Magnetoelectric Decoupling in Bismuth Ferrite

It is still an open question if magnetoelectric coupling occurs at the atomic scale in multiferroic BiFeO3. Nuclear solid-state techniques monitor local fields at the atomic scale. Using such an approach, we show that, contrary to our own expectation, ferroelectric and magnetic ordering in bismuth ferrite (BiFeO3 or BFO) decouple at the unit-cell level. Time differential perturbed angular correlation (TDPAC) data at temperatures below, close, and above the magnetic N´ eel temperature show that the coupling of the ferroelectric order to magnetization is completely absent at the bismuth site. It is common understanding that the antiferromagnetic order and the cycloidal ordering due to the Dzyaloshinskii-Moriya interaction generate a net zero magnetization of the sample canceling out any magnetoelectric effect at the macroscopic level. Our previous data show that a very large coupling of magnetic moment and electrical distortions arises on the magnetic sublattice (Fe site). The oxygen octahedra around the iron site experience a large tilt due to the onset of magnetic ordering. Nevertheless, the Bi-containing complementary sublattice carrying the largest part of ferroelectric order is practically unaffected by this large structural change in its direct vicinity. The magnetoelectric coupling thus vanishes already at the unit cell level. These experimental results agree well with an ab initio density functional theory (DFT) calculation.