Synthesis, structure and magnetic properties of La3Co2SbO9: A double perovskite with competing antiferromagnetic and ferromagnetic interactions

The synthesis, structural characterization, and magnetic properties of La3Co2SbO9 double perovskite are reported. The crystal structure has been refined by X-ray and neutron powder diffraction data in the monoclinic space group P21/n. Co2+ and Sb5+ have the maximum order allowed for the La3Co2SbO9 stoichiometry. Rietveld refinements of powder neutron diffraction data show that at room temperature the cell parameters are a=5.6274(2) Å, b=5.6842(2)  Å, c=7.9748(2)  Å and β=89.999(3)°. Magnetization measurements indicate the presence of ferromagnetic correlations with TC=55 K attributed to the exchange interactions for non-linear Co2+–O–Sb5+–O–Co2+ paths. The effective magnetic moment obtained experimentally is μexp=4.38 μB (per mol Co2+), between the theoretical one for spin only (3.87 μB) and spin-orbit value (6.63 μB), indicating partially unquenched contribution. The low magnetization value at high magnetic field and low temperature (1 μB/f.u., 5 T and 5 K) and the difference between ZFC and FC magnetization curves (at 5 kOe) indicate that the ferromagnetism do not reach a long range order and that the material has an important magnetic frustration.

Co–O–Co (Yellow octahedra only) rich zones (antiferromagnetic) are in contact with Co–O–Sb–O–Co (Red and yellow octahedra) rich zones (Ferromagnetic) to give the peculiar magnetic properties, as a consequence, a complex hysteresis loop can be observed composed by a main and irreversible curve in all the measured range, superimposed with a ferromagnetic component at low fields.Figure optionsDownload as PowerPoint slideHighlights
► La3Co2SbO9 has small Goldschmidt Tolerance Factor (t) due to the small size of La3+.
► Small t determines an angle for the path Co2+–O–Sb5+–O–Co2+ of 153°.
► Ferromagnetism is attributed to exchange interactions for Co2+–O–Sb5+–O–Co2+ paths.
► Ferromagnetic nanoclusters are embedded in an antiferromagnetic matrix.