The effect of oxidation on the surface-near lattice relaxation in FeNi nanoparticles

The near-surface oxidation-induced lattice relaxation and compositional changes of FeNi alloy nano-particles are investigated. Using a newly developed transfer system, the particle structure was characterised by means of aberration-corrected HR-TEM prior to exposing the particles to ambient air. This allows for a comparison of oxidised and un-oxidised particles, respectively. Independent of the oxidation, the surface-near and/or interface-near metal lattice was found to be expanded by up to 3%. EELS profiles clearly reveal an enrichment of Fe at the particle surfaces. MD simulations in combination with HR-TEM contrast simulations were conducted to investigate the effect of the Fe enrichment on the structural relaxation. The results show that a surface-near over-stoichiometric enrichment of Fe indeed causes a dilation that counteracts a compression of the lattice at the particle surface as obtained for homogeneously alloyed particles. Besides, the large lattice mismatch between the metallic cores and the NiFe₂O₄ shells causes the formation of step dislocations in the close vicinities of the interface. In essence, the surface-near lattice relaxation in oxide free particles is found to be due to a segregation of Fe to the surface, whereas in the case of shell–core particles, no systematic influence of the oxide on the lattice relaxation was found.