Physica E 95 (2018) 125131

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Physica E
journal homepage: www.elsevier.com/locate/physe

Structural and electronic properties of double-walled boron nitride MARK

nanocones

E. Britoa, T.S. Silvaa, T. Guerraa, L. Leitea, S. Azevedoa, A. Freitasb, J.R. Kaschnyc,
a
Departamento de Fsica, Universidade Federal da Paraba, Caixa Postal 5008, 58059-900 Joo Pessoa, PB, Brazil
b
Departamento de Fsica, Universidade Federal do Rio Grande do Norte, Caixa Postal 1641, 59078-900 Natal, RN, Brazil
c
Instituto Federal da Bahia Campus Vitoria da Conquista, Av. Amazonas 3150, 45075-265 Vitria da Conquista, BA, Brazil

A R T I C L E I N F O A BS T RAC T

Keywords: First principles calculations were applied to study the structural and electronic properties of dierent
First-principles calculations congurations of double-walled boron nitride nanocones with a disclination angle of 60. The analysis includes
Carbon dierent rotation angles, distance between apexes, as well as distinct types of antiphase boundaries. The
Boron nitride calculations indicate that the non-rotated conguration of double-walled nanocone with a defective line
Nanocones
composed by C and N atoms, forming C-N bonds, is the most stable conguration. It was found that the yam
angle, apexes distance and defective line composition present signicant inuence on the electronic properties
of such structures. Moreover, analyzing the spin charge density, for the electronic states near the Fermi level, it
was also found that the conguration with a defective line containing C atoms presents a net magnetic moment.

1. Introduction
The structural characteristics of hexagonal boron nitride (h-BN)
and carbon nanomaterials have been the main subject of several
scientic investigations. A special emphasis of such studies is given
to the estimation, or even determination, of the structural and
electronic properties of nanotubes [1,2], nanocones [3,4] and full-
erenes [5,6]. The main expectation is that such nanostructures may
have extraordinary electronic and mechanical properties, which can be
applied to future device technologies. In particular, theoretical and
experimental studies have indicated that h-BN and carbon nanocones
are good candidates for cold-eld electron sources. Indeed, it was
found that the topology and the atomic arrangement are important
factors which aect the electron emission eciency [7,8].
Geometrically, a nanocone can be obtained using a cut and glue
process, also known as Volterra process, where a slice of angle D() -
the disclination angle, is removed from a round sheet, and the two cut
sides are joined together. For boron nitride nanocones (BNNCs), with
disclination angle equal to odd multiples of 60, occurs the formation
of an antiphase boundaries (APBs) composed by a defective line with
non-BN bonds [9]. It was usually thought that the APBs present a
greater energy cost than the lower elastic-energy cost of a disclination
with smaller angles [10]. Nevertheless, this picture changes due to
experimental results [4,6]. Moreover, the theoretical study of Azevedo
et al. [11] demonstrated that BNNCs containing APBs can be more
stable than defect-free structures. It was also shown that structures
which incorporate a carbon atom at the defective line are the most
stable structures, for both, boron-rich and nitrogen-rich environments.
Experimental studies indicate that the actual synthesis processes of
BNNCs lead to the formation of multi-walled structures, composed by
an ordered stack of nanocones [4]. Nishiwaki and Oku, using arc-
melting, have concluded that the BN cone structures are stabilized by
the stacking [12]. Furthermore, recent work indicates that the inter-
action between rotated double-walled carbon nanocones, forming
Moir patterns, have signicant inuence on the energy of the Fermi
level and localized states [13]. On the other hand, it was systematically
found that mechanical strain can strongly modify the electronic
properties of graphene, graphene bilayers, ZnO and Si nanostructures
[1419]. Such observations may be a relevant point for the future
development of nanomechanical sensors.
Motivated by the basic points mentioned above, in the present
contribution we investigated the structural stability and the electronic
properties of dierent congurations of double walled BN nanocones
(DWBNNCs) using rst principles calculations. All calculated struc-
tures present a disclination angle of 60. In addition, the corresponding
inuence of the defective line in the structure properties was carefully
analyzed. It was considered stacked structures with distinct rotation
angles and inter-cone distances, which represents a compressive strain
applied on the whole structure along the main axis. The most stable
DWBNNCs conguration was found to be the non-rotated structure

Corresponding author.
E-mail address: kaschny@ifba.edu.br (J.R. Kaschny).

http://dx.doi.org/10.1016/j.physe.2017.09.019
Received 30 July 2017; Received in revised form 20 September 2017; Accepted 22 September 2017
Available online 23 September 2017
1386-9477/ 2017 Elsevier B.V. All rights reserved.
E. Brito et al.
composed by two nanocones containing a line of defects which consists
of C atoms bonded to N ones. Such result is partially supported by
previous ab-initio calculations, which demonstrate that the incorpora-
tion of carbon at the antiphase boundary leads to highly stable BNNCs
structures [11].
2. Calculations details
All calculations were carried out using the density functional theory
(DFT) [20]. The generalized gradient approximation, parametrized by
Perdew et al. [21], was applied for the exchange and correlation
functional, as implemented in the SIESTA code [22,23]. It was
assumed the norm-conservative Troullier-Martins pseudopotentials
[24], in the Kleinmann-Bylander factorized form [25], and a linear
combination of numeric atomic orbitals of nite range to represent a
double- basis set, including polarized functions and using a cuto
radius of about 15.0 . All the geometries were fully relaxed, until
residual forces become smaller than 0.1 eV/. In addition, it was
adopted a convergence criterion where the self-consistency is achieved
when the maximum dierence between the output and the input of
each element of the density matrix, in a self-consistent cycle, is smaller
than 104. Furthermore, in order to estimate numerical errors, addi-
tional calculations were performed using a convergence criterion of
106. The obtained results demonstrate that the uctuations in the total
energy calculation are smaller than 2 meV.
All structures were initially built using the geometrical cut and glue
procedure, as mentioned above, with a disclination angle of 60.
Fig. 1. Ball and stick illustration of the relaxed structures. The atomic species are indicated in the inset. The defective line composed by B-B, C-N and N-N bonds are indicated in (a), (b)
and (c) by the grey areas, respectively, for the SWBNNCs. Figures (d), (e), (f) and (g) illustrate the side view of the DWBNNCs and the corresponding top view of such structures for
dierent values of .
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Physica E 95 (2018) 125131
Moreover, it is important to emphasize that all dangling bonds are
passivated by hydrogen atoms. Therefore, such H atoms are located at
the border of the nanocone base forming H-B, H-N and H-C bonds.
Fig. 1 illustrates the top and side views of the obtained relaxed
structures. In Fig. 1a-c are shown the top view of single walled BNNCs,
with dierent defective lines (APBs), composed by B-B bonds
(SWBNNCBB), C-N bonds (SWBNNCCN) and N-N bonds
(SWBNNCNN), respectively. Fig. 1d-f show the stacked structures of
the DWBNNCs, which were constructed piling two of the SWBNNCs
shown in the previous Figures. It is worth to point out that such
DWBNNCs were built using two BNNCs with the same type of line
defects, forming the DWBNNCBB, DWBNNCCN and DWBNNCNN,
respectively. Contrary, Fig. 1g shows a double walled structure
consisting of a nanocone with a defective line composed by N atoms
on top of a nanocone with a defective line composed by B atoms
(DWBNNCNNBB). In addition, each DWBNNC structure were nally set
by the rotation of the top nanocone in respect to the other one i.e.
rotating by an yaw angle , as indicated in the Fig. 1d-g, which show
the top view and illustrate the Moir patterns.
3. Results and discussion
3.1. Structural stability
In order to analyze the stability of the DWBNNCs, the formation
energy i.e. the energy required to form a given structure, EForm, was
calculated using a thermodynamical approach based on the previous
E. Brito et al.
determination of the chemical potentials of each atomic specie involved
in the synthesis of the structure, as described elsewhere [9,2628].
Using such approach, EForm is given by:
EForm = (ETot nBB nN N nC C nHBHB nHN HN nHC HC )/ nT ,
where ETot is the calculated total energy, as given by the SIESTA code,
nT is the total number of atoms in the structure, nB, nN and nC are the
number of B, N and C atoms, and B, N and C are the corresponding
chemical potentials. The number of H-B, H-N and H-C bonds and
chemical potentials attributed to the presence of such bonds are given
by nHB, nHN, nHC, HB, HN and HC, respectively.
To calculate the amount of energy involved in the interaction
between the top and bottom cones, of a given DWBNNC, Eint, one
may consider that the total energy associated to the structure can be
written as:
ETot = Ebottom + Etop + Eint ,
where Ebottom and Etop are the total energies corresponding to the
bottom and top nanocones, respectively, as given by the SIESTA code.
These energies were obtained from additional calculations considering
only the SWBNNCs relaxed structures. Therefore, the interaction
energy can be easily obtained by Eint = ETot Ebottom Etop.
Fig. 2a illustrates schematically some of the structural parameters
of the DWBNNCs, which are the diameters of the bottom (Dbottom =
19.3 ) and top (Dtop = 18.9 ) nanocone, and the heights of the
bottom (Hbottom = 4.9 ) and top (Htop = 5.1 ) cones. In general, one
can see that the nanocone located at the bottom has a greater diameter,
and consequently the smaller height, when compared with the top one.
This behavior can be attributed to the interaction between the
nanocone walls, which compresses the bottom nanocone. Such infer-
ence can be better evaluated by the analysis of the electronic charge
densities, as discussed below. Additionally, it was veried that the
diameters and heights of the cones present very small variations for a
given conguration, with negligible eect of the rotation angle i.e. the
yam angle, , and the distance between apexes, h.
A plot of the formation energy of the DWBNNCs structures, as a
function of the distance between apexes, is shown in Fig. 2b for selected
values of . The conguration with the smaller formation energy is the
one with a defective line composed by C atoms (DWBNNCCN), which
have no B-B or N-N bonds. On the other hand, the DWBNNCs with the
greater formation energy are those with a defective line composed by B
Fig. 2. (a) Schematic illustration indicating the structural parameter of the DWBNNCs and (b) their formation energies, Eform, plotted as a function of the distance between apexes, h,
for rotation angles, , of 0 and 36. The dierent curves are indicated by the inset.
Physica E 95 (2018) 125131
atoms (DWBNNCBB). This behavior can be attributed to the fact that
the length of the B-B bond is much greater than the B-N bond, inducing
deformations in the cone wall, with a corresponding energetic cost.
Indeed, since N-N bond are smaller than B-B bond, DWBNNCNN
(1)
structures, which have a defective line composed by N atoms, present
intermediate values of EForm. Moreover, it is possible to observe that
the DWBNNCNNBB cones present formation energies that decrease with
the distance between apexes. It is also possible to see, in Fig. 2b, that
for h > 4.9 the formation energy of such structures are quite small. In
addition, one can observe that Eform slightly increases with . This
behavior can be attributed to the interaction between B and N atoms,
and the hypothetical tendency of the formation of B-N bond i.e. the
formation of bridges between the top and bottom cones.
It is expected that the interaction between the stacked cones could
stabilize the double walled system [14]. Therefore, since such interac-
tion depends on the distance between apexes, one can suppose the
(2)
existence of an optimal value of h which minimize Eint. Furthermore,
the study of the interaction energy as a function of the distance
between apexes can also give information about the eect of a
compressive force (strain) applied perpendicularly to the double walled
cone structures. In fact, taking into account that mechanical strain can
modify the electronic properties of graphene and graphene bilayers
[15], it is also expected signicant modications in the electronic
properties of the DWBNNCs.
Fig. 3 shows the interaction energy plotted as a function of the
distance between the apexes. It is possible to observe that the h values
which minimizes Eint for the DWBNNCBB, with rotation angle of = 0
and 36, are 4.10 and 4.18 , respectively. For the DWBNNCNN such
distances are 4.20 and 4.25 , for the DWBNNCNNBB, 4.34 and
4.35 , and for the DWBNNCCN, 4.20 and 4.28 . It is also possible to
see that the rotated conguration ( = 36) is always more stable than the
non-rotated one ( = 0). This behavior can be explained by the greater
interaction energy associated to the rotation. The non-rotated structures
have the defective line, composed by B-B or N-N bonds, which are
located one above each other. Therefore, the atomic pairs which form the
defective line of the top nanocone interact with an identical defective line
of the bottom cone, decreasing the interaction energy. Contrary, when the
top nanocone, or the bottom one, is rotated, these atoms are not above
each other and the interaction energy increases. For the DWBNNCNNBB,
the non-rotated conguration is more stable than the rotated one. In such
structure, the defective lines of the top and bottom nanocones are
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E. Brito et al.
Fig. 3. The interaction energy, Eint, plotted against the distance of the apexes, h, for (a)
DWBNNCBB., (b) DWBNNCNN, (c) DWBNNCNNBB and (d) DWBNNCCN. The calculations
were done for both, rotated ( = 36) and non-rotated ( = 0) congurations.
composed by N and B atoms, respectively. Hence, the non-rotated
conguration is more stable due to the fact that these N atoms are
directly above B atoms, increasing the structural stability.
Furthermore, it is possible to observe in Fig. 3 that DWBNNCCN
presents a similar behavior to the DWBNNCNNBB i.e. the non-rotated
conguration is more stable than the rotated one. To understand this
behavior one can speculate that the rotated conguration may be
associated to an additional energetic cost corresponding to the rotation
itself. This contribution may be, eventually, more signicant than the
energetic cost due to the interaction between the defective lines. In
general, the most stable DWBNNCs is the DWBNNCCN, probably to the
fact that the C-N bond is more stable than the B-B and N-N bonds.
Additionally, one can see in Fig. 3 that the h values which minimize Eint
are basically independent from .
3.2. Electronic structure
The density of states of all DWBNNCs have been calculated as a
function of the distance between the apexes for both, rotated ( = 36)
and non-rotated ( = 0) congurations. Initially, one can see in Fig. 4,
the calculated density of states (DOS), of the SWBNNCs structures. It is
found that SWBNNCBB and SWBNNCNN present a semiconducting
behavior, while the SWBNNCCN is metallic.
Fig. 4. Density of states calculated for: (a) SWBNNCBB, (b) SWBNNCCN and (c)
SWBNNCNN Structures. It is possible to observe that SWBNNCBB and SWBNNCNN are
semiconductors, while SWBNNCCN is metallic.
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Physica E 95 (2018) 125131
Figs. 5 and 6 show the obtained DOS for the non-rotated and
rotated DWBNNCs, respectively. It is possible to observe from Figs. 5a
and 6a that all DWBNNCBB congurations present a signicant
number of deep localized states above the Fermi level. These energy
levels are associated to the defective line composed by B atoms, which
introduce an excessive number of holes. This feature is very similar to
the one found for the SWBNNCBB (see Fig. 4a). Comparing the DOS of
such structures, it is possible to see that these localized states are
shifted toward higher energies as the distance between apexes in-
creases. The same behavior is also observed for the rotated congura-
tions. However, it is possible to observe that, in this case, the obtained
energy shift is more signicant. Such inference can be associated to the
energetic cost of the rotation.
As shown in Figs. 5b and 6b, all DWBNNCNN structures present a
number of deep localized states below the Fermi level. Such electronic
states are associated to the presence of the defective line composed by
N atoms, which introduce an excessive number of electrons. Such
peculiarity is quite similar to the one observed for the SWBNNCNN
(see Fig. 4c). In addition, one can observe that the corresponding
energy levels are shifted toward the Fermi level as h increases, with no
apparent dependency on . Moreover, when the distance between
apexes increases, the general appearance of the DOS tends to be
analogous to the one obtained for the SWBNNCNN.
For the DWBNNCNNBB structure (see Figs. 5c and 6c), where the
top nanocone have a defective line composed by N atoms and the
bottom one by B atoms, occurs the introduction of electrons and holes
simultaneously. Therefore, on the one hand, it is found the introduc-
tion of deep localized states below the Fermi level, which can be
associated to the top nanocone. On the other hand, it is also found the
introduction of deep localized states above the Fermi level, which can
be associated to the bottom nanocone. In addition, it is observed that
the increasing in the distance h induces the energy shift of the localized
states associated to the top nanocone toward the Fermi level, and the
ones associated to the bottom nanocone toward higher energies. It is
interesting to keep in mind that the bottom nanocone presents the
most signicant deformations, as mentioned before. Therefore, one can
speculate that such deformations, induced by the interaction between
walls, may contribute for the energy shift of such electronic states. Such
speculation can be corroborated by the analysis, and corresponding
estimation, of the electronic charge density of top and bottom
nanocones. It was observed that the increment of h induces a
signicant reduction on the dierence between the electronic charge
densities of such structures, producing remarkable modications in the
density of states. These modications include the above mentioned
energy shift of the localized electronic states. In fact, as the distance
between apexes grows, the obtained DOS tends to be quite similar to
the one calculated for isolated nanocones.
In the SWBNNCCN structure, there is a defective line where an odd
number of C atoms are bonded to an even number of N ones. Such line
of defects provides the sucient condition to create unpaired electrons
from the pz orbitals of the C atoms. Consequently, in addition to the
electronic states located above the valence band, another energy state is
introduced upon the Fermi level. For most of the DWBNNCCN (see
Figs. 5d and 6d) congurations, one can nd a similar behavior. The
exceptions are the non-rotated congurations with h = 4.0 and h =
4.6 , where the electronic states located close to the Fermi level
present no overlapping. As the distance between apexes increases, one
can also observe that, for both, non-rotated and rotated congurations,
the density of states tends to present a similar appearance to the one
obtained for the SWBNNCCN.
One can see in Figs. 7a and 7b the energy gap, Egap, plotted as a
function of the distance between apexes, for rotated and non-rotated
congurations of the DWBNNCBB and DWBNNCNN structures, respec-
tively. It is possible to verify that the energy gap increases with the
increasing distance h. This behavior can be associated to interaction
between the atoms located at the defective line of the nanocones.
E. Brito et al. Physica E 95 (2018) 125131

Fig. 5. Density of states obtained for the DWBNNCs with rotation angle of 0 and distance between apexes of 4.0, 4.6 and 5.0 . (a) Shows the results for the DWBNNCBB, (b) for the
DWBNNCNN, (c) for the DWBNNCNNBB and (d) for the DWBNNCCN.

Fig. 6. Density of states obtained for the DWBNNCs with rotation angle of 36 and distance between apexes of 4.0, 4.4 and 5.0 . (a) Shows the results for the DWBNNCBB, (b) for the
DWBNNCNN, (c) for the DWBNNCNNBB and (d) for the DWBNNCCN.

Therefore, when the distance between apexes decreases, the interaction DWBNNCNN conguration with = 36 is the one which show the
magnitude increases and Egap decreases. Moreover, it is worth to greater energy gap value. Contrary, for the DWBNNCNNBB (see Fig. 7c),
emphasize that, among all values assumed for the rotation angle, the the energy gap decreases with the distance between the apexes, due to

Fig. 7. Calculated energy gap, Egap, plotted as a function of the distance between apexes, h, for (a) DWBNNCBB, (b) DWBNNCNN, (c) DWBNNCNNBB and (d) DWBNNCCN. For the
DWBNNCBB and DWBNNCNN were obtained similar behavior, with increasing energy gap with the distance. For the DWBNNCNNBB the energy gap decreases with the distance. The
DWBNNCCN behaves like a metal.

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E. Brito et al. Physica E 95 (2018) 125131

Fig. 8. Density of states calculated for dierent rotation angle, , for (a) DWBNNCBB, (b) DWBNNCNN, (c) DWBNNCNNBB and (d) DWBNNCCN structures. The corresponding values of
are indicated by the insets.

Fig. 9. Localized density of states obtained for (a) SWBNNCBB, (b) SWBNNCCN and (c) SWBNNCNN. The corresponding spin charge densities are shown in (d), (e) and (f), respectively.
Only the SWBNNCCN presents net spin polarization. All structures are illustrated by sticks following the indications on the inset.

the interaction between N and B atoms located at the defective lines of
top and bottom nanocones, respectively [17]. In addition, for the
DWBNNCCN (see Fig. 7d), it is obtained a metallic behavior (Egap =
0 eV) which can be attributed to the free electrons introduced by the C
atoms, as mentioned above.
For all DWBNNCs, the eect of the rotation on the electronic
structure was analyzed for the angles where Moir patterns are
obtained, that is 9, 18 and 36. For such analysis it was arbitrarily
assumed the smallest distance between apexes, h = 4.0 . The obtained
DOS are shown in Fig. 8. It is observed, for the DWBNNCBB (see
Fig. 8a), that the distance between the electronic states associated to
the conduction band and the Fermi level tends to increase with . It is
also found that the rotation presents quite small inuence over the
energy states associated to the valence band of such structure.
Contrary, for the DWBNNCNN (see Fig. 8b), the rotation angle presents
little inuence on the calculated electronic structure. It is possible to
see in Fig. 8c, for the DWBNNCNNBB, that the deep localized electronic
states associated to the top nanocone tends to be shifted toward the
Fermi level and, simultaneously, the localized states associated to the
bottom cone tends to be shifted away from it. As mentioned before,
such behavior can be attributed to the increasing curvature of the
bottom nanocone, which depends on the rotation angle. As shown in
Fig. 8d, for the DWBNNCCN, the most signicant feature is the overlap
of the energy states close to the Fermi level. In fact, these electronic
states get closer as increases due to the increment in the distance
between the C atoms located at the top cone and the ones from the
bottom nano cone. For = 36, the distance between C atoms, from
distinct nanocones, is similar to the distance found in a Bernal bilayer
conguration, which leads to the overlap of localized energy states at
the Fermi level.
The localized density of states (LDOS), associated to the energy
states located close to the Fermi level, is illustrated in Fig. 9a-c, for
single walled cones. As mentioned above, such electronic states
correspond to energy levels associated to the top of the valence band
and to the bottom of the conduction band, which are originated from
the presence of the defective line. For the sake of simplicity, this
Figure shows only the calculated results for single walled structures.
Such choice can be justied by the fact that nanocones with identical
structures present the same LDOS, regardless of its position in
relation to other nanocones. In Fig. 9a, one can see that most of
the charge density is located at the positions of the B atoms. A similar
feature is also observed in Fig. 9c, for the N atoms, and analogously
in Fig. 9b, for the N and C atoms, with a more signicant contribution
of the carbon ones. Furthermore, the spin charge density for the
electronic states near the Fermi level are shown in Fig. 9d-f.
Analyzing these results, it is possible to conclude that only the
DWBNNCCN structure show a net spin charge density. Therefore,
this is the only double walled structure which presents a net magnetic
moment, with an intensity of 2 B, where each nanocone contributes
with 1 B. Additionally, one can infer that such magnetic moment is
attributed to the extra electrons introduced by the substitutional C
atoms.

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4. Conclusions
First-principle calculations were applied to investigate the stability
and electronic structures of double-walled boron nitride nanocones,
analyzing dierent values for the rotation angles and distance between
apexes, as well as distinct types of antiphase boundaries. The obtained
results indicate dierent energetic behaviors between DWBNNCNN,
DWBNNCBB, DWBNNCNNBB and DWBNNCCN structures. The non-
rotated DWBNNCNN and DWBNNCBB double walled cones present
smaller formation energies i.e. they are more stable, than the
corresponding rotated structures. Contrary, for the DWBNNCNNBB
and DWBNNCCN, it was found that the rotated structures are more
stable. The analysis of the electronic structure shows that all structures
are semiconductors, with the exception of the DWBNNCCN which is
metallic. Indeed, the DWBNNCCN present an electronic state located on
the Fermi level, which can be attributed to the pz orbitals of the C
atoms. It was found that the yam angle, apexes distance and defective
line composition present signicant inuence on the electronic proper-
ties of such structures. The analysis of the localized charge density, for
the electronic states near the Fermi level, shows that most of the
electronic charge density, for all DWBNNCs, is located in the defective
lines. Furthermore, the analysis of the spin charge density demon-
strates that only the DWBNNCCN structure show a net spin charge
density. Therefore, this is the only double walled structure which
presents a net magnetic moment. Finally, it is interesting to point out
that the a better understanding about the modications in the
electronic properties of such structures, induced by strain and rotation,
can play a key role for the design of future eld emission devices using
these nanomaterials.
Acknowledgments
This work was supported by the Brazilian Agencies, CNPq, INCT-
Nanomateriais de Carbono, and Capes/Nanobiotec.
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Physica E 95 (2018) 125131
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