Materials Letters 153 (2015) 132–135

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Effects of H2 annealing on polycrystalline copper substrates

for graphene growth during low pressure chemical vapor deposition
Jian Liu a, Siva P. Adusumilli b, John J. Condoluci a, Alok C. Rastogi b, William E. Bernier a,
Wayne E. Jones Jr.a,n
a
Department of Chemistry, Binghamton University—State University of New York, Binghamton, NY 13902, United States
b
Department of Electrical and Computer Engineering, Binghamton University—State University of New York, Binghamton, NY 13902, United States

art ic l e i nf o a b s t r a c t

Article history: It has been shown that the hydrogen annealing process plays an important role on the crystallographic
Received 4 February 2015 orientation changes of polycrystalline copper substrates during low pressure chemical vapor deposition
Accepted 31 March 2015 (LPCVD) of graphene, which subsequently influence the generation of graphene films. X-ray diffraction
Available online 9 April 2015
(XRD) and scanning electron microscopy (SEM) were used to study the copper foil crystallographic
Keywords: orientation and morphology changes with and without hydrogen annealing. Graphene films were
Chemical vapor deposition successfully synthesized on copper foils by LPCVD at 1000 1C with hydrogen annealing process. Raman
Graphene spectroscopy was also performed to determine the formation of graphene films as well as their quality.
Hydrogen annealing Without hydrogen annealing no significant graphene Raman signal are detected and it is hypothesized
Raman spectroscopy
that this is related to the different crystallographic orientations of copper substrates.
& 2015 Elsevier B.V. All rights reserved.

1. Introduction
Graphene, a single atomic layer of sp2 bonded carbon arranged
in a hexagonal crystal lattice, has received great attention due to
its unique physical properties, such as large specific surface area
(2630 m2 g
1) [1], fast electron mobility [2] and high thermal
conductivity [3]. These extraordinary properties make graphene
potentially useful in many smart energy technologies including
solar cells [4], high frequency transistors [5] and ultracapacitors
[6]. Recently, several synthetic methods to prepare graphene have
been introduced, such as mechanical exfoliation of graphite [7],
reduction of graphene oxide [8], and epitaxial growth on SiC
substrate [9]. Chemical vapor deposition (CVD) on transition
metals would be an ideal alternative as it is relatively simple to
achieve, low-cost and can be easily applied to multiple substrates.
CVD preparation of graphene can be achieved with the assis-
tance of different types of transition metal catalysts such as nickel
[10] and copper [11]. The growth mechanism is greatly influenced
by substrates surface structures, lattice parameters and thermo-
dynamic factors. Joshua et al. [12] reported that Cu substrate
crystallographic orientations affected graphene growth and mor-
phology greatly. Li et al. [13] determined that high-quality mono-
layer graphene could be obtained using hydrogen-rich (1 1 1)
copper films. It is clear from these studies that the surface
crystallographic orientation of the substrate is crucial for CVD
processes.
Hydrogen can potentially affect the surface crystallographic
orientations during CVD processing including the annealing pro-
cess before deposition and gaseous flow process during the
deposition process. Ivan et al. [14] studied the role of hydrogen
during the deposition period, which served a double role as an
activator of surface-bound carbon and as an etching reagent.
Independently, Xiuyun et al. [15] observed that hydrogen played
a role in terminating the graphene edges, which favored the
growth of bilayer graphene. In order to apply these results to
large area devices it is critical to understand the influence of the
hydrogen annealing process on the copper substrate before the
deposition period, which consequently affects the graphene
growth during the CVD deposition process. Here we report for
the first time the role of hydrogen annealing before deposition on
copper foil surface and its subsequent influence on graphene
LPCVD process.
2. Experimental

LPCVD Graphene Synthesis: All materials were used as received

n
Corresponding author. Tel.: þ 1 607 777 2421. unless otherwise noted. The LPCVD process was adapted from a
E-mail address: wjones@binghamton.edu (W.E. Jones Jr.). report by Li et al. [11], which included heating, annealing,

http://dx.doi.org/10.1016/j.matlet.2015.03.150
0167-577X/& 2015 Elsevier B.V. All rights reserved.
 J. Liu et al. / Materials Letters 153 (2015) 132–135 133

deposition and cooling periods. The specific conditions for the
sample preparations are shown in Table 1.
Characterization: The morphological and structural character-
istics of the copper foils were measured by field emission scanning
electron microscopy (FESEM, Supra 55 VP from Zeiss), and X-ray
diffraction (XRD, PANalytical’s X’Pert PRO Materials Research)
respectively. Raman analyses were performed using Thermo
Scientific DXR Raman microscope with the laser wavelength of
532 nm. The intensity of Raman peaks was reported after baseline
correction over the range from 1000 to 3000 cm
1, which
encompassed all the possible peak positions for the graphene
being studied (1300–1400 cm
1 for ‘D’ band, 1560–1600 cm
1 for
‘G’ band and 2620–2760 cm
1 for ‘2D’ band).
3. Results and discussion
To study the influence of hydrogen annealing on the underlying
copper foil and to determine any changes on the surface crystal
structure with and without hydrogen annealing, SEM and XRD
were performed on the as-received copper foil, copper foil without
hydrogen annealing (LPCVD 8) and copper foil after hydrogen
annealing (LPCVD 7). In Fig. 1, the copper foil surface morphologies
varied substantially between LPCVD 8 and LPCVD 7. The copper
surface became much rougher than others with domains of 10–20
square micrometers after hydrogen annealing in LPCVD 7.
XRD patterns for the as-received copper foil had multiple
crystallographic orientations as shown in Fig. 2. After hydrogen
annealing, Cu(2 0 0) (3 1 1) (2 2 2) facets disappeared as shown by
the decrease in the XRD peak intensity of Cu(1 1 1) and Cu(2 2 0)
facets. Without hydrogen annealing the Cu(2 0 0) peaks domi-
nated the XRD of the copper foil. This suggests the hydrogen
annealing process rearranged the surface structure of the copper
foil, which is one of the key factors in the graphene LPCVD process.
To analyze the effects of these different copper crystallographic
orientation changes on LPCVD graphene growth, six different LPCVD
experiments with and without hydrogen annealing (LPCVD 1–6) were
performed. The surface morphologies after graphene deposition did
not change greatly compared with their separate copper substrates
before the deposition process. There were some narrow black lines in
Fig. 3a, which may indicate graphene growth lines. Compared with
Fig. 3a (LPCVD 1), in Fig. 3d (LPCVD 4) it had smaller irregular Cu grain
islands and there was no indication of the graphene deposition.
Raman spectroscopy of LPCVD1-6 were performed to determine
the extent of formation of graphene films and their quality. Four points
were randomly chosen from each sample in Fig. 3. Raman peaks in the
G band (1580 cm
1) and 2D band (2700 cm
1) confirmed the
presence of graphene layers existing in LPCVD 1–3 as shown in
Fig. 4. Those correspond to samples which included the hydrogen
annealing process. No significant graphene Raman signals were
detected in LPCVD 4 & 5 which were prepared without hydrogen
annealing. It can be hypothesized that different adsorption and
diffusion capacities of carbon species on different cooper facets would
lead to this difference [12]. The observation that Cu(1 1 1) favored
more carbon nucleation and preferential growth of continuous gra-
phene films is consistent with it having a lower surface energy
compared to Cu(2 0 0). As the hydrogen/methane ratio increased from
Fig. 4d–f, Raman signals associated with graphene films were obs-
erved. This suggests that higher hydrogen flow favored the for-
mation of graphene layers. By comparison decreased hydrogen flow
prevented any graphene layer formation. This further highlights the
important role that hydrogen plays in the LPCVD deposition process.
During the graphene growth process, hydrogen serves as a co-catalyst
for carbon activation by decomposition of methane [13,14]. Since
graphene growth on Cu is regarded as a consequence of a surface-
adsorption mechanism [16], more hydrogen would activate more

Table 1
LPCVD sample preparation conditions under different gas flow using Cu foil as
substrate.

Samples Heating (H2: Annealing (H2: Growth (H2: Cooling (H2:

CH4) (sccm) CH4) (sccm) CH4) (sccm) CH4) (sccm)

LPCVD 1 2:0 2:0 2:35 2:35

LPCVD 2 2:0 2:0 2:7 2:7
LPCVD 3 2:0 2:0 2:1 2:1
LPCVD 4 0:0 N/A 2:35 2:35
LPCVD 5 0:0 N/A 2:7 2:7
LPCVD 6 0:0 N/A 2:1 2:1
LPCVD 7 2:0 2:0 N/A 2:0 Fig. 2. XRD patterns of as-received copper foil, copper foil after heating without
LPCVD 8 0:0 N/A N/A 0:0 hydrogen annealing (LPCVD 8) and copper foil after heating with hydrogen
annealing (LPCVD 7).

Fig. 1. SEM images of (a) as-received copper foil; (b) copper foil after heating without hydrogen annealing (LPCVD 8); (c) copper foil after heating with hydrogen annealing
(LPCVD 7).
134 J. Liu et al. / Materials Letters 153 (2015) 132–135

Fig. 3. SEM images of CVD graphene on Cu foil after growth under different conditions (a) LPCVD 1 (b) LPCVD 2 (c) LPCVD 3 (d) LPCVD 4 (e) LPCVD 5 (f) LPCVD 6.

Fig. 4. Raman spectra from four random locations on each sample of (a) LPCVD 1, (b) LPCVD 2, (c) LPCVD 3, (d) LPCVD 4, (e) LPCVD 5, (f) LPCVD 6. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)

methane decomposition and increase carbon adsorption on the Cu
surface resulting in continuous graphene film formation.
4. Conclusions
The effects of hydrogen annealing processes on copper foil and the
subsequent growth of graphene by LPCVD were studied. Compared
with as-received copper foil, both copper surface morphology and
crystallographic orientations changed as a result of hydrogen anneal-
ing. XRD showed that Cu foils had a pronounced {1 1 1}, {110} and
{100} texture with and without hydrogen annealing. Raman spectro-
scopy showed that graphene films were likely to grow on the copper
foils preferentially under hydrogen annealing. This was attributed to
different adsorption and diffusion capacities of carbon species on the
different copper facets. Moreover, graphene films were only formed
under high hydrogen/methane flow ratios without hydrogen anneal-
ing providing new insights for bulk processing of graphene by LPCVD.
 J. Liu et al. / Materials Letters 153 (2015) 132–135
Acknowledgements
We acknowledge funding from National Science Foundation
IIP-1318202. This work was carried out with support from the
Center of Autonomous Solar Power (CASP) and the Department of
Chemistry at Binghamton University. This work was supported in
part by a grant from the NY State Strategic Partnerships for
Industrial Resurgence (SPIR) program in collaboration with Cus-
tom Electronics, Inc.
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