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Cite this: New J. Chem., 2013,

polycrystalline Co film by plasma enhanced chemical
37, 1616
vapor deposition
Shumin Wang,a Liang Qiao,b Cuimei Zhao,a Xiaoming Zhang,a Jianli Chen,a
Hongwei Tian,a Weitao Zheng*a and Zhengbo Hanc

Graphene is deposited on polycrystalline Co film by radio-frequency plasma enhanced chemical vapor

Received (in Montpellier, France)
14th December 2012,
Accepted 11th March 2013
DOI: 10.1039/c3nj41136b
www.rsc.org/njc
deposition (RF-PECVD), and the effect of deposition time on the crystallinity of graphene, such as
graphitic degree and in-plane crystallite size, is explored. The findings are that graphene can be
obtained on polycrystalline Co film for only 15 s, suggesting that a direct growth mechanism plays an
important role in the formation of graphene. The first-principles density functional theory (DFT) results
also reveal that the graphene is more easily formed on Co via a surface direct growth mechanism than
that via a precipitation mechanism. Our studies are critical in guiding the graphene growth process as
we try to achieve the highest quality graphene for electronic devices.

1. Introduction And, the PECVD technique has an advantage over thermal

Graphene is a two-dimensional honeycomb lattice material
bonded with a single layer of sp2-hybridized carbon atoms,
which exhibits excellent physical properties, including the
quantum Hall effect, extremely high electronic mobility, ther-
modynamic stability, and great elasticity,1–5 etc. Since graphene
was obtained by Geim and Novoselov et al. using a mechanical
exfoliation method in 2004,1 great interest has been attracted to
synthesize and explore its potential applications in the fields of
field-effect transistors,1,6,7 gas sensors,8 transparent electrodes
of batteries,4,9 and supercapacitors.10–12 In general, graphene
can be synthesized by mechanical exfoliation of highly ordered
pyrolytic graphite (HOPG),1,2 thermal chemical vapor deposi-
tion (CVD) and plasma-enhanced chemical vapor deposition
(PECVD) on single crystal or polycrystalline transition
metals,4,13–20 and chemical reduction of dispersed graphene oxide
(RGO).9 However, the PECVD technique is the most promising
route to produce large area and high quality graphene with
shorter deposition time and lower substrate temperature.19,20
a
Department of Materials Science, Key Laboratory of Mobile Materials, MOE, and
State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012,
People’s Republic of China. E-mail: wtzheng@jlu.edu.cn; Fax: +86 431 85168246;
Tel: +86 431 85168246
b
College of Science, Changchun University, Changchun 130022,
People’s Republic of China
c
Light Industry College of Liaoning University, Shenyang, 110036,
People’s Republic of China. E-mail: ceshzb@lnu.edu.cn
CVD in that the former can generate reactive species (CHx,
species impinging from the gas phase in plasma, x = 0, 1, 2, 3)
in the plasma at relatively low temperature.20
The carbon solubility in Ni and Cu metal is 2.7 at% and
0.04 at%, respectively.21 Therefore, most of the reports assume
that the typical proposed dissolution precipitation process
plays a major role in the graphene growth mechanism on Ni
substrate;4,14,21–24 and a surface-catalyzed process causes the
growth of single layer graphene on Cu substrate.13,16,18,20,25 The
order of the carbon solubility in metal is Co (4.1 at%) > Ni > Cu,21
suggesting that the growth mechanism of graphene on Co might
be a dissolution precipitation process. However, Co has surface
catalytic properties.26,27 This will be in favor of a direct surface-
catalyzed growth of graphene on Co. According to the above
discussion, there is an intense dispute about the growth mecha-
nism for graphene on catalyst metal and the growth mechanism
of graphene on Co should be revealed clearly. In our previous
work, few-layer graphene has been successfully prepared on
polycrystalline Co film at relatively low temperature (800 1C)
with a slow total gas flow rate (78 sccm) by the radio-frequency
plasma enhanced chemical vapor deposition (RF-PECVD)
technique.19 In this work, we report the effect of deposition time
on the crystallinity of graphene including graphitic degree and
in-plane crystallite size using Raman spectroscopy as well as
X-ray photoelectron spectroscopy (XPS). Meanwhile, we try to
reveal the growth mechanism for graphene deposited on poly-
crystalline Co film experimentally and theoretically.

1616 New J. Chem., 2013, 37, 1616--1622 This journal is c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2013

Paper
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Fig. 1 (a) SEM image and (b) XRD pattern of polycrystalline Co film synthesized
by direct current magnetron sputtering. SEM images of (c) G1, (d) G2, (e) G3 and
(f) G4.
2. Experimental and theoretical details
2.1 Synthesis of graphene by RF-PECVD
A polycrystalline Co film, deposited on a Si (100) wafer by direct
current magnetron sputtering according to our previous
method,19 with a thickness of about 450 nm was used as the
substrate for graphene growth. After the Co substrate was
put into the reaction chamber of the RF-PECVD system, the
chamber was evacuated to a pressure of 13 Pa. Then a pressure
of 220 Pa via introducing mixed H2 (10 sccm) and Ar (20 sccm)
gases was maintained. Subsequently, the substrate was heated
up to 800 1C and the growth started. During deposition, the
plasma power was kept at 200 W. The deposition time was
changed (15 s, 40 s, 90 s, 360 s, 20 min, respectively), while the
flow rate of Ar, H2 and CH4 were kept at 60, 15 and 3 sccm,
respectively. After deposition, the obtained samples were
cooled down to room temperature (RT) rapidly in a H2 and Ar
atmosphere.
2.2 Characterization
The crystal structure of the Co film was determined by X-ray
diffraction (XRD) using a Bragg–Brentano diffractometer
(D8_tools) in y–2y configuration with a Cu Ka line at
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0.15418 nm as the source, while the morphology, microstruc-
ture, and chemical bonding of the obtained graphene were
characterized by scanning electron microscopy (SEM) (JEOL
JSM-6700F operated at 8 kV), transmission electron microscopy
(TEM), high resolution transmission electron microscopy
(HRTEM) (JEOL JEM-2100F operated at 200 kV), Raman spectra
measurements (T64000 (Horiba), with a 514.5 nm Ar+ laser
excitation, a laser power of 5 mW, and an accumulation time of
30 s) and XPS (ESCALAB-250 performed with a monochromatic
Al Ka (1486.6 eV) radiation source and a hemisphere detector
with an energy resolution of 0.1 eV).
2.3 Theoretical calculations
All calculations were performed using first-principles DFT code
provided by the CASTEP program.28 The ion–electron inter-
action was modeled by the ultrasoft pseudopotential.29 The
exchange and correlation potential was considered in the
generalized gradient approximation in the scheme of Perdew–
Burke–Ernzerhof functional.30 The plane wave energy cutoff
was set to 400 eV. To sample the first Brillouin zone,
Monkhorst–Pack grids31 of 6  6  6 and 6  6  1 special
k-point meshes were adopted for bulk Co and Co (111) surface.
The transition state search for the diffusions of carbon atom
was performed using the linear synchronous transit and quad-
ratic synchronous transit (LST/QST) method.
The Co (111) surface was represented using a slab mode,
which contained a 2  2 surface with six Co layers (24 atoms)
and was separated from its periodic images by a vacuum layer
of 15 Å. The atoms in the top three layers were allowed to relax
according to the atomic forces, while the atoms in the bottom
three layers were fixed to the bulk positions to mimic the bulk.
3. Results and discussion
Fig. 1(a) and (b) show the SEM image and the XRD pattern of Co
film, respectively, prepared by direct current magnetron sputtering.
For the XRD pattern, only one peak at 2y = 44.61 from Co (111)
appears, and the SEM image exhibits the rough surface
morphology of the polycrystalline Co film, which is the same
as what we have reported in previous work.19 Fig. 1(c)–(f) show
the surface morphologies for samples grown for 15, 40, 90 and
360 s (named G1, G2, G3 and G4, respectively), respectively.
Obviously it is difficult to know whether the graphene is
obtained, and only some Co particles can be observed.
The high resolution XPS C1s spectra of G1, G2, G3 and G4
display three most prominent deconvoluted components: the
first one is assigned to sp2-hybridized carbon bonding
(at B284.6 eV), the second one is attributed to sp3-hybridized
carbon bonding (at B285.3 eV) and the third one is C–O
bonding (at B286.4 eV).32,33 The detailed deconvoluted com-
ponents for the XPS C1s spectrum is listed in Table 1, from
which we can find that the peak intensity of the sp2-hybridized
carbon bonding is higher than either the sp3-hybridized carbon
bonding or the C–O bonding for all the four samples, which
confirms that the four graphene samples have dominant sp2
CQC bonding. Furthermore, the percentages of sp2-hybridized
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Table 1 The portion of chemical species for G1, G2, G3 and G4 based on XPS
results
Samples G1 G2 G3
2 could be evaluated based on the equation: La (nm) =
sp (CQC)% 74.0 74.2 74.4
sp3 (C–C)% 20.2 20.1 19.9
C–O% 5.8 5.7 5.7
carbon bonding, sp3-hybridized carbon bonding and C–O
bonding in G1, G2, G3 and G4 exhibit no significant differ-
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ences, indicating the four graphene samples have almost the
same bonding structure.
Raman spectroscopy is a relatively easy, nondestructive,
non-contact and fast technique, which can give structural
information of graphene, and has been widely used to char-
acterize the structural properties of graphene, such as graphitic
degree, in-plane crystallite size (La) and graphene layers.20,34,35
The representative Raman spectra for G1, G2, G3 and G4 are
shown in Fig. 2(a)–(d), which were taken without transferring
the graphene from the Co substrates to insulating substrates.
There are two main peaks between 1000 and 3000 cm 1: G band
at B1584 cm 1 and 2D band at B2700 cm 1, which are the
characteristics of graphene. Besides the G band and 2D band, a
disorder-induced D band around B1354 cm 1 is also observed
in Fig. 2. The D band originates from the graphene edges, grain
boundaries, sp3-hybridized carbon bonds and oxidation func-
tional groups. The G band corresponds to the in-plane vibra-
tion of sp2 carbon atoms (E2g), which presents the Raman active
for sp2 carbon networks. For a qualitative analysis of the
graphene, the integrated intensity ratio of the D band to G
band (ID/IG) can be used to evaluate the graphitic degree of
graphene. The 2D band, the overtone of the D band, is due to
the two-phonon double resonance Raman scattering process
and it is sensitive to the stacking order of graphene sheets
along the c axis. Therefore, the lineshape, the frequency and the
Fig. 2 Raman spectra of (a) G1, (b) G2, (c) G3, (d) G4 and (e) graphene grown
for 20 min.
1618 New J. Chem., 2013, 37, 1616--1622 This journal is c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2013
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full width at half maximum of the 2D band (FWHM2D) are used
to distinguish the graphene layers.35
G4 La is inversely proportional to the ID/IG value and
74.3
19.9 (2.4  10 10)llaser4(ID/IG) 1, where La (nm) is the crystallite size
5.8 in the surface layer of few-layer graphene, llaser (nm) is the
wavelength of incident light.34,36–39 According to the Raman
spectra, we have evaluated the average value of ID/IG, in-plane
grain size (La), I2D/IG and FWHM2D of graphene, as shown in
Fig. 3(a)–(d). The ID/IG dramatically decreases with increasing
deposition time from 15 s to 40 s, while the ID/IG greatly
increases with increasing deposition time from 40 s to 360 s,
indicating the highest graphitic degree and the largest grain
size of G2. The I2D/IG and FWHM2D values for four samples are
>1.2 and o80 cm 1, respectively, which provides direct evidence
of few layer graphene (average number of layers r 3).18,35,40
Furthermore, the Raman spectra from G2 reveal that the
FWHM2D value as well as standard deviation of I2D/IG and
FWHM2D are the smallest among the four samples. These
suggest that G2 has a relatively uniform number of layers,
compared to either of G1, G3 and G4, although the four
samples are all few-layer graphene.14,18,35
There are a lot of linear defects with higher activity at the
grain boundaries of polycrystalline Co film,14,17 which will lead
to the easy absorption and the enhanced diffusion of carbon
radicals on these defects. Considering La as an average grain
size of graphene, one can assume that the higher the number of
grains, the higher the D peak intensity, and hence the smaller
La.34 When the deposition time is 15 s, only a few discharging
carbon radicals can be provided to grow graphene, causing a lot
of small graphene domains to appear on the surface of the Co
film. Upon increasing the deposition time to 40 s, there are
enough discharging carbon radials for graphene growth. Thus,
graphene domains rapidly grow up by gathering C2 radicals on
the active sites of graphene boundaries. If the deposition time
is further increased (90 s and 360 s), the graphene domains
Fig. 3 (a) ID/IG, (b) in-plane grain size (La), (c) I2D/IG and (d) FWHM2D values of
graphene as a function of the deposition time.

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Fig. 4 (a) and (b) SEM images of graphene grown for 20 min. The SEM images
were obtained by tilting the sample stage with (a) 01 and (b) 451.
near the Co grain rapidly grow up and cover the Co grains. For
the second layer growth of graphene, the catalytic nature of Co
film is greatly weakened. The CHx radicals can not be further
dissociated by the Co surface,23 and the attachment of CHx
(x = 1, 2, 3) radicals on the active sites of graphene boundaries
will terminate the extension of graphene domains. Meanwhile,
new nucleation sites of graphene are formed and then grow
up on the Co grain, which leads to a large number of
graphene boundaries on the Co grain, and thus the ID/IG value
increases.
In order to reveal the influence of grain boundaries of Co
film on the formation of graphene, the deposition time was
increased to 20 min. Fig. 4(a) and (b) show the SEM images of
the sample grown for 20 min, obtained by tilting the sample
stage at 01 and 451, respectively, from the e-beam direction,
from which it can be observed that many vertical flakes are
formed at the boundaries of Co grains, resulting from the high
activity of defects at the grain boundaries. It is well-known that
different kinds of metals, such as Co, Ni, Cu, etc., can be used
as substrates to grow graphene. An important reason for the
high efficiency growth of graphene is that the solubility of
carbon into metals is low but enough for the formation of
graphene. However, for the polycrystalline substrates, as grain
boundaries are highly active and can enhance the diffusion rate
of carbon radicals, this will lead to the formation of graphene at
the grain boundaries preferentially. If two growing graphene
domains meet each other, graphene sheets are forced to rise
upwards, causing the formation of vertical flakes.41 Fig. 2(e)
shows the Raman spectrum of the sample grown for 20 min, in
which three peaks at 1355 cm 1, 1584 cm 1 and 2710 cm 1
appear, corresponding to the D, G and 2D bands of graphene,
respectively, and its ID/IG and I2D/IG are 0.33 and 1.23, respec-
tively, which indicates that few-layer graphene with a high
graphitic degree has been prepared.
TEM and HRTEM images provide an insight into the mor-
phology and atomic structure of the graphene film grown for
20 min. It is apparent that the graphene film grown for 20 min
is transparent with many black impurities (Fig. 5(b) and (c)),
which is proposed to be due to the presence of vertical graphite
flakes on the graphene film, while the graphene grown for 40 s
(Fig. 5(a)) is clear and transparent. The lines in Fig. 5(d) (taken
from the area indicated with an arrow in Fig. 5(c)) show that the
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Fig. 5 (a) TEM image of graphene grown for 40 s. (b) and (c) TEM images of
graphene grown for 20 min. (d) HRTEM image taken from the area indicated
with an arrow in (c).
impurities are crystalline particles with different orientations16,42
and the inter-planar spacing for these crystalline particles is
0.232 and 0.198 nm, agreeing well with that of (100) and (101)
planes, respectively, for graphite.
It is worth noting that XRD patterns in Fig. 1(b) and in our
previous work19 show a higher intensity of the Co (111) peak
than that of the Co (200) peak of polycrystalline Co film before
and after annealing. Also, the triangular Co (111) plane is prone
to have more similarities in crystallographic geometry with the
hexagonal graphene lattice than other Co crystal planes, thus
reducing the nucleation barrier, since the lattice mismatch between
graphene and underlying metal can not be ignored.21,43 Hence
we will investigate how the Co (111) plane influences the formation
of graphene. In order to verify the growth mechanism of
graphene on the Co (111) surface, the diffusion of carbon
atoms from the subsurface octahedral sites to the Co (111)
surface and the diffusion of carbon atoms over the Co (111)
surface using DFT code is explored.
The calculated lattice constant of bulk Co is 3.554 Å, which
is in good agreement with the previous theoretical result.44
There are four unique high-symmetry positions for the adsorp-
tion of carbon atoms on a Co(111) surface: the top site, the
face-centered cubic (fcc) site, the hexagonal close-packed (hcp)
site, and the bridge site.45–47 Fig. 6(a) shows the schematic
representations of the high symmetry sites on the Co(111)
surface. The adsorbed surface is fully relaxed and the adsorbed
carbon atom comes to its favorable position. For the adsorption
on the top and bridge sites of the Co (111) surface, the carbon
atom moves to the neighboring hcp site after the geometry
optimization. The calculated results indicate that the carbon
atom prefers to adsorb only on the three-fold hollow sites (hcp
and fcc) of the Co (111) surface.
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Fig. 6 (a) Adsorption sites of carbon atoms on the Co (111) surface. Co1, Co2
and Co3 denote the Co atoms of the first, second and third surface layers,
respectively. (b) Relative energy versus the diffusion path. Cos denotes the
configuration that one carbon atom is in the subsurface octahedral cavity (os),
Chcp and Cfcc denote the configurations that one carbon atom is adsorbed on the
hcp site and fcc site, respectively.
The mobility of the carbon atoms plays an important role in
the growth of graphene.48–50 Therefore, the investigation of the
reaction pathways for the penetration of carbon atoms from the
Fig. 7 Schematic illustration of the growth mechanism of graphene on polycrystalline Co film by RF-PECVD.
1620 New J. Chem., 2013, 37, 1616--1622 This journal is c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2013
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subsurface to the surface and the consequent diffusion on the
Co (111) surface is of great importance. In the first subsurface
layer of Co (111), three Co atoms in the first layer and three Co
atoms in the second layer form a Co6 octahedral cavity (os, as
shown in Fig. 6(a)). The overall barriers for the carbon atom
penetrating the subsurface and diffusion on the Co (111) sur-
face are shown in Fig. 6(b), from which the barriers for the
carbon atom migration from the os site to fcc and hcp sites are
2.36 and 2.40 eV, respectively. On the other hand, the diffusion
barrier on the surface from the fcc site to hcp site is 0.23 eV, and
that from the hcp site to fcc site is 0.44 eV, demonstrating that
the penetration of the carbon atom from the subsurface to the
surface shows extremely high barriers compared with the
diffusion on the surface.
Based on the experimental and DFT results, the growth
mechanism of graphene on polycrystalline Co film is revealed
in Fig. 7. (1) After the Co film is heated up to 800 1C in the
protection gas, plasma power (200 W) is applied to decompose
methane into carbon radicals (CHx, species impinging from the
gas phase in plasma, x = 0, 1, 2, 3). The C2 radical is favored to
grow continuous graphene, while the other carbon radicals will
prevent the extension of the sp2 network of graphene; (2) in the
case of a thermal substrate, carbon radicals will further dissociate
on the Co surface, providing more C2 radicals for growing
graphene; (3) some of the carbon radicals diffuse into the Co
film, while other carbon radicals will cause the direct growth of
graphene at the grain boundaries and on the surface of the Co
film. If the Co surface is covered by the first graphene layer, the
catalytic nature of the Co surface to dissociate carbon radicals is
greatly weakened. Then more CHx (x = 1, 2, 3) radicals are
attached to the edges of graphene domains, causing the
formation of graphene with smaller grain size in the second layer
than in the first layer; (4) afterwards, in the process of cooling,
some carbon atoms segregate from the interior of the Co film and
migrate to the Co surface to extend the graphene network.

Paper
4. Conclusions
The growth and structure of graphene produced by RF-PECVD
were investigated, and it is revealed that a direct growth
mechanism plays a larger role than a precipitation mechanism
in the formation of graphene on polycrystalline Co film by
RF-PECVD. The first-principles DFT results show that the
diffusion of carbon atoms over the (111) surface is easier than
the penetration of carbon atoms from subsurface octahedral
sites to the (111) surface, which provides evidence that graphene
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is more easily formed by a surface direct growth process.
Acknowledgements
The support from National Natural Science Foundation of
China (grant no. 50525204, 50832001, 51002061, 51002014,
21203070 and 51102110), the special PhD program (grant no.
200801830025) from MOE, Major science and technology
project of Jilin Province (grant no.11ZDGG010), program for
Changjiang Scholars and Innovative Research Team in Univer-
sity, the Natural Science Foundation of Jilin Province (grant no.
201115019), and the ‘‘211’’ and ‘‘985’’ project of Jilin University,
China, is highly appreciated.
Notes and references
1 K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang,
Y. Zhang, S. V. Dubonos, I. V. Grigorieva and A. A. Firsov,
Science, 2004, 306, 666–669.
2 A. K. Geim and K. S. Novoselov, Nat. Mater., 2007, 6, 183–191.
3 Y. B. Zhang, Y. W. Tan, H. L. Stormer and P. Kim, Nature,
2005, 438, 201–204.
4 K. S. Kim, Y. Zhao, H. Jang, S. Y. Lee, J. M. Kim, K. S. Kim,
J. H. Ahn, P. Kim, J. Y. Choi and B. H. Hong, Nature, 2009,
457, 706–710.
5 A. K. Geim, Science, 2009, 324, 1530–1534.
6 V. Ryzhii and M. Ryzhii, Phys. Rev. B: Condens. Matter Mater.
Phys., 2009, 79, 245311.
7 Z. S. Wu, S. F. Pei, W. C. Ren, D. M. Tang, L. B. Gao,
B. L. Liu, F. Li, C. Liu and H. M. Cheng, Adv. Mater., 2009,
21, 1756–1760.
8 Y. P. Dan, Y. Lu, N. J. Kybert, Z. T. Luo and A. T. C. Johnson,
Nano Lett., 2009, 9, 1472–1475.
9 L. J. Zhi, X. Wang and K. Mullen, Nano Lett., 2008, 8,
323–327.
10 Y. W. Zhu, S. Murali, M. D. Stoller, K. J. Ganesh, W. W. Cai,
P. J. Ferreira, A. Pirkle, R. M. Wallace, K. A. Cychosz,
M. Thommes, D. Su, E. A. Stach and R. S. Ruoff, Science,
2011, 332, 1537–1541.
11 X. H. Cao, Y. M. Shi, W. H. Shi, G. Lu, X. Huang, Q. Y. Yan,
Q. C. Zhang and H. Zhang, Small, 2011, 7, 3163–3168.
12 X. C. Dong, H. Xu, X. W. Wang, Y. X. Huang, M. B.
Chan-Park, H. Zhang, L. H. Wang, W. Huang and P. Chen,
ACS Nano, 2012, 6, 3206–3213.
13 X. S. Li, W. W. Cai, L. Colombo and R. S. Ruoff, Nano Lett.,
2009, 9, 4268–4272.
This journal is c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2013
View Article Online
NJC
14 Y. Zhang, L. Gomez, F. N. Ishikawa, A. Madaria, K. Ryu,
C. A. Wang, A. Badmaev and C. W. Zhou, J. Phys. Chem. Lett.,
2010, 1, 3101–3107.
15 B. Y. Dai, L. Fu, Z. Y. Zou, M. Wang, H. T. Xu, S. Wang and
Z. F. Liu, Nat. Commun., 2011, 2, 522.
16 W. Liu, H. Li, C. Xu, Y. Khatami and K. Banerjee, Carbon,
2011, 49, 4122–4130.
17 X. Liu, L. Fu, N. Liu, T. Gao, Y. F. Zhang, L. Liao and
Z. F. Liu, J. Phys. Chem. C, 2011, 115, 11976–11982.
18 Y. G. Yao, Z. Li, Z. Y. Lin, K. S. Moon, J. Agar and C. P. Wong,
J. Phys. Chem. C, 2011, 115, 5232–5238.
19 S. M. Wang, Y. H. Pei, X. Wang, H. Wang, Q. N. Meng,
H. W. Tian, X. L. Zheng, W. T. Zheng and Y. C. Liu, J. Phys.
D: Appl. Phys., 2010, 43, 455402.
20 T. Terasawa and K. Saiki, Carbon, 2012, 50, 869–874.
21 N. Liu, L. Fu, B. Y. Dai, K. Yan, X. Liu, R. Q. Zhao,
Y. F. Zhang and Z. F. Liu, Nano Lett., 2011, 11, 297–303.
22 S. J. Chae, F. Gunes, K. K. Kim, E. S. Kim, G. H. Han,
S. M. Kim, H. J. Shin, S. M. Yoon, J. Y. Choi, M. H. Park,
C. W. Yang, D. Pribat and Y. H. Lee, Adv. Mater., 2009, 21,
2328–2333.
23 M. Losurdo, M. M. Giangregorio, P. Capezzuto and
G. Bruno, Phys. Chem. Chem. Phys., 2011, 13, 20836–20843.
24 J. L. Qi, L. X. Zhang, J. Cao, W. T. Zheng, X. Wang and
J. C. Feng, Chin. Sci. Bull., 2012, 57, 3040–3044.
25 H. Ago, Y. Ogawa, M. Tsuji, S. Mizuno and H. Hibino,
J. Phys. Chem. Lett., 2012, 3, 2228–2236.
26 K. F. Tan, J. Xu, J. Chang, A. Borgna and M. Saeys, J. Catal.,
2010, 274, 121–129.
27 E. S. Kim, H. J. Shin, S. M. Yoon, G. H. Han, S. J. Chae,
J. J. Bae, F. Gunes, J. Y. Choi and Y. H. Lee, Appl. Phys. Lett.,
2011, 99, 223102.
28 M. D. Segall, P. J. D. Lindan, M. J. Probert, C. J. Pickard,
P. J. Hasnip, S. J. Clark and M. C. Payne, J. Phys.: Condens.
Matter, 2002, 14, 2717–2744.
29 D. Vanderbilt, Phys. Rev. B: Condens. Matter Mater. Phys.,
1990, 41, 7892–7895.
30 J. P. Perdew, K. Burke and J. Ernzerhof, Phys. Rev. Lett., 1996,
77, 3865–3868.
31 H. J. Monkhorst and J. D. Pack, Phys. Rev. B: Solid State,
1976, 13, 5188–5192.
32 H. Ago, T. Kugler, F. Cacialli, W. R. Salaneck, M. S. P.
Shaffer, A. H. Windle and R. H. Friend, J. Phys. Chem. B,
1999, 103, 8116–8121.
33 D. Zhan, Z. H. Ni, W. Chen, L. Sun, Z. Q. Luo, L. F. Lai, T. Yu,
A. T. S. Wee and Z. X. Shen, Carbon, 2011, 49, 1362–1366.
34 A. C. Ferrari, Solid State Commun., 2007, 143, 47–57.
35 L. M. Malard, M. A. Pimenta, G. Dresselhaus and
M. S. Dresselhaus, Phys. Rep., 2009, 473, 51–87.
36 F. Tuinstra and J. L. Koenig, J. Chem. Phys., 1970, 53, 1126–1130.
37 D. S. Knight and W. B. White, J. Mater. Res., 1989, 4, 385–393.
38 L. G. Cancado, K. Takai, T. Enoki, M. Endo, Y. A. Kim,
H. Mizusaki, A. Jorio, L. N. Coelho, R. Magalhaes-Paniago
and M. A. Pimenta, Appl. Phys. Lett., 2006, 88, 163106.
39 A. Salehi-Khojin, D. Estrada, K. Y. Lin, M. H. Bae, F. Xiong,
E. Pop and R. I. Masel, Adv. Mater., 2012, 24, 53–57.
New J. Chem., 2013, 37, 1616--1622 1621

NJC
40 A. Reina, X. T. Jia, J. Ho, D. Nezich, H. B. Son, V. Bulovic,
M. S. Dresselhaus and J. Kong, Nano Lett., 2009, 9, 30–35.
41 S. M. Wang, H. W. Tian, Y. H. Pei, Q. N. Meng, J. L. Chen,
H. Wang, Y. Zeng, W. T. Zheng and Y. C. Liu, J. Solid State
Chem., 2012, 186, 235–239.
42 H. J. Song, M. Son, C. Park, H. Lim, M. P. Levendorf,
A. W. Tsen, J. Park and H. C. Choi, Nanoscale, 2012, 4,
3050–3054.
43 B. S. Hu, H. Ago, C. M. Orofeo, Y. Ogawa and M. Tsuji, New J.
Chem., 2012, 36, 73–77.
Published on 13 March 2013. Downloaded by Hacettepe Universitesi on 5/11/2022 1:27:50 PM.
44 C. Liu, T. R. Cundari and A. K. Wilson, J. Phys. Chem. C,
2012, 116, 5681–5688.
1622 New J. Chem., 2013, 37, 1616--1622 This journal is c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2013
View Article Online
Paper
45 J. C. W. Swart, E. van Steen, I. M. Ciobica and R. A. van
Santen, Phys. Chem. Chem. Phys., 2009, 11, 803–807.
46 L. C. Jia, X. Wang, B. Hua, W. L. Li, B. Chi, J. Pu, S. L. Yuan
and L. Jian, Int. J. Hydrogen Energy, 2012, 37, 11941–11945.
47 W. Zhao, S. M. Kozlov, O. Hofert, K. Gotterbarm, M. P. A.
Lorenz, F. Vines, C. Papp, A. Gorling and H. P. Steinruck,
J. Phys. Chem. Lett., 2011, 2, 759–764.
48 J. Xu and M. Saeys, J. Phys. Chem. C, 2008, 112, 9679–9685.
49 L. J. Meng, Q. Sun, J. L. Wang and F. Ding, J. Phys. Chem. C,
2012, 116, 6097–6102.
50 F. Cinquini, F. Delbecq and P. Sautet, Phys. Chem. Chem.
Phys., 2009, 11, 11546–11556.