Effects of the flow rate of hydrogen on the growth of graphene

Abstract

Graphene samples with different morphologies were fabricated on the inside of copper enclosures by low pressure chemical vapor deposition and tuning the flow rate of hydrogen. It is found that the flow rate of hydrogen greatly influences the growth of graphene. Thermodynamic analysis indicates that a higher flow rate of hydrogen is favorable to the formation of good quality graphene with regular morphology. However, the mass-transfer process of methane dominates the growth driving force. At very low pressure, mass-transfer proceeds by Knudsen diffusion, and the mass-transfer flux of methane decreases as the flow rate of hydrogen increases, leading to a decrease in the growth driving force. At a higher pressure, mass-transfer proceeds by Fick’s diffusion, and the mass-transfer flux of methane is dominated by the gas velocity, whose variation determines the growth driving force variation of graphene.

Keywords

graphene / crystal growth / morphology / diffusion / mass transfer / chemical vapor deposition

References

[1] Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, Grigorieva IV, Firsov AA. Electric field effect in atomically thin carbon films. Science, 2004, 306(5696): 666.

[2] Chen WF, Yan LF, Bangal PR. Preparation of graphene by the rapid and mild thermal reduction of graphene oxide induced by microwaves. Carbon, 2010, 48(4): 1146.

[3] Neto AHC, Guinea F, Peres NMR, Novoselov KS, Geim AK. The electronic properties of graphene. Rev. Mod. Phys., 2009, 81(1): 109.

[4] Bunch JS, van der Zande AM, Verbridge SS, Frank IW, Tanenbaum DM, Parpia JM, Craighead HG, McEuen PL. Electromechanical resonators from graphene sheets. Science, 2007, 315(5811): 490.

[5] Wehling TO, Novoselov KS, Morozov SV, Vdovin EE, Katsnelson MI, Geim AK, Lichtenstein AI. Molecular doping of graphene. Nano. Lett., 2008, 8(1): 173.

[6] Lin YM, Dimitrakopoulos C, Jenkins KA, Farmer DB, Chiu HY, Grill A, Avouris Ph. 100-GHz transistors from wafer-scale epitaxial graphene. Science, 2010, 327(5966): 662.

[7] Wang X, Zhi LJ, Tsao N, Tomović Li JL, Müllen K. Transparent carbon films as electrodes in organic solar cells. Angew. Chem. Int. Ed., 2008, 47(16): 2990.

[8] Lv RT, Cui TX, Jun MS, Zhang Q, Cao AY, Su DS, Zhang ZJ, Yoon SH, Miyawaki J, Mochida I, Kang FY. Open-ended, N-doped carbon nanotube-graphene hybrid nanostructures as high-performance catalyst support. Adv. Funct. Mater., 2011, 21(5): 999.

[9] Bae S, Kim H, Lee Y, Xu XF, Park JS, Zheng Y, Balakrishnan J, Lei T, Kim HR, Song YI, Kim YJ, Kim KS, Özyilmaz B, Ahn JH, Hong BH, Lijima S. Roll-to-roll production of 30-inch graphene films for transparent electrodes. Nat. Nanotechnol., 2010, 5(8): 574.

[10] Soldano C, Mahmood A, Dujardin E. Production, properties and potential of graphene. Carbon, 2010, 48(8): 2127.

[11] Li XS, Cai WW, An J, Kim S, Nah J, Yang DX, Piner R, Velamakanni A, Jung I, Tutuc E, Banerjee SK, Colombo L, Ruoff RS. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science, 2009, 324(5932): 1312.

[12] Zhang Y, Zhang LY, Kim P, Ge MY, Li Z, Zhou CW. Vapor trapping growth of single-crystalline graphene flowers: synthesis, morphology, and electronic properties. Nano. Lett., 2012, 12(6): 2810.

[13] Li XS, Magnuson CW, Venugopal A, Tromp RM, Hannon JB, Vogel EM, Colombo L, Ruoff RS. Large-area graphene single crystals grown by low-pressure chemical vapor deposition of methane on copper. J. Am. Chem. Soc., 2011, 133(9): 2816.

[14] Chen SS, Ji HX, Chou H, Li QY, Li HY, Suk JW, Piner R, Liao L, Cai WW, Ruoff RS. Millimeter-size single-crystal graphene by suppressing evaporative loss of Cu during low pressure chemical vapor deposition. Adv. Mater., 2013, 25(14): 2062.

[15] Ma LP, Ren WC, Dong ZL, Liu LQ, Cheng HM. Progress of graphene growth on copper by chemical vapor deposition: growth behavior and controlled synthesis. Chin. Sci. Bull, 2012, 57(23): 2995.

[16] Yu QK, Jauregui LA, Wu W, Colby R, Tian JF, Su ZH, Cao HL, Liu ZH, Pandey D, Wei DG, Chung TF, Peng P, Guisinger NP, Stach EA, Bao JM, Pei SS, Chen YP. Trol and characterization of individual grains and grain boundaries in graphene grown by chemical vapour deposition. Nat. Mater., 2011, 10, 443.

[17] Yan Z, Lin J, Peng ZW, Sun ZZ, Zhu Y, Li L, Xiang CS, Samuel EL, Kittrell C, Tour J M. Toward the synthesis of wafer-scale single-crystal graphene on copper foils. ACS Nano, 2012, 6(10): 9110.

[18] Ferrari AC. Raman spectroscopy of graphene and graphite: disorder, electron-phonon coupling, doping and nonadiabatic effects. Solid State Commun., 2007, 143(1–2): 47.

[19] Phys. Rev. Lett., 2006, 97(18)

[20] Jorio A, Cançado LG. Perspectives on Raman spectroscopy of graphene-based systems: from the perfect two-dimensional surface to charcoal. Phys. Chem. Chem. Phys., 2012, 14(44): 15246.

[21] Sunagawa I. Morphology of Crystals, 1987, Tokyo, Terra Science Publishers, 27.

[22] Irisawa T. Crystal Growth Technology, 2003, New York, William Andrew Inc, 25.

[23] Ohring M. The Materials Science of Thin Films, 1991, New York, Academic Press, 68.

[24] Levine IN. Physical Chemistry, 1988, New York, McGraw-Hill Book, 187.

[25] Gurvich LV, Veyts IV, Alcock CB. Thermodynamic Properties of Individual Substances, 1990, New York, CRC Press, 452.

[26] Park HJ, Meyer J, Roth S, Skakalova V. Growth and properties of few-layer graphene prepared by chemical vapor deposition. Carbon, 2010, 48(4): 1088.

[27] Oran ES, Boris JP. Numerical Simulation of Reactive Flow, 2001, Cambridge, Cambridge University Press, 45.

[28] Atkins P, Paula JD. Physical Chemistry, 2006, New York, W. H. Freeman and Company, 212.

[29] Kaldis E, Piechotka M. Handbook of Crystal Growth, 1994, Amsterdam, Elsevier Science, 615.