Understanding the depolarization phenomena in (1−x) Na0.5Bi0.5TiO3. (x) Ba0.85Ca0.15Ti0.90Zr0.10O3 solid solutions using in-situ temperature dependent Raman spectroscopy

A decrease in depolarization temperature (Td) from 456 K to 352 K was observed with an increase in BCZT substitution in the NBT for the (1-x) Na0.5Bi0.5TiO3. (x) Ba0.85Ca0.15Ti0.90Zr0.10O3 solid solutions. A transition towards a higher ergodic state was elucidated with an increase in BCZT content that helped to reduce the free energy barrier, hence lesser thermal energy was required to depolarize the modified systems. Furthermore, a decrease in remnant polarization and coercive field, coupled with an increase in energy storage (Wstored) and efficiency (ƞ%) with higher BCZT content. In-situ temperature-dependent Raman spectra provide additional insights, highlighting the faster changes in phonon shifts and lifetimes corresponding to the A-O, B-O, and BO6 vibrations around the depolarization temperature (Td). The observed phase transformation to a P4bm phase at temperatures significantly higher than Td is substantiated by Raman shift and phonon lifetime variations in the modes associated with the A-O and B-O vibrations. The transitions can be understood as: at T~Td the Polar Nano Regions (PNRs) start to appear due to weakening of bonds, T>Td all the long-range ferroelectric domains transform to PNRs converting the material to a fully ergodic state, and at much higher temperatures (T>>Td) the R3c PNRs vanish and P4bm PNRs appear.&#xD.