326
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY
J. Nanosci. Nanotech. 2004, Vol. 4, No. 4 © 2004 by American Scientic Publishers 1533-4880/2004/04/326/020/$17.00+.25 doi:10.1166/jnn.2004.069
*
Author to whom correspondence should be addressed.
RESEARCH ARTICLE
1. INTRODUCTION
Carbon nanotubes were discovered by Iijima,
1
using the
arc discharge method to synthesize fullerenes. They were
multi-walled nanotubes, but soon it was realized that
single-walled carbon nanotubes (SWNTs) could be syn-
thesized in the presence of transition metal catalysts.
2, 3
SWNTs are promising materials because of their outstand-
ing mechanical, electrical, and thermal conductivity prop-
erties; therefore, great effort has been devoted to optimizing
their synthesis conditions. In addition to the arc discharge
method,
4
the laser ablation method,
5
and solar energy fur-
nace method
6
are all high temperature processes (2500–
5000 °C) with which carbon and metal catalysts are obtained
by evaporation of graphite and metal powders.
Concomitantly, catalytic methods were introduced with
which the carbon source is obtained from the decomposi-
tion of hydrocarbons (methane, ethylene, etc.) or CO on
supported metal particles
7–9
or on metal particles directly
injected into the reaction chamber.
10
The catalytic methods
operate at low temperature (800–1200 °C). Table I shows a
comparison of the various results obtained on supported
metal catalysts.
It can be seen that the presence of transition metals is
indispensable for the production of SWNTs. We shall come
On the Growth Mechanism of Single-Walled
Carbon Nanotubes by Catalytic Carbon Vapor
Deposition on Supported Metal Catalysts
J. B. Nagy,
a, *
G. Bister,
a, b
A. Fonseca,
a
D. Méhn,
a
Z. Kónya,
b
I. Kiricsi,
b
Z. E. Horváth,
c
and L. P. Biró
c
a
Nuclear Magnetic Resonance Laboratory, Facultés Universitaires Notre-Dame de la Paix, Namur, Belgium
b
Applied and Environmental Chemistry Department, University of Szeged, Szeged, Hungary
c
Research Institute for Technical Physics and Materials Science, Budapest, Hungary
A comprehensive kinetic study was performed to throw light on the formation mechanism of single
walled carbon nanotubes (SWNTs) in chemical vapor deposition processes. SWNTs were synthe-
sized by catalytic decomposition of methane or ethylene on supported transition metal catalysts.
Kinetic curves (the amount of SWNT as a function of time) were obtained as a function of the nature
and the preparation of the supported catalysts, temperature, the uxes of the gases (the reagent
hydrocarbon and the carrying gas), and the partial pressure of the hydrocarbon. The nal products
were characterized by transmission electron microscopy, Raman spectroscopy, chemical analysis,
and thermogravimetric measurements. The fundamental factors determining the SWNT formation
are discussed in detail, taking into consideration several observations from the literature as well.
Keywords: Nanotube, Growth, Synthesis, Mechanism, Catalyst, Catalytic Chemical Vapor Depo-
sition, Carbon.
back to their role later in the discussion on the mechanism
of SWNT formation.
In most cases the supports used are Al
2
O
3
, SiO
2
, SiO
2
/
Al
2
O
3
, MgO, Y zeolite, CaSiO
3
, or ZrO
2
. For special appli-
cations, metal lms were also used.
32
The pyrolysis of
tripropylamine occluded in the AlPO
4
-5 linear channels
merits particular attention.
30, 31
Indeed, SWNTs having the
smallest diameter known of 0.4 nm could be obtained,
because the diameter was imposed by the diameter of the
channel (0.73 nm). It has to be emphasized that a strong
metal support interaction is present in most of the systems
studied.
The methods of preparation are quite varied. In many
cases, however, the simplest method of direct impregna-
tion by precursor solutions was used. The main purpose is
the highest dispersion for metal particles. Indeed, the dia-
meter of isolated nanoparticles directly inuences the
diameter of the SWNTs.
8, 9, 21
In the formation of a solid solution by combustion syn-
thesis, the metal ion precursor is also highly dispersed: ¬ -
Al
222 x
Fe
2x
O
3,
11–14
Mg
0.8
M
y
M9
2
Al
2
O
4
with M or M95
Fe, Co, or Ni,
22
or Mg
0.9
Co
0.1
O
24,25
or Mo
x
Co
y
Mg
1 2x 2y
O.
28
In these cases a direct inorganic SWNT composite can be
obtained.
Special cases include the formation of a LaFeO
3
per-
ovskite phase,
36
the mechanical mixing of the metal pow-
der and the support,
41
spin coating of Fe/Mo on Pb(Zr
0.5