AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Invisible vapor catalysis in graphene growth by chemical vapor deposition

Xiucai Sun1,2, Xiaoting Liu1,3, Zhongti Sun4, Xintong Zhang2, Yuzhu Wu1,2, Yeshu Zhu1,3, Yuqing Song2, Kaicheng Jia2, Jincan Zhang2,5, Luzhao Sun2, Wan-Jian Yin2,6( ), Zhongfan Liu1,2( )
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
Beijing Graphene Institute (BGI), Beijing 100095, China
Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China
School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, China
Department of Engineering, University of Cambridge, Cambridge CB3 0FA, UK
College of Energy, Soochow Institute for Energy and Materials InnovationS (SIEMIS), Jiangsu Provincial Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies, Soochow University, Suzhou 215006, China
Show Author Information

Graphical Abstract

Cu vapor dominated by substrate evaporation exhibits excellent catalytic activity than the Cu(111) surface owing to the quantum confinement effect and abundant catalytic surface. Cu clusters in vapor phase can significantly promote the adsorption and dehydrogenation of CH4 molecules and also accelerate the decomposition of larger hydrocarbon species (e.g., C4H10) aggregated from insufficiently dehydrogenated CH3 groups in the gas phase, thus providing sufficient supply of active C atoms for the rapid graphene growth and improving the surface cleanliness of synthesized graphene.

Abstract

Vapor catalysis was recently found to play a crucial role in superclean graphene growth via chemical vapor decomposition (CVD). However, knowledge of vapor-phase catalysis is scarce, and several fundamental issues, including vapor compositions and their impact on graphene growth, are ambiguous. Here, by combining density functional theory (DFT) calculations, an ideal gas model, and a designed experiment, we found that the vapor was mainly composed of Cui clusters with tens of atoms. The vapor pressure was estimated to be ~ 10−12–10−11 bar under normal low-pressure CVD system (LPCVD) conditions for graphene growth, and the exposed surface area of Cui clusters in the vapor was 22–269 times that of the Cu substrate surface, highlighting the importance of vapor catalysis. DFT calculations show Cu clusters, represented by Cu17, have strong capabilities for adsorption, dehydrogenation, and decomposition of hydrocarbons. They exhibit an adsorption lifetime and reaction flux six orders of magnitude higher than those on the Cu surface, thus providing a sufficient supply of active C atoms for rapid graphene growth and improving the surface cleanliness of the synthesized graphene. Further experimental validation showed that increasing the amount of Cu vapor improved the as-synthesized graphene growth rate and surface cleanliness. This study provides a comprehensive understanding of vapor catalysis and the fundamental basis of vapor control for superclean graphene rapid growth.

Keywords

vapor catalysisgraphene growthchemical vapor depositionfirst-principles calculation

Electronic Supplementary Material

Download File(s)
12274_2023_6260_MOESM1_ESM.pdf (3 MB)

References

[1]

Bae, S.; Kim, H.; Lee, Y.; Xu, X. F.; Park, J. S.; Zheng, Y.; Balakrishnan, J.; Lei, T.; Ri Kim, H.; Song, Y. I. et al. Roll-to-roll production of 30-inch graphene films for transparent electrodes. Nat. Nanotechnol. 2010, 5, 574–578.
Crossref Google Scholar
[2]

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
[3]

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
[4]

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
[5]

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
[6]

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 Prim. 2021, 1, 5.
Crossref Google Scholar
[7]

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
[8]

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
[9]

Gao, J. F.; Yip, J.; Zhao, J. J.; Yakobson, B. I.; Ding, F. Graphene nucleation on transition metal surface: Structure transformation and role of the metal step edge. J. Am. Chem. Soc. 2011, 133, 5009–5015.
Crossref Google Scholar
[10]

Artyukhov, V. I.; Hao, Y. F.; Ruoff, R. S.; Yakobson, B. I. Breaking of symmetry in graphene growth on metal substrates. Phys. Rev. Lett. 2015, 114, 115502.
Crossref Google Scholar
[11]

Chen, Z. L.; Qi, Y.; Chen, X. D.; Zhang, Y. F.; Liu, Z. F. Direct CVD growth of graphene on traditional glass: Methods and mechanisms. Adv. Mater. 2019, 31, 1803639.
Crossref Google Scholar
[12]

Rümmeli, M. H.; Gorantla, S.; Bachmatiuk, A.; Phieler, J.; Geißler, N.; Ibrahim, I.; Pang, J. B.; Eckert, J. On the role of vapor trapping for chemical vapor deposition (CVD) grown graphene over copper. Chem. Mater. 2013, 25, 4861–4866.
Crossref Google Scholar
[13]

Teng, P. Y.; Lu, C. C.; Akiyama-Hasegawa, K.; Lin, Y. C.; Yeh, C. H.; Suenaga, K.; Chiu, P. W. Remote catalyzation for direct formation of graphene layers on oxides. Nano Lett. 2012, 12, 1379–1384.
Crossref Google Scholar
[14]

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
[15]

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
[16]

Li, X. S.; Cai, W. W.; Colombo, L.; Ruoff, R. S. Evolution of graphene growth on Ni and Cu by carbon isotope labeling. Nano Lett. 2009, 9, 4268–4272.
Crossref Google Scholar
[17]

Li, Q. C.; Zhao, Z. F.; Yan, B. M.; Song, X. J.; Zhang, Z. P.; Li, J.; Wu, X. S.; Bian, Z. Q.; Zou, X. L.; Zhang, Y. F. et al. Nickelocene-precursor-facilitated fast growth of graphene/h-BN vertical heterostructures and its applications in OLEDs. Adv. Mater. 2017, 29, 1701325.
Crossref Google Scholar
[18]

Shan, J. Y.; Fang, S. M.; Wang, W. D.; Zhao, W.; Zhang, R.; Liu, B. Z.; Lin, L.; Jiang, B.; Ci, H. N.; Liu, R. J. et al. Copper acetate-facilitated transfer-free growth of high-quality graphene for hydrovoltaic generators. Natl. Sci. Rev. 2021, 9, nwab169.
Crossref Google Scholar
[19]

Kim, H.; Song, I.; Park, C.; Son, M.; Hong, M. S.; Kim, Y.; Kim, J. S.; Shin, H. J.; Baik, J.; Choi, H. C. Copper-vapor-assisted chemical vapor deposition for high-quality and metal-free single-layer graphene on amorphous SiO2 substrate. ACS Nano 2013, 7, 6575–6582.
Crossref Google Scholar
[20]

Sun, J. Y.; Chen, Z. L.; Yuan, L.; Chen, Y. B.; Ning, J.; Liu, S. W.; Ma, D. L.; Song, X. J.; Priydarshi, M. K.; Bachmatiuk, A. et al. Direct chemical-vapor-deposition-fabricated, large-scale graphene glass with high carrier mobility and uniformity for touch panel applications. ACS Nano 2016, 10, 11136–11144.
Crossref Google Scholar
[21]

Xu, Z. W.; Zhao, G. H.; Qiu, L.; Zhang, X. Y.; Qiao, G. J.; Ding, F. Molecular dynamics simulation of graphene sinking during chemical vapor deposition growth on semi-molten Cu substrate. npj Computat. Mater. 2020, 6, 14.
Crossref Google Scholar
[22]

Yamada, I.; Usui, H.; Takagi, T. Formation mechanism of large clusters from vaporized solid material. J. Phys. Chem. 1987, 91, 2463–2468.
Crossref Google Scholar
[23]

Itoh, M.; Kumar, V.; Adschiri, T.; Kawazoe, Y. Comprehensive study of sodium, copper, and silver clusters over a wide range of sizes 2 ≤ N ≤ 75. J. Chem. Phys. 2009, 131, 174510.
Crossref Google Scholar
[24]

Lecoultre, S.; Rydlo, A.; Félix, C.; Buttet, J.; Gilb, S.; Harbich, W. Optical absorption of small copper clusters in neon: Cu n , ( n = 1–9). J. Chem. Phys. 2011, 134, 074303.
Crossref Google Scholar
[25]

Hammer, B.; Norskov, J. K. Why gold is the noblest of all the metals. Nature 1995, 376, 238–240.
Crossref Google Scholar
[26]

Hammer, B.; Nørskov, J. K. Electronic factors determining the reactivity of metal surfaces. Surf. Sci. 1995, 343, 211–220.
Crossref Google Scholar
[27]

Hao, Y. F.; Wang, L.; Liu, Y. Y.; Chen, H.; Wang, X. H.; Tan, C.; Nie, S.; Suk, J. W.; Jiang, T. F.; Liang, T. F. et al. Oxygen-activated growth and bandgap tunability of large single-crystal bilayer graphene. Nat. Nanotechnol. 2016, 11, 426–431.
Crossref Google Scholar
[28]

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
[29]

Popov, I.; Bügel, P.; Kozlowska, M.; Fink, K.; Studt, F.; Sharapa, D. I. Analytical model of CVD growth of graphene on Cu(111) surface. Nanomaterials (Basel) 2022, 12, 2963.
Crossref Google Scholar
[30]

Niu, T. C.; Zhou, M.; Zhang, J. L.; Feng, Y. P.; Chen, W. Growth Intermediates for CVD Graphene on Cu(111): Carbon clusters and defective graphene. J. Am. Chem. Soc. 2013, 135, 8409–8414.
Crossref Google Scholar
[31]

Cheng, T.; Liu, Z. R.; Liu, Z. F.; Ding, F. The mechanism of graphene vapor-solid growth on insulating substrates. ACS Nano 2021, 15, 7399–7408.
Crossref Google Scholar
[32]

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
[33]

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
[34]

Wang, M. H.; Luo, D.; Wang, B.; Ruoff, R. S. Synthesis of large-area single-crystal graphene. Trends Chem. 2021, 3, 15–33.
Crossref Google Scholar
[35]

Jia, K. C.; Ci, H. N.; Zhang, J. C.; Sun, Z. T.; Ma, Z. T.; Zhu, Y. S.; Liu, S. N.; Liu, J. L.; Sun, L. Z.; Liu, X. T. et al. Superclean growth of graphene using a cold-wall chemical vapor deposition approach. Angew. Chem., Int. Ed. 2020, 59, 17214–17218.
Crossref Google Scholar
[36]

Sun, L. Z.; Lin, L.; Wang, Z. H.; Rui, D. R.; Yu, Z. W.; Zhang, J. C.; Li, Y. L. Z.; Liu, X. T.; Jia, K. C.; Wang, K. X. et al. A force-engineered lint roller for superclean graphene. Adv. Mater. 2019, 31, 1902978.
Crossref Google Scholar
[37]

Vlassiouk, I.; Regmi, M.; Fulvio, P.; Dai, S.; Datskos, P.; Eres, G.; Smirnov, S. Role of hydrogen in chemical vapor deposition growth of large single-crystal graphene. ACS Nano 2011, 5, 6069–6076.
Crossref Google Scholar
[38]

Gelb, A.; Cardillo, M. Classical trajectory studies of hydrogen dissociation on a Cu(100) surface. Surf. Sci. 1976, 59, 128–140.
Crossref Google Scholar
[39]

Gelb, A.; Cardillo, M. J. Classical trajectory study of the dissociation of hydrogen on copper single crystals: II Cu(100) and Cu(110). Surf. Sci., 64, 197–208
Crossref Google Scholar
[40]

Vlassiouk, I.; Smirnov, S.; Surwade, S. P.; Regmi, M.; Srivastava, N.; Feenstra, R.; Eres, G.; Parish, C.; Lavrik, N.; Datskos, P.et al. Graphene nucleation density on copper: Fundamental role of background pressure. J. Phys. Chem. C 2013, 117, 18919.
Crossref Google Scholar
[41]

Vlassiouk, I.; Smirnov, S.; Ivanov, I.; Fulvio, P. F.; Dai, S.; Meyer, H.; Chi, M. F.; Hensley, D.; Datskos, P.; Lavrik, N. V. Electrical and thermal conductivity of low temperature CVD graphene: The effect of disorder. Nanotechnology 2011, 22, 275716.
Crossref Google Scholar
[42]

Qi, M.; Ren, Z. Y.; Jiao, Y.; Zhou, Y. X.; Xu, X. L.; Li, W. L.; Li, J. Y.; Zheng, X. L.; Bai, J. T. Hydrogen kinetics on scalable graphene growth by atmospheric pressure chemical vapor deposition with acetylene. J. Phys. Chem. C 2013, 117, 14348–14353.
Crossref Google Scholar
[43]

Lin, Y. C.; Lu, C. C.; Yeh, C. H.; Jin, C. H.; Suenaga, K.; Chiu, P. W. Graphene annealing: How clean can it be. Nano Lett. 2012, 12, 414–419.
Crossref Google Scholar
[44]

Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953–17979.
Crossref Google Scholar
[45]

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.
Crossref Google Scholar
[46]

Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758–1775.
Crossref Google Scholar
[47]

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
Crossref Google Scholar
[48]

Grimme, S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem. 2006, 27, 1787–1799.
Crossref Google Scholar
[49]

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
[50]

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
[51]

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
[52]

Zhang, J. C.; Lin, L.; Sun, L. Z.; Huang, Y. C.; Koh, A. L.; Dang, W. H.; Yin, J. B.; Wang, M. Z.; Tan, C. W.; Li, T. R. et al. Clean transfer of large graphene single crystals for high-intactness suspended membranes and liquid cells. Adv. Mater. 2017, 29, 1700639.
Crossref Google Scholar
Nano Research
Volume 17 Issue 5,
May 2024
Pages 4259-4269
DOI: 10.1007/s12274-023-6260-3
Cite this article:
Sun X, Liu X, Sun Z, et al. Invisible vapor catalysis in graphene growth by chemical vapor deposition. Nano Research, 2024, 17(5): 4259-4269. https://doi.org/10.1007/s12274-023-6260-3
Topics:
Chemical vapor deposition

796

Views

1

Crossref

3

Web of Science

2

Scopus

0

CSCD

Altmetrics
Received: 22 August 2023
Revised: 10 October 2023
Accepted: 11 October 2023
Published: 01 December 2023
© Tsinghua University Press 2023
Return