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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 PbZr0.2Ti0.8O3 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.

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.

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 PbZr1-xTixO3 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.

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 PbZr1-xTixO3 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.