APPLIED PHYSICS LETTERS 99, 041901 (2011)

Mechanical and thermal transport properties of graphene with defects

Feng Hao,1 Daining Fang,1,2 and Zhiping Xu1,3,a)
1
Department of Engineering Mechanics, Tsinghua University, Beijing 100084, China
2
College of Engineering, Peking University, Beijing 100871, China
3
Center for Nano and Micro Mechanics, Tsinghua University, Beijing 100084, China
(Received 18 May 2011; accepted 1 July 2011; published online 25 July 2011)
The roles of defects including monatomic vacancies and Stone-Wales dislocations in the
mechanical and thermal properties of graphene are investigated here through molecular dynamics
(MD) simulations. The results show that Young’s modulus of a defected graphene sheet has a
gentle dependence with the concentration of defects, while the thermal conductivity is much more
sensitive. Analysis based on the effective medium theory (EMT) indicates that this sensitivity
originates from the scattering of phonons by defects and delocalized interaction between
them, which leads to a transition from propagating to diffusive mode as the concentration
C 2011 American Institute of Physics. [doi:10.1063/1.3615290]
increases. V

Graphene, the extremely monolayer material, attracts in-
tensive research interests recently owing to its outstanding
mechanical, thermal, and electronic properties, which are,
more interestingly, very sensitive to its microstructures.1 For
example, the tensile stiffness and strength of graphene sheet
are on the order of 1 TPa and 100 GPa, respectively2 and the
thermal conductivity of monolayer graphene sheet is
observed to be 5500 W/mK,3–5 that is one order higher than
common engineering materials with high thermal conductiv-
ities, such as copper that has a thermal conductivity of 400
W/mK. In contrast to metals where electrons carry most of
the heat and define the heat transport processes, the high
thermal conductivity of graphene is attributed to phonons.
Apparently, the key of these features relies on the structural
perfection of the hexagonal graphene lattice and strong in-
plane sp2 bond between carbon atoms. However, defects
unavoidably present in the graphene materials from various
synthesis methods and their effects on the mechanical and
thermal properties need to be clarified.6–8
The experimental techniques to produce graphene sheets
can be classified into two categories. In physical methods
including both mechanical peeling and chemical vapor depo-
sition, defects such as vacancies and dislocations are widely
observed,6–8 for example, dislocation concentration as high as
3.6% is observed by atomic resolution transmission electron
microscopy image.8 In chemical methods such as reduced gra-
phene oxide approach, epoxy groups reside on the graphene
basal-plane.9–11 Furthermore, under electron irradiation or
severe Joule-heating condition, sublimation, evaporation, and
doping can lead to considerable defects concentration.12–14
Open edges and edge roughness also scatter the heat flux but
are only critical for narrow graphene nanoribbons.15 In order
to evaluate their effects, here we pursue both equilibrium and
nonequilibrium molecular dynamics (MD) simulations for
some insights of the underlying mechanisms, which will
advise fabrications of graphene materials towards specified
mechanical and thermal applications.
a)
Author to whom correspondence should be addressed. Electronic mail:
xuzp@tsinghua.edu.cn.
In our MD simulations, we use the LAMMPS package.16
Periodic boundary condition is applied to a square graphene
sheet with length L ¼ 6 nm. The adaptive intermolecular reac-
tive empirical bond-order potential functions and correspond-
ing parameters are used for the interatomic interactions
between carbon atoms.17 This method is widely used to pre-
dict the mechanical and thermal transport properties of gra-
phene materials and their derivatives. In this work, only
monatomic vacancies and Stone-Wales (SW) dislocations
with varying concentration are considered. The mechanical
properties under tensile loads and in-plane thermal conductiv-
ities are calculated at a concentration up to the critical value
(4%) that leads to structural failure at 300 K, for monatomic
vacancies or saturation of Stone-Wales dislocations.
The structure with a certain defect concentration is
firstly equilibrated at ambient condition (temperature
T ¼ 300 K where the quantum correction is negligible, and
pressure P ¼ 1 atm) under a Nosé-Hoover thermostat for 500
ps. In the tensile simulation, a uniaxial load is applied in ei-
ther the armchair and zigzag direction and the other direction
is relaxed to obtain its Young’s modulus. In the equilibrium
Green-Kubo simulation, the system is subsequently switched
to a microcanonical ensemble. The atomic positions and
velocities are collected to calculate the thermal flux and its
correlation functions. The thermal conductivity is thus
obtained by following the Green-Kubo formula and averag-
ing on three samples and two runs for each. In the nonequili-
brium Müller-Plathe simulations, the graphene sheet with
certain defects concentrations are sandwiched between two
pristine graphene sheets of the same sizes. Elastic collisions
between the hottest atom in the left and the right “contacts”
are forced every 50 fs to produce a thermal flux. To utilize
the periodic boundary condition, the sandwich structure is
mirrored.18,19 This simulation lasts for 5 ns to obtain the spa-
tial pattern of directed thermal flux.
We define the concentration f of monatomic vacancies
as the number density of atoms removed from the pristine
graphene sheet. For a Stone-Wales dislocation, f is defined
by considering two defected atoms. Young’s modulus and
thermal conductivity of the monolayer graphene sheets are

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V

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041901-2 Hao, Fang, and Xu
plotted in Figs. 1(a) and 1(b), where the results at various
concentrations are summarized.
For the mechanical properties, it can be seen that Young’s
moduli Y of defected graphene sheets feature a linear depend-
ence on the defect concentration. Young’s modulus Y0 of a
defect-free graphene sheet is 1.1 TPa when a thickness of 3.2
nm is used. We plot the relative Young’s modulus of defect
graphene sheets Ymv/Y0 and YSW/Y0 in Fig. 1(a). The curve
can be fitted into a linear function for monatomic vacancies as
Ymv/Y0 ¼ 0.996  0.028 f and a much more smoothly decreas-
ing for Stone-Wales dislocations, which can be explained as
that it contains two heptagons and two pentagons, which pre-
serve interatomic sp2 bonding, while monatomic vacancy
breaks the integrity of pristine sheet that results in a higher
formation energy about Emv ¼ 14 eV in comparison with the
nucleation energy ESW ¼ 6 eV for the Stone-Wales disloca-
tion. A linear fitting for the Stone-Wales dislocations fails
here as is hard to define the concentration.
In contrast to the gentle dependence of Young’s modu-
lus, the thermal conductivity j, however, is much more sen-
sitive to the presence of these two defects. We can consider
the defected graphene sheet as a composite with the pristine
graphene lattice as the matrix and defects as inclusions. The
overall conductivity of a composite can be estimated by the
thermal conductivities of the inclusion and matrix as
jcomp1 ¼ jinc1 þ jmat1. Fitting the simulation results in
Fig. 1(b) gives jmv/j0 ¼ (1.008 þ 5.718 f)1 for monatomic
vacancies and jSW/j0 ¼ (1.001 þ 3.330 f)1, where j0 is the
thermal conductivity of pristine graphene at 300 K. As a
result, the thermal conductivity of a pristine monolayer gra-
phene sheet is reduced to its half by introducing monatomic
vacancies at a concentration f1/2 ¼ 0.175% or Stone-Wales
defects at a concentration of 0.3%. Using a characteristic
size a ¼ 0.14 nm that is the diameter of one carbon atom in
the basal plane of graphene, the prediction from the Max-
well-Garnett formula based effective medium theory (EMT)
jEMT/j0 ¼ (1  f)/(1 þ 0.5f) is also plotted in Fig. 1(b),
which shows distinct difference with the simulation results.
The contradiction suggests that at this length scale of defect,
the compatible boundary condition is broken by the strong
scattering at the interfaces between pristine graphene lattice
and defects. Thus, a question is raised for practical applica-
tions that how Maxwell-Garnett formula could be improved.
The thermal conductivity of a solid can be approxi-
mately estimated by j ¼ Cvl/3, where C is the specific heat,
and v is the group speed of sound wave in solid in the spirit
of Debye. For graphene v ¼ (Y/q)1/2 ¼ 21.3 km/s for longitu-
dinal acoustic (LA) phonons. l is the mean phonon free path
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Appl. Phys. Lett. 99, 041901 (2011)
FIG. 1. (Color online) (a) Young’s modulus and (b)
thermal conductivity of a monolayer graphene sheet
with monatomic vacancies or Stone-Wales disloca-
tions. Inset in (a): a monatomic vacancy and Stone-
Wales defect in graphene as usually encountered in
experiments. Numerical fitting and predictions from
the Maxwell-Garnett EMT are also plotted for the
thermal conductivities in subplot (b). Point defects
scatter phonons at a larger scale than the defect size
and scatter centers have strong correlation at elevated
concentration. These effects are not included in EMT
and lead to large deviation from the simulation results.
that is reported as 775 nm for graphene sheets from experi-
mental measurements that is the origin of their ultrahigh
thermal conductivities in combination with the high
stiffness.5
We calculate the phonon spectrum based on the Fourier
transformation of the velocity auto-correlation functions
hvð0ÞvðtÞi from molecular dynamics simulation.18 The
results show that even at a monatomic vacancy concentration
as high as 1%, the shape and peaks are preserved well, which
demonstrates that the specific heat C ¼ kB(hx/kBT)2exp(hx/
kBT)/[exp(hx/kBT)  1]2 and group velocities v ¼ dx/dk for
a phonon mode with a frequency x and wave vector k have
negligible change. A quantitative estimation based on the
shift of peaks shows that it only leads to less than 5% reduc-
tion of thermal conductivity if the reduction of l is not taken
into account.
This result suggests that the presence of defects of low
concentration has less effects on the group speed v and spe-
cific heat C for the phonons in graphene that is consistent
with the gentle reduction of Young’s modulus as we observe
before. However, the impacts of defects on the thermal con-
ductivity ldefectphonon is dominantly accounted by the mean
free path l1 ¼ l1defect-phonon þ l1phonon-phonon in addition to
the phonon-phonon scattering mechanism. Moreover, Fig.
1(b) also shows that when the defect concentration is high
enough, l becomes less sensitive in comparison with the sit-
uation of low concentration, suggesting a transition from
propagating to diffusive mechanism.20 This is also reflected
in our further calculations for the temperature dependence of
thermal conductivities when 2% monatomic vacancies are
introduced. In Fig. 2, it is shown that not only the thermal
conductivity j and the temperature dependence is much
reduced but also there exists a peak at T ¼ 200 K, and the
low-temperature reduction of j is attributed to scattering of
phonons with small wave vectors.15 Moreover, as f increases,
the sensitivity of j on f is much reduced due to the disorder
nature of phonon transport processes.
To obtain more insights into the sensitivities of mechan-
ical and thermal properties on the defect concentration, we
plot the stress distribution around a monatomic vacancy in
Fig. 3(a) and the heat flux in Fig. 3(b). These plots show
distinct difference between the stress and heat flux distribu-
tion around the defect, i.e., the influence region of stress dis-
tribution is much more localized in comparison with the heat
flux and significant scattering occurs around the defects.
To predict the effective thermal properties of a nano-
composite, Nan and his collaborators apply the Maxwell-
Garnett effective medium theory by introducing a so-called
041901-3 Hao, Fang, and Xu
FIG. 2. (Color online) Temperature dependence of the thermal conductiv-
ities j/j0 of pristine graphene and defected graphene with monatomic
vacancies.
Kapitza radius for the interfacial thermal resistance.21 This
theory is further modified for nanocomposites with spheroi-
dal inclusions.22,23 However, here it is difficult to define an
interface between the defected atoms and others in a pristine
hexagonal lattice. To quantitatively characterize this differ-
ence, we introduce an influence coefficient R in the
Maxwell-Garnett formula instead, i.e.,
 
dðRf Þb j  jm
jeff ¼ jm 1 þ ; b¼ ; (1)
1  ðRf Þb j þ ðd  1Þjm
where d ¼ 3 is dimension of the problem, and jeff, j, and jm
are the thermal conductivities of the whole defected gra-
phene sheet, defects, and the pristine graphene sheet, respec-
tively. Our calculations show that R is strongly correlated to
the defect concentration f, which can be fitted into
R ¼ (0.002 þ 0.011f)1. At low defect concentration, the
point defects serve as local scattering centers to the heat flux
through them. While at elevated concentrations, the fast
decaying of R with respect to increasing f indicates that dif-
ferent scattering centers interact with each other, which
results in a delocalized scattering to the propagating modes
phonons and the overall scattering cross-section is reduced
in comparison with discrete and non-interacting defects.
When this delocalization is established as the defect concen-
tration is high enough, both R and l become less sensitive
with respect to that of low concentration.
In summary, we performed molecular dynamics simula-
tions for defected graphene sheets. It is found that Young’s
modulus is reduced with a linear dependence for vacancies and
a much more smooth decrease for Stone-Wales dislocations.
On the other hand, thermal conductivity relies dramatically on
the defect concentration, especially at low concentration. The
shortening of phonon mean free path l is responsible for this
reduction. At higher defect concentrations, the scattering cen-
ters percolates throughout the whole material and the thermal
conductivity of defected graphene sheet behaves similarly as
in disordered materials, where diffusive modes dominates the
thermal transfer process and the temperature dependence is
much reduced. These understadings could be used to evaluate
the quality of graphene for related applications. Similar
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Appl. Phys. Lett. 99, 041901 (2011)
FIG. 3. (Color online) (a) Stress and (b) heat flux distribution in a pristine
graphene sheet and around a monatomic vacancy defect.
phenomena are expected for functionalized or doped graphene
sheets, e.g., hydrogenated, oxidized, or fluorinated ones where
functional groups behave as the scattering centers as defects do
here, that could inspire nanoengineering approaches to tune the
mechanical and thermal properties of graphene.11,24
This work is supported by Tsinghua University through
the Key Talent Support Program and the National Science
Foundation of China through Young Scholar Grant 11002079
(Z.X.). This work is also supported by the Shanghai Super-
computer Center of China.
1
Z. Xu, Q.-S. Zheng, and G. Chen, Appl. Phys. Lett. 90(22), 223115
(2007).
2
Z. Xu, J. Comput. Theor. Nanosci. 6(3), 625 (2009).
3
J. H. Seol et al., Science 328(5975), 213 (2010).
4
A. A. Balandin et al., Nano Lett. 8(3), 902 (2008).
5
S. Ghosh et al., Appl. Phys. Lett. 92(15), 151911 (2008).
6
D. Sen et al., Small 6(10), 1108 (2010).
7
S. S. Verbridge et al., Appl. Phys. Lett. 93(1), 013101 (2008).
8
9
J. Kotakoski et al., Phys. Rev. Lett. 106(10), 105505 (2011).
C. Gómez-Navarro et al., Nano Lett. 10(4), 1144 (2010).
10
W. Gao et al., Nat. Chem. 1(5), 403 (2009).
11
Z. Xu and K. Xue, Nanotechnology 21(4), 045704 (2010).
12
J. Y. Huang et al., Proc. Natl. Acad. Sci. U.S.A. 106(25), 10103 (2009).
13
J.-W. Jiang, B.-S. Wang, and J.-S. Wang, Appl. Phys. Lett. 98(11), 113114
(2011).
14
M. Engelund et al., Phys. Rev. Lett. 104(3), 036807 (2010).
15
D. L. Nika et al., Phys. Rev. B 79(15), 155413 (2009).
16
S. Plimpton, J. Comp. Phys. 117(1), 1 (1995).
17
D. W. Brenner et al., J. Phys.: Condens. Matter 14(4), 783 (2002).
18
Z. Xu and M. J. Buehler, Nanotechnology 20(18), 185701 (2009).
19
Z. Xu and M. J. Buehler, ACS Nano 3(9), 2767 (2009).
20
Y. He et al., ACS Nano 5(3), 1839 (2011).
21
C.-W. Nan et al., Appl. Phys. Lett. 85(16), 3549 (2004).
22
A. Minnich and G. Chen, Appl. Phys. Lett. 91(7), 073105 (2007).
23
J. Ordonez-Miranda, R. Yang, and J. J. Alvarado-Gil, Appl. Phys. Lett.
98(23), 233111 (2011).
24
S.-K. Chien, Y.-T. Yang, and C.-K. Chen, Appl. Phys. Lett. 98(3), 033107
(2011).