Study of monoclinic-tetragonal-cubic phase transition in Pb(Zn1/3Nb2/3)O3–0.08PbTiO3 single crystals by micro-Raman spectroscopy

High-energy x-ray diffraction experiments peformed on rhombohedral (1-x)Pb(Zn1/3Nb2/3)O3-xPbTiO3(PZN-xPT) crystals with x= 4.5 and 8% show that an electric field applied along the [001] direction induces the tetragonal phase, as proposed by Park and Shrout. Our experiments reveal that in 4.5PT such phase change occurs via a third phase with monoclinic symmetry, MA, which is observed at intermediate field values. This is in agreement with first-principles calculations by Fu and Cohen predicting the rotation of the polarization between the rhombohedral and tetragonal phases in this material. A different polarization path between the rhombohedral and tetragonal phases, through a second monoclinic phase, MC, has been previously reported in 8PT. The microscopic characterization of these crystals allows us to explain the ultra-high macroscopic strain observed in PZN-x%PT under an electric field. Moreover, some unusual scattering profiles displayed by exceptionally good crystals, are experimental evidence of the high anharmonicities and near-degeneracy of the different phases in these extremely deformable materials.