Oxygen vacancy formation and electronic reconstruction in strained LaNiO$_3$ and LaNiO$_3$/LaAlO$_3$ superlattices (2206.11028v1)

Abstract: By using DFT+U, we explore the formation of oxygen vacancies and their impact on the electronic and magnetic structure in strained bulk LaNiO3 and (LaNiO3)$_1$/(LaAlO3)$_1$(001) superlattices. For bulk LaNiO3, we find that epitaxial strain induces a substantial anisotropy in the oxygen vacancy formation energy. In particular, tensile strain promotes the selective reduction of apical oxygen, which may explain why the recently observed superconductivity of infinite-layer nickelates is limited to strained films. For (LaNiO3)$_1$/(LaAlO3)$_1$(001) superlattices, the simulations reveal that the NiO2 layer is most prone to vacancy formation, whereas the AlO2 layer exhibits generally the highest formation energies. The reduction is consistently endothermic, and a largely repulsive vacancy-vacancy interaction is identified as a function of the vacancy concentration. The released electrons are accommodated exclusively in the NiO2 layer, reducing the vacancy formation energy in the AlO2 layer by 70% with respect to bulk LaAlO3. By varying the vacancy concentration from 0% to 8.3% in the NiO2 layer at tensile strain, we observe an unexpected transition from a localized site-disproportionated (0.5%) to a delocalized (2.1%) charge accommodation, a re-entrant site disproportionation leading to a metal-to-insulator transition despite a half-filled majority-spin Ni $e_g$ manifold (4.2%), and finally a magnetic phase transition (8.3%). While a band gap of up to 0.5 eV opens at 4.2% for compressive strain, it is smaller for tensile strain or the system is metallic, which is in sharp contrast to the defect-free superlattice. The strong interplay of electronic reconstructions and structural modifications induced by oxygen vacancies in this system highlights the key role of an explicit supercell treatment and exemplifies the complex response to defects in artificial transition metal oxides.