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A detailed investigation of the onion structure of exchanged coupled magnetic Fe3−δO4@CoFe2O4@Fe3−δO4 nanoparticles

DOI: 10.1021/acsami.0c18310 DOI Help

Authors: Kevin Sartori (Université de Strasbourg, CNRS; SOLEIL; Laboratoire Léon Brillouin) , Anamaria Musat (Université de Strasbourg, CNRS) , Fadi Choueikani (Synchrotron SOLEIL) , Jean-Marc Grenèche (Université du Maine) , Simon Hettler (CSIC-Universidad de Zaragoza) , Peter Bencok (Diamond Light Source) , Sylvie Begin-Colin (Université de Strasbourg, CNRS) , Paul Steadman (Diamond Light Source) , Raul Arenal (CSIC-Universidad de Zaragoza; Fundacion ARAID) , Benoit Pichon (Université de Strasbourg, CNRS)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Acs Applied Materials & Interfaces

State: Published (Approved)
Published: March 2021

Abstract: Nanoparticles that 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 nanoparticles which hampers potential applications such as data storage or sensors. In this manuscript, we report on the design of nanoparticles with an onion-like structure which has been scarcely reported yet. These nanoparticles consist of a Fe3−δO4 core covered by a first shell of CoFe2O4 and a second shell of Fe3−δO4, e.g., a Fe3−δO4@CoFe2O4@Fe3−δO4 onion-like structure. They were synthesized through a multistep seed-mediated growth approach which consists consists in performing three successive thermal decomposition of metal complexes in a high-boiling-point solvent (about 300 °C). 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 increasing. We investigated very precisely the structure of nanoparticles in performing high resolution (scanning) TEM imaging and geometrical phase analysis (GPA). The chemical composition and spatial distribution of atoms were studied by electron energy loss spectroscopy (EELS) mapping and spectroscopy. The chemical environment and oxidation state of cations were investigated by 57Fe Mössbauer spectrometry, soft X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD). The combination of 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, whereas 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 Fe3−δO4 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 nanoparticles, thus demonstrating the high potential of onion-like nanoparticles to accurately tune the magnetic properties of nanoparticles according to the desired applications.

Journal Keywords: exchanged-coupling; onion-type; nanoparticles; magnetism; XMCD; Mössbauer; EELS

Subject Areas: Materials, Physics

Instruments: I10-Beamline for Advanced Dichroism

Other Facilities: DEIMOS beamline at SOLEIL

Discipline Tags:

Material Sciences Physics Magnetism

Technical Tags:

Spectroscopy Circular Dichroism (CD) X-ray Magnetic Circular Dichroism (XMCD)