Dopant-induced modulation of ferroelectricity in perovskite nitride LaWN$_3$

Abstract: Perovskite nitrides are starting to be explored for their promising properties distinct from their oxide counterparts. Here, through first-principles density functional computations, we study the intricate relationship between ferroelectricity and metallicity in the ferroelectric nitride LaWN$_3$. We systematically assess the impact of electron and hole doping via the background charge method, revealing that both types of charge carriers diminish the propensity for ferroelectricity in LaWN$_3$, although to remarkably different extents. Specifically, the introduction of electrons leads to centrosymmetry at a lower concentration value of nearly 0.2 electrons per formula unit. In contrast, the addition of holes does not result in centrosymmetry at reasonable doping values of up to 0.3 holes per formula unit. We present the underlying mechanisms behind these findings, noting that adding electrons fills the valence orbitals of both W and N atoms. This filling leads to a screening effect on the long-range repulsion between these atoms, thereby reducing the off-centering of W. On the other hand, hole doping does not significantly alter the W-N bonding nature, resulting in a more robust off-centering. Furthermore, we introduce explicit impurity atoms and analyze the influence of the different factors contributing to the change in polarization, namely, the size of the dopant, charge carriers introduced by the dopant, and changes in lattice constants. We discover that doped LaWN$_3$ can be a promising polar metal, especially with acceptor dopants. Our study comprehensively shows the interplay between polarity and metallicity in this prototypical perovskite nitride.