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Phys. Status Solidi B 249, No. 12, 2625–2628 (2012) / DOI 10.1002/pssb.201200144

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basic solid state physics
Carbon nanowalls synthesis by means
of atmospheric dcPECVD method
,1 1,2 1 1,3 4 1
Marcel Meško* , Viliam Vretenár , Peter Kotrusz , Martin Hulman , Ján Šoltýs , and Viera Skákalová
1
Danubia NanoTech, s.r.o., Ilkovičova 3, 841 04 Bratislava, Slovakia
2
Institute of Physics, Slovak Academy of Science, Dúbravská cesta 9, 845 11 Bratislava, Slovakia
3
International Laser Centre, Ilkovičova 3, 841 04 Bratislava, Slovakia
4
Institute of Electrical Engineering, Slovak Academy of Science, Dúbravská cesta 9, 841 11 Bratislava, Slovakia

Received 4 May 2012, revised 14 September 2012, accepted 19 September 2012

Published online 6 November 2012

Keywords atmospheric dcPECVD, carbon nanowalls

* Corresponding author: e-mail mesko@danubiananotech.com, Phone: þ421 (02) 64282144, Fax: þ421 (02) 64282144

Carbon nanowalls (CNWs) were grown by atmospheric dc carbon sources we can control CNWs density. Growth of
plasma enhanced chemical vapour deposition method. Main- sparsely distributed CNWs can be achieved by using ethanol,
taining plasma at atmospheric pressure give us possibility to while hexane gives densely packed CNWs films.
synthetize CNWs at high rate. By using two different liquid

ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction Graphene has been considered a
strong candidate for next generation electrode material in
supercapacitors. It is because of its unique physical proper-
ties (high charge carriers mobilities 10 000–15 000 cm2 V
1)
[1], excellent chemical stability and exceptional large
specific surface (2600 m2 g
1) [2]. Carbon nanowalls
(CNWs) are practical realization of graphene containing
nanostructures. CNWs are two-dimensional carbon struc-
tures that consist of stacked graphene sheets standing
vertically on substrates [3]. CNWs are mainly synthetized
by low-pressure hot filament CVD [4], radio frequency (RF;
13.56 MHz) [5] and microwave (2.45 GHz) [6–8] PECVD
methods. More recently, it was shown that CNWs can be
grown by an atmospheric dcPECVD method [9]. This
method allows CNWs to be synthetized at a high rate due to
the presence of large amount of radicals [10]. Furthermore,
this method is easier scalable compared to the RF or
microwave PECVD methods. Unlike the conventional
high surface materials [11, 12], CNWs do not contain pores
[13, 14]. Thus the effective surface area of CNWs depends
on the wall density. On the other hand, CNWs should not
stack too closely in order to allow electrolyte ions to
penetrate efficiently into the network of CNWs. In this
work, we emphasize a possibility to control the density
of CNWs grown by an atmospheric dc plasma enhanced
chemical vapour (dcPECVD) method. This can be achieved
by different kinds of liquid carbon sources used. The growth
of sparsely distributed CNWs has been accomplished by
using ethanol while hexane gives densely packed CNWs
films.
2 Experimental Experimental set-up of atmospheric
dcPECVD reactor for CNWs synthesis is sketched in
Fig. 1. It combines a thermal CVD reactor with a discharge
electrode system. Discharge electrodes system is wired
hermetically through the flanges and is positioned in the
middle of the furnace.
The electrode system is in a point-plane configuration
as shown in Fig. 2a. Cathode is 2 mm in diameter. Anode
electrode has a square shape with the dimension of 20 mm.
The cathode–anode distance is 10 mm. The electrode system
is connected to a homemade dc power supply. Applying
high voltage of 2 kV the cathode ignites a discharge. After
the plasma discharge is on, the applied voltage is further
decreased and plasma is maintained at 1 kV and 10 mA.
Carbon nanowalls formation gases are hydrogen and
argon mixed up with ethanol or hexane vapours. CNWs are
synthetized in a two-step process consisting of pre-treatment
and deposition (Fig. 2b). Ni substrates were thermally
annealed at the temperature of 800 8C in the plasma
environment of Ar and H2 gas mixture for 5 min. After that,
additional amount of gas with an identical composition
flowing through the bubbler with ethanol or hexane was
introduced into the reactor chamber. The growth of CNWs

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Figure 1 (online colour at: www.pss-b.com) Sketch of the exper-
imental set-up for the CNWs growth by an atmospheric pressure
dcPECVD.
Figure 2 (online colour at: www.pss-b.com) (a) Electrode system
of an atmospheric dcPECVD, (b) process time line for the CNWs
growth.
lasted for 5 min. Samples were then allowed to cool down
to room temperature in Ar atmosphere. Ni plates for the
CNWs growth is produced by rolling. They are 0.2 mm thick
with lateral dimensions of 20  20 mm2. CNWs grow on
circular patches with the diameter corresponding approxi-
mately to the plasma diameter on the ground electrode
which is 3 mm. CNWs growth is always accompanied
with a grey colour circular shape surrounding concentric
to the CNWs one. Its diameter is approximately 10 mm.
Later it will be shown that nanocrystalline graphite (NCG)
is present in this area. The NCG film growth in this
region can be enhanced by presence of radical species
originating from the plasma column. Samples morphology
was examined by scanning electron microscope (SEM)
FE-SEM FEI Inspect F50. Low-resolution scanning trans-
mission electron microscopy (STEM) analysis of CNWs was
performed on JEOL JSM-7500F. For STEM observations,
CNWs were scratched out from the Ni foil by tweezers and
placed on lacey carbon-coated grids. CNWs films were also
studied by Raman spectroscopy via ISA DILOR JOBIN
YVON spectrometer with the excitation wavelength of
632.8 nm.
3 Results and discussions Figure 3 shows SEM
image of CNWs grown using ethanol as a carbon source. The
images reveal that the CNWs deposit consists of individual
vertically oriented sheets. As can be seen from the inset of
Fig. 3, they have an elongated shape and almost a branch free
structure. While using a similar growth technique, CNWs
ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
M. Meško et al.: Carbon nanowalls synthesis
Figure 3 SEM image of CNWs synthetized on a Ni substrate using
ethanol as a carbon source (observation under tilted angle of 458).
morphology in our case differs from that previously reported
in Ref. [9].
In the latter, the growth of CNWs pointing away from
the substrate and oriented randomly was showed. CNWs
interlace together and form a nest-like structure. Similar
CNWs morphology was found for methods preferring a
catalyst-free growth. The crucial stage for the latter is
nucleation. At this stage, carbon species condense forming
nanoislands with dangling bonds. Subsequently, small
sized disordered carbon nanoflakes are nucleated at these
dangling bonds. This is followed by the two-dimensional
growth and formation of nanographene sheets. At this stage,
other nucleation step appears forming a branch like structure.
Among the randomly oriented nucleated graphene sheets
those standing almost vertically on the substrate grow faster
building up vertically standing nanosheets [15]. We think
that in our case of the catalytic growth on a Ni surface,
nucleation and growth proceed in a different way. We
suggest the following scenario. Initially, a graphite thin
film is formed by decomposition of activated carbonaceous
species on the Ni surface. We assume that sequences of the
graphite thin film growth is similar to those described by
Obraztsov et al. [16]. As soon as the graphite film is built up,
strong electric fields present in the plasma discharge bend
the growing graphite layers along the electric field intensity
lines. Bended graphite layers then grow further forming
graphite flakes standing perpendicular to the substrate.
Zhu et al. [17] found this process especially effective at
grain boundaries of graphite layers. However, in their case,
alignment mechanism was not fully pronounced mainly due
to the screening effect between graphite layers which start
to detach simultaneously. It is because of a very restricted
area and a specific graphite layers formation in nanoislands
due to the limited Si catalytic activity.
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Phys. Status Solidi B 249, No. 12 (2012)
In addition to SEM, as-grown films were characterized
by Raman spectroscopy. The measurements taken from
the area outside the CNWs growth (Fig. 4a, right panel) are
characteristic for NCG film [18]. The SEM image (Fig. 4a,
left panel) of this area reveals a flat surface where CNWs are
absent. This region is located outside the plasma. Thus, it
clearly shows that the plasma contribution is essential for
the CNWs formation. Raman spectra measured on the CNWs
growth area are shown in Fig. 4b (right panel). As compared
to the spectrum of NCG, the D band (1330 cm
1) is much
stronger than the G band (1585 cm
1) which in addition
contains a shoulder at 1620 cm
1 designed as the D0 band.
The intensity of both the D and D0 bands is related to the
breaking of the q ¼ 0 Raman selection rule (q is the phonon
momentum) due to the presence of defects, grain boundaries,
disorder, etc. in the sample. In Ref. [19], a similar spectrum
was obtained for Ar ion-irradiated graphene samples with a
defect–defect distance in the order of a few nanometers. Also
Raman spectra of NCG show similar features when the
crystalline size is of the same order [20].
On the other hand, the average length of CNWs can be
determined from the peak intensity ratio of the D band to G
band (ID/IG) [21]. Our calculated ID/IG  2 corresponds to
the length of 0.5 mm. This value is in a good agreement with
the SEM observation (Fig. 3 inset). It can be seen that the
length of the nanowalls reaches roughly the same value.
The existence of two different length scales also agrees with
the shape of the nanowalls. Therefore, it is reasonable to
Figure 4 SEM image and Raman spectra taken (a) outside the
CNWs growth area and inside of (b) sparse CNWs (ethanol as a
carbon source) and (c) dense CNWs grown from hexane as a
carbon source (observation under tilted angle of 458).
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Figure 5 STEM image of CNWs deposits grown using hexane
as a carbon source.
assign the shorter length scale to the average thickness of the
CNWs.
Figure 4c shows a SEM image of CNWs grown using
hexane as a carbon precursor. The morphology is very
different from that of the ethanol-grown sample. Surpris-
ingly, the Raman spectra are almost identical for both
samples besides the lower ID/IG ratio for the hexane-grown
one. This suggests that the carbon film may consist of densely
packed CNWs of roughly the same size as in the case of
the sparse CNWs. This assumption is supported by the
STEM image in Fig. 5 where the nanosheets thin enough to
be transparent for the electron beam are clearly visible.
Concerning the morphology, we hypothesize that in this
case the electric field induced alignment mechanism is not
effective due to the screening effect because the individual
nanowalls are closely adjacent to each other from the very
beginning of the growth process. In this case, carbon
nanosheets align themselves making up a random structure.
It is also clear from the SEM image that a higher amount
of carbon is deposited on a Ni substrate when hexane is
used for the CNWs growth. A natural explanation is that
the vapour pressure of hexane at room temperature is
about three times higher than that for ethanol meaning that
a larger amount of carbon is transported to the reaction
chamber. This gives rise to a much thicker deposit when
other growth parameters remain the same in both cases.
In either case (vertical and dense CNWs), we observed
a growth rate which can be as high as 100 nm min
1. It
is approximately one order of magnitude higher when
compared to low-pressure methods [22].
4 Conclusions We have demonstrated the synthesis
of vertically aligned CNWs with different densities grown by
an atmospheric dcPECVD method. By using two carbon-
aceous sources, ethanol and hexane, we have grown sparse
and dense CNWs films, respectively. It was shown that
ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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CNWs growth rate is much higher compared to low-pressure
methods. Furthermore, this method does not require
expensive vacuum sealing and is therefore promising for
industrial applications. However, it is essential to optimize
the method for the CNWs film growth with a different
thickness, owing its practicability in, for instance, super-
capacitor applications.
Acknowledgements This work was supported by funding
from the European Union’s Seventh Framework Programme
(FP7/2007-2013) under grant agreement no. 266391 (Electrograph).
MH acknowledges support from the project 1254/12 of the VEGA
grant agency. J. Š. acknowledges the project implementation:
Development of a universal HD video platform for broadcasting,
education and research applications, ITMS code 26240220041.
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