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Sm-doped BiFeO3 compacted powders with composition across the morphotropic phase boundary region were prepared by sol-gel method. Crystal structure, morphology and magnetic state of the compounds were analyzed as a function of dopant concentration, temperature and external pressure using synchrotron and laboratory X-ray diffraction, electron microscopy, Raman and Mossbauer spectroscopy. Application of external pressure shifts the phase transition from the rhombohedral structure to the nonpolar orthorhombic structure towards lower concentration of the dopant content, wherein the amount of the anti-polar orthorhombic phase notably decreases. Raman and Mossbauer spectroscopy data provides additional information about the structural distortion on local scale level which testifies faster formation of nonpolar orthorhombic phase and associated modification in the magnetic state in the compounds subjected to high pressure. Temperature increase leads to the structural transition to the nonpolar orthorhombic phase regardless the structural state at room temperature; furthermore, application of external pressure decreases the phase transition temperature. more...

Single phase barium titanate-bismuth ferrite ((1-x)BaTi$_3$-(x)BiFe$_3$, BTO-BFO) solid solutions were prepared using citric acid and ethylene glycol assisted sol-gel synthesis method. Depending on the dopant content the samples are characterized by tetragonal, tetragonal-pseudocubic, pseudocubic and rhombohedral structure as confirmed by Raman spectroscopy and XRD measurements. An increase of the BFO content leads to a reduction in the cell parameters accompanied by a decrease in polar distortion of the unit cell wherein an average particle size increases from 60 up to 350 nm. Non zero piezoresponse was observed in the compounds with pseudocubic structure while no polar distortion was detected in their crystal structure using X-ray diffraction method. The origin of the observed non-negligible piezoresponse was discussed assuming a coexistence of nanoscale polar and non-polar phases attributed to the solid solutions with high BFO content. A coexistence of the nanoscale regions having polar and non-polar character is considered as a key factor to increase macroscopic piezoresponse in the related compounds due to increased mobility of the domain walls and phase boundaries. more...

Samarium doped BiFeO3 compounds having nano-size crystallites were prepared by the ethylene glycol assisted sol-gel synthesis method. X-ray diffraction and SEM measurements as well as Raman spectroscopy and FTIR experiments were used to clarify the evolution of the crystal structure on microscopic and local scale levels in the compounds having formula Bi1-xSmxFeO3, where x equals from 0 to 1. Magnetization measurements along with the structural data were used to determine a correlation between magnetic properties and crystal structure of the compounds. The compounds with from x 0.1-0.2 are characterized by the sequence of the structural transitions driven by the dopant increase, from the polar rhombohedral phase to the non-polar orthorhombic phase via two-phase regions characterized by the presence of the anti-polar orthorhombic phase. The concentration regions ascribed to a coexistence of the rhombohedral and the anti-polar orthorhombic phases as well as theanti-polar orthorhombic and the non-polar orthorhombic phases are observed in the ranges from 0.12 to 0.15 and from 0.15 to 0.18 respectively. The compounds having single-phase rhombohedral structure are characterized by a release of remnant magnetization as compared to ceramics with similar chemical compositions but synthesized by the solid-state reaction method and having microscopic size crystallites. A correlation between the type of structural distortion, morphology of crystallites and an onset of remnant magnetization is discussed highlighting a difference in the evolution of crystal structure and magnetization observed for the Sm-doped ceramics prepared by modified sol-gel method and conventional solid-state reaction technique. more...