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激光合成铁纳米颗粒作为生长具有非晶态壳层的垂直排列多壁碳纳米管的有效催化剂。

Laser synthesis of iron nanoparticles as effective catalysts for the growth of vertically aligned MWCNTs with amorphous shell.

作者信息

Parshina Liubov, Novodvorsky Oleg, Egorov Alexander, Putilin Felix, Khramova Olga

机构信息

ILIT RAS - Branch of the FSRC "Crystallography and Photonics" RAS, Moscow region, Shatura 140700, Russia.

ILIT RAS - Branch of the FSRC "Crystallography and Photonics" RAS, Moscow region, Shatura 140700, Russia.

出版信息

Micron. 2022 Sep;160:103323. doi: 10.1016/j.micron.2022.103323. Epub 2022 Jun 30.

DOI:10.1016/j.micron.2022.103323
PMID:35797830
Abstract

Vertically aligned multi-walled carbon nanotubes (MWCNTs) are attractive for use in nanoelectronics, nanosensors, electrodes for energy storage and harvesting devices, composites, weaving yarns and many other devices. However, in order to reach practical relevance in these applications, the vertically aligned MWCNTs must be dense and sufficient height. Fulfilling those requirements is often challenging. Herein, we report production of high density vertically aligned MWCNTs with amorphous shell on iron nanoparticles by the modified CVD method in the tube flow reactor via catalytic pyrolysis of acetylene. The iron thin films of thickness from 0.5 to 68 nm were obtained by the pulsed laser deposition in droplet-free mode on single crystal silicon substrates (100). The obtained films of the thickness from 0.5 to 20 nm were arrays of nanoparticles with a size from 5 to 17 nm as a result of thermal annealing. These nanoparticles were used as catalysts for the growth of MWCNTs. SEM investigations have shown that height of the obtained vertically aligned MWCNTs depends on the thickness of the initial iron film. The height of the MWCNTs array of 42 µm was achieved on the iron nanoparticles obtained after annealing the metal film of 5 nm thickness. The growth temperature of the obtained MWCNTs array was 700 °C at the volume flow ratio of the CH and H(5%)/Ar gas mixture was 1:4. TEM investigations have shown that the diameter of the obtained MWCNTs reached 15-20 nm with amorphous shell thickness of 5-10 nm. Four distinguished Raman peaks at 1360, 1603, 2711, and 2932 cm- 1 correspond to the D-band, G-band, 2D-band, and (D + G)-band, respectively and confirm the formation MWCNTs with good graphitization.

摘要

垂直排列的多壁碳纳米管(MWCNTs)在纳米电子学、纳米传感器、能量存储与收集装置的电极、复合材料、编织纱线及许多其他装置中具有应用潜力。然而,为了在这些应用中具有实际意义,垂直排列的MWCNTs必须致密且具有足够的高度。满足这些要求通常具有挑战性。在此,我们报告了通过改进的化学气相沉积(CVD)方法,在管式流动反应器中通过乙炔的催化热解,在铁纳米颗粒上制备具有非晶壳的高密度垂直排列MWCNTs。通过脉冲激光沉积以无液滴模式在单晶硅衬底(100)上获得了厚度为0.5至68nm的铁薄膜。经过热退火后,获得的厚度为0.5至20nm的薄膜是尺寸为5至17nm的纳米颗粒阵列。这些纳米颗粒被用作MWCNTs生长的催化剂。扫描电子显微镜(SEM)研究表明,所获得的垂直排列MWCNTs的高度取决于初始铁膜的厚度。在对5nm厚的金属膜进行退火后获得的铁纳米颗粒上,MWCNTs阵列的高度达到了42μm。在所获得的MWCNTs阵列的生长过程中,当CH与H(5%)/Ar气体混合物的体积流量比为1:4时,生长温度为700°C。透射电子显微镜(TEM)研究表明,所获得的MWCNTs的直径达到15 - 20nm,非晶壳厚度为5 - 10nm。在1360、1603、2711和2932cm⁻¹处的四个明显的拉曼峰分别对应于D带、G带、2D带和(D + G)带,并证实了具有良好石墨化的MWCNTs的形成。

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