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V0.5Mo0.5Nx/MgO(001) layers grown at 100-900 °C: composition, nanostructure, and mechanical properties
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.ORCID iD: 0000-0002-4898-5115
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.ORCID iD: 0000-0003-3277-1945
Grupo de Capas Finas e Ingeniería de Superficies, Facultad de Física. Universidad de Barcelona. Dep. Física Aplicada y Óptica, Barcelona, Spain.
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2014 (English)Manuscript (preprint) (Other academic)
Abstract [en]

V0.5Mo0.5Nx/MgO(001) alloys with the B1-NaCl structure are grown by ultra-highvacuum reactive magnetron sputter deposition in 5 mTorr mixed Ar/N2 atmospheres at temperatures Ts which are varied from 100 and 900 °C. Alloy films grown at Ts ≤ 500 °C are polycrystalline with a strong 002 texture; layers grown at Ts ≤ 700 °C are epitaxial single-crystals. The N/Me ratio x ranges from 0.64±0.05 with Ts = 900 °C to 0.94±0.05 at 700 °C to 1.02±0.05 with Ts = 500 to 100 °C. The N loss at higher growth temperatures leads to a corresponding decrease in the relaxed lattice parameter ao from 4.212 Å with x = 1.02 to 4.175 Å with x = 0.94 to 4.121 Å with x = 0.64. V0.5Mo0.5Nx nanoindentation hardnesses H and elastic moduli E increase with increasing Ts from 17±3 GPa and 274±31 GPa at 100 °C to 26±1 GPa and 303±10 GPa at 900 °C. Films deposited at higher Ts also exhibit enhanced wear resistance. Scanning electron micrographs of nanoindents performed in single-crystal V0.5Mo0.5Nx films and films deposited at 100 and 300 °C reveal no evidence of cracking; instead they exhibit material pile-up around the indents characteristic of plastic flow in ductile materials. Valence band x-ray photoelectron spectroscopy analyses show an enhanced volume density of the shear sensitive d-t2g – d-t2g metallic states in V0.5Mo0.5Nx compared to VN and the density of these orbitals increases with increasing deposition temperature, i.e., the metallic  states become more populated with the introduction of N vacancies.

Place, publisher, year, edition, pages
2014.
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:liu:diva-106352OAI: oai:DiVA.org:liu-106352DiVA: diva2:715547
Available from: 2014-05-05 Created: 2014-05-05 Last updated: 2016-08-31Bibliographically approved
In thesis
1. Toughness Enhancement in Hard Single-Crystal Transition-Metal Nitrides: V-Mo-N and V-W-N Alloys
Open this publication in new window or tab >>Toughness Enhancement in Hard Single-Crystal Transition-Metal Nitrides: V-Mo-N and V-W-N Alloys
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Transition-metal nitrides are known for their high hardness, good wear resistance, high-temperature stability, and chemical inertness. Because of these properties, they are extensively used in many industrial applications, notably as protective wear, erosion, and scratch resistant coatings, which are often subjected to high thermo-mechanical stresses. While high hardness is essential, most applications also require high ductility, to avoid brittle failure due to cracking. However, transitionmetal nitrides, as most ceramics, generally exhibit low ductility and hence poor toughness.

Improving toughness, the combination of hardness and ductility, of ceramic materials requires suppression of crack initiation and/or propagation, both of which depend on the microstructure, electronic structure, and bonding nature of the coating material. This, however, is an extremely challenging task that requires a fundamental understanding of the mechanical behavior of materials. Theoretical studies, for example, ab initio calculations and simulations are therefore useful in the design of “unbreakable” materials by providing information about the electronic origins of hardness and ductility. Recent density functional theory calculations predicted that alloying can increase toughness in a certain family of transition-metal nitrides such as V-Mo-N and V-W-N alloys. Toughness enhancement in these alloys arises from a near optimal filling of the metallic d-t2g states, due to their high valence electron concentrations, leading to an orbital overlap which favors ductility during shearing.

This thesis focuses on the growth and characterization of V1-xMoxNy (0 ≤ x ≤ 0.7, 0.55 ≤ y ≤ 1.03) and V1-xWxNy (0 ≤ x ≤ 0.83, 0.75 ≤ y ≤ 1.13) cubic alloy thin films. I show that alloying VN with WN increases the alloy hardness and reduces the elastic modulus, an indication of enhanced toughness. I investigated the growth, nanostructure, and atomic ordering of as-deposited V1-xWxNy(001)/MgO(001) thin films. In addition, I studied the growth, structural and mechanical properties,  and electronic structure of V1-xMoxNy(001)/MgO(001) and V0.5Mo0.5Ny(111)/Al2O3(0001) thin films. I demonstrate that these alloys exhibit not only higher hardness than the parent binary compound, VN, but also dramatically increased ductility. V0.5Mo0.5N hardness is more than 25% higher than that of VN. Using nanoindentation I show that while VN and TiN reference samples undergo severe cracking typical of brittle ceramics, V0.5Mo0.5N films do not crack. Instead, they exhibit material pile-up around nanoindents, characteristic of plastic flow in ductile materials. Furthermore, the wear resistance of V0.5Mo0.5N is significantly higher than that of VN. I also show, for the first time, anion-vacancyinduced toughening of single-crystal V0.5Mo0.5Ny/MgO(001) films. Nanoindentation hardness of these alloys increases with the introduction of N-vacancies, while the elastic modulus remains essentially constant. In addition, typical scanning electron micrographs of nanoindents show no cracks, which demonstrate that N-vacancies lead to toughness enhancement in these alloys. Valence band x-ray photoelectron spectroscopy analyses show that vacancy-induced toughening is due to a higher electron density of d-t2g(Metal) – d-t2g(Metal) orbitals with increasing N-vacancy concentration, and essentially equally dense p(N) – d-eg(Metal) first neighbor bonds.

Overall, I demonstrate that it is possible to design and deposit hard and ductile transition-metal nitride coatings. My research results thus provide a pathway toward the development of new tough materials.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2014. 69 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1578
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-106472 (URN)10.3384/diss.diva-106472 (DOI)978-91-7519-392-2 (ISBN)
Public defence
2014-06-02, Planck, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2014-05-08 Created: 2014-05-08 Last updated: 2016-08-31Bibliographically approved

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Kindlund, HannaGreczynski, GrzegorzBroitman, EstebanLu, JunJensen, JensPetrov, IvanGreene, JosephBirch, JensHultman, Lars

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