Proceedings of the 7th IEEE International Conference on Nanotechnology August 2 - 5, 2007, Hong Kong

Electronic and Transport Properties of Graphene Nanoribbons

Zhufeng Hou* and Marcus Yee
Atomistix Asia Pacific Pte Ltd, Singapore

Abstract We present the electronic structures and transport properties of hydrogen-saturated graphene ribbons and its dependence on its termination edge, ribbon width, and impurity. The band structures, transmission spectrum, and current-voltage (I-V) characteristics of graphene ribbons have been calculated by using first-principles electronic structure methods and nonequilibrium Green's functions technique. Our calculated results show that the graphene ribbons with zigzag shaped edges exhibit nonlinear behavior of I-V characteristics due to the overlapping of * and bands around Fermi level. As the width of zigzag chain of graphene ribbons increases, the overlapping of * and bands is enhanced and the voltage range for linear I-V response becomes narrower. The graphene ribbons with armchair shaped edges exhibit semiconducting properties and the band gap decreases with increasing ribbon width. The doping of B or N in graphene ribbons with armchair shaped edges slightly increases the current at lower bias voltage. Keywords Graphene, nanoribbon, electronic transport, and first-principles.

I.

INTRODUCTION

along the zigzag line of zigzag GRs, dz, is 3 dC-C, and the corresponding primitive periodic length along the armchair line of armchair GRs, da, is 3dC-C. In this paper, we studied the properties of zigzag GRs with ribbon width of wz and 2 wz, armchair GRs with ribbon width of wa and 2 wa, and B (or N) doped armchair GRs with ribbon width of 2 wa as shown in Fig. 1(a), (b), (c), (d), and (e), respectively. To analyse quantum transport through ab initio method, one must deal with open systems within the density-functional theory formalism as the system is either isolated or periodic and can be considered as two semi-infinite electrodes coupled via a contact region. Hence to study the electronic transport properties of GRs, the open system is divided into three regions: left electrode, center scattering region, and right electrode. For each system shown in Fig.1, the electrodes are marked by red line, and the remaining part corresponds to the center scattering region. For B (or N) doped armchair GRs, one of carbon atoms in center scattering region is substituted by a B (or N) atom, as shown in Fig. 1(e).

Graphene, one-atom-thick sheet of carbon atoms arranged in a honeycomb lattice, has been obtained experimentally recently [1, 2]. It is attracting much more attention in carbonbased electronics due to its very peculiar electronic properties [3] such as ballistic transport [1] and quantum Hall effect (QHE) [4]. The former makes graphene a promising candidate for future electronic applications, such as ballistic field-effect transistors (FETs) [3]. Recent progresses in electronic structure calculation that incorporated the non-equilibrium Greens function (NEGF) method allows the study of quantum transport in nanodevices based on ab initio model [5,6]. Here we demonstrate how the study of electronic transport in graphene nanoribbons will shed more light on the potential applications of graphene nanoribbons as FETs. II. COMPUTATIONAL METHOD AND DETAILS
Figure 1. Open systems of hydrogen-saturated graphene nanoribbons: (a) zigzag shaped edges with ribbon width of wz; (b) zigzag shaped edges with ribbon width of 2wz; (c) armchair shaped edges with ribbon width of wa; (d) armchair shaped edges with ribbon width of 2 wa; and (e) armchair shaped edges with ribbon width of 2 wa and with one B (or N) impurity. The open system consists of two electrodes and the scattering region. The electrode regions are marked by red lines. The remaining part corresponds to the scattering region. The optimized bond lengths of carbon-carbon and carbonhydrogen are 1.42 and 1.10 , respectively.

A. Model A graphene ribbon (GR), created by cutting a graphene sheet along two parallel zigzag or armchair lines, exhibits zigzag or armchair edges. We will consider the hydrogen terminated GRs with zigzag and armchair shaped edges, as illustrated in Fig. 1. If the bond length of C-C atoms in graphene is denoted by dC-C, the narrowest width of zigzag GR, wz, will be 2dC-C, while the narrowest width of armchair GR, wa, will be

3 dC-C. In addition, the primitive periodic length

B. Density-functional theory and non-equilibrium Greens function methods In order to study the electronic transport through open systems of graphene ribbons as shown in Fig. 1, we employ the

*Corresponding author. Email: zh@atomistix.com.

1-4244-0608-0/07/$20.00 2007 IEEE.

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fully self-consistent density-functional theory (DFT) methods based on a flexible linear combination of atomic orbital basis set and first-principles norm-conserving pseudopotentials methods [7], together with the NEGF method [5] [6], which are implemented in Atomistix ToolKit (ATK) [8]. ATK is able to fully model the electrical properties of nanoscale devices that consist of an atomic scale system coupled with two semiinfinite electrodes self-consistently. First, the electronic structures of two electrodes are calculated separately using DFT to get the self-consistent Kohn-Sham potentials and Hamiltonian matrices. For the DFT calculations implemented in ATK, the Kohn-Sham Hamiltonian has the following form:
2 & & + V H (r ) + V NA (r ) + V xc (r ) (r r ' ) & & & H = 2 & & + V NL (r , r ' ) . (1) xc & Here V ( r ) is the exchange-correlation potential of electrons; & V NL (r ) represents the local pseudopotential screened by the

with being the numerical basis orbtials. This allows us to compute the DFT Hamiltonian elements H in Eq. 3 through Eqs. 1 and 2. The whole procedure for open system is iterated until self-consistency is achieved. Once the self-consistency is achieved, the current through the system is calculated as [9]

I (Vb ) = G0 d [nF ( L ) nF ( R )]

Tr[Im L ( )G + ( ) Im R ( )G ( )] ,
where G0 = 2e2/h, and

(6)

potentials of each electrode, i.e.,

R are the electrochemical L R = eV b .

The (left-to-right) transmission amplitude matrix t is identified from Landauer-Bttiker formula [10] as

t ( ) = Tr[Im L ( )G + ( ) Im R ( )G ( )] .

(7)

addition of charge density of the neutral isolated atoms is the screened Hartree potential which solves the corresponding Poisson equation

NA (r ) [7]; V H (r )

&

&

& & & 2V H (r ) = 4 (r ) NA (r ) .

& &

(2)

The corresponding Hamiltonian matrix H is obtained by multiplying with two numerical basis orbitals and and integrating over dr and dr ' . The Greens function of open system, G, is evaluated by inverting the finite matrix

In the calculations of GRs, we employed Troullier-Martins pseudopotential [11] and standard double-zeta polarized basis set [7]. The exchange-correlation potential of electrons is treated by the local density approximation [12]. The bondlengths of C-C atoms (dC-C) and C-H atoms (dC-H) are obtained as 1.42 and 1.1 , respectively, through the optimization and relaxation of graphene ribbons. For the solution of the Poisson equation in the electrode calculations we use the Fast Fourier transform (FFT) technique. For open systems, a multigrid technique [13] is used to solve the Poisson equation. III. RESULTS AND DISCUSSIONS

H L + L + VL 0

VL HC VR+

VR , H R + R 0

(3)

where HL, HC, HR are the Hamiltonian matrices in the left electrode, center scattering region, and right electrode, respectively, and VL (VR) is the interaction between left (right) electrode and center scattering region. L and R are the selfenergies due to coupling to the left and right electrodes, respectively. From the Greens function we can obtain the density matrix

In order to gain some basic information on the electronic structures of GRs, we first calculated the band structures of zigzag and armchair GRs with different widths. For zigzag GRs with ribbon width of wz and 2 wz, their band structures are presented in Fig. 2(a) and (b), respectively, and we can see that two bands cross the Fermi energy near wave vector k = / d z . These lower and upper bands corresponds to and * orbtials of carbon atoms, respectively. Here we used E * to characterize the overlapping of and * bands at

k = / d z . For narrowest zigzag GR, its E * is estimated

to be 0.59 eV. While for zigzag GR with ribbon width of 2 wz, the E * is about 0.08 eV. These indicate that the overlapping of and * bands in zigzag GRs will be enhanced with increasing ribbon width. As shown in Fig. 1(c) and (d), armchair GRs exhibit the characteristics of direct bandgap semiconductor. The band gap of narrowest armchair GR is about 1.60 eV and its transition at k = 0. For armchair GR with ribbon width of 2 wa, its band gap decreases to 0.29 eV. These indicate that the band gap of armchair GRs will decrease as the ribbon width increases. This energy band gap behaviour of GR is also predicted in a systematical study [14] and demonstrated experimentally [15]. The origin of energy gaps for armchair is ascribed to both quantum confinement and the crucial effect of the edges [14].

D =

Im G ( )n F ( )d ,

(4)

where nF is the Fermi function and is the chemical potential of the system. The electron density is given by

(r ) = (r ) D (r ) ,
,

&

&

&

(5)

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For B (or N) doped armchair GR with ribbon width of 2 wa, the I-V characteristic is very similar to that of the undoped armchair GR. However we notice that the doping of B (or N) slightly increases the current compared to that of undoped armchair GR with ribbon width of 2 wa at voltages from 0.3 V to 0.8 V (or from 0.3 V to 1.2V), but decreases the current at voltages above 0.9 V (or above 1.3 V). Note that the concentration of B (or N) impurity in center scattering region is only about 1.1%. Thus at such low concentration, the effect of doping of B (or N) on the I-V characteristics of armchair GR may seem very trivial. More work needs to be done to understand the effects of higher doping.

Figure 2. Band structures of hydrogen-saturated graphene ribbons: (a) zigzag shaped edges with ribbon width of wz; (b) zigzag shaped edges with ribbon width of 2 wz; (c) armchair shaped edges with ribbon width of wa; and (d) armchair shaped edges with ribbon width of 2 wa. The 1D unit cell distances for graphene ribbons with zigzag and armchair shaped edges are denoted by dz and da, respectively.

Figure 3. Current-voltage characteristics of hydrogen-saturated graphene nanoribbons.

In Fig. 3 we show the current-voltage (I-V) characteristics of hydrogen-saturated GRs. For zigzag GRs, their I-V characteristics exhibit nonlinear behavior. That is, within a certain range the current increases linearly with increasing applied bias voltage (Vb), however this dependence does not appear when the applied bias voltage exceeds a certain range. For the narrowest zigzag GR, the current increases linearly when the bias voltage increases from -0.8 V to 0.8 V before saturating at voltages above 0.8V. For zigzag GR with ribbon width of 2 wz, the linear current regime is between -0.04 V to 0.04 V, above which the current also tends to saturate. These indicate that the range of bias voltage for the linear response regime decreases as the ribbon width of zigzag GRs increases, suggesting that the overlapping of and * bands in zigzag GRs is enhanced accordingly. In this linear response regime of the zigzag GRs, the conductance is about 2G0 (G0 = 2e2/h) based on the slopes of the I-V graph. This can also be seen from their transmission spectra in Figure 4, reflecting the presence of two conducting channels at the Fermi energy. For armchair GRs, voltage turn on characteristics are observed. This can be understood as armchair GRs exhibit semiconductor properties with different band gap energies. For armchair GR with width wa and 2 wa, the turn on voltage is ~1.7 V and 0.4V respectively. These also indicate that band gaps of armchair GRs decrease with increasing ribbon width.

The transmission spectra of H-saturated GRs are plotted in Fig. 4. Zigzag GRs exhibit step-like transmission spectra. For narrowest zigzag GR, the transmission coefficient is 2 for energy 0.3 eV and 1 for energy range between 0.3 eV < | | 2.3 eV. For zigzag GR with ribbon width of 2 wz, within the energy range of | | 0.04 eV the transmission coefficient is 2. This shows that there are two conducting channels around the Fermi energy F, and these channels are due to the and * intra-band transmissions from the left electrode to the right electrode. For armchair GRs, the transmission coefficient is zero around Fermi energy F and the widths of these zero transmission energy windows are very close to their corresponding band gaps. Beyond these energy windows, the transmission coefficient is close to 1 as only one band appears at the top of valence bands and only one * band at the bottom of conduction bands. From Fig. 4(e) and (f), we can see that the characteristics of the transmission spectra of B and Ndoped armchair GRs are close to that of the undoped airchair GRs. This also explains why the doping of B or N only slightly affects the I-V characteristic of armchair GR.

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The authors wish to acknowledge the assistance and support of Dr. Shaw Choon Chuang and Dr. Zhenhua Yao. REFERENCES
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[2]

[3] [4]

Figure 4. Transmission spectrum of hydrogen-saturated graphene nanoribbons at zero bias voltage: (a) zigzag shaped edges with ribbon width of wz; (b) zigzag shaped edges with ribbon width of 2wz; (c) armchair shaped edges with ribbon width of wa; (d) armchair shaped edges with ribbon width of 2 wa; (e) armchair shaped edges with ribbon width of 2 wa and with one B impurity; (f) armchair shaped edges with ribbon width of 2 wa and with one N impurity.

[5]

[6]

[7]

IV.

CONCLUSION
[8] [9] [10]

Using the density function theory method and nonequilibrium Green's function technique, we study the electronic structures of hydrogen-saturated zigzag and armchair graphene ribbons with different ribbon widths and the electronic transport through these graphene ribbon under finite bias voltage. Our results show that graphene ribbon exhibits peculiar electronic structures and transport properties. Zigzag graphene ribbons possess nonlinear I-V characteristics and the width of bias window for the linear response regime decreases as the increasing of ribbon width. Armchair graphene ribbons exhibits the properties of semiconductor and their band gaps decreases with increasing ribbon width. All of these behaviors are ascribed to the interaction and intra-band transition of and * bands around Fermi energy. ACKNOWLEDGMENT

[11] [12] [13] [14] [15]

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