Flexophotovoltaic Effect and Above-Band-Gap Photovoltage Induced by Strain Gradients in Halide Perovskites.

We have measured the flexophotovoltaic effect of single crystals of halide perovskites MAPbBr_{3} and MAPbI_{3}, as well as the benchmark oxide perovskite SrTiO_{3}. For halide perovskites, the flexophotovoltaic effect is found to be orders of magnitude larger than for SrTiO_{3}, and indeed large enough to induce photovoltages bigger than the band gap. Moreover, we find that in MAPbI_{3} the flexophotovoltaic effect is additional to a native bulk photovoltaic response that is switchable and ferroelectric-like. The results suggest that strain gradient engineering can be a powerful tool to modify the photovoltaic output even in already well-established photovoltaic materials.

Photostrictive Actuators Based on Freestanding Ferroelectric Membranes.

Complex oxides offer a wide range of functional properties, and recent advances in the fabrication of freestanding membranes of these oxides are adding new mechanical degrees of freedom to this already rich functional ecosystem. Here, photoactuation is demonstrated in freestanding thin film resonators of ferroelectric Barium Titanate (BaTiO3) and paraelectric Strontium Titanate (SrTiO3). The free-standing films, transferred onto perforated supports, act as nano-drums, oscillating at their natural resonance frequency when illuminated by a frequency-modulated laser. The light-induced deflections in the ferroelectric BaTiO3 membranes are two orders of magnitude larger than in the paraelectric SrTiO3 ones. Time-resolved X-ray micro-diffraction under illumination and temperature-dependent holographic interferometry provide combined evidence for the photostrictive strain in BaTiO3 originating from a partial screening of ferroelectric polarization by photo-excited carriers, which decreases the tetragonality of the unit cell. These findings showcase the potential of photostrictive freestanding ferroelectric films as wireless actuators operated by light.

Switchable tribology of ferroelectrics.

Switchable tribological properties of ferroelectrics offer an alternative route to visualize and control ferroelectric domains. Here, we observe the switchable friction and wear behavior of ferroelectrics using a nanoscale scanning probe-down domains have lower friction coefficients and show slower wear rates than up domains and can be used as smart masks. This asymmetry is enabled by flexoelectrically coupled polarization in the up and down domains under a sufficiently high contact force. Moreover, we determine that this polarization-sensitive tribological asymmetry is widely applicable across various ferroelectrics with different chemical compositions and crystalline symmetry. Finally, using this switchable tribology and multi-pass patterning with a domain-based dynamic smart mask, we demonstrate three-dimensional nanostructuring exploiting the asymmetric wear rates of up and down domains, which can, furthermore, be scaled up to technologically relevant (mm-cm) size. These findings demonstrate that ferroelectrics are electrically tunable tribological materials at the nanoscale for versatile applications.

Translational Boundaries as Incipient Ferrielectric Domains in Antiferroelectric PbZrO_{3}.

In the archetypal antiferroelectric PbZrO_{3}, antiparallel electric dipoles cancel each other, resulting in zero spontaneous polarization at the macroscopic level. Yet in actual hysteresis loops, the cancellation is rarely perfect and some remnant polarization is often observed, suggesting the metastability of polar phases in this material. In this work, using aberration-corrected scanning transmission electron microscopy methods on a PbZrO_{3} single crystal, we uncover the coexistence of the common antiferroelectric phase and a ferrielectric phase featuring an electric dipole pattern of ↓↑↓. This dipole arrangement, predicted by Aramberri et al. to be the ground state of PbZrO_{3} at 0 K, appears at room temperature in the form of translational boundaries. The dual nature of the ferrielectric phase, both a distinct phase and a translational boundary structure, places important symmetry constraints on its growth. These are overcome by sideways motion of the boundaries, which aggregate to form arbitrarily wide stripe domains of the polar phase embedded within the antiferroelectric matrix.

Tunable Molecular Electrodes for Bistable Polarization Screening.

The polar discontinuity at any ferroelectric surface creates a depolarizing field that must be screened for the polarization to be stable. In capacitors, screening is done by the electrodes, while in bare ferroelectric surfaces it is typically accomplished by atmospheric adsorbates. Although chemisorbed species can have even better screening efficiency than conventional electrodes, they are subject to unpredictable environmental fluctuations and, moreover, dominant charged species favor one polarity over the opposite. This paper proposes a new screening concept, namely surface functionalization with resonance-hybrid molecules, which combines the predictability and bipolarity of conventional electrodes with the screening efficiency of adsorbates. Thin films of barium titanate (BaTiO3 ) coated with resonant para-aminobenzoic acid (pABA) display increased coercivity for both signs of ferroelectric polarization irrespective of the molecular layer thickness, thanks to the ability of these molecules to swap between different electronic configurations and adapt their surface charge density to the screening needs of the ferroelectric underneath. Because electron delocalization is only in the vertical direction, unlike conventional metals, chemical electrodes allow writing localized domains of different polarity underneath the same electrode. In addition, hybrid capacitors composed of graphene/pABA/ferroelectric have been made with enhanced coercivity compared to pure graphene-electode capacitors.

Deconvolution of Phonon Scattering by Ferroelectric Domain Walls and Point Defects in a PbTiO3 Thin Film Deposited in a Composition-Spread Geometry.

We present a detailed analysis of the temperature dependence of the thermal conductivity of a ferroelectric PbTiO3 thin film deposited in a composition-spread geometry enabling a continuous range of compositions from ∼25% titanium deficient to ∼20% titanium rich to be studied. By fitting the experimental results to the Debye model we deconvolute and quantify the two main phonon-scattering sources in the system: ferroelectric domain walls (DWs) and point defects. Our results prove that ferroelectric DWs are the main agent limiting the thermal conductivity in this system, not only in the stoichiometric region of the thin film ([Pb]/[Ti] ≈ 1) but also when the concentration of the cation point defects is significant (up to ∼15%). Hence, DWs in ferroelectric materials are a source of phonon scattering at least as effective as point defects. Our results demonstrate the viability and effectiveness of using reconfigurable DWs to control the thermal conductivity in solid-state devices.

Metallic Diluted Dimerization in VO2 Tweeds.

The observation of electronic phase separation textures in vanadium dioxide, a prototypical electron-correlated oxide, has recently added new perspectives on the long standing debate about its metal-insulator transition and its applications. Yet, the lack of atomically resolved information on phases accompanying such complex patterns still hinders a comprehensive understanding of the transition and its implementation in practical devices. In this work, atomic resolution imaging and spectroscopy unveils the existence of ferroelastic tweed structures on ≈5 nm length scales, well below the resolution limit of currently used spectroscopic imaging techniques. Moreover, density functional theory calculations show that this pretransitional fine-scale tweed, which on average looks and behaves like the standard metallic rutile phase, is in fact weaved by semi-dimerized chains of vanadium in a new monoclinic phase that represents a structural bridge to the monoclinic insulating ground state. These observations provide a multiscale perspective for the interpretation of existing data, whereby phase coexistence and structural intermixing can occur all the way down to the atomic scale.

Non-linear nanoscale piezoresponse of single ZnO nanowires affected by piezotronic effect.

Zinc oxide (ZnO) nanowires (NWs) as semiconductor piezoelectric nanostructures have emerged as material of interest for applications in energy harvesting, photonics, sensing, biomedical science, actuators or spintronics. The expression for the piezoelectric properties in semiconductor materials is concealed by the screening effect of the available carriers and the piezotronic effect, leading to complex nanoscale piezoresponse signals. Here, we have developed a metal-semiconductor-metal model to simulate the piezoresponse of single ZnO NWs, demonstrating that the apparent non-linearity in the piezoelectric coefficient arises from the asymmetry created by the forward and reversed biased Schottky barriers at the semiconductor-metal junctions. By directly measuring the experimental I-V characteristics of ZnO NWs with conductive atomic force microscope together with the piezoelectric vertical coefficient by piezoresponse force microscopy, and comparing them with the numerical calculations for our model, effective piezoelectric coefficients in the range d 33eff ∼ 8.6 pm V-1-12.3 pm V-1 have been extracted for ZnO NWs. We have further demonstrated via simulations the dependence between the effective piezoelectric coefficient d 33eff and the geometry and physical dimensions of the NW (radius to length ratio), revealing that the higher d 33eff is obtained for thin and long NWs due to the tensor nature proportionality between electric fields and deformation in NW geometries. Moreover, the non-linearity of the piezoresponse also leads to multiharmonic electromechanical response observed at the second and higher harmonics that indeed is not restricted to piezoelectric semiconductor materials but can be generalized to any type of asymmetric voltage drops on a piezoelectric structure as well as leaky wide band-gap semiconductor ferroelectrics.

Strain-Engineered Ferroelastic Structures in PbTiO3 Films and Their Control by Electric Fields.

We study the interplay between epitaxial strain, film thickness, and electric field in the creation, modification, and design of distinct ferroelastic structures in PbTiO3 thin films. Strain and thickness greatly affect the structures formed, providing a two-variable parameterization of the resulting self-assembly. Under applied electric fields, these strain-engineered ferroelastic structures are highly malleable, especially when a/c and a1/a2 superdomains coexist. To reconfigure the ferroelastic structures and achieve self-assembled nanoscale-ordered morphologies, pure ferroelectric switching of individual c-domains within the a/c superdomains is essential. The stability, however, of the electrically written ferroelastic structures is in most cases ephemeral; the speed of the relaxation process depends sensitively on strain and thickness. Only under low tensile strain-as is the case for PbTiO3 on GdScO3-and below a critical thickness do the electrically created a/c superdomain structures become stable for days or longer, making them relevant for reconfigurable nanoscale electronics or nonvolatile electromechanical applications.

Photoflexoelectric effect in halide perovskites.

Harvesting environmental energy to generate electricity is a key scientific and technological endeavour of our time. Photovoltaic conversion and electromechanical transduction are two common energy-harvesting mechanisms based on, respectively, semiconducting junctions and piezoelectric insulators. However, the different material families on which these transduction phenomena are based complicate their integration into single devices. Here we demonstrate that halide perovskites, a family of highly efficient photovoltaic materials1-3, display a photoflexoelectric effect whereby, under a combination of illumination and oscillation driven by a piezoelectric actuator, they generate orders of magnitude higher flexoelectricity than in the dark. We also show that photoflexoelectricity is not exclusive to halides but a general property of semiconductors that potentially enables simultaneous electromechanical and photovoltaic transduction and harvesting in unison from multiple energy inputs.

Investigation of The Cellular Response to Bone Fractures: Evidence for Flexoelectricity.

The recent discovery of bone flexoelectricity (strain-gradient-induced electrical polarization) suggests that flexoelectricity could have physiological effects in bones, and specifically near bone fractures, where flexoelectricity is theoretically highest. Here, we report a cytological study of the interaction between crack stress and bone cells. We have cultured MC3T3-E1 mouse osteoblastic cells in biomimetic microcracked hydroxyapatite substrates, differentiated into osteocytes and applied a strain gradient to the samples. The results show a strong apoptotic cellular response, whereby mechanical stimulation causes those cells near the crack to die, as indicated by live-dead and caspase staining. In addition, analysis two weeks post-stimulation shows increased cell attachment and mineralization around microcracks and a higher expression of osteocalcin -an osteogenic protein known to be promoted by physical exercise. The results are consistent with flexoelectricity playing at least two different roles in bone remodelling: apoptotic trigger of the repair protocol, and electro-stimulant of the bone-building activity of osteoblasts.

Ferroelectric Domain Walls in PbTiO3 Are Effective Regulators of Heat Flow at Room Temperature.

Achieving efficient spatial modulation of phonon transmission is an essential step on the path to phononic circuits using "phonon currents". With their intrinsic and reconfigurable interfaces, domain walls (DWs), ferroelectrics are alluring candidates to be harnessed as dynamic heat modulators. This paper reports the thermal conductivity of single-crystal PbTiO3 thin films over a wide variety of epitaxial-strain-engineered ferroelectric domain configurations. The phonon transport is proved to be strongly affected by the density and type of DWs, achieving a 61% reduction of the room-temperature thermal conductivity compared to the single-domain scenario. The thermal resistance across the ferroelectric DWs is obtained, revealing a very high value (≈5.0 × 10-9 K m2 W-1), comparable to grain boundaries in oxides, explaining the strong modulation of the thermal conductivity in PbTiO3. This low thermal conductance of the DWs is ascribed to the structural mismatch and polarization gradient found between the different types of domains in the PbTiO3 films, resulting in a structural inhomogeneity that extends several unit cells around the DWs. These findings demonstrate the potential of ferroelectric DWs as efficient regulators of heat flow in one single material, overcoming the complexity of multilayers systems and the uncontrolled distribution of grain boundaries, paving the way for applications in phononics.

Periodicity-Doubling Cascades: Direct Observation in Ferroelastic Materials.

Very sensitive responses to external forces are found near phase transitions. However, transition dynamics and preequilibrium phenomena are difficult to detect and control. We have observed that the equilibrium domain structure following a phase transition in ferroelectric and ferroelastic BaTiO_{3} is attained by halving of the domain periodicity multiple times. The process is reversible, with periodicity doubling as temperature is increased. This observation is reminiscent of the period-doubling cascades generally observed during bifurcation phenomena, and, thus, it conforms to the "spatial chaos" regime earlier proposed by Jensen and Bak [Phys. Scr. T 9, 64 (1985)PHSTER0281-184710.1088/0031-8949/1985/T9/009] for systems with competing spatial modulations.

Flexoelectric Fracture-Ratchet Effect in Ferroelectrics.

The propagation front of a crack generates large strain gradients and it is therefore a strong source of gradient-induced polarization (flexoelectricity). Herein, we demonstrate that, in piezoelectric materials, a consequence of flexoelectricity is that crack propagation is helped or hindered depending on whether it is parallel or antiparallel to the piezoelectric polar axis. The discovery of crack propagation asymmetry proves that fracture physics cannot be assumed to be symmetric in polar materials, and indicates that flexoelectricity should be incorporated in any realistic model.

Converse flexoelectricity yields large piezoresponse force microscopy signals in non-piezoelectric materials.

Converse flexoelectricity is a mechanical stress induced by an electric polarization gradient. It can appear in any material, irrespective of symmetry, whenever there is an inhomogeneous electric field distribution. This situation invariably happens in piezoresponse force microscopy (PFM), which is a technique whereby a voltage is delivered to the tip of an atomic force microscope in order to stimulate and probe piezoelectricity at the nanoscale. While PFM is the premier technique for studying ferroelectricity and piezoelectricity at the nanoscale, here we show, theoretically and experimentally, that large effective piezoelectric coefficients can be measured in non-piezoelectric dielectrics due to converse flexoelectricity.

Piezoelectric Mimicry of Flexoelectricity.

The origin of "giant" flexoelectricity, orders of magnitude larger than theoretically predicted, yet frequently observed, is under intense scrutiny. There is mounting evidence correlating giant flexoelectriclike effects with parasitic piezoelectricity, but it is not clear how piezoelectricity (polarization generated by strain) manages to imitate flexoelectricity (polarization generated by strain gradient) in typical beam-bending experiments, since in a bent beam the net strain is zero. In addition piezoelectricity changes sign under space inversion but giant flexoelectricity is insensitive to space inversion, seemingly contradicting a piezoelectric origin. Here we show that, if a piezoelectric material has its piezoelectric coefficient asymmetrically distributed across the sample, it will generate a nonzero bending-induced polarization impossible to distinguish from true flexoelectricity even by inverting the sample. The effective flexoelectric coefficient caused by piezoelectricity is functionally identical to, and often larger than, intrinsic flexoelectricity: our calculations show that, for standard perovskite ferroelectrics, even a tiny gradient of piezoelectricity (1% variation of piezoelectric coefficient across 1 mm) is sufficient to yield a giant effective flexoelectric coefficient of 1 µC/m, three orders of magnitude larger than the intrinsic expectation value.

Flexoelectricity in Bones.

Bones generate electricity under pressure, and this electromechanical behavior is thought to be essential for bone's self-repair and remodeling properties. The origin of this response is attributed to the piezoelectricity of collagen, which is the main structural protein of bones. In theory, however, any material can also generate voltages in response to strain gradients, thanks to the property known as flexoelectricity. In this work, the flexoelectricity of bone and pure bone mineral (hydroxyapatite) are measured and found to be of the same order of magnitude; the quantitative similarity suggests that hydroxyapatite flexoelectricity is the main source of bending-induced polarization in cortical bone. In addition, the measured flexoelectric coefficients are used to calculate the (flexo)electric fields generated by cracks in bone mineral. The results indicate that crack-generated flexoelectricity is theoretically large enough to induce osteocyte apoptosis and thus initiate the crack-healing process, suggesting a central role of flexoelectricity in bone repair and remodeling.

Ferroelectrics as Smart Mechanical Materials.

The mechanical properties of materials are insensitive to space inversion, even when they are crystallographically asymmetric. In practice, this means that turning a piezoelectric crystal upside down or switching the polarization of a ferroelectric should not change its mechanical response. Strain gradients, however, introduce an additional source of asymmetry that has mechanical consequences. Using nanoindentation and contact-resonance force microscopy, this study demonstrates that the mechanical response to indentation of a uniaxial ferroelectric (LiNbO3 ) does change when its polarity is switched, and use this mechanical asymmetry both to quantify its flexoelectricity and to mechanically read the sign of its ferroelectric domains.