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Ferroelectric materials have been known for almost one century [1]. While their potential for applications was rapidly recognized, the possibility of combining ferroelectricity with magnetic order -preferably with ferromagnetism- has resulted in an enormous deal of interest during the last decade. Several new materials combining both types of order have been recently reported, although their promising multifunctionalities have been obscured by two facts: on one side, most of them are antiferromagnetic; on the other, their transition temperatures, typically below 40K, are too low for most practical applications. The oxygen-defficient double perovskite YBaFeCuO5 constitutes a remarkable exception. Spontaneous electric polarization has been recently reported to exist below an unusually high temperature of TC ≍ 200K [2] coinciding with the occurrence of a commensurate - to - incommensurate reorientation of the Fe3+ and Cu2+ magnetic moments [3,4]. From a more fundamental point of view the observation of incommensurable magnetic order in a tetragonal material at such high temperatures is rather surprising. In particular, the nature of the relevant competing magnetic interactions and its possible link to low dimensionality or geometrical frustration is not understood at present. Although the existence of the spin reorientation in this material is known since 1995 [3] the low temperature magnetic structure has not yet been solved. Using neutron powder diffraction we have recently been able to propose a spiral model which satisfactorily describes the measured magnetic intensities below TC. Further, investigation of the crystal structure showed the existence of small anomalies in the lattice parameters and some interatomic distances at TC. The relevance of these findings for the magnetoelectric coupling, the direction of the polarization, the modification of the different exchange paths in the structure and the stabilization of the incommensurate magnetic order below TC is discussed.
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The interplay between superconductivity, magnetism and crystal structure in iron-based superconductors has attracted a great interest in the recent years as it is considered to be the key for understanding the mechanisms responsible for high temperature superconductivity. Alkali metal intercalated iron chalcogenide superconductors (A122) exhibit unique behavior which is not observed in other iron-based superconducting materials such as antiferromagnetic ordering above room temperature and iron vacancies ordering. These materials have complex crystal structures with several phase transitions and are mixtures of phases even in the form usually described as a single crystal. A pronounced reversible phase separation revealed in A122 single crystals, as well as controversies regarding the origin of superconductivity and the stoichiometry and symmetry of the superconducting phase are still in the forefront of scientific activity. Here we will present a diffraction study of the crystal structures, antiferromagnetic ordering and intrinsic phase separation in alkali-metal iron chalcogenides [1]. The complementary scanning electron microscope study, including high-resolution electron back-scatter diffraction mapping will be also presented [2].