Accurate prediction of band gaps and optical properties of HfO$_2$

Abstract: We report on optical properties of various polymorphs of hafnia predicted within the framework of density functional theory. The full potential linearised augmented plane wave method was employed together with the Tran-Blaha modified Becke-Johnson potential for exchange and local density approximation for correlation. Unit cells of monoclinic, cubic, and tetragonal crystalline, and a simulated annealing-based model of amorphous hafnia were fully relaxed with respect to internal positions and lattice parameters. The thus obtained band gaps of 5.76 eV, 5.88 eV, 6.54 eV, and 5.5 eV for monoclinic, cubic, tetragonal, and amorphous hafnia, respectively, are in excellent agreement with available experimental data. Dielectric functions were calculated and a shift of spectral weights to higher energies with respect to experimental data was predicted. This was attributed to the random phase approximation used to calculate the dielectric function, rather than inaccuracies in the band structure.