Synthesis of bamboo-shaped carbon-nitrogen nanotubes using C2H2-NH3-Fe(CO)5 system

Article abstract of DOI:10.1016/S0009-2614(02)00655-3

Carbon nanotubes have potential applications in vehicles for large hydrocarbon storage. Carbon-nitrogen (CN) nanotubes were massively produced by the pyrolysis of Fe(CO)₅ and C₂H₂ with NH₃ as the source of nitrogen at 750°-950°C. The compositions of CN nanotubes synthesized at 750°, 850°, and 950°C were C₃₆N, C₂₄N, and C₁₅N, respectively. With nitrogen doping, the growth rate of nanotubes decreased, and crystallinity of nanotubes was degraded. The CN nanotubes had a bamboo-like structure with waving morphology. The nitrogen played a crucial role in generating a compartment layer. A base-growth model was adequate to explain the growth of CN nanotubes.

Full text of DOI:10.1016/S0009-2614(02)00655-3

1
3 June 2002
Chemical Physics Letters 359 (2002) 115–120
www.elsevier.com/locate/cplett
Synthesis of bamboo-shaped carbon–nitrogen nanotubes
using C H –NH –FeðCOÞ system
2
2
3
5
a,
Cheol Jin Lee , Seung Chul Lyu , Hyoun-Woo Kim , Jin Ho Lee ,
a
b
c
*
c
Kyoung Ik Cho
a
Department of Nanotechnology, Hanyang University, 17 Haengdang-dong, Seongdong-gu, Seoul 133-791, Republic of Korea
b
School of Materials Science and Engineering, Inha University, Inchon 402-751, Republic of Korea
Microelectronics Labs, Next Generation Semiconductor Research Department of ETRI, Taejon 305-350, Republic of Korea
c
Received 21 February 2002; in final form 16 April 2002
Abstract
Aligned bamboo-shaped carbon–nitrogen nanotubes have been massively produced by the pyrolysis of iron pen-
tacarbonyl ðFeðCOÞ Þ and acetylene ðC
2
H
2
Þ mixtures with ammonia ðNH Þ being the source of nitrogen. With nitrogen
3
5
doping, the nanotubes have a bamboo-like structure and reveal degraded crystallinity of graphite sheets. Nitrogen plays
a key role in generating compartment layers inside the nanotube. A base-growth model is adequate to explain the
carbon–nitrogen nanotube growth. Ó 2002 Elsevier Science B.V. All rights reserved.
1
. Introduction
ested in the synthesis of carbon–nitrogen (CN)
nanotubes, with an expectation to improve the
nanotube properties.
Since the first observation by Iijima [1], carbon
nanotubes have attracted much interest due to
their novel electronic and mechanical properties
Although many research groups have reported
on the CN nanotube growth by various methods
such as magnetron sputtering [11], chemical vapor
deposition (CVD) [12–14], and pyrolysis [15–20],
there were not many systematic studies on the
structure and crystallinity of CN nanotubes.
In this Letter, we report a large-scale synthesis
of CN nanotubes using the reaction gases (C H
[
2–4]. Carbon nanotubes have numerous potential
applications such as flat panel displays [5], vehicles
for large hydrogen storage [6], chemical sensors [7],
and nanoscale electronic devices [8].
Recently, some research groups predicted that
carbon nitrides are superhard and metallic in
comparison with pure carbon structures [9,10].
Accordingly, many researchers have been inter-
2
2
and NH ) and the catalyst source ðFeðCOÞ Þ in a
3
5
single-furnace quartz reactor at the temperature
range of 750–950 °C. We also investigate the
structure and crystallinity of CN nanotubes
in comparison with those of carbon nanotubes
by transmission electron microscopy (TEM),
*
Corresponding author.
E-mail address: cjlee@hanyang.ac.kr (C.J. Lee).
0
009-2614/02/$ - see front matter Ó 2002 Elsevier Science B.V. All rights reserved.
PII: S0009-2614(02)00655-3

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C.J. Lee et al. / Chemical Physics Letters 359 (2002) 115–120
thermogravimetric analysis (TGA), and Raman
spectroscopy. Based on TEM observation, we
suggest a growth mechanism of CN nanotubes.
A scanning electron microscope (SEM) (Hitachi
S-800, 30 kV) was used to measure the length and
diameter of nanotubes. A TEM (Philips, CM20T,
200 kV) was used to investigate the structure and
crystallinity of nanotubes, with the deposits sepa-
rated from the quartz tube and dispersed on a
carbon TEM microgrid. A Raman spectrometer
(Renishaw micro-Raman 2000) and a TGA (SDT
2960, TA instrument) were used to evaluate the
overall crystallinity of nanotubes. The stoichiom-
etry of the carbon and nitrogen atoms in the na-
notubes were examined by X-ray photoelectron
spectroscopy (XPS) (VG scientific ESCA LAB).
2
. Experimental
The apparatus for vapor phase growth consists
of a horizontal quartz tube with an inner diameter
of 20 mm and a heating zone of 200 mm. Previous
studies reveal that the iron particle is an efficient
catalyst for synthesizing carbon nanotubes [21,22].
To supply a iron catalyst source into the reactor,
C
2
H
bubbler which was maintained at room tempera-
2
gas was flowed through the liquid FeðCOÞ
5
ture. The reaction gases ðC H ; NH Þ and the
3. Results and discussion
2
2
3
carrier gas (Ar) were directly introduced into the
reactor. The flow rates of C
2
H
0, 30, and 1500 sccm, respectively. A high-flow
2
, NH
3
, and Ar were
A dense film was deposited homogeneously
along the total heating zone inside the quartz re-
actor at all temperatures in the range of 750–950
°C. Figs. 1a–c show SEM micrographs of na-
2
rate of Ar carrier gas was used for even distribu-
tion of the catalyst within a quartz tube [23]. The
synthesis temperature ranged from 750 to 950 °C
for 30 min. After the reaction, Ar carrier gas with
the flow rate of 500 sccm was flowed into the re-
actor while cooling down to room temperature. In
order to compare CN nanotubes with carbon na-
notubes, the carbon nanotubes were synthesized at
notubes synthesized with NH
3
at 750–950 °C. The
average lengths of nanotubes are about 24, 26, and
30 lm, respectively, at 750, 850, and 950 °C. To
evaluate the nitrogen doping effect on the growth
of nanotubes, we synthesized nanotubes at the
same condition without NH
SEM micrographs of nanotubes synthesized
3
gas. Figs. 1d–f show
3
the same condition without flowing NH gas.
Fig. 1. SEM micrographs of nanotubes synthesized at 750–950 °C with 20 sccm of C
2 2
H , 1500 sccm of Ar. Nanotubes synthesized with
NH (d) at 750 °C, (e) at 850 °C, and (f) at 950 °C, respectively.
3
(a) at 750 °C, (b) at 850 °C, and (c) at 950 °C, without NH
3

C.J. Lee et al. / Chemical Physics Letters 359 (2002) 115–120
117
without NH
are about 140, 220, and 280 lm, respectively, at
50, 850, and 950 °C. By adding NH gas, the
3
. The average lengths of nanotubes
(a)
7
3
growth rate of nanotubes decreases regardless of
the growth temperature. The diameters of na-
3
notubes synthesized with NH are about 30, 35,
and 37 nm, respectively, at 750, 850, and 950 °C.
The diameter of nanotubes slightly increases with
increasing growth temperature in the range of 750–
9
50 °C. As the growth temperature increases, more
agglomeration occurs at a higher temperature,
resulting in a larger sized catalyst with low density.
XPS analysis shows that the nanotubes consist
of carbon accompanied by traces of nitrogen. In
Fig. 2a, XPS spectrum shows that the C1s signal is
at 285 eV and the N 1s signal is at around 400 eV
[
18]. We estimated the ratio of carbon to nitrogen
by taking the ratio of the integrated peak areas
under the C 1s and N 1s signal (without spectral
decomposition) and dividing them by the respec-
tive photoionization cross sections. Fig. 2b shows
the average concentration of nitrogen at the na-
notubes according to the growth temperature. The
nitrogen concentrations of nanotubes (atomic
percent) grown at 750, 850, and 950 °C are 2.8%,
(b)
4
.2%, and 6.6%, respectively, and their composi-
tions are about C36N, C24N, and C15N. The ni-
trogen concentration of nanotubes increases with
increasing growth temperature. In our experi-
ments, the incorporation of nitrogen into na-
notubes was clearly confirmed by adding NH gas
3
and this result agrees with a previous study [20].
To investigate the structure and crystallinity of
nanotubes according to nitrogen doping, we ana-
lyzed TEM images of CN nanotubes (Figs. 3a–d)
and carbon nanotubes (Figs. 3e and f) simulta-
neously. Fig. 3a shows TEM images of CN na-
notubes synthesized at 850 °C. The high-purity CN
nanotubes without carbonaceous particles are
grown on the inner surface of the quartz tube, al-
though some metal catalyst particles are included
inside the tubes. The CN nanotubes reveal hollow
inside and the outer diameter of the CN nanotubes
is almost constant over a long distance. Fig. 3b
shows that CN nanotubes have a bamboo-like
structure with compartment layers. The closed tip
of a CN nanotube is shown in Fig. 3c. A high-res-
olution TEM (HRTEM) image of a CN nanotube
Fig. 2. XPS analysis of CN nanotubes. (a) XPS spectrum of C
and N elements. (b) Nitrogen concentration of CN nanotubes
according to the growth temperature. The average composition
of CN nanotubes synthesized at 750, 850, and 950 °C are about
C36N, C24N, and C15N, respectively.
indicates defective graphite sheets with waving
morphology (Fig. 3d). In general, the waving
morphology of graphite sheets is from a defective
structure, caused by the appearance of pentagons
and hexagons instead of hexagons [24]. In our
experiments, all the CN nanotubes reveal a bam-
boo-like structure and corrugated graphite sheets
regardless of growth temperature in the range of
750–950 °C. Fig. 3e shows a TEM image of carbon
nanotubes without nitrogen doping, showing rare

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C.J. Lee et al. / Chemical Physics Letters 359 (2002) 115–120
(a)
(c)
(e)
(b)
(d)
(f)
Fig. 3. TEM images of nanotubes synthesized at 850 °C. (a)–(d) With nitrogen doping. (e)–(f) Without nitrogen doping. (a) Low
magnification TEM image of CN nanotubes. (b) The CN nanotubes showing a bamboo-like structure with compartment layers. (c) A
closed tip of a CN nanotube. (d) HRTEM image of a CN nanotube, revealing defective graphite sheets. (e) Low magnification TEM
image of carbon nanotubes. (f) HRTEM image of a carbon nanotube, revealing straight graphite fringes.
compartment layers. Fig. 3f shows a HRTEM im-
age of a carbon nanotube, revealing that graphite
sheets have straight fringes without waving mor-
phology. It means that the CN nanotubes have
more defective structures than carbon nanotubes.
TGA analysis is carried out to obtain the
overall information on the crystalline perfection of
nanotubes synthesized at 850 °C. Fig. 4 shows a
plot for weight loss in percentage vs. oxidation
temperature, measured by heating up the nanotu-
bes in the air ambience. The percentage weight loss
curve between 200 and 800 °C is plotted by ad-
justing 100% for the weight loss at 800 ° C, which
is presumably the weight of catalyst (usually 10%

C.J. Lee et al. / Chemical Physics Letters 359 (2002) 115–120
119
Fig. 4. TGA data of weight loss in percentage vs. oxidation
temperature for the nanotubes grown at 850 °C. The nanotubes
a) with and (b) without nitrogen doping start to gasify at 370
(
and 450 °C, respectively.
of total weight). The CN nanotubes start to gasify
at a lower temperature (370 °C) compared with the
carbon nanotubes, which burn at 450 °C. It is
consistent with HRTEM images, revealing that the
crystallinity of nanotubes degrades with nitrogen
doping.
Fig. 5 shows Raman spectra of nanotubes
grown at 850 °C with and without nitrogen dop-
ing. All spectra show mainly two Raman bands at
Fig. 5. Raman spectra of nanotubes (a) with and (b) without
nitrogen doping. The relative peak intensity of D and G bands
increases with nitrogen doping.
The formation of compartment layers caused
by nitrogen was observed in previous studies
[14,18,19]. In our experiment, it is clear that ni-
trogen plays an important role in generating
compartment layers during the nanotube growth.
ꢁ
1
ꢁ1
ꢀ
1335 cm (D band) and ꢀ1580 cm (G band).
The D band indicates the defective structure of
graphite sheets [25]. The peak intensity ratio of D
and G bands increases with nitrogen doping, in-
dicating that the crystallinity of CN nanotubes is
lower than that of carbon nanotubes. The result of
Raman spectra agrees strongly with HRTEM im-
ages and TGA data.
3
By adding NH , the nitrogen adsorbed on the
surface of the catalyst particle restrains the surface
diffusion of carbon. As a result, the wall growth,
due to surface diffusion, is reduced and thus, the
growth rate of CN nanotubes decreases compared
with carbon nanotubes. On the other hand, by
We investigated TEM images to explain a
growth mechanism of CN nanotubes. Fig. 3b in-
dicates that CN nanotubes consist of hollow
compartments, similar to a bamboo-like structure.
Fig. 3c shows that a CN nanotube has compart-
ment layers with a curvature directed toward the
closed tip which has no encapsulated catalyst
particle. In Figs. 3b and d, the wall thickness in-
creases due to the generation of compartment
layers, but the outer diameter remains constant.
From TEM observation, we suggest that the
growth of CN nanotubes follows a base-growth
mechanism [26].
3
adding NH , the bulk diffusion of carbon increases
relatively. Accordingly, the carbon accumulation
at the inner surface of the catalyst particle is en-
hanced, resulting in the formation of compartment
layers.
In summary, CN nanotubes are synthesized
massively on the inner surface of the quartz tube
2 2 3
by the catalytic reaction of C H , NH , and
FeðCOÞ mixtures at 750–950 °C. The composi-
5
tions of CN nanotubes synthesized at 750, 850,
and 950 °C, respectively, are about C36N, C24N,

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C.J. Lee et al. / Chemical Physics Letters 359 (2002) 115–120
[
[
11] K. Suenaga, M.P. Johansson, N. Hellgren, E. Broitman,
and C15N. With nitrogen doping, the growth rate
of nanotubes decreases and the crystallinity of
nanotubes is degraded. The CN nanotubes have a
bamboo-like structure with waving morphology.
The nitrogen plays a crucial role in generating a
compartment layer. A base-growth model is suit-
able to explain the growth of CN nanotubes.
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