TiSiN films exhibit excellent comprehensive properties in terms of hardness, toughness, thermal stability, and oxidation resistance. The structural evolution of TiSiN thin films is influenced by various deposition parameters, among which the nitrogen flow rate, as a key factor determining nitrogen content, plays a critical role in regulating the nucleation and growth behavior of TiN and the formation of the amorphous Si3N4 phase. This study provides a systematic investigation into the effect of the nitrogen flow rate, varied from 4 to 14 mL/min, on the microstructure and mechanical properties of TiSiN thin films deposited on Si (100) substrates by mid-frequency magnetron sputtering. All other process parameters, including argon flow, bias voltage, target current, and deposition time, are held constant to isolate the influence of nitrogen supply. A comprehensive suite of advanced characterization techniques are employed to analyze the resulting films. X-ray diffraction (XRD) and transmission electron microscopy (TEM) are used to examine phase composition, crystallinity, and nanostructural evolution. X-ray photoelectron spectroscopy (XPS) provides detailed insights into chemical bonding states, particularly the relative proportions of Ti—N and Si—N bonds. Atomic force microscopy (AFM) is utilized to assess surface morphology and roughness, while Raman spectroscopy offers additional evidence of structural changes through phonon mode analysis. The mechanical properties, including hardness, elastic modulus, resistance to plastic deformation (quantified by H3/E2 ratio), and adhesion strength, are rigorously evaluated through nanoindentation and scratch tests. The results demonstrate a pronounced dependency of film properties on the nitrogen flow rate. The optimal performance is achieved at a flow rate of 10 mL/min, where the film exhibits a peak hardness of 16.2 GPa, an elastic modulus of 149.3 GPa, a H³/E² value of 0.19 GPa, and a maximum critical adhesion load of 8.67 N. Structural analyses at this condition reveal a well-defined nanocomposite structure comprising finely dispersed TiN nanocrystals (5-10 nm in size) with strong (111) orientation, effectively surrounded by a continuous amorphous Si3N4 phase that inhibits grain growth and enhances ductility. XPS analysis confirms that nitrogen is predominantly bonded as Ti—N, while the content of N—Si bonds initially increases with nitrogen flow up to 10 mL/min before decreasing at higher flows, correlating directly with the observed mechanical performance. Beyond the optimum value, excessive nitrogen flow (12-14 mL/min) results in coarse TiN grains, a reduction in the grain-refining effect of Si3N4, and a consequent decline in mechanical properties. AFM studies indicate variations in surface roughness influenced by ion bombardment efficiency, which itself is modulated by nitrogen concentration. Raman spectroscopy further corroborates these findings, showing shifts in acoustic and optical phonon modes consistent with changes in grain size and internal stress. In conclusion, this work elucidates the crucial role of nitrogen flow rate in tailoring the nanocomposite structure and mechanical properties of TiSiN thin films. The identified optimum flow rate of 10 mL/min facilitates an ideal balance between nanocrystallinity and amorphous phase content, yielding superior hardness, toughness, and adhesion. These insights not only deepen the understanding of process-structure-property relationships in nanocomposite coatings but also provide practical guidance for optimizing deposition parameters aimed at high-performance industrial applications.
Key words
TiSiN thin films /
nitrogen flow rate /
magnetron sputtering /
nanocomposite structure /
mechanical properties
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Funding
The National Key Research and Development Program of China (2023YFB3712300); Natural Science Foundation of Gansu Province (24JRRA954); Henan Province Key Research and Development Project (261111223000); China Aerospace Foundation Space and Aerospace Power Fund Project (KDJJ2025030109)
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