MSA  Vol.6 No.11 , November 2015
A Two-Step Method for the Preparation of Highly Conductive Graphene Film and Its Gas-Sensing Property
Abstract: In this research, a highly conductive graphene film was synthesized through the chemical reduction of graphene oxide (RGO) nanosheets followed by thermal treatment at 1100℃ (RGO-1100℃) under H2 ambient. The as-prepared graphene films were characterized by using X-ray photoelectron spectroscopy, fourier transform infrared spectroscopy, X-ray diffractions, raman spectroscopy, transmission electron microscopy, scanning electron microscopy, atomic force microscopy and by electrical conductivity measurements. The results showed that the thermal treatment efficiently removed residual oxygen-containing functional groups on the surface of the RGO sheets and simultaneously restored the sp2 carbon networks in the graphene sheets. As a result, the electrical conductivity of RGO-1100℃ (~210 S/cm) film was greatly improved compared with that of RGO (~24 S/cm) and graphene oxide (4.2 × 10–4 S/m) films. In addition, the NO2 gas sensing characteristics of the as-prepared RGO films were studied. The results indicated that RGO films were highly responsive to NO2 at temperature of 200℃.
Cite this paper: Khai, T. , Lam, T. , Thu, L. and Kim, H. (2015) A Two-Step Method for the Preparation of Highly Conductive Graphene Film and Its Gas-Sensing Property. Materials Sciences and Applications, 6, 963-977. doi: 10.4236/msa.2015.611097.

[1]   Zhu, Y., Murali, S., Cai, W., Li, X., Suk, J.W., Potts, J.R. and Ruoff, R.S. (2010) Graphene and Graphene Oxide: Synthesis, Properties, and Applications. Advanced Materials, 22, 3906-3924.

[2]   Rao, C.N.R., Sood, A.K., Subrahmanyam, K.S. and Govindaraj, A. (2009) Graphene: The New Two-Dimensional Nanomaterial. Angewandte Chemie International Edition, 48, 7752-7777.

[3]   Basnayaka, P.A., Ram, M.K., Stefanakos, L. and Kumar, A. (2013) Graphene/Polypyrrole Nanocomposite as Electrochemical Supercapacitor Electrode: Electrochemical Impedance Studies. Graphene, 2, 81-87.

[4]   Novoselov, K.S., Geim, A.K., Morozov, S.V., Jiang, D., Zhang, Y., Dubonos, S.V., Grigorieva, I.V. and Firsov, A.A. (2004) Electric Field Effect in Atomically Thin Carbon Films. Science, 306, 666-669.

[5]   Hummers, W.S. and Offeman, R.E. (1958) Preparation of Graphitic Oxide. Journal of the American Chemical Society, 80, 1339.

[6]   Lerf, A., He, H., Forster, M. and Kliowski, J. (1998) Structure of Graphite Oxide Revisited. Journal of Physical Chemistry B, 102, 4477-4482.

[7]   He, H., Riedl, T., Lerf, A. and Klinowski, J. (1996) Solid-State NMR Studies of the Structure of Graphite Oxide. Journal of Physical Chemistry, 100, 19954-19958.

[8]   Watcharotone, S., Dikin, D.A., Stankovich, S., Piner, R., Jung, I., Dommett, G.H.B., Evmenenko, G., Wu, S.E., Chen, S.F., Liu, C.P., Nguyen, S.B.T. and Ruoff, R.S. (2007) Graphene-Silica Composite Thin Films as Transparent Conductors. Nano Letters, 7, 1888-1892.

[9]   Eda, G., Fanchini, G. and Chhowalla, M. (2008) Large-Area Ultrathin Films of Reduced Graphene Oxide as a Transparent and Flexible Electronic Material. Nature Nanotechnology, 3, 270-274.

[10]   Gilje, S., Han, S., Wang, M., Wang, K.L. and Kaner, R.B. (2007) A Chemical Route to Graphene for Device Applications. Nano Letters, 7, 3394-3398.

[11]   Li, D., Müller, M.B., Gilje, S., Kaner, R.B. and Wallace, G.G. (2008) Processable Aqueous Dispersions of Graphene Nanosheets. Nature Nanotechnology, 3, 101-105.

[12]   Wang, X., Zhi, L.J. and Muellen, K. (2008) Transparent, Conductive Graphene Electrodes for Dye-Sensitized Solar Cells. Nano Letters, 8, 323-327.

[13]   Becerril, H.A., Mao, J., Liu, Z.F., Stoltenberg, R.M., Bao, Z.N. and Chen, Y.S. (2008) Evaluation of Solution-Processed Reduced Graphene Oxide Films as Transparent Conductors. ACS Nano, 2, 463-470.

[14]   Novoselov, K.S., Geim, A.K., Morozov, S.V., Jiang, D., Katsnelson, M.I., Grigorieva, I.V., Dubonos, S.V. and Firsov, A.A. (2005) Two-Dimensional Gas of Massless Dirac Fermions in Graphene. Nature, 438, 197-200.

[15]   Berger, C., Song, Z.M., Li, X.B., Wu, X.S., Brown, N., Naud, C., Mayo, D., Li, T.B., Hass, J., Marchenkov, A.N., Conrad, E.H., First, P.N. and de Heer, W.A. (2006) Electronic Confinement and Coherence in Patterned Epitaxial Graphene. Science, 312, 1191-1196.

[16]   Novoselov, K.S., McCann, E., Morozov, S.V., Fal’ko, V.I., Katsnelson, M.I., Zeitler, U., Jiang, D., Schedin, F. and Geim, A.K. (2006) Unconventional Quantum Hall Effect and Berry’s Phase of 2π in Bilayer Graphene. Nature Physics, 2, 177-180.

[17]   Zhang, Y.B., Small, J.P., Amori, M.E.S. and Kim, P. (2005) Electric Field Modulation of Galvanomagnetic Properties of Mesoscopic Graphite. Physical Review Letters, 94, Article ID: 176803.

[18]   Lemme, M.C., Echtermeyer, T.J., Baus, M. and Kurz, H. (2007) A Graphene Field-Effect Device. IEEE Electron Device Letters, 28, 282-284.

[19]   Schedin, F., Geim, A.K., Morozov, S.V., Hill, E.W., Blake, P., Katsnelson, M.I. and Novoselov, K.S. (2007) Detection of Individual Gas Molecules Adsorbed on Graphene. Nature Materials, 6, 652-655.

[20]   Sundaram, R.S., Navarro, C.G., Balasubramanian, K., Burghard, M. and Kern, K. (2008) Electrochemical Modification of Graphene. Advanced Materials, 20, 3050-3053.

[21]   Ang, P.K., Chen, W., Wee, A.T.S. and Loh, K.P. (2008) Solution-Gated Epitaxial Graphene as pH Sensor. Journal of the American Chemical Society, 130, 14392-14393.

[22]   Leenaerts, O., Partoens, B. and Peeters, F.M. (2008) Adsorption of H2O, NH3, CO, NO2, and NO on Graphene: A First-Principles Study. Physical Review B, 77, Article ID: 125416.

[23]   Huang, B., Li, Z.Y., Liu, Z.R., Zhou, G., Hao, S.G., Wu, J., Gu, B.L. and Duan, W.H. (2008) Adsorption of Gas Molecules on Graphene Nanoribbons and Its Implication for Nanoscale Molecule Sensor. The Journal of Physical Chemistry C, 112, 13442-13446.

[24]   Peng, S. and Cho, K. (2003) Ab Initio Study of Doped Carbon Nanotube Sensors. Nano Letters, 3, 513-517.

[25]   Yeung, C.S., Liu, L.V. and Wang, Y.A. (2008) Adsorption of Small Gas Molecules onto Pt-Doped Single-Walled Carbon Nanotubes. The Journal of Physical Chemistry C, 112, 7401-7411.

[26]   Ao, Z.M., Yang, J., Li, S. and Jiang, Q. (2008) Enhancement of CO detection in Al Doped Graphene. Chemical Physics Letters, 461, 276-279.

[27]   Qazi, M., Vogt, T. and Koley, G. (2007) Trace Gas Detection Using Nanostructured Graphite Layers. Applied Physics Letters, 91, Article ID: 233101.

[28]   Jung, I., Dikin, D., Park, S., Cai, W., Mielke, S.L. and Ruoff, R.S. (2008) Effect of Water Vapor on Electrical Properties of Individual Reduced Graphene Oxide Sheets. The Journal of Physical Chemistry C, 112, 20264-20268.

[29]   Robinson, J.T., Perkins, F.K., Snow, E.S., Wei, Z. and Sheehan, P.E. (2008) Reduced Graphene Oxide Molecular Sensors. Nano Letters, 8, 3137-3140.

[30]   Fowler, J.D., Allen, M.J., Tung, V.C., Yang, Y., Kaner, R.B. and Weiller, B.H. (2009) Practical Chemical Sensors from Chemically Derived Graphene. ACS Nano, 3, 301-306.

[31]   Wu, Z.S., Ren, W., Gao, L., Liu, B., Jiang, C. and Cheng, H.M. (2009) Synthesis of High-Quality Graphene with a Pre-Determined Number of Layers. Carbon, 47, 493-499.

[32]   Stankovich, S., Dikin, D.A., Piner, R.D., Kohlhaas, K.A, Kleinhammes, A., Jia, Y., Wu, Y., Nguyen, S.B.T. and Ruoff, R.S. (2007) Synthesis of Graphene-Based Nanosheets via Chemical Reduction of Exfoliated Graphite Oxide. Carbon, 45, 1558-1565.

[33]   Thema, F.T., Moloto, M.J., Dikio, E.D., Nyangiwe, N.N., Kotsedi, L., Maaza, M. and Khenfouch, M. (2013) Synthesis and Characterization of Graphene Thin Films by Chemical Reduction of Exfoliated and Intercalated Graphite Oxide. Journal of Chemistry, 2013, Article ID: 150536.

[34]   Muthoosamy, K., et al. (2015) Exceedingly Biocompatible and Thin-Layered Reduced Graphene Oxide Nanosheets Using an Eco-Friendly Mushroom Extract Strategy. International Journal of Nanomedicine, 10, 1505-1519.

[35]   Hung, P.V., Cuong, T.V., Hur, S.H., Shin, E.W., Kim, J.S., Chung, J.S. and Kim, E.J. (2010) Fast and Simple Fabrication of a Large Transparent Chemically-Converted Graphene Film by Spray-Coating. Carbon, 48, 1945-1951.

[36]   Hontorialucas, C., Lopezpeinado, A.J., Lopezgonzalez, J.D.D., Rojascervantes, M.L. and Martinaranda, R.M. (1995) Study of Oxygen-Containing Groups in a Series of Graphite Oxides: Physical and Chemical Characterization. Carbon, 33, 1585-1592.

[37]   Chandra, V. and Kim, K.S. (2011) Highly Selective Adsorption of Hg2+ by a Polypyrrole-Reduced Graphene Oxide Composite. Chemical Communications, 47, 3942-3944.

[38]   Ricci, M., Trinquecoste, M., Auguste, F., Canet, R., Delhaes, P., Guimon, C., Pfister-Guillouzo, G., Nysten, B. and Issi, J.P. (1993) Relationship between the Structural Organization and the Physical Properties of PECVD Nitrogenated Carbons. Journal of Materials Research, 8, 480-488.

[39]   Ren, Z.M., Lu, Y.F., Song, W.D., Chan, D.S.H., Low, T.S., Gamani, K., Chen, G. and Li, K. (1998) Studies of Carbon Nitride Thin Films Synthesized by KrF Excimer Ablation of Graphite in Nitrogen Atmosphere. MRS Proceedings, 526, 343-348.

[40]   Ferrari, A.C., Meyer, J.C., Scardaci, V., Casiraghi, C., Lazzeri, M., Mauri, F., Piscanec, S., Jiang, D., Novoselov, K.S. and Roth, S. (2006) Raman Spectrum of Graphene and Graphene Layers. Physical Review Letters, 97, Article ID: 187401.

[41]   Ferrari, A.C. and Robertson, J. (2000) Interpretation of Raman Spectra of Disordered and Amorphous Carbon. Physical Review B, 61, Article ID: 14095.

[42]   Tuinstra, F. and Koenig, J.L. (1970) Raman Spectrum of Graphite. The Journal of Chemical Physics, 53, 1126-1130.

[43]   Jiang, B.J., Tian, C.G., Wang, L., Xu, Y.X., Wang, R.H., Qiao, Y.J., Ma, Y.G. and Fu, H.G. (2010) Facile Fabrication of High Quality Graphene from Expandable Graphite: Simultaneous Exfoliation and Reduction. Chemical Communications, 46, 4920-4922.

[44]   Chouciar, M., Thordarson, P. and Stride, J.A. (2009) Gram-Scale Production of Graphene Based on Solvothermal Synthesis and Sonication. Nature Nanotechnology, 4, 30-33.

[45]   Park, S., An, J., Piner, R.D., Jung, I., Yang, D., Velamakanni, A., Nguyen, S.B.T and Ruoff, R.S. (2008) Aqueous Suspension and Characterization of Chemically Modified Graphene Sheets. Chemistry of Materials, 20, 6592-6594.

[46]   Wei, D.C., Liu, Y.Q., Yang, Y., Zhang, H.L., Huang, L.P. and Yu, G. (2009) Synthesis of N-Doped Graphene by Chemical Vapor Deposition and Its Electrical Properties. Nano Letters, 9, 1752-1758.

[47]   Lee, D.H., Lee, W.J. and Kim, S.O. (2009) Highly Efficient Vertical Growth of Wall-Number-Selected, N-Doped Carbon Nanotube Arrays. Nano Letters, 9, 1427-1432.

[48]   Gómez-Navarro, C., Weitz, R.T., Bittner, A.M., Scolari, M., Mews, A., Burghard, M. and Kern, K. (2007) Electronic Transport Properties of Individual Chemically Reduced Graphene Oxide Sheets. Nano Letters, 11, 3499-3503.

[49]   Ren, P.G., Yan, D.X., Ji, X., Chen, T. and Li, Z.M. (2011) Temperature Dependence of Graphene Oxide Reduced by Hydrazine Hydrate. Nanotechnology, 22, Article ID: 055705.

[50]   Kinoshita, K. (1998) Carbon: Electrochemical and Physicochemical Properties. John Wiley & Sons, New York, 560.

[51]   Geng, J., Liu, L., Yang, S.B., Youn, S.C., Kim, D.W., Lee, J.S., Choi, J.K. and Jung, H.T. (2010) A Simple Approach for Preparing Transparent Conductive Graphene Films Using the Controlled Chemical Reduction of Exfoliated Graphene Oxide in an Aqueous Suspension. The Journal of Physical Chemistry C, 114, 14433-14440.

[52]   Lopez, V., Sundaram, R.S., Gomez-Navarro, C., Olea, D., Burghard, M., Gomez-Herrero, J., Zamora, F. and Kern, K. (2009) Graphene Monolayers: Chemical Vapor Deposition Repair of Graphene Oxide: A Route to Highly-Conductive Graphene Monolayers. Advanced Materials, 21, 4683-4686.

[53]   Jin, M., Kim, T.H., Lim, S.C., Duong, D.L., Shin, H.J., Jo, Y.W., Jeong, H.K., Chang, J., Xie, S. and Lee, Y.H. (2011) Facile Physical Route to Highly Crystalline Graphene. Advanced Functional Materials, 21, 3496-3501.

[54]   Wang, S.J., Geng, Y., Zheng, Q. and Kim, J.K. (2010) Fabrication of Highly Conducting and Transparent Graphene Films. Carbon, 48, 1815-1823.

[55]   Moser, J., Verdaguer, A., Jiménez, D., Barreiro, A. and Bachtold, A. (2008) The Environment of Graphene Probed by Electrostatic Force Microscopy. Applied Physics Letters, 92, Article ID: 123507.

[56]   Ko, G., Kim, H.W., Ahn, J., Park, Y.M., Lee, K.Y. and Kim, J. (2010) Graphene-Based Nitrogen Dioxide Gas Sensors. Current Applied Physics, 10, 1002-1004.

[57]   Yavari, F., Chen, Z., Thomas, A.V., Ren, W., Cheng, H.M. and Koratkar, N. (2011) High Sensitivity Gas Detection Using a Macroscopic Three-Dimensional Graphene Foam Network. Scientific Report, 1, Article No.: 166.

[58]   Moseley, P.T. (1997) Solid State Gas Sensors. Measurement Science and Technology, 8, 223-237.

[59]   Kong, J., Franklin, N.R., Zhou, C., Chapline, M.G., Peng, S., Cho, K. and Dai, H. (2000) Nanotube Molecular Wires as Chemical Sensors. Science, 287, 622-625.

[60]   Collins, P.G., Bradley, K., Ishigami, M. and Zettl, A. (2000) Extreme Oxygen Sensitivity of Electronic Properties of Carbon Nanotubes. Science, 287, 1801-1804.

[61]   Khaledian, M., Ismail, R., Saeidmanesh, M., Ghadiry, M. and Akbari, E. (2015) Sensitivity Modelling of Graphene Nanoscroll Based NO2 Gas Sensors. Plasmonics, 10, 1033-1040.

[62]   Lu, G., Ocola, L.E. and Chen, J.H. (2009) Gas Detection Using Low-Temperature Reduced Graphene Oxide Sheets. Applied Physics Letters, 94, Article ID: 083111.

[63]   Penza, M., Gassano, G., Rossi, R., Alvisi, M., Rizzo, A., Signore, M.A., Dikonimos, T., Serra, E. and Giorgi, R. (2007) Enhancement of Sensitivity in Gas Chemiresistors Based on Carbon Nanotube Surface Functionalized with Noble Metal (Au, Pt) Nanoclusters. Applied Physics Letters, 90, Article ID: 173123.

[64]   Zhang, H., Feng, J.C., Fei, T., Liu, S. and Zhang, T. (2014) SnO2 Nanoparticles-Reduced Graphene Oxide Nanocomposites for NO2 Sensing at Low Operating Temperature. Sensors and Actuators B: Chemical, 190, 472-478.

[65]   Qin, J.W., Cao, M.H., Li, N. and Hu, C.W. (2011) Graphene-Wrapped WO3 Nanoparticles with Improved Performances in Electrical Conductivity and Gas Sensing Properties. Journal of Materials Chemistry, 21, 17167-17171.