Heteroanionic Stabilization of Ni${}^{1+}$ with Nonplanar Coordination in Layered Nickelates

Abstract

We present electronic structure calculations on layered nickelate oxyfluorides derived from the Ruddlesden-Popper arisotype structure in search of unidentified materials that may host nickelate superconductivity. By performing anion exchange of oxygen with fluorine, we create two heteroanionic La${}_2$NiO${}_3$F polymorphs and stabilize Ni${}^{1+}$ in 4-coordinate and 5-coordinate square planar and square pyramidal geometries, respectively. We further predict chemical reactions with high thermodynamic driving forces to guide their synthesis. These oxyfluorides are weakly correlated antiferromagnetic insulators and their nonmagnetic phases exhibit quasi-2D Fermi surfaces dominated by Ni $d_{x^2-y^2}$ states, which strikingly resemble undoped cuprate superconductors. We discuss how the oxyfluoride anion chemistry promotes Ni-O covalency and single-band character that is more similar to the cuprates than homoanionic infinite-layer nickelates. We use our understanding to propose doping strategies and layered LaSrNiO${}_2$F${}_2$ and La${}_3$Ni${}_2$O${}_4$F${}_3$ nickelate oxyfluorides with tunable electronic and magnetic structures for experimentation.

8 pages, 4 figures

References in corpus (17)

• Restoring the density-gradient expansion for exchange in solids and surfaces
• Generalized gradient approximation for solids and their surfaces
• Quantum oscillations and the Fermi surface in an underdoped high-Tc superconductor
• Orbital order and possible superconductivity in LaNiO3/LaMO3 superlattices
• Physics of ultrathin films and heterostructures of rare earth nickelates
• A superconducting praseodymium nickelate with infinite layer structure
• Imaging the impact on cuprate superconductivity of varying the inter-atomic distances within individual crystal unit-cells
• Materials design of dynamically stable $d^9$ layered nickelates
• Chemical control of orbital polarization in artificially structured transition-metal oxides: La2NiXO6 (X=B, Al, Ga, In) from first principles
• Reconstructing the polar interface of infinite-layer nickelate thin films
• Nickelate superconductors: an ongoing dialog between theory and experiments
• Fermi surface pockets in ortho-II YBa${}_2$Cu${}_3$O${}_{6.5}$: the origin of quantum oscillations?
• Seebeck coefficient in a cuprate superconductor: particle-hole asymmetry in the strange metal phase and Fermi surface transformation in the pseudogap phase
• Assessing exchange-correlation functional performance for structure and property predictions of oxyfluoride compounds from first principles
• Geometric effects in the infinite-layer nickelates
• Fermi-surface pockets in $YB{a}_{2}C{u}_3{O}_{6.5}$ : A comparison of ab initio techniques
• Single-layer T'-type nickelates: Ni${}^{1+}$ is Ni${}^{1+}$