Spin-assisted ferroelectricity in ferrimagnetic CaBaCo\({}_{4}\)O\({}_{7}\)

The magnetoelectric effect--the induction of magnetization by means of an electric field and induction of polarization by means of a magnetic field--was first presumed to exist by Pierre Curie, and subsequently attracted a great deal of interest in the 1960s and 1970s (refs 2-4). More recently, related studies on magnetic ferroelectrics have signalled a revival of interest in this phenomenon. From a technological point of view, the mutual control of electric and magnetic properties is an attractive possibility, but the number of candidate materials is limited and the effects are typically too small to be useful in applications. Here we report the discovery of ferroelectricity in a perovskite manganite, TbMnO3, where the effect of spin frustration causes sinusoidal antiferromagnetic ordering. The modulated magnetic structure is accompanied by a magnetoelastically induced lattice modulation, and with the emergence of a spontaneous polarization. In the magnetic ferroelectric TbMnO3, we found gigantic magnetoelectric and magnetocapacitance effects, which can be attributed to switching of the electric polarization induced by magnetic fields. Frustrated spin systems therefore provide a new area to search for magnetoelectric media.

Ferroelectric and magnetic materials are a time-honoured subject of study and have led to some of the most important technological advances to date. Magnetism and ferroelectricity are involved with local spins and off-centre structural distortions, respectively. These two seemingly unrelated phenomena can coexist in certain unusual materials, termed multiferroics. Despite the possible coexistence of ferroelectricity and magnetism, a pronounced interplay between these properties has rarely been observed. This has prevented the realization of multiferroic devices offering such functionality. Here, we report a striking interplay between ferroelectricity and magnetism in the multiferroic TbMn2O5, demonstrated by a highly reproducible electric polarization reversal and permanent polarization imprint that are both actuated by an applied magnetic field. Our results point to new device applications such as magnetically recorded ferroelectric memory.