Light-Driven Ultrafast Polarization Manipulation in a Relaxor Ferroelectric.

Relaxor ferroelectrics have been intensely studied for decades based on their unique electromechanical responses which arise from local structural heterogeneity involving polar nanoregions or domains. Here, we report first studies of the ultrafast dynamics and reconfigurability of the polarization in freestanding films of the prototypical relaxor 0.68PbMg1/3Nb2/3O3-0.32PbTiO3 (PMN-0.32PT) by probing its atomic-scale response via femtosecond-resolution, electron-scattering approaches. By combining these structural measurements with dynamic phase-field simulations, we show that femtosecond light pulses drive a change in both the magnitude and direction of the polarization vector within polar nanodomains on few-picosecond time scales. This study defines new opportunities for dynamic reconfigurable control of the polarization in nanoscale relaxor ferroelectrics.

Ultrahigh capacitive energy density in ion-bombarded relaxor ferroelectric films.

Dielectric capacitors can store and release electric energy at ultrafast rates and are extensively studied for applications in electronics and electric power systems. Among various candidates, thin films based on relaxor ferroelectrics, a special kind of ferroelectric with nanometer-sized domains, have attracted special attention because of their high energy densities and efficiencies. We show that high-energy ion bombardment improves the energy storage performance of relaxor ferroelectric thin films. Intrinsic point defects created by ion bombardment reduce leakage, delay low-field polarization saturation, enhance high-field polarizability, and improve breakdown strength. We demonstrate energy storage densities as high as ~133 joules per cubic centimeter with efficiencies exceeding 75%. Deterministic control of defects by means of postsynthesis processing methods such as ion bombardment can be used to overcome the trade-off between high polarizability and breakdown strength.

Defect-Enhanced Polarization Switching in the Improper Ferroelectric LuFeO3.

Results of switching behavior of the improper ferroelectric LuFeO3 are presented. Using a model set of films prepared under controlled chemical and growth-rate conditions, it is shown that defects can reduce the quasi-static switching voltage by up to 40% in qualitative agreement with first-principles calculations. Switching studies show that the coercive field has a stronger frequency dispersion for the improper ferroelectrics compared to a proper ferroelectric such as PbTiO3 . It is concluded that the primary structural order parameter controls the switching dynamics of such improper ferroelectrics.

Designing Optimal Perovskite Structure for High Ionic Conduction.

Solid-oxide fuel/electrolyzer cells are limited by a dearth of electrolyte materials with low ohmic loss and an incomplete understanding of the structure-property relationships that would enable the rational design of better materials. Here, using epitaxial thin-film growth, synchrotron radiation, impedance spectroscopy, and density-functional theory, the impact of structural parameters (i.e., unit-cell volume and octahedral rotations) on ionic conductivity is delineated in La0.9 Sr0.1 Ga0.95 Mg0.05 O3- δ . As compared to the zero-strain state, compressive strain reduces the unit-cell volume while maintaining large octahedral rotations, resulting in a strong reduction of ionic conductivity, while tensile strain increases the unit-cell volume while quenching octahedral rotations, resulting in a negligible effect on the ionic conductivity. Calculations reveal that larger unit-cell volumes and octahedral rotations decrease migration barriers and create low-energy migration pathways, respectively. The desired combination of large unit-cell volume and octahedral rotations is normally contraindicated, but through the creation of superlattice structures both expanded unit-cell volume and large octahedral rotations are experimentally realized, which result in an enhancement of the ionic conductivity. All told, the potential to tune ionic conductivity with structure alone by a factor of ≈2.5 at around 600 °C is observed, which sheds new light on the rational design of ion-conducting perovskite electrolytes.

Defect-Induced (Dis)Order in Relaxor Ferroelectric Thin Films.

The effect of intrinsic point defects on relaxor properties of 0.68 PbMg_{1/3}Nb_{2/3}O_{3}-0.32 PbTiO_{3} thin films is studied across nearly 2 orders of magnitude of defect concentration via ex post facto ion bombardment. A weakening of the relaxor character is observed with increasing concentration of bombardment-induced point defects, which is hypothesized to be related to strong interactions between defect dipoles and the polarization. Although more defects and structural disorder are introduced in the system as a result of ion bombardment, the special type of defects that are likely to form in these polar materials (i.e., defect dipoles) can stabilize the direction of polarization against thermal fluctuations, and in turn, weaken relaxor behavior.

Mechanical-force-induced non-local collective ferroelastic switching in epitaxial lead-titanate thin films.

Ferroelastic switching in ferroelectric/multiferroic oxides plays a crucial role in determining their dielectric, piezoelectric, and magnetoelectric properties. In thin films of these materials, however, substrate clamping is generally thought to limit the electric-field- or mechanical-force-driven responses to the local scale. Here, we report mechanical-force-induced large-area, non-local, collective ferroelastic domain switching in PbTiO3 epitaxial thin films by tuning the misfit-strain to be near a phase boundary wherein c/a and a1/a2 nanodomains coexist. Phenomenological models suggest that the collective, c-a-c-a ferroelastic switching arises from the small potential barrier between the degenerate domain structures, and the large anisotropy of a and c domains, which collectively generates much larger response and large-area domain propagation. Large-area, non-local response under small stimuli, unlike traditional local response to external field, provides an opportunity of unique response to local stimuli, which has potential for use in high-sensitivity pressure sensors and switches.

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.

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.

Reducing Coercive-Field Scaling in Ferroelectric Thin Films via Orientation Control.

The desire for low-power/voltage operation of devices is driving renewed interest in understanding scaling effects in ferroelectric thin films. As the dimensions of ferroelectrics are reduced, the properties can vary dramatically, including the robust scaling relationship between coercive field ( Ec) and thickness ( d), also referred to as the Janovec-Kay-Dunn (JKD) law, wherein Ec ∝ d-2/3. Here, we report that whereas (001)-oriented heterostructures follow JKD scaling across the thicknesses range of 20-330 nm, (111)-oriented heterostructures of the canonical tetragonal ferroelectric PbZr0.2Ti0.8O3 exhibit a deviation from JKD scaling wherein a smaller scaling exponent for the evolution of Ec is observed in films of thickness ≲ 165 nm. X-ray diffraction reveals that whereas (001)-oriented heterostructures remain tetragonal for all thicknesses, (111)-oriented heterostructures exhibit a transition from tetragonal-to-monoclinic symmetry in films of thickness ≲ 165 nm as a result of the compressive strain. First-principles calculations suggest that this symmetry change contributes to the deviation from the expected scaling, as the monoclinic phase has a lower energy barrier for switching. This structural evolution also gives rise to changes in the c/ a lattice parameter ratio, wherein this ratio increases and decreases in (001)- and (111)-oriented heterostructures, respectively, as the films are made thinner. In (111)-oriented heterostructures, this reduced tetragonality drives a reduction of the remanent polarization and, therefore, a reduction of the domain-wall energy and overall energy barrier to switching, which further exacerbates the deviation from the expected scaling. Overall, this work demonstrates a route toward reducing coercive fields in ferroelectric thin films and provides a possible mechanism to understand the deviation from JKD scaling.

Giant Polarization Sustainability in Ultrathin Ferroelectric Films Stabilized by Charge Transfer.

Ferroelectricity is generally deteriorated or even vanishes when the ferroelectric films are downsized to unit cell scale. To maintain and enhance the polarization in nanoscale ferroelectrics are of scientific and technological importance. Here, giant polarization sustainability is reported in a series of ultrathin PbTiO3 films scaled down to three unit cells grown on NdGaO3 (110) substrates with La0.7 Sr0.3 MnO3 as bottom electrodes. Atomic mappings via aberration-corrected scanning transmission electron microscopy demonstrate the robust ferroelectricity for the sub-10 nm thick film. For the 1.2 nm thick film, the polarization reaches ≈50 µC cm-2 . The 2 nm thick film possesses a polarization as high as the bulk value. The films ranging from 10 to 35 nm display a giant elongation of out-of-plane lattice parameter, which corresponds to a polarization of 100 µC cm-2 , 20% larger than that of the bulk PbTiO3 . The giant enhancement of polarization in the present films is proposed to result from the charge transfer at the La0.7 Sr0.3 MnO3 /PbTiO3 interface, as supported by the anomalous decrease of Mn valence measured from X-ray photoelectron spectroscopy. These results reveal the significant role of charge transfer at interfaces in improving large polarizations in ultrathin ferroelectrics and are meaningful for the development of future electronic devices.

Three-State Ferroelastic Switching and Large Electromechanical Responses in PbTiO3 Thin Films.

Leveraging competition between energetically degenerate states to achieve large field-driven responses is a hallmark of functional materials, but routes to such competition are limited. Here, a new route to such effects involving domain-structure competition is demonstrated, which arises from strain-induced spontaneous partitioning of PbTiO3 thin films into nearly energetically degenerate, hierarchical domain architectures of coexisting c/a and a1 /a2 domain structures. Using band-excitation piezoresponse force microscopy, this study manipulates and acoustically detects a facile interconversion of different ferroelastic variants via a two-step, three-state ferroelastic switching process (out-of-plane polarized c+ → in-plane polarized a → out-of-plane polarized c- state), which is concomitant with large nonvolatile electromechanical strains (≈1.25%) and tunability of the local piezoresponse and elastic modulus (>23%). It is further demonstrated that deterministic, nonvolatile writing/erasure of large-area patterns of this electromechanical response is possible, thus showing a new pathway to improved function and properties.

Pressurizing Field-Effect Transistors of Few-Layer MoS2 in a Diamond Anvil Cell.

Hydrostatic pressure applied using diamond anvil cells (DAC) has been widely explored to modulate physical properties of materials by tuning their lattice degree of freedom. Independently, electrical field is able to tune the electronic degree of freedom of functional materials via, for example, the field-effect transistor (FET) configuration. Combining these two orthogonal approaches would allow discovery of new physical properties and phases going beyond the known phase space. Such experiments are, however, technically challenging and have not been demonstrated. Herein, we report a feasible strategy to prepare and measure FETs in a DAC by lithographically patterning the nanodevices onto the diamond culet. Multiple-terminal FETs were fabricated in the DAC using few-layer MoS2 and BN as the channel semiconductor and dielectric layer, respectively. It is found that the mobility, conductance, carrier concentration, and contact conductance of MoS2 can all be significantly enhanced with pressure. We expect that the approach could enable unprecedented ways to explore new phases and properties of materials under coupled mechano-electrostatic modulation.

Enhanced Electrical Resistivity and Properties via Ion Bombardment of Ferroelectric Thin Films.

A novel approach to on-demand improvement of electronic properties in complex-oxide ferroelectrics is demonstrated whereby ion bombardment - commonly used in classic semiconductor materials - is applied to the PbTiO3 system. The result is deterministic reduction in leakage currents by 5 orders of magnitude, improved ferroelectric switching, and unprecedented insights into the nature of defects and intergap state evolution in these materials.

New modalities of strain-control of ferroelectric thin films.

Ferroelectrics, with their spontaneous switchable electric polarization and strong coupling between their electrical, mechanical, thermal, and optical responses, provide functionalities crucial for a diverse range of applications. Over the past decade, there has been significant progress in epitaxial strain engineering of oxide ferroelectric thin films to control and enhance the nature of ferroelectric order, alter ferroelectric susceptibilities, and to create new modes of response which can be harnessed for various applications. This review aims to cover some of the most important discoveries in strain engineering over the past decade and highlight some of the new and emerging approaches for strain control of ferroelectrics. We discuss how these new approaches to strain engineering provide promising routes to control and decouple ferroelectric susceptibilities and create new modes of response not possible in the confines of conventional strain engineering. To conclude, we will provide an overview and prospectus of these new and interesting modalities of strain engineering helping to accelerate their widespread development and implementation in future functional devices.

Large Flexoelectric Anisotropy in Paraelectric Barium Titanate.

The bending-induced polarization of barium titanate single crystals has been measured with an aim to elucidate the origin of the large difference between theoretically predicted and experimentally measured flexoelectricity in this material. The results indicate that part of the difference is due to polar regions (short-range order) that exist above T(C) and up to T*≈200-225 °C. Above T*, however, the flexovoltage coefficient still shows an unexpectedly large anisotropy for a cubic material, with (001)-oriented crystals displaying 10 times more flexoelectricity than (111)-oriented crystals. Theoretical analysis shows that this anisotropy cannot be a bulk property, and we therefore interpret it as indirect evidence for the theoretically predicted but experimentally elusive contribution of surface piezoelectricity to macroscopic bending-induced polarization.