目的 本研究旨在探究氮气流量对TiSiN薄膜微观结构及力学性能的影响,通过优化制备参数,提升薄膜的综合性能,为其在耐磨涂层等工业领域的应用提供理论依据。方法 采用中频磁控溅射技术在Si（100）基底上制备TiSiN薄膜,通过调节氮气流量（4~14 mL/min）调控薄膜结构。利用X射线衍射（XRD）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）、原子力显微镜（AFM）、拉曼光谱（Raman）等技术分析薄膜的晶相组成、化学键状态及表面形貌,并通过纳米压痕仪测试其硬度、弹性模量,采用划痕仪测试其结合力。结果 当氮气流量为10 mL/min时,薄膜表现出最优性能,硬度（16.2 GPa）和弹性模量（149.3 GPa）达到峰值,抗塑性变形能力（H3/E2=0.19 GPa）和结合力（临界载荷8.67 N）最佳。XRD与TEM显示薄膜为TiN纳米晶镶嵌于非晶Si3N4基体的复合结构,氮气流量增加促进TiN形核,但过量氮气（>10 mL/min）导致Si3N4抑制效应减弱,晶粒粗化,硬度下降。XPS证实N元素以Ti—N键为主,N—Si键含量先增后减,与硬度变化趋势一致。结论 氮气流量通过调控TiN形核和Si3N4非晶相抑制效应,显著影响TiSiN薄膜的纳米复合结构与力学性能。10 mL/min为最佳氮气流量,此时薄膜兼具高硬度、强韧性和优异结合力,为工业应用提供了优化方向。
Abstract
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.
关键词
TiSiN薄膜 /
氮气流量 /
磁控溅射 /
纳米复合结构 /
力学性能
Key words
TiSiN thin films /
nitrogen flow rate /
magnetron sputtering /
nanocomposite structure /
mechanical properties
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基金
国家重点研发计划（2023YFB3712300）; 甘肃省自然科学基金（24JRRA954）; 河南省重点研发专项（261111223000）; 中国航天基金会空天动力基金（KDJJ2025030109）
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