CARBON 7 2 ( 2 0 1 4 ) 3 7 2 –3 8 0

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Synthesis and characterization of carbon nanowalls

on different substrates by radio frequency plasma
enhanced chemical vapor deposition

Keivan Davami a,1, Mehrdad Shaygan a,1, Nazli Kheirabi a,1, Jiong Zhao b,1,
Daria A. Kovalenko c,d, Mark H. Rümmeli b,e, Joerg Opitz c,d, Gianaurelio Cuniberti a,c
,
Jeong-Soo Lee a,*, M. Meyyappan f,*
a
Division of IT Convergence Engineering, Pohang University of Science and Technology, Pohang, Republic of Korea
b
IFW Dresden, 01069 Dresden, Germany
c
Technical University of Dresden, Dresden, Germany
d
Fraunhofer Institute for Non-Destructive Testing, Dresden Branch, 01109 Dresden, Germany
e
Center for Integrated Nanostructure Physics, Institute for Basic Science, Department of Energy Science, Sungkyunkwan University,
Republic of Korea
f
NASA Ames Research Center, Moffett Field, CA 94035, USA

A R T I C L E I N F O A B S T R A C T

Article history:
Received 28 April 2013
Accepted 8 February 2014
Available online 13 February 2014
A radio frequency plasma enhanced chemical vapor deposition system was used for the
successful growth of thin vertical carbon nanowalls, also known as vertical graphene, on
various substrates. Transmission electron microscopy studies confirmed the presence of
vertical graphene walls, which are tapered, typically consisting of 10 layers at the base
tapering off to 2 or 3 layers at the top. The sides of the walls are facetted at quantized
angles of 30 and the facetted sides are usually seamless. Growth occurs at the top open
edge which is not facetted. Hydrogen induced etching allows for nucleation of branch walls
apparently involving a carbon onion-like structure at the root base. Characterization by a
superconducting quantum interference device showed magnetic hysteresis loops and weak
ferromagnetic responses from the samples at room temperature and below. Temperature
dependence of the magnetization revealed a magnetic phase transition around T = 50 K
highlighting the coexistence of antiferromagnetic interactions as well as ferromagnetic
order.
Published by Elsevier Ltd.

1. Introduction surface to volume ratio and transparency make graphene an

interesting candidate for applications such as gas sensors,
Graphene has been attracting much attention due to its large-capacity electrodes in Li batteries, composite additive,
interesting physical, chemical, electrical and other properties electronic devices and others [1–9]. In the last several years,
[1–3]. Characteristics such as high mechanical strength, high carbon nanosheets as another type of carbon structure have

* Corresponding authors: Address: NASA Ames Research Center, Moffett Field, CA 94035, USA. Fax: +1 650 604 5244 (M. Meyyappan).
E-mail addresses: ljs6951@postech.ac.kr (J.-S. Lee), m.meyyappan@nasa.gov (M. Meyyappan).
1
These authors contributed equally.
http://dx.doi.org/10.1016/j.carbon.2014.02.025
0008-6223/Published by Elsevier Ltd.
 CARBON 7 2 (2 0 1 4) 3 7 2–38 0
received attention; this type of carbon is also called carbon
nanowalls (CNWs) or vertical graphene (VG) wherein the car-
bon nanoflakes with their sharp edges and perpendicular to
the substrate are distinctive from other carbon structures.
Consistent with the terminology used in the literature, the
terms VG and CNW are used here interchangeably. These
structures can be useful for catalyst support in fuel cells, con-
ductive electrodes in photovoltaics and energy storage de-
vices such as lithium ion batteries and supercapacitors.
CNWs can be readily synthesized using low temperature
plasmas including DC, RF and microwave discharges [10–18].
A variety of different source gases, diluents or etchants, and
substrates have been investigated to assess the impact on
growth results. The main advantage realized in many of these
studies on plasma enhanced chemical vapor deposition
(PECVD) of vertical graphene is the non-catalytic growth
process [10]. This makes the synthesis possible on any kind
of substrates including Si, Ni, Ti, Pt, Cu, Ge, W, Ta, Mo, SiO2,
Al2O3 and stainless steel [15,18]. Thus PECVD enables the
use of diverse substrates, low temperature growth and is
catalyst-free, which are advantages compared to other tech-
niques. Each type of substrate can influence applications of
vertical graphene in some domain, for example, copper would
be useful as a potential substrate in energy storage devices. In
addition, most of the substrates mentioned above are com-
monly used in microelectronics. A review of the current sta-
tus of PECVD of graphene and unanswered questions at this
stage can be found in [19–21] which include growth mecha-
nism, nature of vertical growth and substrate-independent
growth characteristics. In this work we report the synthesis
of vertical graphene structures by radio-frequency PECVD
on various substrates along with thorough characterization
including the magnetic properties and discuss the growth
mechanisms. Microstructural characterization by transmis-
sion electron microscopy (TEM) allows us to put forward a
growth mechanism. Raman spectroscopy allows character-
ization of the number of walls comparing samples grown on
various substrates. Finally, the graphene samples have been
magnetically characterized. Various magnetic characteristics
from diamagnetism to ferromagnetism have been theoreti-
cally predicted or experimentally observed from different car-
bon allotropes [7–9]. In carbonaceous materials the electronic
structure and magnetic properties are sensitive to the crystal
orientation, edge termination and structural defects. In the
case of graphene, the number of layers, sample area and edge
states of non-bonding electrons can affect magnetic proper-
ties as well as the electronic structure [7]. The characteriza-
tion reveals intrinsic ferromagnetic behavior at room
temperature, an attribute desirable for magneto-resistive
and magnetic memory devices.
2. Experimental work
The synthesis was conducted in a radio-frequency plasma en-
hanced chemical vapor deposition (RF-PECVD) system. An
amorphous carbon layer usually accumulates on the chamber
walls when the PECVD apparatus is used for the deposition of
carbon materials. This semi-insulating layer can affect the
plasma conditions, and as a result, the CNWs. In order to
373
avoid this problem, the chamber was cleaned before each
growth using oxygen plasma for 90 min with a sample stage
temperature of 750 C and plasma power of 900 W. Thus, the
growth conditions for all the samples were the same. A vari-
ety of substrates including copper, Si, and Si covered with a
150 nm film of either Ni or Au (thermally deposited) were
used. The substrates were cleaned first using sonication in
isopropyl alcohol solution and rinsed with de-ionized water,
followed by drying using nitrogen gas. The substrates were
placed on a sample stage (chuck) with resistive heating capa-
bility, and the chuck was positioned 50 mm below the quartz
window using an automatic control system. Vertical graphene
can be grown in a wide range of temperatures from 600 C to
1100 C at different growth pressures between 103 Torr and
atmospheric pressure. Pressure, temperature, flow rates and
other parameters were varied to identify the impact on
growth characteristics. Some of these parametric effects are
known from previous studies [11,15]. Here the focus is on
the morphology of the vertical graphene and magnetic prop-
erties and therefore, the results presented below are for iden-
tical optimized conditions. For the growth of samples here, a
pressure of 1 Torr was maintained and the sample stage was
warmed up to 680 C with a rate of 22 C/min using a current
of 60 A. Plasma was ignited using a mixture of methane and
hydrogen at an RF power of 900 W for a fixed deposition time
of 20 min.
A scanning electron microscope (JEOL JSM-7401F) operat-
ing at 5.00 kV was used for imaging and studying the mor-
phology of the vertical graphene. A JEOL JEM-2010F
transmission electron microscope (TEM) retrofitted with two
CEOS third-order spherical aberration correctors for the
objective lens (CETCOR) and the condenser system (CESCOR)
was used to characterize the grown material. The TEM was
operated using an acceleration voltage of 80 kV. Micrograph
image simulations were obtained using JEMS electron micros-
copy software. The samples were also investigated on disper-
sive Raman microscope Bruker Senterra with a green laser
(excitation wavelength 532 nm) at an intensity of 20 mW. An
exposure time of 10 s per single spectrum was used with 10
accumulations per each point. Lateral resolution of 2 lm on
the sample surface was reached by the use of the 100· objec-
tive. Spectral resolution varied between 3 and 9 cm1 depend-
ing on the diffraction grating used in recording the spectra in
the wavenumber range of 80–4400 cm1. The Raman spectra
of the vertically grown graphene were measured with illumi-
nation parallel to the substrates. Illumination perpendicular
or almost perpendicular to the plane of the nanowalls was
also attempted but the edges are believed to affect the results
and interpretation of the number of layers.
Magnetic characterization was performed using the super-
conducting quantum interference device (SQUID) magnetom-
eter (MPMS XL Quantum Design) operating from 2 K to 300 K.
The scratched graphene powder from the samples with a
mass of 1 mg was loaded into the machine chamber and the
changes in magnetization as a function of the external mag-
netic field were detected at different temperatures. The sam-
ple container itself did not have significant effect on the
measured magnetization. The scan X-ray photoelectron
spectroscopy (XPS) measurements were recorded with VG
scientific (Escalab 220ixl) spectrometer, equipped with
374 CARBON 7 2 ( 2 0 1 4 ) 3 7 2 –3 8 0
monochromatic Al Ka radiation (hm = 1486.58 eV) with a
1 · 1 m2 spot size. The fixed analyzer was employed with pass
energies of 100 and 50 eV for the survey and high-resolution
spectra, respectively. XPS analysis is useful to investigate
the purity of graphene grown on different substrates.
3. Results and discussion
Fig. 1(a–d) show SEM images of as-grown sheets of carbon
nanowalls on Si, Si/Au, Si/Ni, and Cu substrates respectively
and Fig. 1(e) shows a cross-section SEM image of CNWs on
the Si substrate, all indicating vertical graphene structures.
The height of the CNWs is around 1 lm for a growth period
of 20 min, with a growth rate somewhat lower than that of
microwave PECVD [12,16]. Note that the microwave plasma
is a high density discharge compared to conventional
13.56 MHz rf discharges. While CNWs on different substrates
have some differences, their general morphologies are quite
the same. In general, CNWs on Si substrates are denser and
thinner compared to those on Si/Ni and Si/Au substrates.
CNWs on Cu substrates are much finer than all other sub-
strates. The graphene sheets have leaf shape morphologies
in all the samples. The CNWs appear similar to the blade of
a knife where the base of the layers is thicker compared to
the top. CH4 was used without a diluent in the growth of
the above samples as the precursor gas. In contrast, Fig. 1(f)
shows CNWs on a Si substrate grown with CH4/H2 (19:1)
where the basal plane of graphene becomes eroded due to
hydrogen-induced etching. New branches grow out of the
main wall from the eroded areas, which act as nucleation
Fig. 1 – Vertical graphene sheets on various substrates:
(a) Si, (b) Si/Au, (c) Si/Ni and (d) Cu. (e) A cross-section SEM
image of CNWs on the Si substrate. (f) CNWs on Si substrate
grown with slight amount of hydrogen dilution.
locations for new carbon atoms [10]. As a result of this pro-
cess, CNWs show a cabbage shape as seen in Fig. 1(f).
Several growth mechanisms for CNWs have been sug-
gested based on the early stages of the synthesis process
[11,14,16–18] with the type of the substrate material affecting
the growth in the initial nucleation stages. A significant differ-
ence between the graphite and the substrate material lattice
will cause formation of an amorphous carbon layer [10]. Car-
bide forming substrate materials form an intermediate car-
bide layer instead of amorphous carbon [16]. After the
formation of this intermediate layer, the growth is indepen-
dent of the substrate type. In general, the growth mechanism
includes three stages. First, a thin base layer is formed due to
the adsorption of the carbon containing radicals onto the
intermediate layer [11]. The base layer is not completely
smooth and uniform but has a large amount of graphitic do-
mains with random cracks and dangling bonds [10]. In the
second stage, the growth direction changes from parallel to
perpendicular when the growing edges curl upward to release
the stress that accumulates when the growth of graphitic do-
mains continue parallel to the substrate and they encroach
upon one another [16]. In the last stage, rapid growth of
graphene layers continues from the perpendicular edges
due to radical accumulation at these sites. The high rate of
accumulation at these sharp edges is due to strong bonds
on the graphene planes compared to weak bonds in other
directions, i.e. stacking direction, and also due to diffusion
of radicals in the direction of the plasma sheath which is per-
pendicular to the substrate [11,17]. Detailed microstructure
characterization below provides further insight into the
growth mechanism, along with differences in morphology
due to the underlying substrates.
3.1. Microstructure of CNWs
TEM analysis reveals that the overall morphology of the verti-
cal graphene occurs in one of two forms, either in a petal-like
form or as a graphitic flake. The petal-like structures (Fig. 2
panels a–c, and h) tend to have a central core from which a
petal or petals extend outwards. Closer examination of the
core indicates a structure closely resembling a carbon onion.
The graphitic petals are on the whole curved which can be
attributed to the spherical curvature introduced at the root
of a petal at its interface with the carbon onion. The petal-like
structures were observed for Si and Si/Ni substrates while
graphitic flakes were obtained for the Cu and Si/Au sub-
strates. Diffraction data extracted from the Fourier domain
for both petal-like and graphitic flakes showed lattice spacing
consistent with graphite. For AB (Bernal) stacked graphite,
only six reflex spots in the form of a hexagon are observed
(due to graphene’s 3-fold diffraction symmetry), as shown
on the inset of panel k in Fig. 2. However, if the stacking be-
tween sheets rotates, then additional hexagonal reflex spots
are introduced. The number of additional hexagon spots de-
pends on the number of rotational stacking disorders present
in the layers (and/or grains in a layer). Usually multiple hex-
agonal reflexes were observed for the graphene flakes or pe-
tal-like structures (see inset in panels b and f of Fig. 2)
indicating that rotational stacking disorder dominates in the
carbon nano-walls. Measurements of the distance between
 CARBON 7 2 (2 0 1 4) 3 7 2–38 0 375

Fig. 2 – Selection of TEM images showing the typical carbon nanostructures obtained from the PECVD for the following
substrates (top to bottom): Si/Ni, Cu, Si and Si/Au. Insets in panels b, f and k show the Fourier transform of the corresponding
image. Panels a–c, g and h show petal-like graphene flakes. Panels e, f, i, j, k and l show graphene flakes. Panel d shows
graphene shells.

layers show a spacing of 3.5 ± 0.05 Å concomitant with graph-
ite (e.g. panel i of Fig. 2). Closer inspection of the flakes and
the petals show them to taper off at their outer edge; typically
the base has 10–20 graphene layers, whilst the tips have 2–3
layers.
Both the flakes and the petals show facetted sides as can
be seen in panels a and b of Fig. 3. Panel b of Fig. 3 shows a
carbon nanowall directly rooted to its Au substrate, and sim-
ilar to the petals one sees that the sides leading to the sub-
strate are facetted. The edge contrast of the facetted edges
though differs from the facetted edges of petal structures. Pe-
tal structures tend to have curved graphene that can be ob-
served as facets in a 2D micrograph, while folded graphene
has clear facets and edges formations. Two types of facetted
edges exist in this form, either as folded graphene or seam-
less graphene edges as discussed below. Closer inspection
shows faceting of the edges closely matching that from folded
graphene where the lowest energy configurations are to fold
at zigzag or armchair positions [22]. This is evidenced by mea-
surements of the angles between folds nearly always having
angles divisible by 30. In other words, the folding is quan-
tized at angles of 30 along armchair and zigzag edges (see
Fig. S1 in Supplementary information). Typically changes in
contrasts on the graphene wall are also observable due to
thickness change from the folded flaps (see Fig. S1). However
in some cases no such changes in contrast are observed even
though after inspection of the diffraction patterns at the
edges, armchair or zigzag axis terminations are confirmed.
For example, the diffraction pattern (inset) of micrograph k
in Fig. 2 confirms the edge to be armchair. At times it is not
possible to trace a graphene flap from a fold (i.e. no changes
in contrast due to thickness changes from a flap are ob-
served), suggesting pairs of edges may have closed, viz. seam-
less edges. Seamless edges look very similar to folded edges
[23]. To better determine if seamless edges are truly present,
a variety of facetted edges were investigated in greater detail.
376 CARBON 7 2 ( 2 0 1 4 ) 3 7 2 –3 8 0
Fig. 3 – (a) Petal graphite flake with facetted sides. (b)
Graphite flake stemming from Au substrate. Facetted sides
are easily observed. (c) Graphite flake with facetted edges.
(d) Open (non-facetted edge) from top of a graphite flake.
Flakes with clear changes in contrast due folding are dis-
carded (See Fig. S2 in Supplementary Information) as they
cannot provide reliable information as to whether the edges
are seamless. However, in some flakes with facetted edges,
no changes in contrast over large areas are observed. In addi-
tion, studies in the Fourier domain over different regions of
these flakes show consistent reflexes suggesting the flake is
homogeneous with no folds. An example of such a flake is
provided in Fig. 4a. Panel b of Fig. 4 shows the intensity pro-
files across the corners of the three images in panels c
through e. Panel c is taken from an actual TEM image of a fac-
etted flake (boxed region in panel a). Panel d shows an image
simulation of a tri-layer graphene flake (see inset) with two of
the layers seamlessly bound and panel e shows an image sim-
ulation of a folded edge such that only one edge (at the fold) is
seamless (see inset). From visual inspection of panels c, d and
e, it is clear that panels c and d match each other very well.
Indeed, the change in contrast at the edges also match very
well as can be seen when comparing the red and blue curves
in panel b, while the green curve only shows matching edge
contrast to the red curve on the right side where the edge is
folded/seamless while the contrast on the open edge termina-
tion (left side) is significantly less. This confirms that two of
the three edges of the flake in panel a of Fig. 4 are seamless
and do not arise from a fold. This verifies that graphene flakes
with seamless edges do exist.
The presence of a scrolled, folded or seamless edge adds
mechanical stability [24] to a graphene petal or flake and helps
to maintain the nanowall vertical during growth. The edges at
the tip of a flake or petal are not facetted (see panel d of Fig. 3)
and presumably growth occurs at these edges. It is possible to
envisage that as a carbon wall gets ever bigger during growth,
its structural stability is weakened until a sheet edge collapses
thus introducing a new fold. If the edges between layers link to
form a seamless edge, the seam may close in a zipper-like
fashion. If the zipping-up edge becomes unstable, it may
change orientation (by 30). These processes could explain
the facets observed on graphene flakes and are illustrated in
Fig. 5. In addition to the graphitic flakes or petals, some amor-
phous carbon species was present in all samples. In the case of
the Cu substrate, graphitic shells could also be observed (see
panel d of Fig. 2). For samples in which petal graphene struc-
tures were found, carbon onions were also present (see
Fig. S3 in Supplementary Information). These carbon onions
are probably the nucleation seeds for petal growth. This is in
keeping with the work of Thornton [10] in which hydrogen in-
duced etching leads to new branches growing out of a main
wall from etched regions. This in effect provides new nucle-
ation sites and involves a structure resembling a cabbage,
much like the carbon onions we observe here.
3.2. Raman spectroscopy
Typical Raman spectrum of graphene includes three most
prominent bands: G-band at 1582 cm1, G 0 -band at around
2700 cm1 and D-band at 1350 cm1 [25–32]. G-band is tan-
gential vibration mode of crystalline graphite and is caused
by vibrations between the neighbour carbon atoms within
the graphene plane. D-band is induced by defects in the crys-
tal lattice and is depressed or absent in the Raman spectra of
defect-free graphite and graphene. D-band does not depend
on the amount of layers in the graphene sample. However,
D-band can have higher intensity when spectrum is mea-
sured near to the edge of graphene sheet because of lots of
‘‘cut’’-ends and therefore higher defect probability. G 0 is the
second order disorder mode whose Raman shift depends on
the excitation wavelength. Raman spectra of CNWs grown
on different substrates are compared to each other below
and interpreted according to the characteristics mentioned
above.
Raman spectra of vertical graphene grown on Si, Si/Au and
Si/Ni substrates are shown in Fig. 6. No Raman spectrum
could be measured from the samples grown on Cu substrate,
which is likely due to the high background signal from copper
and weak graphene signal from the relatively low density of
grown material. All the three spectra in Fig. 6 have common
features: D-band at approximately 1350 cm1 and G-band at
around 1580 cm1. D-band is a characteristic feature depict-
ing defects and can be caused by excitation of the edges of
graphene sheets and their random orientation, and by the
presence of amorphous carbon [25–32]. G-band shows sp2-
vibrations in the graphitic plane and confirms presence of
graphene sheets. These two bands reflect crystallinity of the
structure, which can be determined by the ratio of intensities
of D- and G-bands ID/IG. Crystallinity becomes higher when
the ratio ID/IG decreases [29], and this ratio for the samples
on Si, Si/Au and Si/Ni is 0.73, 0.90 and 1.08, respectively. Thus,
the carbon nanowalls grown on Si substrate possess less dis-
ordered structure than the others. This is also confirmed by
the absence of the D 0 -peak in the Raman spectrum of CNWs
grown on Si (Fig. S4 in Supplementary Information). D 0 -band
appears at around 1620 cm1 as a shoulder of G-band and rep-
resents structural disorder. This feature can be clearly seen in
 CARBON 7 2 (2 0 1 4) 3 7 2–38 0 377

Fig. 4 – Panel a: TEM micrograph of a tri-layer graphene wall with two layers bound seamlessly at the edges. Panel b shows
the intensity profiles across the dashed lines across the edges in panels c (red profile), d (blue profile) and e (green profile).
Panel c shows the real TEM image taken from the highlighted square in panel a, panel d is an image simulation of tri-layer
graphene with two layers bound to form a seamless edge (see inset) and panel e shows a folded strip of graphene two yield
one folded edge and open edge (see inset). (A colour version of this figure can be viewed online.)

Fig. 5 – Schematic showing growth history of a graphite flake with quantized folds. (A colour version of this figure can be
viewed online.)

the Raman spectra of the samples on the Si/Au and Si/Ni sub-
strates (Figs. S5 and S6 in Supplementary Information). How-
ever, well defined 2D-band at 2698 cm1 in the Raman spectra
of these two samples points to the graphitic structure. Such
shape, width (FWHM) and relative intensity of the 2D-band
are peculiar for mono- or bilayer graphene [33,34].
According to the above results, the three samples of CNWs
grown on Si, Si/Au and Si/Ni substrates include graphitic
structures, however, the structure is highly disordered. It
can be caused by random orientation of the graphene sheets
and their finite size [29]. Carbon nanowalls obtained on the Si
substrate tend to have more crystalline character than the
CNWs grown on Si/Au and Si/Ni. At the same time, according
to the shape, width and relative intensity of the 2D-band,
nanowalls synthesized on Si/Au and Si/Ni substrates could
be comprised of mono- or bi-layered graphene. This corre-
sponds well with results of TEM investigations, confirming
bi-layered graphene structure with rotational stacking.
3.3. Magnetic properties
One important characteristic of any material is its behaviour
in response to external magnetic field. It would be specifically
interesting to discover that CNWs are potentially capable of
demonstrating ferromagnetic behaviour even in room tem-
perature, since organic magnets are highly desirable and have
always been searched for, however they mostly tend to oper-
ate at very low temperatures.
378 CARBON 7 2 ( 2 0 1 4 ) 3 7 2 –3 8 0
Fig. 6 – Raman spectra of carbon nanowalls grown on
different substrates: Si, Si/Au, Si/Ni. (A colour version of this
figure can be viewed online.)
Graphene powder scratched from the silicon substrate
exhibits magnetic hysteresis loops at room temperature and
lower. Fig. 7 shows the magnetization curve obtained at
T = 300 K in the field intensity range of 1000 Oe < -
H < 1000 Oe. The magnetization is about 0.013 emu/g for a
magnetic field of H = 1000 Oe. The remanent magnetization
and coercive field can be estimated to be Mr = 0.002 emu/g
and Hc = 30 Oe, respectively from the hysteresis curve. Simi-
lar room temperature weak ferromagnetic responses have
been reported before from many carbon based nanostruc-
tures such as carbon nanospheres grown by CVD [35], and car-
bon nanosheets slowly synthesized by the RF-PECVD [36].
Wang et al. [37] attributed the ferromagnetic behavior of
graphene to the existence of various kinds of defects.
Temperature dependence of the magnetization at a con-
stant field intensity of H = 500 Oe shown in Fig. 8 reveals that
magnetization saturates to about 7 · 103 emu/g, and is
almost independent of the temperature for T > 70 K. Magnetic
Fig. 7 – The magnetization hysteresis curve obtained at
300 K from the graphene powder scratched from Si
substrate in the field range of 1000 Oe < H < 1000 Oe. (A
colour version of this figure can be viewed online.)
Fig. 8 – Temperature dependence of the magnetization of the
graphene powder scratched from Si substrate at H = 500 Oe.
(A colour version of this figure can be viewed online.)
susceptibility saturation for temperatures above 100 K was
reported before for nano-graphite samples [38]. A hump is
seen around T = 50 K; such anomalies in the susceptibility
curve are related to magnetic phase transitions. The esti-
mated negative Curie–Weiss temperature as well as a local
maximum in the magnetization curve at low temperatures
were also reported before for graphene prepared by various
methods in Ref. [9] where such magnetic behavior was attrib-
uted to the coexistence of antiferromagnetic interactions be-
sides the ferromagnetic order.
Ferromagnetism in organic carbon based materials has
been a controversial issue, particularly, if the reported magne-
tism is an intrinsic property or if it originates from magnetic
impurities and contaminations. Our VG samples show ferro-
magnetic response at room temperature and below, providing
experimental support for the hypothesis of the existence of
intrinsic ferromagnetism in pure carbon based materials.
Moreover they suggest the possibility of considering CNWs
as organic magnets at room temperature.
Finally, the C1s spectra from the XPS analysis of three VG
samples grown on different substrates (Fig. 9) contain only
Fig. 9 – XPS analysis of graphene on different substrates. (A
colour version of this figure can be viewed online.)
 CARBON 7 2 (2 0 1 4) 3 7 2–38 0
one component, located at a binding energy of 283.3 eV, which
can be attributed to SiC as observed previously by Johansson
et al. [39] and Shah et al. [40]. The existence of this carbide on
some substrates can be related to an intermediate step of
graphene growth before the nucleation of the base layer.
Malesevic et al. [16] noted that silicon substrate, in contrast
to quartz, has a very strong contribution to carbide formation
for short growth periods. Interestingly, the formation of a car-
bide layer creates stronger adhesion between the graphene
layers and the substrate surface. They succeeded in removing
the dependency of binding energies to the type of substrate by
increasing the growth time. It is worth mentioning that the
substrate does not affect the growth mechanism of graphene;
it only determines the chemical composition of the base layer
and the adhesion of graphene layers.
4. Conclusion
Vertically aligned graphene nanowalls were grown by PECVD
on various conductive and non-conductive substrates with-
out the aid of catalysts, and characterized extensively. The
collective data enable us to put forward a growth mechanism
for the CNWs. In this growth mechanism, the edges of the
graphene walls are seamless (joined) except at the top of
the sheets where growth takes place. The seamless edges lead
to faceting of the graphene sheets and provide mechanical
strength to them. The faceting occurs at angles divisible by
30 due to the preferential joining of graphene layers at the
edges with zigzag and armchair terminations. Even though
the substrate can be reduced (to a carbide), this does not
influence the growth, however, it does affect the chemical
composition of the base layer and the adhesion of the graph-
ene layers. The presence of few layer graphene was confirmed
by Raman spectroscopy. In particular bi-layer graphene is of-
ten observed which is probably due to the top tapered ends of
the graphene vertical walls narrowing down to bi-layer graph-
ene with rotational stacking disorder. Magnetic hysteresis
loops and weak ferromagnetic responses were observed from
the samples at room temperature and below. This magnetic
behavior is attributed to the coexistence of antiferromagnetic
interactions alongside ferromagnetic order.
Acknowledgements
This research was supported by the World Class University
program funded by the Ministry of Education, Science and
Technology through the National Research Foundation of Kor-
ea (R31-10100) and DAAD and Siemens (A/08/98783). Support
from the German Excellence Initiative via the Cluster of Excel-
lence EXC 1056 ‘‘Center for Advancing Electronics Dresden’’
(cfAED) is also acknowledged. Preliminary TEM analysis by
Hessam Ghassemi is acknowledged.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.carbon.
2014.02.025.
379
R E F E R E N C E S
[1] Choi WB, Lee JW. Graphene: synthesis and applications. Boca
Raton, FL: CRC Press; 2012.
[2] Zhu Y, Murali S, Cai WW, Li XS, Suk JW, Potts JR, et al.
Graphene and graphene oxide: synthesis, properties and
applications. Adv Mater 2010;22:3906–24.
[3] Rümmeli MH, Rocha CG, Ortmann F, Ibrahim I, Sevincli H,
Börrnert F, et al. Graphene: piecing it together. Adv Mater
2011;23:4471–90.
[4] Yoo EJ, Kim J, Hosono E, Zhou HS, Kudo T, Honma I. Large
reversible Li storage of graphene nanosheet families for use
in rechargeable lithium ion batteries. Nano Lett
2008;8:2277–82.
[5] Rao CNR, Sood AK, Subrahmanyam KS, Govindaraj A.
Graphene: the new two-dimensional nanomaterial. Angew
Chem Int Ed 2009;48:7752–77.
[6] Prasad KE, Das B, Maitra U, Ramamurty U, Rao CNR.
Extraordinary synergy in the mechanical properties of
polymer matrix composites reinforced with 2 nanocarbons.
PNAS 2009;106(32):13186–9.
[7] Matte HSSR, Subrahmanyam KS, Rao CNR. Novel magnetic
properties of graphene: presence of both ferromagnetic and
antiferromagnetic features and other aspects. J Phys Chem C
2009;113:9982–5.
[8] Kopelevich Y, Esquinazi P. Ferromagnetism and
superconductivity in carbon-based systems. J Low Temp Phys
2007;146:629–39.
[9] Fernández-Rossier J, Palacios JJ. Magnetism in graphene
nanoislands. Phys Rev Lett 2007;99:177204.
[10] Thornton JDM. Carbon nanowalls: processing, structure and
electrochemical properties [Ph.D. thesis]. Raleigh, NC, USA:
North Carolina State Univ.; 2011.
[11] Kondo S, Kawai S, Takeuchi W, Yamkawa K, Den S, Kano H,
et al. Initial growth process of carbon nanowalls synthesized
by radical injection plasma-enhanced chemical vapor
deposition. J Appl Phys 2009;106(9):094302.
[12] Chatei H, Belmahi M, Assouar MB, Le Brizoual L, Bourson P,
Bougdira J. Growth and characterisation of carbon
nanostructures obtained by MPACVD system using CH4/CO2
gas mixture. Diamond Relat Mater 2006;15(4–8):1041–6.
[13] Vizireanu S, Stoica SD, Mitu B, Husanu MA, Galca A, Nistor L,
et al. Radiofrequency plasma beam deposition of various
forms of carbon based thin films and their characterization.
Appl Surf Sci 2009;255(10):5378–81.
[14] Teii K, Shimada S, Nakashima M, Chuang ATH. Synthesis and
electrical characterization of n-type carbon nanowalls. J Appl
Phys 2009;106(8):084303.
[15] Wang J, Zhu M, Outlaw RA, Zhao X, Manos DM, Holloway BC.
Synthesis of carbon nanosheets by inductively coupled radio-
frequency plasma enhanced chemical vapor deposition.
Carbon 2004;42:2867–72.
[16] Malesevic A, Vitchev R, Schouteden K, Volodin A, Zhang L,
Tendeloo GV, et al. Synthesis of few-layer graphene via
microwave plasma-enhanced chemical vapour deposition.
Nanotechnology 2008;19(30):305604.
[17] Hiramatsu M, Hori M. Fabrication of carbon nanowalls using
novel plasma processing. Jpn J Appl Phys 2006;45(6B):5522–7.
[18] French BL, Wang JJ, Zhu MY, Holloway BC. Evolution of
structure and morphology during plasma-enhanced
chemical vapor deposition of carbon nanosheets. Thin Solid
Films 2006;494(1–2):105–9.
[19] Meyyappan M. Plasma nanotechnology: past, present and
future. J Phys D: Appl Phys 2011;44:1–11.
[20] Meyyappan M, Lee JS. Graphene growth by PECVD. In:
Sankaran M, editor. Plasma processing of
nanomaterials. Boca Raton, FL: CRC Press; 2012.
380 CARBON 7 2 ( 2 0 1 4 ) 3 7 2 –3 8 0
[21] Ostrikov K, Neyts EC, Meyyappan M. Plasma nanoscience:
from nano-solids in plasmas to nano-plasmas in solids. Adv
Phys 2013;62:113–224.
[22] Zhang J, Xiao J, Meng X, Monroe C, Huang Y. Quantitative
analysis of graphene folded edges using electron diffraction.
Microsc Microanal 2010;16:1482–3.
[23] Börrnert F, Barreiro A, Wolf W, Katsnelson M, Büchner B,
Vanderspysen L, et al. Lattice expansion in seamless bilayer
graphene constrictions at high bias. Nano Lett
2012;12:4455–9.
[24] Zheng Y, Wei N, Fan Z, Xu L, Huang Z. Mechanical properties
of grafold: a demonstration of strengthened graphene.
Nanotechnology 2011;22:405701(9).
[25] Gupta A, Chen G, Joshi P, Tadigadapa S, Eklund PC. Raman
scattering from high-frequency phonons in supported n-
graphene layer films. Nano Lett 2006;6:2667–73.
[26] Ferrari AC, Robertson J. Interpretation of Raman spectra of
disordered and amorphous carbon. Phys Rev B
2000;61:14095–107.
[27] Wu Y, Yang B, Zong B, Sun H, Shen Z, Feng Y. Carbon
nanowalls and related materials. J Mater Chem
2004;14:469–77.
[28] Ferrari AC, Robertson J. Resonant Raman spectroscopy of
disordered, amorphous, and diamondlike carbon. Phys Rev B
2001;64:075414.
[29] Vizireanu S, Nistor L, Haupt M, Katzenmaier V, Oehr C,
Dinescu G. Carbon nanowalls growth by radio frequency
plasma-beam-enhanced chemical vapor deposition. Plasma
Processes Polym 2008;5:263–8.
[30] Ni ZH, Fan HM, Feng YP, Shen ZX, Yang BJ, Wu YH. Raman
spectroscopic investigation of carbon nanowalls. J Chem
Phys 2006;124:204703.
[31] Alexander M, Roumen V, Koen S, Alexander V, Liang Z,
Gustaaf Van T, et al. Synthesis of few-layer graphene via
microwave plasma-enhanced chemical vapour deposition.
Nanotechnology 2008;19:305604.
[32] Kurita S, Yoshimura A, Kawamoto H, Uchida T, Kojima K,
Tachibana M, et al. Raman spectra of carbon nanowalls
grown by plasma-enhanced chemical vapor deposition. J
Appl Phys 2005;97:104320.
[33] Malard L, Pimenta M, Dresselhaus G, Dresselhaus M. Raman
spectroscopy in graphene. Phys Rep 2009;473:51–87.
[34] Ismach A, Druzgalski C, Penwell S, Schwartzberg A, Zheng M,
Javey A, et al. Direct chemical vapor deposition of graphene
on dielectric surfaces. Nano Lett 2010;10:1542–8.
[35] Miao J-Y, Hwang DW, Narasimhulu KV, Lin P-I, Chen Y-T, Lin
S-H, et al. Synthesis and properties of carbon nanospheres
grown by CVD using Kaolin supported transition metal
catalysts. Carbon 2004;42:813–22.
[36] Rao BPC, Ramaswamy S, Gopalakrishnan C, Vijayakumar NS,
Ganesh KR, Thiruvadigal DJ, et al. Magnetic properties of
carbon nanosheets. Philos Mag 2010;90:3463–73.
[37] Wang Y, Huang Y, Song Y, Zhang X, Ma Y, Liang J, et al. Room-
temperature ferromagnetism of graphene. Nano Lett
2009;9:220–4.
[38] Osipov VY, Enoki T, Takai K, Takahara K, Endo M, Hayashi T,
et al. Magnetic and high resolution TEM studies of
nanographite derived from nanodiamond. Carbon
2006;44:1225–34.
[39] Johansson LI, Owman F, Ma rtensson P. High-resolution
core-level study of 6H-SiC.0001. Phys Rev B
1996;53:13793–802.
[40] Shah SI, Waite MM. Effect of oxygen on the nucleation and
growth of diamond thin films. Appl Phys Lett 1992;61:3113.