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High Si content TiSiN films with superior oxidation resistance
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, Faculty of Science & Engineering.ORCID iD: 0000-0002-4898-5115
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, Faculty of Science & Engineering.
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, Faculty of Science & Engineering.ORCID iD: 0000-0002-2837-3656
Linköping University, Department of Physics, Chemistry and Biology, Nanostructured Materials. Linköping University, Faculty of Science & Engineering.ORCID iD: 0000-0002-2286-5588
2020 (English)In: Surface & Coatings Technology, ISSN 0257-8972, E-ISSN 1879-3347, Vol. 398, article id 126087Article in journal (Refereed) Published
Abstract [en]

The high-temperature oxidation resistance of Ti1-xSixN films with Si content varying in wide range, 0.13 <= x <= 0.91, is evaluated. Films are grown in Ar/N-2 atmospheres using a hybrid high-power impulse and dc magnetron sputtering (HiPIMS/DCMS) configuration with Si target powered by HiPIMS and Ti target operated in DCMS mode. The substrate bias is synchronized to the Si+-rich portions of the HiPIMS pulses in order to promote solid solution formation. A combination of X-ray photoelectron spectroscopy, elastic recoil detection analysis, and cross-sectional scanning electron microscopy reveals a sharp increase in the oxidation resistance for layers with x > 0.50. The thickness of the oxide layer, following 1 h anneal at 800 degrees C in air, is in the range 150-200 nm for 0.13 <= x <= 0.50 and decreases to only 4 nm with x = 0.91, which is similar to 30 times lower than for the best performing Ti1-xAlxN film (x = 0.64) tested under the same conditions. The oxide forming on top of Ti1-xSixN films with x = 0.41 consists of a SiO2-TiO2 two-phase mixture with a molar ratio given by Si/Ti ratio. In Ti1-xSixN layers with x <= 0.31, the presence of grain boundaries, which act as diffusion paths facilitates Si diffusion towards the bulk of the film resulting in that TiO2, the thermodynamically more stable oxide, terminates the surface. Ti0.09Si0.91N films, are essentially unaffected by the anneal and exhibit a hardness of 23 GPa, which is similar to 30% higher than for the reference SiNz film. Moreover, we demonstrate that 25 nm thick Ti0.09Si0.91N capping layers successfully prevent Ti(0.36A)l(0.64)N oxidation at 800 degrees C. Such approach provides superior oxidation protection compared to alloying TiAlN with Si. Our results suggest that multilayers including nm thin layers of high Si-content TiSiN is a most effective approach to improve high-temperature oxidation resistance of functional ceramic thin films.

Place, publisher, year, edition, pages
ELSEVIER SCIENCE SA , 2020. Vol. 398, article id 126087
Keywords [en]
Oxidation resistance; TiSiN; TiAlN; XPS; thin films
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:liu:diva-168180DOI: 10.1016/j.surfcoat.2020.126087ISI: 000549325000022OAI: oai:DiVA.org:liu-168180DiVA, id: diva2:1460273
Note

Funding Agencies|Knut and Alice Wallenberg Foundation Scholar Grant [KAW2016.0358]; Competence Center Functional Nanoscale Materials (FunMat-II) VINNOVA grantVinnova [2016-05156]; Swedish Research Council VR Grant [2018-03957]; VINNOVA grantVinnova [2019-04882]; Carl Tryggers Stiftelse for Vetenskaplig Forskning [CTS 17:166, CTS 15:219, CTS 14:431]; Swedish Research Council VR-RFISwedish Research Council [2017-00646_9]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research [RIF14-0053]

Available from: 2020-08-23 Created: 2020-08-23 Last updated: 2020-08-23

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Greczynski, GrzegorzBakhit, BabakHultman, LarsOdén, Magnus
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