Ferroelectric thin films have recently received considerable attention because of their potential in a range of device applications including both volatile and non-volatile memories, optical data storage, and other electrooptic applications (e.g. waveguides, switches, and modulators). The Pb-based perovskites, such as Pb(Zr,Ti)O3, have many properties that make them attractive for such applications because of their high switchable remanant polarization. In addition, many applications require integration of the ferroelectric with semiconductors. In our work we are studying the crystallization sequence of PZT 40/60 (PbZr0.40Ti0.60O3) grown on platinized silicon substrates, with an overall structure given as PZT/Pt/Ti/SiO2Si. The Ti and Pt are sequentially evaporated onto the oxidized Si substrate. Alkoxide-derived films are spun onto these substrates to form a dry amorphous gel2. The crystallization of the sol-gel film proceeds upon heating to temperatures in the range of 400-700°C. Lead volatility is one of the critical issues in the crystallization of Pb-based perovskite thin films. We have carried out a systematic study on the role of a lead atmosphere in crystallization for PZT (40/60). When heat treated the film forms a transitory pyrochlore phase at intermediate temperatures before transforming to the perovskite phase. This non-ferroelectric pyrochlore phase may stabilize if lead stoichiometry is not maintained, leading to poor optical and ferroelectric properties in the thin films.