Spin reorientation in CoV2O4 thin film: A first principles study

Abstract

Spinel vanadates (AV2O4) are a class of materials where an interesting interplay between spin and orbital degrees of freedom on a frustrated lattice is manifested in the multiple structural and magnetic phase transitions. CoV2O4 is unique among the spinel vanadates as it shows no or very weak cubic to tetragonal structural phase transition but two magnetic (paramagnetic to collinear ferrimagnetic and collinear to noncollinear ferrimagnetic) phase transitions at lower temperatures in its bulk form. In a recent experiment (Thompson et al., Phys. Rev. Mater. 2 (2018) 104411), an epitaxial thin film of CoV2O4 grown on the SrTiO3 (001) substrate, is observed to have an orthorhombic structural phase accompanied by a noncollinear magnetic state where the spin moments of Co and V are reoriented from [001] (seen in the bulk form) to the [110] direction. In this work, we have explored the mechanism behind this complex spin-reorientation and noncollinear magnetic ground state by investigating the electronic structure, magnetic, and structural properties of CoV2O4 in its orthorhombic phase and compared with the corresponding properties of the cubic phase using the first principles density functional theory. Our GGA+U+SO calculations on orthorhombic CoV2O4 reveal that spin moments prefer to lie in the ab-plane with the crystallographic b-direction being the preferred direction in the collinear ferrimagnetic state where it has a larger band gap and orbital moment (of V) as compared to the cases with spin moments aligned parallel to a and c-directions. We further observe competing magnetic exchange interaction values in orthorhombic phase when the spins lie in the ab-plane giving rise to more frustration and hence more canting in the non-collinear magnetic ground stateas compared to the cubic phase, consistent with experiment. With the help of source-free exchange–correlation (XC) functional we were able to capture the non-collinear magnetic ground state and the spin-reorientation in this system. We also discussed the possible orbital ordering in the orthorhombic phase of CoV2O4.