Expanding the trilayer Ruddlesden-Popper nickelate family: Synthesis and characterization of Sm${}_4$Ni${}_3$O${}_{10-\delta }$ single crystals

Abstract

The discovery of high-temperature superconductivity in Ruddlesden-Popper (RP) nickelates has attracted significant attention. Bulk superconductivity emerges under pressure in trilayer nickelates La${}_4$Ni${}_3$O${}_{10-\delta }$ (T${}_c$ $\approx$ 30 K) and Pr${}_4$Ni${}_3$O${}_{10-\delta }$ (T${}_c$ $\approx$ 40.5 K), where the reduced ionic radius of Pr${}^{3+}$ may generate internal chemical pressure and enhance T${}_c$. However, synthesizing trilayer RP phases with smaller rare-earth elements (Ln) is extremely challenging. So far, only the La, Pr, and Nd analogues have been synthesized with stable phases in the single rare-earth form. Here we report the first successful high-pressure and high-temperature (HPHT) synthesis of samarium-based compound Sm${}_4$Ni${}_3$O${}_{10-\delta }$. Magnetization and transport measurements consistently confirm a density wave (DW) transition at ~180 K at ambient pressure. Through a careful fitting to the structural data of Sm${}_4$Ni${}_3$O${}_{10-\delta }$, it is found that the bond angle of (Ni-O-Ni) associating with the interlayer apical oxygen is much smaller than 180${}^{\circ }$, which was assumed to be the key factor for the occurrence of superconductivity. By applying pressures up to 80 GPa, despite partial suppression of insulating behavior and the DW order, but superconductivity is not observed in our present study. Density functional theory calculations suggest that the 3d${}_{z^2}$ and 3d${}_{x^2-y^2}$ are separated from other t${}_{2g}$ orbitals and make a primary contribution to the Fermi surface. The newly synthesized trilayer nickelate Sm${}_4$Ni${}_3$O${}_{10-\delta }$ offers a unique platform for probing the fundamental physics of RP nickelates.

21 pages, 4 figures