Paper detail

A Detailed Investigation of the Onion Structure of Exchanged Coupled Magnetic Fe(3-delta)O4@CoFe2O4@Fe(3-delta)O4 Nanoparticles

Nanoparticles (NPs) which combine several magnetic phases offer wide perspectives for cutting edge applications because of the high modularity of their magnetic properties. Besides the addition of the magnetic characteristics intrinsic to each phase, the interface that results from core-shell and, further, from onion structures leads to synergistic properties such as magnetic exchange coupling. Such a phenomenon is of high interest to overcome the superparamagnetic limit of iron oxide NPs which hampers potential applications. In this manuscript, we report on the design of NPs with an onion-like structure which have been scarcely reported yet. These NPs consist in a Fe(3_delta)O4 core covered by a first shell of CoFe2O4 and a second shell of Fe(3-delta)O4. They were synthesized by a multi-step seed mediated growth approach. Although TEM micrographs clearly show the growth of each shell from the iron oxide core, core sizes and shell thicknesses markedly differ from what is suggested by the size increase. We investigated very precisely the structure of NPs in performing high resolution (scanning) TEM imaging and GPA. The chemical composition and spatial distribution of atoms were studied by EELS. The chemical environment and oxidation state of cations were investigated by Mössbauer spectrometry, soft XAS and XMCD. These techniques allowed us to estimate the increase of Fe2+ content in the iron oxide core of the core@shell structure and the increase of the cobalt ferrite shell thickness in the core@shell@shell one, while the iron oxide shell appears to be much thinner than expected. Thus, the modification of the chemical composition as well as the size of the Fe(3-delta)O4 core and the thickness of the cobalt ferrite shell have a high impact on the magnetic properties. Furthermore, the growth of the iron oxide shell also markedly modifies the magnetic properties of the core-shell NPs.