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The Ruddlesden–Popper (RP) layered perovskite structure is of great interest due to its inherent tunability, and the emergence and growth of the compositionally complex oxide (CCO) concept endows the RP family with further possibilities. Here, a comprehensive assessment of thermodynamic stabilization, local order/disorder, and lattice distortion was performed in the first two reported examples of lanthanum-deficient Lan+1BnO3n+1 (n = 1, B = Mg, Co, Ni, Cu, Zn) obtained via various processing conditions. Chemical short-range order (CSRO) at the B-site and the controllable excess interstitial oxygen (δ) in RP-CCOs are uncovered by neutron pair distribution function analysis. Reverse Monte Carlo analysis of the data, Metropolis Monte Carlo simulations, and extended x-ray absorption fine structure analysis implies a modest degree of magnetic element segregation on the local scale. Further, ab initio molecular dynamics simulations results obtained from special quasirandom structure disagree with experimentally observed CSRO but confirm Jahn–Teller distortion of CuO6 octahedra. These findings highlight potential opportunities to control local order/disorder and excess interstitial oxygen in layered RP-CCOs and demonstrate a high degree of freedom for tailoring application-specific properties. They also suggest a need for expansion of theoretical and data modeling approaches in order to meet the innate challenges of CCO and related high-entropy phases.

Control over the concurrent occurrence of structural (monoclinic to tetragonal) and electrical (insulator to the conductor) transitions presents a formidable challenge for VO₂-based thin film devices. Speed, lifetime, and reliability of these devices can be significantly improved by utilizing solely electrical transition while eliminating structural transition. We design a novel strain-stabilized isostructural VO₂epitaxial thin-film system where the electrical transition occurs without any observable structural transition. The thin-film heterostructures with a completely relaxed NiO buffer layer have been synthesized allowing complete control over strains in VO₂films. The strain trapping in VO₂thin films occurs below a critical thickness by arresting the formation of misfit dislocations. We discover the structural pinning of the monoclinic phase in (10 ± 1 nm) epitaxial VO₂films due to bandgap changes throughout the whole temperature regime as the insulator-to-metal transition occurs. Using density functional theory, we calculate that the strain in monoclinic structure reduces the difference between long and short V-V bond-lengths (Δ_V−V) in monoclinic structures which leads to a systematic decrease in the electronic bandgap of VO₂. This decrease in bandgap is additionally attributed to ferromagnetic ordering in the monoclinic phase to facilitate a Mott insulator without going through the structural transition.