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Simultaneous growth of monolayer graphene

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DOI: 10.1039/C6RA04197C

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Cite this: RSC Adv., 2016, 6, 41447

Simultaneous growth of monolayer graphene on

NiCu bimetallic catalyst by atmospheric pressure
CVD process
Choon-Ming Seah,ab Brigitte Vigolo,*a Siang-Piao Chai,c Satoshi Ichikawa,d
e
a
b
Jero
me Gleize, Jaafar Ghanbaja and Abdul Rahman Mohamed
CVD is the most ecient way to produce wafer scale monolayer graphene. Although Ni and Cu are widely
reported catalysts for monolayer graphene formation, but both Ni and Cu are requiring dierent extreme
conditions to grow graphene in single layer. Here, we show that monolayer graphene could be grown
simultaneously on polycrystalline Ni and Cu under single atmospheric pressure CVD for the rst time.
Our catalyst system combines carbon solubility divergence between the two catalysts to limit the

Received 16th February 2016

Accepted 20th April 2016

exposure to the carbon source. Structure and quality of the grown graphene were characterized by
HRTEM and Raman spectroscopy mapping. The growth mechanism shows that the role of grain

DOI: 10.1039/c6ra04197c

boundaries is crucial for carbon diusion tuning. The results show that free-standing high-quality

www.rsc.org/advances

monolayer graphene can be produced in a controlled and simple way with an aordable catalyst system.

1. Introduction
Graphene, a thin lm of carbon arranged in a sp2 honeycomb
lattice with monoatomic thickness, is a popular new material.1
The rst mechanical exfoliation of graphene akes from
graphite has kickstarted interest in this unique material.2 The
attractiveness of graphene is mainly attributed to its remarkable
mechanical, optical, thermal and electrical properties, enabling
graphene to be potentially used in various applications. Graphene can be synthesized through reduction of graphene
oxide,3 sublimation of SiC4 and Chemical Vapour Deposition
(CVD). Among these techniques, sublimation of SiC and CVD
are two promising methods to produce wafer-scale graphene;
and CVD especially because it allows an easier separation of
graphene from the catalyst substrate.
Ni and Cu are two most promising catalysts due to moderate
and low carbon solubility into Ni5 and Cu6, respectively. The
growth mechanism of graphene on Cu is known to be surface
mediated, and Cu possesses self-limiting surface deposition

a
Institut Jean Lamour, CNRS-Universite de Lorraine, BP 70239,
Vanduvre-l`es-Nancy, France. E-mail: brigitte.vigolo@univ-lorraine.fr

54506

School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia,

14300 Nibong Tebal, Seberang Perai Selatan, P. Pinang, Malaysia

c
Chemical Engineering Discipline, School of Engineering, Monash University, Jalan
Lagoon Selatan, 46150 Bandar Sunway, Selangor, Malaysia
d

Institute for NanoScience Design, Osaka University, 1-3, Machikaneyama-cho,

Toyonaka, Osaka 560-8531, Japan

Laboratoire de Chimie Physique-Approche Multi-echelle de Milieux ComplexesUniversite de Lorraine, 1 Bd Arago, 57078 Metz, France
Electronic supplementary
10.1039/c6ra04197c

information

(ESI)

This journal is The Royal Society of Chemistry 2016

available.

See

DOI:

which enhances the formation of predominantly monolayer

graphene. However, Cu requires strict process conditions to
grow monolayer graphene, including high vacuum conditions,
a low carbon concentration environment and a synthesis
temperature near to the melting point of Cu.7 Ni rather follows
a bulk-mediated graphene formation mechanism, which
unfortunately favors the formation of multilayer graphene. The
formation of monolayer graphene on Ni requires high-speed
cooling aer CVD or the use a very thin Ni lm as the catalyst.
Cu and Ni could form binary isomorphous alloys for which
both metals are mutually miscible.8 Some researchers had
investigated the possibility of using both Cu and Ni to grow
graphene with the hope to combine the benets of Cu and Ni.
Two strategies have been reported to grow graphene from
bimetallic catalysts, either by using layer-by-layer bimetallic
catalyst foils9,10 or by using alloy foils.11,12 However, the synthesis
process is rather complex, and it requires high vacuum condition and low carbon precursor/diluting gas to grow monolayer
graphene.
In the present work, a facile technique is demonstrated to
grow uniform monolayer graphenes simultaneously on both
polycrystalline Ni and Cu foils by NiCu bilayer catalyst. The
CVD reaction was carried out under atmospheric pressure. High
uniformity and quality of the crystalline structure of the grown
graphene was evidenced by Raman spectroscopy mapping and
High Resolution Transmission Electron Microscope (HRTEM).
Our straightforward bimetallic catalyst allows the control of
carbon diusion to the area between the Ni and Cu surfaces. In
particular, carbon access is reduced at the inner Ni surface,
while Cu behaving as a carbon barrier. The growth mechanism
of monolayer graphene facilitated by carbon diusion through

RSC Adv., 2016, 6, 4144741452 | 41447

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the bulk and Ni grain boundary, the driving force coming from
carbon-rich surface to carbon-lacked surface. The grain
boundaries are shown to play a crucial role in carbon control
during the growth stage. The robustness of this bilayer catalyst
allows a facile separation of the grown graphene from the
catalyst and transfer to the desired support.

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2.
2.1

Experimental
Graphene synthesis

Ni foil (99.9% purity, Sigma-Aldrich) with a thickness of ca. 125

mm and polycrystalline surface was cut into 5 mm  5 mm,
meanwhile polycrystalline Cu foil (99.9% purity, Sigma-Aldrich)
with the thickness of ca. 25 mm was cut into 7 mm  7 mm. Cu
foil was then wrapped rmly onto Ni foil to form a bilayer
catalyst with the bottom of catalyst fully covered with Cu, and
the upper surface of the Ni catalyst exposed around 3 mm  3
mm of Ni, while the 4 edges were covered with 1 mm of Cu
respectively. The bilayer catalyst was pressed with a hydraulic
press with a pressure of 20 N to guarantee a good contact
between Ni and Cu.
In general, the NiCu bilayer catalyst was placed into
a quartz boat with Ni surface facing upward. The quartz boat
was then placed at the centre of a quartz tube (inner diameter:
30 mm). The NiCu foil was then heated from room temperature in tubular furnace (Carbolite) up to the desired temperature (8001050  C) with a heating rate of 10  C min 1. During
the heating, high purity H2 gas (99.999%) with a ow rate of
80 sccm was owed into the quartz tube to reduce the oxide
present on the Ni surface. As the desired temperature was obtained, high purity CH4 (99.999%) was fed into the reactor at
a ow rate of 20 sccm with the H2 ow rate remained
unchanged. Aer reaction (37 min) the quartz boat along with
the Ni foil was displaced from the heating zone to an ambient
temperature zone for rapid cooling. At the same time, CH4 and
H2 gases were switched o and N2 gas (99.999%) subsequently
introduced into the quartz tube to quench the reaction.13
2.2

Graphene transfer

Once the temperature was cooled to room temperature, the Ni

Cu substrate was taken out from the reactor for graphene
separation process. The Cu foil was unwrapped gently from Ni
foil. Nitric acid with a concentration of 1.44 mol L 1 (6.5%)
from nitric acid of 65%, provided by Merck was used to separate
graphene from the Ni foil. The Cu foil was etched with an
iron(III) nitrate solution of a concentration of 0.20 mol L 1 (by
diluting iron(III) nitrate nonahydrate, >99.95% provided by
Sigma-Aldrich). The unwanted surface of Ni and Cu were rst
rubbed with sand paper (800 mesh) before being oated onto
their respective etchant. The purpose is to create a larger
contact area with the etchant for etching enhancement. Aer
the graphene and Ni were separated, iron nitrate and nitric acid
were diluted with a huge amount of DI water to minimize the
contamination on the graphene sheet. The graphene lm was
oating on DI water; because of its high transparency it could
barely observed with naked eye. Separated graphene could be

41448 | RSC Adv., 2016, 6, 4144741452

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transferred onto a silicon wafer coated with silicon oxide (1000

Analysis was performed either on the transferred graphene
A).
or directly on graphene grown on the catalyst.
2.3

Characterization

Raman spectra were collected at room temperature (300 K).

Point-based Raman spectra were collected through a Renishaw
inVia Raman microscope. A 632.8 nm HeNe laser was focused
on the samples and no lter was used. The range of Raman shi
from 1100 cm 1 to 3000 cm 1 was scanned. For Raman
mapping, a Horiba LabRAM HR 800 micro-Raman spectrometer
was used. The area of 50 mm  50 mm was scanned under the
same incident wavelength and the same operating procedure as
aforementioned. The samples were scanned in a range of
Raman shi of 15001700 cm 1 for the G-band, and 25502750
cm 1 for the 2D-band. Each zone was scanned with 30 s incident time for 2 cycles. The HRTEM images were taken with JEOL
ARM 200F operating at 80 kV. To increase the image contrast,
holey grids (300 mesh size) were used. For each sample, several
locations were observed and only typical images are shown in
the manuscript.
A JEOL JEM-09100IS Ion Slicer apparatus was utilized for
thinning of the Ni foil in order to observe the element composition at the middle of the bulk Ni foil. First, a strip of Ni with
a thickness of 250 mm was cut from the centre of the Ni foil used
for CVD reaction. It was further polished with sand paper
(micro-mesh 4000) to diminish the thickness down to 100 mm.
The Ni strip was placed into the ion slicer apparatus and
a shield belt with a thickness of 10 mm was placed onto of the
strip. An Ar+ ion beam was then irradiated onto the Ni strip from
the top and the Ni strip was kept oscillating by 3 at both sides
until an etched hole appear. The Ni strip was transferred to a Fei
Tecnai 20 transmission electron microscope for imaging and
energy-dispersive X-ray spectroscopy (EDS) analysis for
elementary composition between Ni grains and grain boundaries aer the CVD process. A Keithley 220 programmable
current source in conjunction with a Hewlett-Packard 34401A
multimeter was used for the four-point probe sheet resistance
measurement of graphene grown at inner surface of Ni in
ambient environment and at room temperature.

3.

Results and discussion

The reaction temperature and duration employed for graphene

synthesis were varied in this study. The temperature was ranged
from 850 to 1050  C and the durations of 5, 6 and 7 min were
investigated. Graphitic materials were found at 4 dierent
planes of the bilayer catalyst as shown in Fig. 1a. Meanwhile
Fig. 1b shows the photograph of graphene separated from both
inner surfaces of Ni and Cu with CVD temperature 950  C for
5 min.
The graphene samples were successfully separated from
their respective metal foil and deposited onto a silicon wafer for
Raman analysis. Three main bands in the Raman spectrum of
graphitic materials are normally used to determine structural
information: (1) D-(disorder) band at 1350 cm 1; the relative

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above 1.4 for the graphene grown at inner surface of Ni, but the
area of such samples were small and not fully covered the Ni
surface. Interestingly, at a temperature of 950  C, large area of
graphene that fully covered the catalyst surface were grown on
both inner surfaces of Ni and Cu, and the I2D/IG are well.
All of the regions of graphene grown from inner surfaces of
Ni and Cu display a ratio I2D/IG much higher than 1.4 (Fig. 2a
and c). The overall of the fwhm2D of the Raman 2D-band are
below 36 cm 1 (Fig. 2b) and below 37 cm 1 (Fig. 2d) for graphene grown on inner surface of Ni and Cu, respectively,
furthermore, the 2D-bands well tted into single Lorentzian
curve. The range of I2D/IG ratio and that of fwhm2D is relatively
large due to the trapped moisture and air between graphene
and silicon wafer causing some stress to CC bonds of graphene. From point based Raman spectra (see ESI, Fig. S1), the
D-band is very weak compared with G-band, showing that the
grown graphene contains low amount of defects. HRTEM
observations were randomly carried out at the several folded
edges of the graphene sheets. A clear single straight line is
visibly monitored for graphene grown at both inner surface of
Ni (Fig. 2e) and inner surface of Cu (Fig. 2f). Enlarged images

(a) The schematic of the cross section of the bilayer catalyst;

orange colour indicates Cu foil and silver colour is for Ni foil. (b)
Photograph of graphene lms grown at (left) inner surface of Ni and
(right) inner surface of Cu at 950  C for 5 min after deposited onto
silicon wafer. (c) Average and standard deviation of I2D/IG for graphene
lms grown on the 4 dierent surfaces of the CVD device in the
temperature range 8501000  C for 5 min. Coral colour area indicating the area of monolayer graphene and striped area is graphene of
more than one layer.
Fig. 1

intensity of this peak is related to the degree of disorder,

dangling bonds or relative sp3 carbon content, in the carbon
structure; (2) G-band at 1580 cm 1 is the peak which indicating the sp2 graphitic bond; (3) 2D-band at 2680 cm 1 is the
second harmonic of the D-band. The main Raman features used
to evidence a graphitic material with one single sheet are: (i)
a single, highly symmetric and narrow 2D-band with a single
Lorentzian component; (ii) a relative intensity of the 2D- and
G-bands, I2D/IG, higher than 1.4;1416 (iii) a full width half
maximum of the 2D-band (fwhm2D) below 40 cm 1.11,16,17
For conventional micro-Raman analysis, ve spectra were
taken randomly from each graphene sample grown at dierent
temperatures for 5 min and at each surface of the CVD device;
the corresponding I2D/IG are summarized in Fig. 1c. For Cu, 900

C and below were too low to synthesize pristine wafer scale
graphene; no signal of the 2D-band was obtained. On the other
hand, for a temperature of 1050  C, just below the melting point
of Cu (1085  C), disordered thick graphitic layers were obtained.
For our CVD system, thermal decomposition of methane
signicantly observed at 1050  C. The uncontrolled decomposition of methane ended up with both the catalyst and wall of
the CVD reactor covered with a thick layer of disorder graphitic
materials. For a temperature of 900  C, I2D/IG are found to be

This journal is The Royal Society of Chemistry 2016

Fig. 2 Raman maps of (a) I2D/IG and (b) fwhm2D for graphene grown
on inner surface of Ni, and (c) I2D/IG and (d) fwhm2D for graphene
grown on inner surface of Cu at 950  C for 5 min. The colour gradient
bar is given on the right of each map. HRTEM images of monolayer
graphene grown on inner surface of (e) Ni and (f) Cu taken at the edge
under CVD of 950  C and 5 min. (Insert at top) FFTs taken for
respective graphene sheet. (Insert at bottom) Enlarged images are
cropped from the boxed region in respective graphene sheets.

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(inserted at the bottom of Fig. 2e and f) of respective graphene

in the boxed areas show how the hexagonal graphene structure
is oriented. As can be seen from the Fast Fourier Transform
(FFT) images the graphene lm generate a single set of hexagon
diraction pattern (Fig. 2e and f (inserted at top)) indicating the
present of monolayer graphene. AFM images (Fig. S2) show
that the thickness of graphene is less than 0.5 nm which is
a sign of high selectivity of monolayer graphene on both
samples. Since we have used polycrystalline Ni and Cu as
catalyst, the roughness certainly corresponds to the grain
boundary visible under AFM.
All the data obtained are pointing to the presence of monolayer graphene on both inner surfaces on Ni and Cu with CVD
temperature of 950  C and 5 min. As mentioned earlier, Ni has
a relatively higher carbon solubility and higher carbon diusion
rate. Formation of monolayer graphene on Ni catalyst is dicult
by using atmospheric pressure CVD conditions; and few layers
of graphene are usually obtained. An alternative process
involving the diusion of carbon adatoms across the Ni lm was
then proposed; graphene being formed at the opposite
surface.1820 A carbon-poor environment is created to reduce the
carbon-concentration and lead to successful synthesis of graphene with a minimum number of layers. Moreover, the
uniformity of graphene layers was much improved under such
a strategy, compared with conventional Ni catalysed CVD.
However, the graphene grown with such methods is normally
rmly attached onto the silicon that served as substrate, making
it dicult to obtain free-standing graphene.
We propose a simple approach to facilitate the formation of
monolayer graphene that enables the following separation
process to obtain free-standing monolayer graphene. Cu with
almost no carbon solubility is a good candidate to insulate
carbon atoms.21 Our system combines the properties of Ni and
Cu in order to dramatically reduce the carbon content at the
inner Ni surface. Additional experiments with addition of
silicon wafer to the catalyst system were carried out (Fig. S3).
Silicon wafer which has no carbon solubility and is inactive for
graphene formation was used to act as a carbon shield. A silicon
wafer was rst placed between Cu and Ni (Fig. S3a); no graphene formation was observed on the inner surface of Cu: i.e.
no graphene could be separated. On the contrary, on inner
surfaces of Ni, graphene could be observed aer the Ni etched
away. For the second experiment, the silicon wafer was placed
on the Ni surface so that Ni was sandwiched in between Cu and
silicon (Fig. S3b). Aer the CVD reaction, no graphene could be
found on both Ni surfaces aer Ni were etched away. That
means that carbon atoms involved in graphene formation
mainly come through diusion over the bulk Ni foil, neither
through the leak of gases into that area nor diusion over the
Cu foil. Although, carbon diusion was reported through the
grain boundaries of 100 nm-thick Cu foil;22 our Cu foil being
much thicker (25 mm) is able to eciently inhibit carbon
diusion and the access to the inner surface of Ni is completely
inaccessible through the Cu foil.
As the sequence of the two catalysts was ipped over (Ni foil
wrapped over Cu foil), monolayer graphenes were as well found
aer the CVD reaction done at 950  C and 5 min at inner surface

41450 | RSC Adv., 2016, 6, 4144741452

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of Ni and that of Cu (Fig. S4). To further identify the path of

carbon diusion though Ni, we have investigated the characterization of the Ni foil aer the synthesis process. Since the
reaction was quenched by the use of high-speed cooling, this
analysis provides a snapshot of the state during the reaction.
Analysis was performed on a cross section of the Ni foils thinned down to around 20 nm (for the position around 90 mm from
the surface). The bright eld TEM image (Fig. 3a) reveals grain
boundaries enriched by carbon atoms (Fig. 3b). EDS analysis
conrms that carbon concentration is higher at the Ni grain
boundaries; C content is higher at the grain boundary
compared to that at a location within the Ni grain (Fig. 3c). A

Fig. 3 (a) Bright eld TEM images of a Ni grain boundary at the center
of Ni foil after the CVD reaction at 950  C and 5 min. (b) Schematic
showing the distribution on carbon adatoms at the middle of Ni foil
after CVD. Grey area indicting the grains of Ni, black dots illustrating
the carbon adatoms. (c) EDS spectra taken at the middle of Ni grain
(red) and near grain boundary (black). The intensity has been
normalized to the maximum of Ni La peak. Inserted is the magnied
spectra at energy range of 0.01.0 keV.

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precise quantication of the C/Ni ratio is not possible because

of the too high absorption dierence between Ni and C element.
However, C Ka line is very obvious (Fig. 3c, insert) showing the
higher content of carbon near grain boundaries, especially
since very low C concentration is involved in the CVD reaction.
Fig. 4 shows optical micrographs of the graphene samples
transferred to silicon wafer. Their formation was obtained aer
5 min (Fig. 4a and b) and 7 min (Fig. 4c and d) of reaction.
Under shorter growth durations of 3 min and below (not shown
here), small akes of graphene sheet were scattered over the
inner surface of Ni and cannot be transferred eectively. The
optical micrographs (Fig. 4a and b) show uniform contrast
across the imaged area for the graphene obtained at both inner
surfaces of Ni and Cu under reaction duration of 5 min, indicative of uniform monolayer graphene coverage. The variation of
colour contrast become signicant as the CVD duration
extended to 7 min, for graphene obtained from inner surface on
Ni (Fig. 4c), indicating that the lm is not uniform in thickness
and consist of multi layered graphene. Comparable areas of
multi layered graphene were also found on Cu surfaces (Fig. 4d).
The graphene that was obtained on the inner surface of Cu
displays a similar topography as the graphene grown on the
respective Ni surface. However, the same pattern of grain
boundaries was not seen onto the graphene on Cu. The graphene grown on the inner surface of Cu possesses instead
a weakness, where small scales of voids were appearing on the
graphene lm.
The Ni foil selected is a conventional and low-cost polycrystalline Ni foil. Contrary to monocrystalline Ni, it is made of
grains with irregular sizes and shapes. Diusion of carbon
adatoms is consequently not uniformed towards the Ni foil. It
could take place either through the bulk of the grain and also

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through the gap in between the grains, known as grain

boundary. The solubility of carbon into bulk Ni at 950  C is
around 1.0 at%.23 Diusion rate of carbon atoms is favoured at
the grain boundaries. The carbon concentration gradient
between the Ni surface facing carbon-rich CVD atmosphere
(outer surface of Ni) and the carbon poor region of Ni (inner
surface of Ni) would be the main force facilitating the carbon
diusion. The carbon diusion mechanism is illustrated in
Fig. 5. Carbon adatoms are diusing faster through the grain
boundary, but at the same time, some carbon adatoms are
diluted into the grain due to the concentration gradient (red
arrows in Fig. 5a). Our process allows the control of the carbon
concentration within Ni grains leading to a uniform carbon
distribution over the whole Ni surface. Combined with post
CVD fast cooling, uniform graphene in term of number of layer
is easily obtained. Under higher temperature (1030  C), the
diusion of carbon through the gap between the grains being
increased, much faster compared to its dilution into the Ni
grain (Fig. 5b), the CVD reaction duration applied was intentionally reduced. No graphene lm was obtained but instead
web-liked carbon material could be observed (see ESI, Fig. S5).
The time allowed for the carbon to dilute within Ni grains was
too short and carbon distribution was obviously non-uniform
throughout the Ni surface. Aer a fast cooling, graphitic materials segregated at the locations enriched by carbon (grain
boundaries) while no carbon material was formed on the
surface far from grain boundary. It was here as well conrmed

The pathways of carbon diusion through the polycrystalline Ni

foil at (a) 950  C and (b) 1030  C. The black arrow is indicating the
diusion of carbon through the grain boundary of Ni. The red arrows
show the dilution of carbon from grain boundary into the bulk of Ni
grain.
Fig. 5

Optical micrographes of graphene grown at inner surface of (a)

Ni with 5 min, (b) Cu under 5 min, (c) Ni under 7 min, (d) Cu under 7 min
(for a CVD temperature of 950  C) after transferred onto silicon wafer.

Fig. 4

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that the grain boundary was the major channel for the carbon
supply to the interface between Ni and Cu. The sheet resistance
(Rs) of monolayer graphene grown was measured to be 1900
ohm sq 1, near of the values reported in previous reports on
stacked monolayer graphene.24
What is usually observed from the polycrystalline Ni in
atmospheric pressure CVD is the formation of multilayer graphene.14,25 The misalignment of the distance of the lattice of Ni
is reported to provide abundant nucleation sites for graphene to
segregate and that leads to the formation of more layers of
graphene.26 This is the main reason why Ni foil is normally
forsaken to grow graphene. With our bilayer catalyst system,
accumulation of the carbon at grain boundaries is reduced,
inhibiting the excessive carbon segregation and thus enhancing
the formation of monolayer graphene. Multilayer graphene is
more likely to form on Cu due to the excessive supply of carbon.
But, through our strategy, the carbon-poor atmosphere is
present at the interface of NiCu. The main carbon supply was
from the contact with Ni.

4. Conclusion
In summary, by utilizing bilayer bimetallic catalyst through
wrapping of a Cu foil over a Ni foil, we manage to control the
supply of carbon adatoms at the interface of Ni and Cu. Under
proper tuning of the operating conditions and with the aid of
fast cooling monolayer graphene could be grown on both inner
surfaces of Ni and Cu under single atmospheric pressure CVD.
The graphene that was grown at the outer surface for both Ni
and Cu had the same characteristics of graphene that was
grown on single Ni and Cu under same operating conditions.
The proposed growth mechanism shows that the gap between
the grains of Ni foil is certainly the main channel to supply
a controlled amount of carbon adatoms to the inner surface of
Ni. Meanwhile, the contact between Ni and Cu was the pathway
for the carbon supply to the Cu surface.

Acknowledgements
The authors gratefully acknowledge the nancial support
provided by Universiti Sains Malaysia (USM Fellowship), Les
Bourses du Gouvernement Franais, the IRec grant (1002/
PJKIMIA/910404), and the Fundamental Research Grant
Scheme (FRGS) (203/PJKIMIA/6071278). The authors also thank
Pascal Franchetti for his technical help and expertise during
Raman measurements. The authors thank F. Le Normand and
F. Aweke for their help for the sheet resistance measurements.

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