Mechanism and controlled growth of shape and size variant core/shell FeO/Fe3O4nanoparticles

Abstract

We report a novel synthesis approach for the growth of core/shell FeO/Fe₃O₄ nanoparticles with controlled shape and size. FeO particles were partially oxidized to form core/shell FeO/Fe₃O₄ structures, as evidenced from transmission electron microscopy, X-ray diffraction, and magnetometry analysis. We find that the molar ratios and concentrations of surfactants are the key parameters in controlling the particle size. The particles can grow in either isotropic or anisotropic shapes, depending upon a chemical reaction scheme that is controlled kinetically or thermodynamically. The competitive growth rates of {111} and {100} facets can be used to tune the final shape of nanoparticles to spherical, cubic, octahedral, octopod, and cuboctahedral geometries. FeO particles can also be oxidized chemically or thermally to form Fe₃O₄ nanoparticles. By following the same synthesis technique, it is possible to synthesize rods and triangles of Fe₃O₄ by introducing twinnings and defects into the crystal structure of the seed. The thermally activated first-order Verwey transition at ∼120 K has been observed in all the synthesized FeO/Fe₃O₄ nanoparticles, indicating its independence from the particle shape. These core/shell nanoparticles exhibit a strong shift in field-cooled hysteresis loops accompanied by an increase in coercivity (the so-called exchange bias effect), but the low field-switching behavior appears to vary with the particle shape.