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.

We explore the effect of growth conditions on the cation and anion chemistry, electrical leakage, conduction mechanisms, and ferroelectric and dielectric behavior of BiFeO3. Although it is possible to produce single-phase, coherently strained films in all cases, small variations in the pulsed-laser deposition growth process, specifically the laser repetition rate and target composition, result in films with chemistries ranging from 10% Bi-deficiency to 4% Bi-excess and films possessing Bi gradients as large a 6% across the film thickness. Corresponding variations and gradients in the O chemistry are also observed. As a result of the varying film chemistry, marked differences in surface and domain morphology are observed wherein Bi-deficiency stabilizes atomically smooth surfaces and ordered stripe domains. Subsequent investigation of the current–voltage response reveals large differences in leakage current density arising from changes in both the overall stoichiometry and gradients. In turn, the film stoichiometry drives variations in the dominant conduction mechanism including examples of Schottky, Poole–Frenkel, and modified Poole–Frenkel emission depending on the film chemistry. Finally, slightly Bi-excess films are found to exhibit the best low-frequency ferroelectric and dielectric response while increasing Bi-deficiency worsens the low-frequency ferroelectric performance and reduces the dielectric permittivity.

Epitaxial strain can be used to tune the properties of complex oxides with perovskite structure. Beyond just lattice mismatch, the use of octahedral rotation mismatch at heterointerfaces could also provide an effective route to manipulate material properties. Here, we examine the evolution of the structural motif (i.e., lattice parameters, symmetry, and octahedral rotations) of SrRuO3 films grown on substrates engineered to have the same lattice parameters, but different octahedral rotations. SrRuO3 films grown on SrTiO3 (001) (no octahedral rotations) and GdScO3-buffered SrTiO3 (001) (with octahedral rotations) substrates are found to exhibit monoclinic and tetragonal symmetry, respectively. Electrical transport and magnetic measurements reveal that the tetragonal films exhibit higher resistivity, lower magnetic Curie temperatures, and more isotropic magnetism as compared to those with monoclinic structure. Synchrotron-based quantification of the octahedral rotation network reveals that the tilting pattern in both film variants is the same (albeit with slightly different magnitudes of in-plane rotation angles). The abnormal rotation pattern observed in tetragonal SrRuO3 indicates a possible decoupling between the internal octahedral rotation and lattice symmetry, which could provide new opportunities to engineer thin-film structure and properties.

Self-assembly via nanoscale phase separation offers an elegant route to fabricate nanocomposites with physical properties unattainable in single-component systems. One important class of nanocomposites are optical metamaterials which exhibit exotic properties and lead to opportunities for agile control of light propagation. Such metamaterials are typically fabricated via expensive and hard-to-scale top-down processes requiring precise integration of dissimilar materials. In turn, there is a need for alternative, more efficient routes to fabricate large-scale metamaterials for practical applications with deep-subwavelength resolution. Here, we demonstrate a bottom-up approach to fabricate scalable nanostructured metamaterials via spinodal decomposition. To demonstrate the potential of such an approach, we leverage the innate spinodal decomposition of the VO2–TiO2 system, the metal-to-insulator transition in VO2, and thin-film epitaxy, to produce self-organized nanostructures with coherent interfaces and a structural unit cell down to 15 nm (tunable between horizontally and vertically aligned lamellae) wherein the iso-frequency surface is temperature-tunable from elliptic to hyperbolic dispersion producing metamaterial behavior. These results provide an efficient route for the fabrication of nanostructured metamaterials and other nanocomposites for desired functionalities.Keywords: epitaxial thin films; metamaterials; nanoscale phase separation; self-assembly; spinodal decomposition; VO2

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.

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.Keywords: compositionally-graded heterostructures; ferroelectrics; PbZr1−xTixO3; permittivity; thin films;

Next-generation devices will rely on exotic functional properties not found in traditional systems. One class of materials of particular interest for applications are those possessing metal-to-insulator transitions (MITs). In this work, we probe the relationship between variations in the growth process, subsequent variations in cation stoichiometry, and the MIT in NdNiO3 thin films. Slight variations in the growth conditions, in particular the laser fluence, during pulsed-laser deposition growth of NdNiO3 produces films that are both single-phase and coherently strained to a range of substrates despite possessing as much as 15% Nd-excess. Subsequent study of the temperature-dependence of the electronic transport reveals dramatic changes in both the onset and magnitude of the resistivity change at the MIT with increasing cation nonstoichiometry giving rise to a decrease (and ultimately a suppression) of the transition and the magnitude of the resistivity change. From there, the electronic transport of nearly ideal NdNiO3 thin films are studied as a function of epitaxial strain, thickness, and orientation. Overall, transitioning from tensile to compressive strain results in a systematic reduction of the onset and magnitude of the resistivity change across the MIT, thinner films are found to possess sharper MITs with larger changes in the resistivity at the transition, and (001)-oriented films exhibit sharper and larger MITs as compared to (110)- and (111)-oriented films as a result of highly anisotropic in-plane transport in the latter.Keywords: epitaxial thin films; nickelates; stoichiometry; strain; transport