Ferroelectric materials provide a useful model system to explore the jerky, highly nonlinear dynamics of elastic interfaces in disordered media. The distribution of nanoscale switching event sizes is studied in two $\mathrm{Pb}\left({\mathrm{Zr_{}}_{\mathrm{0.2}}}{\mathrm{Ti_{}}_{\mathrm{0.8}}}\right){\mathrm{O_{}}_{\mathrm{3}}}$ thin films with different disorder landscapes using piezoresponse force microscopy. While the switching event statistics show the expected power-law scaling, significant variations in the value of the scaling exponent $\tau$ are seen, possibly as a consequence of the different intrinsic disorder landscapes in the samples and of further alterations under high tip bias applied during domain writing. Importantly, higher exponent values (1.98–2.87) are observed when crackling statistics are acquired only for events occurring in the creep regime. The exponents are systematically lowered when all events across both creep and depinning regimes are considered—the first time such a distinction is made in studies of ferroelectric materials. These results show that distinguishing the two regimes is of crucial importance, significantly affecting the exponent value and potentially leading to incorrect assignment of universality class.

The ability to manipulate domains underpins function in applications of ferroelectrics. While there have been demonstrations of controlled nanoscale manipulation of domain structures to drive emergent properties, such approaches lack an internal feedback loop required for automatic manipulation. Here, using a deep sequence-to-sequence autoencoder we automate the extraction of latent features of nanoscale ferroelectric switching from piezoresponse force spectroscopy of tensile-strained PbZr_0.2Ti_0.8O₃ with a hierarchical domain structure. We identify characteristic behavior in the piezoresponse and cantilever resonance hysteresis loops, which allows for the classification and quantification of nanoscale-switching mechanisms. Specifically, we identify elastic hardening events which are associated with the nucleation and growth of charged domain walls. This work demonstrates the efficacy of unsupervised neural networks in learning features of a material’s physical response from nanoscale multichannel hyperspectral imagery and provides new capabilities in leveraging in operando spectroscopies that could enable the automated manipulation of nanoscale structures in materials.

Temperature‐ and electric‐field‐induced structural transitions in a polydomain ferroelectric can have profound effects on its electrothermal susceptibilities. Here, the role of such ferroelastic domains on the pyroelectric and electrocaloric response is experimentally investigated in thin films of the tetragonal ferroelectric PbZr_0.2Ti_0.8O₃. By utilizing epitaxial strain, a rich set of ferroelastic polydomain states spanning a broad thermodynamic phase space are stabilized. Using temperature‐dependent scanning‐probe microscopy, X‐ray diffraction, and high‐frequency phase‐sensitive pyroelectric measurements, the propensity of domains to reconfigure under a temperature perturbation is quantitatively studied. In turn, the “extrinsic” contributions to pyroelectricity exclusively due to changes between the ferroelastic domain population is elucidated as a function of epitaxial strain. Further, using highly sensitive thin‐film resistive thermometry, direct electrocaloric temperature changes are measured on these polydomain thin films for the first time. The results demonstrate that temperature‐ and electric‐field‐driven domain interconversion under compressive strain diminish both the pyroelectric and the electrocaloric effects, while both these susceptibilities are enhanced due to the exact‐opposite effect from the extrinsic contributions under tensile strain.

The ability to control thin-film growth has led to advances in our understanding of fundamental physics as well as to the emergence of novel technologies. However, common thin-film growth techniques introduce a number of limitations related to the concentration of defects on film interfaces and surfaces that limit the scope of systems that can be produced and studied experimentally. Here, we developed an ion-beam based subtractive fabrication process that enables creation and modification of thin films with pre-defined thicknesses. To accomplish this we transformed a multimodal imaging platform that combines time-of-flight secondary ion mass spectrometry with atomic force microscopy to a unique fabrication tool that allows for precise sputtering of the nanometer-thin layers of material. To demonstrate fabrication of thin-films with in situ feedback and control on film thickness and functionality we systematically studied thickness dependence of ferroelectric switching of lead-zirconate-titanate, within a single epitaxial film. Our results demonstrate that through a subtractive film fabrication process we can control the piezoelectric response as a function of film thickness as well as improve on the overall piezoelectric response versus an untreated film.

Polarization switching is a fundamental feature of ferroelectric materials, enabling a plethora of applications and captivating the attention of the scientific community for over half a century. Many previous studies considered ferroelectric switching as a purely physical process, whereas polarization is fully controlled by the superposition of electric fields. However, screening charge is required for thermodynamic stability of the single domain state that is of interest in many technological applications. The screening process has always been assumed to be fast; thus, the rate-limiting phenomena were believed to be domain nucleation and domain wall dynamics. In this manuscript, we demonstrate that polarization switching under an atomic force microscopy tip leads to reversible ionic motion in the top 3 nm of PbZr_0.2Ti_0.8O₃ surface layer. This evidence points to a strong chemical component to a process believed to be purely physical and has major implications for understanding ferroelectric materials, making ferroelectric devices, and interpreting local ferroelectric switching.

Electric-field switching of polarization is the building block of a wide variety of ferroelectric devices. In turn, understanding the factors affecting ferroelectric switching and developing routes to control it are of great technological significance. This work provides systematic experimental evidence of the role of defects in affecting ferroelectric-polarization switching and utilizes the ability to deterministically create and spatially locate point defects in PbZr_0.2Ti_0.8O₃ thin films via focused-helium-ion bombardment and the subsequent defect-polarization coupling as a knob for on-demand control of ferroelectric switching (e.g., coercivity and imprint). At intermediate ion doses (0.22-2.2×10¹⁴ ions cm^-2), the dominant defects (isolated point defects and small clusters) show a weak interaction with domain walls (pinning potentials from 200-500 K MV cm^-1), resulting in small and symmetric changes in the coercive field. At high doses (0.22-1 x 10¹⁵ ions cm^-2), on the other hand, the dominant defects (larger defect complexes and clusters) strongly pin domain-wall motion (pinning potentials from 500 to 1600 K MV cm^-1), resulting in a large increase in the coercivity and imprint, and a reduction in the polarization. This local control of ferroelectric switching provides a route to produce novel functions; namely, tunable multiple polarization states, rewritable pre-determined 180° domain patterns, and multiple zero-field piezoresponse and permittivity states. Such an approach opens up pathways to achieve multilevel data storage and logic, nonvolatile self-sensing shape-memory devices, and nonvolatile ferroelectric field-effect transistors.

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. 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.

A range of modern applications require large and tunable dielectric, piezoelectric or pyroelectric response of ferroelectrics. Such effects are intimately connected to the nature of polarization and how it responds to externally applied stimuli. Ferroelectric susceptibilities are, in general, strongly temperature dependent, diminishing rapidly as one transitions away from the ferroelectric phase transition (T_C). In turn, researchers seek new routes to manipulate polarization to simultaneously enhance susceptibilities and broaden operational temperature ranges. Here, we demonstrate such a capability by creating composition and strain gradients in Ba_1−xSr_xTiO₃ films which result in spatial polarization gradients as large as 35 μC cm⁻² across a 150 nm thick film. These polarization gradients allow for large dielectric permittivity with low loss (ɛ_r≈775, tan δ<0.05), negligible temperature-dependence (13% deviation over 500 °C) and high-dielectric tunability (greater than 70% across a 300 °C range). The role of space charges in stabilizing polarization gradients is also discussed.

Ginzburg-Landau-Devonshire models are used to explore ferroelectric phases and pyroelectric coefficients of symmetric free-standing, thin-film trilayer heterostructurescomposed of a ferroelectric and two identical non-ferroelectric layers. Using BaTiO₃ as a model ferroelectric, we explore the influence of temperature, in-plane misfit strain, and the non-ferroelectric layer (including effects of elastic compliance and volume fraction) on the phase evolution in the ferroelectric. The resulting phase diagram reveals six stable phases, two of which are not observed for thin films on semi-infinite cubic substrates. From there, we focus on heterostructures with non-ferroelectric layers of commonly available scandate materials which are widely used as substrates for epitaxial growth. Again, six phases with volatile phase boundaries are found in the phase diagram for the NdScO₃/BaTiO₃/NdScO₃trilayerheterostructures. The evolution of polarization and pyroelectric coefficients in the free-standing NdScO₃ trilayer heterostructures is discussed with particular attention to the role that heterostructure design plays in influencing the phase evolution and temperature-dependence with a goal of creating enhanced pyroelectric response and advantages over traditional thin-film heterostructures.

Despite extensive studies on the effects of epitaxial strain on the evolution of the lattice and properties of materials, considerably less work has explored the impact of strain on growth dynamics. In this work, we demonstrate a growth-mode transition from 2D-step flow to self-organized, nanoscale 3D-island formation in PbZr_0.2Ti_0.8O₃/SrRuO₃/SrTiO₃ (001) heterostructures as the kinetics of the growth process respond to the evolution of strain. With increasing heterostructure thickness and misfit dislocation formation at the buried interface, a periodic, modulated strain field is generated that alters the adatom binding energy and, in turn, leads to a kinetic instability that drives a transition from 2D growth to ordered, 3D-island formation. The results suggest that the periodically varying binding energy can lead to inhomogeneous adsorption kinetics causing preferential growth at certain sites. This, in conjunction with the presence of an Ehrlich-Schwoebel barrier, gives rise to long-range, periodically-ordered arrays of so-called “wedding cake” 3D nanostructures which self-assemble along the [100] and [010].

Domains and domain walls are critical in determining the response of ferroelectrics, and the ability to controllably create, annihilate, or move domains is essential to enable a range of next-generation devices. Whereas electric-field control has been demonstrated for ferroelectric 180° domain walls, similar control of ferroelastic domains has not been achieved. Here, using controlled composition and strain gradients, we demonstrate deterministic control of ferroelastic domains that are rendered highly mobile in a controlled and reversible manner. Through a combination of thin-film growth, transmission-electron-microscopy-based nanobeam diffraction and nanoscale band-excitation switching spectroscopy, we show that strain gradients in compositionally graded PbZr_1−xTi_xO₃ heterostructures stabilize needle-like ferroelastic domains that terminate inside the film. These needle-like domains are highly labile in the out-of-plane direction under applied electric fields, producing a locally enhanced piezoresponse. This work demonstrates the efficacy of novel modes of epitaxy in providing new modalities of domain engineering and potential for as-yet-unrealized nanoscale functional devices.

Epitaxial strain has been widely used to tune crystal and domain structures in ferroelectric thin films. New avenues of strain engineering based on varying the composition at the nanometer scale have been shown to generate symmetry breaking and large strain gradients culminating in large built-in potentials. In this work, we develop routes to deterministically control these built-in potentials by exploiting the interplay between strain gradients, strain accommodation, and domain formation in compositionally graded PbZr_1–xTi_xO₃ heterostructures. We demonstrate that variations in the nature of the compositional gradient and heterostructure thickness can be used to control both the crystal and domain structures and give rise to nonintuitive evolution of the built-in potential, which does not scale directly with the magnitude of the strain gradient as would be expected. Instead, large built-in potentials are observed in compositionally-graded heterostructures that contain (1) compositional gradients that traverse chemistries associated with structural phase boundaries (such as the morphotropic phase boundary) and (2) ferroelastic domain structures. In turn, the built-in potential is observed to be dependent on a combination of flexoelectric effects (i.e., polarization–strain gradient coupling), chemical-gradient effects (i.e., polarization–chemical potential gradient coupling), and local inhomogeneities (in structure or chemistry) that enhance strain (and/or chemical potential) gradients such as areas with nonlinear lattice parameter variation with chemistry or near ferroelastic domain boundaries. Regardless of origin, large built-in potentials act to suppress the dielectric permittivity, while having minimal impact on the magnitude of the polarization, which is important for the optimization of these materials for a range of nanoapplications from vibrational energy harvesting to thermal energy conversion and beyond.

Synthesis of compositionally graded versions of PbZr_1‐xTi_xO₃ thin films results in unprecedented strains (as large as ≈4.5 × 10⁵ m⁻¹) and correspondingly unexpected crystal structures, ferroelectric domain structures, and properties. This includes the observation of built‐in electric fields in films as large as 200 kV/cm. Compositional and strain gradients could represent a new direction of strain‐control of materials.

We investigate the origin of large built-in electric fields that have been reported in compositionally graded ferroelectric thin films using PbZr_1-xTi_xO₃ as a model system. We show that the built-in electric fields that cause a voltage offset in the hysteresis loops are dependent on strain relaxation (through misfit dislocation formation) and the accompanying polarization distribution within the material. Using a Ginzburg-Landau-Devonshire phenomenological formalism that includes the effects of compositional gradients, mechanical strain relaxation, and flexoelectricity, we demonstrate that the flexoelectric coupling between the out-of-plane polarization and the gradient of the epitaxial strain throughout the thickness of the film, not other inhomogeneities (i.e., composition or polarization), is directly responsible for the observed voltage offsets. This work demonstrates the importance of flexoelectricity in influencing the properties of ferroelectric thin films and provides a powerful mechanism to control their properties.

Pyroelectric materials have been widely used for a range of thermal-related applications including thermal imaging/sensing, waste heat energy conversion, and electron emission. In general, the figures of merit for applications of pyroelectric materials are proportional to the pyroelectric coefficient and inversely proportional to the dielectric permittivity. In this context, we explore single-layer and compositionally graded PbZr_1–xTi_xO₃ thin-film heterostructures as a way to independently engineer the pyroelectric coefficient and dielectric permittivity of materials and increase overall performance. Compositional gradients in thin films are found to produce large strain gradients which generate large built-in potentials in the films that can reduce the permittivity while maintaining large pyroelectric response. Routes to enhance the figures of merit of pyroelectric materials by 3–12 times are reported, and comparisons to standard materials are made.

We have investigated the contribution of 90° domain walls and thermal expansion mismatch to pyroelectricity in PbZr_0.2Ti_0.8O₃ thin films. The first phenomenological models to include extrinsic and secondary contributions to pyroelectricity in polydomain films predict significant extrinsic contributions (arising from the temperature-dependent motion of domain walls) and large secondary contributions (arising from thermal expansion mismatch between the film and the substrate). Phase-sensitive pyroelectric current measurements are applied to model thin films for the first time and reveal a dramatic increase in the pyroelectric coefficient with increasing fraction of in-plane oriented domains and thermal expansion mismatch.