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Research Article | Online First

Kinetics of hydrogen constrained graphene growth on Cu substrate

Xiucai Sun1,§( ), Shuang Lou1,2,§, Weizhi Wang1,3, Xuqin Liu1,2, Xiaoli Sun1, Yuqing Song1, Weimin Yang2, Zhongfan Liu1,4( )
Beijing Graphene Institute (BGI), Beijing 100095, China
College of Mechanical and Electrical Engineering, Beijing University of Chemical Technology, Beijing 100029, China
School of Instrument and Electronics, North University of China, Taiyuan 030051, China
Center for Nanochemistry, Beijing Science and Engineering Center for Nanocarbons, Beijing National Laboratory for Molecular Science, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

§ Xiucai Sun and Shuang Lou contributed equally to this work.

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Abstract

Chemical vapor deposition (CVD) has shown great promise for the large-scale production of high-quality graphene films for industrial applications. Atomic-scale theoretical studies can help experiments to deeply understand the graphene growth mechanism, and serve as theoretical guides for further experimental designs. Here, by using density functional theory calculations, ab-initio molecular dynamics simulations, and microkinetic analysis, we systematically investigated the kinetics of hydrogen constrained graphene growth on Cu substrate. The results reveal that the actual hydrogen-rich environment of CVD results in CH as the dominating carbon species and graphene H-terminated edges. CH participated island sp2 nucleation avoids chain cyclization process, thereby improving the nucleation and preventing the formation of non-hexameric ring defects. The graphene growth is not simply C-atomic activity, rather, involves three main processes: CH species attachment at the growth edge, leading to a localized sp3 hybridized carbon at the connecting site; excess H transfer from the sp3 carbon to the newly attached CH; and finally dehydrogenation to achieve the sp2 reconstruction of the newly grown edge. The threshold reaction barriers for the growth of graphene zigzag (ZZ) and armchair (AC) edges were calculated as 2.46 and 2.16 eV, respectively, thus the AC edge grows faster than the ZZ one. Our theory successfully explained why the circumference of a graphene island grown on Cu substrates is generally dominated by ZZ edges, which is a commonly observed phenomenon in experiments. In addition, the growth rate of graphene on Cu substrates is calculated and matches well with existing experimental observations.

Keywords

chemical vapor depositiontheoretical calculationgraphene growthCu substratehydrogen constraint effect

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References

[1]

Novoselov, K. S.; Fal′ko, V. I.; Colombo, L.; Gellert, P. R.; Schwab, M. G.; Kim, K. A roadmap for graphene. Nature 2012, 490, 192–200.
Crossref Google Scholar
[2]

Li, X. S.; Cai, W. W.; An, J.; Kim, S.; Nah, J.; Yang, D. X.; Piner, R.; Velamakanni, A.; Jung, I.; Tutuc, E. et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 2009, 324, 1312–1314.
Crossref Google Scholar
[3]

Jia, K. C.; Zhang, J. C.; Lin, L.; Li, Z. Z.; Gao, J.; Sun, L. Z.; Xue, R. W.; Li, J. Y.; Kang, N.; Luo, Z. T. et al. Copper-containing carbon feedstock for growing superclean graphene. J. Am. Chem. Soc. 2019, 141, 7670–7674.
Crossref Google Scholar
[4]

Lin, L.; Zhang, J. C.; Su, H. S.; Li, J. Y.; Sun, L. Z.; Wang, Z. H.; Xu, F.; Liu, C.; Lopatin, S.; Zhu, Y. H. et al. Towards super-clean graphene. Nat. Commun. 2019, 10, 1912.
Crossref Google Scholar
[5]

Xu, X. Z.; Zhang, Z. H.; Dong, J. C.; Yi, D.; Niu, J. J.; Wu, M. H.; Lin, L.; Yin, R. K.; Li, M. Q.; Zhou, J. Y. et al. Ultrafast epitaxial growth of metre-sized single-crystal graphene on industrial cu foil. Sci. Bull. 2017, 62, 1074–1080.
Crossref Google Scholar
[6]

Zhang, J. C.; Sun, L. Z.; Jia, K. C.; Liu, X. T.; Cheng, T.; Peng, H. L.; Lin, L.; Liu, Z. F. New growth frontier: Superclean graphene. ACS Nano 2020, 14, 10796–10803.
Crossref Google Scholar
[7]

Li, X. S.; Colombo, L.; Ruoff, R. S. Synthesis of graphene films on copper foils by chemical vapor deposition. Adv. Mater. 2016, 28, 6247–6252.
Crossref Google Scholar
[8]

Zhang, L. N.; Dong, J. C.; Ding, F. Strategies, status, and challenges in wafer scale single crystalline two-dimensional materials synthesis. Chem. Rev. 2021, 121, 6321–6372.
Crossref Google Scholar
[9]

Wang, X. L.; Yuan, Q. H.; Li, J.; Ding, F. The transition metal surface dependent methane decomposition in graphene chemical vapor deposition growth. Nanoscale 2017, 9, 11584–11589.
Crossref Google Scholar
[10]

Lin, L.; Deng, B.; Sun, J. Y.; Peng, H. L.; Liu, Z. F. Bridging the gap between reality and ideal in chemical vapor deposition growth of graphene. Chem. Rev. 2018, 118, 9281–9343.
Crossref Google Scholar
[11]

Zhang, J. C.; Lin, L.; Jia, K. C.; Sun, L. Z.; Peng, H. L.; Liu, Z. F. Controlled growth of single-crystal graphene films. Adv. Mater. 2020, 32, 1903266.
Crossref Google Scholar
[12]

Qiu, Z. Y.; Li, P.; Li, Z. Y.; Yang, J. L. Atomistic simulations of graphene growth: From kinetics to mechanism. Acc. Chem. Res. 2018, 51, 728–735.
Crossref Google Scholar
[13]

Shu, H. B.; Tao, X. M.; Ding, F. What are the active carbon species during graphene chemical vapor deposition growth. Nanoscale 2015, 7, 1627–1634.
Crossref Google Scholar
[14]

Sun, X. C.; Luo, X. Y.; Su, Z.; Yu, F. P.; Li, Y. L.; Cheng, X. F.; Zhao, X. Effect of BN seeds on locating and promoting the initial nucleation of graphene on cu substrate and its mechanism: A theoretical study. Appl. Surf. Sci. 2020, 523, 146469.
Crossref Google Scholar
[15]

Zhang, Y. H.; Zhang, H. R.; Li, F.; Shu, H. B.; Chen, Z. Y.; Sui, Y. P.; Zhang, Y. Q.; Ge, X. M.; Yu, G. H.; Jin, Z. et al. Invisible growth of microstructural defects in graphene chemical vapor deposition on copper foil. Carbon 2016, 96, 237–242.
Crossref Google Scholar
[16]

Li, P.; Li, Z. Y. Theoretical insights into the thermodynamics and kinetics of graphene growth on copper surfaces. J. Phys. Chem. C 2020, 124, 16233–16247.
Crossref Google Scholar
[17]

Dong, J. C.; Zhang, L. N.; Ding, F. Kinetics of graphene and 2D materials growth. Adv. Mater. 2019, 31, 1801583.
Crossref Google Scholar
[18]

Shu, H. B.; Chen, X. S.; Ding, F. The edge termination controlled kinetics in graphene chemical vapor deposition growth. Chem. Sci. 2014, 5, 4639–4645.
Crossref Google Scholar
[19]

Sun, X. C.; Su, Z.; Zhang, J.; Liu, X. Z.; Li, Y. L.; Yu, F. P.; Cheng, X. F.; Zhao, X. Graphene nucleation preference at CuO defects rather than Cu2O on Cu(111): A combination of DFT calculation and experiment. ACS Appl. Mater. Interfaces 2018, 10, 43156–43165.
Crossref Google Scholar
[20]

Zhang, X. Y.; Wang, L.; Xin, J.; Yakobson, B. I.; Ding, F. Role of hydrogen in graphene chemical vapor deposition growth on a copper surface. J. Am. Chem. Soc. 2014, 136, 3040–3047.
Crossref Google Scholar
[21]

Luo, D.; Wang, X.; Li, B. W.; Zhu, C. Y.; Huang, M.; Qiu, L.; Wang, M. H.; Jin, S.; Kim, M.; Ding, F. et al. The wet-oxidation of a Cu(111) foil coated by single crystal graphene. Adv. Mater. 2021, 33, 2102697.
Crossref Google Scholar
[22]

Murdock, A. T.; Koos, A.; Britton, T. B.; Houben, L.; Batten, T.; Zhang, T.; Wilkinson, A. J.; Dunin-Borkowski, R. E.; Lekka, C. E.; Grobert, N. Controlling the orientation, edge geometry, and thickness of chemical vapor deposition graphene. ACS Nano 2013, 7, 1351–1359.
Crossref Google Scholar
[23]

Sun, L. Z.; Chen, B. H.; Wang, W. D.; Li, Y. L. Z.; Zeng, X. Z.; Liu, H. Y.; Liang, Y.; Zhao, Z. Y.; Cai, A. L.; Zhang, R. et al. Toward epitaxial growth of misorientation-free graphene on Cu(111) foils. ACS Nano 2022, 16, 285–294.
Crossref Google Scholar
[24]

Li, B. W.; Luo, D.; Zhu, L. Y.; Zhang, X.; Jin, S.; Huang, M.; Ding, F.; Ruoff, R. S. Orientation-dependent strain relaxation and chemical functionalization of graphene on a Cu(111) foil. Adv. Mater. 2018, 30, 1706504.
Crossref Google Scholar
[25]

Wu, P.; Zhang, Y.; Cui, P.; Li, Z. Y.; Yang, J. L.; Zhang, Z. Y. Carbon dimers as the dominant feeding species in epitaxial growth and morphological phase transition of graphene on different Cu substrates. Phys. Rev. Lett. 2015, 114, 216102.
Crossref Google Scholar
[26]

Sun, L. Z.; Yuan, G. W.; Gao, L. B.; Yang, J.; Chhowalla, M.; Gharahcheshmeh, M. H.; Gleason, K. K.; Choi, Y. S.; Hong, B. H.; Liu, Z. F. Chemical vapour deposition. Nat. Rev. Methods Primers 2021, 1, 5.
Crossref Google Scholar
[27]

Li, Z. C.; Zhang, W. H.; Fan, X. D.; Wu, P.; Zeng, C. G.; Li, Z. Y.; Zhai, X. F.; Yang, J. L.; Hou, J. G. Graphene thickness control via gas-phase dynamics in chemical vapor deposition. J. Phys. Chem. C 2012, 116, 10557–10562.
Crossref Google Scholar
[28]

Li, G.; Huang, S. H.; Li, Z. Y. Gas-phase dynamics in graphene growth by chemical vapour deposition. Phys. Chem. Chem. Phys. 2015, 17, 22832–22836.
Crossref Google Scholar
[29]

Zhang, W. H.; Wu, P.; Li, Z. Y.; Yang, J. L. First-principles thermodynamics of graphene growth on Cu surfaces. J. Phys. Chem. C 2011, 115, 17782–17787.
Crossref Google Scholar
[30]

Zeng, X. Z.; Qiu, Z. Y.; Li, P.; Li, Z. Y.; Yang, J. L. Steric hindrance effect in high-temperature reactions. CCS Chem. 2020, 2, 460–467.
Crossref Google Scholar
[31]

Zhang, X.; Liu, J. X.; Zijlstra, B.; Filot, I. A. W.; Zhou, Z. Y.; Sun, S. G.; Hensen, E. J. M. Optimum Cu nanoparticle catalysts for CO2 hydrogenation towards methanol. Nano Energy 2018, 43, 200–209.
Crossref Google Scholar
[32]

Zhang, H. R.; Zhang, Y. H.; Zhang, Y. Q.; Chen, Z. Y.; Sui, Y. P.; Ge, X. M.; Yu, G. H.; Jin, Z.; Liu, X. Y. Edge morphology evolution of graphene domains during chemical vapor deposition cooling revealed through hydrogen etching. Nanoscale 2016, 8, 4145–4150.
Crossref Google Scholar
[33]

Van de Walle, C. G.; Neugebauer, J. First-principles surface phase diagram for hydrogen on GaN surfaces. Phys. Rev. Lett. 2002, 88, 066103.
Crossref Google Scholar
[34]

Xu, S.; Wu, L. L.; Fan, Y. F.; Liu, Y. F.; Zeng, X. Z.; Li, Z. Y. Hydrocarbon species on the Cu(111) surface studied with a neural network potential. J. Phys. Chem. C 2024, 128, 5697–5707.
Crossref Google Scholar
[35]

Li, P.; Li, Z. Y.; Yang, J. L. Dominant kinetic pathways of graphene growth in chemical vapor deposition: The role of hydrogen. J. Phys. Chem. C 2017, 121, 25949–25955.
Crossref Google Scholar
[36]

Shu, H. B.; Chen, X. S.; Tao, X. M.; Ding, F. Edge structural stability and kinetics of graphene chemical vapor deposition growth. ACS Nano 2012, 6, 3243–3250.
Crossref Google Scholar
[37]

Yu, Q. K.; Jauregui, L. A.; Wu, W.; Colby, R.; Tian, J. F.; Su, Z. H.; Cao, H. L.; Liu, Z. H.; Pandey, D.; Wei, D. G. et al. Control and characterization of individual grains and grain boundaries in graphene grown by chemical vapour deposition. Nat. Mater. 2011, 10, 443–449.
Crossref Google Scholar
[38]

Tian, J. F.; Cao, H. L.; Wu, W.; Yu, Q. K.; Chen, Y. P. Direct imaging of graphene edges: Atomic structure and electronic scattering. Nano Lett. 2011, 11, 3663–3668.
Crossref Google Scholar
[39]

Ma, T.; Ren, W. C.; Zhang, X. Y.; Liu, Z. B.; Gao, Y.; Yin, L. C.; Ma, X. L.; Ding, F.; Cheng, H. M. Edge-controlled growth and kinetics of single-crystal graphene domains by chemical vapor deposition. Proc. Natl. Acad. Sci. USA 2013, 110, 20386–20391.
Crossref Google Scholar
[40]

Chen, H.; Sun, X. C.; Song, X. F.; Chen, B. H.; Ma, Z. T.; Yin, W. J.; Sun, L. Z.; Liu, Z. F. Fast scanning growth of high-quality graphene films on Cu foils fueled by dimeric carbon precursor. Nano Res. 2023, 16, 12246–12252.
Crossref Google Scholar
[41]

Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953–17979.
Crossref Google Scholar
[42]

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
Crossref Google Scholar
[43]

Kresse, G.; Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 1993, 47, 558–561.
Crossref Google Scholar
[44]

Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169–11186.
Crossref Google Scholar
[45]

Grimme, S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem. 2006, 27, 1787–1799.
Crossref Google Scholar
[46]

Henkelman, G.; Uberuaga, B. P.; Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 2000, 113, 9901–9904.
Crossref Google Scholar
[47]

Mills, G.; Jónsson, H.; Schenter, G. K. Reversible work transition state theory: Application to dissociative adsorption of hydrogen. Surf. Sci. 1995, 324, 305–337.
Crossref Google Scholar
[48]

Kühne, T. D.; Iannuzzi, M.; Del Ben, M.; Rybkin, V. V.; Seewald, P.; Stein, F.; Laino, T.; Khaliullin, R. Z.; Schütt, O.; Schiffmann, F. et al. CP2K: An electronic structure and molecular dynamics software package-quickstep: Efficient and accurate electronic structure calculations. J. Chem. Phys. 2020, 152, 194103.
Crossref Google Scholar
[49]

Filot, I. A. W.; van Santen, R. A.; Hensen, E. J. M. The optimally performing Fischer-tropsch catalyst. Angew. Chem., Int. Ed. 2014, 53, 12746–12750.
Crossref Google Scholar
[50]

Li, J. Y.; Yao, Z. H.; Zhao, J. Y.; Deng, S. W.; Wang, S. B.; Wang, J. G. Microkinetic simulations of acetylene(acetylene-d2) hydrogenation(deuteration) on Ag nanoparticles. Mol. Catal. 2023, 535, 112845.
Crossref Google Scholar
Nano Research
DOI: 10.1007/s12274-024-6945-2
Cite this article:
Sun X, Lou S, Wang W, et al. Kinetics of hydrogen constrained graphene growth on Cu substrate. Nano Research, 2024, https://doi.org/10.1007/s12274-024-6945-2
Topics:
Graphene

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Received: 11 June 2024
Revised: 02 August 2024
Accepted: 05 August 2024
Published: 03 September 2024
© Tsinghua University Press 2024
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