Small grain size zirconium-based coatings deposited by magnetron sputtering at low temperatures

Hard, partly amorphous, ZrTiB(N) coatings were deposited by Physical Vapour Deposition (PVD) onto (111) silicon wafers at low substrate temperatures of 85 and 110 °C using Closed Field Unbalanced Magnetron Sputtering. A segmented rectangular sputter target composed of three pieces (Zr/TiB₂/Zr) was used as the source of evaporation of coating components. Two different substrate biases (i.e. floating potential and - 50 V) and N₂ reactive-gas flow rates of 2, 4 and 6 sccm were employed as the main deposition parameter variables. The chemical composition, structure, morphology and mechanical properties were investigated using a variety of analytical techniques such as Glow-Discharge Optical Emission Spectroscopy, cross-sectional Scanning Electron Microscopy (SEM), Glancing Angle X-ray Diffraction (GAXRD) and nanoindentation. With other parameters fixed, coating properties were found to be dependent on the substrate negative bias and nitrogen flow rate. Linear scan profiles and SEM imaging revealed that all coatings were smooth, dense and featureless (in fracture cross section) with no apparent columnar morphology or macro-defects. GAXRD structural analysis revealed that mostly metallic phases were formed for coatings containing no nitrogen, whereas a solid solution (Zr,Ti)N single phase nitride was found in most of the reactively deposited coatings - exhibiting a very small grain size due to nitrogen and boron grain refinement effects. Hardness values from as low as 8.6 GPa up to a maximum of 25.9 GPa are related mainly to solid solution strengthening effects. The measured elastic moduli correlated with the trends in hardness behaviour; values in the range of 120-200 GPa were observed depending on the selected deposition parameters. Also, high H/E values (> 0.1) were achieved with several of the coatings.