Structure, stress, and mechanical properties of Mo-Al-N thin films deposited by dc reactive magnetron cosputtering: Role of point defects
Résumé
In this work, the structural and mechanical properties of ternary Mo-Al-N alloys are investigated by combining thin film growth experiments and density functional theory (DFT) calculations. Mo 1−x Al x N y thin films (∼300 nm thick), with various Al fractions ranging from x = 0 to 0.5 and nitrogen-to-metal (Al + Mo) ratio ranging from y = 0.78 to 1.38, were deposited by direct-current reactive magnetron cosputtering technique from elemental Mo and Al targets under Ar + N 2 plasma discharges. The Al content was varied by changing the respective Mo and Al target powers, at a fixed N 2 (20 SCCM) and Ar (25 SCCM) flow rate, and using two different substrate temperatures T s = 350 and 500°C. The elemental composition, mass density, crystal structure, residual stress state, and intrinsic (growth) stress were examined by wavelength dispersive x-ray spectroscopy, x-ray reflectivity, x-ray diffraction, including pole figure and sin 2 ψ measurements, and real-time in situ wafer curvature. Nanoindentation tests were carried out to determine film hardness H and elastic modulus E IT , while the shear elastic constant C 44 was measured selectively by surface Brillouin light spectroscopy. All deposited Mo 1−x Al x N y films have a cubic rock-salt crystal structure and exhibit a fiber-texture with a [001] preferred orientation. The incorporation of Al is accompanied by a rise in nitrogen content from 44 to 58 at. %, resulting in a significant increase (2%) in the lattice parameter when x increases from 0 to 0.27. This trend is opposite to what DFT calculations predict for cubic defect-free stoichiometric Mo 1−x Al x N compounds and is attributed to variation in point defect concentration (nitrogen and metal vacancies) when Al substitutes for Mo. Increasing T s from 350 to 500°C has a minimal effect on the structural properties and phase composition of the ternary alloys but concurs to an appreciable reduction of the compressive stress from −5 to −4 GPa. A continuous increase and decrease in transverse sound velocity and mass density, respectively, lead to a moderate stiffening of the shear elastic constant from 130 to 144 GPa with increasing Al fraction up to x = 0.50, and a complex and nonmonotonous variation of H and E IT is observed. The maximum hardness of ∼33 GPa is found for the Mo 0.81 Al 0.19 N 1.13 film, with nitrogen content close to the stoichiometric composition. The experimental findings are explained based on structural and elastic constant values computed from DFT for defect-free and metal-or nitrogen-deficient rock-salt MoAlN compounds.
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