Unusual crystal structure evolution, multiple phase boundaries and phase coexistence in (1-x)Ba(Cu1/3Nb2/3)O-3-(x)PbTiO3 perovskite solid solution

Exploring the functionalities of materials requires a profound understanding of the crystal structure. In this paper, room temperature crystal structures of a new solid solution (1 - x)Ba(Cu1/3Nb2/3)O-3-(x)PbTiO3 have been investigated in the entire compositional span and different crystallographic phases and phase coexistence regions have been discovered. The confirmation of the symmetry of these crystal structures has been done with the help of Rietveld analysis of the high-resolution XRD data. Despite both the end components, Ba(Cu1/3Nb2/3)O-3 and PbTiO3, having tetragonal (P4mm) symmetry, new cubic and monoclinic phases have been discovered for the intermediate compositions with multiple phase boundaries. The composition region 0.05 = x = 0.55 exhibits a cubic crystal structure and increasing PbTiO3 concentration to 0.62 results in a unique coexistence of two tetragonal phases with different tetragonalities. This transformation is mediated by coexisting cubic and tetragonal phases, for 0.59 and 0.60. The crystal structure of the solid solution later transforms into coexisting monoclinic and tetragonal phases for a wider compositional span i.e., 0.65 = x = 0.85. This composition region is very fascinating, as two phenomenologically different monoclinic structures have been observed in it. Finally, a tetragonal phase at x = 1 is achieved through the mediation of two coexisting tetragonal phases, for the region 0.85 < x = 0.975. The evolution of different crystallographic structures and the coexisting phases are critically comprehended using the variations in the lattice parameters and unit cell volume. The presence of multiple phase boundaries spread across a wide range of compositions makes this solid solution very intriguing and a viable choice for exploring different properties with compositional tuning.

Automated summary

In this paper, the crystal structures of a new solid solution (1 - x)Ba(Cu1/3Nb2/3)O-3-(x)PbTiO3 have been investigated at room temperature. Different crystallographic phases and phase coexistence regions have been discovered. The confirmation of the symmetry of these crystal structures has been done with the help of Rietveld analysis of the high-resolution XRD data.