Journal of Materials Science & Technology xxx (2015) 1e8

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Journal of Materials Science & Technology

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Defects in Graphene: Generation, Healing, and Their Effects

on the Properties of Graphene: A Review
Lili Liu 1, Miaoqing Qing 1, Yibo Wang 1, Shimou Chen 2, *
1
2

Department of Chemistry, School of Science, Beijing Technology and Business University, Beijing 100048, China
Key Laboratory of Green Process and Engineering, Institute of Process Engineering (IPE), Chinese Academy of Sciences (CAS), Beijing 100190, China

a r t i c l e i n f o
Article history:
Received 28 September 2014
Received in revised form
15 November 2014
Accepted 19 November 2014
Available online xxx
Key words:
Graphene
Vacancy
Defect healing
Band gap modulation
Properties of defective graphene

Graphene has attracted immense investigation since its discovery. Lattice imperfections are introduced
into graphene unavoidably during graphene growth or processing. These structural defects are known to
signicantly affect electronic and chemical properties of graphene. A comprehensive understanding of
graphene defect is thus of critical importance. Here we review the major progresses made in defectrelated engineering of graphene. Firstly, we give a brief introduction on the types of defects in graphene. Secondly, the generation and healing of the graphene defects are summarized. Then, the effects of
defects on the chemical, electronic, magnetic, and mechanical properties of graphene are discussed.
Finally, we address the associated challenges and prospects on the future study of defects in graphene
and other nanocarbon materials.
Copyright 2015, The editorial ofce of Journal of Materials Science & Technology. Published by Elsevier
Limited. All rights reserved.

1. Introduction
Graphene has raised extensive interest in the worldwide for its
extraordinary thermal, mechanical, electrical and other properties[1,2]. Among all properties, the unique electronic properties are
assumed to be the most intriguing aspect of graphene, for example,
outstanding ballistic transport properties and longest mean free
path at room temperature[3], distinctive integral and half-integral
quantum hall effect[4,5], the highest mobility to increase the
speed of devices[6], and so on. The mobility of graphene is signicantly higher than that of the widely-used Si, of approximately
1400 cm2 V
1 s
1. Consequently, graphene has been considered as a
candidate material for applications in post-silicon electronics.
Graphene has a honeycomb lattice structure and a unit cell that
contains two carbon atoms. Just like in carbon nanotubes, there are
two different kinds of graphene ribbon edges: armchair and zigzag,
which can inuence the electronic properties of graphene. However, most electronic applications are handicapped by the absence
of a semiconducting gap in pristine graphene. For example, devices
made from the zero-bandgap graphene are difcult to switch off,
losing the advantage of the low static power consumption of the

* Corresponding author. Prof., Ph.D.; Tel.: 86 10 82544800; Fax: 86 10

82544875.
E-mail address: chenshimou@ipe.ac.cn (S. Chen).

complementary metal oxide semiconductor (CMOS) technology.

Quantitatively, the Ion/Ioff ratios for graphene-based eld-effect
transistors (GFETs) are less than 100[7], while any successor to the Si
MOSFET should have excellent switching capabilities in the range of
104e107. Therefore, opening a sizeable and well-tuned band-gap in
graphene is a signicant challenge for graphene-based electrondevices, introducing defects have shown great potential on this
important issue.
The electronic and mechanical properties of graphene samples
with high perfection of the atomic lattice are outstanding, but
structural defects, which may appear during growth or processing,
deteriorate the performance of graphene-based devices. However,
deviations from perfection can be useful in some applications, as
they make it possible to tailor the local properties of graphene and
to achieve new functionalities. Like in any other real material,
structural defects do exist in graphene and can dramatically alter its
properties. Defects can also be deliberately introduced into graphene, for example, by irradiation or chemical treatments.
Because sp2-hybridized carbon atoms can arrange themselves
into a variety of different polygons to form different structures, the
nonhexagonal rings may either introduce curvature in the sheet or
leave it at when the arrangement of polygons satises certain
symmetry rules. This property is not included in other bulk crystals,
for example, semiconductors such as silicon. Reconstructions in the
atomic network permit a coherent defective lattice without undercoordinated atoms. Although they have no dangling bonds, these

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L. Liu et al. / Journal of Materials Science & Technology xxx (2015) 1e8

reconstructed defects locally increase the reactivity of the structure

and allow adsorption of other atoms on graphene[8].
In this review, we summarized the major progresses made in
defect engineering of graphene, including the types of defects in
graphene, the generation and healing of the graphene defects are
summarized, as well as the effects of the defects on the chemical,
electronic, magnetic, and mechanical properties of graphene. To
keep the length manageable, our attention is mainly focused on the
major developments of graphene defects in recent ve years.
2. Different Type of Defects in Graphene
There are two kinds of defects in graphene. One is point defects,
typically vacancies or interstitial atoms are zero-dimensional. The
other is on one dimensional line of defects. It is well-known that
the defects are not always stationary and that their migration can
have an important inuence on the properties of a defective crystal.
In graphene, each defect has certain mobility parallel to the graphene plane. The mobility might be immeasurably low, for
example, for extended vacancy complexes, or very high, for
example, for adatoms on an unperturbed graphene lattice. The
migration is usually governed by an activation barrier which depends on the defect type and therefore increases exponentially
with temperature.

formation of a ve-membered and a nine-membered ring [V1(5-9)

defect].
2.3. Multiple vacancies
Double vacancies (DV) can be created either by the coalescence
of two SVs or by removing two neighboring atoms. Because no
dangling bond is present in a fully reconstructed DV, two pentagons
and one octagon [V2(5-8-5) defect] appear instead of four hexagons
in perfect graphene. The atomic network remains coherent with
minor perturbations in the bond lengths around the defect. Simulations indicate that the formation energy Ef of a DV is of the same
order as that of an SV (about 8 eV)[11,12]. As two atoms are now
missing, the energy permissing atom (4 eV per atom) is much lower
than that for an SV. Hence, DVs are thermodynamically favored
over SVs. Furthermore, the removal of more than two atoms may be
expected to result in larger and more complex defect congurations. Generally, as an even number of missing atoms allows a full
reconstruction (complete saturation of dangling bonds), such vacancies are energetically favored over structures with an odd
number of missing atoms where an open bond remains[13].
2.4. One dimensional defects

Since the graphene lattice can be reconstructed by forming

nonhexagonal rings, the simplest example is the StoneeWales (SW)
defect[9], which does not involve any removed or added atoms. As
shown in Fig. 1, four hexagons are transformed into two pentagons
and two heptagons [SW(55-77) defect] by rotating one of the CeC
bonds by 90 . The SW(55-77) defect has a formation energy
Ef 5 eV[10].

This kind of defect has been observed in many experimental

studies of graphene[14e17]. In general, these line defects are tilt
boundaries separating two domains of different lattice orientations
with the tilt axis normal to the plane. Such defects can be thought
of as a line of reconstructed point defects with or without dangling
bonds[18e20], as shown in Fig. 3. One example is a domain boundary
which has been observed to appear due to lattice mismatch in
graphene grown on a Ni surface[17]. This defect makes up of an
alternating line of pairs of pentagons separated by octagons (Fig. 3).
Obviously, such a defect can be formed by aligning (5-8-5) divacancies along the zigzag lattice direction of graphene.

2.2. Single vacancies

2.5. Defects at the edges of graphene

The simplest defect in any material is the missing one lattice

atom. Single vacancies (SV) in graphene have been experimentally
observed by TEM[10]. As can be seen in Fig. 2, the SV undergoes a
JahneTeller distortion which leads to the saturation of two of the
three dangling bonds toward the missing atom. One dangling bond
always remains owing to geometrical reasons. This leads to the

Each graphene layer is terminated by edges with the edge atom

being either free or passivated with hydrogen atoms. The simplest
edge structures are the armchair and the zigzag orientation.
Defective edges can appear because of local changes in the reconstruction type or because of sustained removal of carbon atoms
from the edges. This can be achieved by sputtering edge atoms[21,22].

2.1. StoneeWales defect

Fig. 1. StoneeWales defect SW(55-77), formed by rotating a carbonecarbon bond by 90 : (a) experimental TEM image of the defect; (b) its atomic structure as obtained from our
Density functional theory (DFT) calculations (Copyright 2008 American Chemical Society)[10].

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L. Liu et al. / Journal of Materials Science & Technology xxx (2015) 1e8

Fig. 2. Single vacancy V1(5-9): (a) as seen in an experimental TEM image; (b) its atomic structure obtained from our DFT calculations (Copyright 2008 American Chemical
Society)[10].

Under these conditions, armchair edges can be turned to zigzag

edges[21]. An intermediate structure can be regarded as a defective
edge. A simple example of an edge defect is the removal of one
carbon atom from a zigzag edge. This leads to one pentagon in the
middle of a row of hexagons at the edge. Other edge reconstructions
result in different combinations of pentagons and heptagons at the
edge as shown in Fig. 4[23]. Besides, hydrogen atoms and other
chemical groups that can saturate dangling bonds at the edge under
ambient conditions may be considered as disorder, dramatically
increasing the number of possible edge defects.
3. Generation of Defects in Graphene
The high formation energy of a single vacancy in graphene
(7.5 eV) does not allow any detectable concentration of point

defects in thermal equilibrium at temperatures below the melting

temperature. However, there are three mechanisms which can lead
to nonequilibrium defects in graphene: (1) crystal growth; (2)
irradiation with energetic particles, for example, electrons or ions;
and (3) chemical treatment[8].
3.1. Crystal growth
Since the large-scale growth of a graphene layer does normally
not occur slowly atom-by-atom from one nucleus but rather as a
relaxation of a metal carbon system with many nuclei, for example,
in chemical vapor deposition (CVD), it is natural to expect defects in
the as-grown material. Generally, high temperature growth facilitates the relaxation toward thermal equilibrium, and defects can be
annealed rapidly. However, defects are a well-known problem in

Fig. 3. (a) Grain boundary defect structure consisting of pentagon-pairs and octagons in graphene grown on a Ni substrate; (b) the DFT relaxed geometry of the defect structure; (c)
the calculated adsorption energies for two domains are similar, but both are lower in energy than a third possible adsorption conguration with all carbon atoms on hollow sites
(Copyright 2010 Nature Publishing Group)[17].

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Fig. 4. Different edge reconstructions in graphene: (a) reconstructed zigzag; (b) armchair edge; (c) (677) reconstructed armchair edge; (d) zigzag edge (Copyright 2008 American
Physical Society)[23].

low temperature growth. Because of the high formation energy of

vacancies and fast migration of adatoms in graphene, it is unlikely
that there are any isolated vacancies in graphene after growth. This
has been conrmed by the high carrier mobility in CVD-grown
graphene, which would not be expected at a considerable density
of vacancies. The temperature dependence of the mobility indicates
that impurity scattering dominates at the interface even for the
merged domains with the same orientation[24].
3.2. Particle irradiation
Irradiation of graphene with ions or electrons can produce
point defects due to the ballistic ejection of carbon atoms[25e27].
The atom can be kicked out from graphene or adsorb on the sheet
and migrate on its surface as an adatom. The effect of irradiation
has been studied in detail by electron microscopy[28,29], where
irradiation and imaging can be done with the same electron beam,
and the formation of defects is observable in situ at atomic resolution. Uniform irradiation of larger areas results in a generation of
randomly distributed vacancies. However, due to increased strain
and/or under-coordinated atoms, the defective areas, for example,
where a vacancy already exists, show an increased rate of defect
formation. Defects can also be generated in preselected positions
with a highly focused electron beam or by using masking techniques. Modern electron microscopes with aberration-corrected
condensers allow focusing an electron beam onto a spot of
approximately 1 in diameter thereby creating vacancies with
almost atomic selectivity[30]. Another physical method which has
been used for defect production in graphene is ion irradiation[31e35]. It can be used to selectively produce certain defects or
to pattern and cut graphene with a precision down to 10 nm
utilizing a focused ion beam[36,37]. However, for the bilayer graphene, contrary to theoretical estimates based on the conventional binary collision model, experimental results indicate that
the number of defects in the lower layer of the bilayer graphene
sample is smaller than that in the upper layer (as shown in
Fig. 5)[35]. This observation is explained by in situ self-annealing of
the defects.

3.3. Chemical methods

The reactions of carbon atoms in a graphene layer with other
species can lead to the loss of atoms and hence to defects. However,
the high inertness of graphene (apart from edge positions that are
highly reactive) only allows a very limited number of possible reactions at room temperature. Oxidation is the most common one,
for example, in an oxidizing acid (HNO3 or H2SO4). In such a
treatment it is possible to attach oxygen and hydroxyl (OH) or
carboxyl (COOH) groups to graphene[38]. When graphene is covered
more or less uniformly with hydroxyl or carboxyl groups, the material is called graphene oxide, which is essentially a highly
defective graphene sheet functionalized with oxygen groups[39].
Plasma treatments and adsorption of atomic hydrogen on a graphene surface followed by its self-organization and hydrogen island formation can also be referred to in the context of graphene
treatment by chemical methods[40].
4. Healing of Defects in Graphene
It has been directed that defects play a crucial role in tailoring
the material properties of carbon-based structures such as graphite,
carbon nanotubes, and graphene sheets [26,41,42]. For example, it
was found that defects are responsible for the inherent ferromagnetic behavior of carbon-based materials, due to the presence
around the defects of localized electron states with energies close
to that of the Fermi level[43,44].
On the other hand, defects are well-known for their ability to
scatter charge carriers and phonons, thus decreasing the ballistic
transport path length and adversely affecting carrier mobility and
thermal conductivity. The detrimental effects of defects are
particularly pronounced in graphene lms. For example, defects
were held responsible for a remarkable reduction in charge carrier
mobility in graphene lms obtained by micromechanical cleavage[45]. The transport properties of graphene lms produced by
chemical methods, such as the exfoliation and chemical reduction
of graphene oxide, have also been ascribed to defects[46]. In this
respect, defects are undesirable, and the ability to heal them is

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Fig. 5. Schematic illustration of the experimental setups for creating defects on graphene. The samples were formed by subsequent transfer of 12C and 13C graphene sheets on Si/
SiO2 substrate and irradiated by Ar ions with various doses followed by Raman probing. The right panel is a snapshot from molecular dynamics simulations showing a typical
atomic conguration after an ion impact (Copyright 2013 WILEY-VCH Verlag GmbH & Co. KGaA)[35].

important for generating carbon nanostructures with high electrical and thermal conductivities and, potentially, enhanced
mechanical strength.
4.1. Thermal annealing
One promising approach for removing crystalline lattice defects
and restoring graphitic structures is high temperature processing in
the presence of a hydrocarbon gas. Utilizing appropriate conditions,
the hydrocarbon gas might decompose to supply carbon atoms that

pez et al. demonstrated that
can repair defective sites. Recently, Lo
chemical vapor deposition (CVD) processing of chemically derived
graphene lms using ethylene carbon source improved lm conductivity by two orders of magnitude, to room temperature (RT)
values of 10e350 S cm
1. The authors attributed the improvement
to defect healing[47]. In addition, direct observation of the modication of defective sites on graphitic surfaces under gaseous hydrocarbon atmospheres was reported by Liu et al. [48]. They studied
the reactivity of defects on highly oriented pyrolytic graphite
(HOPG) surfaces exposed to acetylene at elevated temperatures by
scanning tunneling microscopy (STM).
4.2. Self-healing
By using rst-principles calculations based on densityfunctional theory, Tsetseris et al. found that pairs of C adatoms

and clusters of four or more self-interstitials stay idle unless the

system is heated to very high temperatures, while clustering of
three C adatoms leads to removal of hillock-like features and creates mobile species, resulting in self-healing of defective structures[49]. Liu et al. found that in the single layer vacancy defects
prefer to coalesce into larger vacancy holes, while in the multi-layer
graphene the vacancies tend to be concentrated into a single hole in
one layer through both intra- and inter-layer migrations (Fig. 6).
The vacancy inter-layer migration is facilitated by the interaction of
defects in neighboring layers[50].
4.3. Healing by absorption
Wang et al. proposed a strategy of controllable vacancy healing
and N-doping of graphene[51], as shown in Fig. 7, vacancies can be
healed by sequential exposure to CO and NO molecules in a twostep recipe. Firstly, the CO molecule can be easily absorbed at the
site of graphene defects. Then, NO can remove the extra O atom in a
chemical way by forming NO2 molecule that binds to graphene
weakly. Encouraged by this observation, they further study the
controllable N-doping in graphene with a similar procedure, which
involved creating vacancy and subsequent exposure to NO molecules. That is to say, a combination of CO and NO molecules can
potentially provide simultaneous healing and doping at a desirable
ratio, which is very important for band-gap modulation of
graphene.

Fig. 6. A diagram of the vacancy migration between graphene layers leads to vacancies holes formation in one layer and the self-healing of other layers (Copyright 2014 the Royal
Society of Chemistry)[50].

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5. Properties of Defective Graphene

5.1. Chemical properties

Fig. 7. Schematic view of the vacancy healing and N-doping process of graphene with
vacancies by CO and NO molecules (Copyright 2011 American Physical Society)[51].

4.4. Metal-assisted healing

The healing of graphene grown from a metallic substrate is
investigated by Karoui et al. using tight-binding Monte Carlo simulations[52]. At temperatures (ranging from 1000 to 2500 K), an
isolated graphene sheet can anneal a large number of defects
suggesting that their healings are thermally activated. Wherein, in
the presence of a nickel substrate, a perfect graphene layer can be
obtained. The probable mechanism is that the nickel carbon
chemical bonds keep breaking and reforming around defected
carbon zones, providing a direct interaction, necessary for the
healing. As shown in Fig. 8, as in the case of the isolated graphene
sheet, the sheet is far from being healed and a non-negligible
concentration of defects remains at 1000 K (Fig. 8(b)). Once again,
large rings are healed at 1000 and 1500 K, whereas pentagons and
heptagons cancel out at higher temperatures. At 2500 K the graphene sheet is completely healed as seen in Fig. 8(c).

It is well-known that defects associated with dangling bonds

should enhance the reactivity of graphene. Numerous simulations
suggested that hydroxyl, carboxyl, or other groups could easily be
attached to vacancy-type defects[53,54]. Simulations also showed
that reconstructed defects without dangling bonds such as SW
defects or reconstructed vacancies locally changed the density of
p-electrons and may also increase the local reactivity[55,56]. For
example, Pablo et al. found that when two phenyl groups are
attached onto perfect graphene, the StoneeWales defect becomes
more reactive than the 585 double vacancy and 555e777 reconstructed double vacancy[56]. The largest increase of reactivity is
observed for the functional groups whose binding energy onto
perfect graphene is small. Thus, the controlled creation of defects
with a high spatial selectivity can be used for the local functionalization of graphene, and for the creation of graphene ribbons with
the designed properties by various chemical methods.
5.2. Electronic properties
Defects strongly affect the electronic properties of graphene.
From a theoretical point of view, the Dirac equation has to be
modied when defects are in the lattice. This will naturally have an
impact on the electronic structure. The overlap of p-orbitals determines the electronic properties but is altered in the vicinity of
structural defects. Firstly, bond lengths in the strain elds of defects
are different from those in the perfect lattice. Secondly, defects lead
to a local rehybridization of sigma and piorbitals which again
change the electronic structure. A local curvature around defects

Fig. 8. Graphene sheet in the presence of the Ni lattice: (a) side and top views of the initial congurations; equilibrium congurations at (b) 1000 and (c) 2500 K (Copyright 2010
American Chemical Society)[52].

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Fig. 9. Schematic of strained graphene functionalization: (a) after being transferred to polydimethylsiloxane (PDMS), the polycrystalline graphene is strained by elongation; (b)
after strain is applied, the aqueous solution of aryl diazonium salt is pipetted onto the graphene surface, the inset shows a photograph of several droplets on a graphene/PDMS
substrate; (c) after functionalization, the solution is removed and the substrate rinsed and dried. Because of the increased reactivity of defect sites along boundaries, there is an
increased concentration of functional molecules at these locations. (Copyright 2013 American Chemical Society)[67].

also has an inuence on the rehybridization. Thirdly, all defects lead

to scattering of the electron waves and change the electron
trajectories[57,58].
5.3. Magnetic properties
Magnetism in pure carbon systems has recently been the subject
of intense experimental and theoretical research, which is very
important to understand a fundamental problem: the origin of
magnetism in a system which traditionally has been thought to
show diamagnetic behavior only. In addition to fullerenes, nanotubes, graphite, and nanodiamonds, magnetism was recently reported for graphene produced from graphene oxide [8,59e62]. Based
on the calculations, the observed magnetic behavior in all these
systems was explained in terms of defects in the graphitic network.
Such defects have local magnetic moments and may give rise to at
bands and eventually to the development of magnetic ordering.
Magnetism may also originate from impurity atoms which are
nonmagnetic by themselves, but because the specic chemical
environment give rise to local magnetic moments.
5.4. Mechanical properties
The inuence of defects on the mechanical properties of graphene has not yet been studied experimentally. However, based on
a large body of experimental and theoretical data for carbon
nanotubes[63e66], one can expect that point defects, in particular
vacancies, will decrease the Young's modulus and tensile strength
of graphene samples. Existence of defects may remarkably reduce
the tensile strength, and mechanical properties should be
decreased as the number of defects increase. Conversely, efcient
reconstruction and healing of vacancy-type defects should minimize their detrimental effects. Line defects (dislocations) should be
important for plastic deformation of graphene ribbons under tensile strain[8]. On the other hand, Bissett et al. found that mechanical
strain can alter the structure of graphene, and dramatically increase
the reactivity of the graphene. As shown in Fig. 9, the reaction rate
of aryl diazonium functionalization can be increased up to 10 times
by applying external strain to the graphene[67].

defects are frequently unavoidable in experiments; hence their

effect on electronic properties of graphene, along with their healing
to enrich the functionalities of graphene, should be investigated.
Such studies can provide insight into the interplay of the defects in
graphene and related nanocarbon materials and facilitate the
rational design of novel carbon materials with new functionalities.
Furthermore, the following key points are suggested for future
studies of the graphene defects.
(1) Most of the study on the inuence of defects on the electronic properties of graphene is based on theoretical simulation, and graphene akes with different sizes and borders
are employed. This should have some difference with the real
graphene materials. Experimental data directly reveal the
defects effects on the electronic and other characteristics of
graphene are urgently needed.
(2) It is also very important to nd a way to heal vacancy defects
in graphene in a controlled way. It seems that a high temperature thermal annealing, adding foreign atoms or drawing support from some metal substrates can serve as efcient
approaches to remove unwanted defects. However, it is still
difcult to regulate the concentration of the defects in the
real experiments, especially for the large area of graphene or
batch processing. The nature of the healing mechanism
should be explored.
(3) There is a huge demand for developing the applications of
graphene in electronics and optics, in which opening the
band gap of graphene is the most important issue. Introducing defects have shown promising prospect in the bandgap modulation of graphene, even though the inuences of
the defects on pristine graphene are widely studied. More
attention should be paid on the understanding of defects of
graphene in the vicinity of surface, interface, reactant, and
environment, etc. In-situ studies of the graphene and their
prototype devices are also very important, which will
provide new insights into the structures and properties of
graphene, and boost further exploration of graphene
applications.

6. Concluding Remarks

Acknowledgments

Graphene have a big role in nanoscience today because of their

rich and promising electrical, mechanical and optical properties.
However, achieving these properties requires understanding the
underlying structure and its behavior. In addition to ideal systems,

This work was supported by the National Natural Science

Foundation of China (Nos. 21276257 and 2110600) and the
Research Foundation for Youth Scholars of Beijing Technology and
Business University (No. QNJJ2014-14).

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Please cite this article in press as: L. Liu, et al., Journal of Materials Science & Technology (2015), http://dx.doi.org/10.1016/j.jmst.2014.11.019