  The asymmetry of chemical nature at the hetero-structural interface offers an
unique opportunity to design desirable electronic structure by controlling
charge transfer and orbital hybridization across the interface. However, the
control of hetero-interface remains a daunting task. Here, we report the
modulation of interfacial coupling of (La0.67Sr0.33MnO3)n/(SrTiO3)n
superlattices by manipulating the periodic thickness with n unit cells of
SrTiO3 and n unit cells La0.67Sr0.33MnO3. The easy axis of magnetic anisotropy
rotates from in-plane (n = 10) to out-of-plane (n = 2) orientation at 150 K.
Transmission electron microscopy reveals enlarged tetragonal ratio > 1 with
breaking of volume conservation around the (La0.67Sr0.33MnO3)n/(SrTiO3)n
interface, and electronic charge transfer from Mn to Ti 3d orbitals across the
interface. Orbital hybridization accompanying the charge transfer results in
preferred occupancy of 3d3z2-r2 orbital at the interface, which induces a
stronger electronic hopping integral along the out-of-plane direction and
corresponding out-of-plane magnetic easy axis for n = 2. We demonstrate that
interfacial orbital hybridization in superlattices of strongly correlated
oxides may be a promising approach to tailor electronic and magnetic properties
in device applications.
