表面技术2026，Vol.55Issue(6)：232-240,269,10.DOI:10.16490/j.cnki.issn.1001-3660.2026.06.017
碳基复合薄膜中碳纳米管原位生长与机理研究
In-Situ Growth Mechanism of Carbon Nanotubes Embedded in Carbon-Based Nanocomposite Films
摘要
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分类
机械制造引用本文复制引用
王伟奇,王曼,杨世豪,余璐瑶,令晓明..碳基复合薄膜中碳纳米管原位生长与机理研究[J].表面技术,2026,55(6):232-240,269,10.基金项目
国家自然科学基金(52305195) （52305195）
甘肃省自然科学基金(25JRRA187) （25JRRA187）
甘肃省高校教师创新基金项目(2026A-055) The Natural Science Foundation of China(52305195) （2026A-055）
The Natural Science Foundation of Gansu Province(25JRRA187) （25JRRA187）
Innovation Fund Project for University Teachers of Gansu Province(2026A-055) （2026A-055）
