Influence of Plasma Treatment Parameters on the Structural-Phase Composition, Hardness, Moisture-Resistance, and Raman-Enhancement Properties of Nitrogen-Containing Titanium Dioxide

The paper shows, for the first time, the prospects of treatment with a quasi-equilibrium low-temperature nitrogen plasma in an open atmosphere for the formation of super-hard, super-hydrophobic TiN/TiO(2) composite coatings with pronounced Raman-enhancement properties. X-ray diffractometry (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and Raman spectroscopy, as well as the analysis of hardness and moisture-resistance properties, are used as analytical research methods. During plasma treatment of titanium films on sapphire with a mass average temperature of 4–6 kK, an X-ray amorphous hydrophilic titanium oxide film with a low nitrogen content is formed. The nitrogen content in titanium oxide films increases with increasing treatment temperature up to 6–7 kK. In this case, an X-ray amorphous hydrophobic film is formed. With a further increase in temperature to 7–10 kK, a TiN/TiO(2) composite structure based on polycrystalline rutile is formed with increased hydrophobicity and pronounced Raman enhancement properties due to the effective excitation of surface plasmon polaritons. The presence of the crystalline phase increases the dephasing time, which determines the quality of the resonance and the achievable amplification of the electromagnetic field near the TiN inclusions. All treated films on sapphire have a super-hardness above 25 GPa (Vickers hardness test) due to high grain size, the presence of nitrogen-containing inclusions concentrated along grain boundaries, and compressive stresses.