New structural transformations in congruent ferroelectric LiNbO3 fibres evidenced by Raman spectroscopy

Temperature dependent Stokes and anti-Stokes Raman-scattering experiments have been performed to study the ferroelectric phase of congruent LiNbO3 fibres in the external and internal mode regions. Mode splittings and changes in the slope of frequency-temperature plots at 590 and 790 K show the occurrence of two structural transformations at these temperatures. The anisotropy of the correlation time associated with the width of the central component and anomalies observed in previous neutron investigations are related to a migration process of the lithium atoms along the hexagonal axis and along the pseudo-cubic axis of the highly distorted related perovskite structure. The observed transformations are tentatively assigned to long-range correlated rearrangements in the intrinsic defect structure of the crystal.