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- Aghda, Soheil Karimi, et al.
(författare)
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Valence electron concentration- and N vacancy-induced elasticity in cubic early transition metal nitrides
- 2023
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Ingår i: Acta Materialia. - : Elsevier. - 1359-6454 .- 1873-2453. ; 255
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Tidskriftsartikel (refereegranskat)abstract
- Motivated by frequently reported deviations from stoichiometry in cubic transition metal nitride (TMNx) thin films, the effect of N-vacancy concentration on the elastic properties of cubic TiNx, ZrNx, VNx, NbNx, and MoNx (0.72 & LE; x & LE; 1.00) is systematically studied by density functional theory (DFT) calculations. The predictions are validated experimentally for VNx (0.77 & LE; x & LE; 0.97). The DFT results indicate that the elastic behavior of the TMNx depends on both the N-vacancy concentration and the valence electron concentration (VEC) of the transition metal: While TiNx and ZrNx exhibit vacancy-induced reductions in elastic modulus, VNx and NbNx show an increase. These trends can be rationalized by considering vacancy-induced changes in elastic anisotropy and bonding. While introduction of N-vacancies in TiNx results in a significant reduction of elastic modulus along all directions and a lower average bond strength of Ti-N, the vacancy-induced reduction in [001] direction of VNx is overcompensated by the higher stiffness along [011] and [111] directions, resulting in a higher average bond strength of V-N. To validate the predicted vacancy-induced changes in elasticity experimentally, close-to-singlecrystal VNx (0.77 & LE; x & LE; 0.97) are grown on MgO(001) substrates. As the N-content is reduced, the relaxed lattice parameter a0, as probed by X-ray diffraction, decreases from 4.128 & ANGS; to 4.096 & ANGS;. This reduction in lattice parameter is accompanied by an anomalous 11% increase in elastic modulus, as determined by nanoindentation. As the experimental data agree with the predictions, the elasticity enhancement in VNx upon N-vacancy formation can be understood based on the concomitant changes in elastic anisotropy and bonding.
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| 2. |
- Karimi Aghda, Soheil, et al.
(författare)
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Unravelling the ion-energy-dependent structure evolution and its implications for the elastic properties of (V,Al)N thin films
- 2021
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Ingår i: Acta Materialia. - : Elsevier. - 1359-6454 .- 1873-2453. ; 214
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Tidskriftsartikel (refereegranskat)abstract
- Ion irradiation-induced changes in the structure and mechanical properties of metastable cubic (V,Al)N deposited by reactive high power pulsed magnetron sputtering are systematically investigated by correlating experiments and theory in the ion kinetic energy (Ek) range from 4 to 154 eV. Increasing Ek results in film densification and the evolution from a columnar (111) oriented structure at Ek ≤ 24 eV to a fine-grained structure with (100) preferred orientation for Ek ≥ 104 eV. Furthermore, the compressive intrinsic stress increases by 336 % to -4.8 GPa as Ek is increased from 4 to 104 eV. Higher ion kinetic energy causes stress relaxation to -2.7 GPa at 154 eV. These ion irradiation-induced changes in the thin film stress state are in good agreement with density functional theory simulations. Furthermore, the measured elastic moduli of (V,Al)N thin films exhibit no significant dependence on Ek. The apparent independence of the elastic modulus on Ek can be rationalized by considering the concurrent and balancing effects of bombardment-induced formation of Frenkel pairs (causing a decrease in elastic modulus) and evolution of compressive intrinsic stress (causing an increase in elastic modulus). Hence, the evolution of the film stresses and mechanical properties can be understood based on the complex interplay of ion irradiation-induced defect generation and annihilation.
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