A Raman scattering study of pressure-induced phase transitions in nanocrystalline Bi₂MoO₆

Lattice dynamics calculations and a high-pressure Raman scattering study of nanocrystalline Bi(2)MoO(6), a member of the bismuth-layered Aurivillius family of ferroelectrics, are presented. These studies showed the onset of two reversible second-order or weakly first-order phase transitions near 2.5 and 4.5 GPa as well as some subtle structural changes at 8.2 GPa. Symmetry increases upon application of pressure and the first phase transition involves, most likely, the loss of the MoO(6) tilt mode around a pseudo-tetragonal axis. The second phase transition is associated with the instability of a low wavenumber mode, which behaves as a soft mode. This soft mode most likely corresponds to the polar E(u) mode of the tetragonal I4/mmm aristotype and Bi(2)MoO(6) transforms at 4.5 GPa into the centrosymmetric orthorhombic phase. The sequence of the pressure-induced phase transitions in nanocrystalline Bi(2)MoO(6) is similar to that observed for bulk Bi(2)WO(6) but the critical pressures are significantly lower for the molybdenum compound. Our results also show that the critical pressure of the first phase transition is slightly lower for the nanocrystalline Bi(2)MoO(6) (2.5 GPa) than for the microcrystalline (bulk) Bi(2)MoO(6) (2.8 GPa).