Lead zirconate titanate (PZT) thin films on platinized silicon were fabricated and their structural development upon annealing was characterized by x-ray diffraction and transmission electron microscopy (TEM). The amount of a transient intermetallic phase Pt3Pb was found initially to increase with annealing time and to decay after reaching a maximum. The kinetic process of growth and decay was simulated by using the Avrami equation. The Avrami coefficient n and growth rate constant k were determined by comparing the experimental results and the simulated curves, from which activation energies of 40 and 145 kJ/mol were obtained for the growth and decay of the intermetallic Pt3Pb phase, respectively. The perovskite PZT was found by using TEM to nucleate epitaxially on top of the Pt3Pb phase. Evidence is presented that the Pt3Pb phase plays a major role in determining the crystallite's orientation at the nucleation stage of the perovskite PZT. This depends strongly on the annealing temperature and the orientation changes little during the following growth process. (C) 1999 American Institute of Physics. [S0021-8979(99)10115-4].