Dielectric and Raman scattering experiments were performed on various ceramics with composition Ba(Ti1−xZrx)O3. Such lead-free, environmental-friendly materials were shown, from dielectric measurements, to exhibit behaviours extending from conventional to relaxor ferroelectrics on increasing the zirconium concentration. The evolution of the Raman spectra was studied as a function of temperature for various compositions, and the spectroscopic signature of the corresponding phases was determined. In the relaxor state, the variation of the integrated intensity of the Raman lines with temperature showed a plateau at low temperature. This anomaly was also detected as a peak in depolarization current measurements, and attributed to ergodicity breaking which characterizes usual relaxor systems. Raman results hint at locally rhombohedral polar nanoregions resulting from the random fields associated with Zr ions.
We have performed x-ray diffraction and Raman spectroscopy measurements in the temperature range of 300–873 K on a single phase epitaxially oriented BaTiO3 thin film grown by pulsed laser deposition on a single crystal MgO substrate. The θ–2θ room temperature diffraction measurements and asymmetric rocking curves indicate that the film is very weakly tetragonal with the c-axis parallel to the plane of the film. X-ray diffraction measurements up to high temperature reveal only a change in slope in the perpendicular to the plane lattice parameter around 450 K (in bulk Tc=395 K) indicating that a diffuse-like of phase transition is taking place. Room temperature polarized Raman spectra show that the film is indeed tetragonal with C4v symmetry and with the a-axis perpendicular to the film plane. Monitoring of the overdamped soft mode and the 308 cm−1 mode confirms that the phase transition is taking place over a wide temperature range according to the x-ray results. The increase of the phase transition temperature is attributed to the stress effect induced by the substrate.
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