Enhancement of TN Induced by Magnetic Dilution in the Linear Magnetoelectric Mn4Nb2O9

Ferroelectric polarization induced by the magnetic field is one of the properties reported in honeycomb antiferromagnetic linear magnetoelectrics (LME) belonging to the A4M2O9P3¯c1 class of corundum compounds with A = Co, Fe, and Mn and M = Nb or Ta. Among them, Mn4Nb2O9 exhibits the highest TN of 108 K. We show that it can even be increased by substituting partly Mn by Fe. The study of Mn4−xFexNb2O9 allows one to reach a TN up to 126 K at x = 1.5. This beneficial effect, confirmed also for Fe substituted Mn4Ta2O9, is compared to substitutions by Co or by Zn, both cations inducing a TN decrease. The linear decrease in the unit cell volume with x in Mn4−xFexNb2O9 shows that the cation size effect only cannot be inferred to explain the TN(x) curve. Furthermore, the spin flop magnetic field of Mn4Nb2O9 decreases, thanks to the Fe for Mn substitution, a LME effect is evidenced at 10 K, ΔP(9T)10K = 11 μC/m2. These features, TN increase and LME properties, demonstrate the important role of substitutions to enhance the properties of such antiferrromagnets.