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Valence electron concentration- and N vacancy-induced elasticity in cubic early transition metal nitrides
Rhein Westfal TH Aachen, Germany.
Rhein Westfal TH Aachen, Germany.
Rhein Westfal TH Aachen, Germany.
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2023 (English)In: Acta Materialia, ISSN 1359-6454, E-ISSN 1873-2453, Vol. 255, article id 119078Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
PERGAMON-ELSEVIER SCIENCE LTD , 2023. Vol. 255, article id 119078
Keywords [en]
TMN; Elastic modulus; Elastic anisotropy; Point defects; Vacancies; Density functional theory; Single crystal; Thin films
National Category
Other Materials Engineering
Identifiers
URN: urn:nbn:se:liu:diva-196837DOI: 10.1016/j.actamat.2023.119078ISI: 001019099600001OAI: oai:DiVA.org:liu-196837DiVA, id: diva2:1791084
Note

Funding Agencies|Deutsche Forschungsgemeinschaft (DFG) [SFB-TR 87/3]; Swedish research council; VR-RFI [2021-03826]; Swedish Foundation for Strategic Research (SSF); Swedish Research Council (VR); [2017-00646_9]; [RIF14-0053]

Available from: 2023-08-24 Created: 2023-08-24 Last updated: 2023-08-24

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