Skip to main content Accessibility help

Synchronous chemical vapor deposition of large-area hybrid graphene–carbon nanotube architectures

  • Maziar Ghazinejad (a1), Shirui Guo (a2), Wei Wang (a3), Mihrimah Ozkan (a4) and Cengiz S. Ozkan (a5)...


We report on the successful synthesis of a graphene–carbon nanotube (CNT) hybrid architecture by a parallel chemical vapor deposition (CVD) of the two carbon allotropes. The carbon hybrid is a three-dimensional (3D) nanostructure with tuneable architecture comprising vertically grown CNTs as pillars and a large-area graphene plane as the floor. The formation of CNTs and graphene occurs simultaneously in a single CVD growth that we describe as a synchronous synthesis method. Unique nature of the fabrication approach contributes significantly to the quality and composure of final nanohybrid. Detailed characterization elucidates the cohesive structure and robust contact between the graphene floor and the CNTs in the hybrid structure. The functionality of the synthesized graphene hybrid structure has been demonstrated by its incorporation into a supercapacitor cell. Our fabrication approach provides an attractive pathway for the fabrication of novel 3D hybrid nanostructures and efficient device integration.


Corresponding author

b)Address all correspondence to this author. e-mail:


Hide All
1.Novoselov, K.S., Geim, A.K., Morozov, S.V., Jiang, D., Katsnelson, M.I., Grigorieva, I.V., Dubonos, S.V., and Firsov, A.A.: Two-dimensional gas of massless Dirac fermions in graphene. Nature 438, 197200 (2005).
2.Novoselov, K.S., Geim, A.K., Morozov, S.V., Jiang, D., Zhang, Y., Dubonos, S.V., Grigorieva, I.V., and Firsov, A.A.: Electric field effect in atomically thin carbon films. Science 306, 666669 (2004).
3.Zhang, Y., Tan, Y-W., Stormer, H.L., and Kim, P.: Experimental observation of the quantum Hall effect and Berry’s phase in graphene. Nature 438, 201204 (2005).
4.Geim, A.K. and Novoselov, K.S.: The rise of graphene. Nat. Mater. 6, 183191 (2007).
5.Chen, J-H., Jang, C., Xiao, S., Ishigami, M., and Fuhrer, M.S.: Intrinsic and extrinsic performance limits of graphene devices on SiO2. Nat. Nanotechnol. 3, 206209 (2008).
6.Balandin, A.A., Ghosh, S., Bao, W., Calizo, I., Teweldebrhan, D., Miao, F., and Lau, C.N.: Superior thermal conductivity of single-layer graphene. Nano Lett. 8, 902907 (2008).
7.Lee, C., Wei, X., Kysar, J.W., and Hone, J.: Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321, 385388 (2008).
8.Schedin, F., Geim, A.K., Morozov, S.V., Hill, E.W., Blake, P., Katsnelson, M.I., and Novoselov, K.S.: Detection of individual gas molecules adsorbed on graphene. Nat. Mater. 6, 652655 (2007).
9.Wang, X., Zhi, L., and Mullen, K.: Transparent, conductive graphene electrodes for dye-sensitized solar cells. Nano Lett. 8, 323327 (2007).
10.Yan, J., Wei, T., Shao, B., Fan, Z., Qian, W., Zhang, M., and Wei, F.: Preparation of a graphene nanosheet/polyaniline composite with high specific capacitance. Carbon 48, 487493 (2009).
11.Lin, J., Teweldebrhan, D., Ashraf, K., Liu, G., Jing, X., Yan, Z., Li, R., Ozkan, M., Lake, R.K., Balandin, A.A., and Ozkan, C.S.: Gating of single-layer graphene with single-stranded deoxyribonucleic acids. Small 6, 11501155 (2010).
12.Yoo, E., Kim, J., Hosono, E., Zhou, H-S., Kudo, T., and Honma, I.: Large reversible Li storage of graphene nanosheet families for use in rechargeable lithium ion batteries. Nano Lett. 8, 22772282 (2008).
13.Iijima, S.: Helical microtubules of graphitic carbon. Nature 354, 5658 (1991).
14.Dresselhaus, M.S., Dresselhaus, G., and Jorio, A.: Unusual properties and structure of carbon nanotubes. Annu. Rev. Mater. 34, 247278 (2004).
15.Popov, V.N.: Carbon nanotubes: Properties and application. Mater. Sci. Eng., R 43, 42 (2004).
16.Collins, P.G., Arnold, M.S., and Avouris, P.: Engineering carbon nanotubes and nanotube circuits using electrical breakdown. Science 292, 706709 (2001).
17.Javey, A., Guo, J., Wang, Q., Lundstrom, M., and Dai, H.: Ballistic carbon nanotube field-effect transistors. Nature 424, 654657 (2003). Heer, W.A., Chatelain, A., and Ugarte, D.: A carbon nanotube field-emission electron source. Science 270, 11791180 (1995).
19.Lee, D.H., Kim, J.E., Han, T.H., Hwang, J.W., Jeon, S., Choi, S-Y., Hong, S.H., Lee, W.J., Ruoff, R.S., and Kim, S.O.: Versatile carbon hybrid films composed of vertical carbon nanotubes grown on mechanically compliant graphene films. Adv. Mater. 22, 12471252 (2010).
20.Jeong, H.Y., Lee, D-S., Choi, H.K., Lee, D.H., Kim, J-E., Lee, J.Y., Lee, W.J., Kim, S.O., and Choi, S-Y.: Flexible room-temperature NO2 gas sensors based on carbon nanotubes/reduced graphene hybrid films. Appl. Phys. Lett. 96, 213105–213105-3 (2010).
21.Yu, D. and Dai, L.: Self-assembled graphene/carbon nanotube hybrid films for supercapacitors. J. Phys. Chem. Lett. 1, 467470 (2009).
22.Tung, V.C., Chen, L-M., Allen, M.J., Wassei, J.K., Nelson, K., Kaner, R.B., and Yang, Y.: Low-temperature solution processing of graphene carbon nanotube hybrid materials for high-performance transparent conductors. Nano Lett. 9, 19491955 (2009).
23.Dimitrakakis, G.K., Tylianakis, E., and Froudakis, G.E.: Pillared graphene: A new 3-D network nanostructure for enhanced hydrogen storage. Nano Lett. 8, 31663170 (2008).
24.Stoller, M.D., Park, S., Zhu, Y., An, J., and Ruoff, R.S.: Graphene-based ultracapacitors. Nano Lett. 8, 34983502 (2008).
25.Lee, D.H., Lee, J.A., Lee, W.J., Choi, D.S., Lee, W.J., and Kim, S.O.: Facile fabrication and field emission of metal-particle-decorated vertical N-doped carbon nanotube/graphene hybrid films. J. Phys. Chem. C 114, 2118421189 (2010).
26.Lee, D.H., Lee, J.A., Lee, W.J., and Kim, S.O.: Flexible field emission of nitrogen-doped carbon nanotubes/reduced graphene hybrid films. Small 7, 95100 (2011).
27.Gomez-Navarro, C., Meyer, J.C., Sundaram, R.S., Chuvilin, A., Kurasch, S., Burghard, M., Kern, K., and Kaiser, U.: Atomic structure of reduced graphene oxide. Nano Lett. 10, 11441148 (2010).
28.Blake, P., Brimicombe, P.D., Nair, R.R., Booth, T.J., Jiang, D., Schedin, F., Ponomarenko, L.A., Morozov, S.V., Gleeson, H.F., Hill, E.W., Geim, A.K., and Novoselov, K.S.: Graphene-based liquid crystal device. Nano Lett. 8, 17041708 (2008).
29.Ponomarenko, L.A., Schedin, F., Katsnelson, M.I., Yang, R., Hill, E.W., Novoselov, K.S., and Geim, A.K.: Chaotic Dirac billiard in graphene quantum dots. Science 320, 356358 (2008).
30.Reina, A., Jia, X., Ho, J., Nezich, D., Son, H., Bulovic, V., Dresselhaus, M.S., and Kong, J.: Large area, few-layer graphene films on arbitrary substrates by chemical vapor deposition. Nano Lett. 9, 3035 (2008).
31.Kim, K.S., Zhao, Y., Jang, H., Lee, S.Y., Kim, J.M., Kim, K.S., Ahn, J-H., Kim, P., Choi, J-Y., and Hong, B.H.: Large-scale pattern growth of graphene films for stretchable transparent electrodes. Nature 457, 706710 (2009).
32.Li, X., Cai, W., An, J., Kim, S., Nah, J., Yang, D., Piner, R., Velamakanni, A., Jung, I., Tutuc, E., Banerjee, S.K., Colombo, L., and Ruoff, R.S.: Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324, 13121314 (2009).
33.Levendorf, M.P., Ruiz-Vargas, C.S., Garg, S., and Park, J.: Transfer-free batch fabrication of single layer graphene transistors. Nano Lett. 9, 44794483 (2009).
34.Dong, X., Li, B., Wei, A., Cao, X., Chan-Park, M.B., Zhang, H., Li, L-J., Huang, W., and Chen, P.: One-step growth of graphene–carbon nanotube hybrid materials by chemical vapor deposition. Carbon 49, 29442949 (2011).
35.Fan, Z., Yan, J., Zhi, L., Zhang, Q., Wei, T., Feng, J., Zhang, M., Qian, W., and Wei, F.: A three-dimensional carbon nanotube/graphene sandwich and its application as electrode in supercapacitors. Adv. Mater. 22, 37233728 (2010).
36.Paul, R.K., Ghazinejad, M., Penchev, M., Lin, J., Ozkan, M., and Ozkan, C.S.: Synthesis of a pillared graphene nanostructure: A counterpart of three-dimensional carbon architectures. Small 6, 23092313 (2010).
37.Lin, J., Zhong, J., Bao, D., Reiber-Kyle, J., and Wang, W.: Supercapacitors based on pillared graphene nanostructures. J. Nanosci. Nanotechnol. 12, 17701775 (2012).
38.Lahiri, I., Seelaboyina, R., Hwang, J.Y., Banerjee, R., and Choi, W.: Enhanced field emission from multi-walled carbon nanotubes grown on pure copper substrate. Carbon 48, 15311538 (2010).
39.Li, G., Chakrabarti, S., Schulz, M., and Shanov, V.: Growth of aligned multiwalled carbon nanotubes on bulk copper substrates by chemical vapor deposition. J. Mater. Res. 24, 28132820 (2009).
40.Wang, H., Feng, J., Hu, X., and Ng, K.M.: Synthesis of aligned carbon nanotubes on double-sided metallic substrate by chemical vapor deposition. J. Phys. Chem. C 111, 1261712624 (2007).
41.Delzeit, L., Nguyen, C.V., Chen, B., Stevens, R., Cassell, A., Han, J., and Meyyappan, M.: Multiwalled carbon nanotubes by chemical vapor deposition using multilayered metal catalysts. J. Phys. Chem. B 106, 56295635 (2002).
42.Perrot, P., Arnout, S., and Vrestal, J.: Copper – iron – oxygen; ternary alloy systems, in Landolt-börnstein database 11D3. Iron systems, Part 3, (Springer Materials, 2008), pp. 509539.
43.Askeland, D.R. and Phule, P.P.: The Science and Engineering of Materials (Thomson Learning, Independence, KY, 2005).
44.De Yoreo, J.J. and Vekilov, P.G.: Principles of crystal nucleation and growth. Rev. Mineral. Geochem. 54, 5793 (2003).
45.Wang, Z.L., Liu, Y., and Kluwer, Z.Z.: Handbook of Nanophase and Nanostructured Materials (Academic/Plenum Publishers, New York, NY, 2002).
46.Wang, C.P., Liu, X.J., Jiang, M., Ohnuma, I., Kainuma, R., and Ishida, K.: Thermodynamic database of the phase diagrams in copper base alloy systems. J. Phys. Chem. Solids 66, 256260 (2005).
47.Haluska, M., Hirscher, M., Becher, M., Dettlaff-Weglikowska, U., Chen, X., and Roth, S.: Interaction of hydrogen isotopes with carbon nanostructures. Mater. Sci. Eng., B 108, 130133 (2004).
48.Park, H.J., Meyer, J., Roth, S., and Skákalová, V.: Growth and properties of few-layer graphene prepared by chemical vapor deposition. Carbon 48, 10881094 (2010).
49.Baker, R.T.K.: Catalytic growth of carbon filaments. Carbon 27, 315323 (1989).
50.Cassell, A.M., Raymakers, J.A., Kong, J., and Dai, H.: Large scale CVD synthesis of single-walled carbon nanotubes. J. Phys. Chem. B 103, 64846492 (1999).
51.Sveningsson, M., Morjan, R.E., Nerushev, O.A., Sato, Y., Bäckström, J., Campbell, E.E.B., and Rohmund, F.: Raman spectroscopy and field-emission properties of CVD-grown carbon-nanotube films. Appl. Phys. A 73, 409418 (2001).
52.Li, Y., Zhang, X.B., Tao, X.Y., Xu, J.M., Huang, W.Z., Luo, J.H., Luo, Z.Q., Li, T., Liu, F., Bao, Y., and Geise, H.J.: Mass production of high-quality multi-walled carbon nanotube bundles on a Ni/Mo/MgO catalyst. Carbon 43, 295301 (2005).
53.Meyer, J.C., Geim, A.K., Katsnelson, M.I., Novoselov, K.S., Booth, T.J., and Roth, S.: The structure of suspended graphene sheets. Nature 446, 6063 (2007).
54.Meyer, J.C., Geim, A.K., Katsnelson, M.I., Novoselov, K.S., Obergfell, D., Roth, S., Girit, C., and Zettl, A.: On the roughness of single- and bi-layer graphene membranes. Solid State Commun. 143, 101109 (2007).
55.Futaba, D.N., Hata, K., Yamada, T., Hiraoka, T., Hayamizu, Y., Kakudate, Y., Tanaike, O., Hatori, H., Yumura, M., and Iijima, S.: Shape-engineerable and highly densely packed single-walled carbon nanotubes and their application as super-capacitor electrodes. Nat. Mater. 5, 987994 (2006).
56.Zhu, Y., Murali, S., Stoller, M.D., Ganesh, K.J., Cai, W., Ferreira, P.J., Pirkle, A., Wallace, R.M., Cychosz, K.A., Thommes, M., Su, D., Stach, E.A., and Ruoff, R.S.: Carbon-based supercapacitors produced by activation of graphene. Science 332, 15371541 (2011).
57.Yu, A., Roes, I., Davies, A., and Chen, Z.: Ultrathin, transparent, and flexible graphene films for supercapacitor application. Appl. Phys. Lett. 96, 253105 (2010).
58.Hu, L., Choi, J.W., Yang, Y., Jeong, S., La Mantia, F., Cui, L-F., and Cui, Y.: Highly conductive paper for energy-storage devices. Proc. Natl. Acad. Sci. U.S.A. 106, 2149021494 (2009).

Synchronous chemical vapor deposition of large-area hybrid graphene–carbon nanotube architectures

  • Maziar Ghazinejad (a1), Shirui Guo (a2), Wei Wang (a3), Mihrimah Ozkan (a4) and Cengiz S. Ozkan (a5)...


Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed