INSTITUTE OF PHYSICS PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS

J. Phys. D: Appl. Phys. 35 (2002) 2779–2784 PII: S0022-3727(02)39332-X

Carbon nanotubes deposition in glow

barrier discharge enhanced catalytic CVD
Tomohiro Nozaki, Yoshihito Kimura and Ken Okazaki
Department of Mechanical and Control Engineering, Tokyo Institute of Technology,
2-12-1 O-okayama, Meguro-ku, Tokyo, 152-8552, Japan
E-mail: tnozaki@mech.titech.ac.jp

Received 11 July 2002, in final form 2 September 2002

Published 22 October 2002
Online at stacks.iop.org/JPhysD/35/2779

Abstract
This study discusses the development of an atmospheric pressure glow
discharge enhanced CVD system for the catalytic growth of carbon
nanotubes (CNTs). He/H2 /CH4 (900 : 100 : 0–20 scc min−1 ) gas mixture
was processed in the barrier discharge reactor operated at 760 Torr.
Ni-coated (20 nm) quartz substrate was used up to 600˚C to achieve low
temperature catalytic growth of CNTs. Special pretreatment of substrate
using metal plating technique was employed for uniform growth; minimum
requirements for CNTs growth were specified in terms of substrate
temperature, H2 /CH4 ratio and deposition time. SEM and TEM
micrographs confirmed multi-wall CNTs with outside diameter and number
density of 40–50 nm and 109 –1010 cm−2 , respectively. On the other hand,
some of those CNTs included considerable wall defects associated with Ni
particle aggregation. We also applied DBD enhanced catalytic CVD, but
CNTs could not synthesized.

1. Introduction CO2 mitigation would lend this non-equilibrium technique

Atmospheric pressure non-equilibrium plasmas, currently
exclusively produced by dielectric barrier discharge (DBD)
[1–3] and atmospheric pressure glow discharge (APG) [4–6],
have made remarkable progress in formation technique, their
applications are expanding into various engineering fields of
not only material processing, but also energy and environment,
due to their special advantages. A highly reactive non-
equilibrium condition is readily available with a simply
configured reaction system operated almost independently
with pressure and temperature.
Our research group especially focuses on carbon nanotube
(CNT) synthesis using non-equilibrium plasma catalytic
decomposition of methane at atmospheric pressure [7].
CNT synthesis using this technique provides great benefits:
(1) Atmospheric pressure non-equilibrium plasma is a potential
alternative to vacuum plasma CVD or micrometre-scale,
nanometre-scale fabrication. (2) Atmospheric pressure
operation is strongly desired for large-scale industrial
applications. (3) Wide spectrum applications of CNTs
are expected, and sufficient amount of CNTs would be
processed and distributed with minimum energy consumption
and installation size required. Also, growing demands for
to simultaneous production of CNTs and hydrogen; carbon
fixation as CNTs rather than carbon black is strongly desired
from a practical viewpoint [8, 9]. For these reasons, we
first developed a new method of synthesizing CNTs using
APG enhanced catalytic chemical vapour deposition. Our
main objective is to specify minimum requirements for CNT
growth in terms of growth temperature, gas composition
(H2 /CH4 ratio), and deposition time. We also discuss DBD
(microdischarge) enhanced CVD for this purpose. Properties
of synthesized nanostructured carbon materials were compared
to those reported in the literature by focusing on thermal CVD
[9–11] and vacuum plasma CVD [12–15] on Ni catalyst using
H2 /CH4 mixture, considering our experimental conditions.
2. Basic properties of APG and DBD
Two kinds of atmospheric pressure non-equilibrium plasma
sources were examined in a barrier discharge reactor: APG
and DBD. Detailed properties of APG and DBD have already
been discussed by other researchers [16–18].
The spatiality of barrier discharge reactor is the insertion
of dielectric material on at least one metallic electrode.
Figure 1(a) shows voltage and current waveforms for APG

0022-3727/02/212779+06$30.00 © 2002 IOP Publishing Ltd Printed in the UK 2779

T Nozaki et al
generated between two parallel-plate electrodes. When a
working gas was diluted with a large amount of helium, a single
current pulse appeared at every half cycle of voltage. Electron
temperature is elevated much higher than gas temperature
Figure 1. AC voltage and current waveforms for (a) APG
(He : CH4 = 98 : 2) and (b) DBD (CH4 ). Total pressure was
760 Torr [18].
Figure 2. ICCD photographs for (a) APG during negative discharge current, (b) positive discharge current, and (c) DBD [18].
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during current evolution, but it terminates before arcing
due to presence of a dielectric barrier. Corresponding
emission distributions in the visible spectrum range are
described in figures 2(a) and (b). Figure 2(a) shows
a superposition of 100 discharge events during negative
discharge current (metallic cathode–dielectric anode), whereas
figure 2(b) shows the situation during positive discharge
current. APG is characterized as radially uniform plasma
accompanied by negative glow having several tens of
micrometre thickness [18]. Particularly, negative glow
intensity significantly increases when it contacts with the
metallic electrode. Generally, APG is operated near break
down field; thus current density per voltage half cycle
is uniquely determined by gap separation and dielectric
properties.
DBD is characterized as a number of nanosecond
current pulses (figure 1(b)) associated with microdischarge
formation (figure 2(c)). Due to the charge accumulated
on the barrier, microdischarges were uniformly distributed
between electrodes. The light distribution is localized into
a number of filamentary regions and spreads along a dielectric
barrier. DBD does not require helium dilution, which
makes it very favourable for practical applications. However,
microdischarges ionize a wide range of gas gap, leading to
particle formation in the gas phase.
3. Experimental
Figure 3 shows the barrier discharge reactor used in this
experiment. The high voltage electrode (upper) was covered by
a 500-µm-thick alumina plate and separated by 3.0 mm from
the GND electrode (lower). Ni-coated (20 nm) quartz substrate
was placed on heated GND electrode to provide intense
negative grow near the metallic substrate [18]. Temperature
increase of substrate by plasma heating was as small as 50˚C
due to low input power (10 W). Substrate temperature was
detected by thermocouple and elevated up to 600˚C with
the embedded electric heater. AC 125 kHz high voltage
was applied between metallic electrodes without DC bias.
The electrode system was placed in a vacuum chamber.
The chamber was once evacuated below 10−3 Torr; then,
He/H2 /CH4 gas mixture was introduced while maintaining
flow rate and pressure (760 Torr).
 Carbon nanotubes deposition in catalytic CVD

We prepared a Ni-coated quartz substrate using metal 4. Results and discussion

plating technique instead of the conventional sputtering
method for several reasons: (1) To achieve highly smooth 4.1. Initial stage of CNT growth and growth model
and uniform surface conditions. Otherwise, filamentary
Figure 4 shows surface conditions of Ni-coated substrate and
microdischarge was likely superimposed and this condition
initial stage of CNTs growth observed after 5 min deposition
could not deposit fibrous materials as discussed in section 4.3.
by APG. The view angle was 45˚. The surface was flat, but
(2) To obtain uniform coating thickness. This is important for
diameters of Ni particle widely distributed between 20–70 nm.
uniform distribution of Ni grain size, and thus uniform CNTs
Individual CNTs hold Ni particles having almost identical
diameter distribution. Ni thin film with 20 nm thickness was
diameter. These evidences indicate the basic catalyst-cap
uniformly coated on a quartz substrate at a mirror-smooth state.
growth mechanism first proposed by Baker et al [21] as widely
It was then preheated up to 600˚C in hydrogen atmosphere and
accepted by many researchers [11, 22]. Figure 5 schematically
maintained for 30 min before deposition. The metal plating
describes Baker’s growth model. It is divided into four
technique used in our experiment did not allow Fe and Co
stages: (1) Nickel nanoparticles are formed. (2) Methane
catalyst as coatings. However, Ni catalyst is the most common
decomposes on the Ni surface to form Ni–carbon alloy,
catalyst used in many studies; therefore, basic properties of
releasing a considerable amount of heat. (3) Carbon diffuses
CNT itself and deposition processes can be understood.
deep into the Ni–carbon alloy; melting temperature of the alloy
Higher H2 content and higher growth temperature is
decreases. At this moment, the alloy must have properties of
the general tendency for deposition of optimized CNTs.
liquid; alloy distortion takes place. (4) Carbon precipitate
On other hand, Ishida et al [19] have observed excellent
CNTs in CH4 -dominant plasma CVD (H2 : CH4 = 1 : 9). as nanocrystalline graphite and the particle detaches from
Hayashi et al [20] have reported that optimized substrate the support. Formation of saturated Ni–carbon alloy, i.e.
temperature for well-aligned CNTs was between 600˚C and the second–third stages, required several minutes in our
630˚C in microwave plasmas. Otherwise, curved nanotubes experiment. These alloys are recognized as white-coloured
were grown at lower density. Due to these facts, we first particles in figure 4. After that, CNTs growth rate increases
specified minimum requirements for CNT growth in terms rapidly. Although CNT quality depends strongly on initial
of substrate temperature, H2 /CH4 ratio, and deposition time conditions of Ni particles, figure 6 represents the best quality
as shown in table 1. Deposited materials were characterized of CNTs with almost uniform diameters of 40–50 nm and
by Raman spectroscopy (JASCO NRS-1000, Green laser density of 109 –1010 cm−2 . CNTs obtained by our experiment
532 nm), HRTEM (JEOL JEM-3010), and FE-SEM (JEOL were randomly grown due to lack of DC bias. Presence of
JEM-2010F).

Figure 4. Surface conditions of Ni-coated substrate and the initial

stage of CNTs growth (after 5 min).

Figure 3. Electrode configuration.

Table 1. Growth parameters.

Growth temperature (˚C) 400, 500, 600

Growth time (min) 5–30
H2 /CH4 ration (-) 0, 5, 10
Flow rate of gas mixture APG: He : H2 : CH4 = 900 : 100 : 0–20
(scc min−1 ) DBD: He : H2 : CH4 = 150 : 150 : 15
Pressure (Torr) 760
Power (current peak) ∼4 W cm−2 (∼15 mA cm−2 ) Figure 5. Catalyst-cap growth mechanism for a multi-wall CNT
first proposed by Baker et al [21].

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dielectric material forces the use of alternating voltage in order
to maintain a series of pulsed discharges. On the other hand,
aligned CNTs will likely grow with existence of directional
electric field and sufficient amount of space charges [22].
4.2. Detailed wall structure of nanostructured graphite
High-resolution TEM images shown in figures 7(a)–(d)
confirmed hollow multi-wall structure with external diameter
Figure 6. CNTs with uniform diameter of 40–50 nm and number
density of 109 –1010 cm−2 obtained after 30 min deposition.
(a)
(c)
Figure 7. (a)–(d) High-resolution TEM images showing detailed wall structure of multi-wall CNTs. H2 /CH4 ratio was 10 and growth
temperature was 600˚C.
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of 20–50 nm. Some of the tubes (figure 7(a)) more resemble
hollow nanofibres than nanotubes; they tend to include a
number of structural defects. Figure 7(b) shows a conical
wall structure rather than a concentric one. A detailed
growth mechanism to account for a stacked-cones structure
was presented by Endo et al [23] and Terrones et al [24]. Ishida
et al [19] also observed similar fully-plugged stacked-cones
structured graphite in low-pressure glow plasma enhanced
CVD. Figures 7(c) and (d) show that the grain size determines
the external diameter of CNTs, but inside diameter depends
significantly on various Ni catalyst geometric factors. Ni
particles shown in figures 7(a), (c), and (d) imply that a number
of Ni nanoparticles aggregated to form a much larger one;
this situation was the main reason for formation of hollow
nanofibres having considerable wall imperfections.
Figure 8 shows Raman spectra of CNTs for different
H2 /CH4 ratios and growth temperatures. The G-band
located around 1586 cm−1 attributes C–C stretching vibration
of graphite layers, indicating well-graphitized carbon
nanostructure; an intense G-band peak was obtained when the
growth temperature was 600˚C (#2). Intensity of the G-band
decreased with decreasing hydrogen content; it eventually
disappeared when the H2 /CH4 ratio fell short of five (#4).
We observed no specific peak when the growth temperature
was below 500˚C (#5). Imperfect graphite structure was
also characterized from the D-band near 1350 cm−1 . The
D-/G-band intensity ratio of individual samples is presented
(b)
(d)
 Carbon nanotubes deposition in catalytic CVD

in table 2 along with those estimated from the literature.
Table 2 especially focuses on thermal CVD and vacuum plasma
CVD on Ni catalyst using H2 /CH4 mixture, considering our
experimental conditions.
Otsuka et al [9] and Choi et al [12] synthesized
nanostructured carbon materials at relatively low temperature
(∼500˚C) with a hydrogen rich condition. They confirmed
clear D- and G-band with the intensity ratio between
1.2 and 1.4. The intensity of G-band peak increases
with increasing growth temperature, indicating that a well-
graphitized carbon nanostructure can be easily formed at
elevated temperature. However, disordered graphite structure
also increases; consequently, D-/G-band intensity ratio
significantly increases [10, 13]. According to Choi et al
[10], remarkable increase in D-band intensity was associated
with generation of amorphous carbonaceous fragments rather
than structural imperfections of nanocrystalline graphite.
Graphitization as well as hydrogenation of disordered graphite
effectively proceeded at much elevated temperature (>900˚C),
resulting in a very low intensity ratio [10, 15]. Due to TEM
observation, imperfect aggregation of catalyst particles, as
in figures 7(a) and (c), implies that melting temperature of
Ni–carbon alloy seems to be higher than a given growth
temperature. Most aggregated particles did not fuse together,
and a droplet-shaped alloy, such as figure 7(d), was hardly
observed. As a result, catalytic activity as well as carbon
diffusion rate within the alloy was unexpectedly low at a given
growth temperature, thus we could not obtain clear D- and
G-band peak at 500˚C or zero hydrogen content.

4.3. Effect of microdischarges on catalytic CVD

Figure 8 also presents the result obtained by filamentary DBD

Figure 8. Raman spectra: (#1) DBD at 600˚C and H2 /CH4 = 10,
(#2)–(#4) APG at different H2 /CH4 ratios, (#5) APG at 500˚C.
with 48% helium dilution (He/H2 /CH4 = 150 : 150 : 15).
Substrate temperature and input power were 600˚C and
10 W. Although faint G-band and D-band peaks were
observed, SEM micrograph does not show fibrous materials
(figure 9). In contrast to APG, DBD is characterized
as volumetric discharges that will likely produce particles
in the gas phase reactions: figure 9 more resembles like
particle precipitation than film deposition. Also, radical
formation due to microdischarge propagation is terminated
within 10 ns or sooner, leading to insufficient supply of
radical species to the substrate surface where Ni catalyst exist.
Spatial inhomogeneities may also contribute to significant
deterioration of deposited material.

Table 2. Comparison of D/G intensity ratios (ND: not detected).

Feed gas
Temperature Pressure
Ref. (˚C) (Torr) C n Hm H2 /Cn Hm Catalyst D/G ratio Source
This work 600 760 CH4 10 20 nm Ni film 1.3 APG
600 760 CH4 5 20 nm Ni film 1.2 APG
600 760 CH4 0 20 nm Ni film D-, G-: ND APG
500 760 CH4 10 20 nm Ni film D-, G-: ND APG
600 760 CH4 10 20 nm Ni film 1.0 DBD
[9] 500 760 CH4 0 5%Ni/SiO2 1.3 Thermal
[10] 500 760 C 2 H4 rich 10–40 min Ni film 0.8 Thermal
600 760 C 2 H4 rich 10–40 min Ni film 0.7 Thermal
700 760 C 2 H4 rich 10–40 min Ni film 1.2 Thermal
800 760 C 2 H4 rich 10–40 min Ni film 0.6 Thermal
900 760 C 2 H4 rich 10–40 min Ni film D-: ND Thermal
[11] 800–900 760 C 2 H4 0 100 nm-Co/Ni 1.4 Thermal
[12] 520 10 CH4 2.3 70 nm Ni film 1.2–1.4 Microwave
[13] 600 10 CH4 4 70 nm Ni film 1.1 Microwave
650 10 CH4 4 70 nm Ni film 1.6 Microwave
700 10 CH4 4 70 nm Ni film 2.3 Microwave
[14] 720 15 CH4 40 Fe-oxide particle 0.7 Microwave
[15] 1050 100 CH4 9 Non-catalytic 0.2 DC glow

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Figure 9. Carbonaceous materials deposited by DBD enhanced
CCVD on Ni-coated substrate.
5. Conclusions
Newly developed atmospheric pressure glow plasma enhanced
catalytic CVD successfully synthesized high-density, multi-
wall CNT; minimum requirements for CNT growth were
specified. The structure of multi-wall CNTs depends strongly
on Ni catalyst geometric factors. Especially, imperfect
aggregation of Ni particles severely deteriorates wall structure.
DBD enhanced catalytic CVD could not achieve CNT
synthesis even with presence of a Ni catalyst: the material
synthesis or micrometre-scale, nanometre-scale fabrication
using APG would be highly controlled and optimized for
desired purposes. Further experiments using various transition
metal catalysts at different growth temperatures will be our next
challenge for controlled growth of aligned CNTs.
Acknowledgments
The authors wish to thank associate professor Naoto Ohtake
(Tokyo Institute of Technology) for his helpful support,
Dr Akira Genseki and Dr Jun Kouki for technical support in
the SEM/TEM analysis (Tokyo Institute of Technology), and
Dr Shigeru Kado (Tokyo Institute of Technology) for intensive
discussion.
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