Dielectric, infrared, and Raman response of undopedSrTiO3ceramics: Evidence of polar grain boundaries

Abstract

Thorough Raman and infrared (IR) reflectivity investigations of nominally pure ${\mathrm{SrTiO}}_{3}$ ceramics in the 10--300 K range have revealed a clear presence of the polar phase whose manifestation steeply increases on cooling. The Raman strengths of the Raman-forbidden IR modes are proportional to ${\ensuremath{\omega}}_{\mathrm{TO}1}^{\ensuremath{-}\ensuremath{\alpha}}(\ensuremath{\alpha}\ensuremath{\approx}1.6)$ where ${\ensuremath{\omega}}_{\mathrm{TO}1}$ is the polar soft mode frequency. No pronounced permittivity dispersion is observed below the soft mode frequency so that, as in single crystals, the static permittivity is essentially determined by the soft mode contribution. A theory is suggested which assumes a frozen dipole moment connected with the grain boundaries which induces the polar phase in the grain bulk in correlation with the bulk soft-mode frequency. This stiffens slightly the effective soft mode response and reduces the low-temperature permittivity compared to that of single crystals. Moreover, the polar soft mode strongly couples to the ${E}_{g}$ component of the structural soft doublet showing that the polar axis is perpendicular to the tetragonal axis below the structural transition which is shifted to 132 K in our ceramics. Whereas the ${\mathrm{TiO}}_{6}$ octahedra tilt (primary order parameter) below the structural transition corresponds to that in single crystals, much smaller ${A}_{1g}\ensuremath{-}{E}_{g}$ splitting of the structural soft doublet shows that the tetragonal deformation (secondary order parameter) is nearly 10 times smaller, apparently due to the grain volume clamping in ceramics.