Abstract
The phase transformation from the pyrochlore phase into the perovskite phase in ferroelectric films of lead zirconate titanate on silicon substrates due to annealing of samples has been investigated experimentally and theoretically. It has been proved that this transformation is a typical first-order phase transition, which is accompanied by a change in the density of the phases and the release of the latent heat of the phase transition. The quantitative evaluations have demonstrated that the difference in the densities of two phases, namely, the perovskite phase and the original parent pyrochlore phase, leads to the generation of elastic stresses in the original parent phase. In turn, these stresses bring about the nucleation of micropores in the bulk of the lead zirconate titanate film. The thermodynamic conditions providing the formation of micropores have been established and the critical size of the micropores has been calculated. A characteristic relationship between the critical size of nuclei of the perovskite phase and the radius of micropores at which the perovskite phase is separated from the parent pyrochlore phase has been derived. This relationship has been verified experimentally. The sizes of the micropores have been determined using scanning electron microscopy, and the changes in the phase composition during the phase transformation have been found using an electron probe X-ray microanalysis. It has been demonstrated theoretically and experimentally that the relaxation of elastic stresses in the lead zirconate titanate thin films during the phase transition occurs through the nucleation and growth of micropores at the interface between the new and parent phases.
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