种子法生长碳纳米管的反应分子动力学

doi:10.12066/j.issn.1007-2861.2685

摘要/Abstract

摘要： 未来碳基电子器件的构筑材料需要特定直径及能带带隙的单壁碳纳米管(single-walledcarbon nanotubes,SWCNTs),但目前在实验上实现特定直径和手性的碳纳米管选择性制备仍面临巨大挑战.利用碳纳米管作为种子模板可以生长特定直径和手性的SWCNTs,但对其微观生长机制还缺乏清晰理解.首次基于自主开发的新一代ReaxFF全碳反应力场,采用分子动力学模拟系统研究了种子法选择性生长SWCNTs的微观过程.通过设计不同直径、手性指数及边缘结构的开口短碳纳米管作为种子,系统揭示了SWCNTs上下边缘结构演化和生长机制及其微观调控规律.此外,还探讨了氢在SWCNTs生长过程中的作用,发现氢在SWCNTs形成的关键步骤中发挥重要影响,为理解氢对SWCNTs选择性生长的作用机制提供了新的视角.不仅阐明了种子法生长SWCNTs的微观机制,还为实现特定直径和手性的可控实验制备提供了理论依据,对碳基电子器件材料的设计与应用具有一定参考价值.

关键词: 单壁碳纳米管, 种子法生长, 分子动力学模拟, ReaxFF反应力场, 选择性生长

Abstract: The construction of future carbon-based electronic devices requires single-walled carbon nanotubes (SWCNTs) with specific diameters and electronic bandgaps. However, the selective synthesis of carbon nanotubes with controlled diameters and chirality remains a significant experimental challenge. Using carbon nanotubes as seed templates can promote the growth of SWCNTs with specific diameters and chirality, yet the microscopic growth mechanisms remain poorly understood. This study systematically investigated the microscopic processes of seed-based growth of SWCNTs through molecular dynamics simulations based on a newly developed next-generation all-carbon ReaxFF reactive force field. By designing open-ended short carbon nanotubes with varying diameters, chiral indices, and edge configurations, the study revealed the structural evolution and growth mechanisms at both ends of SWCNTs, along with their microscopic regulation principles. Moreover, the role of hydrogen during the growth process was explored, demonstrating its critical influence in key steps of SWCNT formation. These findings provide new insights into the role of hydrogen in the selective growth of SWCNTs. This work not only elucidates the mechanism of seed-based growth of SWCNTs but also offers theoretical guidance for the controlled experimental synthesis of SWCNTs with specific diameters and chirality, contributing to the design and application of carbon-based electronic device materials.

Key words: single-walled carbon nanotube, seed-based growth, molecular dynamics simulation, ReaxFF reactive force field, selective growth

中图分类号:

O469

习思思, 刘馥, 董自强, 孙强, 邓振炎, 赵新洛, 刘轶. 种子法生长碳纳米管的反应分子动力学[J]. 上海大学学报(自然科学版), 2025, 31(4): 571-590.

XI Sisi, LIU Fu, DONG Ziqiang, SUN Qiang, DENG Zhenyan, ZHAO Xinluo, LIU Yi. Reactive molecular dynamics of seed-based growth of carbon nanotubes[J]. Journal of Shanghai University（Natural Science Edition）, 2025, 31(4): 571-590.

参考文献

[1] Bachtold A, Hadley P, Nakanishi T, et al. Logic circuits with carbon nanotube transistors [J]. Science, 2001, 294(5545): 1317-1320.
[2] Choi W B, Chung D S, Kang J H, et al. Fully sealed, high-brightness carbon-nanotube field-emission display [J]. Applied Physics Letters, 1999, 75(20): 3129-3131.
[3] Martel R, Schmidt T, Shea H R, et al. Single- and multi-wall carbon nanotube field-effect transistors [J]. Applied Physics Letters, 1998, 73(17): 2447-2449.
[4] Tans S, Verschueren A, Dekker C. Room-temperature transistor based on a single carbon nanotube [J]. Nature, 1998, 393: 49-52.
[5] Takakura A, Beppu K, Nishihara T, et al. Strength of carbon nanotubes depends on their chemical structures [J]. Nature Communications, 2019, 10(1): 3040.
[6] Yang F, Wang X, Zhang D, et al. Chirality-specific growth of single-walled carbon nanotubes on solid alloy catalysts [J]. Nature, 2014, 510(7506): 522-524.
[7] Yang F, Wang M, Zhang D, et al. Chirality pure carbon nanotubes: growth, sorting, and characterization [J]. Chemical Reviews, 2020, 120(5): 2693-2758.
[8] Javey A, Guo J, Wang Q, et al. Ballistic carbon nanotube field-effect transistors [J]. Nature, 2003, 424(6949): 654-657.
[9] Jiang S, Hou P X, Chen M L, et al. Ultrahigh-performance transparent conductive films of carbon-welded isolated single-wall carbon nanotubes [J]. Science Advances, 2018, 4(5): eaap9264.
[10] Avouris P, Chen Z, Perebeinos V. Carbon-based electronics [J]. Nature Nanotechnology, 2007, 2(10): 605-615.
[11] Saito R, Fujita M, Dresselhaus G, et al. Electronic-structure of chiral graphene tubules [J]. Applied Physics Letters, 1992, 60: 2204-2206.
[12] Tahvili M S, Jahanmiri S, Sheikhi M H. High-frequency transmission through metallic single-walled carbon nanotube interconnects [J]. International Journal of Numerical Modelling: Electronic Networks, Devices and Fields, 2009, 22(5): 369-378.
[13] He M, Dong J, Zhang K, et al. Precise determination of the threshold diameter for a single-walled carbon nanotube to collapse [J]. ACS Nano, 2014, 8(9): 9657-9663.
[14] Wang N, Tang Z K, Li G D, et al. Single-walled 4 A carbon nanotube arrays [J]. Nature, 2000, 408(6808): 50-51.
[15] Liang Y X, Wang T H. A double-walled carbon nanotube field-effect transistor using the inner shell as its gate [J]. Physica E: Low-dimensional Systems and Nanostructures, 2004, 23(1): 232-236.
[16] McLean B, Mitchell I, Ding F. Mechanism of alcohol chemical vapor deposition growth of carbon nanotubes: catalyst oxidation [J]. Carbon, 2022, 191: 1-9.
[17] Charlier J C. Defects in carbon nanotubes [J]. Accounts of Chemical Research, 2002, 35(12): 1063-1069.
[18] Sanchez-Valencia J R, Dienel T, Gröning O, et al. Controlled synthesis of single-chirality carbon nanotubes [J]. Nature, 2014, 512(7512): 61-64.
[19] Liu H P, Nishide D, Tanaka T, et al. Large-scale single-chirality separation of single-wall carbon nanotubes by simple gel chromatography [J]. Nature Communications, 2011, 2(1): 309.
[20] Zhang S, Kang L, Wang X, et al. Arrays of horizontal carbon nanotubes of controlled chirality grown using designed catalysts [J]. Nature, 2017, 543(7644): 234-238.
[21] Tu X, Manohar S, Jagota A, et al. DNA sequence motifs for structure-specific recognition and separation of carbon nanotubes [J]. Nature, 2009, 460(7252): 250-253.
[22] Arnold M S, Green A A, Hulvat J F, et al. Sorting carbon nanotubes by electronic structure using density differentiation [J]. Nature Nanotechnology, 2006, 1(1): 60-65.
[23] Ding L P, McLean B, Xu Z, et al. Why carbon nanotubes grow [J]. Journal of the American Chemical Society, 2022, 144(12): 5606-5613.
[24] Qiu L, Ding F. Is the carbon nanotube-catalyst interface clean during growth? [J]. Small, 2022, 18(47): 2204437.
[25] Yang F, Zhao H, Li R, et al. Growth modes of single-walled carbon nanotubes on catalysts [J]. Science Advances, 2022, 8(41): eabq0794.
[26] Akbarzadeh Z, Maavara T, Slowinski S, et al. Effects of damming on river nitrogen fluxes: a global analysis [J]. Global Biogeochemical Cycles, 2019, 33(11): 1339-1357.
[27] Li R, Antunes E F, Kalfon-Cohen E, et al. Low-temperature growth of carbon nanotubes catalyzed by sodium-based ingredients [J]. Angew Chem Int Ed Engl, 2019, 58(27): 9204-9209.
[28] Liu J, Wang C, Tu X, et al. Chirality-controlled synthesis of single-wall carbon nanotubes using vapour-phase epitaxy [J]. Nature Communications, 2012, 3(1): 1199.
[29] Pimonov V, Tran H N, Monniello L, et al. Dynamic instability of individual carbon nano -tube growth revealed by in situ homodyne polarization microscopy [J]. Nano Letters, 2021, 21(19): 8495-8502.
[30] Yoshikawa R, Hisama K, Ukai H, et al. Molecular dynamics of chirality definable growth of single-walled carbon nanotubes [J]. ACS Nano, 2019, 13(6): 6506-6512.
[31] Hourahine B, Aradi B, Blum V, et al. DFTB plus, a software package for efficient approximate density functional theory based atomistic simulations [J]. Journal of Chemical Physics, 2020, 152(12): 124101.
[32] Kharlamova M V. Investigation of growth dynamics of carbon nanotubes [J]. Beilstein Journal of Nanotechnology, 2017, 8: 826-856.
[33] Raty J Y, Gygi F, Galli G. Growth of carbon nanotubes on metal nanoparticles: a microscopic mechanism from ab initio molecular dynamics simulations [J]. Physical Review Letters, 2005, 95(9): 096103.
[34] Ding F, Bolton K, RosÉn A. Nucleation and growth of single-walled carbon nanotubes: a molecular dynamics study [J]. The Journal of Physical Chemistry, 2004, 108: 17369-17377.
[35] Penev E S, Artyukhov V I, Yakobson B I. Extensive energy landscape sampling of nanotube end-caps reveals no chiral-angle bias for their nucleation [J]. ACS Nano, 2014, 8(2): 1899-1906.
[36] Qiu L, Ding F. Understanding single-walled carbon nanotube growth for chirality controllable synthesis [J]. Accounts of Materials Research, 2021, 2(9): 828-841.
[37] Xu Z, Qiu L, Ding F. The kinetics of chirality assignment in catalytic single-walled carbon nanotube growth and the routes towards selective growth [J]. Chemical Science, 2018, 9(11): 3056-3061.
[38] Shibuta Y, Maruyama S. Molecular dynamics simulation of formation process of single-walled carbon nanotubes by CCVD method [J]. Chemical Physics Letters, 2003, 382(3): 381-386.
[39] Shibuta Y, Maruyama S. Molecular dynamics simulation of generation process of SWNTs [J]. Physica B: Condensed Matter, 2002, 323: 187-189.
[40] Ding F, Bolton K. The importance of supersaturated carbon concentration and its distribution in catalytic particles for single-walled carbon nanotube nucleation [J]. Nanotechnology, 2006, 17(2): 543-548.
[41] Ding F, RosÉn A, Bolton K. The role of the catalytic particle temperature gradient for SWNT growth from small particles [J]. Chemical Physics Letters, 2004, 393(4/5/6): 309-313.
[42] Ding F, Larsson P, Larsson J A, et al. The importance of strong carbon-metal adhesion for catalytic nucleation of single-walled carbon nanotubes [J]. Nano Letters, 2008, 8(2): 463-468.
[43] Wang X, Ding F. How a solid catalyst determines the chirality of the single-wall carbon nanotube grown on it [J]. Journal of Physical Chemistry Letters, 2019, 10(4): 735-741.
[44] Ding F, RosÉn A, Bolton K. Molecular dynamics study of the catalyst particle size dependence on carbon nanotube growth [J]. Journal of Chemical Physics, 2004, 121(6): 2775-2779.
[45] Charlier J C, Amara H, Lambin P. Catalytically assisted tip growth mechanism for single-wall carbon nanotubes [J]. ACS Nano, 2007, 1(3): 202-207.
[46] NosÉ S. A unified formulation of the constant temperature molecular dynamics methods [J]. The Journal of Chemical Physics, 1984, 81(1): 511-519.
[47] He M, Amara H, Jiang H, et al. Key roles of carbon solubility in single-walled carbon nanotube nucleation and growth [J]. Nanoscale, 2015, 7(47): 20284-20289.
[48] Amara H, Bichara C. Modeling the growth of single-wall carbon nanotubes [J]. Topics in Current Chemistry, 2017, 375(3): 55.
[49] Luo M, Penev E S, Harutyunyan A R, et al. Effect of cap-catalyst structural correlation on the nucleation of carbon nanotubes [J]. The Journal of Physical Chemistry C, 2017, 121(34): 18789-18794. [50刘馥. 全碳反应力场的开发与碳纳米线形成机理的研究[D]. 上海: 上海大学, 2023.
[51] Plimpton S. Fast parallel algorithms for short-range molecular dynamics [J]. Journal of Computational Physics, 1995, 117(1): 1-19.
[52] Thompson A P, Aktulga H M, Berger R, et al. LAMMPS: a flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scales [J]. Computer Physics Communications, 2022, 271: 108171.
[53] Aktulga H M, Fogarty J C, Pandit S A, et al. Parallel reactive molecular dynamics: numerical methods and algorithmic techniques [J]. Parallel Computing, 2012, 38(4): 245-259.
[54] Rappe A K, Goddard Ⅲ, W A. Charge equilibration for molecular dynamics simulations [J]. The Journal of Physical Chemistry, 1991, 95(8): 3358-3363.
[55] Shi L, Rohringer P, Suenaga K, et al. Confined linear carbon chains as a route to bulk carbyne [J]. Nature Materials, 2016, 15(6): 634-639.
[56] Liu F, Wang Q, Tang Y, et al. Carbon nanowires made by the insertion-and-fusion method toward carbon-hydrogen nanoelectronics [J]. Nanoscale, 2023, 15(13): 6143-6155.
[57] Chang W W, Liu F, Liu Y F, et al. Smallest carbon nanowires made easy: long linear carbon chains confined inside single-walled carbon nanotubes [J]. Carbon, 2021, 183: 571-577.
[58] Chen R, Liu F, Tang Y, et al. Combined first-principles and machine learning study of the initial growth of carbon nanomaterials on metal surfaces [J]. Applied Surface Science, 2022, 586: 152762.