Secondary phase limited metal-insulator phase transition in chromium nitride thin films

Chromium nitride (CrN) is a well-known hard coating material that has found applications in abrasion and wear-resistant cutting tools, bearings, and tribology applications due to its high hardness, hightemperature stability, and corrosion-resistant properties. In recent years, CrN has also attracted significant interest due to its high thermoelectric power factor, and for its unique and intriguing metal-insulator phase transition. While CrN bulk single-crystals exhibit the characteristic metal-insulator transition accompanied with structural (orthorhombic-to-rocksalt) and magnetic (antiferromagnetic-to-paramagnetic) transition at similar to 260-280 K, observation of such phase transition in thin-film CrN has been scarce, and the exact cause of the absence of such transitions in several studies is not well-understood. In this work, the formation of the secondary metallic Cr2N phase during the growth is demonstrated to inhibit the observation of metal-insulator phase transition in CrN thin films. When the Cr-flux during deposition is reduced below a critical limit, epitaxial and stoichiometric CrN thin film is obtained that reproducibly exhibits the phase transition. Annealing of the mixed-phase film inside reducing NH3 environment converts the Cr2N into CrN, and a discontinuity in the electrical resistivity at similar to 277 K appears, which supports the underlying hypothesis. Demonstration of the inhibited metal-semiconductor phase transition in CrN due to the presence of secondary Cr2N phase is similar to the previous finding of the substantial change in its mechanical hardness and reduction in thermoelectric properties. A clear demonstration of the origin behind the controversy of the metal-insulator transition in CrN thin films marks significant progress and would enable its nanoscale device realization. (C) 2022 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.