Two Perovskite Modifications of BiFe0.6Mn0.4O3 Prepared by High-Pressure and Post-Synthesis Annealing at Ambient Pressure

Abstract

BiFeO3-related perovskite-type materials attract a lot of attention from the viewpoint of applications and fundamental science. In this work, we prepared two modifications of heavily Mn-doped BiFeO3 with the composition of BiFe0.6Mn0.4O3. A high-pressure (HP) modification was prepared at about 6 GPa and 1400 K. An ambient pressure (AP) modification was prepared by heating the HP modification at 780 K in the air at AP (post-synthesis annealing). Crystal structures of both modifications and in situ transformation were investigated with synchrotron powder X-ray diffraction. The transformation started at about 700 K and finished at about 780 K. The HP modification crystallized in space group Pnma with a = 5.57956 Å, b = 15.70576 Å, and c = 11.22557 Å, and the AP modification crystallized in space group Pbam with a = 5.63839 Å, b = 11.2710 Å, and c = 7.75923 Å (all parameters were at room temperature). Post-synthesis annealing of the HP modification (conversion polymorphism) is the only way to prepare the Pbam modification of oxygen stoichiometric BiFe0.6Mn0.4O3. Magnetic properties of both modifications have been reported. The Néel temperatures are TN = 350 K (HP) and TN = 335 K (AP). HP modification shows larger spin canting. Both modifications show negative magnetization phenomena at low temperatures in low magnetic fields.