Vibrational Anharmonicity Assisted Phase Transitions in Perovskite Oxides under Terahertz Irradiation

Abstract

Despite extensive research interests in perovskite oxides, low energy consumption, non-destructive and maneuverable methods for phase transition in perovskite oxides are still the under its exploration, and the underlying mechanisms remain ambiguous. Here, optical susceptibility including electronic and anharmonic phononic contributions is used to evaluate Gibbs free energy variations of $\mathrm{PbTiO}_3$ and $\mathrm{BaTiO}_3$ under terahertz irradiation. This corresponds to an off-resonant light-controlled phase transition, rather than the resonant approaches that excites hot carriers over electronic band or infrared-active vibrations in the phonon band. We show that intermediate terahertz light can trigger polarization change between ferroelectric orientation variants of $\mathrm{PbTiO}_3$ at room temperature 300 K. Furthermore, the phase transition from low symmetric ferroelectric phase to high symmetric paraelectric structure in $\mathrm{PbTiO}_3$ can be driven by changing the direction and intensity of the incident light under the same conditions. Similar results are observed in $\mathrm{BaTiO}_3$. In detail, phonon spectrum and optical susceptibility are obviously modified and show temperature dependence, in which we show the significant effects of anharmonic vibration. In order to show its nonlinear optical nature, we perform an alternating electric field dressed ab initio molecular dynamics simulation, which maps the Raman-active phonon excitation under off-resonant terahertz irradiation.