Critical scattering and incommensurate phase transition in antiferroelectric PbZrO3 under pressure.

Antiferroelectric lead zirconate is the key ingredient in modern ferroelectric and piezoelectric functional solid solutions. By itself it offers opportunities in new-type non-volatile memory and energy storage applications. A highly useful and scientifically puzzling feature of this material is the competition between the ferro- and antiferroelectric phases due to their energetic proximity, which leads to a challenge in understanding of the critical phenomena driving the formation of the antiferroelectric structure. We show that application of hydrostatic pressure drastically changes the character of critical lattice dynamics and enables the soft-mode-driven incommensurate phase transition sequence in lead zirconate. In addition to the long known cubic and antiferroelectric phases we identify the new non-modulated phase serving as a bridge between the cubic and the incommensurate phases. The pressure effect on ferroelectric and incommensurate critical dynamics shows that lead zirconate is not a single-instability-driven system.

Velocity Control of 180° Domain Walls in Ferroelectric Thin Films by Electrode Modification.

The velocity of individual 180° domain walls in thin ferroelectric films of PbZr0.1Ti0.9O3 is strongly dependent on the thickness of the top Pt electrode made by electron-beam induced deposition (EBID). We show that when the thickness is varied in the range <100 nm the domain wall velocity is seen to change by 7 orders of magnitude. We attribute this huge range of velocities to the similarly large range of resistivities for the EBID Pt electrode as extrapolated from four-point probe measurements. The domain wall motion is governed by the supply of charges to the domain wall, determined by the top electrode resistivity, and which is described using a modified Stefan Problem model. This has significant implications for the feasibility of ferroelectric domain wall nanoelectronics, wherein the speed of operation will be limited by the maximum velocity of the propagating domain wall front. Furthermore, by introducing sections of either modified thickness or width along the length of a "line" electrode, the domain wall velocity can be changed at these locations, opening up possibilities for dynamic regimes.

Controlling domain wall motion in ferroelectric thin films.

Domain walls in ferroic materials have attracted significant interest in recent years, in particular because of the unique properties that can be found in their vicinity. However, to fully harness their potential as nanoscale functional entities, it is essential to achieve reliable and precise control of their nucleation, location, number and velocity. Here, using piezoresponse force microscopy, we show the control and manipulation of domain walls in ferroelectric thin films of Pb(Zr,Ti)O3 with Pt top electrodes. This high-level control presents an excellent opportunity to demonstrate the versatility and flexibility of ferroelectric domain walls. Their position can be controlled by the tuning of voltage pulses, and multiple domain walls can be nucleated and handled in a reproducible fashion. The system is accurately described by analogy to the classical Stefan problem, which has been used previously to describe many diverse systems and is here applied to electric circuits. This study is a step towards the realization of domain wall nanoelectronics utilizing ferroelectric thin films.

Elastic coupling between nonferroelastic domain walls.

We reveal a strong elastic interaction between nonferroelastic domain walls in ferroelectric thin films. This interaction, having no analogue in bulk materials, is governed by elastic fields that are associated with the domain walls and extends to distances comparable to the film thickness. Such elastic widening of the nonferroelastic domain walls is shown to be particularly strong in common ferroelectric perovskites. The results are especially relevant for the control of domain wall propagation and the understanding of polarization dynamics.

Fundamentals of flexoelectricity in solids.

The flexoelectric effect is the response of electric polarization to a mechanical strain gradient. It can be viewed as a higher-order effect with respect to piezoelectricity, which is the response of polarization to strain itself. However, at the nanoscale, where large strain gradients are expected, the flexoelectric effect becomes appreciable. Besides, in contrast to the piezoelectric effect, flexoelectricity is allowed by symmetry in any material. Due to these qualities flexoelectricity has attracted growing interest during the past decade. Presently, its role in the physics of dielectrics and semiconductors is widely recognized and the effect is viewed as promising for practical applications. On the other hand, the available theoretical and experimental results are rather contradictory, attesting to a limited understanding in the field. This review paper presents a critical analysis of the current knowledge on the flexoelectricity in common solids, excluding organic materials and liquid crystals.

The origin of antiferroelectricity in PbZrO3.

Antiferroelectrics are essential ingredients for the widely applied piezoelectric and ferroelectric materials: the most common ferroelectric, lead zirconate titanate is an alloy of the ferroelectric lead titanate and the antiferroelectric lead zirconate. Antiferroelectrics themselves are useful in large digital displacement transducers and energy-storage capacitors. Despite their technological importance, the reason why materials become antiferroelectric has remained allusive since their first discovery. Here we report the results of a study on the lattice dynamics of the antiferroelectric lead zirconate using inelastic and diffuse X-ray scattering techniques and the Brillouin light scattering. The analysis of the results reveals that the antiferroelectric state is a 'missed' incommensurate phase, and that the paraelectric to antiferroelectric phase transition is driven by the softening of a single lattice mode via flexoelectric coupling. These findings resolve the mystery of the origin of antiferroelectricity in lead zirconate and suggest an approach to the treatment of complex phase transitions in ferroics.

Ferroelectricity in asymmetric metal-ferroelectric-metal heterostructures: a combined first-principles-phenomenological approach.

We present an approach to the size effect problem in ferroelectric-electrode systems which combines first-principles calculations and phenomenological theory. The parameters of the model can be extracted from calculations on ultrathin films, while experimentally verifiable predictions can be made on thick films. We illustrate the approach for the case of SrRuO3/BaTiO3/SrRuO3 heterostructures with asymmetric interfaces. This enables us to provide a quantitative description of a number of manifestations of such asymmetry in films of technologically meaningful thickness.

In-plane and out-of-plane ferroelectric instabilities in epitaxial SrTiO3 films.

The in-plane and out-of-plane ferroelectric instabilities in compressed (100)-epitaxial SrTiO3 films were examined by infrared reflection spectroscopy. The strongly stiffened in-plane soft mode frequency softened very slowly on cooling. On the other hand, the silent mode appeared at around 150 K, indicating an out-of-plane ferroelectric transition. This behavior points to a split of in-plane and out-of-plane ferroelectric instability temperatures due to the lowered symmetry of the SrTiO3 lattice caused by mechanical misfit strain. Infrared spectroscopy provides a possibility to detect such an effect in the strained epitaxial ferroelectric films.

Ionic polarizability of conductive metal oxides and critical thickness for ferroelectricity in BaTiO3.

We report a first-principles investigation of ultrathin BaTiO(3) films with SrRuO(3) electrodes. We find that the ionic relaxations in the metal-oxide electrode play a crucial role in stabilizing the ferroelectric phase. Comparison with frozen-phonon calculations shows that the degree of softness of the SrRuO(3) lattice has an essential impact on the screening of ferroelectric polarization in BaTiO(3). The critical thickness for ferroelectricity in BaTiO(3) is found to be 1.2 nm. The results of our calculations provide a possible explanation for the beneficial impact of oxide electrodes on the switching and dielectric properties of ferroelectric capacitors.

Surface-stimulated nucleation of reverse domains in ferroelectrics.

We present a model for reverse domain nucleation in ferroelectrics, which takes into account ferroelectric-electrode coupling in both homogeneous and random cases. The model provides a solution to the coercivity paradox--i.e., the large discrepancy between the observed and predicted coercive fields, common to many systems. We demonstrate the possibility of not thermally activated nucleation of reverse domains. We find that small inhomogeneities in the ferroelectric-electrode interface may lead to an exponentially wide spectrum of waiting times for switching. The model predicts that switching is facilitated near morphotropic phase boundaries in perovskite-type ferroelectrics.

Room-temperature ferroelectricity in strained SrTiO3.

Systems with a ferroelectric to paraelectric transition in the vicinity of room temperature are useful for devices. Adjusting the ferroelectric transition temperature (T(c)) is traditionally accomplished by chemical substitution-as in Ba(x)Sr(1-x)TiO(3), the material widely investigated for microwave devices in which the dielectric constant (epsilon(r)) at GHz frequencies is tuned by applying a quasi-static electric field. Heterogeneity associated with chemical substitution in such films, however, can broaden this phase transition by hundreds of degrees, which is detrimental to tunability and microwave device performance. An alternative way to adjust T(c) in ferroelectric films is strain. Here we show that epitaxial strain from a newly developed substrate can be harnessed to increase T(c) by hundreds of degrees and produce room-temperature ferroelectricity in strontium titanate, a material that is not normally ferroelectric at any temperature. This strain-induced enhancement in T(c) is the largest ever reported. Spatially resolved images of the local polarization state reveal a uniformity that far exceeds films tailored by chemical substitution. The high epsilon(r) at room temperature in these films (nearly 7,000 at 10 GHz) and its sharp dependence on electric field are promising for device applications.