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Available at www.sciencedirect.com

ScienceDirect
journal homepage: www.elsevier.com/locate/carbon

Elucidating the effect of heating induced structural

change on electrical and thermal property
improvement of single wall carbon nanotube
Naoyuki Matsumoto a,b, Azusa Oshima a,b, Guohai Chen
Motoo Yumura a,b, Kenji Hata a,b,*, Don N. Futaba a,b,*
a
b

a,b

, Masako Yudasaka b,

Technology Research Association for Single Wall Carbon Nanotubes (TASC), Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
National Institute of Advanced Industrial Science and Technology (AIST), Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan

A R T I C L E I N F O

A B S T R A C T

Article history:

We have clarified that the electrical and thermal properties of single-walled carbon nan-

Received 16 October 2014

otubes (SWCNTs) are improved by multiple structural changes (wall number, diameter,

Accepted 22 January 2015

and crystallinity) induced by high temperature treatment. Focusing on the relationship

Available online 7 February 2015

between structural change and electrical and thermal properties, high-purity SWCNTs
were fabricated using the water-assisted CVD method and treated at high temperatures
(15002000 C) in an argon atmosphere. We showed that the electrical and thermal properties of the SWCNTs were improved by 2.9 and 3.0, respectively, which required lower
treatment temperatures than for multi-walled CNTs (MWCNTs). In addition to the crystallinity improvement, the wall number and diameter increased with treatment temperature. When compared to as-grown SWCNTs of similar wall number and diameter,
the heat treated SWCNTs exhibited higher electrical and thermal properties, which suggested that the property improvements could be attributed to not only to the wall number
and diameter but also to the improvement in crystallinity.
 2015 Elsevier Ltd. All rights reserved.

1.

Introduction

In the graphitization process for carbon fibers, a carbonized

carbon fiber is heat-treated in an inert gas ambient at 2500
3000 C where impurities (i.e. carbonaceous, sodium, and
potassium) are removed and the defects in a graphite sheet
are reduced (i.e. improved crystallinity). As a result, the
mechanical (elastic modulus), electrical, and thermal properties are greatly improved [16]. Such improvements have contributed to the increased demand and use of carbon fibers [7].
An apt example is the application to the aerospace industry

where carbon fiber composite materials have reduced the

composite weight by 50% and the overall aircraft weight by
30%.
A defect-free carbon nanotube (CNT) is expected to possess exceptional thermal and electrical properties, with a
thermal conductivity 10-times that of copper, and an electric
mobility 10-times that of silicon [8]. However, in reality,
defects in the graphene structure of CNTs significantly
degrade their thermal and electrical properties and therefore
limit their application [8]. If the crystallinity could be
improved (i.e. reduced crystalline defects) by a process

* Corresponding authors at: National Institute of Advanced Industrial Science and Technology (AIST), Central 5, 1-1-1 Higashi, Tsukuba,
Ibaraki 305-8565, Japan.
E-mail addresses: kenji-hata@aist.go.jp (K. Hata), d-futaba@aist.go.jp (D.N. Futaba).
http://dx.doi.org/10.1016/j.carbon.2015.01.042
0008-6223/ 2015 Elsevier Ltd. All rights reserved.

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analogous to that to the graphitization of carbon-fibers, CNTs

would be available with excellent quality to spur new applications as well as experience increased demand. It has been
reported that by graphitizing multi-walled CNTs (MWCNTs),
the crystallinity, purity, and thermal, electrical, and mechanical properties could all be improved. For example, heat treating MWCNTs at 12002000 C in high vacuum showed a
decrease in the interlayer spacing and an increase in the
Raman G-band, D-band ratio (an indicator of crystallinity).
As a result, the electrical properties improved 2 times [9].
Another report demonstrated that by graphitizing MWCNTs
at 20002800 C in an argon (Ar) atmosphere, both the CNT
purity and the crystallinity improved, and demonstrated a
2 and 1.5 times increase in the electrical conductivity
and thermal diffusivity, respectively [10,11]. In addition,
annealing a vertically aligned MWCNT mat at 15002000 C
in an Ar ambient resulted in a significant increase in stiffness
and macroscopic compressive strength [12].
High temperature treatment of single-walled CNTs
(SWCNTs) has also been reported which has led to improved
crystallinity and purity, and increased wall number and diameter. For example, when SWCNTs were treated at high temperatures, reports have shown the aggregation of defects and
self-healing of the graphene lattice to increase the overall crystallinity [13]. In addition, molecular dynamics simulations
have shown that the diameter and wall number increase due
to the thermal coalescence of adjacent SWCNTs by a physical
patching-and-tearing mechanism [14,15]. Further, by heating SWCNTs (HiPCOs) at 10002400 C in a vacuum or Ar, the
diameter and wall number of CNTs have been shown to
increase to double-walled CNTs (DWCNTs) and even
MWCNTs, while the levels of metal catalysts and carbonaceous impurities decreased [16,17]. In fact, Monte Carlo
simulation have shown that heating of SWCNT bundles under
high pressure (12 GPa) follows a graphitization pathway leading to a transformation to layered graphite crystals [18]. However, while the thermally-induced changes in the SWCNT
structure and impurities have been well documented, unlike
MWCNTs, there is a surprising absence of reports on the investigation in the change in physical properties, e.g. thermal and
electrical properties, of SWCNTs by high temperature heating.
Since purification processes to remove metal catalysts and
carbonaceous impurities from SWCNTs also damages the
CNT structure, isolating the influence of the structural
changes by high temperature treatments on SWCNTs on the
thermal and electrical properties is no simple task. The damage to the CNT structure and degradation of SWCNT properties are significant during the purification process because
as-grown SWCNTs typically contain a substantial amount of
metal catalyst and carbonaceous impurities. Attempts to
develop SWCNT purification processes, either through physical or chemical methods, prior to high temperature heating
have not successfully overcome the problem of damage to
the CNT structure [19,20]. Carbonaceous impurities accumulate on the CNT outer walls and at high levels forms an additional layer during the high temperature heating, which
effectively increases the wall number [21]. Metal catalysts
remaining in the CNT material can be removed through high
temperature heating, but this process also causes structural
damage as the metal catalyst migrates along the CNT surface.

Therefore, rather than purifying as-grown CNTs, catalyst-free

and high purity SWCNTs were grown by the Super Growth
(SG), water-assisted CVD, method. Because the SWCNTs
grown by this method have shown to not contain metal catalysts material and almost no carbonaceous impurities, we
could isolate the changes to the thermal and electrical properties to the high temperature-induced structural changes
(i.e. wall number and diameter).
In this report, the enhancement of the electrical and thermal properties of high-purity SG-SWCNTs, treated at high
temperatures similar to carbon fibers and MWCNTs, and the
influence of the structural change of these CNTs on the physical properties were investigated. We found that for
SWCNTs, the electrical and thermal properties could be
improved significantly (3-times) and at lower heating temperatures compared to similar treatments on MWCNTs.
Investigation into the underlying reasons revealed that these
property improvements were not only due to the improvement of crystallinity as reported for MWCNTs but also due
to increases in both wall number and diameter.

2.

Experimental

2.1.

Sample preparation

High purity SG-SWCNT forests were synthesized using the

water-assisted CVD method as previous reports [22,23]. A forest describes the vertically aligned structure of CNTs when
they self-assemble into a single cohesive unit. Briefly, a silicon
wafer, which was sequentially sputtered with catalyst/support layer Fe (1.8 nm)/Al2O3 (40 nm), was reduced in a hydrogen ambient (H2/He: 90%: 10%) at 815 C for 15 min at a total
flow of 2000 standard cubic centimeters per minute (sccm)
to form catalyst nanoparticles. To grow CNTs, C2H4 was introduced to the growth ambient for 10 min at the rate of
(80 sccm) and water vapor (200250 ppm) using a carrier
gas of He (900 sccm). The as-grown forests were removed
from the substrates and dispersed in an organic solvent
(MIBK: Methyl isobutyl ketone), SG-SWCNT buckypaper was
fabricated by filtration and then vacuum-dried at 180 C to
remove the solvent [24,25]. The heat treatment consisted of
annealing the high purity SG-SWCNT forests (10 10 mm)
and buckypaper (10 10 mm) in a carbon resistance furnace
at 15002000 C for 2 h in Ar gas flow (600 sccm).

2.2.

Characterization

Electrical sheet conductance (inverse of the sheet resistance)

of the SWCNT forest before and after heat treatment was
measured by a lithographically fabricated micro-4-probe as
described in previous paper [25,26]. The conductivity of
buckypaper was evaluated by a standard-sized 4-probe [25].
The thermal diffusivity (through plane, along the CNT axis)
of CNT forests was measured before and after the high temperature heating by the flash method at room temperature
in air using a flash analyzer (NETZSCH, LFA-464) with a Xenon
lamp. In addition, the thermal diffusivity (in plane) of
buckypaper was measured at room temperature in air by a
thermo-wave analyzer (Bethel TA3). The change in wall number, diameter, and crystallinity of CNTs were evaluated by

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Raman spectroscopy (wavelength: 532 nm) and by transmission electron microscopy (TEM, TOPCOM EM-002B).

3.

Results and discussion

To clarify the influence of the CNT structural (wall number,

diameter, and crystallinity) change induced by the high temperature heating, the high purity SG-SWCNTs were heattreated at several temperatures. High purity SG-SWCNT forests (diameter: 2.8 nm, carbon purity: >99.9%, CNT purity:
9395%) were synthesized by water-assisted CVD (SuperGrowth CVD) method mentioned above [22,23]. It should be
noted that SWCNTs made by this method have been reported
to possess virtually no residual metal catalyst material and
low levels of carbonaceous impurities (i.e. an absolute purity
as high as 97% [27]); therefore, the effect of these impurities
on the properties could be neglected. Furthermore, buckypapers were fabricated to clarify the influence of the SWCNT
form on the property improvements by high temperature
heating. Both SG-SWCNT forests and buckypapers were
heat-treated at temperatures ranging from 1500 to 2000 C
for 2 h in Ar, and the thermal and electrical properties were
found to improve because of the structural changes (Fig. 1a).
Our results clarified that the improvement in thermal and
electrical properties of the heat-treated SG-SWCNT samples
was greater at higher annealing temperature and that this
improvement occurred at lower heating temperatures than
for MWCNTs. The thermal (thermal diffusivity) and electrical
(sheet conductance or electrical conductivity) properties of
the heat-treated forests and buckypapers were measured

241

and plotted versus the heating temperature (Fig. 1b and c).

The sheet conductance of SG-SWCNT forests increased with
heating temperature: about 2.7 times from 0.11 103 S/h
(as-grown) to 0.29 103 S/h (2000 C). Furthermore, the electrical conductivity of buckypaper improved in similar fashion
as the forests: 2.9 times from 24.1 S/cm (as-grown) to 68.6 S/
cm (2000 C) (Fig. 1b). The through-plane and in-plane thermal diffusivities for the heat-treated forests and buckypapers,
respectively increased with increased treatment temperatures: from 51.4 (through plane) and 11.6 mm2/s (inplane) before the heat treatment to 171 and 33.8 mm2/s,
respectively after the heating at 2000 C, respectively (Fig. 1c).
In a previous report on the graphitization (high temperature heating) process of MWCNTs, the thermal and electrical properties improved only up to 2 and 1.2 times,
respectively, and, for additional improvement, further
increase in treatment temperature were required [911]. The
observation that the SG-SWCNT properties improved effectively at lower heating temperatures compared to MWCNT
can be explained by the single layer structure and smaller diameter. Therefore, the thermal stability is lower due to the
smaller radius of curvature in the graphene lattice affording
the SWCNT structure to be more prone to change than
MWCNTs, resulting in the improvement of the thermal and
electrical properties at lower temperatures [28]. It should be
noted that an increase in electrical conductivity, but no
change in thermal diffusivity, has been observed for longer
SWCNTs [25]; therefore, lengthening of the SWCNTs due to
our heat treatments is not likely as we have observed increases in both electrical conductivity and thermal diffusivity.

Fig. 1 (a) Process scheme of high temperature annealing for SG-SWCNT forests. (b) Electrical and (c) thermal property before
and after treatment.

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Raman measurement and transmission electron microscopy (TEM) observations showed that the wall number and
the diameter of SG-SWCNTs increased with the heating temperature. The G 0 -band peak (26002700 cm1) in the Raman
spectrum of SG-SWCNT forests blue-shifted as the heating
temperature increased (Fig. 2a). The blue-shift in G 0 -band
peak is indicative to an increase in wall number, and therefore this result is a qualitative indication that the wall number
increased from the high temperature heating [29]. In addition,
heat treatments at increased temperature led to the extinction of the Raman radial breathing modes (RBM) (50
300 cm1) at high wave number (150300 cm1) (corresponding to smaller diameter SWCNTs) and the increase in intensity of the peaks at low wave number (150 cm1) (Fig. 2a).
Since the RBM wavenumber is related to the CNT diameter,
this result is further evidence of the decrease in the relative
population of small diameter SWCNTs and increase in relative population of that large diameter SWCNTs with increasing treatment temperatures [30].
TEM observation directly confirmed the increase in the
wall number and diameter of the heat-treated SG-SWCNTs.
Specifically, TEM showed the presence of only SWCNTs after
heating at 1500 C, both SWCNTs and DWCNTs at 1750 C,
and only DWCNTs and MWCNTs at 2000 C (Fig. 2b). Diameter
and wall number distributions for each of the treatment temperatures from the TEM observations shows the quantitative
increase in mean diameter with the heating temperature
from 2.7 nm (as-grown) to 5.0 nm (2000 C) and the increase
in mean wall number with heating temperature from 1.0
(as-grown) to 2.4 (2000 C) (Fig. 2c and d).
We clarified that the crystallinity of SG-CNTs was
improved by the high temperature heating from Raman
spectra. It is well-known that the ratio between the Raman
Graphitic-band (1590 cm1) and the Disorder-band
(1340 cm1) intensities is an index for the crystallinity of
CNTs; however, due to the sensitivity to the wall number, it
cannot be used to estimate the crystallinity in the case where
wall number increases. Therefore, we compared the crystallinity change before and after the heat treatment by using
a different indicator, the intensity ratio of the Raman
G 0 double resonance peak (26002800 cm1), to the D-band
(1340 cm1), peak (Fig. 2d). The G 0 peak has been reported
to not depend on increases in the wall number [31]. Therefore,
the G 0 /D ratio indicates the level of defects in the CNT graphitic structure, in which a high crystallinity would result in a
high ratio. The G 0 /D ratio was found to increase monotonically with the heating temperature. Therefore, the improvement
of the G 0 /D ratio indicates improvement in the crystallinity of
SG-SWCNTs. Previous reports have shown an improvement in
crystal structure in SWCNTs and MWCNTs by high temperature treatments, which they concluded was the result
of the aggregation of defects and the reconstruction of the
graphene lattice. Therefore, we expect that our observed
improvement in crystallinity by the high temperature heating
follows the same process.
In previous reports on the high temperature heating of
MWCNTs, the presence of large quantities of metal catalyst
material and carbonaceous impurities made the investigation
into the influence of the CNT structural change on the thermal and electrical properties impossible. We found that the

improvement to the crystallinity as well as changes to the

structure (increase in wall number and diameter) all contribute to the observed improvement of the electrical and
thermal properties. This point had not previously been
reported due to the inability to synthesize highly pure
SWCNTs not containing metal catalysts and carbonaceous
impurities. Previous studies on the heat treatment of
SWCNTs have been limited to examination of the structural
changes and not the changes to the electrical and thermal
properties. To investigate the relationship between the
change in thermal and electrical properties and the thermally-induced structural change to the SG-SWCNTs, the thermal
diffusivity and electrical conductivity were plotted as a function of the diameter, the wall number, and the G 0 /D ratio
(crystallinity) of the heat-treated buckypaper (Fig. 3ad).
These plots showed that the thermal and electrical properties
improved with the increases in wall number and diameter
induced by the high temperature treatment (Fig. 3a and b).
In addition, they also showed that the thermal and electrical
properties improved by the crystallinity (G 0 /D ratio) improvement by the heat treatment (Fig. 3c and d).
We found that the improvement of thermal and electrical
properties occurred not selectively but rather simultaneously
for the high temperature treatment of SWCNTs. To clarify the
correlation between thermal and electrical properties in relation to the high temperature heating of SG-SWCNTs, Fig. 4
shows the relationship between thermal property (thermal
diffusivity) (x-axis) and electrical property (electrical conductivity) (y-axis) from Fig. 4. This plot shows that both the thermal and electrical properties of SG-CNTs improved with the
heat treatment temperature and a proportionate relationship
existed between the two quantities.
A number of structural factors (wall number and crystallinity) are known to determine the electrical and thermal
properties of CNTs. The wall number is known to affect the
electrical properties, but its effect on the thermal properties
has not been clarified [24]. In addition, crystallinity has been
experimentally known to improve the thermal properties of
SWCNT [26]. However, the connection between increases in
thermal and electrical properties in this report could not elucidate which structure, wall number or crystallinity, more
strongly affected the thermal and electrical properties. Therefore, to address this issue, we synthesized SG-CNT forests
having the same crystallinity and height, while differing only
by the wall number, and evaluated their thermal and electrical
properties to clarify the factors to improve the thermal and
electrical properties during the high temperature treatment
of SG-SWCNTs. As reported previously [24], SG-CNT forests
were synthesized to have the same crystallinity and different
wall numbers (diameters) by varying the thickness of the Fe
catalyst between 1.8 and 6.0 nm on an Al2O3 support layer
on silicon substrates. The synthesis was carried out at 800 C
at a total flow of 1000 sccm using a C2H2 carbon source (30
60 sccm), water as the growth enhancer (100270 ppm). The
thermal and electrical properties of this set of SG-CNT forests
with different wall numbers (diameters) were evaluated by the
same methods as described above, and the results are plotted
in Fig. 4 (black squares). As the wall number increased from
SWCNTs to 5.5-walled CNTs, the electrical conductivity
showed an increase from 26.0 (SWCNTs) to 47.5 S/cm

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243

Fig. 2 CNT structure characterization of SG-CNT before and after annealing (a)Raman spectra; (b) transmission electron
microscope (TEM) images (Bar: 10 nm); TEM histograms of the (c) diameter and (d) wall number; and (e) Plot of the Raman G 0 /D
ratio SWCNT forests and buckypapers.

(2.7-walled) followed by a decrease to 34.3 S/cm (5.5-walled

CNTs). In contrast, the thermal diffusivity showed a strict
monotonic increase from 13.7 (SWCNTs) to 28.9 mm2/s

(5.5-walled CNTs). While the thermal diffusivity of the asgrown 5.5-walled CNTs (28.9 mm2/s) was comparable to the
SWCNTs heat treated at 2000 C (33.8 mm2/s), the electrical

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Fig. 3 Plots of the buckypaper (a) electrical conductivity versus the wall number (inset: electrical conductivity versus
diameter); (b) thermal diffusivity versus the wall number (inset: thermal diffusivity versus diameter); (c) electrical
conductivity versus G 0 /D ratio; and (d) thermal diffusivity versus G 0 /D ratio.
conductivity was found to differ significantly: 34.3 S/cm versus 68.6 S/cm for the synthesized 5.5-walled CNT and heattreated SWCNTs, respectively. When comparing the properties for CNTs of similar wall number, the properties of the heat
treated SWCNTs (at 2000 C), which were characterized to be
2.2-walled CNTs, outperformed the as-grown 2.1-walled SGCNTs. In addition, the thermal and electrical properties after
heat treatment at 2000 C (of 33.8 mm2/s and 68.6 S/cm,
respectively) were exceeded those of the 2.1-walled CNT
(14.6 mm2/s and 41.7 S/cm, respectively). From these results,
we conclude that the observed significant improvement of
electrical and thermal properties in high temperature heating
process could not be completely explained by the increase in
wall number (diameter) and therefore was a result of the
improvement in crystallinity.

4.

Fig. 4 Plot of the thermal diffusivity versus electrical

property for as-grown SWCNTs, treated SWCNTs, and CNT
forests grown with different wall number.

Conclusion

We have examined the changes to the electrical and thermal

properties of SWCNTs due to high temperature treatments,
which have not previously been reported. We clarified that
the electrical and thermal properties of heat-treated SWCNTs
could be improved, and the improvement was attributed to
the change in the CNT structure (wall number, diameter, and
crystallinity). Heat treatment of high purity SWCNTs,

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synthesized by the water-assisted CVD method at 15002000 C

in an Ar atmosphere, showed proportionate increases in the
electrical and thermal properties with the treatment temperatures. Furthermore, when compared to similar heat treatments to MWCNTs, the required heating temperatures were
found to be significantly lower. Evaluation of the change in
the CNT structure for each temperature treatment clarified
that the wall number and diameter increased with treatment
temperature as well as the crystallinity. Through the direct
comparison with as-grown SWCNTs of similar wall number
and diameter, the properties of heat-treated CNT exhibited
higher electrical and thermal properties. These results provide
experimental evidence that in addition to wall number and diameter increase, the improvement in crystallinity was an important factor for improving thermal and electrical properties.

Acknowledgments
This paper is based on results obtained from a project commissioned by the New Energy and Industrial Technology
Development Organization (NEDO). We acknowledge support
from Technology Research Association for Single Wall Carbon
Nanotubes (TASC). The authors are grateful for Sachiko
Ishizawa and Jinping He to synthesize SWCNT forest and
buckypaper.

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