Lattice instabilities in bulk EuTiO3

The phase purity and the lattice dynamics in bulk EuTiO3 were investigated both microscopically, using x-ray and neutron diffraction, Eu-151-Mossbauer spectroscopy, and Eu-151 nuclear inelastic scattering, and macroscopically using calorimetry, resonant ultrasound spectroscopy, and magnetometry. Furthermore, our investigations were corroborated by ab initio theoretical studies. The perovskite symmetry, Pm (3) over barm, is unstable at the M- and R-points of the Brillouin zone. The lattice instabilities are lifted when the structure relaxes in one of the symmetries: I4/mcm, Imma, R (3) over barc with relative relaxation energy around -25 meV. Intimate phase analysis confirmed phase purity of our ceramics. A prominent peak in the Eu specific density of phonon states at 11.5 meV can be modeled in all candidate symmetries. A stiffening on heating around room temperature is indicative of a phase transition similar to the one observed in SrTiO3, however, although previous studies reported the structural phase transition to the tetragonal I4/mcm phase our detailed sample purity analysis and thorough structural studies using complementary techniques did not confirm a direct phase transition. Instead, in the same temperature range, Eu delocalization is observed which might explain the lattice dynamical instabilities.