Ginzburg-Landau-Devonshire models are used to explore ferroelectric phases and pyroelectric coefficients of symmetric free-standing, thin-film trilayer heterostructures composed 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/NdScO3 trilayerheterostructures. 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.

The orientation-dependent equilibrium ferroelectric domain structures and dielectric properties of polydomain PbZr1-xTixO3 thin films are investigated using a phenomenological Ginzburg-Landau-Devonshire thermodynamic model. We develop and describe three-dimensional polydomain models for (001)-, (101)-, and (111)-oriented films and explore the evolution of the structure and dielectric permittivity of the system as a function of epitaxial strain across the composition range 0.5 ≤ x ≤ 1.0. Our studies reveal that the film orientation, epitaxial strain, and composition can combine in unexpected ways to drive exotic phase stability and transformations which have intriguing implications for the properties. In particular, in (101)- and (111)-oriented films, the application of epitaxial strains along non-〈001〉-type crystallographic directions significantly reduces the stability range of the parent tetragonal phase [which is dominant in (001)-oriented films] and results in a variety of new symmetries. We also observe that the film orientation can be used to tune the relative fraction of intrinsic (i.e., within a domain) and extrinsic (i.e., from domain wall motion) contributions to the dielectric permittivity. Ultimately these studies reveal how composition, epitaxial strain, and film orientation provide for comprehensive control of the structure and properties of ferroelectrics.

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.