Role of fluorite formation in orientation selection in Sol-Gel derived Pb(Zr, Ti)O₃ films on Pt electrode layers

We present evidence that the microstructure of the metastable fluorite phase Pb2(Zr, Ti)2O6, which forms during the pyrolysis treatment of sol-gel PZT layers by homogeneous nucleation throughout the film, has a larger impact on orientation selection than has previously been realized. Elaborate TEM studies demonstrate that by varying the pyrolysis time, temperature and duration, the crystallinity of the transient fluorite phase can be greatly influenced. Pyrolysis at 350°C leads to the formation of a well crystallized fluorite phase with a cubic structure (Fd3m space group) and a= 10.5-10.6 Å. Rapid crystallization of the transient fluorite phase is attributed to the low oxygen partial pressure conditions, prevailing during burnoff of acetate groups originating from the lead starting compound. A possible connection between the fluorite formation kinetics and orientation selection in the layers is discussed.