High-resolution transmission electron microscopy, x-ray photoelectron spectroscopy (XPS), and Raman spectroscopy were used to study phase configuration and nanostructure evolutions of Ti–Cx–Ny thin films with different amounts of C incorporation. It was found that the atomic ratio of (C + N)/Ti played a crucial role in phase configuration and nanostructure evolutions as well as mechanical behaviors. When the ratio was less than one unit, a nanocrystalline (nc-) Ti(C, N) solid solution was formed by way of dissolution of C into TiN lattice. When this dissolution reached saturation, precipitation of a small amount of amorphous (a-) C phase along nc-Ti(C, N) grains was followed with more C incorporation. Further increase of C content (up to ∼19 at.% C) made the amorphous phase fully wet nanocrystallites, which resulted in the formation of two-phase nanocomposite thin films with microstructures comprising of ∼5 nm nc-Ti(C,N) crystallites separated by ∼0.5 nm a-(C, CNx) phase. Thicker amorphous walls and smaller sized grains were followed when the C content was further increased, accompanying with the formation of some disorders and defects in nc-grains and amorphous matrices. When the C content was increased to ∼48 at.%, 1–3 nm nanocrystallites with an average size of ∼2 nm were embedded into amorphous matrices. Both microhardness and residual compressive stress values were increased with increase of the atomic ratio in solid solution thin films when the atomic ratio value was less than one unit. Their maximums were obtained at stiochiometry nc-Ti(C,N) solid solution. Enhancement of hardness values was attributed to solid solution effect.
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The authors appreciate the use of the facilities in Advanced Coatings Applied Research Laboratory (ACARL), Hong Kong, China, which was supported by the Innovation Technology Fund of Hong Kong. The work described in this article was supported by the Research Grant of the City University of Hong Kong under Project No. 7001942.
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Lu, Y.H., Shen, Y.G. Nanostructure evolution and properties of two-phase nc-Ti(C, N)/a-(C, CNx) nanocomposites by high-resolution transmission electron microscopy, x-ray photoelectron spectroscopy, and Raman spectroscopy. Journal of Materials Research 22, 2460–2469 (2007). https://doi.org/10.1557/jmr.2007.0304