RESUMO
In this work, we have studied structural and magnetic properties of LaFeO3 as a function of the particle size d, from bulk (d >> 1 µm) to nanoscale (d ≈ 30 nm). A large number of twins were observed for large particles that disappear for small particle sizes. This could be related to the softening of the FeO6 distortion as particle size decreases. It was observed that the bulk sample showed spin canting that disappeared for d ~ 125 nm and can be associated with the smoothening of the orthorhombic distortion. On the other hand, for d < 60 nm, the surface/volume ratio became high and, despite the high crystallinity of the nanoparticle, a notable exchange effect bias appeared, originated by two magnetic interactions: spin glass and antiferromagnetism. This exchange bias interaction was originated by the formation of a "magnetic core-shell": the broken bonds at the surface atoms give place to a spin glass behavior, whereas the inner atoms maintain the antiferromagnetic G-type order. The LaFeO3 bulk material was synthesized by the ceramic method, whereas the LaFeO3 nanoparticles were synthesized by the sol-gel method; the particle size was varied by annealing the samples at different temperatures. The physical properties of the materials have been investigated by XRD, HRTEM, TGA, and AC and DC magnetometry.
RESUMO
Kagome antiferromagnetic lattices are of high interest because the geometric frustration is expected to give rise to highly degenerated ground states that may host exotic properties such as quantum spin liquid (QSL). Ca10Cr7O28 has been reported to display all the features expected for a QSL. At present, most of the literature reports on samples synthesized with starting materials ratio CaO/Cr2O3 3:1, which leads to a material with small amounts of CaCrO4 and CaO as secondary phases; this impurity excess affects not only the magnetic properties but also the structural ones. In this work, samples with starting material ratios CaO/Cr2O3 3:1, 2.9:1, 2.85:1, and 2.8:1 have been synthesized and studied by X-ray diffraction with Rietveld refinements, selected area electron diffraction measurements, high-resolution transmission electron microscopy (HRTEM), low-temperature magnetometry, and magnetic calorimetry. This result shows that a highly pure Ca10Cr7O28 phase is obtained for a CaO/Cr2O3 ratio of 2.85:1 instead of the 3:1 usually reported; the incorrect stoichiometric ratio leads to a larger distortion of the corner-sharing triangular arrangement of magnetic ions Cr+5 with S = 1/2 in the Kagome lattice. In addition, our study reveals that there exists another frustration pathway which is an asymmetric zigzag spin ladder along the directions [211], [12-1], and [1-1-1], in which the Cr-Cr distances are shorter than in the Kagome layers.
