In this study, we investigate the properties, with a
special focus
on the magnetic attributes, of NiFe2O4 (NFO)/BaTiO3 (BTO) multiferroic heterostructures, examining individual
layer thicknesses ranging from 3 to 12 nm. X-ray diffraction reveals
that as BTO thickness increases, NFO transitions from a nonstrained
cubic lattice to a compressively strained tetragonal lattice. In contrast,
thicker NFO layers introduce enhanced tensile stresses on the BTO
layer, counteracting the compressive strain originating from the SrTiO3 (STO) substrate. Piezoresponse force microscopy demonstrates
that the polarization switching voltage escalates with increasing
BTO layer thickness. Through X-ray magnetic circular dichroism measurements
coupled with multiplet theory, we elucidate variations in the magnetic
moments and ionic distributions within the NFO layers. Remarkably,
a larger BTO thickness is associated with a chemical reduction of
Fe ions in the NFO layer, indicative of increased oxygen vacancies,
which are induced by the increasing compressive strain as evidenced
by first-principles calculations. Thinner NFO layers showed increased
tetrahedral (T
d) site vacancies and oxygen
vacancies concomitant with reduced magnetic moments, which can be
optimized by either increasing NFO thickness or through air annealing
at 450 °C. Combining the ionic distribution variation with in-plane
lattice parameter evolution during growth, we postulated that the
reduced magnetic moments originate from a 2–3 nm antiferromagnetic
rock salt NiO/FeO formed at the beginning of NFO growth, while the
air annealing restores the magnetism by oxidizing and arranging the
NiO/FeO into spinel NFO under the synergistic effect of oxygen and
heat. Air annealing at moderate temperature appears as a very efficient
method to restore the magnetization of ultrathin layers of NFO, allowing
us to overcome a major drawback for these compounds, which hampers
their utilization in spintronics applications so far.