Local structure of Ba(1-x)Sr(x)TiO3 and BaTi(1-y)Zr(y)O3 nanocrystals probed by X-ray absorption and X-ray total scattering.

The effect of isovalent chemical substitution on the magnitude and coherence length of local ferroelectric distortions present in sub-20 nm Ba(1-x)Sr(x)TiO3 (x = 0.0, 0.30, 0.50, 1.0) and BaTi(1-y)Zr(y)O3 (y = 0.0, 0.15, 0.50, 1.0) nanocrystals synthesized at room temperature is investigated using X-ray absorption near edge structure (XANES) and pair distribution function analysis of X-ray total scattering data (PDF). Although the average crystal structure of the nanocrystals is adequately described by a centrosymmetric, cubic Pm3m space group, local ferroelectric distortions due to the displacement of the titanium atom from the center of the perovskite lattice are observed for all compositions, except BaZrO3. The symmetry of the ferroelectric distortions is adequately described by a tetragonal P4mm space group. The magnitude of the local displacements of the titanium atom in BaTiO3 nanocrystals is comparable to that observed in single crystals and bulk ceramics, but the coherence length of their ferroelectric coupling is much shorter (≤20 Å). Substitution of Sr(2+) for Ba(2+) and of Zr(4+) for Ti(4+) induces a tetragonal-to-cubic transition of the room temperature local crystal structure, analogous to that observed for single crystals and bulk ceramics at similar compositions. This transition is driven by a reduction of the magnitude of the local displacements of the titanium atom and/or of the coherence length of their ferroelectric coupling. Replacing 50% of Ba(2+) with Sr(2+) slightly reduces the magnitude of the titanium displacement, but the coherence length is not affected. In contrast, replacing 15% of the ferroelectrically active Ti(4+) with Zr(4+) leads to a significant reduction of the coherence length. Deviations from the ideal solid solution behavior are observed in BaTi(1-y)Zr(y)O3 nanocrystals and are attributed to an inhomogeneous distribution of the barium atoms in the nanocrystal. Composition-structure relationships derived for Ba(1-x)Sr(x)TiO3 and BaTi(1-y)Zr(y)O3 nanocrystals demonstrate that the evolution of the room temperature local crystal structure with chemical composition parallels that of single crystals and bulk ceramics, and that chemical control over ferroelectric distortions is possible in the sub-20 nm size range. In addition, the potential of PDF analysis of total scattering data to probe compositional fluctuations in nanocrystals is demonstrated.