Al/TiN界面本征润湿行为及其微观机制研究

孙士阳; 钱远近; 黄胜保; 徐平平; 任元; 谭心; 张文兴

doi:10.16490/j.cnki.issn.1001-3660.2025.18.012

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表面技术 ›› 2025, Vol. 54 ›› Issue (18) : 119-129. DOI: 10.16490/j.cnki.issn.1001-3660.2025.18.012

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Al/TiN界面本征润湿行为及其微观机制研究

孙士阳^*, 钱远近, 黄胜保, 徐平平, 任元, 谭心, 张文兴

作者信息 +

Intrinsic Wetting Behavior and Microscopic Mechanisms of Al/TiN Interface

SUN Shiyang^*, QIAN Yuanjin, HUANG Shengbao, XU Pingping, REN Yuan, TAN Xin, ZHANG Wenxing

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摘要

目的揭示非反应Al/TiN体系的界面润湿行为本征特性及其微观机制,阐明温度与界面原子排列对润湿性的协同作用机理。方法基于第一性原理分子动力学（AIMD）方法,构建Al(100)/TiN(100)界面slab模型（5层TiN基底+7层Al,共902个原子）,采用CP2K软件包中的QUICKSTEP模块进行动力学模拟。通过正则系综（NVT）在700~1 000 K温度范围内进行10 ps弛豫,结合均方位移（M_SD）、径向分布函数（R_DF）和形状图像分析法量化界面原子扩散行为与接触角演变规律。采用OVITO和VMD分析界面分层结构（Al_INT、Al_MID、Al_SURF）的扩散异质性,并构建无序界面模型对比外延生长界面的润湿差异。结果温度升高显著降低Al液接触角（700 K: 83.44°→1 000 K: 61.63°）,其机制归因于热扰动诱导的原子密度降低（2 375.16→2 088.72 kg/m³）和自扩散系数（D）提升（3.68×10^-5→8.02×10^-5 cm²/s）。界面分层分析显示,Al_INT原子保持TiN晶格外延排列（D=0.09×10^-5 cm²/s）,而Al_SURF原子主导铺展动力学（D=6.56×10^-5 cm²/s）。无序界面（仅7%原子扰动）使接触角骤增至120°,证实界面原子有序性是本征润湿的关键：有序排列降低扩散激活能,促进Al液沿基底迁移。结论非反应Al/TiN体系的润湿性由界面原子排列方式和表面原子密度共同调控。温度通过热扰动削弱原子间结合力,降低表面张力并增强扩散能力;界面无序化导致迁移势垒提高从而抑制铺展。该研究为金属-陶瓷复合材料的界面设计提供了原子尺度理论依据。

Abstract

Due to the high oxidation tendency of Al and the high difficulty and complexity of experimental operations, there are significant discrepancies and differences in understanding the intrinsic wetting behavior of Al and ceramics in the engineering field. To reveal the intrinsic characteristics and microscopic mechanisms of the interfacial wetting behavior in the non-reactive Al/TiN system, and elucidate the synergistic effect of temperature and interfacial atomic arrangement on wettability, this study systematically reveals the intrinsic characteristics and microscopic mechanisms of the interfacial wetting behavior of the non-reactive Al/TiN system based on first-principles molecular dynamics (AIMD) simulation method, with a focus on clarifying the synergistic effect of temperature and interfacial atomic arrangement on wettability. A slab model of the Al(100)/TiN(100) interface with a lattice match of 5% (5 layers of TiN substrate + 7 layers of Al, totaling 902 atoms) is constructed and kinetic simulations are performed with the QUICKSTEP module of the CP2K software package. Relaxation is carried out for 10 ps within the temperature range of 700-1 000 K with the canonical ensemble (NVT), combined with mean square displacement (MSD), radial distribution function (RDF), and shape image analysis methods to quantify the diffusion behavior of interfacial atoms and the evolution of contact angles. Software OVITO and VMD are used to analyze the diffusion heterogeneity of the interfacial layered structures (Al_INT, Al_MID, Al_SURF) and compare the wettability differences between the disordered interface model and the epitaxially grown interface. The research results show that as the temperature increases, the RMSD slope value of the TiN substrate gradually increases (700 K: 1.0 Å → 1 000 K: 1.4 Å), while maintaining a stable crystalline structure. The RMSD slope value of the Al liquid at the interface also gradually increases (700 K: 4.8 Å → 1 000 K: 6.8 Å), indicating that the increase in temperature leads to more vigorous vibrations of TiN substrate atoms and significantly enhances the diffusion rate of liquid Al atoms at the interface. The MSD curves show an increasing trend in slope, reflecting a significant improvement in the self-diffusion coefficient D (700 K: 3.68×10^-5 cm²/s → 1 000 K: 8.02×10^-5 cm²/s). This trend indicates that the increase in temperature effectively enhances the mobility of Al atoms, thereby accelerating the atomic diffusion kinetics. The first peak of the g(r) curve, representing the distance between nearest neighbors, gradually decreases from g(r)_max = 20.68 to 16.52, reflecting a reduction in the effective number of neighboring atoms; simultaneously, the peak width gradually expands, indicating that the increased temperature enlarges the range of atomic movement, leading to a more dispersed relative position between atoms. The increase in temperature significantly reduces the contact angle of liquid Al (700 K: 83.44°→1 000 K: 61.63°), which is attributed to the decrease in surface atomic density (2 375.16 → 2 088.72 kg/m³) and the increase in self-diffusion coefficient (3.40×10^-5 → 21.82×10^-5 cm²/s). The interface Al_INT atoms maintain an epitaxial arrangement conforming to the TiN lattice (D = 0.09×10^-5 cm²/s), while Al_SURF atoms exhibit high diffusion activities, dominating the droplet spreading kinetics. The regular epitaxial growth arrangement formed by Al atoms at the TiN interface is a key factor leading to the smaller contact angle of the Al/TiN interface. The disordered arrangement of atoms at the interface can greatly increase the atomic diffusion activation energy, thereby hindering the spreading of liquid Al on the TiN surface; The disordered interface (with only 7% atomic disturbance) causes a sharp increase in the contact angle to 120°, confirming that the ordered arrangement of interfacial atoms is crucial for intrinsic wettability. Ordered arrangement reduces diffusion activation energy, facilitating the migration of liquid Al along the substrate. The wettability of the non-reactive Al/TiN system is jointly regulated by the arrangement of interfacial atomic layers and the surface atomic density. Temperature weakens the interatomic bonding force through thermal disturbance, reduces surface tension, and enhances diffusion capacity; interfacial disordering suppresses spreading by increasing migration barriers. This study provides an atomic-scale theoretical basis for the interfacial design of metal-ceramic composites.

导出引用

孙士阳, 钱远近, 黄胜保, 徐平平, 任元, 谭心, 张文兴. Al/TiN界面本征润湿行为及其微观机制研究[J]. 表面技术. 2025, 54(18): 119-129 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.18.012

SUN Shiyang, QIAN Yuanjin, HUANG Shengbao, XU Pingping, REN Yuan, TAN Xin, ZHANG Wenxing. Intrinsic Wetting Behavior and Microscopic Mechanisms of Al/TiN Interface[J]. Surface Technology. 2025, 54(18): 119-129 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.18.012

中图分类号： TB34

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