LAUSR

Abstract Localized charge injection by formation of vacancies provides an attractive platform for the development of multifunctional nanomaterials with direct implications in spintronics. However, further progress in spintronics critically depends on a deeper understanding of polaronic interactions between the localized charge states. This report is focused on TiN metallic system, which exhibits Pauli paramagnetism due to the absence of unpaired localized spin states. Here, nitrogen vacancies (VN) are used as a variable to tune the magnetic properties of epitaxial TiN thin films by thermal annealing in high-vacuum and N2 environment. Systematic introduction of VN generates robust magnetic ordering in vacuum-annealed TiN1-x films, with Curie temperature (TC) ∼700 K, and saturation magnetization (Ms) at absolute zero of 13.6 emu g−1. The signature spin-glass behavior below the irreversibility temperature (Tir ∼40 K) indicates the Ruderman-Kittel-Kasuya-Yosida (RKKY) coupling interactions between the unpaired localized spin-states. Through spatially resolved electron energy-loss spectroscopy, we have determined the generation of unpaired localized spins at Ti+2 polarons with ∼12 ± 2 at.% VN in TiN1-x films. Such a large concentration of VN results in increased spin stiffness and high TC. These findings open a definitive pathway for tuning the magnetic nature of metallic materials for spintronic applications.