Microwave Plasma Enhanced Chemical Vapor Deposition of Carbon Nanotubes

Ivaylo Hinkov, Samir Farhat, Cristian P. Lungu, Alix Gicquel, François Silva, Amine Mesbahi, Ovidiu Brinza, Cornel Porosnicu, Alexandru Anghel

Laboratoire des Sciences des Procédés et des Matériaux, CNRS, LSPM-UPR 3407, Université Paris 13, Villetaneuse, France.
National Institute for Laser, Plasma and Radiation Physics, Bucharest, Romania.
University of Chemical Technology and Metallurgy, Sofia, Bulgaria.

DOI: 10.4236/jsemat.2014.44023                

Abstract

Multi-walled carbon nanotubes (MWCNTs) were grown by plasma-enhanced chemical vapor deposition (PECVD) in a bell jar reactor. A mixture of methane and hydrogen (CH₄/H₂) was decomposed over Ni catalyst previously deposited on Si-wafer by thermionic vacuum arc (TVA) technology. The growth parameters were optimized to obtain dense arrays of nanotubes and were found to be: hydrogen flow rate of 90 sccm; methane flow rate of 10 sccm; oxygen flow rate of 1 sccm; substrate temperature of 1123 K; total pressure of 10 mbar and microwave power of 342 Watt. Results are summarized and significant main factors and their interactions were identified. In addition a computational study of nanotubes growth rate was conducted using a gas phase reaction mechanism and surface nanotube formation model. Simulations were performed to determine the gas phase fields for temperature and species concentration as well as the surface-species coverage and carbon nanotubes growth rate. A kinetic mechanism which consists of 13 gas species, 43 gas reactions and 17 surface reactions has been used in the commercial computational fluid dynamics (CFD) software ANSYS Fluent. A comparison of simulated and experimental growth rate is presented in this paper. Simulation results agreed favorably with experimental data.

Keywords

Nanotubes, Growth, CVD, Modeling, Kinetics

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	Iijima, S. (1991) Helical Microtubules of Graphitic Carbon. Nature, 354, 56-58. http://dx.doi.org/10.1038/354056a0
[2]	Farhat, S. and Scott, C. (2006) Review of the Arc Process Modeling for Fullerene and Nanotube Production. Journal of Nanoscience and Nanotechnology, 6, 1189-1210. http://dx.doi.org/10.1166/jnn.2006.331
[3]	Yu, B. and Meyyappan, M. (2006) Nanotechnology: Role in Emerging Nanoelectronics. Solid State Electronics, 50, 536-544. http://dx.doi.org/10.1016/j.sse.2006.03.028
[4]	Schäffel, F., Schünemann, C., Rümmeli, M.H., Täschner, C., Pohl, D., Kramberger, C., Gemming, T., Leonhardt, A., Pichler, T., Rellinghaus, B., Büchner, B. and Schultz, L. (2008) Comparative Study on Thermal and Plasma Enhanced CVD Grown Carbon Nanotubes from Gas Phase Prepared Elemental and Binary Catalyst Particles. Physica Status Solidi (b), 245, 1919-1922. http://dx.doi.org/10.1002/pssb.200879605
[5]	Delzeit, L., Nguyen, C.V., Stevens, R.M., Han, J. and Meyyappan, M. (2002) Growth of Carbon Nanotubes by Thermal and Plasma Chemical Vapour Deposition Processes and Applications in Microscopy. Nanotechnology, 13, 280-284. http://dx.doi.org/10.1088/0957-4484/13/3/308
[6]	Hata, K., Futaba, D.N., Mizuno, K., Namai, T., Yumura M. and Ijima, S. (2004) Water-Assisted Highly Efficient Synthesis of Impurity-Free Single-Walled Carbon Nanotubes. Science, 306, 1362-1364. http://dx.doi.org/10.1126/science.1104962
[7]	Zhang, G., Mann, D., Zhang, L., Javey, A., Li, Y., Yenilmez, E., Wang, Q., McVittie, J.P., Nishi, Y., Gibbons, J. and Dai, H. (2005) Ultra-High-Yield Growth of Vertical Single-Walled Carbon Nanotubes: Hidden Roles of Hydrogen and Oxygen. PNAS, 102, 16141-16145. http://dx.doi.org/10.1073/pnas.0507064102
[8]	Lungu, C.P., Mustata, I., Zaroschi, V., Lungu, A.M., Anghel, A., Chiru, P., Rubel, M., Coad, P. and Matthews, G.F. (2007) Beryllium Coatings on Metals for Marker Tiles at JET: Development of Process and Characterization of Layers. Physyca Scripta, T128, 157-161. http://dx.doi.org/10.1088/0031-8949/2007/T128/030
[9]	Lungu, C.P., Mustata, I., Musa, G., Lungu, A.M., Zaroschi, V., Iwasaki, K., Tanaka, R., Matsumura, Y., Iwanaga, I., Tanaka, H., Oi, T. and Fujita, K. (2005) Formation of Nanostructured Re–Cr–Ni Diffusion Barrier Coatings on Nb Superalloys by TVA Method. Surface and Coating Technology, 200, 399-402. http://dx.doi.org/10.1016/j.surfcoat.2005.02.172
[10]	Lungu, C.P. (2005) Nanostructure Influence on DLC-Ag Tribological Coatings. Surface and Coating Technology, 200, 198-202. http://dx.doi.org/10.1016/j.surfcoat.2005.02.103
[11]	Lungu, C.P., Mustata, I., Zaroschi, V., Lungu, A.M., Chiru, P., Anghel, A., Burcea, G., Bailescu, V., Dinuta, G. and Din, F. (2007) Spectroscopic Study of Beryllium Plasma Produced by Thermionic Vacuum Arc. Journal of Optoelectronics and Advanced Materials, 9, 884-886.
[12]	Silva, F., Gicquel, A., Chiron, A. and Achard, J. (2000) Low Roughness Diamond Films Produced at Temperatures Less than 600°C. Diamond and Related Materials, 9, 1965-1970. http://dx.doi.org/10.1016/S0925-9635(00)00347-2
[13]	Scott, C.D., Farhat, S., Gicquel, A., Hassouni, K. and Lefebvre, M. (1996) Determining Electron Temperature and Density in a Hydrogen Microwave Plasma. Journal of Thermophysics and Heat Transfer, 10, 426-435. http://dx.doi.org/10.2514/3.807
[14]	Garg, R.K., Kim, S.S., Hash, D.B., Gore, J.P. and Fisher, T. (2008) Effects of Feed Gas Composition and Catalyst Thickness on Carbon Nanotube and Nanofiber Synthesis by Plasma Enhanced Chemical Vapor Deposition. Journal of Nanoscience and Nanotechnology, 8, 3068-3076. http://dx.doi.org/10.1166/jnn.2008.082
[15]	Marinov, N.M. and Malte, P.C. (1995) Ethylene Oxidation in a Well-Stirred Reactor. International Journal of Chemical Kinetics, 27, 957-986. http://dx.doi.org/10.1002/kin.550271003
[16]	Walter, D., Grotheer, H.H., Davies, J.W., Pilling, M.J. and Wagner, A.F. (1990) Experimental and Theoretical Study of the Recombination Reaction CH3 + CH3 – C2H6. Symposium (International) on Combustion, 23, 107-114. http://dx.doi.org/10.1016/S0082-0784(06)80248-1
[17]	Tsang, W. and Hampson, R.F. (1986) Chemical Kinetic Data Base for Combustion Chemistry. Part 1. Methane and Related Compounds. Journal of Physical and Chemical Reference Data, 15, 1087-1279. http://dx.doi.org/10.1063/1.555759
[18]	Miller, J.A. and Melius, C.F. (1992) Kinetics and Thermodynamic Issues in the Formation of Aromatic Compounds in Flames of Aliphatic Fuels. Combustion and Flame, 91, 21-39. http://dx.doi.org/10.1016/0010-2180(92)90124-8
[19]	Markus, M.W., Woiki, D. and Roth, P. (1992) Two-Channel Thermal Decomposition of CH3. Symposium (International) on Combustion, 24, 581-588. http://dx.doi.org/10.1016/S0082-0784(06)80071-8
[20]	Warnatz, J. (1984) Rate Coefficients in the C/H/O System. In: Gardiner Jr., W.C., Ed., Combustion Chemistry, Book Chapter, Springer-Verlag, New York.
[21]	Dagaut, P., Cathonnet, M., Aboussi, B. and Boettner, J.-C. (1990) Allene Oxidation: A Kinetic Modeling Study. Journal de Chimie Physique et de Physico-Chimie Biologique, 87, 1159-1172.
[22]	Feng, Y., Niiranen, J.T., Bencsura, A., Knyazev, V.D., Gutman, D. and Tsang, W. (1993) Weak Collision Effects in the Reaction C2H5=C2H4+H. Journal of Physical Chemistry, 97, 871-880. http://dx.doi.org/10.1021/j100106a012
[23]	Towell, G.D. and Martin, J.J. (1961) Kinetic Data from Nonisothermal Experiments: Thermal Decomposition of Ethane, Ethylene, and Acetylene. AIChE Journal, 7, 693-698. http://dx.doi.org/10.1002/aic.690070432
[24]	Kiefer, J.H., Kapsalis, S.A., MAlami, M.Z. and Budach, K.A. (1983) The Very High Temperature Pyrolysis of Ethylene and the Subsequent Reactions of Product Acetylene. Combustion and Flame, 51, 79-93. http://dx.doi.org/10.1016/0010-2180(83)90085-8
[25]	Dean, A.M. (1985) Predictions of Pressure and Temperature Effects upon Radical Addition and Recombination Reactions. Journal of Physical Chemistry, 89, 4600-4608. http://dx.doi.org/10.1021/j100267a038
[26]	Fahr, A., Laufer, A., Klein, R. and Braun, W. (1991) Reaction Rate Determinations of Vinyl Radical Reactions with Vinyl, Methyl, and Hydrogen Atoms. Journal of Physical Chemistry, 95, 3218-3224. http://dx.doi.org/10.1021/j100161a047
[27]	Knyazev, V.D., Bencsura, A., Stoliarov, S.I. and Slagle, I.R. (1996) Kinetics of the C2H3+H2=H+C2H4 and CH3+ H2=H+CH4 Reactions. Journal of Physical Chemistry, 100, 11346-11354. http://dx.doi.org/10.1021/jp9606568
[28]	Janardhanan, V.M. and Deutschmann, O. (2006) CFD Analysis of a Solid Oxide Fuel Cell with Internal Reforming: Coupled Interactions of Transport, Heterogeneous Catalysis and Electrochemical Processes. Journal of Power Sources, 162, 1192-1202. http://dx.doi.org/10.1016/j.jpowsour.2006.08.017
[29]	Lysaght, A.C. and Chiu, W.K.S. (2008) Modeling of the Carbon Nanotube Chemical Vapor Deposition Process Using Methane and Acetylene Precursor Gases. Nanotechnology 19, 165607. http://dx.doi.org/10.1088/0957-4484/19/16/165607
[30]	Lacroix, R., Fournet, R., Ziegler-Devin, I. and Marquaire, P.-M. (2010) Kinetic Modeling of Surface Reactions Involved in CVI of Pyrocarbon Obtained by Propane Pyrolysis. Carbon, 48, 132–144. http://dx.doi.org/10.1016/j.carbon.2009.08.041
[31]	Farhat, S., Panham, S., Gicquel, A., Silva, F., Brinza, O. and Lungu, C.P. (2010) Synthèse de Nanotubes Orientés par PECVD. Matériaux 2010, 18-22 October 2010, Nantes.
[32]	Kee, R.J., Rupley, F.M., Miller, J.A., Coltrin, M.E., et al. (2001) CHEMKIN Collection, Release 3.6, Reaction Design, Inc., San Diego.
[33]	JANAF (1965) “Thermochemical tables, National Standards Reference Data Series” Report NSRDS-NBS: Dow Chemikal Company, distributed by Clearinghouse for federal Scientific and Technical Information, PB168370.
[34]	Kee, R.J., Dixon-Lewis, G., Warnatz, J. and Miller, J.A. (1986) A FORTRAN Computer Code Package for Evaluation of Gas-Phase, Multicomponent Transport Properties. Technical Report SAND86-8426, Sandia National Laboratories, Albuquerque.
[35]	Sickafus, E.N. (1970) Sulfur and Carbon on the (110) Surface of Nickel. Surface Science, 19, 181-197. http://dx.doi.org/10.1016/0039-6028(70)90117-2
[36]	Kee, R.J., Miller, J.A. and Jefferson, T.H. (1980) CHEMKIN: A General-Purpose, Problem-Independent, Transportable, Fortran Chemical Kinetics Code Package. Technical Report SAND80-8003, Sandia National Laboratories, Albuquerque.
[37]	Farhat, S., Findeling, C., Silva, F., Hassouni, K. and Gicquel, A. (1997) Third Edition of the International Workshop Microwave Discharges: Fundamentals and Applications. Abbaye de Fontevraud, Fontevraud-l’Abbaye.