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We report the discovery of a novel form of Ruddlesden–Popper (RP) nickelate that stands as the first example of long-range, coherent polymorphism in this class of inorganic solids. Rather than the well-known, uniform stacking of perovskite blocks ubiquitously found in RP phases, this newly discovered polymorph of the bilayer RP phase La3Ni2O7 adopts a novel stacking sequence in which single-layer and trilayer blocks of NiO6 octahedra alternate in a “1313” sequence. Crystals of this new polymorph are described in space group Cmmm, although we note evidence for a competing Imam variant. Transport measurements at ambient pressure reveal metallic character with evidence of a charge density wave transition with an onset at T ≈ 134 K. The discovery of such polymorphism could reverberate to the expansive range of science and applications that rely on RP materials, particularly the recently reported signatures of superconductivity in bilayer La3Ni2O7 with Tc as high as 80 K above 14 GPa.

This study systematically analyzes a two-site, two-orbital model of the La₃Ni₂O₇ thin-film superconductor under ambient pressure within a weakly correlated system, employing the fluctuation exchange (FLEX) approximation, with a focus on the influence of hole doping on superconducting properties. Through a detailed examination of the Fermi surface topology, it is found that when the δ pocket, formed by the d_{z²} antibonding orbital, emerges near the Γ point, the nesting between the δ and γ pockets, together with the nesting between the α and β pockets, collectively enhances s±-wave pairing at the corresponding wave vectors. The study further proposes that this enhancement mechanism of spin-fluctuation-induced pairing, driven by Fermi surface nesting, may provide a feasible route to raising the superconducting transition temperature. This work offers theoretical guidance for understanding the pairing mechanism of nickel-based thin-film superconductors under ambient pressure and for exploring higher-performance superconducting materials.

Given the urgent need to enhance the superconducting transition temperature (Tc) of La₃Ni₂O₇ single- and double-layer thin films under ambient pressure, this study proposes applying a vertical electric field to drive charge transfer for superconductivity enhancement. The vertical field drives electrons from higher-potential layers to lower-potential layers; since the Ni 3d_{z²} orbital is nearly half-filled and cannot accommodate additional electrons, the inflowing electrons primarily fill the 3d_{x²-y²} orbitals of the lower-potential layer, thereby increasing its filling rate. Using a simplified single-orbital model and a comprehensive two-orbital model, combined with slave-boson mean-field theory and density matrix renormalization group methods, numerical calculations reveal that the increased filling suppresses interlayer s-wave pairing but strongly enhances intralayer d-wave pairing, causing the bottom-layer-dominated d-wave superconductivity to rise rapidly. When the interlayer voltage reaches approximately 0.1–0.2 V, Tc can surpass the liquid nitrogen temperature (around 77 K), achieving high-temperature superconductivity in the liquid nitrogen temperature range under ambient pressure. This approach requires no high pressure and avoids chemical doping disorder, providing a feasible route to realize high-Tc superconductivity in La₃Ni₂O₇ ultrathin films, which warrants further experimental verification.

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By electronic doping of the high-pressure bilayer cobaltate La₃Co₂O₇, cobalt-based La₃Ni₂O₇ analogs such as LaTh₂Co₂O₇, La₃Ni₂O₅Cl₂, and La₃Ni₂O₅Br₂ are predicted, which possess similar crystal structures and strongly correlated electronic states. Calculations based on density functional theory plus dynamical mean-field theory (DFT+DMFT) and random phase approximation (RPA) indicate that the cobalt 3d orbitals exhibit half-filled or near-half-filled occupancy, analogous to the nickel orbitals in La₃Ni₂O₇, and display strong Hund coupling and mass enhancement. The local magnetic moments (approximately 0.64 μ_B) of these cobalt-based compounds fall precisely within the optimal window for nickelate superconductivity (0.63–0.68 μ_B), strongly suggesting the possibility of high-temperature superconductivity via a similar spin fluctuation mechanism. RPA calculations further reveal that the leading pairing symmetry in electron-doped cobaltates is s-wave, belonging to the A₁ᵍ irreducible representation. This work provides a theoretical basis for achieving high-temperature superconductivity in cobalt-based systems and encourages further experimental synthesis and characterization.

This study successfully fabricated phase-pure, high-quality Ruddlesden-Popper nickelate Ln₃Ni₂O₇ thin films on LaAlO₃ and SrLaAlO₄ substrates using the giant oxidation atomic layer epitaxy (GAE) method. Films grown under strongly oxidizing ozone atmosphere exhibited superconductivity without requiring post-annealing, with optimized Ln₃Ni₂O₇/SrLaAlO₄ films achieving an onset transition temperature (Tc,onset) as high as 50 K. Systematic investigation identified four key factors governing film crystallinity and superconducting performance: precise control of cation stoichiometry suppresses secondary phase formation; complete atomic layer-by-layer coverage combined with optimized interface reconstruction reduces stacking faults; accurate regulation of oxygen content is essential for achieving a single superconducting transition and high Tc,onset. The study also revealed that deviation in cation stoichiometry leads to the formation of Ni-rich or Ni-deficient secondary phases, inducing metal-insulator transitions or highly insulating behavior, respectively, while deviations in atomic layer coverage (e.g., 101.5%) still allow superconductivity but introduce residual resistance. Interface reconstruction, such as predisposing half-unit-cell Ln₂NiO₄ or annealing the SrLaAlO₄ substrate, significantly improves film crystallinity. These findings provide important guidance for the layer-by-layer epitaxial growth of high-quality oxide high-temperature superconducting thin films.

Through first-principles calculations, this work investigates the crystal and electronic structures of the mixed bilayer-trilayer Ruddlesden-Popper nickelate La₇Ni₅O₁₇ under hydrostatic pressure and biaxial compressive strain. By analyzing the irreducible representations of dynamically unstable phonon modes in the high-symmetry P4/mmm structure, the authors identify a dynamically stable low-symmetry C2/c structure characterized by octahedral tilting. Both applied pressure and compressive strain suppress the octahedral tilting, leading to structural tetragonalization, a behavior akin to conventional Ruddlesden-Popper phases. In terms of electronic structure, the overall features under hydrostatic pressure and strain are similar, but a key difference lies in the position of the d_z² bonding band within the trilayer block: at 30 GPa pressure, this band crosses the Fermi level, whereas any magnitude of compressive strain keeps it below the Fermi level. This strain-induced electronic structure variation aligns with observations in conventional bilayer nickelates, offering critical insights into the distinct effects of pressure and strain on superconductivity in this class of materials.