Spin-Glass Transitions in Zn(1-x)Fe(x)O Nanoparticles

Monophasic Zn(1-x)Fe(x)O nanoparticles with wurtzite structure were synthesized in the 0 ≤ x ≤ 0.05 concentration range using a freeze-drying process followed by heat treatment. The samples were characterized regarding their optical, structural, and magnetic properties. The analyses revealed that iron doping of the ZnO matrix induces morphological changes in the crystallites. Iron is substitutional for zinc, trivalent and distributed in the wurtzite lattice in two groups: isolated iron atoms and iron atoms with one or more neighboring iron atoms. It was also shown that the energy band gap decreases with a higher doping level. The samples are paramagnetic at room temperature, but they undergo a spin-glass transition when the temperature drops below 75 K. The magnetic frustration is attributed to the competition of magnetic interactions among the iron moments. There are a superexchange interaction and an indirect exchange interaction that is provided by the spin (and charge) itinerant carriers in a spin-polarized band situated in the vicinity of the Fermi level of the Fe-doped ZnO semiconductor. The former interaction actuates for an antiferromagnetic coupling among iron ions, whereas the latter constitutes a driving force for a ferromagnetic coupling that weakens, decreasing the temperature. Our results strongly contribute to the literature because they elucidate the controversies reported in the literature for the magnetic state of the Fe-doped ZnO system.