Cation substitution and size confinement effects on structure, magnetism and magnetic hyperthermia of BiFeO3-based multiferroic nanoparticles and hydrogels

Abstract

Highly crystalline BiFeO3 (BFO), Bi0.97Sm0.03FeO3 and BiFe0.97Co0.03O3 nanoparticles are synthesized via the chemical co-precipitation method after calcination at 600 °C in air for 2 h. The effect of cation substitution, Sm for Bi and Co for Fe, on the structural and magnetic properties of BFO nanoparticles is investigated, whereas their magnetically induced heating efficiency in radio frequency alternating magnetic fields is examined. X-ray diffraction indicates the formation of the R3c phase in all compounds, while the corresponding Rietveld refinement reveals a variation of the lattice parameters upon doping, suggesting structural distortion within the BFO lattice due to the ionic radii mismatch between doped and host elements. Transmission electron microscopy unveils smaller particle sizes for the doped nanoparticles, owing to the frustrated particle growth induced by the dopants, whose presence is verified by X-ray photoelectron spectroscopy and energy dispersive X-ray analysis. The combined effect of cation substitution and size confinement results in the suppression of the spiral spin structure of BFO, leading to the significantly enhanced magnetic features of the doped nanoparticles at room temperature. For possible applications in the biomedical sector, we tested them as heating agents in magnetic hyperthermia. The dispersion of BiFe0.97Co0.03O3 nanoparticles in water at a concentration of 4 mg/mL could reach the therapeutic window of 41–45 °C for cancer treatment in 50 mT at 375 kHz, whereas the remarkable temperature increase of the BFO-based multiferroic hydrogels, under the same conditions, is auspicious for an effective local treatment at reduced toxicity.