Lattice anharmonicity effects in fluorite oxide single crystals and anomalous increase in phonon lifetime in ceria at elevated temperature

Abstract

We investigate the temperature dependence of the frequency and linewidth of the triply-degenerate T$_{2g}$ zone-centered optical phonon in flux-grown ceria and hydrothermally-synthesized thoria single crystals from room temperature to 1273 K using Raman spectroscopy. Both crystals exhibit an expected increase in the phonon linewidth with temperature due to enhanced phonon-phonon scattering. However, ceria displays an anomalous linewidth reduction in the temperature range of 1023-1123 K. First-principles phonon linewidth calculations considering cubic and quartic phonon interactions within temperature-independent phonon dispersion fail to describe this anomaly. A parameterization of the temperature-dependent second order interatomic force constants based on previously reported phonon dispersion measured at room and high temperatures, predicts a deviation from the monotonic linewidth increase, albeit at temperatures lower than those observed experimentally for ceria. The qualitative agreement in the trend of temperature-dependent linewidth suggests that lattice anharmonicity-induced phonon renormalization plays a role in phonon lifetime. Specifically, a change in the overlap between softened acoustic and optical branches in the dispersion curve reduces the available phonon scattering phase space of the Raman active mode at the zone center, leading to an increased phonon lifetime within a narrow temperature interval. These findings provide new insights into higher-order anharmonic interactions in ceria and thoria, motivating further investigations into the role of anharmonicity-induced phonon renormalization on phonon lifetimes at high temperatures.