Magneto-electric decoupling in bismuth ferrite

TL;DR

This study reveals that in BiFeO3, ferroelectric and magnetic orders are decoupled at the atomic scale, with magnetic ordering affecting the Fe-site but not the Bi-site, challenging previous assumptions about magnetoelectric coupling.

Contribution

The paper provides direct atomic-scale evidence that ferroelectric and magnetic orders in BiFeO3 decouple at the unit-cell level, supported by experimental TDPAC data and DFT calculations.

Findings

Magnetic ordering affects the Fe-site but not the Bi-site.

Ferroelectric and magnetic orders are decoupled at the atomic scale.

Experimental results align with ab-initio DFT calculations.

Abstract

It is still under intensive discussion, how magnetoelectric coupling actually 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 cancelling 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 sub-lattice (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 sub-lattice carrying the 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.