Highly aligned coiled nitrogen-doped carbon nanotubes synthesized by

injection-assisted chemical vapor deposition

J. Liu, S. Webster, and D. L. Carroll

Citation: Appl. Phys. Lett. 88, 213119 (2006); doi: 10.1063/1.2202191

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 APPLIED PHYSICS LETTERS 88, 213119 共2006兲

Highly aligned coiled nitrogen-doped carbon nanotubes synthesized

by injection-assisted chemical vapor deposition
J. Liu, S. Webster, and D. L. Carrolla兲
The Center for Nanotechnology and Molecular Materials, Department of Physics, Wake Forest University,
Winston-Salem, North Carolina 27109
共Received 2 August 2005; accepted 6 April 2006; published online 26 May 2006兲
Large quantities of coiled nitrogen-doped carbon nanotubes with high purity and uniform diameter
of approximately 25 nm have been synthesized by pyrolysis of pyridine with the assistance of
sublimated melamine using injection-assisted chemical vapor deposition. The coiled tubes were
vertically aligned with high regularity over large areas. The pitch and coil diameter varied between
共1.1– 1.3 ␮m兲/revolution and 0.4– 0.5 ␮m, respectively. The overall nitrogen concentration of the
coiled carbon nanotubes has been measured to be approximately 3.5%. We suggest that the growth
mechanism of these coiled nitrogen-doped carbon nanotubes are related to asymmetric growth rates
resulting from sublimated melamine. © 2006 American Institute of Physics.
关DOI: 10.1063/1.2202191兴

Coiled carbon nanotubes have previously been predicted
by Ihara et al.1 and Dunlap2 based on molecular-dynamics
simulations. Shortly after, coiled multiwalled carbon nano-
tubes were observed in samples grown by catalytic decom-
position of hydrocarbons over transition metal catalysts by
chemical vapor deposition 共CVD兲.3 Coiled and traditionally
straight carbon nanotubes have attracted interest due to their
unique electrical, magnetic, and mechanical properties.4,5 For
instance, they have promising potential applications as nano-
actuators and nanosprings.6 In nanocircuitry, an electrical
current passed through coiled carbon nanotubes could gener-
ate an inductive magnetic field, where they could be used as
electromagnetic nanotransformers or nanoswitches.7 Nitro-
gen doping in carbon nanotubes alters the electronic and
morphological properties of carbon nanotubes.8,9 C3N4 and
CN nanotubes have been theoretically predicted to be super-
hard and metallic respectively.8–10 Efficient field emission
has recently been demonstrated using nitrogen-doped multi-
walled nanotubes.11 Control of the electronic and structural
properties of nanotubes, through substitutional doping
schemes, provides an interesting route to broadening the po-
tential applications of carbon nanotubes.
A fascinating possibility is to introduce nitrogen doping
into the coiled nanotube structures to meet the increasingly
versatile needs for carbon nanotube applications. The synthe-
sis of such structures is challenging and until now has been
unsuccessful. In this work, we report an efficient way to
grow coiled nitrogen-doped carbon nanotubes on a large
scale, by the pyrolysis of pyridine and sublimation of
melamine, using injection CVD. In this context, we intro-
duce the possibility of tailoring the electrical and mechanical
properties of nanocoils based on their structural and dopant
compositions.
The general synthesis of N-CNTs has previously been
described elsewhere.12–14 Briefly, our setup consisted of two
furnaces; a preheater for vaporization of pyridine and subli-
mation of melamine, and a reactor for the nanotube growth
共Fig. 1兲. A solution consisting of ferrocene 共2.7 wt % 兲 in
pyridine was electromechanically injected by a syringe into
the preheater at a rate of 5 ml/ h. Melamine 共2.5 g兲 was sub-
limated in the center of the preheater at 200 ° C. During
growth, the volatized pyridine, ferrocene, and sublimated
melamine were swept into the reactor by pure hydrogen gas
at a flow rate of 320 SCCM 共SCCM denotes cubic centime-
ter per minute at STP兲. The temperature of the reactor was
set to 750 ° C, at which the carbon nanotubes have the high-
est yield and quality as described in our previous studies.12,13
After growth for 1 h, the furnace was cooled to room tem-
perature under an argon flow instead of hydrogen with the
same flow rate. The samples were collected from inside the
quartz tube which also served as the reaction vessel inside
the furnace.
Figure 2共a兲 is a low magnification SEM micrograph of
the as prepared coiled N-CNTs. From Fig. 2共a兲 and other
similar micrographs it is determined that these samples under
the given growth conditions are clean mats. Similar growth
results were previously observed from pyridine without
melamine.14 These high purity carbon nanotubes are verti-
cally aligned and free from amorphous carbon and residual
catalyst. The height of the mats are approximately
90– 100 ␮m after growth for 1 h, which is comparable to
growth without melamine. However, the mats are less
densely packed than mats grown without melamine. Upon
magnification, Figs. 2共b兲 and 2共c兲, the nanotube’s morpholo-
gies are completely different from that without melamine.
After inspecting nanotubes from different areas inside the
quartz reactor, it is found that the carbon nanotubes all are
coiled, aligned, and homogenously distributed over large
growth areas. Careful inspection of the SEM micrographs

a兲
Author to whom correspondence should be addressed; electronic mail: FIG. 1. Schematic diagram of the experimental set up for coiled nitrogen-
carroldl@wfu.edu doped carbon nanotube growth.

0003-6951/2006/88共21兲/213119/3/$23.00 88, 213119-1 © 2006 American Institute of Physics

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213119-2 Liu, Webster, and Carroll
FIG. 2. 共a兲 Low magnification SEM of carbon nanotubes synthesized from
pyridine plus sublimated melamine at 750 ° C; 关共b兲 and 共c兲兴 SEM of coiled
features; 共d兲 TEM of coiled N-MWCNTs.
indicates that the pitch and coil diameters of the coiled tubes
vary between 1.1–1.3 and 0.4– 0.5 ␮m, respectively. Figure
2共d兲 is a micrograph taken with a TEM of the carbon nano-
tubes. Diameters of individual tubes are found to be uniform
and approximately 25 nm. A bamboo structure is clearly seen
for all tubes and is more pronounced than tubes grown with-
out melamine at similar growth conditions. It is suggested
that sublimated melamine plays a crucial role in generating
bamboo structures even if only small amounts of nitrogen
doping are introduced during the growth process.
To quantify nitrogen dopant concentrations x-ray photo
electron spectroscopy 共XPS兲 was performed on the samples.
XPS spectra clearly show the carbon and nitrogen 1s features
at ⬃285 and ⬃400 eV, respectively.15 By dividing the inte-
grated peak areas of the C 1s to the N 1s 共without spectrally
decomposing fine structures within the 1s levels兲 while nor-
malizing the respective photoionization cross section for the
1s level, the nitrogen concentration of carbon nanotubes was
determined to be approximately 3.5%. However, the nitrogen
1s peak ca. 400 eV can be decomposed into three peaks at
398.7, 401, and 405 eV, as shown in Fig. 3. The two peaks at
398.7 and 401 eV correspond to pyridine- and graphitic-type
bonding, respectively,16,17 which are the substitutionally
FIG. 3. XPS spectrum of N 1s for coiled N-MWCNTs.
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Appl. Phys. Lett. 88, 213119 共2006兲
FIG. 4. 共a兲 Raman spectra comparing pure MWCNTs, noncoiled
N-MWCNTs, and coiled N-MWCNTs. 共b兲 Local density of states of coiled
nitrogen-doped carbon nanotubes.
doped nitrogen in the nanotubes carbon lattice. The nitrogen
concentration from these two features combined is approxi-
mately 1.5%. An additional peak was observed at 405 eV,
which is coinciding with the theoretical calculation for pyri-
dine N-oxide17 and was observed before.18 However, this
peak is extremely intense here and may not result from O–N
bonding formation during handing the sample in air. We ten-
tatively suggest that this peak may come from melamine-
based compound formation during growth, because this peak
was not observed from the sample grown without
melamine.14
Shown in Fig. 4共a兲 are Raman spectra from pure multi-
walled carbon nanotubes 共MWCNTs兲 grown from xylene,
N-MWCNTs grown from pyridine, and coiled N-MWCNTs
grown from pyridine and melamine all at equal growth tem-
peratures 共750 ° C兲 and ferrocene catalyst concentration. All
spectra show three general Raman bands at ⬃1330 cm−1 共D
band兲, ⬃1580 cm−1 共G band兲, and ⬃2660 cm−1 共D* band兲.
The D, G, and D* bands are generally attributed to disruption
of the “graphitelike” hexagonal lattice structure of the nano-
tubes 共defects兲, in-plane lattice vibrations, and an energy
conserving second order mode of the D band that is indepen-
dent of the defect concentration, respectively.19 To qualify
defect structures, the ratio of D to G bands are typically
taken in the literature. For pure MWCNTs, N-MWCNTs, and
coiled N-MWCNTs, the measured D / G ratios are 1.26, 2.5,
213119-3 Liu, Webster, and Carroll
and 2.75, respectively. This indicates that nitrogen-doped
carbon nanotubes have more defects, presumably due to ni-
trogen doping. Unfortunately, taking the ratio of D / G is not
always appropriate, especially at high defect concentrations,
since it has been shown that both bands are affected by de-
fect structures.20 To supplement the ratio of D / G, both defect
effected bands should be referenced to a band that is not
influenced by defects, namely, the D* band. Interestingly,
both D / D* and G / D* for coiled nitrogen-doped carbon nano-
tubes are 40.3 and 14.6, respectively, which are much greater
than noncoiled nitrogen-doped carbon nanotubes 共D / D* = 6,
and G / D* = 2.3兲. Since we have determined through XPS that
both structures, coiled and noncoiled, have roughly identical
nitrogen content13,21 we believe that the additional defects
observed in the Raman spectra 共comparing ratios D / G,
D / D*, and G / D*兲 are due to the coiled structure. As previ-
ously mentioned, the coiled structures are likely comprised
of regular insertion of pentagons and heptagons in the hex-
agonal lattice network of the nanotube.1,2
To further investigate and qualify the nature of the nitro-
gen doping in the coiled carbon nanotubes, scanning tunnel-
ing spectroscopy was also performed. From the converted
local density of states 共LDOS兲 关Figure 4共b兲兴, the presence of
a finite electronic density of states at Fermi level indicates
that the coiled tubes are intrinsically metallic. An additional
electronic feature occurs slightly below the conduction band
of the LDOS at ⬃0.17 eV. This result is similar to previous
reports for noncoiled nitrogen-doped nanotubes.22 This elec-
tronic donor feature is associated with the formation of
pyridine-type 共sp2-like兲 structures16,22 within the lattice and
further confirms that the coiled tubes are doped with nitrogen
and are n-type conductors.
We note that the coiled tubes could not be obtained with-
out melamine in these experiments. Thus, for our case, it is
apparent that melamine plays an important role in the forma-
tion of the coiled tubes as well. After the Fe particles deposit
on the quartz substrate, melamine decomposes on the particle
surface to offer nitrogen or CN radicals.23 Suppose this reac-
tion does not occur homogeneously across the whole parti-
cle’s surface, only on the exposed region. It is reasonable
that there exist regions with varying nitrogen concentration.
Since nitrogen has been previously reported to decrease the
carbon nanotube growth rate,14 it is further reasonable that
high nitrogen concentration regions of the catalyst will have
a slower wall growth rate as compared to regions with lower
nitrogen concentration. This may lead to an asymmetric
growth rate for the tube. A lower growth rate on the side of
the particles with higher nitrogen concentration would gen-
erate the “inner” part of the spiral, which suggests that the
inner part of the spiral with larger curvature should have
higher nitrogen concentration than the outer part with
smaller curvature. Qu-Yan et al.24 found that the formation
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Appl. Phys. Lett. 88, 213119 共2006兲
of coils corresponds to an energy-minimum shape and they
derived an optimal condition pitch/coil radius, equal to 2␲,
for the regular coil solution. Our results yield a ratio between
5.5 and 6.5, which is very close to the value of 2␲. This
suggests that the coiled structure obtained by our growth
procedure is in a stable state.
We have demonstrated that highly aligned coiled
nitrogen-doped carbon nanotubes can be synthesized from
pyridine with assistance from sublimated melamine by injec-
tion CVD. The coiled tubes have a relatively uniform diam-
eter approximately 25 nm and 3.5% nitrogen doping level. A
1.5% nitrogen appears to be doped into the carbon lattice of
the coiled carbon nanotubes in two fashions, namely, the
pyridinelike and graphitelike. These n-type conductive coiled
tubes are expected to have potential applications on nanode-
vices and preparing polymer nanocomposites with enhanced
electronic mechanical properties.
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