Illustration of a new high-temperature hard-mask process based on traditional lithography and selective wet-etching of MgO. The hard mask is compatible with standard nano-lithography techniques and heat treatments in excess of 1000 °C. Here, this technique is applied to produce temperature-stable contacts that give rise to low leakage, improved fatigue properties, and excellent high-temperature stability in ferroelectric thin-film capacitors.

In ferroelectrics, the effect of domain wall motion on properties has been widely studied, but non-motional or stationary contributions from the volume of material within the domain wall itself has received less attention. Here we report the measurement of stationary domain wall contributions to permittivity in PbZr(0.2)Ti(0.8)O₃ films. Studies of (001)-, (101)- and (111)-oriented epitaxial films reveal that (111)-oriented films, in which the motional domain wall contributions are frozen out, exhibit permittivity values approximately three times larger than the intrinsic response alone. This discrepancy can only be accounted for by considering a stationary contribution from the domain wall volume of the material that is 6-78 times larger than the bulk response, and is consistent with predictions of the enhancement of susceptibilities within 90° domain walls. This work offers new insights into the microscopic origin of dielectric enhancement and provides a pathway to engineer the dielectric response of materials.

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.

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 PbZr0.2Ti0.8O3/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].

Chemical-alloying is demonstrated to stabilize the mixed-phase structure of highly strained epitaxial BiFeO 3/LaAlO 3 (001) heterostructures. Such mixed-phase structures are essential for the large electromechanical responses (4%-5% strains under applied electric field); however, films with thickness exceeding 250 nm undergo an epitaxial breakdown to a non-epitaxial bulk-like rhombohedral-phase. Such an irreversible transformation of the mixed-phase structure limits the magnitude of the net surface displacement associated with these field-induced phase transformations. Using high-resolution x-ray diffraction reciprocal space mapping and scanning-probe-based studies, we show that chemical-alloying of BiFeO 3 thin films can stabilize these mixed-phase structures and delay the onset of epitaxial breakdown. © 2012 American Institute of Physics.

The local compositional heterogeneity associated with the short-range ordering of Mg and Nb in PbMg1/3Nb2/3O3 (PMN) is correlated with its characteristic relaxor ferroelectric behavior. Fully ordered PMN is not prepared as a bulk material. This work examines the relaxor behavior in PMN thin films grown at temperatures below 1073 K by artificially reducing the degree of disorder via synthesis of heterostructures with alternate layers of Pb(Mg2/3Nb1/3)O3 and PbNbO3, as suggested by the random-site model. 100 nm thick, phase-pure films are grown epitaxially on (111) SrTiO3 substrates using alternate target timed pulsed-laser deposition of Pb(Mg2/3Nb1/3)O3 and PbNbO3 targets with 20% excess Pb. Selected area electron diffraction confirms the emergence of (1/2, 1/2, 1/2) superlattice spots with randomly distributed ordered domains as large as ≈150 nm. These heterostructures exhibit a dielectric constant of 800, loss tangents of ≈0.03 and 2× remanent polarization of ≈11 µC cm−2 at room temperature. Polarization–electric field hysteresis loops, Rayleigh data, and optical second-harmonic generation measurements are consistent with the development of ferroelectric domains below 140 K. Temperature-dependent permittivity measurements demonstrate reduced frequency dispersion compared to short range ordered PMN films. This work suggests a continuum between normal and relaxor ferroelectric behavior in the engineered PMN thin films.

We present the temperature- and thickness-dependent structural and morphological evolution of strain-induced transformations in highly strained epitaxial BiFeO 3 films deposited on LaAlO 3 (001) substrates. Using high-resolution x-ray diffraction and temperature-dependent scanning-probe-based studies, we observe a complex temperature- and thickness-dependent evolution of phases in this system. A thickness-dependent transformation from a single, monoclinically distorted, tetragonal-like phase to a complex mixed-phase structure in films with thicknesses up to ∼200 nm is the consequence of a strain-induced spinodal instability in the BiFeO 3/LaAlO 3 system. Additionally, a breakdown of this strain-stabilized metastable mixed-phase structure to nonepitaxial microcrystallites of the parent rhombohedral structure of BiFeO 3 is observed to occur at a critical thickness of ∼300 nm. We further propose a mechanism for this abrupt breakdown that provides insight into the competing nature of the phases in this system. © 2012 American Physical Society.

Synthesis of compositionally graded versions of PbZr(1-x)Ti(x)O3 thin films results in unprecedented strains (as large as ≈4.5 × 10(5) 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 report thermal to electrical energy conversion from a 150nm thick BaTiO3 film using pyroelectric cycles at 1kHz. A microfabricated platform enables temperature and electric field control with temporal resolution near 1μs. The rapid electric field changes as high as 11×105kV/cm-s, and temperature change rates as high as 6×105K/s allow exploration of pyroelectric cycles in a previously unexplored operating regime. We investigated the effect of phase difference between electric field and temperature cycles, and electric field and temperature change rates on the electrical energy generated from thermal-electrical cycles based on the pyroelectric Ericsson cycle. Complete thermodynamic cycles are possible up to the highest cycle rates tested here, and the energy density varies significantly with phase shifts between temperature and electric field waveforms. This work could facilitate the design and operation of pyroelectric cycles at high cycle rates, and aid in the design of new pyroelectric systems.

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.