CARBON 8 0 ( 2 0 1 4 ) 5 0 4 –5 1 2

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Transformation of chemical vapor deposited

individual graphene crystal with oxidation
of copper substrate

Golap Kalita a,b,*, Remi Papon a, Subash Sharma a, Sachin M. Shinde a,

Riteshkumar Vishwakarma a, Masaki Tanemura a
a
Center for Fostering Young and Innovative Researchers, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
b
Department of Frontier Materials, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan

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

Article history: Here, we reveal the structural transformation process of as-synthesized individual graph-
Received 24 April 2014 ene crystals with oxidation of a copper (Cu) foil. We found that the transformation of a
Accepted 20 August 2014 graphene crystal with Cu oxidation is significantly different for the thermal annealing
Available online 3 September 2014 and room temperature long-term atmospheric oxidation. Annealing creates large cracks
in an individual graphene crystal due to the thermal stress and strain created by rapid oxi-
dation of Cu surface. The cracks are further enhanced with longer annealing duration
enabling oxygen diffusion through cracks, thereby accelerating oxidization of Cu. Eventu-
ally, the graphene crystals are completely damaged, leaving behind the highly oxidized Cu
surface. On the other hand, in case of room temperature long-term atmospheric oxidation,
oxygen diffusion occurs underneath of a graphene crystal through the reactive edge with-
out any large cracks formation. The graphene crystals decouple from Cu surface during the
oxygen diffusion and oxidation process, however no structural deformation is observed.
This finding shows the significant contrast of structural change of graphene crystal and
oxidation behaviors of Cu surface with thermal annealing and room temperature atmo-
spheric oxidation.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction [8–12]. Again, graphene shows exceptional thermal stability

Recently graphene based materials has been significantly
investigated as a thermal, wet, and electrochemical corrosion
resistance barrier for various metals [1–5]. Graphene has been
considered as a potential candidate for anticorrosion coating
owing to its exciting physical and chemical properties [6–9].
Graphene with sp2 hybridized honeycomb structure is an
impermeable membrane due to the presence of delocalized
electron cloud that can even block smallest molecules
and chemical inertness [1,2,12,13]. Considering these proper-
ties, several groups have demonstrated short-term oxidation
and corrosion resistance performance of graphene synthe-
sized by chemical vapor deposition (CVD) [1,14–16]. However,
graphene does not act as a long-term metal oxidation barrier,
rather can stimulate oxidation of the underlying metal sub-
strate [17,18]. It has been explained that electrochemical oxi-
dation of Cu surface occurs in presence of highly conducting
graphene film [18,19]. A continuous CVD synthesized

* Corresponding author at: Center for Fostering Young and Innovative Researchers, Nagoya Institute of Technology, Gokiso-cho, Showa-ku,
Nagoya 466-8555, Japan.
E-mail address: kalita.golap@nitech.ac.jp (G. Kalita).
http://dx.doi.org/10.1016/j.carbon.2014.08.090
0008-6223/Ó 2014 Elsevier Ltd. All rights reserved.
 CARBON 8 0 (2 0 1 4) 5 0 4–51 2
graphene film on polycrystalline metal consists of several
grain boundaries and oxygen diffusion through the grain
boundaries has a significant role in oxidation [20–22]. In this
regard, understanding oxygen diffusion process and struc-
tural deformation of graphene crystal on metal surface can
be a key aspect to overcome the limitations.
Hexagonal single crystals are the ideal building block for
formation of a continuous graphene film on metal catalyst
surface, which allow investigation on their edge dependent
physical and chemical properties [23–27]. Hence, exploring
the chemical properties of CVD synthesized individual
graphene crystals can bring to light the interesting facts of
oxidation process. Recent studies show possibility of synthe-
sizing single crystal graphene in the order of sub-millimeter
scale by a CVD technique [28–34]. The graphene crystals can
grow across the grain and twin boundaries of a polycrystal-
line Cu substrate and then merging together to from a con-
tinuous film [35]. In this study, we reveal the oxygen
diffusion and structural transformation process of as-syn-
thesized individual graphene crystals on Cu foil with ther-
mal annealing and long-term atmospheric oxidation
process. We found that transformation of individual graph-
ene crystal with oxidation of a Cu foil is distinctively differ-
ent for a thermal annealing and long-term atmospheric
oxidation process. In context to previous reports, in what
follows, we discuss our experimental evidences of Cu foil
oxidation process with structural change in individual
graphene crystals.
2. Experimental details
Cu foil (Nilaco Corp.) of thickness 20 lm with a purity of
99.99% was used as substrate for graphene growth. As-
synthesized graphene crystals on Cu foil were annealed at
(150–250 °C) in atmospheric conditions for different dura-
tions. The structural change of crystal with oxidation of
Cu foil was investigated by varying the annealing duration
from 30 min to 3 h. On the other hand, room temperature
long-term oxidation of graphene crystals on Cu foil was car-
ried out by keeping the sample in atmospheric conditions.
The structural change of graphene crystal on Cu foil at room
temperature was investigated by storing the sample for
7 months under atmospheric air. Optical microscopy studies
of synthesized graphene crystals on Cu foils and oxidation
behaviors were analyzed with the digital optical microscope
VHX-Z500. Raman spectra were obtained using NRS 3300
laser Raman spectrometer with a laser excitation energy of
532.08 nm. The incident laser power was fixed at around
0.7 mW, so that there are no laser-induced thermal damage.
Field emission scanning electron microscope studies were
performed with the JEOL JSM-7001FF equipped with an
energy dispersive X-ray (EDX) analyzer. Elemental analysis
of as-synthesized and atmospheric oxidized individual
graphene crystals were also carried out with Auger electron
spectroscopy (AES) in JAMP-7800 Auger microscope. X-ray
photoelectron spectroscopy (XPS) analysis was performed
by VersaProbe using monochromated Al Ka excitation source
(1486.6 eV).
505
3. Results and discussion
We synthesized hexagonal graphene crystals on Cu foil by a
solid precursor based atmospheric pressure CVD method.
Details of the system and graphene growth technique can
be found elsewhere, as reported previously [36,37]. Structure
of the as-synthesized graphene crystals are confirmed by
optical microscope and Raman studies. Fig. 1a and b shows
as-synthesized hexagonal graphene crystals randomly dis-
tributed on the polycrystalline Cu foil with lateral size more
than 20 lm. It has been well established that such graphene
crystals in a CVD process can grow across two different Cu
grain or twin boundaries as observed by optical microscope.
Fig. 1c shows Raman spectra of a graphene crystal taken ran-
domly at various points, presenting highly uniform crystal-
line nature. Graphitic G and second order 2D Raman peaks
are observed at 1590 and 2700 cm 1, respectively. The higher
intensity of 2D peak than that of G peak, indicates the pres-
ence of a single layer graphene. Again, full width at half max-
imum (FWHM) of G and 2D peaks are found to be 20 and
43.5 cm 1, respectively, consistent with reported values for
monolayer graphene [37]. The obtained hexagonal single crys-
tals can merge together to form a continuous graphene film
by increasing the growth duration. Oxidation behavior of Cu
foil in presence of a CVD graphene film has been explored
with thermal annealing and long-term atmospheric oxidation
[17,18]. The oxidation of Cu foil and damaging of graphene
film can be clearly visualized by analyzing a single graphene
crystal degradation process. In this regard, we carried out
thermal annealing experiments of synthesized graphene
crystals in atmospheric conditions.
Fig. 2a and b shows optical image of hexagonal graphene
crystals on Cu foil after annealing at around 200 °C for
30 min. Previously, selective oxidation of Cu surface has been
performed in atmospheric conditions to make graphene crys-
tals clearly visible by optical microscope [37] However,
increasing the annealing duration micrometer long cracks
appears within a graphene crystal (Fig. 2b). Whereas, in a mild
annealing process such type of micro-cracks are not visible
(Supporting Information, Fig. S1a). The result clearly shows
that cracks in a graphene not only appears in the grain
boundaries but also within a crystal itself with rapid atmo-
spheric annealing. Usually, as-synthesized graphene crystals
by a CVD process are coupled with the base Cu surface.
Hence, structural change in the Cu surface with oxidation
can significantly influence the graphene crystals. The appear-
ance of such type of crack can be explained with thermal
stress produced by basal polycrystalline Cu substrate on
graphene crystal. As well as, lattice structure and volume will
change significantly with formation of an oxide surface than
that of unoxidized Cu, which can create a tensile strain on as-
synthesized graphene crystals [38]. XPS analysis of Cu after
the thermal annealing process shows significant structural
change and formation of oxide surface (Supporting Informa-
tion, Fig. S2). Crystalline metallic Cu contains 85 atoms/nm3,
whereas only 52 atoms/nm3 for Cu2O, corresponding to a vol-
ume expansion of more than 60% with oxide formation [39].
Rapid change in volume with oxide formation by thermal
506 CARBON 8 0 ( 2 0 1 4 ) 5 0 4 –5 1 2

Fig. 1 – (a) Optical microscopic image of as-synthesized individual graphene crystals on polycrystalline Cu foil. (b) An
individual hexagonal graphene. (c) Raman spectra of the graphene crystal to study the crystalline nature, layer and defects.
Raman spectra at randomly selected four different points of the crystal show high crystalline structure. (A colour version of
this figure can be viewed online.)

(a) (b)

Crack in crystal

Fig. 2 – Optical microscopic images of (a) individual graphene crystals on Cu foil after atmospheric oxidation at around 200 °C
for 15 min. (b) A graphene crystal presenting micron length cracks across the crystal structure. (A colour version of this figure
can be viewed online.)

annealing process creates substantial stress on the coupled
graphene crystals. The stress created in graphene by volume
expansion of base Cu surface is released by forming the large
cracks.
We performed the annealing experiment for a prolonged
duration (1–3 h) to obtain more information about the cracks
in the graphene. Fig. 3a and b shows graphene crystals with
more enhanced cracks for 1 h annealing at 250 °C. The dark
edges and cracks of hexagonal crystal are now most vulnera-
ble to oxygen diffusion (Fig. 3b). Subsequently, increasing the
annealing duration to 3 h, we observe rapid oxidation of basal
Cu substrate with oxygen diffusion through the edge and
cracks. Fig. 3c shows an optical microscope image of highly
oxidized Cu foil and damaged graphene crystals after 3 h of
 CARBON 8 0 (2 0 1 4) 5 0 4–51 2 507

(a) (b) Crack

(c) (d)
2
1

(e) (f)

Position 2
Position 1

Fig. 3 – Optical microscopic images of (a) individual graphene crystals on Cu foil after atmospheric oxidation at 250 °C for 1 h.
(b) A graphene crystal presenting enhanced micron length cracks in crystal. (c) Rapid oxidation from the cracks and edges
destroy the graphene and (d) complete destruction of the graphene crystal on Cu foil after annealing for 3 h. Raman spectra
taken at position (e) 1 and (f) 2 of a graphene. (A colour version of this figure can be viewed online.)

annealing. The cracks are much widen and graphene crystals
are almost damaged with reactive electrochemical oxidation
process of Cu foil. Fig. 3d shows that some of the graphene
crystals are completely destroyed leaving behind oxidized
Cu surface with 3 h of annealing. Similarly, we can observe
structural damage of interconnected continuous graphene
crystals (Supporting Information, Fig. S1b). Oxygen diffusion
and oxidation through the cracks were also confirmed by
AES analysis (Supporting Information, Fig. S3). These results
clearly show that the thermal annealing create large cracks
within the crystal and stimulate oxygen diffusion; thereby
oxidizing Cu surface and destroying the graphene crystals.
Raman studies were also performed to observe the crystal
degradation and oxidation process. Fig. 3e shows Raman
spectra at the remaining graphene structure of a crystal with
3 h of annealing.
Graphitic G and second order 2D peak can be observed in
this location (position 1), suggesting intact graphene struc-
ture. While, in the position 2 all the graphene structure is
damaged and Cu foil is highly oxidized as shown in Fig. 3f.
In the meantime, we studied the oxidation behavior of
graphene crystals on Cu foil at room temperature keeping
for a long duration (7 months) in atmospheric conditions.
We observe significant difference in oxidation mechanism
of Cu foil than that of thermal annealing process. Fig. 4a–d
shows optical microscope images of graphene crystals kept
at room temperature in atmospheric conditions. It is observed
that the oxidation of Cu foil occurs with diffusion of oxygen
through the reactive crystal edges (Fig. 4b). Graphene crystal
decoupled from Cu surface as the oxidation occurs from edge
toward the center. Only the middle part of graphene remain
coupled with Cu surface, showing a surface topology of as-
synthesized crystals (Fig. 4c). Some of the crystals are totally
decoupled with oxidation of the Cu foil (Fig. 4d). The oxidation
process of an individual crystal can be explain with diffusion
of oxygen to underneath of a crystal through the crystal edge.
We did not observe any kind of large crack formation in the
graphene crystals. This is a sharp contrast between the two
different oxidation process. Hexagonal graphene crystals are
predominantly oriented along the zigzag direction, which
508 CARBON 8 0 ( 2 0 1 4 ) 5 0 4 –5 1 2

(a) (b) Oxygen diffusion

from edge

(c) (d)
Decoupled graphene

1 2

(f)
(e)

Position 1 Position 2

Fig. 4 – Optical microscopic images of (a) graphene crystals on Cu foil after atmospheric oxidation at room temperature by
preserving for 7 months. (b) Oxygen diffusion and Cu oxidation from graphene edge. (c) Enhanced oxidation from crystal
edge, decoupling the graphene from Cu without appearance of any large cracks. (d) Totally decoupled graphene from Cu
surface with atmospheric oxidation. (e) and (f) Raman spectra at two different places of a graphene crystal, where Cu foil is
oxidizing from the edge (position 1 and 2). (A colour version of this figure can be viewed online.)

can be significant for adsorption and desorption of oxygen
molecules in the oxidation processes. Fig. 4e and f shows
Raman spectra at two different places of a crystal, where Cu
foil is oxidizing from the edge. At both the positions, we can
observe graphene structure, however in position 2 much more
intense 2D peak is observed. This can be explained by Cu sub-
strate and graphene interaction at position 1, whereas graph-
ene is decoupled from Cu surface at position 2, reducing the
substrate interaction.
Fig. 5a shows FE-SEM image of a graphene crystal on Cu
foil after long-term room temperature atmospheric oxidation
for 7 months. As explained in the optical microscope studies,
FE-SEM studies also confirm oxidation process of Cu foil from
crystal edge to the center without any large cracks in the crys-
tal. Fig. 5b shows a SEM image at the edge of graphene cou-
pled Cu and oxidized portion. The graphene topology on
unoxidized Cu surface remain intact. In the oxidized surface
of the Cu foil with or without graphene crystals, nanoparti-
cles like morphology can be observed. Fig. 5c shows a SEM
image of graphene crystal with unoxidized (position 1) and
oxidized (position 2) basal Cu surface, where elementary
analysis were performed. Fig. 5d shows EDX analysis at the
position 2, confirming presence of carbon and oxygen atoms.
As shown in the atomic concentration table no oxygen was
detected at position 1. The SEM and EDX analysis confirmed
the oxidation of the Cu foil with individual graphene crystals.
Cu oxidation and graphene structure are further investi-
gated by AES analysis. Fig. 6a shows SEM image of as-synthe-
sized graphene crystal, where selective elementary analysis is
performed. Fig. 6b shows C KLL, and Cu LMM AES spectra
measured on an as-synthesized graphene crystal. The pri-
mary AES spectra shows only carbon of graphene and Cu
 CARBON 8 0 (2 0 1 4) 5 0 4–51 2 509

Fig. 5 – (a) and (b) FE-SEM image of an individual graphene crystal on oxidized Cu surface at room temperature; the center part
of graphene is coupled with Cu. A higher resolution image at the edge of oxidized and unoxidized part presents intact
graphene topology on unoxidized Cu surface. (c) Graphene crystal with unoxidized (position 1) and oxidized (position 2) basal
Cu surface, where elementary analysis were performed. (d) EDX analysis at the position 2, confirming presence of carbon and
oxygen atoms. (A colour version of this figure can be viewed online.)

Fig. 6 – (a) As-synthesized graphene crystal, where selective elementary analysis is performed. (b) C KLL, and Cu LMM AES
spectra measured on the as-synthesized graphene crystal. (c) Graphene crystal after oxidizing the Cu foil at room
temperature. Selective elementary analysis are performed at position 1 and 2. (d) C KLL and Cu LMM AES spectra at position 1,
additional O KLL peak is observed at position 2. (A colour version of this figure can be viewed online.)
510 CARBON 8 0 ( 2 0 1 4 ) 5 0 4 –5 1 2

(a) Oxidation by thermal annealing

(b) Atmospheric oxidation for long duration

Fig. 7 – (a) Oxygen diffusion and oxidation process of Cu surface in presence of graphene crystals with thermal annealing.
Large crystal crack occurs with thermal stress enabling oxygen diffusion and oxidation of Cu surface. In the process the
graphene crystals also damaged only remaining the oxidized Cu surface. (b) Atmospheric oxidation process at room
temperature (25 °C) for 7 months. Oxygen diffuses from the edge and oxidizing the Cu surface toward the center part. In this
process, the graphene crystal decoupled from Cu surface without physical destruction. (A colour version of this figure can be
viewed online.)

from the substrate without any oxygen contamination. Simi-
larly, Fig. 6c show SEM image of graphene crystal after
oxidizing the Cu foil at room temperature for 7 months,
where selective elementary analysis are performed in posi-
tion 1 and 2. Fig. 6d shows C KLL and Cu LMM AES spectra
at position 1, whereas the additional O KLL peak is observed
at position 2. As we observed that the oxygen diffused from
the crystal edge and toward the center position decoupling
the graphene. The center part (position 1) remain unoxidized,
while outer side of the graphene crystal on Cu get oxidized.
This finding evidently shows oxygen diffusion process
through the graphene crystal and the oxidation behavior of
Cu surface. Again, the oxygen diffusion and Cu foil oxidation
process significantly differ for room temperature long-term
and thermal annealing oxidation process.
The oxygen diffusion and oxidation process of Cu surface
in presence of individual graphene crystals can be explained
as shown in Fig. 7a and b. It is observed that large cracks in
individual graphene crystal occurs with thermal annealing
process owing to induced strain created by basal substrate.
The oxygen diffusion through the cracks in graphene crystal
accelerate the oxidation of Cu surface by electrochemical
reaction. Again, crystal cracks were enhanced and
subsequently significant structural damage occurred in the
graphene with increase in annealing duration. After anneal-
ing for 3 h at 250 °C, the graphene crystals are completely
damaged as confirmed by the Raman and AES studies (Sup-
porting Information, Fig. S4). The destruction can be
explained with oxygen adsorption and distortion by the
graphene edges in oxidation process of Cu surface leading
to oxidation of graphene. On the other hand, we do not
observe large distortion of the graphene crystal in the atmo-
spheric oxidation at room temperature for 7 months. As
observed from the optical microscope, Raman, SEM and
AES studies, oxygen diffused from the edge of a crystal
without any large crack formation within the crystal. The
oxidation of Cu surface occurs from the edge toward center
with decoupling the graphene. We can observe increase in
I2D/IG ratio of the Raman spectra at the same graphene crys-
tal with base Cu surface is oxidized or not, without any
apparent increase in D peak. This is due to the fact that
compressive strain from Cu surface will release with oxida-
tion and thereby decoupling the graphene. These observa-
tions further indicate that the oxidation of Cu weaken the
graphene-Cu interaction and enabling oxygen diffusion
toward center of the crystals.
 CARBON 8 0 (2 0 1 4) 5 0 4–51 2
4. Conclusions
We have revealed the structural transformation process of as-
synthesized individual graphene crystals with oxidation of a
Cu foil. The oxidation and degradation process considerably
differed for the rapid thermal annealing and room tempera-
ture long-term atmospheric oxidation. Annealing at tempera-
ture around 200–250 °C created large cracks in the individual
graphene crystal with thermal stress and increase in volume
of oxidized Cu surface. The cracks further enhanced with
longer annealing duration, which enabled oxygen diffusion
through crystal cracks as a result accelerating the oxidization
of Cu. While, in case of room temperature long-term atmo-
spheric oxidation, diffusion of oxygen occurred underneath
the crystal through the reactive crystal edge. The graphene
crystal decoupled from Cu surface with oxygen diffusion
and oxidation without any crack formation. Subsequently,
the graphene crystal without much structural distortion
totally decoupled from Cu surface with oxidation. This find-
ing shows the significant contrast of oxidation behaviors of
Cu surface with annealing and room temperature long-term
atmospheric oxidation.
Acknowledgement
The work is supported by the funds for the development of
human resources in science and technology, Japan.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.car-
bon.2014.0 8.090.
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