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

Quantitative mapping of nanotwin variants in the bulk

Crystallographic twins are critical to the properties of numerous materials from magnesium alloys to piezoelectrics. Since the onset of the twin formation is highly sensitive to the triaxial mechanical boundary conditions, non-destructive bulk microscopy techniques are required. Elastic strains can be mapped via X-ray diffraction with a 100-200 nm resolution. However, the interplay of strains with nanotwins cannot be characterized. Here, a method based on dark-field X-ray microscopy to quantify the density of nanotwin variants with twin lamellae of sizes as small as several tens of nanometers in embedded subvolumes (70x200x600 nm³) in millimeter-sized samples is introduced. The methodology is corroborated by correlating the local density of twin variants to the long-ranging strain fields for a high-performance piezoelectric material. The method facilitates direct, in situ mapping and quantification of nanoscale structural changes together with their elastic driving fields, which is the key towards controlling and engineering material's performance at nanometric scales

Monoclinic distortion, polarization rotation and piezoelectricity in the ferroelectric Na0.5Bi0.5TiO3

The relationship between crystal structure and physical properties in the ferroelectric Na0.5Bi0.5TiO3 (NBT) has been of interest for the last two decades. Originally, the average structure was held to be of rhombohedral (R3c) symmetry with a fixed polarization direction. This has undergone a series of revisions, however, based on high-resolution X-ray diffraction, total neutron scattering, and optical and electron microscopy. The recent experimental findings suggest that the true average symmetry is monoclinic (space group Cc), which allows for a rotatable spontaneous polarization. Neither polarization rotation nor its potentially important real role in enhanced piezoelectricity is well understood. The present work describes an in situ investigation of the average monoclinic distortion in NBT by time-resolved single-crystal X-ray diffraction under external electric fields. The study presents a high-resolution inspection of the characteristic diffraction features of the monoclinic distortion – splitting of specific Bragg reflections – and their changes under a cyclic electric field. The results favour a model in which there is direct coupling between the shear monoclinic strain and the polarization rotation. This suggests that the angle of polarization rotation under a sub-coercive electric field could be 30° or more

Picometer polar atomic displacements in strontium titanate determined by resonant X-ray diffraction

Physical properties of crystalline materials often manifest themselves as atomic displacements either away from symmetry positions or driven by external fields. Especially the origin of multiferroic or magnetoelectric effects may be hard to ascertain as the related displacements can reach the detection limit. Here we present a resonant X-ray crystal structure analysis technique that shows enhanced sensitivity to minute atomic displacements. It is applied to a recently found crystalline modification of strontium titanate that forms in single crystals under electric field due to oxygen vacancy migration. The phase has demonstrated unexpected properties, including piezoelectricity and pyroelectricity, which can only exist in non-centrosymmetric crystals. Apart from that, the atomic structure has remained elusive and could not be obtained by standard methods. Using resonant X-ray diffraction, we determine atomic displacements with sub-picometer precision and show that the modified structure of strontium titanate corresponds to that of well-known ferroelectrics such as lead titanate

Local-scale structures across the morphotropic phase boundary in PbZr1−xTixO3

Lead zirconate titanate (PZT) is one of the most widely studied piezoelectric materials, mainly because of its `mysterious' relationship between the so-called morphotropic phase boundary (MPB) and its strong piezoelectric coupling factor. Using results from a pair distribution function analysis, this paper examines how the complex local structure in PZT affects the long-range average structure across the MPB. A monoclinic MC type structure is discovered in PZT. A first-order transformation between the monoclinic MA and MC components in both the average and local structures explains the sudden change in piezoelectric effect around these compositions. The role of polarization rotation in the enhancement of the piezoelectric properties is discussed with respect to the composition of PZT. The structure–property relationship that is revealed by this study explains the unique properties of PZT, and may be applicable in the design of new MPB-type functional materials

Combining High Time and Angular Resolutions: Time-Resolved X-ray Powder Diffraction using a Multi-Channel Analyser Detector

The design and testing of the new MAD-STROBO data acquisition system are reported. The system realizes stroboscopic collection of high-resolution X-ray powder diffraction profiles under a dynamically applied electric field. It synchronizes an externally applied stimulus and detected X-ray photons. The feasibility of detecting sub-millidegree shifts of powder diffraction profiles with microsecond time resolution is demonstrated. MAD-STROBO may be applied for the investigation of various macroscopic and domain-related processes induced by an external perturbation, such as elasticity or piezoelectricity

Quantitative mapping of nanotwin variants in the bulk

Crystallographic twins are critical to the properties of numerous materials from magnesium alloys to piezoelectrics. Since the onset of the twin formation is highly sensitive to the triaxial mechanical boundary conditions, non-destructive bulk microscopy techniques are required. Elastic strains can be mapped via X-ray diffraction with a 100-200 nm resolution. However, the interplay of strains with nanotwins cannot be characterized. Here, a method based on dark-field X-ray microscopy to quantify the density of nanotwin variants with twin lamellae of sizes as small as several tens of nanometers in embedded subvolumes (70x200x600 nm³) in millimeter-sized samples is introduced. The methodology is corroborated by correlating the local density of twin variants to the long-ranging strain fields for a high-performance piezoelectric material. The method facilitates direct, in situ mapping and quantification of nanoscale structural changes together with their elastic driving fields, which is the key towards controlling and engineering material's performance at nanometric scales

Quantitative mapping of nanotwin variants in the bulk

Crystallographic twins are critical to the properties of numerous materials from magnesium alloys to piezoelectrics. Since the onset of the twin formation is highly sensitive to the triaxial mechanical boundary conditions, non-destructive bulk microscopy techniques are required. Elastic strains can be mapped via X-ray diffraction with a 100-200 nm resolution. However, the interplay of strains with nanotwins cannot be characterized. Here, a method based on dark-field X-ray microscopy to quantify the density of nanotwin variants with twin lamellae of sizes as small as several tens of nanometers in embedded subvolumes (70x200x600 nm3) in millimeter-sized samples is introduced. The methodology is corroborated by correlating the local density of twin variants to the long-ranging strain fields for a high-performance piezoelectric material. The method facilitates direct, in situ mapping and quantification of nanoscale structural changes together with their elastic driving fields, which is the key towards