In this work, Ti–B–N coatings have been prepared by moderate temperature chemical vapor deposition (MTCVD). The effect of a varying boron concentrations (9.6 and 55.4 at.%) on the chemical composition and the oxidation behavior was investigated by XRD, SEM, WDS, XPS and Raman spectroscopy. The results clearly demonstrate a good correlation between the different techniques. The same transition trends were observed in the examined Ti–B–N system in the progression from TiN to TiB2 by the addition of boron. At boron concentrations ≥ 18 at.%, the coatings reveal a two phase structure comprising a nanocrystalline TiN phase embedded in an amorphous TiB2 matrix. In Ti–B–N coatings with boron concentrations ≤ 18 at.%, the high sensitivity of Raman spectroscopy enabled the identification of an amorphous TiB phase. The oxidation behavior of Ti–B–N coatings was found to be affected by the boron concentration as well. Boron concentrations ≤ 18 at.% improve the thermal stability compared to TiN, most likely due to the TiB phase present in these coatings. Ti–B–N coatings with a high boron concentration show a higher degree of oxidation compared to TiN manifested in a higher oxide layer thickness. In addition, these coatings tend to form boron oxides on their surface, which lead to the formation of metastable anatase rather than the thermodynamically stable rutile.
