Effects of Nitrogen Flow Ratio on Structures, Bonding Characteristics, and Mechanical Properties of ZrNx Films

ZrNx (x = 0.67–1.38) films were fabricated through direct current magnetron sputtering by a varying nitrogen flow ratio [N2/(Ar + N2)] ranging from 0.4 to 1.0. The structural variation, bonding characteristics, and mechanical properties of the ZrNx films were investigated. The results indicated that the structure of the films prepared using a nitrogen flow ratio of 0.4 exhibited a crystalline cubic ZrN phase. The phase gradually changed to a mixture of crystalline ZrN and orthorhombic Zr3N4 followed by a Zr3N4 dominant phase as the N2 flow ratio increased up to >0.5 and >0.85, respectively. The bonding characteristics of the ZrNx films comprising Zr–N bonds of ZrN and Zr3N4 compounds were examined by X-ray photoelectron spectroscopy and were well correlated with the structural variation. With the formation of orthorhombic Zr3N4, the nanoindentation hardness and Young’s modulus levels of the ZrNx (x = 0.92–1.38) films exhibited insignificant variations ranging from 18.3 to 19.0 GPa and from 210 to 234 GPa, respectively.