Solid Solution and Segregation Effects in Arc-Deposited Ti1-xSixN Thin Films Resolved on the nanometer scale by 15N Isotopic Substitution in AtomP robe Tomography
(English)Manuscript (preprint) (Other academic)
Nanostructured TiSiN is an important material in wear--‐resistant coatings for extending the lifetime of cutting tools. Yet, the understanding regarding the structure, phase composition, and bonding on the detailed nanometer scale, which determines the properties of TiSiN, is lacking. This limits our understanding of the growth phenomena and eventually a larger exploitation of the material. By substituting natN2 with 15N2 during reactive arc deposition of TiSiN thin films, atom probe tomography (APT) gives elemental sensitivity and sub-nanometer resolution, a finer scale than what can be obtained by commonly employed energy dispersive electron spectroscopy in scanning transmission electron microscopy. Using a combination of analytical transmission electron microscopy and APT we show that arc-deposited Ti0.92Si0.0815N and Ti0.81Si0.1915N exhibit Si segregation on the nanometer scale in the alloy films. APT composition maps and proximity histograms from domains with higher than average Ti content show that the TiN domains contain at least ~2 at. % Si for Ti0.92Si0.08N and ~5 at. % Si for Ti0.81Si0.19N, thus confirming the formation of solid solutions. The formation of relatively pure SiNy domains in the Ti0.81Si0.19N films is tied to pockets between microstructured, columnar features in the film. Finer SiNy enrichments seen in APT possibly correspond to tissue layers around TiN crystallites, thus effectively hindering growth of TiN crystallites, causing TiN renucleation and thus explaining the featherlike nanostructure within the columns of these films. For the stoichiometry of the TiN phase, we establish a global under stoichiometry, in accordance with the tendency for SiNy films to have tetrahedral bonding coordination towards a nominal Si3N4 composition.
IdentifiersURN: urn:nbn:se:liu:diva-122722OAI: oai:DiVA.org:liu-122722DiVA: diva2:872187