Materials Science and Engineering A286 (2000) 11 – 15

www.elsevier.com/locate/msea

Carbon nanotube arrays

Sishen Xie * , Wenzhi Li, Zhengwei Pan, Baohe Chang, Lianfeng Sun
Institute of Physics and Center for Condensed Matter Physics, Chinese Academy of Sciences, PO Box 603, Beijing 100080, PR China

Abstract

As a new frontier in low-dimensional material and nanotechnology, carbon nanotubes research has significant potential for
scientific breakthrough and technological innovation. The corporations of scientists in materials and physics as well as chemistry,
for example, are already beginning to bear fruit. However, the fabrication in large-scale and high quality of carbon nanotubes is
still an essential problem, which entirely correlates with basic properties and potential applications of nanotubes. In this paper,
we outline the recent progress about fabrication of aligned and very long carbon nanotubes, which has been done in our research
group. Carbon nanotube arrays were prepared by chemical vapor deposition (CVD) of hydrocarbon gas on various substrates.
The effect of substrates on the growth, morphology and structure of carbon nanotubes were investigated. Aligned carbon
nanotubes with high density and purity were achieved by CVD on bulk silica substrate. On the film-like substrates, very long
carbon nanotubes of length 2 mm were produced, which is an order of magnitude longer (1 mm vs. 100 mm) than that described
in most previous reports. Published by Elsevier Science S.A.

Keywords: Morphology; Chemical vapor deposition; D-band

1. Introduction substrates on the carbon nanotube growth, they devel-

The discovery of carbon nanotubes (CNTs) [1] has
stimulated great interest in scientific communities [2,3].
Large quantities of CNTs can now be produced by
either arc-discharge [4] or thermal decomposition of
hydrocarbons [5]. Controlled growth of carbon nan-
otubes, both with regard to their length and diameter
and aligmnent, is important either for potential applica-
tions or for detailed characterization of their properties.
It may be a new thought to directly produce aligned
and isolated CNTs by thermal decomposition of hydro-
carbon gas. Because substrates containing catalyst will
affect the growth of CNTs, many works were focused
on the improvement on the substrate [6,7]. In principle,
mesocopic pores distributed in mesoporous substrate
have special effects on the formation and property of
low-dimensional materials formed on the substrate. Li
et al. [8] have studied the impact of various substrates,
especially the mesoporous substrates, on the growth
and morphology of the CNTs. On the basis of system-
atic studies of the effect of as-formed mesoporous
* Corresponding author. Tel.: +86-10-62582078; fax: + 86-10-
62562605.
E-mail address: ssxie@aphy.iphy.ac.cn (S. Xie)
oped a new method to prepare substrates with aligned
pores in which catalyst particles were embedded, and
subsequently, they produced the aligned, isolated, and
dense CNTs on these mesoporous substrates by CVD
[9]. At the same time, Terrones et al. [10] prepared the
aligned nanotubes using laser etched cobalt thin film as
a substrate, in which the tubes grew perpendicularly to
the catalytic substrate ‘only’ in the etched regions. Pan
et al. [11] described the very long (length 2 mm)
aligned nanotubes with uniform length and diameter,
which were prepared by deposition of organic gas over
iron nanoparticles on the surface of the film-like meso-
porous silica. Recently, Ren et al. [12] and Fan et al.
[13] reported the aligned nanotubes grown on the glass
or silicon substrates, respectively.
Here we will discuss the morphology and structure of
CNTs grown on different substrates and the facts that
determine the growth of CNTs. Raman scattering was
performed directly on the as-formed aligned carbon
nanotubes to elucidate the dependence of Raman peak
positions and intensities on the microstructures. Per-
haps, the long and aligned nanotubes are help for both
basic research and potential applications, for example,
strong composite materials and field emission sources.

0921-5093/00/$ - see front matter Published by Elsevier Science S.A.

PII: S 0 9 2 1 - 5 0 9 3 ( 0 0 ) 0 0 6 5 7 - 2
12 S. Xie et al. / Materials Science and Engineering A286 (2000) 11–15
2. Experimental procedure
The experimental procedures employed in the growth
of the aligned CNTs are described as follows:
2.1. Aligned carbon nanotubes production on the bulk
silica substrates
The mesoporous silica substrate with aligned pores
was prepared by a sol – gel process from tetraethoxysilane
((C2H5O)4Si) hydrolysis in iron nitrate aqueous solution
[9]. Analytically pure tetraethoxysilane, ethyl alcohol and
iron nitrate aqueous solution (0.1 – 1.5 M) were mixed
with mole ratio 1:4:(10 14) by magnetic stirring. Then
0.2 ml concentrated hydrogen fluoride or hydrochloric
acid was added into per 30 ml mixture, and the mixture
was stirred for 45 min. After gelation of the mixture, the
gel was dried for 1 week at 60°C to eliminate the excess
water and other solvents. Then the gel was calcined 10
h at 450°C at 10 − 2 torr, in which the relative uniform
pores were formed and embedded by iron oxide nanopar-
ticles. Subsequently, the iron oxide nanoparticles con-
tained in the gel was reduced into iron particles.
Afterwards, a mixture of acetylene and nitrogen was
introduced into the reaction chamber at a flow rate of
110 cc min − 1 and with volume ratio 1:10. During the
reaction, the gas pressure in the chamber was maintained
at 180 torr, and CNTs were formed on the substrate by
the decomposition of acetylene at 700°C.
2.2. Very long aligned carbon nanotubes production on
the film-like silica substrates
The method is similar to that reported by Li et al. [9],
but some improvements on substrate preparation have
been made to obtain the film-like substrate with thickness
of 30–50 mm. The substrates were calcined at 450°C for
10 h under vacuum and then reduced at 500°C for 5 h
in a flow of 9% H2/N2 under 180 torr. At this stage, large
quantities of iron/silica nanoparticles, which acted as a
catalyst for nanotube growth, formed evenly on all
surfaces of the substrates. Afterwards, this gel was used
as a substrate for production of CNTs under the condi-
tions mentioned above. This method can produce carbon
nanotubes with very high yield. Every surface of the
substrate was covered with a nanotube array composed
of large quantities of highly aligned nanotubes. The
length of the nanotube arrays increased with the growth
time, and reached about 2 mm after 48 h growth. We
believe that the length of the nanotubes could be even
longer if the growth time was further increased [11].
3. Results and discussions
The procedure to prepare large quantities of CNTs by
catalytic pyrolysis of organic gas is easily manipulated by
controlling the catalyst particles. In general, the distribu-
tion and size of the CNTs are determined by the catalyst
particles, and have almost the same diameter as catalyst
particles on which the CNTs grow. Theoretical work
indicates that there is a critical radius of the catalyst
particles, and CNTs can only grow on the catalyst
particles with radii smaller than the critical value rather
than those with radii bigger than the critical value [14].
Meanwhile, the well dispersion of catalyst particles on
the substrate also takes a very important role in prepar-
ing pure CNTs with small diameter and uniform thick-
ness.
3.1. Aligned carbon nanotubes
Silica substrate prepared by the sol–gel method has
many aligned mesocopic pores in which catalyst particles
were embedded during the substrate formation, and
CNTs formed on the silica have distinguished morphol-
ogy and structure. Fig. 1A is an scanning electron
microscope (SEM) image of the CNTs layer with a
thickness of about 50 mm. Generally, the thickens of the
CNTs depends on the growth time, pressure and density
of the reacting gases. Under the conditions described
above, the growth rate of CNTs is about 20 mm h − 1.
However, with increasing growth time, the CNTs become
slightly curved. High-magnification SEM image (Fig. 1)
clearly shows that the CNTs formed on the silica
substrate are aligned and approximately perpendicular to
the surface of the substrate. One can see that CNTs with
diameter of about 30 nm are isolated with spacing about
100 nm. Basically, the diameters of CNTs are determined
by the catalyst particles which are embedded in the
substrate, so we can reproduce a specific substrate to
obtain CNTs with the same diameter by applying the
same conditions. Using this method, CNTs with diame-
ters between 7 and 30 nm have been prepared. On the
other hand, the growth direction of the CNTs are
determined by that of the pores because of their template
effect. In order to verify the template effect of the
nanometer pores on the growth direction of the nan-
otubes, mesoporous silica was ground into powder in
micrometers, then the powder was pressed into a pallet
which was used as substrate to produce CNTs under the
same conditions described above. As a result, a thick
layer of CNTs formed on the pallet, this CNTs layer was
composed of randomly grown tubes (Fig. 2). This
indicates that the broken alignment of the pores caused
by grinding make CNTs grow randomly on the pallet.
In addition, whether the pores can take template effect
is also determined by their size. Pores with large diame-
ters cannot take template effect on the tube growth. For
example, CNTs with a diameter of 30 nm can be formed
on the silica substrate with pores 300 nm in diameter, but
these tubes grow randomly (Fig. 3).
 S. Xie et al. / Materials Science and Engineering A286 (2000) 11–15
Fig. 1. (A) Low-magnification SEM image of CNTs formed on silica
substrate with aligned pores, the CNTs are of about 50 mm long. (B)
High-magnification SEM image of aligned CNTs shows that most
nanotubes are approximately perpendicular to the surface of the
substrate.
Fig. 2. CNTs formed on the silica pallet prepared by repressing the
silica powder (see text).
13
Fig. 3. CNTs with diameter of 30 nm grew randomly on silica
substrate with pores 300 nm in diameter.
EDX spectra taken from the tips of aligned tubes
show that the tips are composed mainly of carbon and
a small amount of iron (98.76 and 1.09 wt.%, respec-
tively). Some areas of the tube tips contain trace
amounts of silicon and oxygen, both less 0.2 wt.%,
which may be attributed to small silica fragments. EDX
spectra taken from central parts of the tubes show only
a carbon peaks; tubes filled with iron particles in the
central parts were not detected.
By using large area mesoporous silica substrates,
aligned carbon nanotubes with several square millime-
ters have been prepared. The substrate has been suc-
cessfully removed to retain aligned tubes with neat
roots (Fig. 4A). High-magnification SEM image (Fig.
4B) of the tube roots shows that these tubes roots are
isolated and have almost the same diameter, no other
catalyst particles are observed. EDX spectra collected
from the tube roots demonstrate the presence of carbon
alone, neither silicon nor iron could be detected, indi-
cating no impurity was attached in (or on) the tube
roots.
3.2. Very long aligned carbon nanotubes
Very long aligned carbon nanotubes array were
formed on film-like silica substrate. SEM image (Fig.
5A) shows that carbon nanotubes grow outwards per-
pendicularly from both sides of the film-like substrate
(indicated by an arrow) to form two arrays with a
length of about 2 mm. High magnification SEM show
that nanotubes within these arrays are of uniform
external diameter ( 20–40 nm) with a spacing of
about 100 nm between the tubes. Most of the nan-
otubes in the arrays are highly aligned, although a few
14 S. Xie et al. / Materials Science and Engineering A286 (2000) 11–15

of them appear to slightly tangle or curve. The arrays

can be easily stripped off from the substrates, and SEM
observations of the surfaces of the resulting substrates
show that the iron/silica nanoparticles, which were
present on the surfaces of the substrates before nan-
otube growth, disappear after nanotube growth. But
subsequent reduction of the resulting substrates can
transport most catalyst particles onto the surfaces of
the substrates from within the bulk. Therefore, the
resulting substrates can be reused after reduction to
grow new nanotube arrays with characteristics similar
to the original ones.
In order to confirm whether the superlong nanotubes
really grow unbroken from the bottom to the top
within the nanotube arrays, we cleaved some thinner
nanotube bundles (Fig. 5B) from the arrays and mea-
sured their resistivity from room temperature to 10 K
by a four-probe method. The temperature dependence
was semiconductor-like for most samples, but metallic
behavior was also seen (r  10 − 2 – 10 − 3 Vcm and dr/
dT :10 − 5 –10 − 6 Vcm K − 1 at room temperature).
Fig. 4. SEM images of aligned tube roots obtained by removing the
silica substrate. (A) Low-magnification SEM image of the tube roots.
(B) high-magnification SEM image of the tube roots.
Fig. 5. SEM images of very long CNTs. (A) Very long CNTs arrays
formed on both sides of the film-like substrate (indicated by an
arrow). (B) A nanotube boundle cleaved from a nanotube array along
the growth direction of the tubes. The total length of the bundle is
about 2 mm.
This resistivity is an order of magnitude larger than the
values reported previously [15,16], presumably due to
the presence of large amount of defects in our super-
long nanotubes. The above experimental results indi-
cate that these superlong nanotubes indeed grow
continuously without any interruption within the nan-
otube arrays.
High-resolution transmission electron microscope
(HRTEM) image show that the aligned CNTs are well
graphitized and consist of several tens of concentric
shells of carbon sheets with spacing about 0.34 nm (Fig.
6). Most CNTs are straight, and others are curved due
to the defects resulted from low temperature (−700°C)
growth of tubes.
 S. Xie et al. / Materials Science and Engineering A286 (2000) 11–15
Fig. 6. HRTEM images of the well-graphitized nanotube consisting
of several tens of concentric graphene sheets with a spicing of 0.34
nm. This tube is open-ended on the right side.
3.3. Raman scattering on aligned carbon nanotubes
Raman spectrum of the aligned CNTs shows a very
strong peak at 1581 cm − 1 (G band) with a shoulder at
1617 cm − 1 (D% band) and a strong peak at 1348 cm − 1
(D band). One of the significant differences of Raman
spectra between CNTs produced by CVD and arc-dis-
charge methods [17,18] is the intensity of Raman band
at 1348 cm − 1. Combined with the SEM and HRTEM
studies of the present aligned CNTs, the appearance of
the strong D band can be interpreted as: (1) the lower
graphitization degree of the CNTs or turbostratic struc-
tures formed in some carbon sheets in the tubes; (2) the
highly compacted aligned tubes. In a word, the large
amount of crystalline domains on the nanometer scale
and surface of tubes must account for the enhancement
of D band. The details on Raman scattering of aligned
carbon nanotubes was described elsewhere [19].
4. Conclusions
Growth of CNTs produced by CVD was affected by
both the catalyst particles and the structure of the
substrate. The pores in the bulk substrate take template
effect during the tube growth. In the case of the film-
like substrates, the tip growth mechanism is dominated
and leads to produce the very long aligned carbon
nanotubes. TEM and Raman studies show that the
tubes are well graphitized, the appearance of strong D
band indicates that nanometer scale turbostratic struc-
15
ture may be formed in carbon tubes. Large area
aligned, pure and dense CNTs produced by using these
methods may be useful for their applications.
Acknowledgements
This work was supported by the National Natural
Science Foundation of China.
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