Nano Today (2010) 5, 351372

available at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/nanotoday

REVIEW

Graphene and graphite nanoribbons: Morphology,

properties, synthesis, defects and applications
Mauricio Terrones a,, Andrs R. Botello-Mndez b, Jessica Campos-Delgado c,
Florentino Lpez-Uras d, Yadira I. Vega-Cant d,
noz-Sandoval d,
Fernando J. Rodrguez-Macas d, Ana Laura Elas e, Emilio Mu
Abraham G. Cano-Mrquez d, Jean-Christophe Charlier b,
Humberto Terrones b
a

Department of Materials Science and Engineering & Chemical Engineering, Polytechnic School, Carlos III University of Madrid,
Avenida Universidad 30, Edicio Betancourt, 28911 Legans, Madrid, Spain
b
Institute of Condensed Matter and Nanosciences (IMCN), Universit Catholique de Louvain, Place Croix du Sud 1,
B-1348 Louvain-la-Neuve, Belgium
c
Diviso de Metrologia de Materiais, Instituto Nacional de Metrologia, Normalizaco e Qualidade Industrial (INMETRO),
Duque de Caxias, RJ 25250-020, Brazil
d
Advanced Materials Department, IPICYT, Camino a la Presa San Jos 2055, Col. Lomas 4a seccin, 78216, San Luis Potos,
SLP, Mexico
e
Department of Mechanical Engineering and Materials Science, Rice University, Houston, TX 77005, USA
Received 16 May 2010; received in revised form 26 June 2010; accepted 28 June 2010
Available online 2 August 2010

KEYWORDS
Graphene;
Nanoribbons;
Nanotubes;
Synthesis;
Properties;
Applications

Summary Carbon is a unique and very versatile element which is capable of forming different architectures at the nanoscale. Over the last 20 years, new members of the carbon
nanostructure family arose, and more are coming. This review provides a brief overview on
carbon nanostructures ranging from C60 to graphene, passing through carbon nanotubes. It provides the reader with important denitions in carbon nanoscience and concentrates on novel
one- and two-dimensional layered carbon (sp2 hybridized), including graphene and nanoribbons.
This account presents the latest advances in their synthesis and characterization, and discusses
new perspectives of tailoring their electronic, chemical, mechanical and magnetic properties
based on defect control engineering. It is foreseen that some of the structures discussed in the
review will have important applications in areas related to electronics, spintronics, composites,
medicine and many others.
2010 Elsevier Ltd. All rights reserved.

Corresponding author. Tel.: +34 91 624 9447; fax: +34 91 624 9430.
E-mail address: mtterrones@gmail.com (M. Terrones).

1748-0132/$ see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.nantod.2010.06.010

352

Introduction
The discovery of C60 Buckminsterfullerene, a beautiful
cage-like carbon molecule of 7 in diameter (Fig. 1a)
[1], stimulated the creativity and imagination of scientists and paved the way to a whole new chemistry and
physics of nanocarbons (Fig. 1) [24]. Soon after, carbon
nanostructures related papers started to increase in number almost exponentially. However, it is important to note
that 5 years earlier (1980), Sumio Iijima rst reported
electron microscope images of nested carbon nanocages
(also known as graphitic onions) when studying amorphous carbon lms prepared by thermal vacuum deposition.
In 1988, Kroto and McKay proposed that such graphitic
onions observed by Iijima consisted of nested icosahedral
Fullerenes (C60 @C240 @C540 @C960 .) containing only pentagonal and hexagonal carbon rings (Fig. 1b) [5]. In 1992, Daniel
Ugarte observed the reconstruction of polyhedral graphitic
particles (nested giant fullerenes) into almost spherical
carbon onions [6], due to high-energy electron irradiation
inside a high-resolution transmission electron microscope
(HRTEM). Similarly, Chuvilin et al. have recently observed
the creation of defects on graphene and the eventual formation of C60 upon electron irradiation in a HRTEM [7].
Regarding tubular graphene (rolled graphene sheets
known as nanotubes), Endo, and coworkers appear to be the

M. Terrones et al.
rst to report the existence of thin single and multi-walled
graphitic nanotubes (SWCNTs and MWCNTs) (Fig. 1c) using
HRTEM. These nanotubes were produced using a modied
chemical vapor deposition (CVD) method used to produce
carbon bers [8], but this 1976 paper did not have a broad
impact at that time. The study of carbon nanotubes (CNTs)
started in earnest when Sumio Iijima conrmed in 1991 [9],
using electron diffraction, that the structure of MWCNTs consisted of nested graphene tubules exhibiting fullerene-like
caps [10]. He termed these structures graphite microtubules. They were produced via an arc-discharge between
graphite electrodes in an inert atmosphere (no metal catalyst was used); the same method for producing fullerenes
[9]. The synthesis of SWCNTs was reported a couple of
years later, in 1993, by Iijimas group [11] and Bethunes
group [12] using a carbon arc in conjunction with metal
catalysts. Soon after, other graphitic nanostructures were
successfully produced, including: nanocones (Fig. 1d) [13],
peapods [14], nanohorns (Fig. 1d) [15], carbon rings or
toroids (Fig. 1e) [16]. More recently, the two-dimensional
crystalline allotrope of carbon, called graphene (Fig. 1f),
was isolated using the so-called scotch-tape method,
where an ingenious method for its observation under an
optical microscope was described [17]. As in the case of
CNTs, previous works reporting graphene from the reduction of graphene oxide [18] and torn from graphite with an

Figure 1 Molecular models of different types of sp2 -like hybridized carbon nanostructures exhibiting different dimensionalities,
0D, 1D, 2D and 3D: (a) C60 : Buckminsterfullerene; (b) nested giant fullerenes or graphitic onions; (c) carbon nanotube; (d) nanocones
or nanohorns; (e) nanotoroids; (f) graphene surface; (g) 3D graphite crystal; (h) Haeckelite surface; (i) graphene nanoribbons; (j)
graphene clusters; (k) helicoidal carbon nanotube; (l) short carbon chains; (m) 3D Schwarzite crystals; (n) carbon nanofoams
(interconnected graphene surfaces with channels); (o) 3D nanotube networks, and (p) nanoribbons 2D networks.

Graphene and graphite nanoribbons

353

Figure 2 Low energy DFT 3D band structure and its projection on kx close to k point K (/a*[2/3, 0.0 0.0]) for (a) graphene,
(b) bilayer graphene, (c) trilayer graphene and (d) graphite. (a) shows the characteristic Dirac point of graphene. The Dirac point
(i.e., relativistic fermion characteristic) is lost in bilayer graphene (b), but appears again in trilayer graphene (c); (d) shows the 3D
graphite structure which displays a semimetallic band structure with parabolic-like bands. The Fermi level has been set at zero in
all cases.

STM tip [19] appeared ahead of its time and did not receive
much attention. The relatively easy production of graphene
using Novoselovs method, and the peculiar properties of
this 2D atomic crystal have heavily stimulated an extensive
study of graphene for the rst time. New carbon structures with sp2 hybridization, such as bilayer and few-layer
graphene, graphene and graphitic nanoribbons have subsequently emerged, each with novel and unusual properties
(Fig. 2).
The series of events described above clearly demonstrate
that carbon is a fascinating element and is able to form
various morphologies at the nanoscale, possessing different physicochemical properties, some of them yet unknown.
There are several reviews and dedicated journal issues on
the synthesis and properties of graphene (see, for instance
[20,21]). However, the other sp2 hybridized carbon structures that have emerged from the study of graphene deserve
as much of attention as graphene. This review intends to
summarize the latest theoretical and experimental advances
related to novel one- and two-dimensional layered carbon
(sp2 hybridized).

The different types of graphene-like

nanostructures
By looking at the different morphologies of graphene-based
nanostructures discovered so far, and all other possibilities

still to be found, it is important to provide some important

denitions related to different sp2 -like hybridized nanocarbons. In this manuscript the following denitions regarding
graphene-like structures will be used:

Graphite: A 3D system
We can dene graphite as an innite three-dimensional
crystal made of stacked layers consisting of sp2 hybridized
carbon atoms (Fig. 1g); each carbon atom is connected
to other three making an angle of 120 with a bond
length of 1.42 . Depending on the layers stacking, these
crystals could be hexagonal (ABABAB. . .) or rhombohedral
(ABCABC. . .). The hexagonal and rhombohedal structures
belong to the P63 /mmc (194) and R-3m (166) space groups,
respectively. In both 3D crystals, the layers interact weakly
through van der Waals forces. Graphite crystals can be found
naturally, and can also be articially synthesized by thermolytic processes; such as the production of highly oriented
pyrolytic graphite (HOPG).

Graphene: A 2D system
A graphene crystal is an innite two-dimensional layer consisting of sp2 hybridized carbon atoms (Fig. 1f), which
belongs to one of the ve 2D Bravais lattices called the
hexagonal (triangular) lattice. It is noteworthy that by pil-

354
ing up graphene layers, in an ordered way, one can form 3D
graphite. Graphene was initially considered as a theoretical
building block used to describe the graphite crystal, and to
study the formation of carbon nanotubes (rolled graphene
sheets), and predict their fascinating electronic properties.
This 2D atomic (one atom thick) crystal of carbon has as ngerprint a unique electronic structure with linear dispersion
close to the Fermi level. Charge carriers in graphene are
better described as massless Dirac fermions, which result in
new phenomena.
There are other pseudo-2D sp2 hybridized carbon structures, such as bilayer- and few-layer-graphene, which
exhibit particular properties that are different from both
graphene and graphite (Fig. 2). Whenever these structures
exhibit AB stacking they will be referred as graphitic stacks.
This distinction is made because it has been demonstrated
that the properties of graphene can be recovered in systems with several sp2 hybridized carbon layers when stacking
disorder is introduced. However, the physicochemical properties of graphene appear to be very different from bilayer
graphene and few-layer graphene. Therefore, it is also
important to include these two graphene categories in this
review (see below and Fig. 2).
Theoretical work has been proposed regarding the possibility of stable at sp2 hybridized carbon sheets containing
pentagons, heptagons and hexagons, termed Pentaheptite
(2D sheets possessing heptagons and pentagons only) [22]
or Haeckelites (2D crystals containing pentagons, heptagons
and/or hexagons: Fig. 1h) [23]. These at structures are
intrinsically metallic and could exist in damaged or irradiated graphene. However, further experiments are needed in
order to produce them and identify them successfully.
Some synthesis routes to graphene started to be reported
in 2001, using heat treatments, at 1600 C of diamond
nanoparticles over HOPG [24]. However, extensive studies
on graphene started only after Novoselov et al. [17] were
able to isolate graphene sheets using a simple micromechanical exfoliation method placing scotch-tape over commercial
HOPG. The latter technique allowed scientists all over
the world to isolate single- and double-layered graphene
akes (SLG and DLG). Subsequently, other methods to
obtain graphene akes were reported, including its epitaxial
growth over SiC substrates [25], and CVD growth over thin
metal layers [26,27].

Graphene nanoribbons and graphitic clusters: 1D

and 0D systems
When innite graphene crystals become nite, surface and
boundaries appear, forming non-three coordinated atoms at
the edges, and if the size is in the order of nanometers, we
have a graphitic nanostructure that exhibits different properties from those observed in bulk. Among these graphitic
nanostructures are nanoribbons (Fig. 1i) and nanoclusters
(Fig. 1j). In analogy with the 2D counterpart, one can have
graphene-, bilayer-, few-layer- and graphitic-nanoribbons
or nanoclusters. It is noteworthy that fullerenes (Fig. 1a
and b), graphitic nanotubes (Fig. 1c) and related structures,
such as toroids (Fig. 1e) and carbon helixes (Fig. 1k) can
be treated as separated systems since bending needs to be
considered and curvature effects play an important role.

M. Terrones et al.
In general, a graphitic (graphite or graphene) nanoribbon
could be dened as a one-dimensional sp2 hybridized carbon
crystal with boundaries that expose non-three coordinated
carbon atoms, and possesses a large aspect ratio (Fig. 1i).
Edge terminations could be armchair, zigzag or a combination of both. The graphitic cluster concept arises when the
dimensionality is lost and no periodicity is present (Fig. 1j).
Finally, long carbon chains with alternating (singledouble)
bonds, could be considered as 1D system, and such systems
have been investigated experimentally and theoretically
[28]. If these chains become small or nite, the system could
be considered as a 0D (Fig. 1l) [29]. In both cases, these
chains are fascinating and further experimental work needs
to be performed.
Schwarzites and nanotube networks: Curved graphene in
3D
Schwarzites are hypothetical graphitic (sp2 hybridized)
three-dimensional crystals obtained by embedding nonhexagonal carbon rings (Fig. 1m), thus spanning to different
space groups, in which the most symmetrical cases belong
to cubic Bravais lattices [30]. These structures could be
visualized as microporous carbon (Fig. 1n), exhibiting nanochannels. It is important to note that similar structures
have been synthesized. In this context, the use of mesoporous silicates as templates to introduce a carbon source
(e.g. sucrose), followed by a carbonization and an HF treatment yield microporous carbon in which small regions can be
compared and explained with the structure of Schwarzites
[31,32]. From the theoretical standpoint, these mesoporous
carbon materials have been predicted to have outstanding
performance in the storage of hydrogen due to their large
surface area [33], however further attempts to improve
their storage capacity need to be carried out [34]. Another
type of 3D array of nanocarbons, consists of nanotube
networks (Fig. 1o), which have been predicted to exhibit
outstanding mechanical and electronic properties, besides
having a large surface area (e.g. 3600 m2 /g) [35,36]. Interestingly, these type of random 3D nanotube networks have
been produced using CVD approaches [37,38] and further
theoretical and experimental studies are still needed in
order to achieve crystalline 3D networks.

Properties
Properties of graphene and few-layered graphene
The crystal structure of graphene can be thought of as two
equivalent carbon triangular sub-lattices. Due to symmetry considerations, the hopping of electrons between the
sub-lattices leads to the formation of two energy bands,
which intersect at the K point (Fig. 2a) [39]. Near these
crossing points, the electron energy is linearly dependent on the wave vector. This linear dispersion results
in massless excitons, which are described by the Dirac
equation. Dirac fermions (electrons or holes) exhibit very
different and unusual properties compared to ordinary electrons, thus leading to new phenomena. For instance, the
anomalous integer quantum Hall effect can be observed in
graphene even at room temperature [40,41]. Other outstanding properties of graphene include insensitivity to

Graphene and graphite nanoribbons

external electrostatic potentials (Klein paradox), jittery
motion of the wave function under conning potentials, and
large mean free paths. For a comprehensive review of the
properties of graphene, see Ref. [21].
The electronic properties of graphene change with the
number of layers and by the relative position of atoms in
adjacent layers (stacking order). For bilayer graphene, the
stacking order can be either AA, with each atom on top of
another atom; or AB, where a set of atoms in the second
layer sits on top of the empty center of a hexagon in the rst
layer. As the number of layers increase, the stacking order
can become more complicated. For graphite, there are three
common types of stacking: (i) AB or Bernal stacking, (ii) ABC
or rhombohedral stacking, and (iii) no discernible stacking
order or turbostratic stacking. The most stable stacking is
AB, thus it has been studied more than other graphene-based
stacks. However, the other stacking orders are certainly possible, especially in few-layer graphenes, and remain to be
studied in detail. In fact, it has been recently found that
bilayer graphene often exhibits AA stacking [42].
The limit of thickness at which graphene can still be considered as such, can be determined by the rapid change in
the electronic structure as the number of layers increase.
The rst AB stacks of graphene show very different electronic spectra (Fig. 2). The bilayer (Fig. 2b) shows parabolic
bands (thus no Dirac electrons), which touch at the Fermi
level. Under the presence of an electric eld, the gap on
bilayer graphene can be opened, which is of interest in
technological applications [43]. The trilayer shows an interesting band structure, which looks like a combination of
the monolayer and the bilayer. In general, for few-layer
graphene with N layers (AB stacking), there will be a linear band (Dirac fermions) if N is odd [44]. As the number
of layers increases, the band structure becomes more complicated: several charge carriers appear [17,45], and the
conduction and valence bands start notably overlapping
[17,46]. Therefore, three different types of pseudo-2D crystals are distinguished: graphene, and double- and few-layer
graphene. Thicker structures can be considered as thin lms
or slabs of graphite [20]. The stacking order or disorder has
been found to dramatically change the electronic properties of multilayer graphene, introducing Dirac fermions due
to symmetry breaking, even in graphite crystals to form
graphene stacks [47,48].
The thermal properties of graphene have been recently
measured by Balandin, et al. [49], who found that
a suspended graphene sheet obtained by mechanical exfoliation could exhibit extremely high thermal
conductivity values ranging from (4.84 0.44) 103 to
(5.30 0.48) 103 W/m K; higher than experimental values
for carbon nanotubes and diamond. However, more recent
experimental results on CVD grown suspended graphene
indicate lower values (2500 W/m K) [50]. Nevertheless,
these outstanding thermal properties could be exploited in
the fabrication of heat dissipaters and polymer composites
with high thermal conduction. It is important to note that
a detailed study regarding the thermal properties of dopedgraphene and individual graphene nanoribbons still need to
be performed and compared with the data shown above.
Regarding the mechanical strength of an individual
graphene sheet, Hone and coworkers [51] have demonstrated that graphene has a breaking strength of 200 times

355
larger than that of steel, with a Youngs modulus of ca.
1 TeraPascal (TPa). These measurements appear to depend
upon the number and types of defects present within the
sheet (see defect section below). In this context, McEuen
and coworkers reported [52] using atomic force microcopy, a
Youngs modulus of 0.5 TPa for an individual graphene sheet.
It is noteworthy that the Youngs modulus of graphite along
the basal plane is ca. 1 TPa. To the best of our knowledge,
mechanical property measurements of graphene nanoribbons have not been reported hitherto. However, these
measurements will be very dependent on the number and
types of defects (see below), and type of edge terminations.
In addition, one would expect that although doped-graphene
nanoribbons may be more chemically active, their mechanical modulus and strength would decrease as the number of
dopants increases. However, these sets of experiments are
still needed and should be carried out.
The interplay between mechanical and electronic properties of graphene has been recently studied. Kim and
coworkers have measured the change of resistance of
graphene (grown by CVD on nickel and then transferred
to a exible substrate) upon mechanical strain [27]. When
graphene is bent (ca. 1 mm of diameter), the resistance
(initially ca. 300 ) in the bent direction increases almost
one order of magnitude. Similarly, the resistance changes by
stretching, with one order of magnitude difference between
the resistance parallel and perpendicular to the stretching direction. Theoretical calculations indicate that uniaxial
stress do not change signicantly the electronic properties
of graphene [5355], but that anisotropic strain or out of
plane deformation due to substrate interactions can open a
gap between the valence and conduction bands.
Highly crystalline graphene surfaces appear to be chemically inert, and these surfaces usually interact with other
molecules via physical adsorption ( interactions). However, several chemical groups such as carboxyl (COOH),
carbonyl (COH), hydrogenated (CH) and amines (NH2 ), could
be anchored at the edges of graphene nanoribbons, which
are more chemically reactive. In addition, the chemical
reactivity could change drastically at these edges, depending on their carbon termination, either armchair or zigzag. In
order to make the graphene surface more chemically reactive, either surface defects or high degrees of curvature
need to be introduced (see below).
It is important to emphasize that one way to make the
graphene surface less inert is by reacting it with halogen
atoms such as uorine. Fluorinated graphite has been synthesized for decades. However, graphene has been recently
been uorinated using different techniques including plasma
treatments, F2 high temperature treatments among others
[56,57]. Fluorinated graphene can be dispersed homogenously in solvents and could therefore be used to produce
polymer composites. It is also important to mention that
the electronic properties of graphene could be tuned via
uorination, which controls the band gap of the material
[58].
Regarding the reactivity of graphene, a fully hydrogenated graphene sheet, termed graphane, was predicted by Sofo et al. [59], and reported experimentally by
Novoselov and coworkers [60]. However, the synthesis of
this doped graphane layer still needs to be improved and
further analysis related to the CH bonding nature using X-

356
ray photoelectron spectroscopy (XPS) should be carried out.
For graphene nanoribbons, uorination and hydrogenation
reactions remain to be carried out together with XPS and
other studies. Such studies are important for devices as it
has been shown that electronic properties of graphene can
be changed by passivating its surface followed by desorption
of hydrogen in specic patterns [61].
Finally, it is also possible to produce graphene oxide
materials by attaching oxygenated groups on the sp2
hybridized surface (e.g. carbonyl and carboxyl groups), making them hydrophilic and more reactive [62]. This layered
oxide is commonly produced via wet chemical methods and
could also be dispersed easily in different solvents for fabricating robust polymer composites [63]. Due to the large
number of defects contained in this layered material, details
and other applications of this type of oxidized graphenes
will not be reviewed here, and relevant information could
be found elsewhere [63].

Properties of graphitic nanoribbons

As explained above, graphitic nanoribbons will inevitably
have borders which can exhibit edge states and different
electronic, chemical and magnetic properties depending
on the size and type of border. The most studied chiral
edge congurations, 0 (armchair) and 30 (zigzag), lead to
armchair and zigzag nanoribbons (A-GNRs, Z-GNRs), respectively. Experimental results indicate that these are the most
common type of edges in nanoribbons (Fig. 3) [64], although
edge reconstruction with pentagonal and heptagonal carbon
rings has also been observed (see [65] and Section 5).
Electronic properties
Z-GNRs exhibit edge states not present in the armchair case
[66,67]. These edge states are present as a at band around

M. Terrones et al.
the Fermi level, but extended along the ribbons edge, leading to a metallic nanoribbon if the width is large enough
(e.g. >10 nm) [68,69]. Such at band results in a high density of states located at the edges, indicating that they are
very reactive sites. Furthermore, Z-GNRs exhibit magnetic
properties that are relevant for spintronics (see below).
The properties of A-GNRs have a characteristic dependence on the width. Density functional theory (DFT)
calculations indicate that A-GNRs can be grouped in three
families of decreasing band gaps (Eg ) as the ribbon width
increases. Barone et al. [70] predicted that in order to produce materials with band gaps Eg 0.7 eV (similar to Ge or
InN), the width of the ribbons must range between 2 and
3 nm. The ribbon widths must be reduced to 12 nm if larger
band gaps (1.11.4 eV, such as Si, InP, or GaAs) are needed
[70], and as the width increases the band gap tends to
the zero value of 2D graphene. A nice comparison between
experimental and calculated band gaps can be found in Ref.
[71]. The effect of thickness (i.e., number of stacking layers) has also been studied. According to theoretical studies,
Z-GNRs have increased numbers of edge states, and A-GNRs
have decreased band gaps, when multilayered [72]. The Eg of
a bilayer A-GNR (b-A-GNR), in general, is smaller than that of
an A-GNR, b-A-GNR also exhibits two distinct groups, metal
and semiconductor, whereas an individual A-GNR displays
purely semiconducting behavior. Moreover, Eg of b-A-GNR is
highly sensitive to the interplanar distance [73]. Other studies have shown that A-GNRs exhibit three classes of bilayer
gaps, which decrease with increasing ribbon width [74].
Edges in graphene and few-layer graphene nanoribbons
have highly reactive sites. Thus, the modulation of the electrical, chemical and magnetic properties of graphene, and
multilayer graphene nanoribbons, by anchoring different
atoms or molecules on its edges, has been proposed for
applications such as sensors, memory devices and processing

Figure 3 (a) Model of a graphene nanoribbon edge showing an armchair and a zigzag junction (courtesy of M. Hofmann and X.
Jia); (b) HRTEM image of graphene edges exhibiting overlapping armchair edges (like terraces of graphene layers with armchair
morphology) together with zigzag edges; the image was obtained after applying Joule heating to a graphitic ribbon and resembles
the model shown in (a), and (c) HRTEM image of 3 overlapping zigzag-armchair edges obtained by applying Joule heating to a
graphitic nanoribbon inside a HRTEM; hexagonal models are depicted for clarity [64].

Graphene and graphite nanoribbons

devices [7577]. In addition, it has been found that the electronic properties, and in particular the band gap of few-layer
graphene is strongly modulated by the interlayer distance.
This effect could be used for nano-electromechanical systems (NEMS) [78]. Similarly, strain can induce changes in
the electronic properties of graphene nanoribbons. Theoretical calculations indicate that uniaxial strain [79] and out
of plane deformations can change the band gap of A-GNRs
[80,81].
Quantum transport in graphene nanoribbons
In contrast to carbon nanotubes, quantum transport properties of GNRs are expected to strongly depend on whether
their edges exhibit the armchair or the zigzag congurations.
As discussed above, the electronic properties of GNRs reveal
a strong dependence on the edge topology [66].
All A-GNRs are semiconductors with energy gaps which
decrease as a function of increasing ribbon widths. According to the convention, A-GNRs Z-GNRs can be classied by
the number N of zigzag or CC dimer lines across the ribbon width, as illustrated in Figs. 4 and 10 [82]. The gap of
specic N-aGNRs depend on the N value, separating the ribbons in three different categories (all exhibiting direct band
gaps at the  point). The calculated quantum conductances
of two A-GNRs exhibiting respectively large and small band
gaps, are illustrated in Fig. 4. The 16-A-GNR is a 0.8 eV gap
semiconductor, thus inducing a quite large energy interval
where no transmission is allowed (Fig. 4a), while the gap
of the 17-aGNR is reduced to less than 0.2 eV (Fig. 4b). The
region of zero conductance is also reduced accordingly, and a
very small external electric eld could induce an electronic
transmission through one channel (1G0 : quantum value of
conductance).
Similarly, Z-GNRs also exhibit direct band gaps which
decrease when increasing their width. However, in Z-GNRs,
quantum transport is dominated by edge states which are
expected to be spin-polarized owing to their high degeneracy. Indeed, due to topological reasons, zigzag-shaped

357
edges give rise to specic extended electronic states which
decay exponentially inside the graphene sheet [66]. The
ground state of Z-GNRs with hydrogen passivated zigzag
edges exhibit nite magnetic moments on each edge with
negligible change in atomic structure [83], thus demonstrating that Z-GNRs possess half-metallic (i.e., exhibit a band
gap for only one kind of spin) properties and suggesting them
to be attractive for spintronic applications [84]. Indeed,
upon inclusion of the spin degrees of freedom within ab initio calculations (LSDA), Z-GNRs are predicted to exhibit a
magnetic insulating ground state with ferromagnetic ordering at each zigzag edge, and anti-parallel spin orientation
between the two edges [83]. The total energy difference
between ferromagnetic () and antiferromagnetic ()
couplings between the edges is of the order of 20 meV
per edge atom for an 8-Z-GNR. However, such energy difference decreases as the width of the ribbon increases and
eventually becomes negligible if this width is signicantly
larger than the decay length of the spin-polarized edge
states [85]. Because the interaction between spins on opposite edges increases when decreasing their width, the total
energy of an N-Z-GNR with antiferromagnetic arrangement
across opposite edges is always lower than that of a ferromagnetic arrangement for low value of N (N < 30). The
spin-dependent calculations of quantum conductances of an
8-Z-GNR are illustrated in Fig. 4c and d for the two magnetic
congurations ( and ) of the ribbon edges. The spin
conguration of the 8-Z-GNR preserves the semiconducting
behavior of the GNR family, and its electronic transmission
function displays a gap of 0.5 eV around the Fermi energy
(Fig. 4c). On the contrary, in the spin conguration, the
8-Z-GNR becomes metallic, inducing a non-zero electronic
transmission function at the Fermi energy (Fig. 4d). In addition, the spin-dependent conductance calculation reveals
that the transmission of electrons with one type of spin
orientation (majority-spin) is favored for an energy region
around 0.5 eV, below the charge neutrality point. On the
contrary, * electrons with the other orientation (minority-

Figure 4 Quantum transport in graphene nanoribbons. Atomic structures and electronic transmission of (a) 16-armchair GNR; (b)
17-armchair GNR, 8-zigzag GNR with (c) anti-parallel or (d) parallel spin orientations between the two magnetic edges. The
spin-dependent transport is evaluated for both magnetic congurations of the 8-zGNR (c and d) but is only visible for the parallel
spin orientations (ferromagnetic one). In such case, one spin orientation is labeled majority-spin (in black) while the other is
labeled minority-spin (in red). Adapted from Ref. [82].

358
spin) are more easily transmitted around +0.3 eV above the
Fermi energy.
In conclusion, the unusual electronic and transport properties of GNRs indicate that these carbon nanomaterials
could be excellent new building blocks in future carbonbased nanoelectronics, thus opening alternatives to the
current silicon-based electronics, through the use of new
variable states (e.g. quantum states, spin, etc.).

Synthesis of graphitic and graphene

nanoribbons
There is a wide spectrum of methods available to produce
carbon nanoribbons, from CVD, through chemical treatments of graphite to the unzipping of carbon nanotubes.

Chemical vapor deposition of graphitic nanoribbons

GNRs were rst reported in 1990 by Murayama and Maeda
[86], from hydrocarbon decomposition or disproportionation
of carbon monoxide at 400700 C, catalyzed by metal particles generated from Fe(CO)5 , in owing CO/H2 gas. The

M. Terrones et al.
typical ribbon-like laments were 10 m long, 0.10.7 m
wide and 10200 nm thick, with a catalyst particle at one
end (Fig. 5a and b), and graphitic layers with a uniform
orientation perpendicular to the lament axis. Annealing
treatments at 2800 C resulted in loop formation at the open
edges of graphitic layers. Recent works have conrmed that
loop formation between adjacent sheets is a more stable
conguration after annealing treatments on graphitic nanostructures at temperatures >1500 C [87,42].
Another CVD production method of graphitic nanoribbons
was reported by Campos-Delgado et al. in 2008 (Fig. 5c and
d) [88]. In this work a spray (atomized droplets) of ferrocene
in ethanol, with thiophene, carried by Ar to a furnace at
950 C, produced rippled nanoribbons, several micrometers
long, 20300 nm wide and <15 nm thick. The highly crystalline material had the (0 0 2) planes parallel to the main
ribbon axis. Catalytic particles were not found but ribbons
did not form if ferrocene or thiophene were not used.
Therefore, further studies aiming at understanding their
growth should be carried out. High temperature treatments
of such nanoribbons improve the degree of crystallinity and
promote loop formation at the edges of the graphitic layers
[87]. Interestingly, electron beam irradiation combined with

Figure 5 CVD and other production methods of graphitic nanoribbons. (a and b) Scanning electron micrographs of Murayamas
lamentous graphite, showing Fe particles at the ends of the structures [86]; (c and d) SEM images of the graphitic nanoribbons
produced by pyrolysis of ethanolferrocenethiophene solutions [88]; (e) SEM image of the nanoribbons produced by pyrolysis of
THF and ferrocene solutions [89], (f) low magnication TEM image of the nanoribbons produced by the ZnS template method [94],
(g) AFM image of the nanoribbons obtained through high temperature treatments of diamond nanoparticles [24], (h) 3D STM image
of an 8-nm-wide graphene nanoribbon patterned by STM lithography [95], (i) AFM image of chemically derived nanoribbons from
graphite (scale bars = 100 nm) [71], (j and k) TEM images of an amorphous carbon nanoribbon and graphitic nanobelt, respectively,
produced by hydrothermal processes [97,98], (l) scheme illustrating the structure of a collapsed nanotube [99103].

Graphene and graphite nanoribbons

Joule heating experiments inside a HRTEM, resulted in the
generation of sharp zigzag and armchair edges (Fig. 3) [64].
This demonstrates that the most stable edges in graphene
ribbons are indeed either zigzag or armchair (Fig. 3).
In 2008, Subramanyam, and coworkers reported that
pyrolsis of ferrocene and tetrahydrofuran (THF) at 950 C
produced a mixture of crystalline carbon nanoribbons and
iron lled MWCNTs (Fig. 5e) [89]. The authors neither specify
the relative yield nor the typical dimensions of the produced
nanoribbons. By observation of the published images, we
estimated them to be 200 nm in width and tens of microns
in length. The crystalline nature of the nanoribbons was
conrmed through X-ray powder diffraction, and TEM, with
the orientation of the (0 0 2) lattice planes of carbon being
perpendicular to the axis of growth.

Chemical vapor deposition of graphene

The precipitation of graphene on metals has been reported
by different research groups for over 30 years [90]. More
recently, this method has been applied to obtain and
study the properties of graphene and few-layer graphene
[2426].
In 2008 Sutter et al. [91] reported the epitaxial precipitation of graphene on Ru(1 1 1) in 2008. In 2009, Rouff et al.
[92] reported the large area synthesis of graphene sheets on
Cu foil. This article included the development of a transfer
technique that could be used to place the grown graphene
on another substrate. The transfer process involved the
dissolution of the metal foil assisted by an iron nitrate
solution.
Reina et al. [26] reported the growth of few-layer
graphene on Ni lms, by CVD at atmospheric pressure. After
some months the same group induced graphene precipitation on annealed polycrystalline Ni surfaces [93]. Large
area, single and bilayer graphene sheets were obtained by
this method, in which CH4 was pyrolyzed at 1000 C. Subsequently, poly(methyl methacrylate) (PMMA) was spin coated
on the synthesized graphene surfaces and a wet-etching
treatment with HCl dissolved the metal [93]. PMMA served
as a support for the free standing graphene sheets that could
be placed on different substrates, such as microscopy slides
or TEM grids [93].
Yu et al. reported the CVD synthesis of few-layer
graphene ribbons using ZnS substrates as templates (Fig. 5f)
[94]. Decomposition of CH4 at 750 C on ZnS templates and
further acid treatments to dissolve the ZnS ribbons produced
few-layer graphene nanoribbons (FLGNRs) of 3.4 nm in
thickness, 0.55 m in width and several microns in length.
The authors claim to be able to control the morphologies of
the produced FLGNRs but no details are provided about the
edge structure of the nanoribbons.

Chemical synthesis of graphitic nanoribbons

As discussed above, Affoune, et al. were able to obtain
graphene by an electrophoretic deposition of diamond
nanoparticles on a HOPG substrate followed by heat treatment [24]. Here the diamond nanoparticles were graphitized
into layers forming sheets. Three years later, Canc
ado, et
al. were able to use the same method to produce graphene

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edges and nanoribbons (Fig. 5g). These edges were characterized by Raman spectroscopy [95].
Alternative chemical routes consisting on the exfoliation of commercial expandable graphite, have been more
recently used to produce graphene nanoribbons (Fig. 5i)
[71]. In particular, the process consisted on exfoliation of 3D
graphite by annealing at 1000 C followed by 30 min sonication in a solution of dichloroethane and a polymer. After centrifugation of the suspension, GNRs remained in the supernatant. The shape and electrical properties of these GNR
were thoroughly examined, and FET devices were created.
Small GNRs could also be synthesized by organic chemistry approaches linking tetra- and hexa-phenylbenzenes
through the SuzukiMiyaura reaction [96]. The polyphenylene formed is then subjected to a cyclodehydrogenation
reaction with FeCl3 as the oxidant, resulting in ribbons with
612 polycyclic aromatic repeating units. These GNR are
highly soluble in common organic solvents due to the introduction of branched alkyl side chains. The lengths of these
2D-GNR were found to be 812 nm, and they can form
aligned monolayers, as well as crystallize from solution by
stacking. This report is a true bottom-up approach to
thin and short graphene nanoribbons with armchair edges.
It remains to be seen whether these or similar chemical
reactions can create wider and/or longer GNR or even be
harnessed to create branched GNR.
Amorphous carbon ribbons and crystalline graphitic
ribbons have also been produced via a hydrothermal process involving Teon-lined autoclaves. In order to produce
amorphous carbon nanoribbons, benzene, sodium and ferrocene were kept in the reactor at 210 C for 24 h (Fig. 5j)
[97]. The crystalline ribbon structures were synthesized
using active carbon and polyoxometalates at 160180 C
for 72 h (Fig. 5k) [98]. Finally, it could also be possible to
produce graphene or graphitic nanoribbons by collapsing
large diameter carbon nanotubes (Fig. 5l) [99103]. This
way, transport could occur along the coalesced edges,
and further experimental studies are required in order to
understand the role of the large curvature imposed by the
merging of adjacent edges, the reactivity of such highly
deformed sp2 hybridization states, as well as the effects of
the chirality on the sealed edges.

Graphitic nanoribbons from nanotubes

Carbon nanotubes are often described as rolled up graphene
sheets; therefore, it would seem natural to unroll them to
obtain graphene (Fig. 6). Yet it was not until 2009 that the
rst method to obtain graphitic nanoribbons from nanotubes
appeared published [104]. Two more works related to the
unzipping of nanotubes appeared 2 weeks later [105,106]. A
fourth method, rst suggested by Terrones [107] involved
the use of metal catalytic particles as nanoscissors, was
successfully proved [108], and early this year, it was also
demonstrated that nanotubes could be easily unzipped by
passing high electrical current inside the microscope [109].
These different methods to unroll or unzip nanotubes are
depicted in Fig. 6.
One of the methods, shown in Fig. 6a, relies on the intercalation of lithium in liquid ammonia, followed by acid and
thermal exfoliation treatments (Fig. 7). The resulting mate-

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Figure 6 Sketch showing the different ways nanotubes could be unzipped to yield graphene nanoribbons (GNRs): (a)
intercalationexfoliation of MWCNTs, involving treatments in liquid NH3 and Li, and subsequent exfoliation using HCl and heat
treatments [104]; (b) chemical route, involving acid reactions that start to break carbon-carbon bonds (e.g. H2 SO4 and KMnO4 as
oxidizing agents) [105]; (c) catalytic approach, in which metal nanoparticles cut the nanotube longitudinally like a pair of scissors [107,108], (d) the electrical method, by passing an electric current through a nanotube [109], and (e) physicochemical method
by embedding the tubes in a polymer matrix followed by Ar plasma treatment [106]. The resulting structures are either GNRs or
graphene sheets (f).

Figure 7 Schematics and representative images of the lithium-ammonia intercalation and exfoliation procedure to obtain nanoribbons from nanotubes. The process starts with cut MWCNT, open ends (and wall defects) allow intercalation of Li ions and NH3 (a) in
the negatively charged nanotubes. The intercalants push the walls to twice the interlayer distance of MWCNT initiating the fracture
of nanotube walls (b). After acid and thermal treatments the exfoliation is complete and GNRs (ex-MWCNT) result (c). A HRTEM
image (d) shows a partly opened GNR, a close up on the cleaved part (e) shows that after the process the graphitic layers can
rearrange and recrystallize. The GNRs can comprise several layers of different thicknesses (f, g) The rearrangement to a graphitic
order is conrmed by the hexagonal pattern of the Fast Fourier Transform (inset in g).

Graphene and graphite nanoribbons

rial (ex-MWCNTs) contains up to 60% nanoribbons, with
the rest partly opened (unzipped in parts) and damaged
(sides and tips exfoliated but not unzipped) MWCNT, and
graphene akes peeled off the tube walls [104]. This mixture of products is partly due to the need to cut MWCNT
to facilitate unzipping, as MWCNT longer than 2 m rarely
unzip fully lengthwise. Further improvements are needed to
obtain full unzipping, and could lead to nanoribbons of relatively controlled dimensions dependent on the tubes that
are unwrapped. The current mixture of by-products limits the applications of such materials (e.g. for electronic
devices) unless separation and sorting methods could be
devised. However, we should note that partially unzipped
ex-MWCNTs could be of interest for composites (with the
unwrapped edges interfacing to a matrix) and could also
have interesting properties for nanoelectronics [110].
The group of James Tour [105] reported an oxidation
method where MWCNTs are rst opened due to permanganate oxidation, leading to unzipping nanotubes along their
axis (Fig. 6b). The amount of oxidant used determines the
degree of MWCNTs opening, but high efciency and high
yields (both nearing 100%) are reported. The nanoribbons
obtained have oxidized edges, making them highly soluble
in polar solvents. These ribbons can be reduced by hydrazine
in order to remove the oxygen functional groups, thus restoring their good electrical conductivity. This method can also
be applied to SWCNTs producing highly entangled and randomly stacked graphene sheets and ribbons. Although, it
was believed that this route resulted in highly defective
nanoribbons with relatively low electrical transport properties, Tours group has now demonstrated that it is indeed
possible to obtain highly crystalline graphene nanoribbons
exhibiting extremely high electrical conductivities, which
could be used in the fabrication of eld effect transistors and
other devices. The method involves an efcient chemical
oxidation at 60 C, in the presence of a second acid (C2 HF3 O2
or H3 PO4 ) besides the H2 SO4 KMnO4 mixture [111]. More
recently and along this direction, Dai and coworkers have
reported an alternative chemical method for unzipping carbon nanotubes by treating MWCNTs in air at 500 C followed
by the sonication of the resulting material in a DCE-PmPV
solution [112]. These authors report that: (1) the ribbon
material results in a high yield of unzipped tubes (e.g. 60%);
(2) the edges of the unzipped tubes (or ribbons) appear to be
smooth (although additional studies are needed in this direction); (3) the produced GNRs exhibit high conductance, low
resistance and phase coherent transport and (4) the GNRs
usually exhibit thicknesses of 2 or 3 layers.
The catalytic cutting method is attractive due to its simplicity (Fig. 6c), when compared to other chemical methods.
Nevertheless, the actual amount of nanoribbons produced
by this method (Fig. 8) is still very low (approximately 5% of
the original CNT sample). Previous reports [113115] have
shown that the catalytic metal particle (Co or Ni) can cut
graphene layers only along armchair or zigzag atomic lines
(Fig. 8a). Metal nanoparticles are deposited on the surface
of MWCNTs (via magnetron sputtering or chemically), and
these coated tubes are subsequently placed on Si wafers
and treated at 850 C, under a low ow of H2 Ar (Fig. 8a).
The unzipping mechanism is based on the metal catalyst
dissociating carbon bonds, and such carbon atoms reacting
with H2 to form methane (CH4 ) [116] (see Fig. 8a). The sam-

361
ples revealed that the tubes were either cut, partially open,
or open along the axis (Fig. 8b-e). Larger metal nanoparticles (ca. 40 nm) traveled along the axis of some carbon
nanotubes, performing deeper cuts that opened longitudinally MWCNTs and N-doped MWCNTs (Fig. 8c and d) [108].
A similar route to unzip the tubes occurs by thermal treatment of nanotubes, encapsulating Fe nanoparticles, for 26 h
at 1100 C under an Ar atmosphere (Fig. 8e). It appears
that at 1100 C, the encapsulated Fe nanoparticles start to
react with the surrounding carbon atoms, causing their dissociation and the breakage of the tube compartments. The
nanoribbons produced in this way are typically 1540 nm
wide and 100500 nm long. It is noteworthy that partially
open MWCNTs have been predicted to exhibit a large magnetoresistance effect at low magnetic elds [110].
An alternative method consists in applying an electric
current through a nanotube inside a microscope (Fig. 6d)
[109]. Unfortunately, this method is only able to yield very
low amount of unzipped nanotubes. However, experiments
involving the passage of high currents through bulk nanotube
samples should be tested and evaluated.
Another physicochemical method was also developed by
Dais group in 2009 [106]. MWCNTs are embedded in a
poly(methyl metaacrylate) lm, then turned over to expose
the MWCNT walls which are etched away by an Ar plasma
(Fig. 6e). The etching time determines whether singleor few-layered graphene nanoribbons are obtained. The
method is much more laborious and yield is relatively low,
ca. 20% with some MWCNT remaining, but these nanoribbons
are more uniform in shape than those from other unzipping methods. It should be noted that partial opening of
MWCNT by plasma etching had been reported as early as
2004 [117]. Here, the opened portions were compared to
wings, however the open ribbon-like segments were not
longer than a few tens of a nanometer, and the process was
neither controlled nor further developed.
The physical transformation of MWCNTs into nanoribbons is also possible, with the use of high pressure, though
in many studies the target was to obtain diamond crystals. M. Zhang et al., reported that CVD grown MWCNTs
annealed at high temperatures (9501200 C) under 5.5 GPa
for 25 min, produce ribbon-like and onion-like graphitic
structures [118], and higher temperatures favor ribbons
(possibly collapsed nanotubes) over onions. Later on, the
transformation of SWCNT bundles into nanoribbons has been
reported [101] at high temperatures in vacuum. SWCNTs rst
coalesce into larger diameter SWCNTs or MWCNTs (from 1400
to 1600 C). Such large diameter nanotubes collapse when
the temperature is further increased at (ca. 1800 C) in two
types of GNRs, which can be differentiated by the shape of
their closed ends.
Most of the methods mentioned above could produce very
well dened and relatively crystalline nanoribbons, provided
that the starting material is crystalline, uniform in length,
diameter and number of layers. For some applications where
edge uniformity is not necessary (e.g. composites), the production of kilogram amounts could be more relevant; two
of the methods above appear easy to scale up. The catalytic cutting method is scalable, in principle, if large scale
controlled deposition of nanoparticles over MWCNT can be
achieved. The etching method does not seem amenable to
scale up so easily as the others, but since it uses techniques

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Figure 8 (a) Sketch depicting the carbon dissociation process occurring on the surface of metal nanoparticles (Co or Ni) at
high temperature, and the subsequent formation of CH4 ; (b) SEM micrograph of a graphitic nanoribbon as a result of the cutting
experiments of MWCNTs with Co nanoparticles; (c) and (d) SEM images of N-doped MWCNTs, after hydrogenation of carbon performed
with Ni sputtered catalyst nanoparticles [108], and (e) SEM image of an unzipped tube by the thermal treatment of nanotubes
encapsulating Fe nanoparticles for 26 h at 1100 C under an Ar atmosphere.

known in the semiconductor chip industry, it shows potential

for integration in electronic devices. The chemical methods offer the possibility to control the lengths and widths
of the resulting nanoribbons. However, challenges remain in
controlling the nanotube opening processes, whether this
occurs by exfoliation, etching, reduction or oxidation. In
addition to challenges in controlling the opening of MWCNTs, a scalable process would have to provide conditions
that prevent the agglomeration, wrinkling, and entangle-

ment of the produced nanoribbons which are caused by van

der Waals forces.

Other methods to produce graphene nanoribbons

Another widely used method to produce nanoribbons with
very well dened crystallographic edges is by scanning tunneling lithography (STL). This technique consists on etching

Graphene and graphite nanoribbons

carbon atoms using a scanning tunneling microscope (STM)
tip relatively far from the sample. This approach takes
advantage of a reaction involving the local decomposition
of water molecules due to the electron ux between the tip
and the sample under a negative bias. Upon the dissociation of water molecules, the carbon atoms at the surface
react with oxygen to form carbon monoxide, and are etched
away atom by atom [119]. Of course, such an atomic precision comes with a cost: unpractical production and a limited
amount of ribbons using this method.
Micromechanical cleavage of graphene akes has also
been used to produce GNRs [120]. This technique uses a
poly(dimethylsiloxane) (PDMS) stamp to remove graphite
akes off HOPG, and deposit them over an insulating surface. A second stamp then removes most of the graphite
akes and cleaves further the ones that remain on the surface. This produces a haphazard assortment of GNRs with
widths ranging from 1 nm to a few m and assorted lengths;
most of them extending from a mother ake, and many of
them with heights corresponding to a graphene monolayer.
Although this does not seem a method for controlled and
large scale production of GNRs, it provides a simple route
to measure the electrical properties of assorted lengths and
widths of GNRs. In this case the authors used conductance
AFM for I-V measurements showing that the GNR behaved as
semiconductors.
Electron irradiation at accelerating voltages >90 keV, is
known to induce rearrangement of carbon atoms [121,122],
which can lead to novel ordered structures. Such approach
was used to locally transform electrospun poly(methyl
methacrylate) (PMMA) nanobers into graphene nanoribbons
inside a HRTEM [123]. The graphene sheets align parallel to
the e-beam, and once a nanoribbon is formed, further irradiation could reduce its thickness; suggesting the possibility of
controlling the number of layers. The method however, does
not produce crystalline arrangements at the junctions when
crossed nanobers are irradiated. These authors suggest
that the same transformation might be possible with e-beam
lithography, this however has not been proved and ne control over shape, size and edge structure of the graphene
sheets appears to be difcult. [119,124,125].
Since most of these graphene nanoribbons could be
homogenously dispersed in suspensions, different chemical
reactions could be carried out and their use as drug deliverers, sensors and even composite fabrications could be
tested and improved. All these potential applications are
noteworthy besides the use of nanoribbons in nanoelectronic
devices, as demonstrated above. In addition, these ribbon
materials should now be tested in different toxicity assays.

Defects in graphene and graphitic nanoribbons

Defects play a crucial role in the properties of crystals and
nanostructures, including graphitic systems. Graphene-like
systems are so versatile that they can accommodate different kinds of defects that change completely their structure
and also their physicochemical properties. In particular,
defects which change the structure could also change the
topology or the curvature. However, it is difcult to identify
accurately and quantitatively the type of defects contained
in graphene-like materials, and researchers have not been

363
able to distinguish them systematically. Depending on the
nature of the defective surface, the chemical activity of
graphene may be quite different. For instance, the inclusion of twelve pentagons in a graphitic cluster can form
a Fullerene and thus, the planar cluster becomes round
with no boundaries. Such a spherical structure exhibits
an electronegative surface which results in a very rich
chemistry [4]. Similarly, the presence of heptagons and
octagons could produce Schwarzite-like materials or nanotube networks with micropores where reactions can take
place [33]. The inclusion of vacancies also alters the physicochemical properties of the graphitic systems producing
antidot systems [126]. For graphitic nanoribbons, the
most common defects are: vacancies, heptagon-pentagon
pairs (StoneThrowerWales type transformations, see
below), loops and interstitials. While heptagonpentagon
pairs and loops preserve the connectivity of the nanoribbon,
the interstitials and vacancies do not. Certainly, a challenge
for the future will be the use of defects to design new
graphitic nanoribbons with specicity for sensing different
kinds of molecules or to anchor specic polymer chains in
order to produce stable and well dispersed composites.
In general, defects within graphene-like structures could
be categorized in ve different groups (Fig. 9):
(1) Structural defects, related to imperfections that significantly distort the curvature of the hexagonal carbon
lattice. These defects are usually caused by the presence of non-hexagonal rings (e.g. pentagons, heptagons,
or octagons) surrounded by hexagonal rings. For example if a single or a few pentagons are embedded into the
graphene lattice, nanocones with different apex angles
are obtained (Fig. 9a). A 30 angle in a SWCNT, could also
be explained by the presence of pentagon on one side of
the tube and a heptagon on the opposite side. The reactivity of pentagons, heptagons or octagons with specic
acceptor or donor molecules has still to be determined
from the theoretical and experimental stand points.
(2) Bond rotations or grain boundaries, occurring on
graphene surfaces, which do not result in large curvature distortions of the sheet (Fig. 9b). In particular,
these defects could be 5-7-7-5 pairs embedded in
the hexagonal network or StoneThrowerWales (STWtype) defects [127,128] that could be created by
rotating a carboncarbon bond 90 within four neighbouring hexagons, thus resulting in the transformation
of two pentagons and two heptagons [129,130]. 2D
planar graphene-like systems containing pentagons,
hexagons and heptagons, called Haeckelites, have been
proposed and found to be metallic in theoretical studies
[23]. Nanoribbons constructed from Haeckelites could
be considered as new hypothetical nano-architectures
with fascinating properties that could be applied in electronics. Isolated pentagon-heptagon pairs could also be
introduced to form a grain boundary in graphene [128]
or in a graphitic nanoribbon, thus changing their edge
termination and electronic properties, forming a hybrid
graphitic nanoribbon (Fig. 10). These particular hybrid
nanoribbons exhibit half metallicity in the absence of
an electric eld (Fig. 10b), and could be used to transport electrons with one type of spin; which could be a
step forward in new spintronic devices [131]. It is note-

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M. Terrones et al.

Figure 9 Schematic models representing different types of defects in graphene-like materials. (a) Structural defects induce
signicant structural changes caused by the presence of pentagons or heptagons within the hexagonal sp2 hybridized carbon lattice
(Image of cones courtesy of M. Endo and T.W. Ebbesen); (b) Topological defects, also termed Stone-Thrower-Wales defects, do
not result in big structural changes. Shown here is the formation of 5-7-7-5 pairs created by rotating an individual carbon-carbon
bond 90 ; (c) Doping consists of replacing a carbon atom with another element within the hexagonal lattice (here, N and P) or
a CNT randomly doped with B and N; (d) Non-sp2 hybridized carbon defects, including vacancies, edges, adatoms, interstitials,
carbon chains, etc.; (e) Folding-induced defects, which result from signicant deformation of the graphene sheet, thus altering
the orbitals. The direction of the orbital is then called the orbital axis vector (POAV). The angle  between the POAV and
a direction (i.e., a bond) indicates the degree of pyramidalization and the hybridization. For  = 90 (planar system), the
orbitals are in a sp2 hybridization and the orbital is a pure pz orbital. For a folded graphene sheet,  has an intermediate value
which decreases as the inverse of the radius of the curvature of the folding, and reaches 90 at the limit R .

worthy that the electronic and chemical properties of

these 5-7 or 5-7-7-5 pairs (Fig. 10c) are different from
the structural defects (see above) and their reactivity and detection needs to be investigated theoretically
and experimentally. Recently, Zettl and coworkers were
able to observe directly 5-7 and STW defects on isolated
graphene surfaces using aberration corrected transmission electron microscopy (Fig. 10d, also see movies from
supplementary material of [65]).
(3) Doping-induced defects, arising from substitutional
non-carbon atoms embedded in the graphitic lattice
(Fig. 9c). In this case, it has been demonstrated that
nitrogen and boron atoms can be introduced into the
hexagonal sp2 hybridized carbon lattice. With both
dopants, the chemical reactivity of the graphene surface increases, in one case due to the fact that N
has one electron more than C, in the other because
B has one electron less than C. Therefore, these type
of defects could be used to tune the type of conduction in graphene-like materials, ranging from n-type
transport (substitutional nitrogen doping) to p-type conduction (substitutional boron atoms in the lattice) [132].
Recent studies have demonstrated that other elements
such as P, S, Si and paired dopants such as P-N could

also be introduced in the hexagonal lattice of carbon

tubules [133135,38,136]. Therefore, the insertion of
non-carbon atoms in graphene-like materials could tailor the chemical reactivity and electronic transport of
the layers and further work along this research line
needs to be carried out [136].
(4) Non-sp2 carbon defects caused by the presence of highly
reactive carbons such as dangling bonds, carbon chains,
interstitials (free atoms trapped between SWCNTs or
between graphene sheets), edges (open nanotubes),
adatoms and vacancies (Fig. 9d). These defects are usually observed in a HRTEM, when the adsorbed atoms
on these reactive sites are removed by the electron
beam energy. It has been demonstrated that the creation of such defects could promote the formation of
covalent nanotube junctions [137] and trigger the coalescence of nanotubes [138]. However, for nanoribbons,
the dynamics of these defects has not been investigated
and further research is required in this direction.
(5) High-strain folding of graphene sheets (loop formation), which can be induced by annealing two adjacent
graphene layers (Fig. 9e). These types of loops have
often been observed in thermal annealing occurring
at above 1500 C [42,86,87,139], but their chemical

Graphene and graphite nanoribbons

365

Figure 10 (a) Molecular model of a hybrid structure with zigzag leads connected by 5-7 chains to an armchair segment with NA = 5
(Z-5-Z hybrid structure); (b) Molecular model of ordered arrays of pentagon-heptagon defects on a hybrid-graphene nanoribbon
[131]; (c) Molecular model showing the transformation of 4 adjacent hexagons into a 5-7-7-5 defect or Stone-Thrower-Wales defect,
and (d) HRTEM images showing two 5-7-7-5 defects located on the edges (red circles) of a hole in a graphene surface (images taken
from movies from supplementary material of Ref. [65]).

reactivity and electronic properties have not been

investigated in detail. In fullerene (or carbon cage)
chemistry, the main type of defect is structural, which
deals with the presence of pentagonal rings that induce
a highly curved and reactive molecule caused by the
mixture of and orbitals. In nanotube chemistry,
these structural defects mainly occur on the caps (where
pentagons are located). Narrow or highly curved nanotubes (usually <1 nm diameter) would also be more
reactive. In highly crystalline SWCNT samples, the caps
are a small portion of the structure and other highly
curved areas are not present since the nanotubes usually
have diameters larger than 1 nm. Therefore, graphene
and nanotube chemistry require a better understanding
of the defects mentioned above, in order to induce and
control strong (or weaker) covalent (or ) interactions with other molecules, atoms, or clusters.
It should be noted that buckling and folding can be
induced deliberately in graphene. Bao et al. have reported
controlled rippling of suspended graphene sheets [140]. Li et
al. [141] have also reported deliberate formation of ripples
in graphene akes deposited over polymethylmetacrylate
(PMMA), by heating above the glass transition temperature of PMMA, upon rapid cooling the polymer shrinks
more than the graphene, and the stresses lead to periodic sinusoidal (lambda = 550 nm) buckles in the edges of
graphene sheets. Raman spectroscopy shows a blue shift
consistent with a compressive stress on the graphene sheet.
The authors also report that this process can lead to folding of graphene akes into few-layer graphene but this

does not seem to be a controlled process. Other processing

approaches are likely to appear in the literature extending the possibility of controlling folding and buckling of
GNRs.

Doped graphitic nanoribbons

Doping of graphene and graphene nanoribbons is relevant
because, depending on the location of the dopants and their
concentration, their physicochemical properties could be
tuned and controlled. In this context, Cervantes-Sodi, et
al. [142] reported theoretical studies related to the doping of graphene nanoribbons with N, B and O atoms. They
noted that when doping nanoribbons, edge-type and substitutional doping induce different electronic properties to
the systems and, in some cases, half-metallic behavior. The
band gap could be tuned by doping and when zigzag ribbons
possessed substitutional nitrogen at 1.7 at%, the ribbons
were metallic. Similar studies have reported the effects of
N doping in zigzag nanoribbons [143]. Roche and coworkers predicted the electronic transport of nanoribbons with
different concentration of dopants, and observed that different materials exhibiting different band gaps could be
obtained [144]. Therefore, the doped-graphene nanoribbons
appear to be excellent candidates in the design of novel
electronic devices and transistors and further theoretical
and experimental work are needed; the study of their chemical activity also needs to be carried out.
Experimentally, a N-doped-graphene-like structure has
been realized using a CVD process which generated both
edge-type and substitutional N doping [145]. These authors

366
found that the doped-graphene-like material exhibited an ntype semiconducting behavior, and contained between 2 and
6 layers with a variable N concentration (i.e., 1.28.9 at%),
depending on the NH3 ow rate used in the CVD process.
Subsequently, Dais group successfully produced graphene
nanoribbons doped with nitrogen via joule heating in the
presence of NH3 [146]. The process produced edge-type and
substitutional nitrogen doping, and NH2 groups attached
to the ribbon edges. They also found theoretically that the
presence of C O bonds on edges resulted on p-doped GNRs.
Finally, N-doped graphic nanoribbons have been produced by
unzipping CNx MWNTs via their catalytic hydrogenation [108].
Although the literature regarding doped-graphene
nanoribbons is very scarce, it is clear that doping appears
to be a reliable way to control the electronic and chemical
properties of the ribbons, and further work should focus on
this direction. In this context, doping experiments with B, P
and Si could also lead to novel graphene-like materials and
novel unzipping methods of already available doped-carbon
nanotubes (e.g. Cx By -MWNTs, Cx Siy -MWNTs, Cx Py Nz -MWNTs,
etc.) should be explored.

Characterization of graphene materials by

Raman spectroscopy and other techniques
In the early days of the study of graphene, with the use of
the optical microscope, the identication of graphene akes
was a simple but tedious task. Quantifying the number of
layers implied the use of time consuming techniques (AFM,
TEM) and required prior sample preparation. However, in
2006, Ferrari et al. reported the Raman spectra of single-,
double- and few-layer graphene produced with Novoselovs
scotch-tape technique [147]. Clear signals specic for
each single-, double and few (<5) layer graphene were identied. Therefore, Raman spectroscopy has become a very
useful technique for the characterization of graphene and
GNRs.
Raman spectroscopy stands as a powerful characterization technique of all types of carbon nanostructures.
The most prominent features in the Raman spectra of sp2
hybridized carbon materials are the G-band appearing at
ca.1580 cm1 and the G -band at ca. 2700 cm1 for a laser
excitation energy of 2.41 eV. When carbon materials have a
certain amount of disorder or edges within the structure,
a disorder-induced band appears, the so-called D-band, at
ca.1350 cm1 . The G-band is associated with the doubly
degenerate (iTO and LO) phonon mode (E2g symmetry) at
the Brillouin zone center. On the other hand, the G - and
the D-bands originate from second-order processes, involving two iTO phonons near the K point for the G -band or one
iTO phonon and one defect for the D-band [148].
In Ferraris report, the G -band was shown to have a
different peak shape for single-, double- and few-layer
graphene; it is worth mentioning that the studied graphene
akes were exfoliated from highly oriented pyrolytic
graphite (HOPG), having thus a well achieved AB Bernal
stacking [147]. The G -band of single-layer graphene, measured with a laser energy of 2.41 eV, exhibits a single
excitation at 2700 cm1 with a FWHM of 24 cm1 . In addition, the relative intensity of the G -band is larger than
that of the G-band. The G -band of double-layer graphene

M. Terrones et al.
exhibits four excitations, whereas the spectra of ve layers and more are hardly distinguishable from that of bulk
graphite. Subsequent works allowed the identication of the
number of layers (1, 2, 3 and 4) by Raman spectroscopy
using the G -band. For turbostratic or misoriented double
or few-layer graphene, where the stacking of the graphene
sheets is rotationally random with respect to one another
along the c axis, the Raman G band appears as a single
Lorentzian, very similar to that of single-layer graphene but
with a larger line width [26,148,149]. Thus, when a graphene
sample is produced with other methods than the micromechanical exfoliation of HOPG and the interlayer interaction
is absent or not very strong, the G Raman band cannot be
used as a direct identication tool to quantify the number
of layers.
It is noteworthy that imperfections in the graphene
lattice such as dopants could introduce new features in
the G -band. In this context, the presence of a defectinduced feature (G Def band) in the immediate-vicinity of the
second-order G Pris band (located at 26002700 cm1 for
Elaser = 2.41 eV or  = 514 nm) has provided valuable information about charged defects present in single-walled carbon
nanotubes (Fig. 11) [136]. In addition, it has been demonstrated that for doped nanotubes, the relative intensity of
the G Def is proportional to the amount of dopants in the
tube material. Similarly, the effect of doping graphitic systems either electrochemically or by an electric eld can
be observed by Raman spectroscopy. Due to renormalization of the phonon energies and the resultant change on the
effective force constants of atomic vibrations, there is an
increase of the frequency and a decrease of the line width
of the G-band in monolayer graphene [150]. For the case of
bilayer graphene, a split of the G-band occurs at negative
gate voltages [151]. All these observations demonstrate that
Raman spectroscopy could be very useful in determining the
type of doping in nanoribbons but extensive work needs to
be done in this direction.

Figure 11 The G -band Raman band of different sp2

hybridized carbon materials (nanotubes) measured at room
temperature with Elaser = 2.41 eV (514 nm). The arrows point to
defect-induced peaks in the G for doped SWCNTs (G Def ). The
p/n doping signal arises from substitutional boron or nitrogen
atoms, the nearest neighbours of carbon in the periodic table.
The spectra of graphene and SWCNTs (G Pris ) is shown for comparison (data provided by I.O. Maciel) [136].

Graphene and graphite nanoribbons

367

Figure 12 (a) Simulated high-resolution electron microscopy image of a graphene-like nanostructure with a grain boundary formed
by pentagons and heptagons where the edges of the sheet change from armchair to zigzag. The inset shows a simulated diffraction
pattern showing twelve spots characteristic of armchair and zigzag features in the same structure. (b) Simulated STM image of the
same system illustrating a lack of one to one correspondence between the image and the structure.

Under the right conditions, electron diffraction could be

used to obtain information from graphene-like structures.
In addition, it is possible to simulate images and electron
diffraction patterns using the coordinates of the nanostructure (for example with SimulaTem [152]), and then compare
them with the experimental diffraction patterns and highresolution images. In Fig. 12a a simulated HRTEM image and
its corresponding diffraction pattern of a graphene piece
with a grain boundary formed by 57 defects is shown. It is
therefore clear that defects on graphene surfaces could be
identied by electron diffraction.
Scanning tunneling microscopy (STM) and spectroscopy
(STS) could be powerful tools to identify and obtain electronic information about defects in graphene surfaces and
nanoribbons. These characterization techniques can give
very valuable information on both the structure of the
graphene or GNR surface, and on its electronic structure
close to the Fermi level. However, the interpretation of
such images can be difcult, and thus simulation of such
images is often very helpful (Fig. 12b). Very recently, Batzill
and coworkers identied the presence of a 5-8-5 defect
line within a graphene sheet using STM [153]. In particular, these authors noted that this defect line was able to
behave as a quantum wire. Additionally, as discussed in Section 5, it is conceivable to construct defective graphene-like
sheets with other types of defects similar to Haeckelites.
Therefore, additional theoretical and experimental studies regarding defects in graphene are urgently needed to
develop further graphene-based electronics.

Applications
Graphene is a unique material because its displays an outstanding electron transport at room temperature, in which
electrons behave as massless particles without experiencing
scattering. Therefore, the imminent applications of this layered material are in electronics such as in the fabrication
of ultrafast transistors [154] able to operate in the tera-

hertz frequency range. Its low capacitance is also important

in the fabrication of biosensors or chemical sensors due to
the resulting low values of the signal to noise ratios. However, due to the large number of reactive edges in graphene
nanoribbons, it is expected that the sensing abilities of ribbons are superior to those shown in graphene. In addition,
by doping or by applying different edge spin orientations,
the bandgap of nanoribbons may be controllable, thus having important implications in the fabrication of novel and
ultrafast electronic nanodevices with outstanding sensing
abilities. Research in this direction needs to be addressed
from the experimental and theoretical standpoints but there
are already some promising results. Lin et al. [155] have
shown that wafer scale production of graphene (grown epitaxially over SiC) FETs is possible and such circuits have
100 GHz switching frequencies.
In addition to transistors, GNRs could nd applications in
nano-electromechanical systems (NEMS). An example of this
was reported by Wei et al. [94] who produced a few-layer
graphene ribbon NEM switch with good reversibility, which
was used in an OR gate.
From the materials science point of view, graphene and
graphene nanoribbons could be used as llers in the fabrication of robust polymer composites, highly conducting
transparent lms, high thermal conducting polymers, and
other composites with different metals and ceramics. Due to
the presence of defects and dopants, it may also be possible
to use these locations as catalytic spots for anchoring specic bio-molecules, drugs, heavy metals, and other species.
Another application for graphene is as the thinnest possible support lm for HRTEM, this has been shown to allow, for
example, observation of individual adatoms over graphene
[156] and atomic resolution imaging of soft hard interfaces
[157]. These graphene lm grids can easily be made in the
laboratory by transferring graphene akes over TEM grids,
and are starting to be commercially available. Few-layer
graphene lms have also been shown to offer advantages
in TEM.

368
There are numerous challenges still to be achieved. In
this respect, the bulk production (e.g. tons per year) of
graphene and graphitic nanoribbons may be achieved by
unzipping carbon nanotubes but further experiments need
to be performed. It is clear that graphene nanoribbons could
now be dispersed in suspensions due to the reactivity of the
large number of edges sites. Therefore, edge chemistry and
physics of the ribbons, a eld which is just arising, should
now lead to: (a) novel catalytic reactions, (b) sensor fabrication, (c) the production of eld effect transistors, (d)
the generation of electrodes for Li-ion batteries, (e) the
assembly of heavy metal lters, (f) the fabrication of highly
conducting, transparent polymer composites and other composites with metals and ceramics, g) drug deliverers, etc.
However, controlled defect engineering is needed in order
to ne tune the chemical, electronic, mechanical, magnetic
and thermal properties of graphitic nanoribbons.
Porous graphene or chemically activated graphene
with holes, also referred in the literature as antidots
[126,158,159] should be studied in detail from the experimental and theoretical standpoints. It is possible that this
holey material could be applied in catalysis, heavy metal
adsorption, sensors and other uses. Porous graphene with
controlled passivation of the dangling bonds in the pores
has been predicted to be a very selective membrane for
gas separation [160]. In this context, theoretical research
should also target the use of GNRs as constructing building
blocks to generate more complicated 2D and 3D networks
(Fig. 1p), which will certainly result in novel porous materials with unprecedented mechanical, chemical, magnetic
and electronic properties.

Conclusions
The production of GNRs is a rapidly advancing eld, and
novel synthetic methods and advances towards their applications will be developed. A challenge however will remain
for facile integration of graphene into electronic devices:
control over the deposition of GNRs, control on the atomic
edge arrangements and creating efcient electrical contacts. This is only the tip of the iceberg since other layered
materials such as BN, MoS2 , WS2 , ZnO, TiO2 , etc., could
also generate nanoribbons. In this context, it has been
demonstrated that BN nanoribbons exhibiting zigzag edges
could behave as metal and even emit electrons and low
turn on voltages [161]. Very recently the group of Ajayan
reported the synthesis of a monolayer hybrid BNC material
that exhibits hexagonal structure. The electrical properties
of such hybrid BNC lms range from insulating to conducting, and could be controlled by varying the C concentration
within the sample [162]. Other ribbons such as ZnO [163,164]
or MoS2 [165] could be metallic and even exhibit ferromagnetic properties. Therefore, the possibilities to construct
other types of devices using different types of nanoribbons, and the conception of hybrid ribbons may be the way
to develop layered electronics and materials science. It is
clear that theorists and experimentalists should join efforts
in order to tackle these complicated problems, especially
those related to applications.
We believe that the general principles and concepts laid
out in this account should be useful to readers starting work-

M. Terrones et al.
ing on graphene and graphene nanoribbons. Regarding their
characterization, microscopy (SPM and electronic) together
with micro-Raman spectroscopy will be key tools to identify and understand the basics of defects in graphene-like
systems. The controlled use of defects for tailoring the
physicochemical of graphene and GNRs properties should be
exploited further, similar to doping for the silicon industry.
In addition, the extreme sensitivity of GNRs to small variations in, for instance edge chemistry or stacking order, can
be advantageous for some applications (e.g. sensing, switching, data storage, drug delivery, etc.), and could also be used
to control the performance of different devices. As in many
other discoveries in nanoscience, theoretical and experimental approaches should occur synergistically in order to
advance the eld even more rapidly.

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Mauricio Terrones obtained his B.Sc. degree
in Engineering Physics with rst class honours
at Universidad Iberoamericana, and was distinguished as the Best Student of Mexico in
Engineering Physics in 1992. In 1994 he started
his doctorate degree with Sir Prof. Harold W.
Kroto (Nobel Laureate, FRS) and received his
D.Phil. degree from University of Sussex in
1997. He has co-authored more than 270 publications in international journals, and counts
with more than 9000 citations to his work (His
H index is 52). He has numerous awards including: the Alexander von
Humboldt Fellowship, the Mexican National Prize for Chemistry, the
Javed Husain Prize and the Albert Einstein medal from UNESCO,
the TWAS Prize in Engineering Physics, the Carbon Prize given by
the Japanese Carbon Society, the Somiya Award by the International Union of Materials Research Societies, among others. Aged
41, he currently holds a chair of excellence at Universidad Carlos
III of Madrid, and he was the pioneer of the National Laboratory
for Nanoscience and Nanotechnology Research (LINAN) at IPICYT
in Mexico. His research now concentrates on the theory, synthesis and characterization of novel layered nanomaterials, including
graphene, and he will join Shinshu University (Japan), as outstanding professor, from August 2010.
Andrs R. Botello-Mndez received his BS
in Physics Engineering in 2004 from ITESM
(Mexico), and his PhD in Applied Sciences
(Nanoscience and Nanotechnology) in 2009
from IPICYT (Mexico). He has worked in the
study of the electronic properties of ZnO and
carbon nanostructures. He is mainly involved
in theoretical and experimental studies of
the properties of one-dimensional nanostructures from layered compounds. Presently, he
is doing a postdoctoral stay at the Institute of
Condensed Matter and Nanosciences (ICMN) of the Catholic University of Louvain in Belgium were he obtained the Marcel de Merre
Prize of Louvain.
Jessica Campos-Delgado received her B.S. in
Physics Engineering from the State University of San Luis Potosi, Mexico in 2005. She
enrolled the graduated program of Applied
Sciences at the Institute of Science and Technology of San Luis Potosi in Mexico and
obtained her PhD degree in 2009. She is currently working as a Post-Doc at the National
Institute of Metrology, Standardization and
Industrial Quality of Brazil. Her research
interests are towards the synthesis of carbon

371
nanostructures and their characterization through Raman spectroscopy and electron microscopy.

Florentino Lpez-Uras carried out his

BSc degree in Physical Sciences at the
Autonomous University of Sinaloa (Mxico).
He pursued his MSc. in Physical Sciences
at the Autonomous University of San Luis
Potos (Mxico), and received the PhD degree
in Physics from the University Paul Sabatier
in Toulouse (France). His research interests
include theoretical and experimental aspects
of graphene materials as well as diverse magnetic nanostructures.

Yadira I. Vega-Cant received her Ph.D.

from Rice University (USA) in 2002, where
she worked in Professor W. Edward Billups
research group. Her thesis work, received the
Harry B. Weiser Award, and her postdoctoral
stay dealt with industrial projects. Currently,
she is a Professor in the Nanoscience and
Nanotechnology program at the Advanced
Materials Department at IPICYT. She currently
advises eight graduate students. Her research
interests include chemistry of carbon nanotubes, carbon nanoribbons and graphene, characterization and
processing of polymer nanocomposites and development of applications such as actuators and sensors.

Fernando J. Rodrguez-Macas has a B.S.

(Chemistry, with honours) from ITESM (Mxico). He worked on carbon nanotubes with
Professor Richard E. Smalley at Rice University (USA) during his M.A. (1999). He
participated in interdisciplinary research in
Materials Science at Rice for his Ph.D.
(Chemistry, 2004) and a postdoctoral stay
with Professor Enrique V. Barrera, producing a patent and papers related to
nanotube composites. He joined IPICYT in
2005 and he is currently a Professor in the Nanoscience and
Nanotechnology program, advising ve graduate students. His
research interests include composites of nanocarbons and their
chemical modication to control the interface, doped-carbon nanotubes, graphene, biocompatibility of nanomaterials and bionanotechnology.

Ana Laura Elas received her Ph.D. degree

in Nanoscience and Nanotechnology from
IPICyT (Mxico) in 2006. She has a Physics
background, form her undergraduate degree
(UASLP-Mexico, 2002). Ana Laura has visited
several institutions for research stays, such as
LANL (in New Mexico, USA), MIT (Cambridge,
MA), ASU (Tempe, AZ), UNAM (Mexico City),
Rice University (Houston, TX) and RPI (Troy,
NY). She was a postdoctoral research fellow
at Shinshu University (Japan), in the group of
Prof. Morinobu Endo and at IPICyT (Mexico). Currently, she is a postdoctoral research fellow at Rice University, in Prof. Ajayans group
(since June 2009).

372
Emilio Mu
noz-Sandoval obtained his PhD in
Physics from the Universidad Autnoma de
San Luis Potos (Mxico), and carried out
postdoctoral stays at UNAM (Mxico) and the
Netherlands. His current research deals with
production and characterization of different carbon nanomaterials and ferromagnetic
nanoparticles encapsulated in carbon nanostructures. During the 9 years, working with
Professors Terrones and collaborators Emilio
has acquired invaluable experimental expertise by evolving a multidisciplinary approach combining the
production of nanomaterials with electron microscopy and magnetometry techniques for analysis. In order to control the size and
morphology, he has developed several routes to deposit catalytic
nanoparticles. Magnetron sputtering deposition has been the most
successful method to achieve these goals.
Abraham G. Cano-Mrquez got a Bachelors diploma in Chemistry at the Universidad
Autonoma de San Luis Potos (Mxico),
whence he also received a masters degree in
Physical Chemistry after studying the electromicrogravimetric behaviour of a sulfonated
polyaniline. He will soon nish his PhD studies
at IPICYT (Mxico). His research interests are
the development of carbon-based nanostructures, focusing in the study of graphene-like
materials and devices. He is also interested in
the study of polyanilines and their composites with carbon materials for the development of new actuators for use in robotics and
prosthetics. He is part of the team that introduced the exfoliation
technique for the unzipping of multi-walled carbon nanotubes.

M. Terrones et al.
Jean-Christophe Charlier is Professor at
the Institute of Condensed Matter and
Nanosciences of the University of Louvain (UCL) and Senior Research Associate
of the Fund for Scientic Research (FNRS)
in Belgium. His research interests are in
theoretical condensed matter physics and
nanosciences covering the areas of: electronic and structural properties of crystals
and reduced-dimensional solids; nanotubes,
graphene and related carbon-based nanostructures; quantum transport through single molecules and other
nanosystems. The objective is to explain and predict the properties of materials using rst-principles theories and computational
physics. He is author of about hundred scientic publications in
international peer-reviewed journals.
Humberto Terrones obtained his PhD degree
from Birkbeck College in 1992 (University of
London) under the supervision of Prof. Alan L.
Mackay (FRS). Following a postdoctoral stay at
Cambridge University (UK), Humberto joined
the Institute of Physics at (UNAM) in Mexico
City. He then moved to IPICYT as Head of
the Advanced Materials Department, to work
mainly in nanosciences and nanotechnology
introducing a multidisciplinary character to
research. He is presently visiting Professor at
the Institute of Condensed Matter and Nanosciences of the Universit Catholique de Louvain in Belgium. Alan L. Mackay and
HumbertoTerrones were the rst to introduce the concept of
curvature in layered materials to understand and propose new
nanostructures.