Carbon 42 (2004) 829–835

www.elsevier.com/locate/carbon

Effect of hydrocarbons precursors on the formation of carbon

nanotubes in chemical vapor deposition
Qingwen Li, Hao Yan, Jin Zhang *, Zhongfan Liu
Center for Nanoscale Science and Technology (CNST), College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, PR China
Received 7 July 2003; accepted 17 January 2004

Abstract
High-temperature decomposition of hydrocarbons may lead to the formation of carbon deposits. However in our present studies,
we found that the morphology of carbon deposits over MgO supported Fe catalyst during chemical vapor deposition (CVD) process
was closely related to the thermodynamic properties and chemical structures of hydrocarbon precursors. Six kinds of hydrocarbons
(methane, hexane, cyclohexane, benzene, naphthalene and anthracene) were used as carbon precursors in this study. Methane which
has a pretty simple composition and is more chemically stable was favorable for the formation of high-purity single walled carbon
nanotubes (SWNTs). For high-molecular weight hydrocarbons, it was found that the chemical structures rather than thermody-
namic properties of carbon precursors would play an important role in nanotube formation. Specifically, the CVD processes of
aromatic molecules such as benzene, naphthalene and anthracene inclined to the growth of SWNTs. While the cases of aliphatic and
cyclic hydrocarbon molecules seemed a little more complicated. Based on different pyrolytic behaviors of carbon precursors and
formation mechanism of SWNTs and multi-walled carbon nanotubes (MWNTs), a possible explanation of the difference in CVD
products was also proposed.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: A. Carbon precursor; B. Chemical vapor deposition; C. Raman spectroscopy; D. Thermodynamic properties

1. Introduction best approach for low-cost and large-scale synthesis of

high-quality nanotube materials [11,12].
Since the discovery by Iijima [1], carbon nanotubes As the growth mechanism of carbon nanotube in
have drawn much attention and interest due to their CVD process generally involves the dissociation of
myriad properties and potential applications [2–4]. carbon precursors into carbon atoms, dissolution and
Carbon nanotubes can be classified into single-walled saturation of these atoms in the catalyst metal particles
nanotubes (SWNTs) and multi-walled nanotubes and further precipitation into tubular carbon deposits, it
(MWNTs), which may exhibit unique properties due to is obvious that the types of carbon precursors, furnace
their different atomic structures [5]. It is therefore of temperature, types and particle size of catalysts, and
great significance to comprehensive understanding of types of support materials may greatly affect the growth
the growth mechanism and hence better control of the process of carbon nanotubes. Among these growth
structure properties of the products. Till now, carbon conditions, carbon precursors would undoubtedly play a
nanotubes can be synthesized with arc-discharge, laser key role to affect the structure properties of carbon
ablation, catalytic chemical vapor decomposition deposits. Several hydrocarbons have been used as pre-
(CVD), flame synthesis, solar energy route, etc. [6–10]. cursors for the CVD growth of carbon nanotubes. For
Arc-discharge and laser ablation methods may yield example, Dai and coworkers [11] reported the synthesis
high-quality product. It is however difficult to scale up of high-quality SWNTs with methane and alumina
the production. In contrast, the CVD method has be- supported Fe catalyst at 900 °C. Besides, benzene has
come more popular and considered at the moment the been applied to large-scale production of SWNTs with a
floating catalyst method [13]. On the other hand, Benito
*
Corresponding author. Tel./fax: +86-10-6275-7157.
et al. also reported the growth of MWNTs and carbon
E-mail addresses: [email protected] (J. Zhang), lzf@chem. fibers from benzene CVD [14]. However, there is little
pku.edu.cn (Z. Liu). systematic study on the effect of carbon precursors using
0008-6223/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2004.01.070
830 Q. Li et al. / Carbon 42 (2004) 829–835

a given set of reaction parameters (catalyst, reaction final spectra presented were obtained by averaging at
time, growth mode, etc.) up to now. Investigating the least 15 spectra recorded at different points over entire
CVD product of different carbon precursors within the sample surface.
same reaction system is thus crucial towards under- Thermogravimetric analysis (TGA) was conducted
standing how nanotube formation is influenced by the on a Universal V25H TA instrument. For a typical
features of carbon precursors. experiment,
5 mg purified sample was put in an alu-
In the present study, we addressed this issue by mina crucible and heated in airflow, at a rate of 10 °C/
selecting six hydrocarbons, including methane which min to 800 °C.
was relatively chemically stable at high temperature and Scanning electron microscopy (SEM) was conducted
easily decomposable than high-molecular weight on a JEOL JBM-6301F instrument operating at 25 kV.
hydrocarbons such as saturated aliphatic hexane, For SEM characterization, the purified samples were
unsaturated cyclohexane, and aromatic benzene, naph- dispersed in 1,2-dichlorobenzene to form a brownish
thalene and anthracene as carbon precursors for the solution. A few drops of this solution was then dripped
catalytic decomposition studies with fixed-bed growth on Si wafer and left dry. Transmission electron
mode. It was found that in comparison with their microscopy (TEM) was performed on a Hitachi 810
pyrolytic behaviors, the chemical structures of carbon instrument operating at 200 kV. The samples for TEM
precursors played a much more important role in characterization were dispersed in deionized water and
nanotube formation. Methane and aromatic molecules dripped on copper grid.
were found to favor the growth of SWNTs. Although
aliphatic hydrocarbons of high-molecular weight such as
hexane and cyclohexane which were more chemically 3. Results and discussion
unstable than methane showed similar thermodynamic
parameters, the morphology of as-prepared carbon Gaseous hydrocarbons, such as CH4 , C2 H4 and
deposits was more complicated. Cyclohexane was C2 H2 , have been widely used for the formation of car-
capable of the formation of both SWNTs and MWNTs, bon nanotube deposits. The growth condition for
depending on the ambience. Nevertheless, carbon flakes SWNTs is a bit more rigorous than that for MWNTs,
were mainly formed when hexane was input. The dif- which needs a higher temperature and is more depen-
ference in the nanotube formation is tried to understand dent on the preparation of catalysts. Moreover, methane
by combining their different pyrolytic behaviors and is more preferred for the growth of high-purity SWNTs
growth mechanisms for single-walled and multi-walled rather than any other gaseous hydrocarbons, as it is
nanotubes. comparatively chemically stable at high-temperature
and has the simplest structure. The benefits from the
combination of these two features are supposed to result
2. Experimental in the formation of uniform fragments for the further
growth of single walled carbon nanotubes. However, the
Carbon nanotubes were synthesized by chemical achievement for methane CVD growth of single-walled
vapor deposition of hydrocarbons over MgO supported carbon nanotube deposits would largely depend on the
Fe catalyst, which was prepared by chemical impregna- features of catalysts as well. In our previous study, we
tion method [15]. Briefly, 1 g alkaline magnesium car- found that MgO supported Fe catalyst was highly
bonate was immersed in 10 ml Fe(NO3 )3 Æ 9H2 O aqueous effective for the high-purity formation of SWNTs [15].
solutions (10 mg/ml), followed by sonication and drying Due to the strong interaction between Fe species and
to yield a yellowish powder. The obtained catalyst was MgO support, the catalyst particles may remain well-
then inserted into a tube furnace and heated to desired dispersed status at an elevated temperature, thus keep-
temperature (500–850 °C) in Ar atmosphere at a flow ing their activity and avoiding amorphous carbon
rate of 300 sccm. Carbon sources were fed in by passing deposition. Fig. 1 showed typical Raman and SEM
100 sccm Ar through liquid hydrocarbons (hexane, characterization results of SWNT products obtained by
cyclohexane and benzene) or by heating solid hydro- methane CVD over MgO supported Fe catalysts at an
carbons (naphthalene and anthracene) in an evaporator optimized temperature (750–900 °C) and after removal
set at
150 °C. The reaction time was 30 min, after of MgO and Fe impurities with HCl. In Raman spectra,
which the system was cooled down to room tempera- the radial breath mode (RBM) within the band 100–300
ture. The as-prepared carbon soot was sonicated in 37% cm1 is characteristic of SWNTs [16]. Other signals such
HCl and successively in water to remove the catalyst. as D- and G-bands centered at 1350 and 1590 cm1 can
Micro-Raman experiments were carried out with serve as rough evaluation of the purity of tube products
Renishaw system 1000 in ambient atmosphere and at [16,17]. Raman analysis revealed that SWNTs grown on
room temperature. Raman spectra were recorded using this kind of catalysts showed stronger intensity of RBM
50 mW He–Ne laser (632.8 nm) and CCD detector. The peaks and lower intensity of the D-line. High IG =ID ratio
 Q. Li et al. / Carbon 42 (2004) 829–835 831

comparable to that of high-quality SWNTs prepared by

methane CVD [21]. In SEM image (Fig. 2b), rope-like
bundles, tens of nanometers in diameter, could be ob-
served. High-resolution TEM (Fig. 3) showed that these
bundles consisted of SWNTs with typical diameter of

1 nm. The nanotubes had clear and integrated side-
walls, indicating very little amorphous carbon or de-
fects. Combining Raman, SEM and TEM, it can be
concluded that high-quality SWNTs were formed when
benzene was used as carbon source.
When cyclohexane was introduced as carbon pre-
cursors, the deposit gave a quite different Raman spec-
trum (Fig. 2a), as no RBM peaks but strong D-band
was observed. Thick tubes (20–40 nm in diameter) could
Fig. 1. Raman spectrum and SEM image of SWNTs prepared with be seen in SEM image, suggesting the formation of
methane as carbon source. MWNTs (Fig. 2c). As for hexane, Raman spectrum
indicated no SWNTs in the sample (Fig. 2a), and SEM
revealed that most deposits consisted of flake-like
(
15) indicated that the prepared SWNT material was impurities (Fig. 2d).
of good purity and quality. SEM image (inset of Fig. 1) Thermogravimetric analysis (TGA) can be used to
showed that abundant SWNTs were formed in bundles study the thermal stability of carbon deposits and
and highly entangled. to distinguish the forms of carbon species according to
Besides gaseous hydrocarbons, some liquid hydro- their different combustion temperatures. Fig. 4 showed
carbons such as hexane, benzene, toluene and xylene, the TGA curves of carbon deposits prepared with dif-
etc. have been also effectively used for the growth of ferent six-carbon sources. For the sample prepared with
SWNTs and MWNTs with floating CVD methods [18– benzene, the derivative of weight loss gave a peak at 598
20], in which ferrocene is sublimated or injected as cat- °C, which could be attributed to the combustion of
alysts. The MgO–Fe catalyst has been proved to be a SWNTs [22]. As there was only one peak in the weight
good catalyst for the CVD growth of SWNT by meth- loss curve, the purity of the sample was high, which was
ane, does it also work well for some liquid hydro- correspondent with Raman and SEM results. For
carbons? According to the widely accepted growth cyclohexane as carbon source, the weight loss peak was
mechanism of carbon nanotube in CVD process, hydro- centered at 618 °C. Combined with Raman and SEM
carbon precursors are supposed to thermally decompose results, it could be ascribed to the combustion of
and dissociate into carbon atoms first, then dissolve in MWNTs, which agreed well with previous work [23].
catalytic metal particles until saturation and lastly pre- The fact that MWNTs showed higher thermal stability
cipitate into tubular carbon deposits. So in this sense, than SWNTs might be due to the strong interaction
the intention for us to choose liquid hydrocarbons is between graphene layers in MWNTs, which stabilized
to see if these carbon sources may promote the forma- their structures and made them more inert. With respect
tion of tube deposits since they are much more easily to hexane as carbon source, a board peak centered at
decomposed than methane at high temperatures. In 638 °C could be attributed to the combustion of flake-
our experiment, hexane, cyclohexane and benzene were shaped graphite. This sample showed even higher sta-
tentatively selected for the study, as they typically rep- bility than MWNTs, since graphite sheets were generally
resent different kinds of hydrocarbons (i.e. aliphatic, better crystallized than tubular structures.
cyclic and aromatic) and contain the same number of Table 1 showed the thermodynamic parameters of the
carbon atoms in each molecule. Making a comparison thermally decomposed reactions of some concerned
between them will be helpful for us to understand the hydrocarbons in this study [24]. First, it could be found
effect of the features of chemicals on the formation of that the Gibbs free energies of hexane, cyclohexane and
tube deposits over MgO–Fe catalysts. benzene were pretty lower than that of methane at 800
Fig. 2 showed the Raman spectra and SEM images of °C, which meant at a same temperature these three li-
carbon deposits prepared with different carbon sources. quid hydrocarbons are more seriously decomposed than
For the sample prepared with benzene, the Raman methane and they would have lower decomposition
spectrum was typical of SWNTs, as indicated by strong temperature. However, lower decomposition tempera-
RBM peaks and weak D-band (Fig. 2a). According to ture did not give rise to the lower formation temperature
Bandow’s equation [17], the nanotubes had a wide of tube products. Methane and benzene were both
diameter distribution ranging from 0.9 to 1.5 nm. The available for the formation of SWNTs, the lowest tem-
intensity ratio between G- and D-modes was 13.5, perature in terms of methane was around 650 °C in our
832 Q. Li et al. / Carbon 42 (2004) 829–835

Fig. 2. Raman spectra (a) and SEM images (b–d) of as-prepared carbon deposits with benzene (b), cyclohexane (c) and hexane (d) as carbon sources.

2.4
Derv.Weight (a.u.)

1.6

Hexane

0.8
Cyclohexane

Benzene
0.0

100 300 500 700

o
Temperature ( C)

Fig. 3. HRTEM image of the SWNTs prepared with benzene as Fig. 4. Thermogravimetric analysis of carbon deposits with different
carbon source. carbon sources.

system, while in the case of benzene, it should be kept cyclohexane whose reaction Gibbs free energies are even
high up to 800 °C although benzene can be decomposed much lower than both benzene and methane, no
at lower temperature. With respect to hexane and SWNTs but other forms of carbon deposits such as
 Q. Li et al. / Carbon 42 (2004) 829–835 833

Table 1
The thermodynamic parameters of concerned hydrocarbon precursors at 800 °C
Reactions DH (KJ) DG (KJ) lg k Forms of carbon deposits
CH4 ¼ C + 2H2 90.1 )27.2 1.322 SWNT
C6 H14 (g) ¼ 6C + 7H2 206.4 )480.1 23.38 Graphite flake and MWNT
C6 H12 (g) ¼ 6C + 6H2 155.4 )479.8 23.36 MWNT
C6 H6 (g) ¼ 6C + 3H2 )62.9 )273.7 13.30 SWNT
C10 H8 (g) ¼ 10C + 4H2 )127.3 )439.6 21.40 SWNT
C14 H10 (g) ¼ 14C + 5H2 )202.6 )630.7 30.70 SWNT

MWNT and graphene flakes were produced. It revealed

(a)
that the formation and morphology of carbon deposits 900
was not simply determined by the pyrolytic behaviors of
hydrocarbons.
Compared to hexane and cyclohexane, benzene is a
relatively more stable molecule due to its aromatic 600

Intensity
structure. Mass spectrum data and study on pyrolysis of
benzene indicated that its dissociation behavior showed
more uniform and simpler which mainly involved in the Anthracene
300
cleavage of small conjugated fragments from the mole-
cule [25,26]. Due to its thermal stability [24], there was
Naphthalene
very little self-catalyzed deposition on the sidewall of
primarily nucleated nanotubes, and thus MWNTs were 0
not formed. As for cyclohexane and hexane, their 200 600 1000 1400 1800
decomposition reactions have quite similar DG and Raman shift (cm-1)
reaction rate constant. In comparison with benzene, the 3.0
cleavage of cyclohexane and hexane into small frag- (b)
ments would be much easier. On the other hand, as both 2.5
Derv.Weight (a.u.)

of them are aliphatic compound, their more complicated 2.0

cleavage routes may lead to more kinds of fragments.
This would presumably increase the possibility for other 1.5
unfavorable fragments to deposit on the sidewall of Naphthalene
1.0
primarily nucleated nanotubes, causing the formation of
MWNTs rather than SWNTs. 0.5
In order to confirm that conjugated sp2 structures Anthracene
favored the formation of SWNTs, we further tested 0.0
polycyclic molecules, i.e. naphthalene and anthracene as 0 100
00 200 300 400 500
00 600 700 800
carbon sources. As shown in Fig. 5, both Raman spectra o
Temperature ( C)
and TG analysis indicated the formation of SWNTs.
There are several notable features of nanotube synthesis Fig. 5. Raman spectra (a) and corresponding TGA curves (b) of
with these precursors. First, we could observe the for- carbon deposits prepared with naphthalene and anthracene as carbon
mation of SWNTs with polycyclic precursors when sources.
furnace temperature was raised above 700 °C. While for
benzene, no deposit was found at 700 °C, and SWNTs lower purity than those prepared with benzene, as
started to grow above 800 °C. In other words, the crit- indicated by higher D-band intensities. This might be
ical temperature for SWNT formation was 100 °C lower caused by the non-catalytic pyrolysis of these relatively
for polycyclic molecules than for benzene. This could be large molecules. Second, the Raman spectra of SWNTs
reasonably understood with the data in Table 1. materials prepared with naphthalene and anthracene are
Naphthalene and anthracene are more unstable com- characteristic with a shoulder peak at 1559 cm1 , which
pared with benzene, which meant they were able to was previously attributed to resonant Raman scattering
decompose at lower temperature. The efficiency for the from metallic nanotubes [28]. It should be admitted that
CVD growth of SWNTs with polycyclic molecules may the relative amount of metallic nanotubes within the
be due to the formation of semi-fullerene medium spe- samples cannot be told from Raman spectra, and the
cies [27], which probably serve as the nuclei for nano- mechanism for their abundance is not clear. However,
tubes and facilitate the growth. However, the SWNTs this feature is favored, since it demonstrated the possi-
prepared with naphthalene and anthracene showed bility to control the electronic structure of SWNTs,
834 Q. Li et al. / Carbon 42 (2004) 829–835

which is crucial towards their applications as building the formation of SWNTs. In return, it provided further
blocks for nanoelectronic devices. evidence to show that the chemical structures of
It was worth mentioning that the CVD product was hydrocarbons would play an important role to deter-
also greatly influenced by injection of H2 , which may mine the morphology of carbon deposits.
interfere the decomposition equilibriums of various
carbon sources. Specifically, CVD process of cyclohex-
ane in Ar atmosphere yielded MWNTs. While in H2 4. Conclusion
atmosphere, some SWNTs were formed within the
product according to Raman spectrum, SEM and TG In summary, we demonstrated the dependence of
analysis (Fig. 6). The characteristic RBM band of nanotube formation on the chemical structures of the
SWNTs emerged in the Raman spectrum of as-formed hydrocarbon precursors. It was found that aromatic
carbon deposit. From TGA curve, two combustion molecules were favored for the growth of SWNTs, while
peaks appeared, one at 566 °C and the other at 617 °C, aliphatic molecules generally tended to form MWNTs
corresponding to the characteristic combustion tem- or non-tubular carbon structures. It should be noted
perature of SWNTs and MWNTs respectively. On the that the formation of SWNTs or MWNTs does not
other hand, introduction of H2 into benzene CVD merely depend on carbon precursors, but also has strong
caused severe reduction of purity of the SWNTs, as correlations with other growth conditions such as cata-
indicated by Raman spectra (data not shown). For lyst, temperature and gas flow rate, etc. However, the
aphilitic hydrocarbons, the role of excess H2 may hinder present work shows the possibility of selective synthesis
their serious decomposition reactions at high-tempera- of SWNTs or MWNTs by a choice of carbon precursor.
tures. For aromatic compounds, the possible catalytic Moreover, the study may also shed light on the growth
hydrogenation reaction into aphilitic ones may disturb mechanism of nanotubes, which is crucial towards their
controlled synthesis and future applications.

Acknowledgements

We are grateful for the financial supports from Na-

tional Natural Science Foundation of China (NSFC
90206023, 30000044) and Ministry of Science and
Technology of China (2001CB6105).

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