Design and synthesis of three-dimensional hybrid Ruddlesden-Popper nickelate single crystals

Abstract

Advancement of technologies relies on discovery of new materials with emerging physical properties that are determined by their crystal structures. Ruddlesden-Popper (R-P) phases with formula of $A_{n+1}$$B_n$$X_{3n+1}$ (n=1,2,3...) are among one of the most widely studied class of materials due to their electrical, optical, magnetic, thermal properties and their combined multifunctional properties(Ref.1-6). In R-P phases, intergrowth is well-known in the short range(Ref.7-9); however, no existing compounds have been reported to have different n mixed in bulk single crystals. Here we design a hybrid R-P nickelate $L{a}_{2}Ni{O}_4$$L{a}_{3}N{i}_2{O}_7$ by alternatively stacking bilayers, which is the active structural motif in the newly discovery high-$T_c$ superconductor $L{a}_{3}N{i}_2{O}_7$ and single layers of the antiferromagnetic insulator $L{a}_{2}Ni{O}_4$. We report the successful synthesis of $L{a}_{2}Ni{O}_4$$L{a}_{3}N{i}_2{O}_7$ single crystals, and X-ray diffraction and real-space imaging vis STEM show that the crystal structure consists of single layers and bilayers of $Ni{O}_6$ octahedral stacking alternatively perpendicular to the ab plane, characterized by the orthorhombic Immm (No.71) space group. Resistivity measurements indicate a peculiar insulator-to-metal transition around 140 K on cooling. Correlated density functional theory calculations corroborate this finding, and reveal that the single layer becomes paramagnetic metallic due to charge transfer via LaO layers. The discovery of $L{a}_{2}Ni{O}_4$$L{a}_{3}N{i}_2{O}_7$ opens a door to access a completely new family of 3D hybrid R-P phases with the formula of $A_{n+1}$$B_n$$X_{3n+1}$$A_{m+1}^{\prime }$$B_m^{\prime }$$X_{3m+1}^{\prime }$ which potentially host a plethora of emerging physical properties for various applications.

27 pages, 4 figures

References in corpus (11)

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• Experimental demonstration of hybrid improper ferroelectricity and presence of abundant charged walls in (Ca,Sr)${}_3$Ti${}_2$O${}_7$ crystals
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• Intertwined density waves in a metallic nickelate
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• Effects of Pressure and Doping on Ruddlesden-Popper phases Lan+1NinO3n+1
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• Review on quasi-2D square planar nickelates
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• Sr${}_2$IrO${}_4$/Sr${}_3$Ir${}_2$O${}_7$ superlattice for a model 2D quantum Heisenberg antiferromagnet

Cited by in corpus (20)

• Identification of the superconductivity in bilayer nickelate La${}_3$Ni${}_2$O${}_7$ upon 100 GPa
• Bulk superconductivity up to 96 K in pressurized nickelate single crystals
• Electronic instability, layer selectivity and Fermi arcs in La${}_3$Ni${}_2$O${}_7$
• Band Structure and Pairing Nature of La${}_3$Ni${}_2$O${}_7$ Thin Film at Ambient Pressure
• Superconductivity and Electronic Structures of Nickelate Thin Film Superstructures
• Gigantic-oxidative atomic-layer-by-layer epitaxy for artificially designed complex oxides
• 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
• Out-of-plane bond-order phase, superconductivity, and their competition in the $t$-$J_{\parallel }$-$J_{\perp }$ model: Possible implications for bilayer nickelates
• Phase diagrams and two key factors to superconductivity of Ruddlesden-Popper nickelates
• 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
• Magnetic Correlations and Pairing Tendencies of the Hybrid Stacking Nickelate Superlattice La${}_7$Ni${}_5$O${}_{17}$ (La${}_3$Ni${}_2$O${}_7$/La${}_4$Ni${}_3$O${}_{10}$) under Pressure
• 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
• Electronic Structure, Magnetic and Pairing Tendencies of Alternating Single-layer Bilayer Stacking Nickelate La${}_5$Ni${}_3$O${}_{11}$ Under Pressure
• Origin of the Diagonal Double-Stripe Spin-Density-Wave and Potential Superconductivity in Bulk La${}_3$Ni${}_2$O${}_7$ at Ambient Pressure
• Pairing mechanism and superconductivity in pressurized La${}_5$Ni${}_3$O${}_{11}$
• Pairing mechanism and superconductivity in 1313 phase La${}_3$Ni${}_2$O${}_7$
• Spin Fluctuations in the Rare-Earth Doped Bilayer Nickelates
• $L{a}_{3}P{d}_{2}Na{O}_9$: A High-Valent Insulating Palladate
• Magnetically Mediated Cross-Layer Pairing in Pressurized Trilayer Nickelate La${}_4$Ni${}_3$O${}_{10}$