Phase transformations in sol-gel PZT thin films

Thin films of PZT were deposited onto platinized and bare single crystal NaCl using spin coating and sol-gel precursors. These films were then analyzed using in situ heating in a transmission electron microscope. The results of in situ heating are compared with those of an ex situ heat treatment in a standard furnace, mimicking the heat treatment given to entire wafers of these materials for use in MEMS and ferroelectric applications. Films are shown to transform from amorphous to nanocrystalline over the course of days when held at room temperature. While chemical variations are found between films crystallized in ambient conditions and films crystallized in the vacuum conditions of the microscope, the resulting crystal structures appear to be insensitive to these differences. Significant changes in crystal structure are found at 500 degreesC, primarily the change from largely amorphous to the beginnings of clearly crystalline films. Crystallization does occur over the course of weeks at room temperature in these films. Structural changes are more modest in these films when heated in the TEM then those observed on actual wafers. The presence of Pt significantly influences both the resulting structure and morphology in both in situ and ex situ heated films. Without Pt present, the films appear to form small, 10 nm grains consisting of both cubic and tetragonal phases, whereas in the case of the Pt larger, 100 nm grains of a tetragonal phase are formed.