First-principles Calculations of Raman and Infrared Spectroscopy For Phase Identification and Strain Calibration of Hafnia

Abstract

Using density functional perturbation theory (DFPT) we computed the phonon frequencies, Raman and IR activities of hafnia polymorphs (P4$_{2}$nmc, Pca2$_{1}$, Pmn2$_{1}$, Pbca OI, brookite, and baddeleyite) for phase identification. We investigated the evolution of Raman and IR activities with respect to epitaxial strain and provide plots of frequency differences as a function of strain for experimental calibration and identification of the strain state of the sample. We found Raman signatures of different hafnia polymorphs: $\omega(A_{1g})=300$ cm$^{-1}$ for P4$_{2}$nmc, $\omega(A_{1})=343$ cm$^{-1}$ for Pca2$_{1}$, $\omega(B_{2})=693$ cm$^{-1}$ for Pmn2$_{1}$, $\omega(A_{g})=513$ cm$^{-1}$ for Pbca (OI), $\omega(A_{g})=384$ cm$^{-1}$ for brookite, and $\omega (A_{g}) = 496$ cm$^{-1}$ for baddeleyite. We also identified the Raman $B_{1g}$ mode, an anti-phase vibration of dipole moments, ( $\omega(B_{1g}) = 758$ cm$^{-1}$ for OI, $\omega (B_{1g})= 784$ cm$^{-1}$ for brookite) as the Raman signature of antipolar Pbca structures. We calculated a large splitting between longitudinal optical (LO) and transverse optical (TO) modes ($\Delta{\omega_{\text{LO-TO}}(A^{z}_{1})}=255$ cm$^{-1}$ in Pca2$_{1}$, and $\Delta{\omega_{\text{LO-TO}}(A_{1})}=263$ cm$^{-1}$ in Pmn2$_{1}$) to the same order as those observed in perovskite ferroelectrics, and related them to the anomalously large Born effective charges of Hf atoms ($Z^{*}(\text{Hf}) = 5.54$).