2017 3rd International Conference on Electrical Information and Communication Technology (EICT), 7-9 December 2017, Khulna, Bangladesh

Numerical Simulation of Vibrational Properties of

AGNR with Vacancy and Stone Wales Defects
A. S. M. Jannatul Islam, Md. Rasidul Islam, Md. Sherajul Islam, A. G. Bhuiyan
Department of Electrical and Electronic Engineering, Khulna University of Engineering & Technology, Khulna, Bangladesh
syed.113.kuet@gmail.com, sheraj_ruet@yahoo.com

Abstract— This paper reports the effects of vacancy and stone
wales defects on the vibrational properties of armchair graphene
nanoribbon (AGNR) using molecular dynamic simulation. The
optimized Tersoff and Brenner empirical potential has been used
to calculate the phonon density of states (PDOS) using atomistic
toolkit (ATK) force-field method, which provides a very good
agreement with the Raman spectra of graphene related systems.
The calculated results show a downshift of the PDOS peaks with
the decrease of AGNR width. The vacancy and stone wales
defects strongly affect the PDOS peaks of AGNR. Due to vacancy
defects some new peaks are appeared in the low frequency region
while stone wales defects produce some new peaks in the high
frequency region. However, due to both vacancy and stone wales
defects, a localized in-plane optical mode phonon is appeared
near the edge and defect sites. This paper also discusses the
effects of defects on the phonon transmission spectrum which is
responsible for thermal conductivity and electron transport
properties of AGNRs.
Keywords— Armchair, Zigzag, GNR, Phonon mode, PDOS,
Localized mode, Phonon transmission spectrum.
I. INTRODUCTION
Graphene, a carbon based nanomaterials has been
considered as the promising candidate for next generation
nanoelectronics [1] because of its outstanding electronic,
thermal and mechanical properties. The ultra-high electron
mobility (200,000 cm2/V.s), unbelievable current density (108
A/cm2), strongest structural quality (200 times of steel) and
tunable electron/hole transport properties make it promising
for future nanoelectronic applications [2]. Although graphene
shows outstanding properties, it cannot be used in
semiconductor IC fabrication technology, due to its zero
bandgap [3]. Various approaches have been used to tune a
finite bandgap in graphene structure. It is well known that,
confinement of the electronic wave function in a quasi 1D
system can open the bandgap in graphene [4]. When graphene
is patterned into a finite width, a bandgap is opened due to the
quantum confinement effect. Therefore, graphene nanoribbon
(GNR) can be the candidate for the fabrication of
nanoelectronic devices.
Depending on the edge structure, graphene nanoribbons
may be armchair or zigzag types [5]. The electronic properties
of nanoribbon depend on the types of edge structure and the
width of the ribbon. For example, localized edge states and
intervalley backscattering are found in zigzag and armchair
edges, respectively that affect the electronic as well as
vibrational properties of the nano devices [6]. Therefore, edge
related phenomena are of great interest for future
nanolectronics. GNR structure with armchair shaped edge are
known as the promising candidate for IC fabrication
technology rather zigzag types because it introduces relevant
band gaps for nanelectronic devices [7].
From a practical viewpoint, when armchair graphene
nanoribbon (AGNR) are experimentally fabricated, various
structural defects such as atomic vacancies, stone wales defect
and ad-atom vacancy defect [8] are formed that may alter the
vibrational as well as electronic properties of GNRs. Due to
the strong electron-phonon interaction in the graphene related
allotropes, the electron transportation of AGNRs strongly
depend on the behavior of the edge dependent phonon modes
in addition to the orientation of the atoms of nanoribbon with
different defects [9]. Therefore, we require a clear conception
of the effects of vacancy and stone wales defects on the
phonon modes which noticeably change the electron transport
properties of GNR based nanodevices.
Although several investigations have been performed on
the phonon properties of AGNRs using different theoretical
approaches such as force constant ¿ttings [1], DFT theory
[10], first-principles calculations [11] and force vibrational
method [12,13], most of these are worked mainly on the pure
GNR. However, when defects present in a system, the
symmetry of elemental topological arrangements has been
brokendown, which create very complex lattice structures. As
a result, the dynamical matrix technique needs huge
computational resources.
a b c
Fig. 1. Structure of a) pure AGNR, b) AGNR with vacancy
defect, c) AGNR with stone wales defect

978-1-5386-2307-7/17/$31.00 ©2017 IEEE


These long computational times and convergence problems in
the dynamical matrix techniques limit the systems of interest
to benchmark molecules. Therefore, a signi¿cantly reliable
model is essential for in depth understanding of the vibrational
properties of defective atomic structures.
In this work, molecular dynamic simulation has been used
with optimized Tersoff and Brenner empirical potential [14] to
find out the vibrational properties of vacancy and stone wales
defected AGNR. The molecular dynamic simulation is
implemented on the virtual nanolab using atomistic toolkit
(ATK) force–field calculator. The benefits of ATK force–field
method is that there is no computational and convergence
problem and it shows the result, which are very much
comparable to first principle calculations using DFT theory
and the peaks of Raman spectra. For disordered AGNR with
defects, there may observe phonon modes lying outside of the
permissible frequency range of the pristine crystal. These
modes are known as localized phonon modes. To observe the
localized phonon modes, we have calculated the typical
vibrational pattern of AGNRs considering the effects of stone
wales and vacancy type defects. We mainly analyze the K
point in-plane transverse optical mode phonon due to its
importance in the D band of Raman spectra that suggest that
the armchair edge behaves as a defect.
II. COMPUTATIONAL DETAILS
The analysis of the present work is performed on the
AGNR with vacancy and stone wales defect as shown in
Fig.1. using molecular dynamic simulation with optimized
Tersoff and Brenner empirical potential. According to the
molecular dynamic simulation the local vibrational density of
state (LVDOS) on an atomic site i for a frequency Ȧ is given
by,
ρ i (ω ) = 2ω ¦ ¦ ui ,ν (α ) δ (ω 2 − ων2 )
2
(1)
ν α
where, the summation is performed over all the modes Ȟ and
the space directions Į, ȦȞ and ui,Ȟ(Į) are the frequency and the
(i,Į) component of the Ȟth phonon eigenvector, respectively.
These parameters are calculated by using the lattice-dynamics
equations as,
¦β D (α , β )u ν (β ) = ων u ν (α )
ij j,
2
i, (2)
j,
where, ȕ means the direction along the Cartesian coordinate
and D represent the dynamical matrix expressed by [10],
Φ ij (α , β )
Dij (α , β ) = (3)
MiM j
where, M denotes the masses of ith and jth atoms and Φ ij is
the force constant tensor representing the full information of
the interactions between these atoms of the structure. The
phonon density of states is thus calculated by the summation
of LVDOS as defined by ȡi (Ȧ) in Eq. (1). From Eq. (3), it is
known that Φ ij are the dominant quantities to be obtained in
order to calculate the LVDOS [10]. These force constant
tensors have been calculated with the help of optimized
Tersoff and Brenner empirical potential. The total energy for
AGNR can be expressed as [10],
E = ¦¦ f c ( rij )[VR ( rij ) − bijVA ( rij )]
(4)
i j >i
where, fc(rij) is called the cut-off-distance function between the
atoms and VR(r) is repulsive and VA(r) is attractive parts of the
potential. The bij is a coefficient determined by the angles
between the bond i and j and all other bonds made from the i
and j sites. The parameters of the empirical potential depend
on the local coordination number. A lot of calculations
represent the validity of this potential when addressing
structural properties of carbon based systems, such as
fullerenes, nanotubes and graphene [10]. The optimized
Tersoff and Brenner empirical potential is used to optimize the
force constant tensor. In optimizing geometry the Limited
memory Broyden Fletcher Goldfarb Shanno (LBFGS)
optimizer method is used, where the force tolerance is 0.01
eV/Ang. and stress tolerance is 0.0001 eV/Ang.3 and
maximum number of steps is 200. In the dynamical matrix we
have used central finite difference method with an atomic
displacement of 0.01 Ang. In the PDOS calculation, the C-C
bond length is 1.42086 Ang. and the Brillouin zone is sampled
by Monkhorst pack-grid with 51×1×1 k-point grid whereas for
transmission spectrum it is 60×1×1 k-point grid. The phonon
transmission spectrum has been calculated by a recursive
technique where the average Fermi level is 1×10-6 eV.
III. RESULTS AND DISCUSSION
Fig. 2 represents the calculated phonon density of states
of 32, 24, 18 and 13 atoms wide pure AGNR as a function of
frequency. From PDOS peaks, it is seen that three
characteristic peaks are appeared around 370 cm-1, 830 cm-1
and 1580 cm-1 frequency. The PDOS peaks of wider AGNR
approaches to that of infinite graphene sheet and the peaks are
softened and broadened with the decrease of ribbon width.
Generally, a group of six phonon modes are observed at the Γ
point of GNRs. The physical origin of G peaks around 1580
cm-1 of Raman spectra comes from the longitudinal optical
(LO) and transverse optical (TO) phonon modes at the
Brillouin zone center. Here, our results provide sharp peak
around 1580 cm-1 (LO mode for AGNR) which is very good
outcomes of the used method in comparing with Raman
spectra results [12, 13]. From PDOS curves, it is found that Γ
point LO and TO mode is non-degenerate and shifted down
with the decrease of GNR width. In AGNRs, only the
longitudinal optical (LO) modes are Raman active and the
graphene (G) peak of Raman spectra near the edge side shows
a down shift of the longitudinal optical (LO) mode phonon.
Nevertheless, the transverse optic (TO) phonon modes is
decoupled from electron/hole pairs.
 devices. For example, due to the localized phonon mode, the
thermal conductivity of GNR will be reduced significantly.
Fig.6 shows the phonon transmission spectrum for pure
and defective AGNRs. The results demonstrate that, stone
wales defect is more sensitive than vacancy type defect. We
obtain a very high value (30) of phonon transmission
coefficient for pure AGNR. However, this value is reduced to
15 and 8.5 for vacancy and stone wales defects, respectively.

Fig. 2. Width dependent PDOS of pure armchair graphene

nanoribbon as a function of frequency.

As a result, the TO mode phonon remain same as the original

Γ point frequencies of infinite graphene sheet. Hence, it is
predicted that LO mode phonon has the significant
contribution to the transport of electron in comparing with TO
mode phonon for GNR based nanodevices.
Fig. 3 shows the effect of vacancy defect on the PDOS
peaks of different atoms wide AGNR. Here, it is found that
some edge localized phonon modes are located around 410
cm-1, which denotes the characteristic of AGNRs. It is
observed that some new peaks are appeared in the low
frequency region due to vacancy types defect with respect to
pure AGNR. It is also found that the PDOS peaks are softened
with the decrease of ribbon width. A localized phonon mode
Fig. 3. PDOS of armchair graphene nanoribbon with vacancy
(Fig. 3.) is observed in the defect sites around 1355 cm-1
defect.
which is very good agreement with the D peaks comes from
Raman spectra of disordered GNR. For stone wales defect, we
also calculate the PDOS of 32, 18, 15 and 14 atoms wide
AGNRs. When there is a rotation of 900 of the two atoms,
there occurs stone wales defect. From Fig. 4. it is found that
the stone wales defects dominate the AGNR with small width.
Here we observe that the PDOS peaks are shifted down with
the decrease of ribbon width in the stone wales defected
AGNR. We observe a new peak near 450 cm-1, which may
also due to the stone wales defects. Armchair edge phonon
mode (peaks) are also observed at 1580 cm-1 which are well
agreed with the Raman G peaks come from the LO mode
phonon for AGNRs. From Fig. 4. it is also observed that for
stone wales defect, some new peaks are appeared in the high
frequency region.
The vibrational patterns for pure and disordered AGNRs
have also been calculated as depicted in Fig. 5. The results
show that the K-point TO mode phonon is distributed through
the whole system in the pure AGNR as shown in Fig. 5(a).
However, due to the vacancy or stone wales for both types of Fig. 4. PDOS of armchair graphene nanoribbon with stone
defects phonon propagations is constrained into a particular wales defect.
region which are clearly observed in Fig 5(b) and 5(c). It is
expected that this localization of phonon strongly affects the
electronic as well as vibrational properties of GNR based

a) b) c)
Fig. 5. K point i-TO mode phonon for a) pure AGNR, b)
AGNR with vacancy defect, c) AGNR with stone wales
defect.
Fig. 6. Phonon transmission spectrum for 32-atoms wide
AGNR a) pure AGNR, b) AGNR with vacancy defect c)
AGNR with stone wales defect.
Thermal properties of AGNR change when the structure is
changed due to impurities or defects. The three phonon
transmission spectra in the above Fig. 6 (purple: pure AGNR,
red: AGNR with vacancy defect, dark blue: AGNR with stone
wales defect) are significantly different. The difference is
caused by phonon scattering by the defects. At low energy
(long wavelength) the spectrum is unchanged, while the main
difference is at higher energies (shorter wavelength).
Comparing the results we found that, the transmission spectra
for the distorted GNR are strongly suppressed due to
scattering by the defects.
IV. CONCLUSIONS
In this work, vibrational properties of armchair graphene
nanoribbon with vacancy and stone wales defects are studied.
Molecular dynamic simulation has been used for investigating
the phonon properties of defective AGNR using optimized
Tersoff and Brenner empirical potential in the virtual nanolab.
We observe a softening and broadening of the LO mode
phonon due to the defects and the reduction of the ribbon
width of AGNR. Localized K-point TO mode phonon is
perceived for both vacancy and stone wales defected AGNR.
The K-point TO mode phonon is distributed through the whole
system in the pure AGNR. However, due to the vacancy or
stone wales for both types of defects phonon propagations is
constrained into a particular region. It is expected that this
localization of phonon strongly affects the electronic as well
as vibrational properties of GNR based devices. The phonon
transmission spectrum for 32 atoms wide pure AGNR and
defective AGNR are also analyzed. Our results show the
disordered AGNRs have the small value of phonon
transmission coefficients. These findings are very much
important to understand the heat transport phenomena in GNR
based nanoelectronic devices as well as to apply phononic
engineering by defect to manipulate thermal and electronic
properties in AGNR.
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