${\mathrm{Cr}}_2{\mathrm{O}}_3$ is the archetypal magnetoelectric (ME) material, which has a linear coupling between electric and magnetic polarizations. Quadratic ME effects are forbidden for the magnetic point group of ${\mathrm{Cr}}_2{\mathrm{O}}_3$, due to space-time inversion symmetry. In ${\mathrm{Cr}}_2{\mathrm{O}}_3$ films grown by sputtering, we find a signature of a quadratic ME effect that is not found in bulk single crystals. We use Raman spectroscopy and magnetization measurements to deduce the removal of space-time symmetry and corroborate the emergence of the quadratic ME effect. We propose that metastable site-selective trace dopants remove the space, time, and space-time inversion symmetries from the original magnetic point group of bulk ${\mathrm{Cr}}_2{\mathrm{O}}_3$. We include the quadratic ME effect in a model describing the switching process during ME field cooling and estimate the effective quadratic susceptibility value. The quadratic magnetoelectric effect in a uniaxial antiferromagnet is promising for multifunctional antiferromagnetic and magnetoelectric devices that can incorporate optical, strain-induced, and multiferroic effects.

• Received 3 November 2020
• Revised 16 August 2021
• Accepted 2 September 2021

DOI:https://doi.org/10.1103/PhysRevMaterials.5.094406