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pubs.acs.org/JPCC

Initial Stage of Graphene Growth on a Cu Substrate

Chanyong Hwang,*, K. Yoo, S. J. Kim, E. K. Seo, H. Yu, and L. P. Biro

Center for Nano-imaging Technology, Korea Research Institute of Standards and Science, 267 Gajeong-Ro, Yuseong,
Daejeon 305-340, Korea

Center for Nano-Bio Technology, Korea Research Institute of Standards and Science, 267 Gajeong-Ro, Yuseong,
Daejeon 305-340, Korea

Research Institute for Technical Physics and Materials Science, H-1525 Budapest, POB 49, Hungary
ABSTRACT: The growth of graphene on copper foil has attracted attention in the
last two years due to its feasibility for a controllable growth process. One of the key
issues remaining for practical application of graphene in solid-state devices is
growth with a large grain size. Because the C C bond in graphene is strong
enough to prevent the evaporation condensation process, Smoluchowski ripening is expected to be the dominant process for coalescence. In this article, we
present the initial growth process of graphene on a Cu foil via the chemical vapor
deposition method by using secondary electron microscopy and Raman microscopy. In contrast to the other transition-metal substrates, such as Ir and Rh, the
center of graphene islands binds to the substrate more rigidly than the edge. For
the growth with a large grain size, the graphene should be grown on a substrate
with a low diusion barrier for the carbon clusters (or islands) with low ux; this is
the controlling parameter for the grain size. In addition, high-temperature growth
(or annealing) generally becomes a dominant condition for the completion of graphene growth with large grains after the
coalescence.

INTRODUCTION
Ever since the rst discovery of mechanically exfoliated
graphene from the bulk graphite,1 graphene research has drawn
a lot of attention. Graphenes unique properties distinguish it
from other normal conductors; these include the unusual
quantum Hall eect, the charge carriers behaving like Dirac
fermion, and Klein tunneling.2 4 These fundamental issues
related to graphene have been studied both experimentally and
theoretically for the last 7 years.5 However, the problems of
growth are still under debate. The detailed growth process is
not clearly known, especially in the submonolayer region.
Moreover, the growth of graphene on insulating layers is one
of the most critical issues for its application toward solid-state
devices but was not within the scope of this study. In this report,
we present more details on the initial growth of graphene on a
Cu foil. The growth of graphene on Cu foil was rst reported in
2009 by Ruo,6 and it has drawn a great deal of attention due to
its pure surface chemical process character in contrast with
other transition metals, such as Ni, where the growth involves
bulk diusion processes, too. Though many eorts have been
made for graphene growth on Cu foil,7 9 microscopic details
for the growth on the Cu surface are not clearly understood.
Thus, a recipe to form high-quality graphene has not yet been
established.10 Recently, nonlinearity of the graphene growth
rate with C-adatom density suggests that growth proceeds by
the addition of C atom clusters to the graphene edge.11 However,
there is no experimental support for this cluster behavior.
r 2011 American Chemical Society

This nonlinearity in growth rate can have other origins since

the rebonding process is more critical for the completion of
the graphene growth. One advantage of using Cu foil for
graphene growth is the low solubility of carbon in Cu. In
addition, Cu does not form an alloy with carbon, which means
no carbide formation. This characteristic is attributed to the
almost lled 3d bands; the bonding of graphene with the Cu
substrate is through hybridization of the orbital of graphene
and the unoccupied state of Cu. Thus, the bonding between
graphene and the Cu substrate is the smallest among 3d
transition metals. These characteristics are quite essential
for the catalyst for Cu to lower the dehydrogenation barrier
of the hydrocarbon used in graphene growth. Because the
formation of sp2 honeycomb-chained graphene with fewer
defects needs a high-temperature process during growth,
hydrocarbon cracking at a lower temperature using such
techniques as the plasma method would not be advantageous.
In most cases, the growth time for completion of a single layer
is less than 1 min if the pressure and ow rate of the
hydrocarbon are not extremely low. Moreover, energetic
carbon atoms are more likely to form an sp3 bonding. The
use of acetylene, C2H2, or ethylene, C2H4, cannot be a
solution for the growth of high-quality graphene. However,
this annealing temperature is still much higher than the
Received: June 25, 2011
Revised:
September 29, 2011
Published: October 10, 2011
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Figure 1. SEM images for the initial growth of graphene on Cu foil at the temperature of 1263 K.

temperature for thermal decomposition of methane. Methane

starts to decompose at temperatures above 800 K.12 In addition,
the sticking coecient of methane on copper is extremely small.
When the substrate temperature increases, the methane caught
on it can decompose into successive hydrocarbon intermediates,
that is, CH3 (methyl), CH2 (methylene), and CH (methylidyne).
These hydrocarbon intermediates are more reactive than
methane, so they evolve to a thermodynamically more stable
carbon atom on the Cu surface.

EXPERIMENTAL SECTION
The graphene was synthesized on a polycrystalline Cu foil
(25 m thick) by the thermal CVD method. Initially, Cu foils
were heated inside a chamber covered by the furnace under H2
gas pressure (0.1 2 sccm) up to 1263 K for 30 min. After 40 min
annealing of Cu foils for cleaning at a temperature of 1263 K,
CH4 and H2 mixture gases were simultaneously transferred to the
furnace for a desired growth time. The temperature of the furnace
was immediately lowered to RT at a cooling rate of 50 K/min.
We changed all of the growth parameters to optimize the
graphene growth on this Cu foil. Scanning electron microscopy
and Raman spectroscopy measurements were carried out after
the graphene samples were exposed to the air.
RESULTS AND DISCUSSION
Figure 1 shows a series of SEM images for the initial growth of
graphene on Cu foil at a temperature of 1263 K. As the growth
time increased, the size of the graphene island started to increase.
The size of the grain was in the range of 20 30 m in (c). The
growth temperature was maintained at 1263 K, and the gas
mixture ratio between H2 and CH4 was 0.2:1. The growth time
was varied at (a) 15, (b) 30, (c) 60, and (d) 120 s with a total
pressure of 780 mTorr. The number of nucleation sites increased
by more than 100% between 15 and 30 s growth and decreased
between 30 and 60 s growth. Here, the ow rate of methane,
including the H2 carrier gas, was low, so the growth time required was
relatively high when compared to cases of high ow rates of methane.

As the growth time increased, the size of islands began to grow

to form bigger islands (b d) (Figure 1). At this stage, the island
density is big enough so that the carbon clusters (or atoms)
can easily reach the island in the diusion process. Because the
bond strength between carbon atoms is quite high, two adjacent
islands cannot evolve to coalesce via edge diusion. Instead, if the
temperature is relatively low (below 1273 K), then the total
number of nucleation sites increases, while the size of already
established islands increases with the carbon atoms (or small
clusters) nearby. Here, the island shape was more or less
dendrimer-like instead of fractal. The lobes of the islands have
a backbone, with the orientation determined by the crystalline
structure of the substrate. Usually the transition from fractal to
dendritic growth comes when the ux of the constituent of the
lm increases.13 Because the temperature of the substrate and the
diusion barrier are also aecting the eective ux for the growth,
it is not easy to conclude whether it is a fractal or a dendrimer
based on the ux only. Two factors, including the high temperature and the strong bond strength between carbon atoms, play an
important role on the shape of islands. We will discuss this in
more detail later. Figure 2 shows an SEM image of the graphene
growth depending on the growth temperature with H2/CH4 =
2:35, growth time = 20 s. The formation of a new nucleus is
possible only if a certain supersaturation is reached. The supersaturation increases with increasing temperature as the decomposition rate of the precursor also increases with increasing
temperature. This is what happens from Figure 2a to
Figure 2b. Also, the smaller number of growing islands at higher
temperatures is an indication of the coalescence of smaller islands
with the larger ones, as shown in Figure 2c. Because the
evaporation condensation process due to the dierence in
vapor pressures between two (small and big) islands is not
allowed in graphene growth at this temperature, Ostwald ripening is not possible.14 The bond strength between carbon atoms is
fairly high (3.6 eV) so that the edge diusion is not allowed here.
The shape of the island grown at higher temperatures is much
more complicated than that of the islands grown at lower
temperatures. This indicates that the smaller islands coalescing
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Figure 2. SEM images of graphene growth depending on the growth temperature with the H2/CH4 = 2:35 and a growth time of 20 s: (a) 1213, (b)
1253, (c) 1273, and (d) 1303 K.

Figure 3. Island density of graphene islands vs 1000/T, where T is the

growth temperature: (a) H2/CH4 = 1:5, growth time = 10 s (square),
(b) H2/CH4 = 2:7, growth time = 10 s (circle), and (c) H2/CH4 = 2:35,
growth time = 20 s (diamond).

with the larger ones do not lose their individual crystallographic

orientation completely. In this way, after a coalescence process
takes place, the larger island, which incorporated the smaller
ones, will have new lobes. Figure 3 shows the island density vs
1000/T in log scale for several dierent growth conditions.
Below 1253 K, the variations in the density of the graphene
islands are small. Above this temperature, the slope of the
variation of the island density becomes large. This means that
the coalescence of the islands does not follow the Ostwald
ripening process, but rather the Smoluchowski ripening process,
that is, the ripening via island diusion and aggregation. From the
slope in the Arrhenius plot in Figure 3, the migration barrier of
the carbon islands is dependent on the ow rate of methane.15
Below 1253 K, it ranges from 1.6 to 3.4 eV, whereas above

Figure 4. SEM image that shows the onset of the coalescence of two
islands.

1253 K, it ranges from 4.0 to 8.9 eV depending on the ow rate of

carbon. This type of process was suggested in the graphene
growth on an Ir(111) surface.16 Small graphene islands can
diuse more easily, so they can coalesce with big islands. Once
they form a single island, the rebonding process between carbon
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Figure 5. SEM image of a partly covered graphene overlayer on Cu foil, magnied in series, where the scale bar is marked.

atoms takes place to eventually form a well-characterized graphene

layer. Here, the temperature is again the most critical parameter
for forming a uniform graphene layer. We present an SEM image
in Figure 4 that shows the onset of the coalescence of two big
polygonally shaped islands in several locations on the same
sample. Smoluchowski ripening also involves the edge diusion
in the growth of the metal overlayer. However, due to the strong
C C bond here, the rebonding process between carbon atoms
plays an essential role in graphene growth.
Because the lm growth is basically a nonequilibrium process,
the kinetics of surface diusion plays an important role in
determining the morphology of the lm. On the basis of a kinetic
Monte Carlo simulation of the lm growth, there are three
important factors for the morphology of the island to form in the
monolayer regime: the temperature, diusion barrier on top of
the terraces, and Schwoebel barrier across the step edge. These
three parameters contribute to the overall shape of the lm
morphology. The most distinctive features are the fractal (or
dendrimer)-like or polygon-type islands based on the substrate
structure. Many edges show hexagon-shaped structures, which
means that there exists a substrate eect. Figure 5 shows the
image of the partially covered graphene overlayer on the Cu foil.
The grain boundary of the Cu foil is clearly seen to be near the
center, which crosses from the top left to the bottom right. The
secondary electron yield for copper is far larger than 1, whereas
that of graphic carbon is slightly above 1. Thus, if the graphene
layer covers the top of the copper foil, the number of secondary
electrons decreases compared with that of copper. The graphenecovered area, which was conrmed by the Raman spectroscopy,
is the dark part. The grain boundary or step edge of the Cu
substrate cannot be a nucleation or pinning site for graphene
growth. This means that the dierence between the Schwoebel
barrier and the diusion barrier should be very small. The
constituent carbon atoms (or clusters) involved in nucleation
did not seem very dierent on the terrace or across the steps.
Some regions on the graphene island are less dark (gray)
compared with the black areas in the SEM measurement. These
blacker areas are easily found near the edge of the graphene island,

Figure 6. SEM image of a graphene island on the Cu foil. The edge of

each island shows dark contrast compared with that of the center.

which is shown in Figure 6. This area with enhanced contrast is

clearly distinguished from the dark lines originating from the steps
at the copper substrate, which are similar to wood grain. We show
the optical and Raman mapping of these partially covered
graphene islands in Figure 7. The bright area on the graphene
island (identied by SEM and at the center of island) yields a
higher intensity at Raman spectroscopy (2685 cm 1), while the
darker area yields a higher intensity at (2660 cm 1). This 2D band
stems from the second-order double resonant Raman scattering
near the zone boundary. The shape of the spectrum shows that it is
composed of a single layer, and the wavenumber is very close to the
graphene. The peak shift of the 2D state was studied quite recently,
and many controlling parameters (e.g., number of layers, temperature, excitation wavelengths) are present. Recently, a small
strain of less than 1% has been found to induce a shift in the 2D
state of 20 cm 1.17 This can be due to phonon softening due to the
lesser interaction of graphene with the substrate near the edge.
Sometimes, this phonon softening (less bounding to the substrate)
happens inside the island, but this has been attributed to the
inhomogeneous substrate eect. Peculiar domelike shapes of
graphene clusters have been reported to form on Ir(111) and
Rh(111) surfaces.18,19 This means that, at the edge, the interaction
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Figure 7. Optical and micro-Raman image plot of graphene islands on Cu foil. The Raman intensity scale bar is shown below the image.

Figure 8. Schematic drawing of the graphene growth on Cu.

between graphene and the Ir or the Rh substrates is more rigid

than that at the central region, which is opposite to the case of
graphene islands on a Cu substrate. The dierence between Ir and
Cu may be attributed to the dierent growth paths of carbon
atoms (or clusters). Nucleation of the second layer of graphene on
Ir(111) may take place under the rst layer of graphene,20 which is
not possible in Cu(111). Another possibility is the relatively large
lattice mismatch between graphene and Ir (or Rh) compared with
Cu. The nearest-neighbor distances in Ir(111) and Rh(111) are
2.71 and 2.61 , respectively, whereas it is 2.54 in Cu(111). The
lattice constant in graphene is 2.46 . This means that the size of
the superstructure formed is smallest in Cu, and more Cu atoms
can be located near the local minimum energy position. Considering the lattice constant and the interaction energy between
graphene and substrate, Au will be a better substrate to grow
graphene with a large grain size at a shorter time. Practically, it is
not easy to nd the smooth gold foil since it can be easily scratched.

CONCLUSIONS
In conclusion, the initial growth process of graphene on a Cu
foil was studied by using SEM and Raman microscopy. We
summarize the initial growth of graphene islands on Cu, as shown
in Figure 8. Once the nucleation of graphene starts (a), the
number of nucleation sites increases (b) with the distribution of
dierent sizes of islands. If the temperature is high enough so that
the island diusion is possible, then they start to coalesce to form
a bigger island via island diusion (c, d), that is, the so-called
Smoluchowski ripening process. In the meantime, the small
clusters (or islands) can be attached to the big island to grow
since the smaller clusters diuse easily. However, the edge
diusion is quite limited due to the strong bonding between
carbon atoms. Because the temperature for the growth of
graphene is high, the rebonding process between carbon atoms
dominates to control the overall shape of the island. This edge
part binds to the substrate loosely compared with the central part,
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since the edge part keeps rebonding process during the growth.
This has been conrmed by Raman microscopy that the edge of
the island was identied to have a lower 2D wavenumber than
that of the central part of the island. Once the island becomes big
enough so that the island diusion is not easily accessible, then, at
this stage, they are more or less percolated so that, until the
completion of the single layer, the small carbon clusters or atoms
can be attached to the edge to extend their sizes (e, f). Therefore,
one recipe to grow the graphene with large grains is to use
the substrate with the small diusion barrier. Also, high temperature and the low ux is the essential step toward the growth
of large grains. Actually, the Au substrate seems to be a good
candidate for the graphene growth if it can maintain the at
terrace with low surface roughness.

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(16) Coraux, J.; NDiaye, A. T.; Engler, M.; Busse, C.; Wall, D.;
Buckanie, N.; zu Heringdorf, F.-J. M.; van Gastel, R.; Poelsema, B.;
Michely, T. New J. Phys. 2009, 11, 023006.
(17) Yu, V.; Whiteway, E.; Maassen, J.; Hilke, M. arXiv:1101.1884v1.
(18) Lacovig, P.; Pozzo, M.; Dario, A.; Vilmercati, P.; Baraldi, A.;
Lizzit, S. Phys. Rev. Lett. 2009, 103, 166101.
(19) Wang, B.; Ma, X.; Cao, M.; Schaub, R.; Li, W.-X. Nano Lett.
2011, 11, 424430.
(20) Nie, S.; Walter, A. L.; Bartelt, N. C.; Starodub, E.; Bostwick, A.;
Rotenberg, E.; McCarty, K. F. ACS Nano 2011, 5, 22982306.

AUTHOR INFORMATION
Corresponding Author

*E-mail: cyhwang@kriss.re.kr.

ACKNOWLEDGMENT
This research was supported by the Converging Research
Center Program through the Ministry of Education, Science and
Technology (2010K000980) and Korean-Hungarian Joint Laboratory Program by the Korea Research Council of Fundamental Science and Technology. We wish to thank Prof. J. S. Kim
for his critical reading.
REFERENCES
(1) Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang,
Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Science 2004, 306,
666669.
(2) Zhang, Y.; Tan, Y.-W.; Stormer, H. L.; Kim, P. Nature 2005,
438, 201204.
(3) Zhou, S. Y.; Gweon, G.-H.; Graf, J.; Fedorov, A. V.; Spataru,
C. D.; Diehl, R. D.; Kopelevich, Y.; Lee, D.-H.; Louie, S. G.; Lanzara, A.
Nat. Phys. 2006, 2, 595599.
(4) Katsnelson, M. I.; Novoselov, K. S.; Geim, A. K. Nat. Phys. 2006,
2, 620625.
(5) Neto, A. H. C.; Guinea, F.; Peres, N. M. R.; Novoselov, K. S.;
Geim, A. K. Rev. Mod. Phys. 2009, 81, 109162.
(6) Li, X.; Cai, W.; An, J.; Kim, S.; Nah, J.; Yang, D.; Piner, R.;
Velamakanni, A.; Jung, I.; Tutuc, E.; Banerjee, S. K.; Colombo, L.; Ruo,
R. S. Science 2009, 324, 13121314.
(7) Li, X.; Magnuson, C. W.; Venugopal, A.; Tromp, R. M.; Hannon,
J. B.; Vogel, E. M.; Colombo, L.; Ruo, R. S. J. Am. Chem. Soc. 2011,
133, 28162819.
(8) Woord, J. M.; Nie, S.; McCarty, K. F.; Bartelt, N. C.; Dubon,
O. D. Nano Lett. 2010, 10, 48904890.
(9) Xuesong, Li; Magnuson, C. W.; Venugopal, A.; An, J.; Suk, J. W.;
Han, B.; Borysiak, M.; Cai, W.; Velamakanni, A.; Zhu, Y.; Fu, L.; Vogel,
E. M.; Voelkl, E.; Colombo, L.; Ruo, R. S. Nano Lett. 2010, 10, 43284334.
(10) Rao, C. N. R.; Sood, A. K.; Voggu, R.; Subrahmanyam, K. S.
J. Phys. Chem. Lett. 2010, 1, 572.
(11) Loginova, E.; Bartelt, N. C.; Feibelman, P. J.; McCarty, K. F.
New J. Phys. 2009, 11, 063046.
(12) Chan, C.-J.; Back, M. H.; Back, R. A. Can. J. Chem. 1975,
53, 3580.
(13) Brune, H.; Romainczyk, C.; Roder, H.; Kern, K. Nature 1994,
369, 469471.
(14) Ratsch, C.; Venables, J. A. J. Vac. Sci. Technol., A 2003, A21,
S96S109.
(15) Fichthorn, K. A.; Scheer, M. Phys. Rev. Lett. 2000, 84,
53715374.
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