Computational Condensed Matter 4 (2015) 40e45

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Computational Condensed Matter

journal homepage: http://ees.elsevier.com/cocom/default.asp

Regular article

Electronic structures and transport properties of zigzag BNC

nanoribbons with different combinations of BN and graphene
nanoribbons
Jun Ouyang a, Mengqiu Long a, b, *, Dan Zhang a, Xiaojiao Zhang a, Jun He a,
Yongli Gao a, c, **
a
Institute of Super-microstructure and Ultrafast Process in Advanced Materials, School of Physics and Electronics, Central South University,
Changsha 410083, China
b
Department of Physics and Materials Science, City University of Hong Kong, Hong Kong, China
c
Department of Physics and Astronomy, University of Rochester, Rochester, NY 14627, USA

a r t i c l e i n f o a b s t r a c t

Article history: Using the density functional theory (DFT) and the nonequilibrium Green's function (NEGF) method, we
Received 23 April 2015 study the electronic structures and transport properties of zigzag boronenitrogenecarbon nanoribbons
Received in revised form (BNCNRs), which are constructed by the substructures of the BeN nanoribbons (BNNRs) and graphene
12 July 2015
nanoribbons (GNRs). The different position relationships (center or edge) of the BNNRs and GNRs, and
Accepted 12 August 2015
Available online 28 August 2015
the different edge patterns of the BNCNRs have been considered systematically. We found the electronic
structures and transport properties of BNCNRs are significantly affected. The metallic and semi-
conductive properties of the BNCNRs can be modulated by the different combinations of the BNNRs and
Keywords:
Zigzag boronenitrogenecarbon nanoribbon
GNRs. And our results suggest BNCNRs would have potential applications in graphene-based nano-
Boron nitride nanoribbon devices.
Graphene nanoribbon © 2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND
Electronic structure license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Transport property

1. Introduction semiconductors, and the band gap oscillates with a period 3 dimers
when ribbon width increases [7], while the ZGNRs have stable
Graphene, a two-dimensioal (2D) single atomic layer of antiferromagnetic states, and they can become half-metals under
graphite, has been successfully synthesized in 2004 [1]. Then it has an external transverse electric field [8]. Therefore, much more re-
drawn numerous researchers' interests owing to its high electronic searches have been concentrating on ZGNRs than AGNRs for their
mobility, magnetic zigzag edges, long spin relaxation times and edge magnetism and unique transport properties [9].
lengths, gate tunability, unique transport properties, and so on Since BeN bonds and CeC bonds have the same number of
[2e4]. By different physical and chemical methods, the quasi-1D electrons, boron-nitride (BN) materials are expected to form similar
graphene nanoribbons (GRNs) have already been fabricated suc- covalent structures to the carbon allotropes. Recently, mono-layer
cessfully in experiments [5,6]. According to the direction in which boron nitride (BN) sheets known as hexagonal boron nitride (h-
the truncation is performed, GNRs can mainly be classified into two BN) have been fabricated in experiments [10,11]. Both h-BN and
kinds: armchair graphene nanoribbons (AGNRs) and zigzag gra- graphene have layer structures with similar lattice parameters and
phene nanoribbons (ZGNRs). AGNRs are usually nonmagnetic crystalline structures. Distinct from graphene, h-BN is an insulator
with a large band gap of about 4.64 eV [12,13]. Similarly to gra-
phene, the 2D h-BN sheet also can be cut into armchair boron
* Corresponding author. Institute of Super-microstructure and Ultrafast Process nitride nanoribbons (ABNNRs) and zigzag boron nitride nano-
in Advanced Materials, School of Physics and Electronics, Central South University, ribbons (ZBNNRs). Zeng [14] and Golberg [15] have reported that
Changsha 410083, China BNNRs are stable even under a temperature as high as 1000 K, and
** Corresponding author. Institute of Super-microstructure and Ultrafast Process
more resistant to oxidation than graphene. For ZBNNRs, all are
in Advanced Materials, School of Physics and Electronics, Central South University,
Changsha 410083, China semiconductors with an indirect band gap monotonically decrease
E-mail addresses: [email protected] (M. Long), [email protected] (Y. Gao). with increasing ribbon width [16,17]. While for ABNNRs, all are

http://dx.doi.org/10.1016/j.cocom.2015.08.001
2352-2143/© 2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 J. Ouyang et al. / Computational Condensed Matter 4 (2015) 40e45 41

semiconductors with a direct band gap with three distinct families' there are four models have been proposed. As shown in Fig. 1(aec),
variations following the increasing of ribbon width [13]. each model is constructed by a ZGNR with the width of two in
Benefit from the advantages of GNRs and BNNRs, some re- center and a ZBNNR with width of two in each edge. There are three
searchers proposed the hybridization of them [18e21]. In the lab- kinds of edge patterns have been chosen, namely, both edges are N,
oratory, the graphene-based boron nitride hybridization system one edge is N and the other is B, and both edges are B, respectively.
has been successfully fabricated [22,23], and then many researches Fig. 1(d) presents a model which is constructed by a ZBNNR with
have been explored [24,25]. Fan et al. [26] proposed BN/C hybrid width of 4 in center and a zigzag C chain in each edge. The two-
ribbons by joining a ZGNR and a ZBNNR, and found that the elec- probe system of ZBNCNR for the electronic transport study is
tronic structures of BN/C hybrid ribbons can be tuned by changing shown in Fig. 1(e). According to the four models in Fig. 1(aed), there
the GNR width, whereas independent of the BNNR width. Basheer are also four ZBNCNRs devices have been studied, which are
et al. [27] performed a systematic study about the electronic referred to M1, M2, M3, and M4, respectively. The left and right
structure of zigzag BNC nanoribbons. Liu et al. [28] reported a first- electrodes of each device are semi-infinite repeated unit cell along
principles study of hybrid graphene/boron nitride (CeBN) nano- the z axis.
ribbons with dihydrogenated edge(s), and found that hybrid CeBN The electronic and transport properties of the devices are
nanoribbons possess half-metallicity with a certain range of widths studied by using the Atomistix ToolKit (ATK) package [29e31],
for the graphene and BN sections. which is based on the density functional theory (DFT) and the
As zigzag edge GNRs and BNNRs show interesting and prom- nonequilibrium Green's function (NEGF) method. In our calcula-
ising properties unlike those of their armchair analogues, in this tion, the real space grid technique is used with the energy cutoff of
paper we present a detailed study about the electronic and trans- 150 Ry as the required cutoff energy in numerical integrations. The
port properties of hybrid zigzag BNC nanoribbons (ZBNCNRs). The PerdeweZunger exchange and correlation function within the local
different position relationships (center or edge) of the BNNRs and density approximation (LDA) have been chosen. The k-point grid 1,
GNRs, and the different edge patterns of the BNCNRs have been 1, and 100 is used in the x, y, z direction, respectively, where z is the
considered systematically. direction of electron transport. Open boundary conditions were
used to describe the electronic and transport properties of the
2. Simulation models and calculation methods devices. A vacuum layer of 12 Å is added to avoid the interaction
between adjacent ribbons. The wave functions of all atoms are
The ZBNCNRs structures for our theoretical study are illustrated expanded by double-zeta polarized (DZP) basis set. The tempera-
in Fig. 1, and the width of six is selected, referring to the number of ture of the electrodes is set to 300 K. The geometrical structures are
zigzag chains along the nanoribbon' axis. Each model is constructed fully optimized in the presence of the two probes until the residual
by four BeN chains of ZBNNRs and two CeC chains of ZGNRs, and force on each atom is smaller than 0.01 eV/Å. The current through
both edges are passivated by hydrogen atoms. Depending on the the system is calculated using the Landauer-Büttiker formula [32],
different forms of combination between the BNNRs and GNRs,

Fig. 1. Two-probe system of the BNNRs/ZGNRs devices. (a)e(d) are the super cells of M1, M2, M3 and M4. (e) Shows the configuration of M1 device. The blue shadows represent the
left (right) electrode. The black dash line indicates the unit cell. The white, gray, pink and blue balls denote the hydrogen, carbon, boron, and nitrogen atoms, respectively.
42 J. Ouyang et al. / Computational Condensed Matter 4 (2015) 40e45

mZ
L ðVb Þ
2e
IðVb Þ ¼ fTðE; Vb Þ½fL ðE; Vb Þ  fR ðE; Vb ÞgdE (1)
h
mR ðVb Þ

where e is the electron charge, h is the Planck's constant, and

TðE; Vb Þ is the transmission of an electron. fLðRÞ ðE; Vb Þ is the Fer-
mieDirac distribution function of the left (right) electrode, mLðRÞ ðVb Þ
is the chemical potential of the left (right) electrode, Vb denotes the
external bias voltage. TðE; Vb Þ can be obtained from the equation,
" ( ) (
X
r
TðE; Vb Þ ¼ Tr Im ðE; Vb Þ Gr ðE; Vb Þ  Im
L
) #
X
r
a
 ðE; Vb Þ G ðE; Vb Þ (2)
R

where Gr ðGa Þ is the retarded (advanced) Green's function matrix,

P P
and rL ð rR Þ is the retarded self-energy matrix for the left (right) Fig. 3. The band structures of (a) M1, (b) M2, (c) M3, and (d) M4 unit cells. The blue
electrode. dashed lines denote the Fermi level.

3. Results and discussion

one edge is B and the other is N, M2 is a semiconductor with a band
We firstly consider the energy-dependent configurations of gap of 0.58 eV. Similar to M1, when both edges are B atoms, M3 also
these BNeC nanoribbons, which is very important in practice to shows metallic behavior. As shown in Fig. 3(d), one can see M4
guild experimental synthesis [33,34]. As shown in Fig. 2, the presents metallic property, the p and p* subbands are overlapped
configuration energy is calculated as Econf ¼ ðEribbon  Eatom Þ=N, at Z point, and the band gap is zero. So the Dirac cone akin to
where Eribbon is the total energy of the BNC nanoribbon, Eatom is the graphene also can be observed in M4. In all systems, we can see that
energy per atom in a perfect graphene or BN nanoribbons, and N is as the charging of the edge patterns and the combinations of the
the number of units for the width of the BNC nanoribbon. It is BNNRs and GNRs, the metallic and semiconductive properties of
shown that the average configuration energy are 12.7 eV/ the ZBNCNRs can be modulated, reflecting the characteristics of
unit, 12.8 eV/unit, 12.6 eV/unit and 12.9 eV/unit for M1, M2, both ZGNRs and ZBNNRs.
M3 and M4, respectively, which displays weak width dependence To clearly understand the electronic structures, the electronic
for each system. Addition, we find M4 has the lowest average density distributions have also been plotted in Fig. 4. The electronic
configuration energy, indicating it is more easily synthesized in density distributions of perfect ZGNRs have evenly distribution
experiment. between C and C atoms, C and H atoms, so the bonds between C and
Fig. 3(aed) present the electronic structures of the unit cells of C atoms, C and H atoms are covalent bonds. Once BNNRs are dope in
M1, M2, M3 and M4, respectively. It is shown that there are two ZGNRs, the electronic density distributions change a lot. As shown
subbands of p and p* which come from the valence band maximum in Fig. 4(b)e(e), we can find the electronic density distributions on
(VBM) and conduction band minimum (CBM), meet each other near N atoms are significant, meanwhile those on B atoms are weaker,
the Z point in the Brillouin zone for each system. We find that when
both edges are N atoms, M1 shows metallic behavior, while when

Fig. 2. The configuration energies as a function of the number of the unit for the BNC Fig. 4. The electronic density distributions of (a) pristine ZGNR, (b) M1, (c) M2, (d) M3,
nanoribbons. and (e) M4 unit cells.
 J. Ouyang et al. / Computational Condensed Matter 4 (2015) 40e45 43

contributes to the transmission, we can observe the corresponding

transmission coefficient is 1G0, and if there are two bands pass
through the energy region, and the transmission coefficient is 2G0.
As shown in Fig. 3 (a) and (c), we can find there are two bands pass
through the energy region near the Fermi level, so the corre-
sponding transmission coefficient platforms are 2G0 for M1 and
M3. However, for M4, as shown in Fig. 3(e), we can find the
conductive band and valence band are only overlapped at Z point,
and only an energy band passes through the energy region near the
Fermi level, so the corresponding transmission platform is 1G0.
To understand the effects of the position relationships between
the BNNRs and GNRs on the electronic transport properties of
ZBNCNRs, we have studied the local density of states (LDOS) of the
four devices at the Fermi level under zero bias voltage. For M1, as
shown in Fig. 6(a), we can find the DOS is mainly located at the C
atoms in the central of the ribbon, and the distribution of LDOS is
delocalized through the whole scattering region. When it comes to
M2, it can be found (showing in Fig. 6(b)) that very little LDOS is
highly localized at the boundaries of the scattering region, leading
Fig. 5. The transmission spectra of (a) pristine ZGNR, (b) M1, (c) M2, (d) M3, and (e) to a blockade of electron transport. As a result, the transmission
M4 devices at zero bias voltage. The blue dashed lines denote the Fermi level. coefficient is zero around the Fermi level for M2, as shown in
Fig. 5(c). M3 device is similar to that of M1 device, the LDOS is
mainly located in the central C atoms, and the distribution of LDOS
shows delocalization. The LDOS of M4 device is mainly located at C
which indicates the electrons are tend to move toward the N atoms atoms on the two edges of ribbon and delocalized through the
and away from the B atoms in all doped systems. whole scattering region of the device, thus the transmission plat-
Then we calculate the transmission spectra of the four devices at form appears in Fig. 5(e).
zero bias, as presented in Fig. 5. For the transmission spectra of M1 Actually, the width would have significant effects on the elec-
device, as shown in Fig. 5(b), there is a wide transmission platform tronic or transport properties of these BNC hybrid nanoribbons. In
with the value of 2G0 (G0 ¼ 2e2/h is the quantum conductance) order to understand the width-dependent electronic and transport
around the Fermi level, which indicates the M1 device has a properties, take M2 (Z6) as an example, we expand the width of the
metallic transport property. For that of M2 device, there is a large central graphene nanoribbon, and construct four BNCNR models
transmission gap appears around the Fermi level in Fig. 5(c), which with the width of 7, 8, 9 and 10 (Z7eZ10), as shown in the inserts of
indicates the system show semiconductic property, and it agrees Fig. 7(b)e(e), respectively. We also calculated the width-dependent
well with that of the band structure. While for the transmission electronic and transport properties of the BNCNRs, and the results
spectras of M3 and M4, as shown in Fig. 5(d) and (e), both of them are present in Fig. 7(aee) and (a1ee1). We can find that, with the
show metallic property, and the transmission coefficients at the expanding of width, the band gap is decreased, and the corre-
Fermi level are 2G0 and 1G0, respectively. Actually, the transmission sponding transmission peaks near Fermi level are close to each
coefficient is origin from the band structure of the BNC nanoribbon, other. Thus, we can know that, with the increasing of the width, the
if there is an energy band passes through an energy region, and effect of the edge state of the nanoribbon is weaker, and the

Fig. 6. The LDOS of (a) M1, (b) M2, (c) M3, and (d) M4 devices at the Fermi level under zero bias voltage. The isosurface value is 0.05 Å3 eV1.
44 J. Ouyang et al. / Computational Condensed Matter 4 (2015) 40e45

Fig. 7. (a)e(e) The band structures of Z6, Z7, Z8, Z9, and Z10. (a1)e(e1) The corre-
sponding transmission spectra.
Fig. 9. Currentevoltage (IeV) curves for perfect ZGNR, M1, M2, M3, and M4 devices.

transport properties of the BNC hybrid nanoribbons would be

increased.
Meanwhile, the boundary between BN and C is not very sharp in bias voltage. Comparing the IeV curves of M1 with the pristine
practice. So we also consider the effect of the roughness at the ZGNRs, one can find the current of M1 is much larger than the
boundary. We selected M2 as the example, there are new models pristine ZGNRs, which indicates the BNNRs with two N doped
with roughness boundary between BN and C are constructed, as edges can increase the conductive ability. And M3 device exhibits
shown in the inserts of Fig. 8(bed). The edge of the central GNR (the the same phenomena with M1. Moreover, the current of M3 is
boundary of BN and C) is doped by an N atom, a B atom, and the N slightly larger than that of M1. If the BNNRs doped in the middle of
and B atoms, which refer to RM1, RM2 and RM3, respectively. And 6ZGNRs, there is slightly influence to the IeV curve. While for M2,
the corresponding transmission spectra at zero bias voltage have whose edges are doped by N and B atoms respectively, the IeV
been plotted. And the one with perfect boundary is also present as curve shows completely the opposite situation. One can see the
comparison in Fig. 8(a). We can find the roughness boundary would current of M2 keeps zero with the increasing of bias voltage in low
have effects on the transport properties of the BNC nanoribbons, bias window. When the bias is larger than 1.2 V, the current rises
the transmission coefficients will be suppressed in the higher en- quickly with the increasing of bias voltage and nearly presents
ergy regions, such as the transmission peeks around ±0.4 eV are linear relationship.
suppressed. So we can know the roughness boundary between BN
and C would decrease the transport ability of the BNC nanoribbons
in the higher bias range.
4. Conclusions
In addition, for a further insight into the electronic transport
properties of the ZBNCNRs devices, we present the currentevoltage
In conclusions, by using NEGF method coupled with DFT, we
(IeV) curves for M1, M2, M3, and M4 devices, as shown in Fig. 9. For
have a systematic study about the electronic properties and
the pristine 6ZGNRs, the current is close to zero under finite bias,
transport properties of ZGNRs doped with BNNRs. Our calculation
and begins to increase when the bias is stronger than a threshold
shows that the doping position and the doping patterns have a
huge influence on the electronic properties and transport proper-
ties of ZGNRs. When the BNNRs doped systems possess a sym-
metric structure, the band gaps are zero, and the IeV curve show
metallic properties. Nevertheless, when the symmetry has been
broken, there have two kinds of situations. If the BNNRs doping in
the center, the band show metallic properties, and the IeV curve is
depressed seriously. When the BNNRs doping in the two edges,
there is a large band gap appears, and the IeV curve presents
semiconducting properties. Our results would have theoretical
guidance for the experiments and applications in graphene-based
nano-electronics.

Acknowledgments

This work is supported by Hunan Key Laboratory for Super-

microstructure and Ultrafast Process, and the National Natural
Science Foundation of China (Nos. 61306149 and 11334014), the
Natural Science Foundation of Hunan Province (Nos. 14JJ3026 and
Fig. 8. (a)e(d) The transmission spectra for M2, RM1, RM2 and RM3. 13JJ3003) and Hong Kong Scholars Program (No. XJ2013003).
 J. Ouyang et al. / Computational Condensed Matter 4 (2015) 40e45 45

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