Quasiparticle self-consistent $GW$ band structures and phase transitions of LiAlO$_2$ in tetrahedrally and octahedrally coordinated structures

Abstract

A first-principles computational study is presented of various phases of LiAlO$_2$.The $β$ and $γ$ tetrahedral phases are found to be very close in energy with the $γ$ phase having the lowest energy. The octahedral $α$ phase is a high-pressure phase and the transition pressure from the $γ$ and $β$ phases to $α$ is determined to be about 1 GPa. The electronic band structures are determined using the quasiparticle self-consistent (QS) $GW$ method. The effective masses of the band edges and the nature of the band gaps are presented. The lowest energy $γ$ phase is found to have a pseudodirect gap of 7.69 eV. The gap is direct at $Γ$ but corresponds to a dipole forbidden transition. The imaginary part of the dielectric function and the absorption coefficient are calculated in the long-wavelength limit and the random phase approximation, without local field or electron-hole interaction effects for each phase and their anisotropies are discussed. Si doping on the Al site is investigated as a possible $n$-type dopant in $γ$-LiAlO$_2$ using a 128 atom supercell corresponding to 3.125 \% Si on the Al sublattice in the generalized gradient approximation and a smaller 16 atom cell with 25 \% Si in the QS$GW$ approximation. The Si is found to significantly perturb the conduction band and lower the gap but a clearly separated deep donor defect level is not found. However, the donor binding energy is still expected to be relatively deep, of order a few 0.1 eV in the hydrogenic effective mass approximation.