Polymorphism in Ruddlesden-Popper $L{a}_{3}N{i}_2{O}_7$: Discovery of a Hidden Phase with Distinctive Layer Stacking

Abstract

We report the discovery of a novel form of Ruddlesden-Popper (RP) oxide, which 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 $L{a}_{3}N{i}_2{O}_7$adopts a novel stacking sequence in which single and trilayer blocks of $Ni{O}_6$ octahedra alternate in a 1313 sequence. Crystals of this new polymorph are described in space group Cmmm, although we note evidence for a competing Imcm variant. Transport measurements at ambient pressure reveal metallic character with evidence of a charge density wave transition with onset at T = 134 K, which lies intermediate between that of the standard 2222 polymorph of $L{a}_{3}N{i}_2{O}_7$ (space group Amam) and the trilayer RP phase, $L{a}_{4}N{i}_3{O}_{10}$. 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 with $T_c$ as high as 80 K above 14 GPa in bilayer $L{a}_{3}N{i}_2{O}_7$.

37 pages, 10 figures

References in corpus (7)

• Superconductivity near 80 Kelvin in single crystals of La3Ni2O7 under pressure
• Evidence for charge and spin order in single crystals of La${}_3$Ni${}_2$O${}_7$ and La${}_3$Ni${}_2$O${}_6$
• Signature of superconductivity in pressurized La${}_4$Ni${}_3$O${}_{10}$
• Intertwined density waves in a metallic nickelate
• Effects of Pressure and Doping on Ruddlesden-Popper phases Lan+1NinO3n+1
• Electronic structure of higher-order Ruddlesden-Popper nickelates
• Investigations of key issues on the reproducibility of high-Tc superconductivity emerging from compressed La3Ni2O7

Cited by in corpus (61)

• Visualization of Oxygen Vacancies and Self-doped Ligand Holes in La3Ni2O7-δ
• Ambient-pressure superconductivity onset above 40 K in bilayer nickelate ultrathin films
• Normal and superconducting properties of La${}_3$Ni${}_2$O${}_7$
• Unconventional crystal structure of the high-pressure superconductor La${}_3$Ni${}_2$O${}_7$
• Pressure-enhanced spin-density-wave transition in double-layer nickelate $L{a}_{3}N{i}_2{O}_{7-\delta }$
• Long-Range Structural Order in a Hidden Phase of Ruddlesden-Popper Bilayer Nickelate La${}_3$Ni${}_2$O${}_7$
• Identification of the superconductivity in bilayer nickelate La${}_3$Ni${}_2$O${}_7$ upon 100 GPa
• Effective model and $s_{\pm }$-wave superconductivity in trilayer nickelate La${}_4$Ni${}_3$O${}_{10}$
• Superconductivity and normal-state transport in compressively strained La${}_2$PrNi${}_2$O${}_7$ thin films
• Prediction of $s^{\pm }$-wave superconductivity enhanced by electronic doping in trilayer nickelates La${}_4$Ni${}_3$O${}_{10}$ under pressure
• Theory of magnetic excitations in multilayer nickelate superconductor La${}_3$Ni${}_2$O${}_7$
• Theory of Pressure Dependence of Superconductivity in Bilayer Nickelate La${}_3$Ni${}_2$O${}_7$
• Absence of phonon-mediated superconductivity in La${}_3$Ni${}_2$O${}_7$ under pressure
• Electronic structure and magnetic tendencies of trilayer La${}_4$Ni${}_3$O${}_{10}$ under pressure: structural transition, molecular orbitals, and layer differentiation
• Density-wave-like gap evolution in La${}_3$Ni${}_2$O${}_7$ under high pressure revealed by ultrafast optical spectroscopy
• Bulk superconductivity up to 96 K in pressurized nickelate single crystals
• Design and synthesis of three-dimensional hybrid Ruddlesden-Popper nickelate single crystals
• Ultrafast Dynamics of Bilayer and Trilayer Nickelate Superconductors
• Resolving the Electronic Ground State of La3Ni2O7-δ Films
• Optical properties and electronic correlations in La${}_3$Ni${}_2$O${}_7$ bilayer nickelates under high pressure
• Strain-tuning for superconductivity in La${}_3$Ni${}_2$O${}_7$ thin films
• Electronic instability, layer selectivity and Fermi arcs in La${}_3$Ni${}_2$O${}_7$
• The $s^{\pm }$-Wave Superconductivity in the Pressurized La${}_4$Ni${}_3$O${}_{10}$
• Electronic structure, self-doping, and superconducting instability in the alternating single-layer trilayer stacking nickelates La${}_3$Ni${}_2$O${}_7$
• Electronic structure of Ruddlesden-Popper nickelates: strain to mimic the effects pressure
• Band Structure and Pairing Nature of La${}_3$Ni${}_2$O${}_7$ Thin Film at Ambient Pressure
• Anisotropic Spin Stripe Domains in Bilayer La${}_3$Ni${}_2$O${}_7$
• Superconductivity and Electronic Structures of Nickelate Thin Film Superstructures
• Signature of superconductivity in pressurized La4Ni3O10-x single crystals grown at ambient pressure
• Electronic correlations, layer distinction, and electron doping in the alternating single-layer trilayer La${}_3$Ni${}_2$O${}_7$ polymorph
• Spin-density wave and superconductivity in La${}_4$Ni${}_3$O${}_{10}$ under ambient pressure
• Out-of-plane bond-order phase, superconductivity, and their competition in the $t$-$J_{\parallel }$-$J_{\perp }$ model: Possible implications for bilayer nickelates
• DFT+DMFT study of correlated electronic structure in the monolayer-trilayer phase of La${}_3$Ni${}_2$O${}_7$
• Phase diagrams and two key factors to superconductivity of Ruddlesden-Popper nickelates
• Intertwined charge and spin instability of La${}_3$Ni${}_2$O${}_7$
• The electronic structure and disorder effect of La${}_3$Ni${}_2$O${}_7$ superconductor
• Theoretical study of the crystal structure of the bilayer nickel oxychloride Sr${}_3$Ni${}_2$O${}_5$Cl${}_2$ and analysis of possible unconventional superconductivity
• Possible Liquid-Nitrogen-Temperature Superconductivity Driven by Perpendicular Electric Field in the Single-Bilayer Film of La${}_3$Ni${}_2$O${}_7$ at Ambient Pressure
• Origin of the Diagonal Double-Stripe Spin-Density-Wave and Potential Superconductivity in Bulk La${}_3$Ni${}_2$O${}_7$ at Ambient Pressure
• Electronic Structure, Magnetic and Pairing Tendencies of Alternating Single-layer Bilayer Stacking Nickelate La${}_5$Ni${}_3$O${}_{11}$ Under Pressure
• Superconductivity governed by Janus-faced fermiology in strained bilayer nickelates
• Strain-Engineered Electronic Structure and Superconductivity in La${}_3$Ni${}_2$O${}_7$ Thin Films
• Unifying Strain-driven and Pressure-driven Superconductivity in La${}_3$Ni${}_2$O${}_7$: Suppressed charge/spin density waves and enhanced interlayer coupling
• Pressure Effect on the Spin Density Wave Transition in La${}_2$PrNi${}_2$O${}_{6.96}$
• Charge distribution and magnetism in bilayer La${}_3$Ni${}_2$O${}_7$: a hybrid functional study
• Variational Quantum Monte Carlo investigations of the superconducting pairing in La${}_3$Ni${}_2$O${}_7$
• Stabilizing and Tuning Superconductivity in La${}_3$Ni${}_2$O${}_{7-\delta }$ Films: Oxygen Recycling Protocol Reveals Hole-Doping Analogue
• Damage of bilayer structure in La3Ni2O7-d induced by high pO2 annealing
• Fermi surface reconstruction and enhanced spin fluctuations in strained La${}_3$Ni${}_2$O${}_7$ on LaAlO${}_3$(001) and SrTiO${}_3$(001)
• Electronic reconstruction and interface engineering of emergent spin fluctuations in compressively strained La${}_3$Ni${}_2$O${}_7$ on SrLaAlO${}_4$(001)
• A rutile-based homologous series Na(PtO${}_2$)${}_{2n+1}$ discovered by computationally assisted high-pressure synthesis
• Universal electronic structure of multi-layered nickelates via oxygen-centered planar orbitals
• Pairing mechanism and superconductivity in pressurized La${}_5$Ni${}_3$O${}_{11}$
• Introduction to High-Temperature Superconductivity for Solid State Chemists
• Non-Fermi liquid behavior in La${}_3$Ni${}_2$O${}_7$ thin films under hydrostatic pressure
• Pairing mechanism and superconductivity in 1313 phase La${}_3$Ni${}_2$O${}_7$
• Expanding the trilayer Ruddlesden-Popper nickelate family: Synthesis and characterization of Sm${}_4$Ni${}_3$O${}_{10-\delta }$ single crystals
• Structural stability, electronic structure, and magnetic properties of the single-layer trilayer La3Ni2O7 polymorph
• Multiorbital character of the density wave in trilayer nickelate superconductors
• Magnetically Mediated Cross-Layer Pairing in Pressurized Trilayer Nickelate La${}_4$Ni${}_3$O${}_{10}$
• $L{a}_{3}P{d}_{2}Na{O}_9$: A High-Valent Insulating Palladate