Pressure induced para-antiferromagnetic switching in BiFeO3-PbTiO3 as determined using in-situ neutron diffraction

BiFeO3-PbTiO3 exhibits both ferroelectric and antiferromagnetic order, depending on the composition. Moderate hydrostatic pressures have been used at room temperature to transform the crystallographic phase from P4mm to R3c for the compositions 0.7BiFeO(3)-0.3PbTiO(3) and 0.65BiFeO(3)-0.35PbTiO(3), as determined using in-situ neutron diffraction. Using Rietveld refinements, the resultant data showed that, for both compositions, a transformation from para-to G-type antiferromagnetic order accompanied the structural transition. The transformation occurred over the range 0.4-0.77 and 0.67-0.88GPa for 0.7BiFeO(3)-0.3PbTiO(3) and 0.65BiFeO(3)-0.35PbTiO(3), respectively; at intermediate pressures, a mixture of P4mm and R3c phases were evident. These pressures are far lower than required to induce a phase transition in either the BiFeO3 or PbTiO3 end members. The driving force for this pressure induced first order phase transition is a significant difference in volume between the two phases, P4mm > R3c of 4%-5%, at ambient pressure. Upon removal of the pressure, 0.65BiFeO(3)-0.35PbTiO(3) returned to the paramagnetic tetragonal state, whereas in 0.7BiFeO(3)-0.3PbTiO(3) antiferromagnetic ordering persisted, and the structural phase remained rhombohedral. Using conventional laboratory x-ray diffraction with a hot-stage, the phase readily reverted back to a tetragonal phase, at temperatures between 100 and 310 degrees C for 0.7BiFeO(3)-0.3PbTiO(3), far lower than the ferroelectric Curie point for this composition of 632 degrees C. To our knowledge, the reported pressure induced para-to antiferromagnetic transition is unique in the literature. (C) 2013 AIP Publishing LLC.