Characterization studies of pulse magnetron sputtered hard ceramic titanium diboride coatings alloyed with silicon

The composition, structure and mechanical properties of pulsed-DC unbalanced magnetron sputtered Ti–Si–B thin films—hard coatings with the potential for excellent thermal stability and oxidation resistance—are investigated and reported in this paper. Fully dense, hard (19–37 GPa) Ti–Si–B coatings were deposited at substrate bias voltages (V_s) ranging from floating potential to ?150 V which resulted in substrate temperatures of ～90–135 °C. We found that variation of substrate biasing conditions critically affected film composition, structure and resultant mechanical properties. For instance, concentration of Si in films decreased from 18.4 at.% to 3.8 at.% as V_s was increased from floating potential to ?150 V; composition profile analysis of the near-surface region of films (0–10 nm) revealed them to be rich in Si with significant differences among specimens produced at different substrate bias conditions. Variation of substrate biasing conditions provided coating structures that ranged from completely amorphous at floating substrate potential to nanocrystalline at V_s = ?50 to ?100 V and crystalline nanocolumnar at V_s = ?150 V. We found that each of the structures obtained exhibited different specific values of hardness and elastic modulus, which is also in a good agreement with results reported for other coatings possessing similar micro- and nano-structures. Film structure was analyzed in detail by conventional and analytical transmission electron microscopy. Coatings that exhibited the highest values of hardness (37 GPa) were found to possess features such as crystalline nanocolumnar grains a few nanometres in diameter and disordered intergranular regions of different chemical composition, thus qualifying as nanocomposite films. Results of this work allowed relationships to be drawn between deposition parameters and Ti–Si–B coating composition, structure and mechanical properties. Qualitatively similar relationships are also expected for other biased plasma-assisted physical vapour deposited transition-metal-based ceramic coatings alloyed with Si (e.g. Ti–Si–N, Cr–Si–N, Cr–Al–Si–N).