Structural Behavior and Spin-State Features of BaAl₂O₄ Scaled through Tuned Co³⁺ Doping

Pure and Co³⁺-doped BaAl₂O₄ [Ba(Al_1-Co)₂O₄, x = 0, 0.0077, 0.0379] powder samples were prepared by a facile hydrothermal route. Elemental analyses by static secondary ion mass spectrometry (SIMS), X-ray absorption spectroscopy (XAS) measurements at the Co K-edge, and X-ray diffraction studies were fully correlated, thus addressing a complete description of the structural complexity of Co³⁺-doped BaAl₂O₄ powder. Powder X-ray diffraction (PXRD) patterns indicated that prepared samples were nanocrystalline with a hexagonal P6₃ symmetry. The X-ray absorption near-edge structure (XANES) measurements revealed the presence of cobalt in a +3 oxidation state, while the rarely documented, tetrahedral symmetry around Co³⁺ was extracted from the extended X-ray absorption fine structure (EXAFS) oscillation patterns. Rietveld structure refinements showed that Co³⁺ preferentially substitutes Al³⁺ at tetrahedral Al3 sites of the BaAl₂O₄ host lattice, whereas the (Al3)O₄ tetrahedra remain rather regular with Co³⁺-O distances ranging from 1.73(9) to 1.74(9) Å. The underlying magneto-structural features were unraveled through axial and rhombic zero-field splitting (ZFS) terms. The increased substitution of Al³⁺ by Co³⁺ at Al3 sites leads to an increase of the axial ZFS terms in Co³⁺-doped BaAl₂O₄ powder from 10.8 to 26.3 K, whereas the rhombic ZFS parameters across the series change in the range from 2.7 to 10.4 K, showing a considerable increase of anisotropy together with the values of the anisotropic g-tensor components flowing from 1.7 to 2.5. We defined the line between the Co³⁺ doping limit and influenced magneto-structural characteristics, thus enabling the design of strategy to control the ZFS terms' contributions to magnetic anisotropy within Co³⁺-doped BaAl₂O₄ powder.