The structures and microstructures of a range of Aurivillius phases were investigated by transmission electron microscopy. Systematic rows of superlattice reflections arising from tilting of octahedra around the c axis were identified, and their intensities at room temperature were shown to diminish as the tolerance factor (t) of the perovskite blocks increased. For compounds with t's approaching 1, no superlattice reflections were observed. the paraelectric-to-ferroelectric phase transition temperature (Tc) was monitored through permittivity measurements as a function of temperature, and Tc was also shown to decrease as t increased. Consequently, the onset of octahedral tilting and Tc appeared to be strongly related Aurivillius phases. Planar defects arising from the structural phase transitions and from stacking irregularities were also discussed.
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