Influence of chemical vapor precursor flow rate on the structure and thermal stability of phase-modulated VSiCN/Ag coatings

Ceramic/silver coatings are of interest for tribological and antimicrobial applications. Here, the amorphous phase volume fraction in VSiCN/Ag coatings was varied and the microstructure, mechanical properties, and vacuum annealing behavior of the phase-modulated VSiCN/Ag coatings were compared with columnar VN/Ag coatings. The coatings were deposited by filament-assisted reactive magnetron sputtering in a gas mixture of argon, nitrogen, and hexamethyldisilazane (HMDS). HMDS vapor flow rates were varied to influence coating amorphous phase content (0 at. % ≤ Si ≤ 10 at. %, 0 at. % ≤ C ≤ 20 at. %), and the sputter power supplied to a V₅₈Ag₄₂ target was manipulated to control metal content (3 at. % ≤ Ag ≤ 8 at. %). Silver surface segregation did not occur during coating growth, nor immediately after deposition. VN/Ag coatings exhibited columnar growth structures with >100 nm B1-VN_x grains and 10−50 nm silver inclusions, which preferentially decorated the column boundaries. Columnar growth was completely disrupted in the VSiCN/Ag coatings and discrete silver inclusions were not observed within the microstructure. The hardness of all coatings was similar (12.3–16.5 GPa), while the apparent Young's modulus decreased from 247 to 169 GPa with increasing amorphous phase content. Rockwell indentation tests revealed that coating adhesion began to suffer after deposition at higher HMDS flow rates. Silver surface segregation was observed on all coatings after vacuum annealing at 550 °C for 1 h. The size of the surface particles ranged between 50 and 200 nm for the VN/Ag coating but was below 20 nm for the VSiCN/Ag coatings. Silver segregation occurred preferentially at coating growth defects in the columnar VN/Ag coating while the particle distribution was uniform across the surface of the VSiCN/Ag coatings. The results of this study demonstrate that phase modulation of ceramic/silver coatings may enable high-diffusivity microstructural features to be tailored for improved thermal stability and control of silver surface segregation at elevated temperatures.