Strong impact of low-level substitution of Mn by Fe on the magnetoelectric coupling in TbMnO3

The correlation between static magnetoelectric coupling and magnetic structure was investigated in TbMn0.98Fe0.02O3 with magnetic field up to 8 T and down to 2 K. Single-crystal neutron diffraction experiments reveal a substantial increase in the temperature dependence of the incommensurate modulation wave vector of the antiferromagnetic phase as the magnetic field strength increases. Magnetic field-dependent pyroelectric current measurements revealed significantly higher magnetoelectric coupling at magnetic fields below 4 T than in pure TbMnO3. This is due to the higher sensitivity of the incommensurably modulated cycloid structure to weak magnetic fields. Detailed analysis of our data confirmed that the ferroelectric polarization is induced by inverse Dzyaloshinskii-Moriya interaction for magnetic field strength up to 4 T, but at higher fields a departure from theoretical predictions is ascertained, giving evidence for an additional, as yet misunderstood, contribution to magnetoelectric coupling. It shows that a small 2% substitution of Mn3+ by Fe3+ has a strong impact on the magnetic structure, promoting the destabilization of the incommensurably modulated magnetic cycloidal structure of TbMnO3 in a magnetic field above 5 T. We demonstrate that the magnetoelectric coupling magnitude can be tuned through suitable substitutional elements, even at low level, inducing local lattice distortions with different electronic and magnetic properties.