Orbital Signatures of Density Wave Transition in La3Ni2O7-delta and La2PrNi2O7-delta RP-Nickelates Probed via in-situ X-ray Absorption Near-edge Spectroscopy

TL;DR

This study uses in-situ X-ray absorption spectroscopy to investigate the electronic and structural changes associated with the density wave transition in RP-nickelates La3Ni2O7-delta and La2PrNi2O7-delta, shedding light on their superconducting properties.

Contribution

It provides detailed insights into the orbital and lattice evolutions across the density wave transition in RP-nickelates using temperature-dependent XANES spectroscopy.

Findings

Anomalous decline in Ni 4p orbital energy near DW transition.

Enlarged crystal field splitting indicates increased octahedral distortion.

Pr substitution activates orbital interplay relevant to superconductivity.

Abstract

The report of superconductivity (SC) with Tc~80 K in bilayer Ruddlesden-Popper (RP) nickelate La3Ni2O7-delta have sparked considerable investigations on its normal state properties and SC mechanism under pressure and at low temperature. It is believed that the density wave (DW) at ~150 K plays an important role in SC emergence, but its nature remains largely underexplored. Here, we utilized temperature-dependent in-situ Ni K-edge X-ray Absorption Near-edge Spectroscopy (XANES) to probe the Ni-3d/4p electronic states of La3Ni2O7-delta and La2PrNi2O7-delta samples down to 4.8 K, enabling us to witness the evolution of both in-plane d_(x^2-y^2)/p_x (p_y) and out-of-plane d_(3z^2-r^2)/p_z orbitals of NiO6 octahedron across the DW transition. Main edge energy associated with Ni 4p orbital shows an anomalous decline near DW transition, signifying the occurrence of lattice distortions as a hallmark of charge density wave. Below DW transition, the enlarged crystal field splitting (CFS) indicates an enhanced NiO6 octahedral distortion. Intriguingly, magnetic Pr substituents could activate the mutual interplay of d_(x^2-y^2) and d_(3z^2-r^2) orbitals. We discussed its relevance to the favored bulk SC in the pressurized polycrystalline La2PrNi2O7-delta than pristine.