目的 碳纳米管/非晶碳复合薄膜因具有良好的机械、摩擦学和场发射特性等,在耐磨涂层、集成电路和场发射器件等领域具有重要的应用前景。然而传统方法制备的碳纳米管/非晶碳复合结构所涉及的过程复杂、易引入杂质和缺陷,导致薄膜性能下降并极大限制了其应用。方法 本研究将碳基复合薄膜中碳纳米管结构原位生长自形成技术应用于样品制备中,开展非晶碳复合薄膜中碳纳米管的原位生长与机理研究。结合不同结构表征技术系统研究碳纳米管微观结构与催化金属含量及甲烷气流比之间的作用机制,探讨碳纳米管原位形成的起因和驱动力,建立原位自形成机理模型,实现碳纳米管/非晶碳复合结构的一步法原位生长。结果 20%甲烷气流比下,金属镍含量最高为17.23%（原子数分数）,薄膜中存在的Ni3C（110）晶面可催化诱导sp²杂化碳键重组,原位生长出直径为5~6 nm的碳纳米管。当甲烷气流比高于20%后,靶“中毒”效应导致薄膜中的金属镍含量减少,结合TEM形貌和SAED图案,可知过高的甲烷气流比会使薄膜中催化剂含量不足,缺乏足够多的催化剂诱导碳纳米管生成,薄膜结构主要由分散的Ni3C纳米颗粒和非晶碳组成。场发射性能测试表明：将CNTs掺杂到非晶碳薄膜中可以显著改善a-C:H薄膜的场电子发射行为,增强电流密度、降低开启电压,同时表现出较稳定的发射寿命。结论 利用简单的反应磁控溅射沉积系统,以金属镍靶为催化诱导金属,通过改变甲烷气流比调控薄膜中催化金属含量在合适范围内,实现非晶碳复合薄膜中碳纳米管结构的原位生长,并提出了碳纳米管的原位生长机理。
Abstract
Carbon nanotubes/amorphous carbon (CNTs/a-C) composite films exhibit superior mechanical, tribological, and field electron emission properties, making them highly suitable for applications in anti-wear coatings, integrated circuits, and field emission devices. However, conventional fabrication techniques for these composite structures are often complex and prone to introducing impurities and defects, which significantly degrade film performance. In this study, an in-situ self-organization method is developed to fabricate CNTs within carbon-based films via metal-induced growth using a Ni catalyst. Through systematic structural and compositional characterization, the interdependent relationships between the CNT microstructure, catalytic metal concentration, and methane flow ratio are investigated. The driving forces for spontaneous in-situ CNT growth are elucidated, and a corresponding growth mechanism model is established, enabling the efficient, one-step synthesis of high-quality CNTs/a-C composite films.
In this work, in-situ self-organization is employed to fabricate CNTs in carbon based films via metal-induced growth in the presence of Ni catalyst. Moreover, through comprehensively structural and compositional characterization (including FESEM, TEM, XRD, XPS and Raman spectroscopy), it systematically investigates the interdependent relationships among the microstructure of CNTs, catalytic metal concentration, and methane flow ratio. Meanwhile, the underlying causes and driving forces for CNTs in-situ growth spontaneously are elucidated and a mechanism model is established. This fundamental understanding enables the realization of one-step in-situ growth of CNTs/a-C composite films effectively.
XPS analysis reveals that the C 1s spectra of the composite films can be fitted to four characteristic peaks corresponding to C-Ni, sp2-C, sp3-C, C—O bonds and the carbon predominantly in the form of sp² hybridized, providing favorable condition for CNTs growth. As the methane flow ratio increases from 20% to 60%, the C—Ni bond intensity gradually diminishes accompanied by a decrease in Ni 2p peak intensity—a phenomenon attributed to the target poisoning effect during sputtering. EDS analysis indicates that the Ni content decreases from 17.23at.% to 1.07at.% while the C content rises from 74.49at.% to 93.37at.%. HRTEM characterization demonstrates that the film deposited at 20% methane flow ratio is mainly composed of a-C:H, metallic Ni, nickel carbide nanoparticles and abundant CNTs with uniform size of 5-6 nm. SAED and XRD results confirm the presence of Ni3C (110), CNT (101), and metallic Ni (220) crystal planes in the film. Herein, the NiC3 is proposed to catalyze the rearrangement of sp² hybridized carbon within the film, promoting the in-situ growth process of CNTs. Raman spectroscopy reveals typical signature peaks of carbonaceous material at 1 380 cm-1 (D peak) and 1 570 cm-1 (G peak) for the film deposited 20% methane flow ratio, which further validates the predominant sp² hybridized carbon in the film. In the EDX elemental analysis coupled with TEM in line scans mode, the C signal intensity significantly increases and while the Ni signal intensity correspondingly decreases, which is consistent with the TEM morphology of CNTs regions. The measured length of the enhanced carbon signal is consistent with the CNTs diameters (5-6 nm). Differently, the films prepared at a higher methane flow ratio are composed of a small amount of dispersed Ni3C nanoparticles embedded in amorphous carbon rather than CNTs. Furthermore, a gradient in particle size of Ni3C is observed, with large dimension near the substrate and gradual decrease farther away according to the TEM morphology. This is mainly due to the fact that prolonged deposition time leads to seriously target poisoned, significantly degrading the sputtering efficiency and lowering the Ni content in the film. Concurrently, only a faint Ni3C (110) crystal diffraction ring appear in the SAED pattern, indicating that the catalyst amount is insufficient to induce the growth of CNTs.
关键词
非晶碳薄膜 /
碳纳米管 /
原位生长 /
物理气相沉积 /
自形成 /
机理
Key words
amorphous carbon film /
carbon nanotube /
in-situ growth /
physical vapor deposition /
self-organized /
mechanism
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基金
国家自然科学基金（52305195）; 甘肃省自然科学基金（25JRRA187）; 甘肃省高校教师创新基金项目（2026A-055）
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