Ferroelectricity‐Induced Surface Ferromagnetism in Core–Shell Magnetoelectric Nanoparticles

Magnetoelectric nanoparticles (NPs) present an important class of nanomaterials with a wide interest in piezocatalytic and biomedical applications. Herein, the results of magnetoelectric and magnetization measurements performed on core–shell NPs having magnetic core (MnFe2O4, MFO) and ferroelectric shell (Ba0.85Ca0.15Ti0.5Zr0.5O3, BCZT) synthesized by the microwave hydrothermal method are reported. Magnetic results are compared with the measurements on reference MFO NPs prepared under identical conditions. Detailed SQUID magnetometer measurements of the magnetization hysteresis loops M(H) down to 2 K reveal the existence of a clear exchange bias effect in pure MFO NPs attributed to the coexistence of ferromagnetic and antiferromagnetic short‐range interactions. When the magnetic core is covered by the thin ferroelectric BCZT shell, it is observed that 1) the shell suppresses the apparent bias effect and 2) induces an “extra” ferromagnetic magnetization at T < 20 K. The results indicate that this “extra” ferromagnetism has a 2D character and it is most likely related to the interface interactions between the MFO core and BCZT shell. Ferroelectric properties and strong magnetoelectric effect in core–shell NPs are revealed via piezoresponse force microscopy under magnetic field. The mechanisms of the observed effects are discussed.