Effect of 90 deg ferroelastic twin walls on lattice dynamics of nanocrystalline tetragonal ferroelectric perovskites

A combined transmission electron microscopy (TEM) and Raman spectroscopy study has been performed on nanocrystalline Ba_0.9Sr_0.1TiO₃ (BST) crystals and tubes. TEM investigations revealed the existence of 90 deg ferroelastic twins in the materials. Raman spectra showed an obvious shoulder (∼750 cm^-1) from the broad band at ∼720 cm^-1 that nominally represents the quasimode of E(LO₄) and A₁(LO₃). The intensity of this shoulder increases with the twin population in the nanocrystalline materials, suggesting a correlation between the lattice dynamical characteristics and the long-range ferroelastic strain of the twin wall. The ferroelastic strain is mainly constrained along the c-axis of the BST unit cell, and the effect of this constraint is more pronounced in nanocrystalline materials than in bulks due to a significant wall volume ratio in twinned nano-materials. A₁ phonons showing collective ion dynamics along the c-direction could be then hardened by the strain, while E symmetry exhibiting vibrations perpendicular to the c-axis would be less affected. The theoretically predicted giant LO–TO coupling in tetragonal ferroelectric perovskites [18] suggests that the hardening of the softest A₁(TO₁) mode in A₁ symmetry is accompanied by that of the hardest A₁(LO₃) phonon. Consequently, the shoulder could be ascribed to the ferroelastic strain induced hardening of the quasimode with a considerable contribution from the A₁(LO₃) phonon. PACS 61.72.Ff; 63.22.+m; 77.80.Bh; 77.80.Dj