A polarized Raman study of the relaxor and ferroelectric states of La-modified lead zirconate titanate ceramics

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Abstract
Lanthanum modified lead zirconate titanate ceramics with La/Zr/Ti ratios of 6/40/60, 12/40/60, 5/65/35, and 9/65/35 have been studied by polarized Raman scattering. In the two former (tetragonal-type) compositions, selection rules were rather well defined and allowed an assignment of the Raman lines at lower temperature. These selection rules disappeared for 6/40/60 but remained for 12/40/60 even at higher temperatures. The behavior of the two latter (rhombohedral-type compositions) was quite different. No assignment of lines could be done. In addition, the spectra recorded in parallel and crossed polarizations were almost identical for 5/65/35 regardless of temperature. A very smeared paraelectric to ferroelectric transition was evidenced by Raman intensity measurements for this composition. On the contrary, selection rules were always present for the relaxor composition 9/65/35 which were similar to those for 12/40/60 and 6/40/60. This suggests that both tetragonal and rhombohedral-type local polar order is present for 9/65/35. The spectra of the field induced ferroelectric phase for 9/65/35 revealed no selection rules, similar to 5/65/35. This is attributed to the onset of only medium range ferroelectric order. Finally, Raman spectra recorded on powders of every composition did not reveal any selection rules, suggesting that intergranular effects might play a significant role in the behavior of these materials.