Superlattices and Microstructures 57 (2013) 95101

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Superlattices and Microstructures

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

A recursive Greens function method to study

of monatomic gas adsorption effects
on conductivity in a graphene nanoribbon
A.A. Shokri a,b,, A.H. Mosavat b
a

Department of Physics, Payame Noor University (PNU), 19395-3697, Tehran, Iran

Computational Physical Sciences Research Laboratory, School of Nano-Science, Institute for Studies in Theoretical Physics
and Mathematics (IPM), PO Box 19395-5531, Tehran, Iran

a r t i c l e

i n f o

Article history:
Received 1 December 2012
Received in revised form 18 January 2013
Accepted 27 January 2013
Available online 16 February 2013
Keywords:
Graphene
Ballistic transport
Gas adsorption
Recursive Greens function
Tunneling

a b s t r a c t
In this work, we present a recursive Greens function method to
calculate electronic transport of armchair graphene nanoribbon
(AGNR) and zigzag graphene nanoribbons (ZGNRs) quantum wires
with randomly adsorption of monatomic gas molecules, which
attached to two semi-innite metallic leads. This model reduces
numerical calculations time and enables us to use Greens function
method to investigate transport in a supperlattice device. The calculations based on the Landauer-type formula within the tightbinding approximation, which the recursive Greens function
method is used to solve inhomogeneous differential equations.
The effects of monatomic gas molecules adsorption on electronic
conductance properties are studied for various length and wide
size of wire. Our numerical results show that the transport properties are strongly affected by the quantum interference effect, the
lead interface geometry to the device and also adsorption of gas
molecules on GNR sheets. By controlling the type of contact and
wire geometry, this kind of system can explain the antiresonance
states at the Fermi energy. The results can be used to control and
engineer the graphene-based systems.
2013 Elsevier Ltd. All rights reserved.

Corresponding author at: Department of Physics, Payame Noor University (PNU), 19395-3697, Tehran, Iran. Tel.: +98
2122835061; fax: +98 2122835058.
E-mail address: aashokri@tpnu.ac.ir (A.A. Shokri).
0749-6036/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.spmi.2013.01.009

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1. Introduction
Since the rst successful fabrication of a single layer graphene [1], many attentions have been focused on electronic transport properties of graphene nanoribbons (GNRs) [13]. Graphene is the name
given to at monolayer of carbon atoms tightly packed into a two-dimensional honeycomb lattice
with some extraordinary properties resulting from the fact that charge carriers in graphene obey linear dispersion relation. This can be described by the Dirac equation and the mimicking massless relativistic particles [4]. It has unusual electronic properties such as high carrier mobility, an anomalous
quantum Hall effect and absence of the Anderson localization, making it interesting to study transport
properties of graphene sheets [47]. Moreover the electrical properties of graphene structure could be
controlled by edge shapes and system sizes. Depending on edge structure, zigzag or armchair edges,
and size, GNRs can be either semiconductor or metallic [810]. The energy gap in patterned graphene
nanoribbons can be tuned during fabrication with the appropriate choice of ribbon width [11]. Thus,
the energy gap is necessary to control electronic and transport properties of the nanodevices. In order
to study the transport related properties, the nanowire is generally considered as a scattering region of
nite size connected to the two semi-innite ballistic leads based on a Landauer approach [12]. One of
the simplest ways to calculate transmission coefcients in such systems is recursive Greens function
method based on a tight-binding model [13].
The large surface area makes these nanostructures as potential materials for gas and energy storages. Therefore, it is important to know how adsorbed gas molecules can have an inuence on the performance of graphene devices for almost every application [14,15]. For example, they can detect the
presence of toxic molecules in the environment, which may be known as gas sensors [16].
In the recent work [17], we have introduced a recursive method based on Greens function, to
investigate the electronic properties of quasi one-dimensional systems. This approach is applied to
an armchair graphene nanoribbons (AGNRs) and zigzag graphene nanoribbons (ZGNRs) quantum
wires attached to two semi-innite square lattice leads to evaluate the transmission probability. Also,
the inuences of the GNR length and width have been investigated on the conductance and electric
current at room temperature. It has shown that the lead interface geometry to the device and the
quantum interference effect play an important role in the transport properties of the system. Here,
the paper presents an another important piece of work related to graphene, an important material
offering potential applications, such as gas sensor. We study the effects of monatomic gas molecules
adsorption on electronic properties of the wires within the considered model. The results show that
the conductance curves of the system change by adsorption of gas molecules on GNR sheets.
The paper is organized as follows. In Section 2, the supperlattice quantum wire sandwiches between two semi-innite leads is dened and the proposed model for calculating the conductance
using the recursive Greens function method is described. In Section 3, the numerical results on the
transport properties of the wire due to effects of randomly adsorption of monatomic gas molecules
are discussed. Finally, the results of this work are summarized in the last section.

2. Description of the model

In this section, we study the electronic conductance in a quasi one-dimensional structure formed
by a GNR quantum wire connected to two semi-innite metallic leads. It is assumed that the quantum
wire is nite in the directions perpendicular to the transport (Fig. 1). This approach can also be generalized to layered systems that are periodic in these directions. In this case, translations in the transverse direction can be described in terms of a Bloch wave vector in the two-dimensional Brillouin
zone, kk , which is a good quantum number and the system becomes effectively quasi one-dimensional.
This is cased the system has mapped from real space into mode space. Furthermore, we consider the
adsorbed monatomic gas molecules on the GNR quantum wire, randomly, which be assumed that each
one adsorbed to only one carbon atom (see the red circle in Fig. 1).
According to recursive Greens function method, the system is divided up into N vertical slices (see
the graphene unit cell in Fig. 1) perpendicular to the wire direction between the left lead 1; 0 and
the right lead N 1; 1. Each slice has M lattice points, which the dimension of relevant matrices in

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97

Fig. 1. Schematic picture of (a) AGNR and (b) ZGNR quantum wires attached to two semi-innite metallic square lattice leads in
the real space. The unit cells are denoted by the dotted rectangular. The open and closed circles show the site carbon atoms. W
and N show the width number (number of contacts between the device and the leads) and length number (number of AGNR and
ZGNR unit cells), respectively. In Fig. 1a, the system which consists of two semi-innite leads with N L 9 and a GNR region with
W = 4 (=9.838 ) is shown. Also, in Fig. 1b, the leads with N L 7 and a GNR region with W = 5 (=9.230 ) is represented. The
central scattering region in two panel of the gure consists of 3 (=11.360 ) and 5 (=11.068 ) unit cells, where about 54 and 50
carbon atoms, respectively. Also, the red circle shows the monatomic gas adsorption on a carbon atom, randomly. (For
interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

each slice corresponds to M  M. The thickness of these slices is chosen such that there is only an
interaction between neighboring slices. In this process we do not require to calculate the enormous
matrices hence, the numerical calculation time reduces strongly.
Each slice is labeled with an index i. Thus, the electrons of the both quantum wire and two perfect
leads are described with the effective one-electron Hamiltonian in the tight-binding model in the
nearest neighbor approximation [17]

X
X
jiiHi;i hij
jiiHi;j hjj:
i

hi;ji

The rst term, Hi;i describes the local slice energy element in the localized Wannier state jii, on slice
i. In the last term, Hi;j is the nearest-neighbor hopping matrix element and h  i stands for the summation on the nearest-neighbor sites for an electron on slice i and j. It should be noted that the effect of
gas molecule adsorption on each site (s) is considered in the on-site energy of same atom (es ) as

 
es ! es  t2
s =es  E [18]. Here, e ; t and E are the on-site energy of the gas molecule, hopping energy

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between the atom and gas molecule and incident electron energy, respectively. It is noted that the
adsorption as a surface-based process is the adhesion of atoms, ions, or molecules from a monatomic
noble gas to a surface of the device. Also, it is assumed that the two perfect leads have negligible resistance, whose main contribution of resistance in our ballistic device comes from the contact resistance.
The Greens function matrix relationship for an incident electron with energy E between all the lattice points on slice i is given by

E igI  Hi;i Gi;i  VGi1;i  Vy Gi1;i 0;

where g is an arbitrarily small number added into the above equation to incorporate the convergence
conditions and I is the identity matrix. In Eq. (2) V and Vy is the hopping matrix elements of Hamiltonian linking slice i to right and left slices within the nearest neighbor approximation. The order of
all matrices are M  M. Eq. (2) in the matrix form can be solved by considering the homogenous eigenvalue formulations corresponding to Refs. [1921].
In order to investigate the transport properties in the present structure, we calculate the transmission amplitude using the recursive Greens function method [17]. We should note that, the transmission amplitude t mn depends on the mth lattice point at the rst slice (as incident mode) and nth lattice
point at the Nth slice (as out-going mode) [20,21]. In the coherent regime, the physical properties are
determined by electrons with the energy near the Fermi level at low temperature compared with the
Fermi temperature. This is the linear response regime corresponding to the total conductance of electron through the device as [22]

G G0

*
+
NR X
NL
X
jtmn j2
m1 n1

conf:

Fig. 2. Electronic transmission probability as a function of the incident electron energy for AGNR edge geometries by including
two different widths of atomic row, W = 4 (=9.838 ) and W = 5 (=12.297 ). Each panel of the gures predicts for several
lengths of the graphene ribbon, N = 5 (=19.880 ) and N = 50 (=211.580 ) unit cells. The thin and thick solid lines show without
(p 0%) and with (p 5%) gas adsorption.

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99

which is transmitted from the right electrode. The summation run over the open channels, of which
there are N L and N R in the left and right lead, respectively. In Eq. (3), G0 2e2 =h and h  i denotes
the average over the conguration of monatomic gas adsorption on the device.
3. Numerical results and discussion
In order to investigate the effect of monatomic gas adsorption on electrical conductance of a cubic
matal/GNR structure, several numerical calculations have been performed for the cases based on the
recursive Greens function formalism and considering nearest-neighbor interaction. The GNR wire is
considered with two armchair and zigzag edges, as shown in Fig. 1a and b, respectively. Numerical calculations have done for the cases that all local on-site energies were assumed set to zero, and all nearest-neighbor hopping parameters were assumed, tL t R t GNR 1. Moreover, the coupling between
the GNR device and the leads were taken to be same, tDL t DR 0:75, namely, both barriers are identical. Also, the hopping energy between the GNR device and the gas atom is set to t  2. The whole
energies are measured in the unit of t. In the formalism, we ignore the charging effect in the GNR
due to the electronphonon and electronelectron interactions as it is assumed that the GNR-leads
coupling is not weak. It should be mentioned that the transmission can be efciently controlled by
the considered congurations of GNR, which this property can be useful for a nanoelectronic switching
device. Here, we present the results of the electrical conductance, and discuss the sensitivity of electron transport to the topology of the GNR-lead interface, the width of device and effect of gas adsorption in the proposed nano-device.
In Figs. 2 and 3, we have shown the electronic conductance as a function of the incident electron
energy for two cases of armchair and zigzag GNR edge geometries by including
two different widths
p
of atomic row, W = 4 and 5, respectively. This number of atoms species 3WaCC of the AGNR width,

Fig. 3. Electronic transmission probability as a function of the incident electron energy for ZGNR edge geometries by including
four different widths of atomic row, W = 4 (=7.100 ) and W = 5 (=9.230 ). Each panel of the gures predicts for several lengths
of the graphene ribbon, N = 5 (=11.068 ) and N = 50 (=121.747 ) unit cells. The thin and thick solid lines show without
(p 0%) and with (p 5%) gas adsorption.

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A.A. Shokri, A.H. Mosavat / Superlattices and Microstructures 57 (2013) 95101

and 3W=2  1aCC of the ZGNR width with aCC 1:42 . Also, each panel of the gures has been predicted for two lengths of the
graphene ribbon, N 5 and 50 unit cells. These lengths are determined
p
by 3N  1aCC and 2N  1 3aCC =2 for the AGNR and ZGNR, respectively. As shown in Fig. 1, W and N
point out to the number of contacts between the device and the leads, and the number of unit cells,
respectively. We have specied them in term of angstrom in the caption of Figs. 2 and 3. In order to
investigate the effect of monatomic gas adsorption, we have plotted the results for absence (p 0%)
and presence of gas adsorption (p 5% in relative values of all carbon atoms) on the GNR device by
thin and thick solid lines, respectively. In all cases, we note a small but detectable decrease of conductance after the introduction of the gases. In case with W 4, we can see the conductance value increases about Fermi level in the presence of gas adsorption.
The solid curves in Figs. 2 and 3 are the same with Ref. [17]. The spectral conductance curves represent the resonance peaks for some particular states at certain energy levels. The resonance conductance is related to interference effects induced by quantum size effects of the GNR-lead interface. Also,
it is observed that the conductance peaks do not reach width number value (is known as conductance
channels) and get a much reduced value. The reason of this can be explained by the effect of quantum
interference [23]. Moreover, the strength of the resonant peaks appears to depend on both the length
and the width of the ribbon [24]. As a general trend the peaks of resonance increase with increasing
the width and decrease as the length increases. Moreover, it is obvious that the number of resonance
level increases with increasing of the width and length of GNRs. Thus, it can be noted that the electron
conductance is strongly affected by the quantum interference effect and the lead interface geometry to
the device.
Also, we can see a symmetry and asymmetry in the conductance curves around the Fermi energy in
the features of Figs. 2 (AGNR) and 3 (ZGNR), respectively. The reason for these behaviors is the shape
of the GNR conguration and the contacts between the GNR and the lead interfacial atoms (see Fig. 1).
The contacts act as a lter selecting single transport channels, which may be viewed as the wave-function overlap of the device and the leads due to the nature of transverse coupling. Also, in some energy
regions, the conductance curve becomes zero and there are gaps which the incident electrons cannot
propagate across the structure. The energy gap can be tuned with the appropriate choice of ribbon
width [24,25]. The reason for this effect is the reduced overlap between the bandwidths of the two
leads and the GNR due to the HOMOLUMO gap of the GNR [9,11].
From the features of Fig. 2, it is obvious that the adsorption of gas molecules by AGNR (W 4)
changes the electronic behavior into metallic in both panels of N = 5 and 50. That is, the charge transport is enhanced in these systems. In contrast, the panels of W 5 show that the system tends towards semiconducting behavior. In case N 50, the band gap appears in the system. As shown in
Fig. 3, it can be seen that in N 5 (short length) of both widths W = 4 and 5, the adsorption of gas molecules does not change the electrical transport properties of nanowire. But in long length (N 50) the
system tends towards semiconducting behavior. With reference to the gures, we can see that that the
metallic (semiconducting) system tends towards semiconducting (metallic) behavior. The reason of
this can be explained due to the adsorption of gases, which create addition scattering centers in the
midsection. That is, they affect localization length of the system [11,26] and thus the electron transmission of the system changes.
From the features of Fig. 3, we can see an important effect in the transmission curves, known as the
Fano-type resonance (transmittance zeros) [2730]. Such sharp dips (antiresonance states) are specic
to the interferometric nature of the scattering and do not occur in conventional one-dimensional scattering problems of potential barriers. This may be due to the interference between two channels [31].
It is also observed that the positions of the antiresonances on the energy scale are independent from
the device-electrodes coupling strength. As shown in Fig. 3 with N 50 and P 0%, a Fano resonance
has been created at the Fermi energy E 0, which caused the semimetal behavior. the antiresonance
states are related to the active region and independent from the coupling strength between the device
and the leads [23]. The widths of these states are very small and hence they do not make any significant contribution to the current-voltage characteristics.
The results of the calculations are sensitive to the realization of disorder. In order to achieve an
acceptable accuracy in the conductance, the averaging has been performed over 5000 realizations
in all calculations. This gives an absolute error in GE of 0.001 to be sure that some slight oscillations

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101

seen in their gures are meaningful. Because of ensemble averaging, there are some uctuations in the
central region of curves at resonance energies in the disordered regime.
4. Conclusions
On the basis of the tight-binding model and the recursive Greens function method, we solved inhomogeneous differential equations for studying the electronic transport properties in zigzag and armchair GNRs attached to the two semi-innite metallic square lattice leads. We have investigated the
effects of length and wide size of wire, and the monatomic gas molecule adsorption effects on the electrical conductance for the M/GNR/M structure. It is found that: (i) electronic behavior changes into
metallic then semiconducting; (ii) antiresonance states (transmittance zero), which is known as Fano
resonance were observed and attributed to the interference between two channels but do not induce
any important contribution to IV characteristics; and (iii) electron conductance strongly affected by
quantum interference effect as well as interface geometry to the device. The theoretical results on the
conductivity in terms of adsorbed gas molecules can be made as a gas nanosensor devices based on
graphene.
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