Si incorporation in Ti1-xSixN films grown on TiN(001) and (001)-faceted TiN(111) columns
2014 (English)In: Surface & Coatings Technology, ISSN 0257-8972, E-ISSN 1879-3347, Vol. 257, 121-128 p.Article in journal (Refereed) Published
Thin films consisting of TiN nanocrystallites encapsulated in a fully percolated SiNy tissue phase are archetypes for hard and superhard nanocomposites. Here, we investigate metastable SiNy solid solubility in TiN and probe the effects of surface segregation during the growth of TiSiN films onto substrates that are either flat TiN(001)/MgO(001) epitaxial buffer layers or TiN(001) facets of length 1-5 nm terminating epitaxial TiN(111) nanocolumns, separated by voids, deposited on epitaxial TiN(111)/MgO(111) buffer layers. Using reactive magnetron sputter deposition, the TiSiN layers were grown at 550 degrees C and the TiN buffer layers at 900 degrees C On TiN(001), the films are NaCl-structure single-phase metastable Ti1-xSixN(001) with N/(Ti + Si) = 1 and 0 less than= x less than= 0.19. These alloys remain single-crystalline to critical thicknesses h(c) ranging from 100 +/- 30 nm with x = 0.13 to 40 +/- 10 nm with x = 0.19. At thicknesses h greater than h(c), the epitaxial growth front breaks down locally to form V-shaped polycrystalline columns with an underdense feather-like nanostructure. In contrast, the voided epitaxial TiN(111) columnar surfaces, as well as the TiN(001) facets, act as sinks for SiNy. For Ti1-xSixN layers with global average composition values less than x greater than = 0.16, the local x value in the middle of Ti1-xSixN columns increases from 0.08 for columns with radius r similar or equal to 2 nm to x = 0.14 with r similar or equal to 4 nm. The average out-of-plane lattice parameter of epitaxial nanocolumns encapsulated in SiNy decreases monotonically with increasing Si fraction less than x greater than, indicating the formation of metastable (Ti,Si)N solid solutions under growth conditions similar to those of superhard nanocomposites for which the faceted surfaces of nanograins also provide sinks for SiNy.
Place, publisher, year, edition, pages
Elsevier , 2014. Vol. 257, 121-128 p.
Sputtering; Titanium silicon nitride; Superhardness; Nanocomposite; Solid solution
IdentifiersURN: urn:nbn:se:liu:diva-112640DOI: 10.1016/j.surfcoat.2014.05.043ISI: 000344423100016OAI: oai:DiVA.org:liu-112640DiVA: diva2:769095
Funding Agencies|VINN Excellence Center on Functional Nanoscale Materials (FunMat); Swedish Foundation for Strategic Research through the Synergy Grant FUNCASE; Wallenberg Scholar Grant; Doubly-Corrected Linkoping FEI Titan3 60-300 electron microscope2014-12-052014-12-052016-08-31