Nano Res.

Nano Res. 2011,

2011, 4(8):
4(8): 759–
759–766
766 ISSN 1998-0124
759
DOI 10.1007/s12274-011-0132-y CN 11-5974/O4
Research Article

Ultra-Thin Double-Walled Carbon Nanotubes: A Novel

Nanocontainer for Preparing Atomic Wires

Lei Shi1, Leimei Sheng1 ( ), Liming Yu1, Kang An1, Yoshinori Ando2, and Xinluo Zhao1 ( )

1
Department of Physics, and Institute of Low-Dimensional Carbons and Device Physics, Shanghai University, Shanghai 200444, China
2
Department of Materials Science and Engineering, Meijo University, Nagoya 468-8502, Japan

Received: 27 January 2011 / Revised: 5 March 2011 / Accepted: 16 March 2011

© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2011

ABSTRACT
Double-walled carbon nanotubes (DWCNTs) with high graphitization have been synthesized by hydrogen arc
discharge. The obtained DWCNTs have a narrow distribution of diameters of both the inner and outer tubes,
and more than half of the DWCNTs have inner diameters in the range 0.6–1.0 nm. Field electron emission from
a DWCNT cathode to an anode has been measured, and the emission current density of DWCNTs reached
1 A/cm2 at an applied field of about 4.3 V/μm. After high-temperature treatment of DWCNTs, long linear carbon
chains (C-chains) can be grown inside the ultra-thin DWCNTs to form a novel C-chain@DWCNT nanostructure,
showing that these ultra-thin DWCNTs are an appropriate nanocontainer for preparing truly one-dimensional
nanostructures with one-atom-diameter.

KEYWORDS
Arc discharge, carbon chains, double-walled carbon nanotubes, field electron emission, nanocontainer, nanowires

1. Introduction range 0.6–1.0 nm in order to ensure that linear atomic

The discovery of carbon nanotubes (CNTs) heralded
the beginning of the boom of nanoscience and nano-
technology [1], and the successful synthesis of
graphene, a superlative two-dimensional carbon nano-
material, has promoted further extensive exploration
in the nanoworld [2]. The question is: what is next?
Recently, atomic-scale nanowires have attracted more
and more interest due to their truly one-dimensional
(1D) nanostructures with one-atom-diameter [3–5].
Generally, atomic-scale nanowires are not stable in air
at room temperature. One of the methods to preserve
them is to encapsulate them into CNTs. The innermost
diameters of these CNTs are required to be in the
wires can be formed [3–6]. Double-walled carbon
nanotubes (DWCNTs), consisting of two concentric
graphene cylinders, are the simplest member of the
family of multi-walled carbon nanotubes (MWCNTs),
and have even better electronic, thermal and mech-
anical properties than single-walled carbon nanotubes
(SWCNTs) [7–10]. Therefore, DWCNTs have been
used as a novel nanocontainer for preparation of 1D
materials [4–6].
Many attempts have been made to synthesize high
purity DWCNTs, such as conventional arc discharge
[11–13], high-temperature pulsed arc discharge [14],
high-temperature annealing of peapods [15], and
chemical vapor deposition (CVD) [16–19]. Furthermore,

Address correspondence to Leimei Sheng, shenglm@staff.shu.edu.cn; Xinluo Zhao, xlzhao@shu.edu.cn

760
density gradient ultracentrifugation (DGU) has been
also used to separate DWCNTs from SWCNTs [20].
Arc discharge is a very important technique to pro-
duce fullerenes, MWCNTs, SWCNTs, and graphene
[1, 21–23]. However, the DWCNTs prepared by arc dis-
charge possess large average inner diameters (> 2 nm),
even though they have the highest crystallinity due
to having the highest growth temperature among the
methods mentioned above [11–13].
Herein, we report a simple method for mass-
production of high purity, uniform, and ultra-thin
DWCNTs with high graphitization by hydrogen arc
discharge. More than half of the DWCNTs have inner
diameters in the range 0.6–1.0 nm, and long linear
carbon chains (C-chains) can be grown inside the
ultra-thin DWCNTs to form a new 1D carbon nano-
structure, C-chain@DWCNT, by high-temperature
treatment. Our results will not only enable investigation
of the electronic, thermal, and mechanical properties
of ultra-thin DWCNTs with high crystallinity, but also
provide a new nanocontainer for synthesizing linear
atomic wires, such as C-chain, a novel 1D allotrope of
carbon composed of sp-hybridized carbon atoms.
2. Experimental
A home-made apparatus featuring dc arc discharge
evaporation was used to synthesize DWCNTs, where
two electrodes were installed horizontally. The anode
(6 mm diameter) was prepared from a mixture of
96 wt.% graphite powder and 4 wt.% Fe catalyst. The
cathode (10 mm diameter) was a pure carbon electrode.
A dc arc discharge was generated between these two
carbon electrodes by applying 75 A in an atmosphere
of Ar and H2 mixture (3:2/v:v) at 300 torr. After 30 min
of arc evaporation, over 300 mg of as-grown CNTs
(SWCNTs, DWCNTs, and three-walled CNTs) were
obtained. The as-grown CNT sample was purified by a
three-step process: Oxidation in air at 400 °C for 30 min,
and then at 500 °C for 2 h, and finally immersion
into concentrated hydrochloric acid for 12 h at room
temperature. In the end, a DWCNT buckypaper could
be obtained after washing with distilled water and
filtration using a polytetrafluoroethylene filter.
The samples were characterized by scanning electron
microscopy (SEM) (JEOL JSM-6700F) equipped with an
Nano Res. 2011, 4(8): 759– 766
energy dispersive spectroscopy analyzer (EDS, Oxford
Inca), transmission electron microscopy (TEM) (JEOL
JEM-200CX), high-resolution TEM (HRTEM) (Tecnai G2
F20 S-Twin), Raman spectrometry (Renishaw, inVia Plus
and Horiba Jobin Yvon, T64000), and thermogravimetric
analysis (TGA) (Netzsch, TG209F1). Field emission mea-
surements were carried out in a vacuum chamber with
a base pressure of 3 × 10–5 Pa (Keithley 2410 SourceMeter).
3. Results and discussion
Figures 1(a) and 1(b) show typical SEM and TEM
images of DWCNTs. A compact structure is formed
due to the increase in the attractive van der Waals force
between the DWCNTs after the removal of the Fe
catalyst and other carbon impurities in the three-step
purification process. A representative HRTEM image
is shown in Fig. 1(c). All the CNTs that can be
distinguished are DWCNTs, and about ten isolated
DWCNTs with similar inner diameters of around
0.9 nm can be seen in this image. Examination of about
one hundred such HRTEM images reveals that our
sample consisted mainly of DWCNTs (over 95%,
Fig. 1(d)). The diameter distribution of the DWCNTs
showed inner and outer diameters in the range
0.4–1.8 nm and 1.2–2.6 nm, respectively (Fig. 1(e)). In
particular, more than half of the DWCNTs had inner
diameters in the range 0.6–1.0 nm, and should be
appropriate nanocontainers for linear atomic wires.
The average values of the inner and outer diameters of
the DWCNTs were 0.9 nm and 1.6 nm, respectively.
Generally, there are two reasons which can explain
why DWCNTs, but not other CNTs, were synthesized
using our method: the size of catalyst nanoparticles
and the relative concentration of active carbon species
[11–13, 17]. The catalysts used in the synthesis of
DWCNTs by arc discharge usually include sulfur and
elements in the iron group in the anode [11–13]. Sulfur
has long been used to synthesize carbon fibers, and its
effects on the amount and quality of carbon products
have been discussed in detail [24, 25]. The optimum
sulfur content can improve the carbon deposition on
metal catalyst nanoparticles and promote the growth
of CNTs; high contents of S in the anode will make the
catalyst nanoparticles aggregate into somewhat larger
nanoparticles, resulting in the formation of thick CNTs.
Nano Res. 2011, 4(8): 759– 766 761

Figure 1 (a) SEM, (b) TEM, and (c) HRTEM images of DWCNTs; (d) ratio of single-, double-, and multi-walled CNTs, with the insets
showing HRTEM images of the different CNTs; (e) diameter distribution of DWCNTs based on detailed HRTEM observations; EDS of
the anode (f), and as-grown DWCNTs (g)

In our experiments, the DWCNT synthesis does not
require additional S catalyst, although in actual fact,
about 0.3 wt.% S was present in the anode because the
raw carbon materials contained a little sulfur, and the
high-temperature treatment for preparing the anode
could not remove all of this element (Figs. 1(f) and 1(g)).
The high yield of uniform and ultra-thin DWCNTs
can be attributed to the low content of S in the anode.
In addition, the appropriate current, atmosphere and
pressure are also the reasons for being able to synthesize
ultra-thin DWCNTs with high yield, because these
parameters determine the amount of active carbon
species used to form CNTs as well as the reaction time
that the CNTs stay in the reaction zone. We believe that
enhancing the feed rate of active carbon species and
prolonging the reaction time both benefit the formation
of DWCNTs rather than SWCNTs.
The detailed features of the DWCNTs, such as
purity, structural integrity, diameter distribution, and
nanotube type, were examined using Raman scattering.
Five laser lines at 488, 514, 532, 633, and 785 nm were
used for excitation (Fig. 2) in order to give a general
762 Nano Res. 2011, 4(8): 759– 766

diameter distribution, since different diameter tubes Table 1 Diameter analysis of DWCNTs using Raman spectra
are in resonance with different laser energies. A well- recorded at different excitation wavelengths
known fact is that the outer and the inner tubes of a RBM peak RBM peak
Wave- Interlayer
(cm–1)/ (cm–1)/
DWCNT can be either metallic (M) or semiconducting length spacing ID/IG
Diameter (nm) Diameter (nm)
(S). The use of different laser lines allowed us to study (nm) (nm)
Outer tube Inner tube
different configurations of outer/inner tubes separately, 785 158/1.58 264/0.92 0.33 0.038
such as M/S (outer tube type/inner tube type) and 633 126/2.02 200/1.23 0.395 0.021
S/M DWCNTs. For ease of comparison, Raman spectra 151/1.66 253/0.96 0.35 —
have been normalized to the intensity of the G-band,
532 158/1.58 268/0.91 0.335 0.026
and the radial breathing modes (RBMs) were expanded
514 153/1.64 262/0.93 0.355 0.023
by a factor of 10 except for 785 nm excitation. In the
488 126/2.02 200/1.23 0.385 0.026
high frequency region of the Raman spectra, the
135/1.87 231/1.06 0.405 —
position of the D-band showed a blue shift (from
155/1.61 265/0.92 0.345 —
1313 to 1350 cm–1) with increasing laser energy. The
166/1.50 302/0.80 0.35 —
intensity of the D-band was very low, with the intensity
ratio of the D-band to the G-band (ID /IG) in the region
of 0.02–0.04, meaning that the DWCNT samples We estimated the diameters of DWCNTs using the
have high crystallinity and relatively low amounts of relation
amorphous carbon (Table 1).
ωRBM = 234/dt + 10 cm–1

from the RBM peaks in the low-frequency range from

Figure 2 Raman spectra of DWCNTs with excitation wavelengths
of 488 nm, 514 nm, 532 nm, 633 nm, and 785 nm
100 to 350 cm–1, where ωRBM (cm–1) is the RBM frequency
and dt (nm) is the nanotube diameter (Table 1) [26]. The
RBM bands of DWCNTs clearly indicate the coexistence
of inner and outer tubes. According to the relation,
the strongest RBMs of the outer tubes (153–158 cm–1)
correspond to diameters of 1.58–1.64 nm, and the
diameters of the inner tubes with the strongest RBMs
at 262–268 cm–1 are 0.91–0.93 nm (Fig. 2). The difference
between the outer and inner diameters is 0.65–0.73 nm,
which is twice the lattice spacing of graphite (002), as
expected. The Raman data are consistent with the
HRTEM observations. The Raman and HRTEM results
suggest that the DWCNTs have a narrow diameter
distribution. It is very interesting that the RBM peaks
of the DWCNTs prepared by our method are almost
the same as those of the DWCNTs synthesized by
the CVD method of Endo et al. [16], and by the DGU
technique [20]. Furthermore, all of these samples have
another common characteristic, that is, higher purity
of DWCNTs than other samples previously reported
in the Ref. [11–14, 17, 18].
According to the “Kataura” plot, Elaser = 1.58 eV
M S
(785 nm) is in resonance with E11 and E22 for the outer
and inner tube, respectively [27]. The strongest peak
located ~264 cm–1 is associated with semiconducting
Nano Res. 2011, 4(8): 759– 766 763

tubes belonging to the 2n + m = 22 family and resonant

S
with E22 transitions. This laser energy is useful to detect
the M/S (outer/inner) DWCNTs, while Elaser = 2.41 and
2.33 eV (514 and 532 nm) are selective for the S/M
S S
DWCNTs, which are in resonance with E33 (or E44 )
and E11M for the outer and inner tubes, respectively.
Similarly, for Elaser = 1.96 and 2.54 eV (633 and 488 nm),
are resonant with S/S and M/M DWCNTs, respectively.
Obviously, our DWCNT sample provides an appro-
priate candidate to clearly study the different types
(S or M) of outer and inner tubes by using different
Raman laser energies.
To evaluate the purity and the quality of DWCNTs,
TGA was conducted in air with a heating rate of
10 °C min–1 using a thermogravimetric analyzer. The
residue was less than 3 wt.% after heating to 950 °C,
confirming that the DWCNT sample has a high
Figure 3 (a) TGA and DTG curves of DWCNTs, with the insets
purity (Fig. 3(a)). The two peaks of the differential showing HRTEM image of DWCNTs; (b) photographs of DWCNT
thermogravimetric (DTG) curve correspond to the buckypaper, which is tough and flexible enough to fold
burning of SWCNTs and DWCNTs, in ascending
order of temperature. The DTG peak corresponding
to DWCNTs indicates that the DWCNTs have an
excellent high-temperature oxidation resistance up to
786 °C, which is the highest burning temperature of
DWCNTs to our knowledge.
After a three-step purification process, a DWCNT
“buckypaper” could be obtained (Fig. 3(b)). This
“buckypaper” has a diameter of ~20 mm, and is
tough and flexible enough to fold. Therefore, our
method provides a simple and effective way to mass-
produce high purity, uniform and ultra-thin DWCNTs
with high crystallinity. The high quality of DWCNTs
has relationship with the low S content, the high
growth temperature, and the defect-healing effect by Figure 4 Field emission properties of DWCNTs. Inset (a) shows
hydrogen arc discharge method. an F–N plot with the slope indicated by a red straight line; inset
To demonstrate the excellent electric and thermal (b) is an anode luminescence image with E = 2.4 V/μm
characteristics of our uniform and thin DWCNTs,
field electron emission from a DWCNT cathode to an (F–N) plot and its fitting line, and the inset (b) in
anode was measured. A piece of DWCNT buckypaper Fig. 4 is the anode luminescence image at 2.4 V/μm.
was directly used as emitting cathode. As shown The field enhancement factor can be calculated using
in Fig. 4, the turn-on and threshold electric fields of the relation obtained from the F–N equation [28]:
DWCNTs, corresponding to a current density of
1 μA/cm2 and 1 mA/cm2, are about 0.9 and 2.0 V/μm, β = –BΦ 3/2/SFN
respectively. The emission current density of DWCNTs
reached 1 A/cm2 at an applied field of about 4.3 V/μm. where β is the field enhancement factor, B = 6.83 × 109
The inset (a) of Fig. 4 shows the Fowler–Nordheim eV–3/2 Vm–1, Φ is the work function, and SFN is the slope
764 Nano Res. 2011, 4(8): 759– 766

of the fitting line. Assuming the work function of CNTs

to be 5.0 eV, the field enhancement factor is estimated
to be 3646. By comparison with that of DWCNTs
having a wide diameter distribution [29], the uniform,
ultra-thin, and high-purity DWCNTs with high
crystallinity possess much lower turn-on field, higher
emission current density, and higher field enhancement
factor.
Linear C-chains are a truly 1D carbon nanomaterial,
but they cannot survive in air. A carbon nanowire
consisting of a MWCNT with a long 1D linear C-chain
inserted into its innermost tube of 0.7 nm in diameter
has been discovered in the cathode deposits prepared
by hydrogen arc discharge [3]. It has been proposed Figure 5 Raman spectra of DWCNTs and HT-DWCNTs with
an excitation wavelength of 514 nm
that the CNTs used to confine linear C-chains must
have inner diameters of around 0.7 nm. Since in our
1855 cm–1 is not observed after heat-treating the large
sample more than 15% of the DWCNTs have diameters
diameter SWCNTs or DWCNTs, which provides in-
of 0.6–0.8 nm (Fig. 1(e)), we carried out a high-
direct confirmation of the formation mechanism. Further
temperature treatment on our DWCNTs under an Ar
detailed studies of the mechanism are in progress in
atmosphere at a temperature of 1500 °C for 30 min.
our laboratory.
Figure 5 shows the Raman spectra of DWCNTs and
the heat treated DWCNTs (HT-DWCNTs). The Raman
band at 1856 cm–1 (the corresponding second order 4. Conclusions
Raman peak is located at 3693 cm–1) clearly seen in
the inset of Fig. 5, is considered to be characteristic Uniform and ultra-thin DWCNTs with high graphiti-
of long linear C-chains inside CNTs [3], and indicates zation and high purity have been mass-produced by
the formation of a new 1D carbon nanostructure, a simple hydrogen arc discharge without the need for
C-chain@DWCNT. Endo et al. attributed a Raman an additional sulfur catalyst. The DWCNT cathode has
peak at 1855 cm–1 to the presence of short carbon excellent field emission properties and the emission
chains (e.g., 3–7 atoms long), linked covalently to current density of the DWCNT buckypaper can reach
adjacent tubes after high-temperature treatment of 1 A/cm2 at about 4.3 V/μm. It has been confirmed that
highly pure DWCNTs [30]. We suggest that the band long linear C-chains can be grown inside the ultra-
at 1856 cm–1 in the spectrum of our heat treated thin DWCNTs to form a novel C-chain@DWCNT
material can be taken to indicate the formation of long nanostructure by high-temperature treatment. Both
linear C-chains from carbon atoms contained inside the ultra-thin DWCNTs and C-chain@DWCNT nano-
the inner tubes of the DWCNT sample after high- structure are 1D materials which are candidates for
temperature treatment. It is known that there are use in the fabrication of, for example, nanocomposites,
some carbon atoms existing inside the inner tubes of field emission sources and nanodevices.
DWCNTs. During the high-temperature treatment
process, these carbon atoms move along the tube and Acknowledgements
gradually aggregate into clusters in the case of larger
diameter DWCNTs, which cannot confine the carbon This work was supported by the National Natural
atoms into a line. If the DWCNTs have inner diameters Science Foundation of China (Grant No. 10974131),
of around 0.7 nm, however, a long linear C-chain will the Nanotechnology Program of Shanghai Science and
be formed inside. In fact, the Raman band at around Technology Committee (No. 0952nm07100), the Science
Nano Res. 2011, 4(8): 759– 766
and Technology Innovation Fund of the Shanghai
Education Committee (No. 09ZZ85) and Shanghai
Pujiang Talent Plan (No. 08PJ1405100). We thank
Professor Shoushan Fan of Tsinghua–Foxconn Nano-
technology Research Center for the HRTEM measure-
ments, and Professor Pingheng Tan of the Institute of
Semiconductors for some of the Raman measurements.
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