Crystal structure of solid solutions 0.65BiFeO3–0.35Ba1-xSrxTiO3 in the region of morphotropic phase boundary

Solid solutions 0.65BiFeO₃–0.35Ba_1-xSr_xTiO₃ (0 ≤ x ≤ 1) with the compositions in the vicinity of the morphotropic phase boundary “rhombohedral-cubic” were synthesized by the Solid-state reaction method. The crystal structure and morphology of the ceramics 0.65BiFeO₃–0.35Ba_1-xSr_xTiO₃ were studied based on the data obtained by X-ray diffraction, scanning electron microscopy, Raman spectroscopy, as well as energy-dispersive X-ray spectroscopy methods. It was determined that the chemical substitution of barium ions with strontium ions leads to a decrease in the magnitude of rhombohedral distortions, while the unit cell parameters decrease in the whole substitution concentration range. The solid solutions with x ≥ 0.25 are characterized by a single-phase structural state with a cubic unit cell; the average crystallite size decreases with increase of the dopant ions. The results of the structural studies carried out using Raman spectroscopy indicate the presence of rhombohedral distortions in the structure of all studied compounds, which is caused by the presence of nanosized clusters with rhombohedral symmetry. The obtained results made it possible to determine the sequence of the changes occurred in the phase state and the unit cell parameters in the region of the morphotropic phase boundary “rhombohedral -pseudocubic”; the concentration intervals corresponding to the single-phase and two-phase structural states of the compounds were determined. The region of concentration stability of the polar rhombohedral phase was clarified using the structural data obtained by local and microscopic research methods.

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