Topology and temperature dependence of the diffuse X-ray scattering in Na0.5Bi0.5TiO3 ferroelectric single crystals

The results of high-resolution measurements of the diffuse X-ray scattering produced by a perovskite-based Na0.5Bi0.5TiO3 ferroelectric single crystal between 40 and 620 K are reported. The study was designed as an attempt to resolve numerous controversies regarding the average structure of Na0.5Bi0.5TiO3, such as the mechanism of the phase transitions between the tetragonal, P4bm, and rhombohedral | monoclinic, R3c | Cc, space groups and the correlation between structural changes and macroscopic physical properties. The starting point was to search for any transformations of structural disorder in the temperature range of thermal depoling (420–480 K), where the average structure is known to remain unchanged. The intensity distribution around the {032} pseudocubic reflection was collected using a PILATUS 100K detector at the I16 beamline of the Diamond Light Source (UK). The data revealed previously unknown features of the diffuse scattering, including a system of dual asymmetric L-shaped diffuse scattering streaks. The topology, temperature dependence, and relationship between Bragg and diffuse intensities suggest the presence of complex microstructure in the low-temperature R3c | Cc phase. This microstructure may be formed by the persistence of the higher-temperature P4bm phase, built into a lower-temperature R3c | Cc matrix, accompanied by the related long-range strain fields. Finally, it is shown that a correlation between the temperature dependence of the X-ray scattering features and the temperature regime of thermal depoling is present

Simultaneous resonant x-ray diffraction measurement of polarization inversion and lattice strain in polycrystalline ferroelectrics

International audienceStructure-property relationships in ferroelectrics extend over several length scales from the individual unit cell to the macroscopic device, and with dynamics spanning a broad temporal domain. Characterizing the multi-scale structural origin of electric field-induced polarization reversal and strain in ferroelectrics is an ongoing challenge that so far has obscured its fundamental behaviour. By utilizing small intensity differences between Friedel pairs due to resonant scattering, we demonstrate a time-resolved X-ray diffraction technique for directly and simultaneously measuring both lattice strain and, for the first time, polarization reversal during in-situ electrical perturbation. This technique is demonstrated for BaTiO3-BiZn0.5Ti0.5O3 (BT-BZT) polycrystalline ferroelectrics, a prototypical lead-free piezoelectric with an ambiguous switching mechanism. This combines the benefits of spectroscopic and diffraction-based measurements into a single and robust technique with time resolution down to the ns scale, opening a new door to in-situ structure-property characterization that probes the full extent of the ferroelectric behaviou

X-ray white beam topography of self-organized domains in flux-grown BaTiO3 single crystals

The phenomenon of self-organization of domains into a “square-net pattern” in single-crystal, flux-grown BaTiO3 several degrees below the ferroelectric to paraelectric phase transition was investigated using in situ synchrotron x-ray topography. The tetragonal distortion of the crystal was determined by measuring the angular separation between the diffraction images received from 90° a and c domains in the projection topographs, and shows a rapid decrease towards 110 °C, the onset temperature for self-organization. The onset of self-organization is accompanied by bending of the {100} lattice planes parallel to the crystal surface, which produces a strain that persists up to and beyond the Curie temperature, where the crystal becomes cubic and the self-organized domains disappear. At the Curie point, the bending angle α100=8.1(±0.3)mrad is at a maximum and corresponds to the radius of curvature of the surface being 16.3(±0.6) mm

Simultaneous resonant x-ray diffraction measurement of polarization inversion and lattice strain in polycrystalline ferroelectrics

Structure-property relationships in ferroelectrics extend over several length scales from the individual unit cell to the macroscopic device, and with dynamics spanning a broad temporal domain. Characterizing the multi-scale structural origin of electric field-induced polarization reversal and strain in ferroelectrics is an ongoing challenge that so far has obscured its fundamental behaviour. By utilizing small intensity differences between Friedel pairs due to resonant scattering, we demonstrate a time-resolved X-ray diffraction technique for directly and simultaneously measuring both lattice strain and, for the first time, polarization reversal during in-situ electrical perturbation. This technique is demonstrated for BaTiO₃-BiZn₀.₅Ti₀.₅O₃ (BT-BZT) polycrystalline ferroelectrics, a prototypical lead-free piezoelectric with an ambiguous switching mechanism. This combines the benefits of spectroscopic and diffraction-based measurements into a single and robust technique with time resolution down to the ns scale, opening a new door to in-situ structure-property characterization that probes the full extent of the ferroelectric behaviour.This is the publisher’s final pdf. The published article is copyrighted by the author(s) and published by the Nature Publishing Group. The published article can be found at: http://www.nature.com/srep

Preparation, structural characterisation and antibacterial properties of Ga-doped sol-gel phosphate-based glass

A sol-gel preparation of Ga-doped phosphate-based glass with potential application in antimicrobial devices has been developed. Samples of composition (CaO)(0.30)(Na2O)(0.20-x) (Ga2O3) (x) (P2O5)(0.50) where x = 0 and 0.03 were prepared, and the structure and properties of the gallium-doped sample compared with those of the sample containing no gallium. Analysis of the P-31 MAS NMR data demonstrated that addition of gallium to the sol-gel reaction increases the connectivity of the phosphate network at the expense of hydroxyl groups. This premise is supported by the results of the elemental analysis, which showed that the gallium-free sample contains significantly more hydrogen and by FTIR spectroscopy, which revealed a higher concentration of -OH groups in that sample. Ga K-edge extended X-ray absorption fine structure and X-ray absorption near-edge structure data revealed that the gallium ions are coordinated by six oxygen atoms. In agreement with the X-ray absorption data, the high-energy XRD results also suggest that the Ga3+ ions are octahedrally coordinated with respect to oxygen. Antimicrobial studies demonstrated that the sample containing Ga3+ ions had significant activity against Staphylococcus aureus compared to the control

Growth of single crystals in the (Na1/2Bi1/2)TiO3-(Sr1-xCax)TiO3 system by solid state crystal growth

Ceramics based on (Na1/2B1/2)TiO3 are promising candidates for actuator applications because of large strains generated by an electric field-induced phase transition. For example, the (1-x)(Na1/2Bi1/2)TiO3-xSrTiO(3) system exhibits a morphotropic phase boundary at x = 0.2-0.3, leading to high values of inverse piezoelectric constant d*(33), which can be further improved by the use of single crystals. In our previous work, single crystals of (Na1/2B1/2)TiO3-SrTiO3 and (Na1/2B1/2)TiO3-CaTiO3 were grown by the solid state crystal growth technique. Growth in the (Na1/2B1/2)TiO3-SrTiO3 system was sluggish whereas the (Na1/2B1/2)TiO3-CaTiO3 single crystals grew well. In the present work, 0.8(Na1/2Bi1/2)TiO3-0.2(Sr1-xCax)TiO3 single crystals (with x = 0.0, 0.1, 0.2, 0.3, 0.4) were produced by the solid state crystal growth technique in an attempt to improve crystal growth rate. The dependence of mean matrix grain size, single crystal growth distance, and electrical properties on the Ca concentration was investigated in detail. These investigations indicated that at x = 0.3 the matrix grain growth was suppressed and the driving force for single crystal growth was enhanced. Replacing Sr with Ca increased the shoulder temperature T-s and temperature of maximum relative permittivity T-max, causing a decrease in inverse piezoelectric properties and a change from normal to incipient ferroelectric behavior