Abstract
The origin of the discrepancy between the measured average parameter of the perovskite unit cell of PbTiO3and the unit-cell parameter calculated for an ideal perovskite structure is analyzed with the use of extended x-ray absorption fine structure spectroscopy data, which demonstrate that PbTiO3contains Pb4+ions. The amount of Pb4+depends on the preparation conditions and may attain ≃6 at. %. Assumption is made that the presence of crystallographic shear planes allows a fraction of the Pb2+ions to occupy octahedral sites near the shear planes. The maximum content of Pb2+on the B site is ≃2.5 at. %. The formula proposed for the cation composition of imperfect lead titanate differs from the ideal formula Pb2+Ti4+O3and indicates that lead titanate can be thought of as an internal solid solution. It is shown that the composition of lead titanate influences its electrical properties: e/e0increases with Pb4+concentration and exceeds that in single crystals by an order of magnitude.
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