Resonant domain-wall-enhanced tunable microwave ferroelectrics.

Ordering of ferroelectric polarization1 and its trajectory in response to an electric field2 are essential for the operation of non-volatile memories3, transducers4 and electro-optic devices5. However, for voltage control of capacitance and frequency agility in telecommunication devices, domain walls have long been thought to be a hindrance because they lead to high dielectric loss and hysteresis in the device response to an applied electric field6. To avoid these effects, tunable dielectrics are often operated under piezoelectric resonance conditions, relying on operation well above the ferroelectric Curie temperature7, where tunability is compromised. Therefore, there is an unavoidable trade-off between the requirements of high tunability and low loss in tunable dielectric devices, which leads to severe limitations on their figure of merit. Here we show that domain structure can in fact be exploited to obtain ultralow loss and exceptional frequency selectivity without piezoelectric resonance. We use intrinsically tunable materials with properties that are defined not only by their chemical composition, but also by the proximity and accessibility of thermodynamically predicted strain-induced, ferroelectric domain-wall variants8. The resulting gigahertz microwave tunability and dielectric loss are better than those of the best film devices by one to two orders of magnitude and comparable to those of bulk single crystals. The measured quality factors exceed the theoretically predicted zero-field intrinsic limit owing to domain-wall fluctuations, rather than field-induced piezoelectric oscillations, which are usually associated with resonance. Resonant frequency tuning across the entire L, S and C microwave bands (1-8 gigahertz) is achieved in an individual device-a range about 100 times larger than that of the best intrinsically tunable material. These results point to a rich phase space of possible nanometre-scale domain structures that can be used to surmount current limitations, and demonstrate a promising strategy for obtaining ultrahigh frequency agility and low-loss microwave devices.

Emergent chirality in the electric polarization texture of titanate superlattices.

Chirality is a geometrical property by which an object is not superimposable onto its mirror image, thereby imparting a handedness. Chirality determines many important properties in nature-from the strength of the weak interactions according to the electroweak theory in particle physics to the binding of enzymes with naturally occurring amino acids or sugars, reactions that are fundamental for life. In condensed matter physics, the prediction of topologically protected magnetic skyrmions and related spin textures in chiral magnets has stimulated significant research. If the magnetic dipoles were replaced by their electrical counterparts, then electrically controllable chiral devices could be designed. Complex oxide BaTiO3/SrTiO3 nanocomposites and PbTiO3/SrTiO3 superlattices are perfect candidates, since "polar vortices," in which a continuous rotation of ferroelectric polarization spontaneously forms, have been recently discovered. Using resonant soft X-ray diffraction, we report the observation of a strong circular dichroism from the interaction between circularly polarized light and the chiral electric polarization texture that emerges in PbTiO3/SrTiO3 superlattices. This hallmark of chirality is explained by a helical rotation of electric polarization that second-principles simulations predict to reside within complex 3D polarization textures comprising ordered topological line defects. The handedness of the texture can be topologically characterized by the sign of the helicity number of the chiral line defects. This coupling between the optical and novel polar properties could be exploited to encode chiral signatures into photon or electron beams for information processing.

Stability of Polar Vortex Lattice in Ferroelectric Superlattices.

A novel mesoscale state comprising of an ordered polar vortex lattice has been demonstrated in ferroelectric superlattices of PbTiO3/SrTiO3. Here, we employ phase-field simulations, analytical theory, and experimental observations to evaluate thermodynamic conditions and geometric length scales that are critical for the formation of such exotic vortex states. We show that the stability of these vortex lattices involves an intimate competition between long-range electrostatic, long-range elastic, and short-range polarization gradient-related interactions leading to both an upper and a lower bound to the length scale at which these states can be observed. We found that the critical length is related to the intrinsic domain wall width, which could serve as a simple intuitive design rule for the discovery of novel ultrafine topological structures in ferroic systems.

Ferroelectric polarization reversal via successive ferroelastic transitions.

Switchable polarization makes ferroelectrics a critical component in memories, actuators and electro-optic devices, and potential candidates for nanoelectronics. Although many studies of ferroelectric switching have been undertaken, much remains to be understood about switching in complex domain structures and in devices. In this work, a combination of thin-film epitaxy, macro- and nanoscale property and switching characterization, and molecular dynamics simulations are used to elucidate the nature of switching in PbZr(0.2)Ti(0.8)O3 thin films. Differences are demonstrated between (001)-/(101)- and (111)-oriented films, with the latter exhibiting complex, nanotwinned ferroelectric domain structures with high densities of 90° domain walls and considerably broadened switching characteristics. Molecular dynamics simulations predict both 180° (for (001)-/(101)-oriented films) and 90° multi-step switching (for (111)-oriented films) and these processes are subsequently observed in stroboscopic piezoresponse force microscopy. These results have implications for our understanding of ferroelectric switching and offer opportunities to change domain reversal speed.

180° Ferroelectric Stripe Nanodomains in BiFeO3 Thin Films.

There is growing evidence that domain walls in ferroics can possess emergent properties that are absent in the bulk. For example, 180° ferroelectric domain walls in the ferroelectric-antiferromagnetic BiFeO3 are particularly interesting because they have been predicted to possess a range of intriguing behaviors, including electronic conduction and enhanced magnetization. To date, however, ordered arrays of such domain structures have not been reported. Here, we report the observation of 180° stripe nanodomains in (110)-oriented BiFeO3 thin films grown on orthorhombic GdScO3 (010)O substrates and their impact on exchange coupling to metallic ferromagnets. Nanoscale ferroelectric 180° stripe domains with {112̅} domain walls were observed in films <32 nm thick. With increasing film thickness, we observed a domain structure crossover from the depolarization field-driven 180° stripe nanodomains to 71° ferroelastic domains determined by the elastic energy. These 180° domain walls (which are typically cylindrical or meandering in nature due to a lack of strong anisotropy associated with the energy of such walls) are found to be highly ordered. Additional studies of Co0.9Fe0.1/BiFeO3 heterostructures reveal exchange bias and exchange enhancement in heterostructures based on BiFeO3 with 180° domain walls and an absence of exchange bias in heterostructures based on BiFeO3 with 71° domain walls; suggesting that the 180° domain walls could be the possible source for pinned uncompensated spins that give rise to exchange bias. This is further confirmed by X-ray circular magnetic dichroism studies, which demonstrate that films with predominantly 180° domain walls have larger magnetization than those with primarily 71° domain walls. Our results could be useful to extract the structure of domain walls and to explore domain wall functionalities in BiFeO3.

Real-time observation of local strain effects on nonvolatile ferroelectric memory storage mechanisms.

We use in situ transmission electron microscopy to directly observe, at high temporal and spatial resolution, the interaction of ferroelectric domains and dislocation networks within BiFeO3 thin films. The experimental observations are compared with a phase field model constructed to simulate the dynamics of domains in the presence of dislocations and their resulting strain fields. We demonstrate that a global network of misfit dislocations at the film-substrate interface can act as nucleation sites and slow down domain propagation in the vicinity of the dislocations. Networks of individual threading dislocations emanating from the film-electrode interface play a more dramatic role in pinning domain motion. These dislocations may be responsible for the domain behavior in ferroelectric thin-film devices deviating from conventional Kolmogorov-Avrami-Ishibashi dynamics toward a Nucleation Limited Switching model.

Machine learning guided rational design of a non-heme iron-based lysine dioxygenase improves its total turnover number.

Highly selective C-H functionalization remains an ongoing challenge in organic synthetic methodologies. Biocatalysts are robust tools for achieving these difficult chemical transformations. Biocatalyst engineering has often required directed evolution or structure-based rational design campaigns to improve their activities. In recent years, machine learning has been integrated into these workflows to improve the discovery of beneficial enzyme variants. In this work, we combine a structure-based machine-learning algorithm with classical molecular dynamics simulations to down select mutations for rational design of a non-heme iron-dependent lysine dioxygenase, LDO. This approach consistently resulted in functional LDO mutants and circumvents the need for extensive study of mutational activity before-hand. Our rationally designed single mutants purified with up to 2-fold higher yields than WT and displayed higher total turnover numbers (TTN). Combining five such single mutations into a pentamutant variant, LPNYI LDO, leads to a 40% improvement in the TTN (218±3) as compared to WT LDO (TTN = 160±2). Overall, this work offers a low-barrier approach for those seeking to synergize machine learning algorithms with pre-existing protein engineering strategies.

Controllable multi-halogenation of a non-native substrate by SyrB2 iron halogenase.

Geminal, multi-halogenated functional groups are widespread in natural products and pharmaceuticals, yet no synthetic methodologies exist that enable selective multi-halogenation of unactivated C-H bonds. Biocatalysts are powerful tools for late-stage C-H functionalization, as they operate with high degrees of regio-, chemo-, and stereoselectivity. 2-oxoglutarate (2OG)-dependent non-heme iron halogenases chlorinate and brominate aliphatic C-H bonds offering a solution for achieving these challenging transformations. Here, we describe the ability of a non-heme iron halogenase, SyrB2, to controllably halogenate non-native substrate alpha-aminobutyric acid (Aba) to yield mono-chlorinated, di-chlorinated, and tri-chlorinated products. These chemoselective outcomes are achieved by controlling the loading of 2OG cofactor and SyrB2 biocatalyst. By using a ferredoxin-based biological reductant for electron transfer to the catalytic center of SyrB2, we demonstrate order-of-magnitude enhancement in the yield of tri-chlorinated product that were previously inaccessible using any single halogenase enzyme. We also apply these strategies to broaden SyrB2's reactivity scope to include multi-bromination and demonstrate chemoenzymatic conversion of the ethyl side chain in Aba to an ethylyne functional group. We show how steric hindrance induced by the successive addition of halogen atoms on Aba's C4 carbon dictates the degree of multi-halogenation by hampering C3-C4 bond rotation within SyrB2's catalytic pocket. Overall, our work showcases the synthetic potential of iron halogenases to facilitate multi-C-H functionalization chemistry.

Mode-Matching Enhancement of Second-Harmonic Generation with Plasmonic Nanopatch Antennas.

Plasmonic enhancement of nonlinear optical processes confront severe limitations arising from the strong dispersion of metal susceptibilities and small interaction volumes that hamper the realization of desirable phase-matching-like conditions. Maximizing nonlinear interactions in nanoscale systems require simultaneous excitation of resonant modes that spatially and constructively overlap at all wavelengths involved in the process. Here, we present a hybrid rectangular patch antenna design for optimal second-harmonic generation (SHG) that is characterized by a non-centrosymmetric dielectric/ferroelectric material at the plasmonic hot spot. The optimization of the rectangular patch allows for the independent tuning of various modes of resonances that can be used to enhance the SHG process. We explore the angular dependence of SHG in these hybrid structures and highlight conditions necessary for the maximal SHG efficiency. Furthermore, we propose a novel configuration with a periodically poled ferroelectric layer for an orders-of-magnitude enhanced SHG at normal incidence. Such a platform may enable the development of integrated nanoscale light sources and on-chip frequency converters.

Epitaxial Strain Control of Relaxor Ferroelectric Phase Evolution.

Understanding and ultimately controlling the large electromechanical effects in relaxor ferroelectrics requires intimate knowledge of how the local-polar order evolves under applied stimuli. Here, the biaxial-strain-induced evolution of and correlations between polar structures and properties in epitaxial films of the prototypical relaxor ferroelectric 0.68PbMg1/3 Nb2/3 O3 -0.32PbTiO3 are investigated. X-ray diffuse-scattering studies reveal an evolution from a butterfly- to disc-shaped pattern and an increase in the correlation-length from ≈8 to ≈25 nm with increasing compressive strain. Molecular-dynamics simulations reveal the origin of the changes in the diffuse-scattering patterns and that strain induces polarization rotation and the merging of the polar order. As the magnitude of the strain is increased, relaxor behavior is gradually suppressed but is not fully quenched. Analysis of the dynamic evolution of dipole alignment in the simulations reveals that, while, for most unit-cell chemistries and configurations, strain drives a tendency toward more ferroelectric-like order, there are certain unit cells that become more disordered under strain, resulting in stronger competition between ordered and disordered regions and enhanced overall susceptibilities. Ultimately, this implies that deterministic creation of specific local chemical configurations could be an effective way to enhance relaxor performance.