferroelectric and the paraelectric phases, finding good agreement with the experimental Raman frequencies. Often, the almost ideal displacive character of the soft mode detected by Raman scattering in the paraelectric phase has been contrasted with the order-disorder character of the transition suggested by diffraction experiments. We settle this issue by showing that the soft mode coexists with a strong Debye relaxation associated with thermal disordering of the dipoles. The Debye relaxation feature is centered at zero frequency and appears near the transition temperature in both the ferroelectric and the paraelectric phases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗