The dependence of ferroelectric and fatigue behaviors of PZT films on microstructure and orientation

Microstructure of PbZr, Ti, O, films about 0.2 pm thick was studied as a function of annealing temperature and time using TEM and SEM. The films were heat treated in the temperature range 550- 650°C for times from 10 minutes to 4 hours. The features characterized were crystal structure of individual PZT particles, PZT grain size and shape, porosity, and grain boundaries. The films were prepared by the metallo-organic decomposition (MOD) process which produced films amorphous to x-rays after pyrolysis. A growth mechanism of PZT particles from the amorphous film is discussed. It was found that at mild annealing conditions (Le., low temperature and short annealing times), agglomerates of microcrystallites of perovskite, and probably pyrochlore. were formed. As the temperature was increased, the microcrystallites grew into porous submicron perovskite single crystals. With excessive heating, intraparticle pores were found to migrate and became pinned at the grain boundaries, causing widening of boundaries which probably was responsible for the degradation in ferroelectric properties observed in such films. The dependence of ferroelectric and fatigue behaviors on grain orientation was also investigated. It was found that PZT films oriented in the [I 111 direction demonstrated better fatigue behavior but not necessarily higher polarizations.