Composition, structure and properties of SiNx films fabricated by pulsed reactive closed-field unbalanced magnetron sputtering

Silicon nitride (SiNx) thin films are of special interest in both scientific research and industrial applications due to their remarkable properties such as high thermal stability, chemical inertness, high hardness and good dielectric properties. In this work, SiNx films were fabricated by pulsed reactive closed-field unbalanced magnetron sputtering of high purity single crystal silicon targets in an Ar-N2 mixture. The effect of N2 partial pressure on the film composition, chemical bonding configurations, surface morphology, surface free energy, optical and mechanical properties were investigated. We showed that with increased N2 partial pressure, the N to Si ratio (N/Si) in the film increased and N atoms are preferentially incorporated in the NSi3 stoichiometric configuration. It leads the Si-N network a tendency to chemical order. Films deposited at a high N2 fraction were consistently N-rich. The film surface transformed from a loose granular structure with microporosity to a homogeneous, continuous, smooth and dense structure. A progressive densification of the film microstructure occurs as the N2 fraction is increased. The reduced surface roughness and the increased N incorporation in the film give rise to the increased contact angle with double-distilled water from 24° to 49.6°. To some extent, the SiNx films deposited by pulsed magnetron sputtering are hydrophilic in nature. The as-deposited SiNx films exhibit good optical transparency in the visible region and the optical band gap Eopt can be varied from 1.68 eV for a-Si to 3.62 eV for SiNx films, depending on the synthesis parameters. With the increase of the N/Si atomic ratio, wear resistance of the SiNx films was improved, a consequence of increased hardness and elastic modulus. The SiNx films have lower friction coefficient and better wear resistance than 316L stainless steel under dry sliding friction, where the SiNx films experienced only fatigue wear.