Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Graphical Abstract
Abstract
Keywords
Electronic Supplementary Material
References
Show full outline
Hide outline
Research Article

In situ atomic-scale observation of monolayer graphene growth from SiC

Kaihao Yu1,§, Wen Zhao2,4,§, Xing Wu1,5,§, Jianing Zhuang4, Xiaohui Hu1,6, Qiubo Zhang1, Jun Sun1, Tao Xu1, Yang Chai9, Feng Ding2,3,4(), Litao Sun1,7,8()
SEU-FEI Nano-Pico CenterKey Laboratory of MEMS of Ministry of EducationSchool of Electronic Science and EngineeringSoutheast UniversityNanjing210096China
Center for Multidimensional Carbon MaterialsInstitute for Basic Science, Ulsan689-798Republic of Korea
School of Materials Science and EngineeringUlsan National Institute of Science and TechnologyUlsan689-798Republic of Korea
Institute of Textiles and ClothingHong Kong Polytechnic UniversityHong Kong999077China
Shanghai Key Laboratory of Multidimensional Information ProcessingDepartment of Electrical EngineeringEast China Normal UniversityShanghai200241China
College of Materials Science and EngineeringNanjing Tech UniversityNanjing210009China
Center for Advanced Carbon MaterialsSoutheast University and Jiangnan Graphene Research InstituteChangzhou213100China
Center for Advanced Materials and ManufactureJoint Research Institute of Southeast University and Monash UniversitySuzhou215123China
Department of Applied PhysicsThe Hong Kong Polytechnic UniversityHong Kong999077China

§ Kaihao Yu, Wen Zhao, and Xing Wu contributed equally to this work.

Show Author Information

Graphical Abstract

View original image Download original image

Abstract

Because of its high compatibility with conventional microfabrication processing technology, epitaxial graphene (EG) grown on SiC shows exceptional promise for graphene-based electronics. However, to date, a detailed understanding of the transformation from three-layer SiC to monolayer graphene is still lacking. Here, we demonstrate the direct atomic-scale observation of EG growth on a SiC (1100) surface at 1, 000 ℃ by in situ transmission electron microscopy in combination with ab initio molecular dynamics (AIMD) simulations. Our detailed analysis of the growth dynamics of monolayer graphene reveals that three SiC (1100) layers decompose successively to form one graphene layer. Sublimation of the first layer causes the formation of carbon clusters containing short chains and hexagonal rings, which can be considered as the nuclei for graphene growth. Decomposition of the second layer results in the appearance of new chains connecting to the as-formed clusters and the formation of a network with large pores. Finally, the carbon atoms released from the third layer lead to the disappearance of the chains and large pores in the network, resulting in a whole graphene layer. Our study presents a clear picture of the epitaxial growth of the monolayer graphene from SiC and provides valuable information forfuture developments in SiC-derived EG technology.

Keywords

grapheneepitaxial growthin situtransmission electron microscopy

Electronic Supplementary Material

Download File(s)
12274_2017_1911_MOESM1_ESM.pdf (3.4 MB)
12274_2017_1911_MOESM3_ESM.mpg (10 MB)
12274_2017_1911_MOESM4_ESM.mpg (12.7 MB)
12274_2017_1911_MOESM5_ESM.mpg (20 MB)
12274_2017_1911_MOESM6_ESM.mpg (23.2 MB)
12274_2017_1911_MOESM8_ESM.mpg (15.6 MB)

References

1

Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Electric field effect in atomically thin carbon films. Science 2004, 306, 666-669.

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

Raccichini, R.; Varzi, A.; Passerini, S.; Scrosati, B. The role of graphene for electrochemical energy storage. Nat. Mater. 2015, 14, 271-279.

Crossref Google Scholar
4

Berger, C.; Song, Z. M.; Li, T. B.; Li, X. B.; Ogbazghi, A. Y.; Feng, R.; Dai, Z. T.; Marchenkov, A. N.; Conrad, E. H.; First, P. N. et al. Ultrathin epitaxial graphite: 2D electron gas properties and a route toward graphene-based nanoelectronics. J. Phys. Chem. B 2004, 108, 19912-19916.

Crossref Google Scholar
5

Lin, Y. -M.; Valdes-Garcia, A.; Han, S. -J.; Farmer, D. B.; Meric, I.; Sun, Y. N.; Wu, Y. Q.; Dimitrakopoulos, C.; Grill, A.; Avouris, P. et al. Wafer-scale graphene integrated circuit. Science 2011, 332, 1294-1297.

Crossref Google Scholar
6

Huang, H.; Chen, W.; Chen, S.; Wee, A. T. S. Bottom-up growth of epitaxial graphene on 6H-SiC(0001). ACS Nano 2008, 2, 2513-2518.

Crossref Google Scholar
7

Tanaka, S.; Morita, K.; Hibino, H. Anisotropic layer-by-layer growth of graphene on vicinal SiC(0001) surfaces. Phys. Rev. B 2010, 81, 041406.

Crossref Google Scholar
8

Norimatsu, W.; Kusunoki, M. Transitional structures of the interface between graphene and 6H-SiC (0001). Chem. Phys. Lett. 2009, 468, 52-56.

Crossref Google Scholar
9

Emtsev, K. V.; Bostwick, A.; Horn, K.; Jobst, J.; Kellogg, G. L.; Ley, L.; McChesney, J. L.; Ohta, T.; Reshanov, S. A.; Rohrl, J. et al. Towards wafer-size graphene layers by atmospheric pressure graphitization of silicon carbide. Nat. Mater. 2009, 8, 203-207.

Crossref Google Scholar
10

Johansson, L. I.; Watcharinyanon, S.; Zakharov, A. A.; Iakimov, T.; Yakimova, R.; Virojanadara, C. Stacking of adjacent graphene layers grown on C-face SiC. Phys. Rev. B 2011, 84, 125405.

Crossref Google Scholar
11

Varchon, F.; Mallet, P.; Magaud, L.; Veuillen, J. -Y. Rotational disorder in few-layer graphene films on 6H-SiC(0001): A scanning tunneling microscopy study. Phys. Rev. B 2008, 77, 165415.

Crossref Google Scholar
12

Weng, X. J.; Robinson, J. A.; Trumbull, K.; Cavalero, R.; Fanton, M. A.; Snyder, D. Epitaxial graphene on SiC(0001): Stacking order and interfacial structure. Appl. Phys. Lett. 2012, 100, 031904.

Crossref Google Scholar
13

Borysiuk, J.; Sołtys, J.; Piechota, J. Stacking sequence dependence of graphene layers on SiC (0001)-Experimental and theoretical investigation. J. Appl. Phys. 2011, 109, 093523.

Crossref Google Scholar
14

de Heer, W. A.; Berger, C.; Ruan, M.; Sprinkle, M.; Li, X.; Hu, Y.; Zhang, B.; Hankinson, J.; Conrad, E. Large area and structured epitaxial graphene produced by confinement controlled sublimation of silicon carbide. Proc. Natl. Acad. Sci. USA 2011, 108, 16900-16905.

Crossref Google Scholar
15

Tromp, R. M.; Hannon, J. B. Thermodynamics and kinetics of graphene growth on SiC(0001). Phys. Rev. Lett. 2009, 102, 106104.

Crossref Google Scholar
16

Forbeaux, I.; Themlin, J. M.; Debever, J. M. Heteroepitaxial graphite on 6H-SiC(0001): Interface formation through conduction-band electronic structure. Phys. Rev. B 1998, 58, 16396-16406.

Crossref Google Scholar
17

Hass, J.; Feng, R.; Li, T.; Li, X.; Zong, Z.; de Heer, W. A.; First, P. N.; Conrad, E. H.; Jeffrey, C. A.; Berger, C. Highly ordered graphene for two dimensional electronics. Appl. Phys. Lett. 2006, 89, 143106.

Crossref Google Scholar
18

Kumar, B.; Baraket, M.; Paillet, M.; Huntzinger, J. R.; Tiberj, A.; Jansen, A. G. M.; Vila, L.; Cubuku, M.; Vergnaud, C.; Jamet, M. et al. Growth protocols and characterization of epitaxial graphene on SiC elaborated in a graphite enclosure. Phys. E: Low-dimens. Syst. Nanostr. 2016, 75, 7-14.

Crossref Google Scholar
19

Robinson, J. A.; Wetherington, M.; Tedesco, J. L.; Campbell, P. M.; Weng, X.; Stitt, J.; Fanton, M. A.; Frantz, E.; Snyder, D.; VanMil, B. L. et al. Correlating Raman spectral signatures with carrier mobility in epitaxial graphene: A guide to achieving high mobility on the wafer scale. Nano Lett. 2009, 9, 2873-2876.

Crossref Google Scholar
20

Lin, Y. -M.; Dimitrakopoulos, C.; Jenkins, K. A.; Farmer, D. B.; Chiu, H. -Y.; Grill, A.; Avouris, P. 100-GHz transistors from wafer-scale epitaxial graphene. Science 2010, 327, 662.

Crossref Google Scholar
21

Luxmi; Srivastava, N.; He, G. W.; Feenstra, R. M.; Fisher, P. J. Comparison of graphene formation on C-face and Si-face SiC {0001} surfaces. Phys. Rev. B 2010, 82, 235406.

Crossref Google Scholar
22

Hass, J.; Varchon, F.; Millán-Otoya, J. E.; Sprinkle, M.; Sharma, N.; de Heer, W. A.; Berger, C.; First, P. N.; Magaud, L.; Conrad, E. H. Why multilayer graphene on 4H-SiC(0001) behaves like a single sheet of graphene. Phys. Rev. Lett. 2008, 100, 125504.

Crossref Google Scholar
23

Hicks, J.; Shepperd, K.; Wang, F.; Conrad, E. H. The structure of graphene grown on the SiC (0001) surface. J. Phys. D: Appl. Phys. 2012, 45, 154002.

Crossref Google Scholar
24

Kageshima, H.; Hibino, H.; Tanabe, S. The physics of epitaxial graphene on SiC(0001). J. Phys. : Condens. Matter 2012, 24, 314215.

Crossref Google Scholar
25

Bolen, M. L.; Harrison, S. E.; Biedermann, L. B.; Capano, M. A. Graphene formation mechanisms on 4H-SiC(0001). Phys. Rev. B 2009, 80, 115433.

Crossref Google Scholar
26

Norimatsu, W.; Kusunoki, M. Formation process of graphene on SiC (0001). Phys. E: Low-dimens. Syst. Nanostr. 2010, 42, 691-694.

Crossref Google Scholar
27

Robinson, J.; Weng, X. J.; Trumbull, K.; Cavalero, R.; Wetherington, M.; Frantz, E.; LaBella, M.; Hughes, Z.; Fanton, M.; Snyder, D. Nucleation of epitaxial graphene on SiC(0001). ACS Nano 2009, 4, 153-158.

Crossref Google Scholar
28

Hupalo, M.; Conrad, E. H.; Tringides, M. C. Growth mechanism for epitaxial graphene on vicinal 6H-SiC(0001) surfaces: A scanning tunneling microscopy study. Phys. Rev. B 2009, 80, 041401.

Crossref Google Scholar
29

Norimatsu, W.; Takada, J.; Kusunoki, M. Formation mechanism of graphene layers on SiC (0001) in a high-pressure argon atmosphere. Phys. Rev. B 2011, 84, 035424.

Crossref Google Scholar
30

Camara, N.; Rius, G.; Huntzinger, J. -R.; Tiberj, A.; Magaud, L.; Mestres, N.; Godignon, P.; Camassel, J. Early stage formation of graphene on the C face of 6H-SiC. Appl. Phys. Lett. 2008, 93, 263102.

Crossref Google Scholar
31

Hite, J. K.; Twigg, M. E.; Tedesco, J. L.; Friedman, A. L.; Myers-Ward, R. L.; Eddy, C. R., Jr; Gaskill, D. K. Epitaxial graphene nucleation on C-face silicon carbide. Nano Lett. 2011, 11, 1190-1194.

Crossref Google Scholar
32

Hwang, Y. B.; Lee, E. -K.; Choi, H.; Yun, K. -H.; Lee, M.; Chung, Y. -C. Atomic behavior of carbon atoms on a Si removed 3C-SiC (111) surface during the early stage of epitaxial graphene growth. J. Appl. Phys. 2012, 111, 104324.

Crossref Google Scholar
33

Ryosuke, I.; Takahiro, K.; Yasuyuki, S.; Masato, I.; Yoshihiro, K.; Koichi, K. Molecular dynamics simulation of graphene growth by surface decomposition of 6H-SiC(0001) and (0001). Jpn. J. Appl. Phys. 2014, 53, 065601.

Crossref Google Scholar
34

Tang, C.; Meng, L. J.; Xiao, H. P.; Zhong, J. X. Growth of graphene structure on 6H-SiC(0001): Molecular dynamics simulation. J. Appl. Phys. 2008, 103, 063505.

Crossref Google Scholar
35

Daas, B. K.; Omar, S. U.; Shetu, S.; Daniels, K. M.; Ma, S. Sudarshan, T. S.; Chandrashekhar, M. V. S.; Comparison of epitaxial graphene growth on polar and nonpolar 6H-SiC faces: On the growth of multilayer films. Cryst. Growth Des. 2012, 12, 3379-3387.

Crossref Google Scholar
36

Low, T.; Perebeinos, V.; Tersoff, J.; Avouris, P. Deformation and scattering in graphene over substrate steps. Phys. Rev. Lett. 2012, 108, 096601.

Crossref Google Scholar
37

Ostler, M.; Deretzis, I.; Mammadov, S.; Giannazzo, F.; Nicotra, G.; Spinella, C.; Seyller, T.; La Magna, A. Direct growth of quasi-free-standing epitaxial graphene on nonpolar SiC surfaces. Phys. Rev. B 2013, 88, 085408.

Crossref Google Scholar
38

Lin, J. J.; Guo, L. W.; Jia, Y. P.; Yang, R.; Wu, S.; Huang, J.; Guo, Y.; Li, Z. L.; Zhang, G. Y.; Chen, X. L. Identification of dominant scattering mechanism in epitaxial graphene on SiC. Appl. Phys. Lett. 2014, 104, 183102.

Crossref Google Scholar
39

Deng, D. H.; Pan, X. L.; Zhang, H.; Fu, Q.; Tan, D. L.; Bao, X. Freestanding graphene by thermal splitting of silicon carbide granules. Adv. Mater. 2010, 22, 2168-2171.

Crossref Google Scholar
40

Muehlhoff, L.; Choyke, W. J.; Bozack, M. J.; Yates, J. T. Comparative electron spectroscopic studies of surface segregation on SiC(0001) and SiC(0001). J. Appl. Phys. 1986, 60, 2842-2853.

Crossref Google Scholar
41

Haiss, W. Surface stress of clean and adsorbate-covered solids. Rep. Prog. Phys. 2001, 64, 591-648.

Crossref Google Scholar
42

Rauls, E.; Hajnal, Z.; Deák, P.; Frauenheim, T. Theoretical study of the nonpolar surfaces and their oxygen passivation in 4H- and 6H-SiC. Phys. Rev. B 2001, 64, 245323.

Crossref Google Scholar
43

Seyller, T.; Graupner, R.; Sieber, N.; Emtsev, K. V.; Ley, L.; Tadich, A.; Riley, J. D.; Leckey, R. C. G. Hydrogen terminated 4H-SiC (1100) and (1120) surfaces studied by synchrotron x-ray photoelectron spectroscopy. Phys. Rev. B 2005, 71, 245333.

Crossref Google Scholar
44

Ming, F.; Zangwill, A. Model for the epitaxial growth of graphene on 6H-SiC(0001). Phys. Rev. B 2011, 84, 115459.

Crossref Google Scholar
45

Florian, B. Irradiation effects in carbon nanostructures. Rep. Prog. Phys. 1999, 62, 1181-1221.

Crossref Google Scholar
46

Kusunoki, M.; Suzuki, T.; Hirayama, T.; Shibata, N.; Kaneko, K. A formation mechanism of carbon nanotube films on SiC(0001). Appl. Phys. Lett. 2000, 77, 531-533.

Crossref Google Scholar
47

Pauling, L. The Nature of the Chemical Bond; Cornell University Press: Ithaca, NY, 1960.

48

Bernstein, H. J. Bond energies in hydrocarbons. Trans. Faraday Soc. 1962, 58, 2285-2306.

Crossref Google Scholar
49

Walsh, R. Bond dissociation energies in organosilicon compounds. In: Silicon in Organic, Organometallic and Polymer Chemistry. M. A. Brook, Ed.; Wiley: New York, 1998.

Google Scholar
50

Mélinon, P.; Masenelli, B.; Tournus, F.; Perez, A. Playing with carbon and silicon at the nanoscale. Nat. Mater. 2007, 6, 479-490.

Crossref Google Scholar
51

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
52

Li, J. D.; Croiset, E.; Ricardez-Sandoval, L. Carbon clusters on the Ni (111) surface: A density functional theory study. Phys. Chem. Chem. Phys. 2014, 16, 2954-2961.

Crossref Google Scholar
53

Yuan, Q. H.; Ding, F. Formation of carbyne and graphyne on transition metal surfaces. Nanoscale 2014, 6, 12727-12731.

Crossref Google Scholar
54

Zhang, L. Y.; Zhao, X. J.; Xue, X. L.; Shi, J. L.; Li, C.; Ren, X. Y.; Niu, C. Y.; Jia, Y.; Guo, Z. X.; Li, S. F. Sub-surface alloying largely influences graphene nucleation and growth over transition metal substrates. Phys. Chem. Chem. Phys. 2015, 17, 30270-30278.

Crossref Google Scholar
55

Van Wesep, R. G.; Chen, H.; Zhu, W. G.; Zhang, Z. Y. Communication: Stable carbon nanoarches in the initial stages of epitaxial growth of graphene on Cu(111). J. Chem. Phys. 2011, 134, 171105.

Crossref Google Scholar
56

Zhuang, J. N.; Zhao, R. Q.; Dong, J. C.; Yan, T. Y.; Ding, F. Evolution of domains and grain boundaries in graphene: A kinetic Monte Carlo simulation. Phys. Chem. Chem. Phys. 2016, 18, 2932-2939.

Crossref Google Scholar
57

Ding, F.; Yakobson, B. I. Energy-driven kinetic Monte Carlo method and its application in fullerene coalescence. J. Phys. Chem. Lett. 2014, 5, 2922-2926.

Crossref Google Scholar
58

Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp. Mater. Sci. 1996, 6, 15-50.

Crossref Google Scholar
59

Perdew, J. P.; Zunger, A. Self-interaction correction to density-functional approximations for many-electron systems. Phys. Rev. B 1981, 23, 5048-5079.

Crossref Google Scholar
60

Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953-17979.

Crossref Google Scholar
61

Nosé, S. A unified formulation of the constant temperature molecular dynamics methods. J. Chem. Phys. 1984, 81, 511-519.

Crossref Google Scholar
62

Donald, W. B.; Olga, A. S.; Judith, A. H.; Steven, J. S.; Boris, N.; Susan, B. S. A second-generation reactive empirical bond order (REBO) potential energy expression for hydrocarbons. J. Phys. : Condens. Matter 2002, 14, 783-802.

Crossref Google Scholar
Nano Research
Volume 11 Issue 5,
May 2018
Pages 2809-2820
DOI: 10.1007/s12274-017-1911-x
Cite this article:
Yu K, Zhao W, Wu X, et al. In situ atomic-scale observation of monolayer graphene growth from SiC. Nano Research, 2018, 11(5): 2809-2820. https://doi.org/10.1007/s12274-017-1911-x
Metrics & Citations  
Article History
Copyright
Return