Magnetic properties related to structure and complete composition analyses of nanocrystalline La_1-xMn_1-yO₃ powders

Structural and magnetic properties were studied on La_1-xMnO_3±δ nanocrystalline powders exhibiting different La/Mn ratios. These compounds were prepared using a gel combustion method based on a cation solution soaking by acrylamide polymerization. Structural properties were studied both by transmission electron microscopy and X-ray diffraction (XRD). Complete chemical composition analyses were performed by induced coupled plasma spectroscopy and by iodometric titration. Proportions of parasitic phases in samples, as La₂O₃ or Mn₃O₄, and actual compositions of La_1-xMnO_3±δ phases were then determined from refinements of XRD data and sample chemical compositions. As a result, perovskite structure is not any more stable for La/Mn<0.9 as it decomposes into a mixing of La_0.9MnO₃ and of Mn₃O₄ phases, in agreement with results on thermodynamic equilibrium in the La-Mn-O phase diagram. For La/Mn>0.9, a high oxygen excess is observed and leads to consider the creation of vacancies on both lanthanum and manganese sites, whose concentrations are evaluated. Magnetic properties agree well with the proposed structures and sample compositions since for La/Mn<0.9, for which a La_0.9MnO₃ phase is always found, the Curie temperature remains constant and equal to 295K (the highest temperature never observed before in such series of compositions), while for La/Mn>0.9, there is a formation of Mn vacancies giving rise to a lowering of Curie temperature resulting of a frustration of ferromagnetic interactions.