Piezoelectrics are materials that linearly deform in response to an applied electric field. As a fundamental prerequisite, piezoelectric materials must have a noncentrosymmetric crystal structure. For more than a century, this has remained a major obstacle for finding piezoelectric materials. We circumvented this limitation by breaking the crystallographic symmetry and inducing large and sustainable piezoelectric effects in centrosymmetric materials by the electric field–induced rearrangement of oxygen vacancies. Our results show the generation of extraordinarily large piezoelectric responses [with piezoelectric strain coefficients ( d 33 ) of ~200,000 picometers per volt at millihertz frequencies] in cubic fluorite gadolinium-doped CeO 2− x films, which are two orders of magnitude larger than the responses observed in the presently best-known lead-based piezoelectric relaxor–ferroelectric oxide at kilohertz frequencies. These findings provide opportunities to design piezoelectric materials from environmentally friendly centrosymmetric ones.
Twinning is a common crystallographic phenomenon which is related to the formation and coexistence of several orientation variants of the same crystal structure. It may occur during symmetry-lowering phase transitions or during the crystal growth itself. Once formed, twin domains play an important role in defining physical properties: for example, they underpin the giant piezoelectric effect in ferroelectrics, superelasticity in ferroelastics and the shape-memory effect in martensitic alloys. Regrettably, there is still a lack of experimental methods for the characterization of twin domain patterns. Here, a theoretical framework and algorithm are presented for the recognition of ferroelastic domains, as well as the identification of the coherent twin relationship using high-resolution reciprocal-space mapping of X-ray diffraction intensity around split Bragg peaks. Specifically, the geometrical theory of twinned ferroelastic crystals [Fousek & Janovec (1969). J. Appl. Phys. 40, 135–142] is adapted for the analysis of the X-ray diffraction patterns. The necessary equations are derived and an algorithm is outlined for the calculation of the separation between the Bragg peaks, diffracted from possible coherent twin domains, connected to one another via a mismatch-free interface. It is demonstrated that such separation is always perpendicular to the planar interface between mechanically matched domains. For illustration purposes, the analysis is presented of the separation between the peaks diffracted from tetragonal and rhombohedral domains in the high-resolution reciprocal-space maps of BaTiO3 and PbZr1−x Ti x O3 crystals. The demonstrated method can be used to analyse the response of multi-domain patterns to external perturbations such as electric field, change of temperature or pressure.
Laboratory X-ray diffractometers play a crucial role in X-ray crystallography and materials science. Such instruments still vastly outnumber synchrotron facilities and are responsible for most of the X-ray characterization of materials around the world. The efforts to enhance the design and performance of in-house X-ray diffraction instruments benefit a broad research community. Here, the realization of a custom-built multipurpose four-circle diffractometer in the laboratory for X-ray crystallography of functional materials at Tel Aviv University, Israel, is reported. The instrument is equipped with a microfocus Cu-based X-ray source, collimating X-ray optics, four-bounce monochromator, four-circle goniometer, large (PILATUS3 R 1M) pixel area detector, analyser crystal and scintillating counter. It is suitable for a broad range of tasks in X-ray crystallography/structure analysis and materials science. All the relevant X-ray beam parameters (total flux, flux density, beam divergence, monochromaticity) are reported and several applications such as determination of the crystal orientation matrix and high-resolution reciprocal-space mapping are demonstrated. The diffractometer is suitable for measuring X-ray diffraction in situ under an external electric field, as demonstrated by the measurement of electric-field-dependent rocking curves of a quartz single crystal. The diffractometer can be used as an independent research instrument, but also as a training platform and for preparation for synchrotron experiments.
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, it is revealed that electric field‐and light‐induced ionic motion in MAPbX3 crystals (X = Cl, Br, I and MA = CH3NH3) leads to an unexpectedly high piezoelectric‐like response that is at low frequencies 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‐like response of interplay of ionic motion (MA+1 and X–1) and photoelectrons generated with illumination.
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