Molecular dynamics simulation of graphene growth on Ni(100) facet by chemical vapor

deposition
R. Rasuli, Kh. Mostafavi, and J. Davoodi

Citation: Journal of Applied Physics 115, 024311 (2014); doi: 10.1063/1.4862164

View online: http://dx.doi.org/10.1063/1.4862164
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 JOURNAL OF APPLIED PHYSICS 115, 024311 (2014)

Molecular dynamics simulation of graphene growth on Ni(100) facet

by chemical vapor deposition
R. Rasuli,a) Kh. Mostafavi, and J. Davoodi
Department of Physics, Faculty of Science, University of Zanjan, Zanjan, Iran

(Received 4 October 2013; accepted 31 December 2013; published online 14 January 2014)
We present a molecular dynamics simulation of chemical vapor deposition of graphene. Single
layer graphene growth on a Ni (100) facet was studied at different substrate temperatures, C flow
rates, and C flow energies. Results show that a single layer graphene film grows through a
combined deposition mechanism on a Ni substrate, rather than by surface segregation. These
simulations suggest that high quality graphene deposition is theoretically possible on Ni (100) facet
C 2014 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4862164]
under high flux energy. V

I. INTRODUCTION directions, is transformed into (100) direction.9 However,

Unique properties of graphene introduce it as a most
promising candidate for applications in nanotechnology.1,2 It
has potential application in nano-electronics and nano-
devices.3–5 To realize these potential applications, one needs
to produce high-quality graphene in large quantity.
So far, several methods have been reported to synthe-
size graphene. Mechanical exfoliation,6 chemical methods,7
and transition metal-catalyzed chemical vapor deposition
(CVD)8,9 are commonly use in graphene production.
Presently, CVD is the most promising and low-cost
approach to synthesize graphene in large-area as well as
high-quality.5 Understanding of CVD growth mechanism at
the atomic level is useful for controlling and improving
quality of produced graphene. However, experimental tech-
niques are presently unable to give details of graphene
growth at the atomic scale.
Graphene growth in the large-scale has been subject of
theoretical researches to understand the details of nucleation
and growth of graphene. Loginova et al. have reported that
adhesion of C clusters to the graphene edge is main process in
CVD growth of graphene.10 Chen et al. have predicted that
nucleation of graphene is dependent on the type of transition
metal substrate.11 Gao et al. have studied graphene nucleation
on terrace of metal substrate and near the step edge.8 Cheng
et al. have reported a homogeneous nucleation process for
graphene growth.12 Amara et al.13 revealed that defect healing
occurs when metal substrate is applied for graphene growth.14
Theses studies have explored graphene growth in the static
condition. According to the fact that graphene growth is a ki-
netic and nonequilibrium process, it is instructive to study the
process dynamically on the Ni (100) facet.
Molecular dynamics (MD) is a powerful method to
study dynamic process at the atomic scale. So far, there is
some theoretical work focused on the dynamics of graphene
growth on the Ni (111) facet.15 Chae et al. reported that after
graphene synthesis on poly-crystalline Ni substrates, the
most abundant (110) direction, as well as (100) and (111)
a)
Author to whom correspondence should be addressed. Electronic mail:
r_rasuli@znu.ac.ir. Tel.: 98-241-515-2522. Fax: 98-241-2283203.
these studies focus on the thermodynamic stability of struc-
tures on the (111) facet and have not presented dynamics of
the growth process on Ni (100) facet.
In this study, we investigate the effect of C flow energy,
substrate temperature, and C flow rate as three important pa-
rameters in CVD graphene growth. According to the trans-
formation of (110) and (111) directions to (100) direction
[9], we have selected Ni (100) facet to study the graphene
growth instead of the more stable Ni (111) facet. Results
show that high C mobility significantly improves graphene
quality. In addition, formation of a single layer graphene
film occurs through a combined deposition mechanism on a
Ni substrate, rather than by surface segregation.
II. METHODS
MD simulations were performed using LAMMPS code
by the Verlet algorithm16 with a time step of 0.20 fs.
Temperature of system was controlled by a Berendsen ther-
mostat with a damping constant of 100 fs.17 A four-layer slab
model of Ni (100) surface including 256 Ni atoms was
applied to represent the catalyst surface. We take on a 20 Å
thick vacuum along the z-axis and periodic boundary condi-
tions along the other directions. To mimic the semi-infinite
surface, we fix atoms in the bottom layer of the slab. C atoms
were randomly deposited on the Ni (100) surface at different
substrate temperatures, C flow rates, and C flow energies. We
have applied Airbao, Embedded atom model, and Lenard-
Jones potentials between C-C, Ni-Ni, and Ni-C atoms, respec-
tively. Parameter values of Lenard-Jones potential were set to
0.0486 eV and 3.0665 Å for epsilon and sigma, respectively.18
III. RESULTS AND DISCUSSION
In CVD method, metal catalyst is placed in a mixed
flow of hydrocarbons usually methane and other gases, e.g.,
hydrogen. In this method, graphene growth occurs by C
atom addition on the previous structure. During graphene
growth, C precursor on the catalyst surface dissociates to C
atom and its concentration is raised gradually. To explore
the effect of substrate temperature on the nucleation of gra-
phene, we considered the concentrations with 72 and 144 C

0021-8979/2014/115(2)/024311/4/$30.00 115, 024311-1 C 2014 AIP Publishing LLC

V

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 024311-2 Rasuli, Mostafavi, and Davoodi J. Appl. Phys. 115, 024311 (2014)

FIG. 1. Final configurations of the graphene layers grown on a Ni (100) surface for the various substrate temperatures with concentrations of 72 (a) and 144 C
atoms (b).

FIG. 2. (a) Dissolved C atoms (red

sphere) into Ni substrate, (b) equilib-
rium configuration at 250 K from both
top and side view, (c) surface segrega-
tion of dissolved C in the Ni (100) sur-
face at 1600 K from both top and side
view.

atoms. To maintain the crystalline state of substrate during

the graphene growth sufficiently, low temperatures are
essential. The initial and final structures simulated in 100 ps
at 400–1400 K are presented in Figure 1. Results show that
increase in substrate temperature cause to formation of some
C rings on the substrate due to increase in C atoms diffusion
on the catalyst surface. At the temperature of 1200 K, for
both concentration 72 and 144 C atoms, some hexagonal is
formed. In the case of 144 C atoms, graphene nucleation is
improved while the obtained graphene has defect and dislo-
cation. This is in agreement with the previous reports.19
In a typical CVD graphene growth on Ni substrate, C
monomers readily dissolve into the subsurface. In this part,
we present simulation results of C surface segregation as a
final step in CVD growth of graphene. The barrier for an
adatom to diffuse from the surface to the subsurface is
0.6 eV,12 which is small enough to be overcome easily at
1000 K. C dimmers and trimmers are more stable on the sur- FIG. 3. Flow rate (R) effect versus various temperatures on the number of
face at 1000 K than subsurface. According to snapshots in hexagons at temperature ranged 500–6500 K.

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 024311-3 Rasuli, Mostafavi, and Davoodi
Figure 2, the surface Ni atoms between two C dimers or
trimers lift out of the substrate due to strong C Ni interac-
tion. This was observed in previous ab initio calculation that
justifies validity of the employed potential in this work.20
In CVD growth, flow rate of precursor also affect the
obtained graphene quality. The first step in the CVD growth
of graphene is the decomposition of gas-phase C precursors
on the catalyst surface, which can be controlled by the ther-
mochemistry. Here, we name the rate of C production as C
flow rate. The C ions diffuse on the catalyst surface or
across its interior. Afterward, nucleation of graphene is fol-
lowed by the incorporation of C into the growing process.
At the initial stage of graphene growth, a dimmer acts as a
nucleation center and grows large by adding C atoms. C
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J. Appl. Phys. 115, 024311 (2014)
flow rate is corresponded to the required time for diffusion
and incorporation in graphene growth process. Figure 3
shows the number of 6-membered rings at various flow rate
and temperatures. The process have been simulated in the
flow rate range 0.05–0.5 ps 1 and temperature range
1000–6500 K. Results show that at the flow rate of 0.1 ps 1
and at the flow temperature range 4000–5000 K, the number
of 6-membered rings is maximized. This means that under
such condition, C adatom have enough energy and time to
diffuse on the surface and find a stable location, which
leads to formation of 6-membered C rings. Figure 4 shows
a snapshot of final structure of obtained graphene under dif-
ferent C flux energy. It is apparent that the energy of C flux
has a main role in high quality graphene production.
FIG. 4. Snapshot of final structure of
obtained graphene under different C
flux energy. Substrate temperature and
flow rate are 1200 K and 0.06 ps 1,
respectively.
 024311-4 Rasuli, Mostafavi, and Davoodi
3
Surface diffusion on the substrate is dependent on the C ion
energy. The C ion energy in CVD experiment is corre-
4
sponded to the C flux energy in MD simulation. A C atom
deposited on the catalyst surface with specific energy. After 5
collision to the substrate surface, it diffuses on the substrate
6
until a stable location is found.
To study of graphene growth in detail, we take typical
7
snapshots of formed hexagons after 25, 50, 75, 100, 125,
150 C atom impact on the surface (Figure 5). As shown in
8
Figure 5, graphene grows with the appearance of C chain
and then convert to hexagons by addition of more C atoms. 9
A deposited C atom on the C chain form two bonds with two
other atoms; simultaneously, the bond between these atoms
10
is broken, which finally forms a 6-membered ring.
11
12
IV. CONCLUSIONS
13
Single layer graphene growth on a Ni (100) surface was
studied at different substrate temperatures, C flow rate, and
14
C flow temperature. Results show the formation of a single
layer graphene film occurs through a combined deposition 15
mechanism on a Ni substrate, rather than by surface segrega-
16
tion. These simulations suggest that high quality single layer
graphene deposition is theoretically possible on Ni (100) 17
under high flux energy.
18
1 19
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J. Appl. Phys. 115, 024311 (2014)
FIG. 5. Snapshots of graphene growth
on the Ni (100) surface after 25, 50,
75, 100, 125, 150 C atom impacts on
the surface.
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