Skip to main content Accessibility help

Large-scale synthesis of highly aligned nitrogen doped carbon nanotubes by injection chemical vapor deposition methods

  • J. Liu (a1), R. Czerw (a1) and D.L. Carroll (a1)


In this study, we compare the effects of pyridine (C5H5N) and pyrimidine (C4H4N2) precursors, using ferrocene as a metal source, in the production of nitrogen containing multiwalled carbon nanotubes. Using standard chemical vapor deposition techniques, highly aligned mats of carbon-nitrogen carbon nanotube were synthesized. The maximum nitrogen concentration in these materials is between 1% and 2% when pyridine is used as the precursor and can be increased to 3.2% when pyrimidine is used as the precursor. However, the electronic structure of both materials, as determined using scanning tunneling spectroscopy, suggests that the nitrogen is incorporated into the nanotube lattice in the same way for both precursors.


Corresponding author

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


Hide All
1.Iijima, S.: Helical microtubules of graphitic carbon. Nature 354, 56 (1991).
2.Teter, D.M. and Hemley, R.J.: Low-compressibility carbon nitrides. Science 271, 53 (1996).
3.Miyamoto, Y., Cohen, M.L. and Louie, S.G.: Theoretical investigation of graphitic carbon nitride and possible tubule forms. Solid State Commun. 102, 605 (1997).
4.Hernandez, E., Goze, C., Bernier, P. and Rubio, A.: Elastic properties of single-wall nanotubes. Appl. Phys. A: Mater. Sci. Proc. 68, 287 (1999).
5.Doytcheva, M., Kaiser, M., Verheijen, M.A., Reyes-Reyes, M., Terrones, M. and de Jonge, N.: Electron emission from individual nitrogen-doped multi-walled carbon nanotubes. Chem. Phys. Lett. 396, 126 (2004).
6.Suenaga, K., Johansson, M.P., Hellgren, N., Broitman, E., Wallenberg, L.R., Colliex, C., Sundgren, J-E. and Hultman, L.: Carbon nitride nanotubulite-densely-packed and well aligned tubular nanostructures. Chem. Phys. Lett. 300, 695 (1999).
7.Yudasaka, M., Kikuchi, R., Ohki, Y. and Yoshimura, S.: Nitrogen-containing carbon nanotube growth from Ni phthalocyanine by chemical vapor deposition. Carbon 35, 195 (1997).
8.Sung, S.L., Tsai, S.H., Tseng, C.H., Chiang, F.K., Liu, X.W. and Shih, H.C.: Well-aligned carbon nitride nanotubes synthesized in anodic alumina by electron cyclotron resonance chemical vapor deposition. Appl. Phys. Lett. 74, 197 (1999).
9.Ma, X. and Wang, E.G.: CN x/carobn nanotube junctions synthesized by microwave chemical vapor deposition. Appl. Phys. Lett. 78, 978 (2000).
10.Reyes-Reyes, M., Grobert, N., Kamalakaran, R., Seeger, T., Goldberg, D., Rühle, M., Bando, Y., Terrones, H. and Terrones, M.: Efficient encapsulation of gaseous nitrogen inside carbon nanotubes with bamboo-like structure using aerosol thermolysis. Chem. Phys. Lett. 396, 167 (2004).
11.Terrones, M., Grobert, N., Zhang, J.P., Terrones, H., Olivares, J., Hsu, W.K., Hare, J.P., Cheetham, A.K., Kroto, H.W. and Walton, D.R.M.: Preparation of aligned carbon nanotubes catalysed by laser-etched cobalt thin films. Chem. Phys. Lett. 285, 299 (1998).
12.Terrones, M., Redlich, P., Grobert, N., Trasobares, S., Hsu, W-K., Terrones, H., Zhu, Y-Q., Hare, J.P., Reeves, C.L., Cheetham, A.K., Rühle, M., Kroto, H.W. and Walton, D.R.M.: Carbon nitride nanocomposites: Formation of aligned CxNy nanofibers. Adv. Mater. 11, 655 (1999).
13.Sen, R., Satishkumar, B.C., Govindaraj, A., Harikumar, K.R., Raina, G., Zhang, J-P., Cheetham, A.K. and Rao, C.N.R.: B–C–N, C–N, and B–N nanotubes produced by the pyrolysis of precursor molecules over Co catalysts. Chem. Phys. Lett. 287, 671 (1998).
14.Nath, M., Satishkumar, B.C., Govindaraj, A., Vinod, C.P. and Rao, C.N.R.: Production of bundles of aligned carbon and carbon-nitrogen nanotubes by the pyrolysis of precursors on silica-supported iron and cobalt catalysts. Chem. Phys. Lett. 322, 333 (2000).
15.Terrones, M., Terrones, H., Grobert, N., Trasobares, S., Hsu, W-K., Zhu, Y-Q., Hare, J.P., Kroto, H.W., Walton, D.R.M., Redlich, P.K., Rühle, M., Zhang, J.P. and Cheetham, A.K.: Efficient route to large arrays of CNx nanofibers by pyrolysis of ferrocene/melamine mixtures. Appl. Phys. Lett. 75, 3932 (1999).
16.Han, W-Q., Redlich, P.K., Seeger, T., Emst, F., Rühle, M., Grobert, N., Hsu, W-K., Chang, B-H., Zhu, Y-Q., Kroto, H.W., Walton, D.R.M., Terrones, M. and Terrones, H.: Aligned CN x nanotubes by pyrolysis of ferocene/C60 under NH3 atomosphere. Appl. Phys. Lett. 77, 1807 (2000).
17.Lee, C.J., Lyu, S.C., Kim, H-W., Lee, J.H. and Cho, K.I.: Synthesis of bamboo-shaped carbon-nitrogen nanotubes using C2H2–NH3–Fe(CO)5 system. Chem. Phys. Lett. 359, 115 (2002).
18.Sen, R., Satishkumar, B.C., Govindaraj, S., Harikumar, K.R., Renganathan, M.K. and Rao, C.N.R.: Nitrogen-containing carbon nanotubes. J. Mater. Chem. 12, 2335 (1997).
19.Andrews, R., Jacques, D., Rao, A.M., Derbyshire, F., Qian, D., Fan, X., Dickey, E.C. and Chen, J.: Continuous production of aligned carbon nanotubes: A step closer to commercial realization. J. Chen. Chem. Phys. Lett. 303, 467 (1999).
20.Terrones, M., Ajayan, P.M., Banhart, F., Blase, X., Carroll, D.L., Czerw, R., Foley, B., Grobert, N., Kamalakaran, R., Kohler-Redlich, P., Rühle, M., Seeger, T. and Terrones, H.: N-doping and coalescence of carbon nanotubes: Synthesis and electronic properties. Appl. Phys. A: Mater. Sci. Proc. 74, 355 (2002).
21.Liu, J., Czerw, R., Webster, S., Carroll, D.L., Park, J.H., Park, Y.W. and Terrones, M. Advances in CNx nanotube growth, in Nanotube-Based Devices, edited by Bernier, P., Carroll, D., Kim, G-T., and Roth, S. (Mater. Res. Soc. Symp. Proc. 772, Warrendale, PA, 2003), p. 105.
22.Scofiled, J.H.: Hartree-slater subshell photoionization cross-sections at 1254 and 1487 eV. J. Electron Spectrosc. 8, 129 (1976).
23.Tang, C., Bando, Y., Golberg, D. and Xu, F.: Structure and nitrogen incorporation of carbon nanotubes synthesized by catalytic pyrolysis of dimethylformamide. Carbon 42, 2625 (2004).
24.Shimoyama, I., Wu, G.H., Sekiguchi, T. and Baba, Y.: Evidence for the existence of nitrogen-substituted graphic structure by polarization dependence of near-edge x-ray-absorption fine structure. Phys. Rev. B 62, R6053 (2000).
25.Casanovas, J., Ricart, J.M., Rubio, J., Illas, F. and Jimenez-Mateos, J.M.: Origin of large N 1s binding energy in x-ray photoelectron spectra of calcined carbonaceous materials. J. Am. Chem. Soc. 118, 8071 (1996).
26.Webster, S., Maultzsh, J., Thomsen, C., Liu, J., Czerw, R., Terrones, M., Adar, F., John, C., Whitley, A. and Carroll, D.L.: Raman characterization of nitrogen doped multiwalled carbon nanotubes, in Nanotube-Based Devices, edited by Bernier, P., Carroll, D., Kim, G-T., and Roth, S. (Mater. Res. Soc. Symp. Proc. 772, Warrendale, PA, 2003), p. 129.
27.Glerup, M., Castignolles, M., Holzinger, M., Hug, G., Loiseau, A. and Bernier, P.: Synthesis of highly nitrogen-doped multi-walled carbon nanotubes. Chem. Comm. 20, 2542 (2003).
28.Feenstra, R.M.: Tunneling spectroscopy of the (110) surface of direct-gap III-V semiconductors. Phys. Rev. B 50, 4561 (1994).
29.Czerw, R., Terrones, M., Charlier, J-C., Blase, X., Foley, B., Kamalakaran, R., Grobert, N., Terrones, H., Tekleab, D., Ajayan, P.M., Blau, W., Rühle, M. and Carroll, D.L.: Identification of electron donor states in N-doped carbon nanotubes. Nano Lett. 1, 457 (2001).
30.Choi, H.J., Ihm, J., Louie, S.G. and Cohen, M.L.: Defect, quasibound states, and quantum conductance in metallic carbon nanotubes. Phys. Rev. Lett. 84, 2917 (2000).
31.Nevidomskyy, A.H., Csányi, G. and Payne, M.C.: Chemically active substitutional nitrogen impurity in carbon nanotubes. Phys. Rev. Lett. 91, 105502 (2003).


Related content

Powered by UNSILO

Large-scale synthesis of highly aligned nitrogen doped carbon nanotubes by injection chemical vapor deposition methods

  • J. Liu (a1), R. Czerw (a1) and D.L. Carroll (a1)


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.