  Lead titanate (PbTiO3) is a classical example of a ferroelectric perovskite
oxide illustrating a displacive phase transition accompanied by a softening of
a symmetry-breaking mode. The underlying assumption justifying the soft-mode
theory is that the crystal is macroscopically sufficiently uniform so that a
meaningful free energy function can be formed. In contrast to PbTiO3,
experimental studies show that the phase transition behaviour of
lead-zirconate-titanate solid solution (PZT) is far more subtle. Most of the
studies on the PZT system have been dedicated to ceramic or powder samples, in
which case an unambiguous soft-mode study is not possible, as modes with
different symmetries appear together. Our Raman scattering study on
titanium-rich PZT single crystal shows that the phase transitions in PZT cannot
be described by a simple soft-mode theory. In strong contrast to PbTiO3,
splitting of transverse E-symmetry modes reveals that there are different
locally-ordered regions. The role of crystal defects, random distribution of Ti
and Zr at the B-cation site and Pb ions shifted away from their ideal
positions, dictates the phase transition mechanism. A statistical model
explaining the observed peak splitting and phase transformation to a complex
state with spatially varying local order in the vicinity of the morphotropic
phase boundary is given.
