First-principles quantum molecular dynamics study of TixZr1−xN(111)/SiNy heterostructures and comparison with experimental results

Abstract The heterostructures of five monolayers B1–TixZr1−xN(111), x = 1.0, 0.6, 0.4 and 0.0 (where B1 is a NaCl-type structure) with one monolayer of a Si3N4-like Si2N3 interfacial layer were investigated by means of first-principles quantum molecular dynamics and a structure optimization procedure using the Quantum ESPRESSO code. Slabs consisting of stoichiometric TiN and ZrN and random, as well as segregated, B1–TixZr1−xN(111) solutions were considered. The calculations of the B1–TixZr1−xN solid solutions, as well as of the heterostructures, showed that the pseudo-binary TiN–ZrN system exhibits a miscibility gap. The segregated heterostructures in which Zr atoms surround the SiyNz interface were found to be the most stable. For the Zr-rich heterostructures, the total energy of the random solid solution was lower compared to that of the segregated one, whereas for the Ti-rich heterostructures the opposite tendency was observed. Hard and super hard Zr–Ti–Si–N coatings with thicknesses from 2.8 to 3.5 μm were obtained using a vacuum arc source with high frequency stimulation. The samples were annealed in a vacuum and in air at 1200 °C. Experimental investigations of Zr–Ti–N, Zr–Ti–Si–N and Ti–Si–N coatings with different Zr, Ti and Si concentrations were carried out for comparison with results obtained from TixZr1−xN(111)/SiNy systems. During annealing, the hardness of the best series samples was increased from (39.6 ± 1.4) to 53.6 GPa, which seemed to indicate that a spinodal segregation along grain interfaces was finished. A maximum hardness of 40.8 GPa before and 55 GPa after annealing in air at 500 °C was observed for coatings with a concentration of elements of Si  (7–8) at.%, Ti  22 at.% and Zr  70 at.%.