Growth Mechanisms of Carbon Nanotubes

Jean-Christophe Charlier1 and Sumio Iijima2,3

1
Université Catholique de Louvain
Unité de Physico-Chimie et de Physique des Matériaux
Place Croix du Sud, 1, Bâtiment Boltzmann,
1348 Louvain-la-Neuve, Belgium
charlier@pcpm.ucl.ac.be
2
NEC Corporation, R & D Group
34 Miyukigaoka, Tsukuba, Ibaraki 305, Japan
3
Meijo University, Faculty of Science and Engineering
1-501, Shiogamaguchi Tenpaku, Nagoya, Aichi 4688502, Japan
iijimas@meijo-u.ac.jp

Abstract. This review considers the present state of understanding of the growth
of carbon nanotubes based on TEM observations and numerical simulations. In the
highlights of these experimental and theoretical approaches, various mechanisms,
already proposed in the literature, for single and multi-shell nanotubes nucleation
and growth are reviewed. A good understanding of nanotube growth at the atomic
level is probably one of the main issues either to develop a nanotube mass pro-
duction process or to control growth in order to obtain well-designed nanotube
structures.

Nearly ten years after their discovery [1], carbon nanotubes (CNs) are still
attracting much interest for their potential applications, which largely de-
rives from their unusual structural and electronic properties. Since all these
properties are directly related to the atomic structure of the tube, it is es-
sential to understand what controls nanotube size, the number of shells, the
helicity, and the structure during synthesis. A thorough understanding of
the formation mechanisms for these nanotubular carbon systems is crucial
to design procedures for controlling the growth conditions to obtain more
practical structures, which might be directly available for nanotechnology.
In order to optimize the single- and multi-walled nanotube yield and qual-
ity, three main production methods have been used up to now for their synthe-
sis. Multi-wall carbon nanotubes [1,2] typically grow on the cathode during
an arc discharge between two graphitic electrodes (temperature ∼3000 K).
Single-wall carbon nanotubes were first observed in the arc discharge appa-
ratus by co-evaporating iron [3] or cobalt [4] (as metal catalysts) in a methane
atmosphere. The discovery of a single-shell tube stimulated intense research
to find an efficient way to produce bundles of ordered single-wall nanotubes
(called ropes).
The laser ablation technique uses two lasers to vaporize a graphite tar-
get mixed with a small amount of Co and/or Ni in order to condense the
M. S. Dresselhaus, G. Dresselhaus, Ph. Avouris (Eds.): Carbon Nanotubes,
Topics Appl. Phys. 80, 55–81 (2001)


c Springer-Verlag Berlin Heidelberg 2001
56 Jean-Christophe Charlier and Sumio Iijima

carbon into single-wall tubes. Through this technique [5], the growth condi-
tions are well controlled and maintained over for a long time, leading to a
more uniform vaporization. Another technique [6], based on the carbon-arc
method, also provides similar arrays of single-wall nanotubes, produced from
an ionized carbon plasma which is generated by joule heating during the
discharge. Both techniques synthesize, with yields of more than 70–90 per-
cent, single-wall nanotubes (∼1.4 nm in diameter) self-organized into bundles.
These ropes, which consist of up to a hundred parallel nanotubes packed in
a perfect triangular lattice, are typically more than one-tenth of a millimeter
long and look very promising for engineering applications. Another attrac-
tive synthesis technique, based on a vapor phase growth mechanism which
utilizes the decomposition of hydrocarbons at a temperature of ∼1500 K, has
also been recently used to produce large quantities of rope-like bundles of
high-purity single-wall nanotubes at a very low cost [7]. However, methods
for large-scale production have not really been developed, probably because
so little is understood about the synthesis process at the microscopic level.
In the following, we will address from both an experimental and a theo-
retical point of view, the growth of carbon nanotubes. One of our objectives
will be to show that presently available simulation techniques (semi-empirical
and ab initio) can provide quantitative understanding not only of the stabil-
ity, but also of the dynamics of the growth of carbon nanotube systems. We
will try to summarize the microscopic insight obtained from these theoretical
simulations, which will allow us to isolate the essential physics and to propose
good models for multi-shell and single-shell nanotube growth, and to analyze
a possible consensus for certain models based on experimental data.

1 Experimental Facts for Growth Models

In spite of the enormous progress in synthesis techniques, the theoretical un-
derstanding of the growth of mutli-wall and single-wall nanotubes has lagged
behind. Transition metal catalysts are necessary to produce single-wall nano-
tubes, but are not required for producing multi-wall nanotubes, suggesting
different growth mechanisms. In each synthesis method, the selective for-
mation of a single-wall tube is triggered by enriching the graphite source
material with a single species or a mixture of transition metal catalysts (Co,
Ni, Y,...). Experiments show that the width and the diameter distribution
depend on the composition of the catalyst, the growth temperature, and
various other growth conditions. Since the electric arc-discharge [6] and the
laser-ablation [5] techniques lead to very similar materials, a unique mech-
anism for single-wall nanotube growth should be found. Such a mechanism
should not strongly depend on the details of the experimental conditions, but
more on the kinetics of carbon condensation in a non-equilibrium situation.
The necessity of transition metal catalysts for the synthesis of single-wall
tubes is obvious as they do not grow in the absence of catalysts. However,