Magnetic field directed assembly of superstructures of ferrite-ferroelectric core-shell nanoparticles and studies on magneto-electric interactions

Abstract

Composites of ferromagnetic and ferroelectric are of interest for studies on mechanical strain mediated magneto-electric (ME) interactions and for useful technologies. Here, we report on magnetic-field-assisted-assembly of barium titanate (BTO)-nickel ferrite (NFO) core-shell particles into linear chains and 2D/3D arrays and measurements of ME effects in such assemblies. First, we synthesized the core-shell nano-particles with 50–600 nm BTO and 10–200 nm NFO by chemical self-assembly by coating the ferroic particles with complementary coupling groups and allowing them to self-assemble in the presence of a catalyst via the “click” reaction. The core-shell structure was confirmed with electron microscopy and scanning probe microscopy. We obtained superstructure of the core-shell particles by subjecting them to a magnetic field gradient that exerts an attractive force on the particles and align them toward the regions of high field strengths. At low particle concentration, linear chains were formed and they evolved into 2D and 3D arrays at high particle concentrations. Magnetoelectric characterization on unassembled films and assembled arrays has been performed through measurements of low-frequency ME voltage coefficient (MEVC) by subjecting the sample to a bias magnetic field and an ac magnetic field. The MEVC is higher for field-assembled samples than for unassembled films and is found to be sensitive to field orientation with a higher MEVC for magnetic fields parallel to the array direction than for magnetic fields perpendicular to the array. A maximum MEVC of 20 mV/cm Oe, one of the highest reported for any bulk nanocomposite, is measured across the array thickness. A model is provided for ME coupling in the superstructures of BTO-NFO particulate composites. First, we estimated the MEVC for a free-standing BTO-NFO core-shell particle and then extended the model to include an array of linear chains of the particles. The theoretical estimates are in qualitative agreement with the data.