Origin of ferroelectricity in magnesium-doped zinc oxide

Recent experiments demonstrated robust ferroelectricity in Mg-doped ZnO (ZMO) of the wurtzite structure, hinting at a promising strategy to substantially expand the list of ferroelectrics by doping conventional piezoelectrics. We investigate the origin of ferroelectricity in ZMO with first-principles density functional theory (DFT). The general argument that the Mg alloying could soften the ionic potential energy surface of ZMO for polarization reversal is overly simplified. Our DFT calculations reveal that even at a high Mg concentration, the energy difference ($\mathrm{\ensuremath{\Delta}}U$) between the polar and nonpolar phases remains prohibitively large for ZMO systems when the strain is fixed to the polar phase. Interestingly, the magnitude of $\mathrm{\ensuremath{\Delta}}U$ becomes substantially smaller when the strain relaxation is allowed, approaching the value of typical perovskite ferroelectrics such as ${\mathrm{PbTiO}}_{3}$ with increasing Mg doping concentrations. The enabled switchability of ZMO systems is attributed to a hexagonal phase of MgO that is much lower in energy than its wurtzite counterpart. Detailed orbital and bonding analysis supports that the intra-atomic $3{d}_{{z}^{2}}\text{\ensuremath{-}}4{p}_{z}$ orbital self-mixing of Zn plays an important role in stabilizing the polar wurtzite phase, the lack of which is responsible for the low-energy nonpolar hexagonal phase of MgO.