Absence of morphotropic phase boundary effects in BiFeO(3)-PbTiO(3) thin films grown via a chemical multilayer deposition method

We report an unusual behavior observed in (BiFeO3)1 -x¿(PbTiO3)x (BF¿xPT) thin films prepared using a multilayer chemical solution deposition method. Films of different compositions were grown by depositing several bilayers of BF and PT precursors of varying BF and PT layer thicknesses followed by heat treatment in air. X-ray diffraction showed that samples of all compositions show mixing of two compounds resulting in a single-phase mixture, also confirmed by transmission electron microscopy. In contrast to bulk compositions, samples show a monoclinic (MA-type) structure suggesting disappearance of the morphotropic phase boundary (MPB) at x = 0.30 as observed in the bulk. This is accompanied by the lack of any enhancement of the remanent polarization at the MPB, as shown by the ferroelectric measurements. Magnetic measurements showed an increase in the magnetization of the samples with increasing BF content. Significant magnetization in the samples indicates melting of spin spirals in the BF¿xPT films, arising from a random distribution of iron atoms. Absence of Fe2+ ions was corroborated by X-ray photoelectron spectroscopy measurements. The results illustrate that thin film processing methodology significantly changes the structural evolution, in contrast to predictions from the equilibrium phase diagram, besides modifying the functional characteristics of the BP-xPT system dramatically.