Two phase magnetoelectric epitaxial composite thin films

Abstract

Magnetoelectricity (ME) is a physical property that results from an exchange between polar (electric dipole) and spin (magnetic dipole) subsystem: i.e., a change in polarization (P) with application of magnetic field (H), or a change in magnetization (M) with applied electric field (E). Magnetoelectricity can be found both in single phase and composite materials. Compared with single phase multiferroic materials, composite multiferroics have higher ME effects. Through a strictive interaction between the piezoelectricity of the ferroelectric phase and the magnetostriction of the ferromagnetic phase, said multiferroic composites are capable of producing relatively large ME coefficients. This Dissertation focused on the deposition and characterization of two-phase composite magnetoelectric thin films. First, single phase ferroelectric thin films were studied to improve the multiferroic properties of the composite thin films. Then structural, ferroelectric, ferromagnetic, and magnetoelectric properties of composite thin films were researched. Finally, regular nano-array composite films were deposited and characterized. First, for single phase ferroelectric thin films, the phase stability was controlled by epitaxial engineering. Because ferroelectric properties are strongly related to their crystal structure, it is necessary to study the crystal structures in single phase ferroelectric thin films. Through constraint of the substrates, the phase stability of the ferroelectric thin films were able to be altered. Epitaxial thin-layers of Pb(Fe1/2Nb1/2)O3 (or PFN) grown on (001), (110), and (111) SrTiO3 substrates are tetragonal, orthorhombic, and rhombohedral respectively. The larger constraint stress induces higher piezoelectric constants in tetragonal PFN thin film. Epitaxial thin-layers of Pb(Zr0.52Ti0.48)O3 (or PZT) grown on (001), (110), and (111) SrTiO3 substrates are tetragonal, monoclinic C, and rhombohedral respectively. Enhanced ferroelectric properties were found in the low symmetry monoclinic phase. A triclinic phase in BFO was observed when it was deposited on tilted (001) STO substrates by selecting low symmetry (or interim) orientations of single crystal substrates. Then, in two phase composite magnetoelectric thin films, the morphology stability was controlled by epitaxial engineering. Because multiferroic properties are strongly related to the nano-structures of the composite thin films, it is necessary to research the nano-structures in composite thin films. Nano-belt structures were observed in both BaTiO3-CoFe2O4 and BiFeO3-CoFe2O4 systems: by changing the orientation of substrates or annealing condition, the nano-pillar structure could be changed into nano-belts structure. By doing so, the anisotropy of ferromagnetic properties changes accordingly. The multi-ferroic properties and magnetoelectric properties or (001), (110) and (111) self-assembled BiFeO3-CoFe2O4 nano-composite thin film were also measured. Finally, the regular CoFe2O4-BiFeO3 nano-array composite was deposited by pulsed laser deposition patterned using a focused ion beam. Top and cross-section views of the composite thin film showed an ordered CoFe2O4 nano-array embedded in a BiFeO3 matrix. Multiferroic and magnetoelectric properties were measured by piezoresponse force microscopy and magnetic force microscopy. Results show (i) switching of the magnetization in ferromagnetic CoFe2O4 and of the polarization in ferroelectric BiFeO3 phases under external magnetic and electric field respectively, and (ii) changes of the magnetization of CoFe2O4 by applying an electric field to the BiFeO3 phase.