Self-formation of dual-phase nanocomposite Zr-Cu-N coatings based on nanocrystalline ZrN and glassy ZrCu

A novel type of nanocomposite Zr–Cu–N material based on hard nanocrystalline ZrN and amorphous glassy ZrCu was prepared by atom-by-atom deposition using reactive magnetron co-sputtering. The elemental composition of the coatings was systematically controlled over a wide range, so that the stoichiometry of both phases was the same in all coatings and only phase fractions varied. Experimental results obtained using X-ray diffraction and electron microscopies were complemented by thirteen ab-initio simulations for the same coating compositions. We found that the structure of the as-deposited Zr–Cu–N coatings undergoes a gradual transition from an amorphous to nanograined and finally to nanocolumnar structure. When ZrN fraction exceeds 20 mol.%, both phases exhibit the tendency for spontaneous segregation even without heating, forming a heterogenous dual-phase nanocomposite structure. At approximately 50 mol.% ZrN, the ZrN nanocrystals enveloped by a relatively thin amorphous ZrCu phase reach an optimum size (3–5 nm), resulting in a maximum enhancement of hardness by 38 % compared to the rule of mixture. For ZrN fractions > 80 mol.%, hardness and plastic work fraction follow the trend proposed by the rule of mixture and the coatings with a lower hardness but a higher plasticity compared to the ZrN coating are prepared