Core and surface structure and magnetic properties of mechano-synthesized LaFeO3 nanoparticles and their Eu3+-doped and Eu3+/Cr3+-co-doped variants.

The core and surface structure, and magnetism of mechano-synthesized LaFeO3 nanoparticles (30-40 nm), Eu3+-doped (La0.70Eu0.30FeO3), and Eu3+/Cr3+ co-doped (La0.70Eu0.30Fe0.95Cr0.05O3) are reported. Doping results in a transition from the O'-type to the O-type distorted structure. Traces of reactants, intermediate phases, and a small amount of Eu2+ ions were detected on the surfaces of the nanoparticles. The nanoparticles consist of antiferromagnetic cores flanked by ferromagnetic shells. The Eu3+ dopant ions enhance the magnetization values relative to those of the pristine nanoparticles and result in magnetic susceptibilities compatible with the presence of Eu3+ van Vleck paramagnetism of spin-orbit coupling constant (λ = 363 cm-1) and a low temperature Curie-Weiss like behavior associated with the minority Eu2+ ions. Anomalous temperature-dependent magnetic hardening due to competing magnetic anisotropy and magnetoelectric coupling effects together with a temperature-dependent dopant-sensitive exchange bias, caused by thermally activated spin reversals at the core of the nanoparticles, were observed.