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Organometallic lead halide perovskites are highly efficient materials for solar cells and other optoelectronic applications due to their high quantum efficiency and exceptional semiconducting properties. A peculiarity of these perovskites is the substantial ionic motion under external forces. Here, we reveal that electric field-and light-induced ionic motion in MAPbX3 crystals (X=Cl, Br, I and MA=CH3NH3) leads to unexpected piezoelectric-like response, an order of magnitude larger than in ferroelectric perovskite oxides. The nominal macroscopic symmetry of the crystals is broken by redistribution of ionic species, which can be controlled deterministically by light and electric field. The revealed piezoelectric response is possibly present in other materials with significant ionic activity but the unique feature of organometallic perovskites is the strong effect on the piezoelectric response of interplay of ionic motion (MA+ and X-1) and photoelectrons generated with illumination.

The polarization and strain response of ferroelectric materials at fields below the macroscopic coercive field is of a paramount importance for the operation of many electronic devices. The response of real ferroelectric and related materials is in general complex and difficult to interpret. The reason for this is that many processes in a ferroelectric material contribute to its properties, often concurrently. Examples include motion of ferroelectric and ferroelastic domains, presence of domains within domains, dynamics of different types of polar nano-entities, interaction of polar nano-entities (e.g., polar nanoregions in relaxors) with the strain and polarization within domains, motion of defects and rearrangement of defect clusters and their interaction with polarization and strain. One signature of these processes is nonlinearity of the strain and polarization. Most ferroelectrics exhibit nonlinear response at all practical field levels meaning that the apparent material coefficients depend on the amplitude of the driving excitation. In this paper we show that an investigation of nonlinear behavior is a sensitive way to study various mechanisms operating in dielectric and piezoelectric materials. We review the basic formalism of the nonlinear description of polarization and strain, give a physical interpretation of different terms and illustrate this approach on numerous examples of relaxors, relaxor ferroelectrics, hard and soft ferroelectrics, and morphotropic phase boundary compositions. An experimental approach based on a lock-in technique that is well-suited for such studies is also discussed., Comment: main text 35 pages, 8 figures; supplementary material 3 pages and 5 figures

Ferroelectric materials, upon electric field biasing, display polarization discontinuities known as Barkhausen jumps, a subclass of a more general phenomenon known as crackling noise. Herein, we follow at the nanoscale the motion of 90 degree needle domains induced by an electric field applied in the polarization direction of the prototypical ferroelectric BaTiO3, inside a transmission electron microscope. The nature of motion and periodicity of Barkhausen pulses leads to real-time visualization of distinctive interaction mechanisms of the domains with each other but without coming into contact, a mechanism that has not been observed before, or/and with the lattice where the domain walls appear to be moving through the dielectric medium relatively freely, experiencing weak Peierls-like potentials. Control over the kinetics of ferroelastic domain wall motion can lead to novel nanoelectronic devices pertinent to computing and storage applications.

Macroscopic polarity and its dynamic response to external electric fields and temperature in the nominally ergodic relaxor phase of pristine lead magnesium niobate crystals and ceramics, Pb(Mg1/3Nb2/3)O3 (PMN), were investigated. Dynamic pyroelectric measurements provide evidence for persistent macroscopic polarity of the samples. Annealing experiments below and above Burns temperature of polarized samples relate this polarity to the presence of polar nano entities and their dynamics. The dc electric field strength required for macroscopic polarization reversal is similar to the amplitude of the ac field where dynamic nonlinear dielectric permittivity reaches maximum. Consequently, the aforementioned maximum is related to the reorientation of polar nano entities. The results question the existence of an ergodic state in PMN below Burns temperature., Comment: 14 pages main text, 5 pages supplementary information

We report on the electric field response of 180 degree nanodomain walls in BaTiO$_3$ using in situ electrical biasing in transmission electron microscopy (TEM). The sample is biased on a micro-device designed for reliable testing whose key attributes are confirmed by finite element calculations. The presence of weakly charged zig-zag domain walls at room temperature is attributed to the geometric confinement of the device. The motion of the domain walls under the applied electric field allows to extract local P-E loops where distinct domain wall pinning in deep and random energy potential profiles, characteristic for hard and soft ferroelectrics, respectively, are observed. Hard domain wall pinning results in asymmetrical loops typical for "hard" ferroelectrics while the soft domain wall pinning follows Rayleigh-like behaviour. All effects are measured locally and directly from the imaged domain structure.

The nature of the "forbidden" local- and long-range polar order in nominally nonpolar paraelectric phases of ferroelectric materials has been an open question since the discovery of ferroelectricity in oxide perovskites (ABO3). A currently considered model suggests locally correlated displacements of B-site atoms along a subset of <111> cubic directions. Such offsite displacements have been confirmed experimentally, however, being essentially dynamic in nature they cannot account for the static nature of the symmetry-forbidden polarization implied by the macroscopic experiments. Here, in an atomically resolved study by aberration corrected scanning transmission electron microscopy (STEM) complemented by Raman spectroscopy, we reveal, directly visualize and quantitatively describe static, 2-4 nm large polar nanoclusters in the nominally nonpolar cubic phases of (Ba,Sr)TiO3 and BaTiO3. These results have implications on understanding of the atomic-scale structure of disordered materials, the origin of precursor states in ferroelectrics, and may help answering ambiguities on the dynamic-versus-static nature of nano-sized clusters., Comment: the main text and supplementary information

The dynamic dielectric nonlinearity of barium strontium titanate (Ba1-x,Srx)TiO3 ceramics is investigated in their paraelectric phase. With the goal to contribute to the identification of the mechanisms that govern the dielectric nonlinearity in this family, we analyze the amplitude and the phase angles of the first and the third harmonics of polarization. Our study shows that an interpretation of the field-dependent polarization in paraelectric (Ba1-x,Srx)TiO3 ceramics in terms of the Rayleigh-type dynamics is inadequate for our samples and that their nonlinear response rather resembles that observed in canonical relaxor Pb(Mg1/3Nb2/3)O3., Comment: published in: Sina Hashemizadeh and Dragan Damjanovic, Applied Physics Letters 110 (19), 192905 (2017)

BaTiO3 appears in cubic and hexagonal variants, both of which are centrosymmetric. Samples of cubic BaTiO3 are known to exhibit breaking of the centric symmetry locally and globally. It has been proposed that the local symmetry breaking originates in polar regions, the precursors of the ferroelectric phase. Origins of the macroscopic symmetry breaking, which are not well understood, have been previously tentatively correlated with inhomogeneities in the samples, such as strain gradients that may align or redistribute objects such as charged point defects or polar regions making material macroscopically polar. No such data are available for BaTiO3 with hexagonal symmetry. We compare dielectric, elastic, and pyroelectric properties of the two materials in polycrystalline form. In contrast to cubic BaTiO3, hexagonal BaTiO3 does not exhibit macroscopic pyroelectric response at room temperature. This is consistent with apparent absence of polar regions in the hexagonal material and the fact that in hexagonal BaTiO3 strain rather then polarization is the order parameter for the phase transition into ferroelectric-ferroelastic phase. The thermally stimulated currents measured in hexagonal and cubic BaTiO3, however, show that both materials exhibit noncentric macroscopic symmetry. This result supports the idea that extrinsic factors such as strain gradients, which are apparently common for both materials, may break the macroscopic symmetry, which may then lead to alignment and redistribution of polar regions or charged defects., Comment: accepted in Journal of Applied Physics

Oxygen octahedra tilting is a common structural phenomenon in perovskites and has been subject of intensive studies, particularly in rhombohedral Pb(Zr,Ti)O3 (PZT). Early reports suggest that the tilted octahedra may strongly affect the domain switching behavior, dielectric and piezoelectric properties of PZT ceramics. In a way similar to that proposed for tilts, however, charged defects, associated with oxygen vacancies, may also inhibit the motion of the domain walls, resulting macroscopically in pinched hysteresis loops and reduced piezoelectric response. Here, we revisit the early studies on rhombohedral PZT ceramics with tilted octahedra by considering a possible role of both tilts and charged defects on domain-wall motion. We show that the observed pinched hysteresis loops are likely associated with the presence of defect complexes containing charged oxygen vacancies, and not tilts as suggested in some cases. Regardless of the presence or absence of long-range ordered tilts in rhombohedral PZT, the effect of charged defects is also prominent in weak-field permittivity and piezoelectric properties, particularly at sub-Hz driving conditions where the conductivity, related to the motion of oxygen vacancies, gives rise to strong frequency dispersion., Comment: 8 figures

A centrosymmetric stress cannot induce a polar response in centric materials, piezoelectricity is, for example, possible only in non-centrosymmetric structures. An exception is meta-materials with shape asymmetry, which may be polarized by stress even when the material is centric. In this case the mechanism is flexoelectricity, which relates polarization to a strain gradient. The flexoelectric response scales inversely with size, thus a large effect is expected in nanoscale materials. Recent experiments in polycrystalline, centrosymmetric perovskites [e.g., (Ba,Sr)TiO3] have indicated values of flexoelectric coefficients that are orders of magnitude higher than theoretically predicted, promising practical applications based on bulk materials. We show that materials with unexpectedly large flexoelectric response exhibit breaking of the macroscopic centric symmetry through inhomogeneity induced by the high temperature processing. The emerging electro-mechanical coupling is significant and may help to resolve the controversy surrounding the large apparent flexoelectric coefficients in this class of materials., Comment: typo corrected