Cluster-glass-like behavior in zinc ferrite nanograins

Abstract

Structural and magnetic properties of ZnFe2O4 nanograins, prepared by high-energy ball milling and annealed, were systematically studied by X-ray diffraction, 57Fe Mössbauer spectroscopy and AC magnetic susceptibility measurements. Disordered spinel-like structure, with a grain size of 12 nm, is established after 200 h of milling. While the 300 K Mössbauer spectrum of the as-milled sample (200 h) displays broad magnetic absorption lines, characteristic of a disordered system, the magnetization data do not show a magnetic phase transition between 4 and 300 K. At low temperatures, the Mössbauer spectra suggest the presence of two distinct ferrite magnetic phases: one attributed to the grain core (crystalline-like phase), with magnetic ordering temperature of about 90 K, and one showing a magnetic hyperfine field distribution; the latter is associated with a chemically disordered phase (grain boundary contributions). Annealing the 200 h sample at 973 K leads to an improvement of atomic ordering of the spinel structure (reduction of cationic inversion) and average grain size of about 17 nm. AC magnetic susceptibility shows a cusp at about T≈30K, whilst Mössbauer experiments in the same sample reveal magnetic blocking in the same temperature range. The frequency dependence of susceptibility suggests the formation of a cluster-glass-like state. High temperature susceptibility can be described with a Fulcher law of interacting magnetic clusters.