Electron Doping of $\mathrm{L}{\mathrm{a}}_3\mathrm{N}{\mathrm{i}}_2{\mathrm{O}}_7$ Thin Films: Candidate Metal Dopants and Their Potential Impact on Superconductivity

Abstract

The bilayer Ruddlesden-Popper nickelate $\mathrm{L}{\mathrm{a}}_3\mathrm{N}{\mathrm{i}}_2{\mathrm{O}}_7$ has emerged as a promising platform for exploring and understanding high-temperature superconductivities. While existing doping studies have primarily concentrated on hole doping achieved through strontium substitution or oxygen content tuning, the electron-doped regime in this system remains largely unexplored. In this work, we systematically investigate possible electron doping in $\mathrm{L}{\mathrm{a}}_3\mathrm{N}{\mathrm{i}}_2{\mathrm{O}}_7$ thin films through tetravalent element substitution, employing first-principles density functional theory calculations. Our results suggest that $\mathrm{cerium}$ (Ce) doping is inefficient in introducing electron carriers into the low-energy bands. In contrast, zirconium (Zr), hafnium (Hf), and thorium (Th) emerge as efficient electron donors. We show that Zr and Hf doping preferentially introduce electrons into the $d_{x^2-y^2}$-derived bands, while Th doping delivers more electrons into the $d_{z^2}$-derived bands. Electron dopings notably augment the interlayer hopping $t_{\perp }$ between $d_{z^2}$ orbitals, which could enhance superexchange coupling $J_{\perp }$ and consequently promote an increase in superconducting $T_c$. We evaluate the Coulomb interaction parameters using constrained random phase approximation. Our results identify viable dopants for achieving electron-doped $\mathrm{L}{\mathrm{a}}_3\mathrm{N}{\mathrm{i}}_2{\mathrm{O}}_7$, which not only diversifies the material family but also provides new platforms for disentangling the origins of $\mathrm{L}{\mathrm{a}}_3\mathrm{N}{\mathrm{i}}_2{\mathrm{O}}_7$ superconductivity.

12 pages, 11 figures