Structural and dielectric properties of laser ablated BaTiO3 films deposited over electrophoretically dispersed CoFe2O4 grains

Abstract

Thin film nanocomposites with mixed connectivity, composed by CoFe2O4 grains deposited by electrophoresis on Si|Pt substrates and subsequently covered by a laser ablation deposited BaTiO3 layer were prepared with different cobalt ferrite concentrations. Their structure presented a combination of BaTiO3, with its tetragonal and the orthorhombic phases coexisting at room temperature, and CoFe2O4 with the cubic spinel structure. The cobalt ferrite nanograins were under in-plane tensile stress, while the BaTiO3 phase was under in-plane compressive stress. The dielectric measurements showed that as the barium titanate grain size decreased, its ferroelectric Curie temperature shifted to lower temperatures relative to the bulk. This grain size dependent TC shift was associated and modeled by a core-shell structure of BaTiO3 grains in the films, with a tetragonal core and cubic shell. Additionally a diffuse tetragonal-orthorhombic phase transition was observed and, in agreement with Raman spectroscopy results, associated to the coexistence of barium titanate orthorhombic and tetragonal phases in the room temperature region. This led to the formation of polar nanoclusters with random polarization orientations, which induced a frustrated phase transition between the tetragonal and orthorhombic phases of barium titanate in the films.