Study of graphene growth on copper foil by pulsed laser deposition at reduced

temperature
Abd Elhamid M. Abd Elhamid, Mohamed A. Hafez, Abdelnaser M. Aboulfotouh, and Iftitan M. Azzouz

Citation: J. Appl. Phys. 121, 025303 (2017); doi: 10.1063/1.4973736

View online: http://dx.doi.org/10.1063/1.4973736
View Table of Contents: http://aip.scitation.org/toc/jap/121/2
Published by the American Institute of Physics

Articles you may be interested in

Effects of growth conditions on the quality of B-doped graphene films
J. Appl. Phys. 121, 025305025305 (2017); 10.1063/1.4974010

Graphene nanoplatelets induced tailoring in photocatalytic activity and antibacterial characteristics of MgO/
graphene nanoplatelets nanocomposites
J. Appl. Phys. 121, 024901024901 (2017); 10.1063/1.4972970

Interferometry of Klein tunnelling electrons in graphene quantum rings

J. Appl. Phys. 121, 024302024302 (2017); 10.1063/1.4973902

First-principles study of interfacial interaction between carbon nanotube and Al2O3(0001)

J. Appl. Phys. 121, 025304025304 (2017); 10.1063/1.4973741
 JOURNAL OF APPLIED PHYSICS 121, 025303 (2017)

Study of graphene growth on copper foil by pulsed laser deposition

at reduced temperature
Abd Elhamid M. Abd Elhamid,1 Mohamed A. Hafez,1,a) Abdelnaser M. Aboulfotouh,2
and Iftitan M. Azzouz1
1
Department of Laser Sciences and Interactions, National Institute of Laser Enhanced Sciences,
Cairo University, El-Giza 12613, Egypt
2
Department of Physics, Faculty of Science, Cairo University, El-Giza 12613, Egypt
(Received 1 October 2016; accepted 24 December 2016; published online 10 January 2017)
Graphene has been successfully grown on commercial copper foil at low temperature of 500  C by
pulsed laser deposition (PLD). X-ray diffraction patterns showed that films have been grown in the
presence of Cu(111) and Cu(200) facets. Raman spectroscopy was utilized to study the effects of
temperature, surface structure, and cooling rate on the graphene growth. Raman spectra indicate
that the synthesis of graphene layers rely on the surface quality of the Cu substrate together with
the proper cooling profile coupled with graphene growth temperature. PLD-grown graphene film
on Cu has been verified by transmission electron microscopy. Surface mediated growth of graphene
on Cu foil substrate revealed to have a favorable catalytic effect. High growth rate of graphene and
less defects can be derived using fast cooling rate. Published by AIP Publishing.
[http://dx.doi.org/10.1063/1.4973736]

I. INTRODUCTION free monolayer graphene. Expectation of the transfer-free

graphene growth by PLD has been attempted practically.
Graphene is considered to be the legendry material of the
Interfacial graphene bilayer was obtained directly on silicon
21 century because of its versatile unique properties like large
dioxide film using PLD technique, without the need for a
conductivity, transparency, strength, and thermal conductiv-
transfer process.14 Multilayer and few layer graphene fabri-
ity.1 Many techniques were utilized to fabricate this two-
cated on fused silica substrate from room temperature to
dimensional material including graphite exfoliation, mechani-
700  C by PLD without using any catalyst is reported.13 PLD
cal cleavage, and chemical vapor deposition (CVD).2–7 Yet,
growth of graphene on the Cu surface can be integrated with
the most widely technique in graphene production is CVD,
other deposition systems to have the selection to fabricate
which relies on using hydrocarbon gases as a carbon source
graphene for the required applications. Incorporating Cu sur-
together with a catalytic metal substrate at a high temperature
face along with other types of substrates in the PLD deposi-
of 1000  C. However, the main disadvantages of CVD are
tion system can provide the choice to grow graphene directly
the high growth temperature, carbon source controlling, and
or transfer it onto the required substrate, and this furnishes
long growth time. On the other hand, graphene synthesis at
the flexibility for potential applications in electrical and opti-
relatively low temperature using instantaneous laser ablation
cal devices.
of graphite source was reported,7,8 thanks to the highly ener-
This study reports, for the first time, on the Cu-based
getic deposited particles. Laser-based approaches for gra-
PLD-derived few-layer graphene synthesis at low tempera-
phene fabrication have been reported.9 PLD provides the
ture under high vacuum. A Q-switched Nd:YAG laser was
requirements to control carbon source and yields energetic
used to ablate the graphite target on bare Cu foil and ther-
particles which assist in reducing the growth temperature of
mally coated Cu foil substrates. Effects of empirical growth
the graphene. Thereupon, laser ablation of carbon target has
conditions; temperature, surface structure, and cooling rate
been used in graphene synthesis preferentially on different
on the capability to fabricate graphene layers were investi-
catalytic metals such as Ni and Co.10 Metal thin films such as
gated by Raman spectroscopy and TEM. The mechanism of
Cu, Fe, and Ag were deposited on Si substrates before abla-
graphene growth by PLD is discussed.
tion of carbon source.10,11 In addition, non-metal substrates
such as sapphire12 and fused silica13 were used. Although Cu
II. EXPERIMENTAL
is a low cost metal and usually used as a catalyzed solid-state
transformation, PLD growth of graphene was unattainable on The target pellet was prepared from the graphite powder
Cu.10 The separation of graphene from the catalyst substrate of 98% purity (Loba Chemical). Commercial Cu foil sub-
normally caused many defects and proved inefficient in pro- strates of thickness 0.3 mm cut into of 2  2 cm2 were used.
duction cost. With the interests in graphene-based applica- Prior to deposition, Cu foil substrates were sonicated in etha-
tions, there are potentials for fabrication of high quality nol and then cleaned with diluted HCl, acetic acid, and
defect free few-layer graphene. PLD using a solid carbon deionized water, successively. Thermal evaporation was per-
source is a practical technique to directly obtain the transfer- formed to deposit 1 lm thick Cu (99.95% purity) on the Cu
foils at a pressure of 6  107 Torr to be used as substrates
a)
Electronic mail: hafezm@niles.edu.eg for the PLD growth. The thin films were prepared in a high

0021-8979/2017/121(2)/025303/7/$30.00 121, 025303-1 Published by AIP Publishing.

025303-2 Abd Elhamid et al.
vacuum PLD chamber. The base pressure during the deposi-
tion was 1  105 Torr. A Q-switched Nd:YAG laser
[pulse width 6 ns at the full width at half maximum
(FWHM)] operating at a wavelength of 1064 nm was used to
ablate the graphite target. PLD of graphite on bare Cu foil
and thermally coated Cu foil substrates were performed
using a laser energy of 50 mJ/pulse at a repetition rate of
5 Hz. The laser was incident at an angle of 45 with the tar-
get’s surface and focused on the target using f ¼ 15 cm lens.
The target-to-substrate distance was fixed at 5 cm. The
target was rotated to furnish a fresh spot area for consecutive
laser ablation shots thus minimizing the particulate forma-
tion. Figure 1 shows a schematic diagram of the PLD system
used in this study.
A homemade resistive heater (20–600  C) in conjunc-
tion with a K-type thermocouple were used to control and
monitor the temperature of the substrate surface in the
vacuum chamber. The in situ heating was performed during
pumping down the vacuum chamber to reach the growth
temperature with a gradual increase rate of 15–20 C/min.
Samples of carbon thin films were prepared with different
laser ablation times.
The as-deposited thin films were characterized by the
XRD (X’Pert Pro) and dispersive Raman microscopy with a
laser source with 532 nm and a power of 10 mW (Bruker
Seterraa). The green laser was focused onto the sample with
an optical microscope at lens of 50 magnifications. The
measurements were carried out at 5 different positions for
each sample. Graphene deposited on Cu foil substrates was
subsequently transferred onto the TEM grid and Si substrate
for selective characterization by TEM and Raman spectros-
copy. Protective layer of polymethyl methacrylate (PMMA)
was therefore spin coated on the top of graphene. The gra-
phene coated with PMMA on Cu foil was cut into two
pieces, one is 2  2 mm. Etching of Cu was performed
by FeCl3 solution over 24 h (20 g of iron þ 100 ml DI
FIG. 1. Schematic diagram of the PLD system.
J. Appl. Phys. 121, 025303 (2017)
water þ 100 ml of 37% HCl). Oxidation step of FeCl2 was
performed by adding 200 ml of 3% H2O2. The graphene
coated with PMMA samples were thereafter transferred onto
the Si substrate, which was cleaned by the standard RCA
method. Fishing technique was used to transfer the 2  2 mm
sample onto the TEM Cu grid. Afterwards, they were baked
at 150  C for 15 min and then at 200  C for 10 min under a
vacuum of 1  105 Torr in case of graphene/TEM grid sam-
ples. Prepared graphene on the Si substrate and TEM grid
samples were exposed to acetone vapor to eventually remove
the PMMA.
III. RESULTS AND DISCUSSION
XRD patterns are shown in Fig. 2(a) for the as-deposited
graphitic thin films with an ablation time of 30 min.
Deposition was carried out at different substrate tempera-
tures of 300, 400, and 500  C. For a substrate temperature of
500  C, laser ablation of graphite was carried out simulta-
neously on both types of substrates (bare Cu foil and coated
Cu foil). XRD patterns show two peaks corresponding to
Cu(111) and Cu(200) facets. Their peak positions are cen-
tered at 2h ¼ 43.3 and 50.4 , respectively, for the deposited
film on bare Cu foil at 500  C. As the substrate temperature
increased, the positions of these two peaks were noticed to
undergo small shifts, which may be due to the surface strain
induced by substrate heating during the PLD growth. It is
obvious that Cu grains were well aligned in the (111) and
(200) orientations. The intensity ratio of Cu(111)/Cu(200)
increases with temperatures. The average grain sizes esti-
mated from Cu(111) and Cu(200) peaks for the coated Cu
foil are 28 and 55 nm, respectively, which are relatively
larger compared to the bare Cu foil (19 and 44 nm).
Coating the substrate surface with the Cu thin film, prior to
graphite deposition by the PLD, alter its structure and conse-
quently can influence the growth mode.
025303-3 Abd Elhamid et al.
FIG. 2. (a) XRD patterns of PLD-grown thin films on Cu foil and coated Cu foil substrates at 300, 400, and 500  C for ablation time of 30 min with a laser
energy of 50 mJ/pulse at a repetition rate of 5 Hz. (b) Raman spectra of carbon thin films on Cu foil substrates at 300, 400, and 500  C. (c) Raman spectra of
as-deposited thin films at 500  C on Cu foil and coated Cu substrates.
Raman spectroscopy is the most reliable, non-destructive,
and quick inspection for graphene. Raman spectra in Fig. 2(b)
exhibit typical features of as-grown graphitic materials
together with a background characteristic for Cu surface plas-
mon photoluminescence.15 The thin films on Cu foil at temper-
atures 300 and 400  C exhibit the G band around 1582 and
1596 cm1, respectively, which is related to the in-plane C-C
stretching mode, and indicating a network of sp2 structures.
The rather shoulder representing the in-plane breathing mode
of the disorder-induced D band around 1403 and 1398 cm1 is
activated by sp3 bonding. The broad bump DþD0 centered at
2940 cm1 is due to a combination of phonons with different
momentum around K and C of the first Brillouin zone.16 The
partial overlapping of the G and D peaks signifies the forma-
tion of nano-graphite. Further increase of the deposition tem-
perature to 500  C, a partial resolving and a clear distinguish
are observed for the G and D bands, as shown in Fig. 2(b). The
graphitic G band became narrow indicating a relatively
improved crystallinity. The G band is shifted towards a higher
wavenumber at 1600 cm1 while the D band is downshifted
J. Appl. Phys. 121, 025303 (2017)
at 1378 cm1. The observed Raman shifts in D and G bands
were attributed to decrease in the disorder.17 In addition, Cu
photoluminescence, due to surface resonance emission,
affected the real peak positions. Moreover, a remarkable broad
bump tends to emerge around 2700 cm1 indicating a distorted
band around the 2D typical location.
Next, PLD of graphite target is performed on the
coated Cu foil substrate. In Fig. 2(c), Raman spectra show
the as-deposited thin film at 500  C. The G and D bands are
centered at 1604 and 1383 cm1, respectively. A rather
well-discerned 2D band at 2685 cm1 identified with the
as-grown ratio of I2D/IG ¼ 0.23 indicate the graphene for-
mation. The relative increase in the crystalline carbon
layers on the coated Cu surface compared to the grown
film on bare Cu foil substrate is shown in Fig. 2(c). These
results indicate that the growth temperature and substrate
surface quality play significant roles in PLD-grown crystal-
line graphene layers.
In an attempt to grow fewer layers of graphene with
fewer defects, thin film has been deposited with ablation
025303-4 Abd Elhamid et al.
time of 2 min, simultaneously on both Cu foil and coated Cu
substrates at 500  C. Raman spectra of these two thin films
are presented in Fig. 3(a). Notwithstanding the high back-
ground of Cu photoluminescence of the thin film deposited
on coated Cu substrate exhibited a well-defined 2D band
around 2690 cm1 with an apparent as-grown ratio of I2D/
IG ¼ 0.473. The inset in Fig. 3(a) shows the XRD pattern cor-
responding to the film grown on the coated Cu surface. From
the two Cu(111) and Cu(200) XRD peaks, the estimated
average grain sizes were 25 and 50 nm, respectively. On
the other hand, the deposited thin film on the bare Cu foil
substrate failed to exhibit evidence of typical features of gra-
phene formation. Moreover, the D and G bands were over-
lapped and barely recognized. Figure 3(b) show the Raman
spectra of films grown with ablation time 2 and 30 min on
coated Cu substrates, indicated as samples 1 and 2, respec-
tively. Due to the presence of Cu photoluminescence, a back-
ground subtraction and normalizations were used for Raman
spectra, as seen in Fig. 3(b). In terms of graphene growth
quality, the correction yields a ratio of ID/IG ¼ 0.7 and 0.9
for samples 1 and 2, respectively, which indicates a
FIG. 3. (a) Raman spectra of as-deposited thin films with an ablation time of
2 min on Cu foil and coated Cu foil substrates at 500  C (Inset is the XRD
pattern of as-deposited film on coated Cu foil substrate). (b) Raman spectra
after normalization and background subtraction of samples 1 and 2 on coated
Cu substrates at 500  C (Inset is a Lorentz fit of the 2D peak). Samples 1 and
2 are denoting for PLD at an ablation time of 2 and 30 min.
J. Appl. Phys. 121, 025303 (2017)
reduction in defects in case of sample 1. In addition, the 2D
band is located at 2671 and 2684 cm1, respectively. These
results are comparable quite well with an empirical rela-
tion,18 which showed the dependence of the Raman 2D band
frequency on the laser excitation energy. Accordingly, the
Raman 2D band for graphene on Cu substrate is expected to
emerge around 2680 cm1 for a laser excitation of 532 nm.18
The Lorentz fitted 2D band for sample 2, shown in the
inset of Fig. 3(b), has a full width at half maximum (FWHM)
of about 112 cm1 indicating the multi-layers graphene forma-
tion. This sample showed a modulated bump that evolved into
two Lorentzian fitted peaks at 2684 and 2858 cm1. In con-
trast, the FWHM of the 2D band for sample 1 is 63 cm1,
which is corresponding to about four layers according to the
statistical data of few-layer graphene as reported by Hao
et al.19 The estimated number of graphene layers is in a good
agreement with the experimental findings by Torres et al.,20
which provided that the substrate Si/SiO2 has a little impact on
the broadening of the 2D band. Raman analyses of samples 1
and 2 are summarized in Table I. On account of the reported
doubling of the ratio of I2D/IG for graphene being transferred
on SiO2/Si substrate21 or as free standing suspended layer,22,23
the PLD growth of graphene with an ablation time of 2 min
indicating I2D/IG 0.24, which is likely to incorporate about
four layers. Thereupon, in our work, the actual ratio of I2D/IG
of the as-deposited graphene thin films with the background of
the Cu fluorescence can be invoked as an indication of the
number of graphene layers as well.
Figure 4(a) shows a photographic image of the graphene
coated with PMMA, floating on DI water surface, detached
from the Cu substrate. The corresponding Raman spectra of
the transferred graphene onto Si substrate is shown in Fig.
4(b), which reveal the D and G bands centered at 1348 and
1581 cm1, respectively. Strong well shaped 2D band cen-
tered at 2685 cm1 appears and the intensity ratio I2D/IG
0.55 indicates the three layer graphene. The relatively high
ID/IG ratio about 0.45 could be attributed to the existence of
unorganized carbon domains and varying graphite crystallite
sizes. Although the Cu foil was coated with Cu thin film, the
actual surface roughness has impacts on the growth of gra-
phene layers. The surface structure of Cu foil has various
degrees of dents, irregular step terraces, and grain boundary
grooves that can significantly affect the graphene nucleation
and growth. These surface features are preferential nucle-
ation sites for the laser-ablated carbon species. Diffusion of
carbon species towards different nucleation sites leading to
the formation of graphene layers of varying thicknesses.
Moreover, short range imperfection of the substrate surface
can lead to lack of long range crystalline carbon. Different
domains can be generated when the graphene growth occurs
TABLE I. Raman spectrum data of thin film samples.
After background 2D band
As-deposited subtraction and FWHM
Samples ID/IG I2D/IG normalizations I2D/IG (cm1)
Sample 1 0.7 0.47 0.24 63
Sample 2 0.9 0.23 0.12 114
025303-5 Abd Elhamid et al.
FIG. 4. (a) Photographic image of the graphene coated with PMMA on the DI water surface after etching of Cu. (b) Corresponding Raman spectra of graphene
transferred onto the Si substrate. (d) and (c) TEM images of isolated graphene thin films taken at different locations.
at different locations on the substrate surface. When coales-
cence took place, grain boundaries were formed that acti-
vated the D peak. Moreover, a previous study24 has shown
that the disorder in graphene, which causes significant
changes in the relative intensities in the resonance Raman
bands, appeared to be strongly dependent on the laser excita-
tion energy. The ID/IG ratio for graphene samples was found
to vary with the average interdefect distance.24 The other
possibility that the mechanical transfer of the graphene onto
the Si surface could be led to the formation of corrugation
and defects across the entire graphene layer. Figures 4(c) and
4(d) show the TEM images which were taken for isolated
graphene that attached to the TEM Cu grid. The black areas
with different shades indicate different multi-layer graphene
islands. PLD of carbon target showed the growth of bi, tri,
and multi-layer graphene on Ni/SiO2/Si heterostructure.8
The effect of the cooling profile on thin films grown on
coated Cu substrate at different substrate temperatures has
been investigated for ablation of graphite target for 2 min.
Substrates were cooled down with 40  C/min to 300  C
J. Appl. Phys. 121, 025303 (2017)
followed by natural cooling to room temperature. Raman
spectra of as-grown thin films at substrate temperatures of
450, 500, and 550  C with a similar cooling rate are shown
in Fig. 5(a). The suppression of the 2D peak for samples
grown at 450 and 550  C is obvious. The effect of different
cooling rates on thin films grown at 500  C was investigated
and presented in Fig. 5(b). After deposition, the samples
were cooled down with different cooling rates of about 40,
20 and 2  C/min to 300  C followed by natural cooling to
room temperature. Absence of the 2D peak along with the
relatively higher ID/IG ratio indicates the presence of high
defects when the substrate cooled down with a slower rate.
In the present work, substrate temperature of 500  C with
optimized cooling profile was critical to facilitate the growth
of few-layer graphene on the Cu surface by PLD.
Low temperature graphene synthesis is an interesting
topic for graphene researches. Using the CVD technique,
graphene films were grown on Cu foil at 1035  C,17 while a
temperature of 1100  C was reported to grow graphene on
Cu-Ni alloys.25 PLD of solid carbon was performed to grow
025303-6 Abd Elhamid et al.
FIG. 5. (a) Normalized Raman spectra of as-deposited samples with an abla-
tion time of 2 min on coated Cu foil substrates at 450, 500, and 550  C with
a similar cooling rate. (b) Normalized Raman spectra of as-deposited thin
films on coated Cu foil substrates at 500  C with different cooling rates of
40, 20 and 2  C/min.
graphene on Ni as a catalytic transition metal at 650 and
1010  C.8,14 Although the graphene growth on Cu has been
realized with the CVD process involving a high processing
temperature and chemical reactions with precursors, few tri-
als were attempted to produce graphene using a solid carbon
source with Cu. The low temperature synthesizing method is
excellent for graphene based nanotechnology research and
device fabrication. However, defects is a well-known prob-
lem in low temperature growth. PLD produces highly ener-
getic species with high instantaneous deposition rates.26 Koh
et al. have used the property of the energetic carbon source
from the PLD to influence the segregation process in Ni.10 In
our case, the high kinetic energy of the laser-plume species
assisted the graphene growth as a source of activation energy
for carbon deposits that diffuse on the Cu surface to enhance
crystallinity. The results have shown that graphene can be
synthesized using PLD at relatively a low temperature of
500  C. The growth kinetics can be explained by the ener-
getic and pulsed nature of PLD. Further studies are needed
to achieve controllable synthesis to fabricate high quality
graphene layers. The number of graphene layers can be con-
trolled through the ablation time of the solid target with the
J. Appl. Phys. 121, 025303 (2017)
laser pulse energy. Understanding the kinetics and mecha-
nisms of graphene layer formation by PLD growth still needs
further studies.
In a previous work,10 the growth of graphene on Cu by
PLD was not attained which was attributed to the low solubil-
ity of carbon in Cu (0.05% at 600  C),27 and the surface cata-
lytic behavior as a metal was not considered. Failure to realize
the graphene growth on Cu substrate at 750  C using PLD is
likely correlated with a cessation of sufficient graphene nucle-
ation due to inefficient cooling profile. Presumably, the proper
cooling profile following the deposition cannot decouple from
the graphene growth temperature. On the other hand, the diffu-
sion barrier of carbon on Cu surface is low,28 and negligible on
Cu(111),29 which makes Cu to have a catalytic role different
from other transition metals.30 Therefore, to grow graphene on
Cu substrate, surface mediated growth process should be con-
sidered. Density functional theory calculations show that car-
bon is facet insensitive to Cu facets such as Cu(001), Cu(110),
and Cu(111) because carbon clusters and Cu surfaces interact
more weakly as the carbon cluster grows.31 This is consistent
with our XRD results which showed that few-layers graphene
were grown on the Cu surface despite of the presence of
Cu(200) and Cu(111) facets. In our work, surface mediated
growth mode of graphene on Cu substrate revealed to have a
favorable catalytic effect.
It is essential to mention that the surface quality of the
substrate play a significant role in the nucleation and growth
of graphene. Polycrystalline Cu foil substrate exhibits differ-
ent surface morphologies that determine the density and
shape of the final grain boundaries of the grown graphene. In
our work, low cost commercial Cu foil surface was thermally
coated with the Cu thin film to avoid surface strain/stress in
consequence of lattice mismatch and difference in thermal
expansion coefficient. Moreover, the Cu coating was
expected to minimize the microscopic surface roughness and
enhance purity which induced surface transformation that
enhances few-layer graphene nucleation. Prolonged high
temperature of 1000  C as in CVD complicates the fabrica-
tion process and escalates costs. Therefore, further research
work is needed to advance quality of the graphene growth.
PLD is a challenge thin film deposition technique toward
obtaining high-quality crystalline graphene layers. Our scope
in this work was to investigate the ability to fabricate gra-
phene on Cu surface by the PLD method.
Based on Raman spectroscopy and TEM analysis, few-
layer graphene on Cu foil can be fabricated by PLD method
at low growth temperature. Furthermore, it was observed
that different cooling rates yielded different results for PLD-
grown carbon thin films. Although, PLD and CVD have
different growth approaches, the significance of the cooling
profile on graphene growth has been reported.10,32 In the
case of PLD of carbon on Ni, graphene growth was occurred
by segregation dissolved carbon in metal onto the surface.10
In CVD of graphene on Cu foil, growth was occurred by
decomposing a precursor gas, hydrogen and methane, on the
metal surface, which was used to break down the gaseous
carbon source.32 Therefore, the cooling profiles have differ-
ent rates in the production of graphene. At a moderate cool-
ing rate, few-layer graphene by PLD was observed to form
025303-7 Abd Elhamid et al.
on Ni.10 However, no graphene was formed at a fast cooling
rate, due to lack of mobility to form crystalline carbon.10
While, the fast cooling rate showed the highest quality of
graphene among samples grown by CVD.32 It was found that
different cooling rates induce change in the density of gra-
phene nuclei and growth rate. In this work, the nucleation
and growth of graphene took place through physical surface
processes. The high instantaneous deposition rate of PLD
results in a high nucleation density on the surface which
improves the two-dimensional growth mode. Initially the
laser-ablated carbon species adsorbed on the Cu surface,
which, led to graphene nucleation. The growth rate of the
graphene layer depends on the surface diffusion of carbon
species. In the meanwhile, preferential nucleation probably
occurred at the grain boundary grooves and irregular step ter-
races of the Cu surface, which act as energetically favorable
sites, induced disorders. No 2D peak was detected for sam-
ples cooled at 20 and 2  C/min because of defects formation.
In contrast, as the sample cooled faster, carbon adatoms do
not have a sufficient time to migrate to the surface defect
centers. Instead, carbon adatoms diffused on the surface to
nucleate graphene islands. As deposition was continued,
enlargement of the graphene islands occurred through attach-
ment of carbon species or an additional island could be
nucleated on top of another island forming multi-layer gra-
phene. Therefore, during the cooling process, there is a com-
petition between the growth rate of graphene islands and
capturing of carbon adatoms by different surface nucleation
sites. Careful control of the cooling rate can lead to maintain
the growth pattern on the surface that forms the high quality
of the graphene. The results indicate that the graphene nucle-
ation and growth rate are correlated to the PLD and cooling
conditions.
IV. CONCLUSIONS
In this work, the PLD method was capable of gra-
phene synthesis on Cu foil substrate at a relatively low
temperature of 500  C with a proper cooling rate. The
effects of temperature, surface structure, and cooling rate
of the graphene growth were studied with Raman spec-
troscopy. On the Cu-based PLD derived graphene synthe-
sis, different multi-layers, as indicated by the TEM, is
related to the substrate surface structure. The successful
graphene formation occurred by surface mediated growth
and relies on the optimization between the substrate tem-
perature and cooling rate. Formation of high quality gra-
phene on low cost Cu surface is possible using the PLD
technique with a precise control of temperature, deposi-
tion rate, and cooling rate.
J. Appl. Phys. 121, 025303 (2017)
1
K. S. Novoselov, V. I. Fal‘ko, L. Colombo, P. R. Gellert, M. G. Schwab,
and K. A. Kim, Nature 490, 192 (2012).
2
F. Bonaccorso, A. Lombardo, T. Hasan, Z. Sun, L. Colombo, and A. C.
Ferrari, Mater. Today 15(12), 564 (2012).
3
X. Li, W. Cai, I. Jung, J. An, A. Velamakanni, P. Richard, L. Colombo,
and R. S. Ruoff, ECS Trans. 19(5), 41 (2009).
4
K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, and S.
V. Dubonos, Science 306, 666 (2004).
5
W. Liu, B. L. Jackson, J. Zhu, C.-Q. Miao, C.-H. Chung, Y.-J. Park, K.
6
Sun, J. Woo, and Y.-H. Xie, ACS Nano 4(7), 3927 (2010).
A. Reina, X. Jia, J. Ho, D. Nezich, H. Son, V. Bulovic, M. S. Dresselhaus,
and J. Kong, Nano Lett. 9, 30 (2009).
7
A. T. T. Koh, Y. M. Foong, and H. C. Daniel, Appl. Phys. Lett. 97,
114102 (2010).
8
K. Wang, G. Tai, K. H. Wong, S. P. Lau, and W. Guo, AIP Adv. 1,
022141 (2011).
9
P. Kumar, RSC Adv. 3, 11987 (2013).
10
A. T. T. Koh, Y. M. Foong, and D. H. Chua, Diamond Relat. Mater. 25, 98
(2012).
11
U. Kalsoom, M. S. Rafique, R. Shaheen, and K. Fatima, Int. J. Sci. Eng.
Res. (IJSER) 5(3), 1200 (2014).
12
B. J. Na, T. H. Kim, C. Lee, and S.-H. Lee, Trans. Electr. Electron. Mater.
16(2), 70 (2015).
13
I. Kumar and A. Khare, Appl. Surf. Sci. 317, 1004 (2014).
14
G. K. Hemani, W. G. Vandenberghe, B. Brennan, Y. J. Chabal, A. V.
Walker, R. M. Wallace, M. Quevedo-Lopez, and M. V. Fischetti, Appl.
Phys. Lett. 103, 134102 (2013).
15
L. Tao, J. Lee, H. Chou, M. Holt, R. S. Ruoff, and D. Akinwande, ACS
Nano 6(3), 2319 (2012).
16
A. C. Ferrari and D. M. Basko, Nat. Nanotechnol. 8, 235 (2013).
17
A. Jorio, E. Ferreira, G. Luiz Cançado, C. Achete, and R. Capaz,
“Measuring disorder in graphene with Raman spectroscopy,” in Physics
18
and Applications of Graphene – Experiments (InTech, 2011).
S. D. Costa, A. Righi, C. Fantini, Y. Hao, C. Magnuson, L. Colombo, R.
S. Ruoff, and M. A. Pimenta, Solid State Commun. 152, 1317 (2012).
19
Y. Hao, Y. Wang, L. Wang, Z. Ni, Z. Wang, R. Wang, C. K. Koo, Z.
Shen, and J. T. L. Thong, Small 6(2), 195 (2010).
20
L. Torres, L. G. Armas, and A. C. Seabra, Graphene 3, 1 (2014).
21
Z. H. Ni, T. Yu, Z. Q. Luo, Y. Y. Wang, L. Liu, C. P. Wong, J. Miao, W.
Huang, and Z. X. Shen, ACS Nano 3, 569–574 (2009).
22
Z. Ni, Y. Wang, T. Yu, and Z. Shen, Nano Res. 1, 273–291 (2008).
23
A. C. Ferrari, J. C. Meyer, V. Scardaci, C. Casiraghi, M. Lazzeri, F.
Mauri, S. Piscanec, D. Jiang, K. S. Novoselov, S. Roth, and A. K. Geim,
Phys. Rev. Lett. 97, 187401 (2006).
24
A. Jorio, E. H. M. Ferreira, L. G. Cancado, C. A. Achete, and R. B. Capaz,
in Physics and Applications of Graphene-Experiments, edited by S.
Mikhailov (Intech, 2011), Chap. 18.
25
T. Wu, X. Zhang, Q. Yuan, J. Xue, G. Lu, Z. Liu, H. Wang, H. Wang, F.
Ding, Q. Yu, X. Xie, and M. Jiang, Nat. Mater. 15, 43 (2016).
26
J. C. Miller and R. F. Haglund, Laser Ablation and Desorption,
Experimental Methods in the Physical Sciences (Academic, Boston, 1998),
Vol. 30.
27
P. R. Subramanian and D. F. Laughlin, ASM Handbook, edited by H.
Baker (ASM International, USA, 1992), Vol. 3.
28
A. Reina, S. Thiele, X. Jia, S. Bhaviripudi, M. S. Dresselhaus, and J. A.
Schaeferand Kong, Nano Res. 2, 509 (2009).
29
P. Wu, W. Zhang, Z. Li, J. Yang, and J. G. Hou, J. Chem. Phys. 133,
071101 (2010).
30
C. Seah, S. Chai, and A. Mohamed, Carbon 70, 1 (2014).
31
X. Mi, V. Meunier, N. Koratkar, and Y. Shi, Phys. Rev. B 85, 155436 (2012).
32
D. S. Choi, K. S. Kim, H. Kim, Y. Kim, T. Y. Kim, S.-h. Rhy, C.-M.
Yang, D. H. Yoon, and W. S. Yang, ACS Appl. Mater. Interfaces 6(22),
19574–19578 (2014).