Interlayer Switching of NiO ₆ Octahedra Tilt via Interstitial Oxygen in La _{n + 1} Ni _n O _{3n + 1} ( <i>n</i> = 1, 2, 3)

Abstract

Abstract Oxygen octahedra tilt, an important knob to tune properties of perovskite oxides and their derivatives, determines the coupling patterns and emergent states. Conventional methods, such as strain and doping, are primarily employed to modulate the magnitude of the octahedra tilt. The switching of the tilt, however, is challenging due to the intrinsic interlocked coupling. Here, we achieve the interlayer switching of NiO 6 octahedral tilting via interstitial oxygen insertion in Ruddlesden–Popper La n + 1 Ni n O 3n + 1 ( n = 2). Interstitial oxygen with an alternative occupation in the rock‐salt (LaO) layers induces completely opposite tilt patterns of NiO 6 octahedra in neighboring perovskite (LaNiO 3 ) layers. EELS reveals a lower unoccupied UHB and a spectral‐weight transfer, which may contribute to the suppression of superconductivity in La 3 Ni 2 O 7 as confirmed by our high‐pressure transport experiments. This mechanism of NiO 6 octahedral tilt switching is further validated in La n + 1 Ni n O 3n + 1 ( n = 1 and 3), offering a promising strategy for regulating the properties of layered perovskite oxides.