Thermal stability of copper nitride thin films: The role of nitrogen migration

The atomic composition, structural, morphological, and optical properties of N-rich copper nitride thin films have been investigated prior to and after annealing them in vacuum at temperatures up to $300°C$⁠. Films were characterized by means of ion-beam analysis (IBMA), X-ray diffraction (XRD), atomic force microscopy (AFM), and spectroscopic ellipsometry techniques (SE). The data reveal that even when the total (integrated over the whole thickness) atomic composition of the films remains constant, nitrogen starts to migrate from the bulk to the film surface, without out-diffusing, at temperatures as low as $100°C$⁠. This migration leads to two chemical phases with different atomic concentration of nitrogen, lattice parameters, and crystallographic orientation but with the same crystal structure. XRD experimental and Rietveld refined data seem to confirm that nitrogen excess accommodates in interstitial locations within the anti-$ReO3$ crystal lattice forming a solid solution. The influence of nitrogen migration on the optical (electronic) properties of the films will be discussed.