Copyright © 2011 American Scientific Publishers Journal of

All rights reserved Computational and Theoretical Nanoscience

Printed in the United States of America Vol. 8, 1–6, 2011

Structural and Magnetic Instability of Bilayer and

Trilayer Zigzag Graphene Nanoribbons
Yanna Zhang1 , Xiao-Li Lu1 , Yongjin Jiang1 ∗ , Botao Teng2 , and Jun-Qiang Lu3 ∗
1
Department of Physics and Center for Statistical Physics and Condensed Matter Physics, Zhejiang Normal University,
Jinhua, Zhejiang 321004, China
2
College of Chemistry and Life Science, Zhejiang Normal University, Jinhua, Zhejiang 321004, China
3
Department of Physics and Institute for Functional Nanomaterials, University of Puerto Rico, Mayaguez, PR 00681, USA

Edge states at Fermi energy in layered zigzag graphene nanoribbons are unstable and may lead to
structural deformation or magnetization of edges or both. We report first-principle study on struc-
tural and magnetic instability of bilayer and trilayer zigzag graphene nanoribbons with two different
edge alignments. For layered nanoribbons with -alignment edges, their edges undergo a structural
instability and tend to bend inward; the structural deformation moves edge states away from Fermi
energy to lower the total energy of the system and no further magnetization is needed in the bilayer
nanoribbon, which leads to a nonmagnetic ground state; while structural deformation alone is not
enough to stabilize the electronic structures of the trilayer nanoribbon and thus a further magneti-
zation is needed, which leads to an antiferromagnetic ground state. For layered nanoribbons with
-alignment edges, no structural deformation happens and all layers keep flat; their edges undergo
a magnetic instability to move edge states away from Fermi energy, which leads a magnetic ground
state; the ground state of the bilayer nanoribbon has an antiferromagnetic intra-layer and ferromag-
netic inter-layer magnetic order; the trilayer nanoribbon has a ground state with non-collinear but

RESEARCH ARTICLE
coplanar inter-layer magnetic moments. Our results reveal the relation between the stabilization
mechanism of layered zigzag graphene nanoribbons and their spatial symmetry (determined by
number of layers) and their edge interactions (determined by edge alignments).
Keywords: Layered Zigzag Graphene Nanoribbons, Magnetization, Structural Deformation,
First-Principle Calculations.

1. INTRODUCTION known that structural confinement leads to novel physi-

In recent years, monolayer and few layers of graphene
have been one of the hottest research topics in con-
densed matter physics. Experimental and theoretical stud-
ies demonstrate a series of unique physical properties of
graphene1–2 due to its unique relativistic low-energy spec-
trum. Graphene has been considered as one of promised
candidates for nanoelectronics and spintronics as it is
zero-bandgap semiconductor with very high mobility ( ≈
5000 cm2 V−1 s−1 . In the past few years, remarkable
progress has been made to manipulate the electronic struc-
ture of graphene by applying external electric field or by
controlling the shape of graphene based nanostructures.
For example, a local gating technique has been developed
successfully to control the doping concentration locally in
monolayer graphene.3 In bilayer graphene, electric field
has been used to control the energy band gap.4 It is well
∗
Authors to whom correspondence should be addressed.
cal properties (in particular, transport properties).5 Miscel-
laneous experimental techniques have been developed to
produce graphene nanoribbons (GNRs),6 which also stim-
ulates considerable theoretical attentions.
Tight-binding model predicts edge states at Fermi
energy (also known as zero energy edge states) in mono-
layer GNRs with zigzag-shaped edges (hereinafter referred
to as M-ZGNRs).7 These edge states correspond to Van
Hove singularities in density of states at Fermi energy.
They are unstable and will be moved away from Fermi
energy by magnetization when including e−e interaction
in the calculations, which leads to magnetic ground states
of M-ZGNRs. First-principle calculations8 show antifer-
romagnetic ground states of M-ZGNRs with magnetic
moments at the two edges towards opposite directions. For
bilayer ZGNRs (B-ZGNRs), tight-binding model also pre-
dicts the existence of edge states at Fermi energy.9 Cal-
culations based on the Hubbard model show that these

J. Comput. Theor. Nanosci. 2011, Vol. 8, No. 12 1546-1955/2011/8/001/006 doi:10.1166/jctn.2011.1977 1

 Structural and Magnetic Instability of Bilayer and Trilayer Zigzag Graphene Nanoribbons
edge states also have magnetic instability which leads
to magnetic ground states.10 The magnetic ground states
of B-ZGNRs have also been confirmed by first-principle
calculations.11 While further studies12 including Van der
Waals non-local potential show -alignment edges of
B-ZGNRs favor structural deformation over magnetization
thus the ground states are nonmagnetic; only -alignment
edges still prefer magnetization. The detailed structures of
B-ZGNRs with different edge alignments will be discussed
later.
In this article, we present our systematic study on the
structural and magnetic instability of B-ZGNRs and fur-
ther trilayer ZGNRs (T-ZGNRs) with different edge align-
ments to get insight of their dependence on the symmetry
and inter-layer edge interaction. The symmetry of layered
ZGNRs is determined by their numbers of layers (odd
or even). The inter-layer edge interaction is determined
by their edge alignments. We first confirm the structural
deformation and magnetization of B-ZGNRs from first-
principle calculations12 and further analyze the symme-
try of their structures and magnetic order. Then we carry
out first-principle calculations and analyses on structural
deformation and magnetization of T-ZGNRs. The results
are remarkable different from that of B-ZGNRs because
of the odd symmetry of T-ZGNRs. The whole article is
organized as follows. In Section 2, we first describe the
detailed geometry models of B-ZGNRs and T-ZGNRs and
the first-principle methods we used. Section 3 presents the
RESEARCH ARTICLE
results and analyses for both B-ZGNRs and T-ZGNRs. We
finally conclude our article in Section 4.
2. MODELS AND METHODS
We start with a brief description of the structure of a M-
ZGNR, as shown in Figure 1(a). The atoms in gray are
C atoms and those in white are H atoms. The structure
is repeated infinitely along y-direction. The width of the
M-ZGNR is defined as the number of total zigzag atom
chains along y-direction. A B-ZGNR includes two M-
ZGNRs with Bernal stacking, which means half of the C
atoms (referred to as A atoms) on the top layer are located
right above C atoms on the bottom layer and the other
Fig. 1. (a) Structure and antiferromagnetic ground state; and (b) band
structure near Fermi energy of a M-ZGNR.
2 J. Comput. Theor. Nanosci. 8, 1–6, 2011
Zhang et al.
half (referred to as B atoms) are located right above the
hexagon centers on the bottom layer. There are two differ-
ent edge alignments of B-ZGNRs, as shown in Figure 2.
In Figure 2(a), all the most edge atoms are A atoms
and this edge alignment is called as -alignment.
In Figure 2(b), all the most edge atoms are B atoms and
this alignment is named as -alignment. For T-ZGNRs dis-
cussed in this article, we assume that each atom on the first
layer is right positioned above a corresponding atom on
the third layer, (which is called ABA-type layer stacking).
All our first-principle calculations are carried out by the
Vienna ab-initio simulation package (VASP). In our cal-
culations, we use supercells with 1.5 nm vacuum spacing
in z-direction and 1.5 nm vacuum spacing in x-direction.
The K-point meshes used is 1 × 27 × 1 with a 500 eV
energy cutoff. The equilibrium forces between atoms are
set to be less than 0.005 eV/Å. Because of the magnetic
moments and magnetic energy of edge atoms are almost
independent of the width of ZGNRs,11 all our calcula-
tions in this article will base on ZGNRs with width 8, as
shown in Figure 1(a). The layered ZGNRs under study are
first gone through geometric optimization and then their
electric and magnetic properties are calculated by using
projector-augmented wave (PAW) method. In order to see
the effects of different choices of exchange-correlation
functions, we use both LDA and GGA-PBE to optimize
the inter-layer spacing of bilayer graphene with AB stack-
ing. The result using LDA predicts a spacing of about
3.33 Å, which is close to the results both from other theo-
retical work (3.4 Å) and from experimental measurements
(3.356 Å),7–9 while the result using GGA-PBE gives a
spacing of 4.37 Å. We will then use LDA in all of our
following calculations.
To validate the methods mentioned above, we carry
out calculations of a M-ZGNR. The results confirm the
(a)
(b)
Fig. 2. Bilayer graphene nanoribbons with (a) -alignment and
(b) -alignment edges.
Zhang et al. Structural and Magnetic Instability of Bilayer and Trilayer Zigzag Graphene Nanoribbons
first-principle calculations by Son et al.13 As shown
in Figure 1(a), the ground state has antiferromagnetic
order with opposite magnetic moments at the two edges.
Figure 1(b) shows the calculated band structures near
Fermi energy. Each energy band is spin degenerate.
However spin-resolved spatial density distributions are
non-degenerate. The maximum densities of opposite spin
components are located at the two edges, respectively. The
magnetic ground state of the M-ZGNR is due to the mag-
netic instability of the flat energy bands at Fermi energy.
As a result of magnetization, these bands are moved away
from Fermi energy and become weakly dispersive, open-
ing up an energy gap to stabilize the electronic structure
of the M-ZGNR.
3. RESULTS AND DISCUSSION
3.1. Structural and Magnetic Instability of B-ZGNRs
We first optimize the structures of B-ZGNRs with both
-alignment and -alignment edges. The optimized struc-
tures are shown in Figure 3. With -alignment edges, both
layers undergo structural deformation and are not flat, but
curved towards each other at the two edges (the inter-layer
edge interaction is attractive), as shown in Figure 3(a).
With -alignment edges, no structural deformation happens
and layers remain flat (the inter-layer interaction is much
weaker and repulsive). In order to find out magnetic order
of ground states, we consider five initial magnetic orders
according to symmetry, namely
(1) paramagnetic, denoted by PP;
(2) intra-layer antiferromagnetic ordering with inter-layer
ferromagnetic ordering, as shown in Figure 3(b), denoted
by AF;
(3) intra-layer antiferromagnetic ordering with inter-layer
antiferromagnetic ordering, denoted by AA;
(a)
(b)
Fig. 3. Side view of optimized structures of B-ZGNRs with (a) -
alignment and (b) -alignment edges.
J. Comput. Theor. Nanosci. 8, 1–6, 2011
Table I. The optimized energies from different initial magnetic orders
in B-ZGNRs with -alignment.
Initial magnetic PP (NM) AF AA FF FA
orders
Final magnetic NM AF AA FF FF
orders
Final energy −335.595 −335.657 −335.649 −335.653 −335.653
(eV)
(4) intra-layer ferromagnetic ordering with inter-layer fer-
romagnetic ordering, denoted by FF;
(5) intra-layer ferromagnetic ordering with inter-layer
antiferromagnetic ordering, denoted by FA.
After self-consistency calculations, the ground states can be
determined by comparing the total energies from above ini-
tial magnetic orders. The B-ZGNR with -alignment edges
converges to a PP ground state with energy of −335.926 eV
no matter what the initial magnetic order is. While the
ground state of the B-ZGNR with -alignment edges is AF
(Table I). As shown in Figure 3(b), the magnetic moments
of atoms 1 and 4 are equal in magnitude of 0.119 B , but in
opposite direction; atoms 2 and 3 also have opposite mag-
netic moments with magnitude of 0.118 B .
Our results agree with the conclusions in Ref. [12].
Ref. [12] describes the facts of structural deformation in
B-ZGNRs with -alignment edges and magnetization in
those with -alignment edges without further discussions
and explanations.
RESEARCH ARTICLE
Here we give some qualitative analysis to understand the
different behaviors of different edge alignments. As shown
in Figure 2, the most outside C atoms in the B-ZGNR
with -alignment edges are right above (or below) the H
atoms on the bottom (or top) layer. Those C and H atoms
tend to attract each other to bend the flat layers, trans-
ferring the original sp2 bonds of C atoms to some mix-
ture bonds between sp2 and sp3 . Furthermore, A atoms in
Bernal stacking have stronger interaction with neighboring
layers than B atoms, thus become more likely to change
their positions when they are at edge positions.
To support our analysis, we calculate the total energy
of the B-ZGNR with -alignment edges and the atomic
forces when the two layers keep flat. The total energy is
−335.749 eV, which is 0.177 eV higher than that of the
ground state with deformed edges. Without deformation,
the attracting force acting on the most edge C atoms is
0.175 eV/Å. Furthermore, the above analysis can also be
confirmed by the band structure calculations. Figure 4(a) is
the energy bands of the B-ZGNR with -alignment edges
near Fermi energy. Obviously, there are no energy bands at
Fermi energy. For comparison, we plot the band structures
of the B-ZGNR with -alignment edges with non-spin-
polarized calculations in Figure 4(b). At Fermi energy,
there are flat bands as that in M-ZGNRs which are results
from the sp2 nature of the edge C atoms. In the B-ZGNR
with -alignment edges, it is the structural deformation
3
 Structural and Magnetic Instability of Bilayer and Trilayer Zigzag Graphene Nanoribbons
Fig. 4. (a) Band structures near Fermi energy of the B-ZGNR with
-alignment edges; (b) (c) Band structures near Fermi energy of the B-
ZGNR with -alignment edges (b) without spin-polarization and (c) with
RESEARCH ARTICLE
spin-polarization.
and hence the sp3 nature of the edge C atoms eliminating
the flat energy bands at Fermi energy, and thus no mag-
netization is needed. With the flat bands at Fermi energy,
the electronic structure of the B-ZGNR with -alignment
edges presented in Figure 4(b) is unstable. Spin-polarized
calculations show a magnetic symmetry breaking happens,
which opens energy gap near Fermi energy to lower total
energy, as shown in Figure 4(c). This kind of magnetic
instability is a common property in systems with very nar-
row energy band.14 The resulted magnetic moments keep
certain symmetry from the structure of the B-ZGNR, e.g.,
the 2-fold rotation symmetry according to the central rota-
tion axis along y-direction, (x to −x and z to −z).
3.2. Structural and Magnetic Instability of T-ZGNRs
In order to calculate ground states of T-ZGNRs with dif-
ferent edge alignments, we need include the possibility of
non-collinear interlayer magnetic order. Besides the five
initial magnetic orders used in previous section, we con-
sider two additional non-collinear cases: (1) the magnetic
moment between neighboring layers are in an angle of
120 with each other, as shown in Figure 5(b), denoted by
120 order; (2) the magnetic moment between neighbor-
ing layers are in an angle of 90 with each other, denoted
4 J. Comput. Theor. Nanosci. 8, 1–6, 2011
Zhang et al.
(a)
(b)
Fig. 5. Side view of optimized structures of T-ZGNRs with (a) -
alignment and (b) -alignment edges.
by 90 order. (We also include the non-collinear initial
magnetic orders in the calculations of B-ZGNRs. Since
they always converge to collinear magnetic orders, they are
not mentioned earlier.) Table II gives the converged total
energy of T-ZGNRs with both edge alignments, starting
from different initial magnetic orders. The edges of the top
and bottom layers of optimized structure of the T-ZGNR
with -alignment edges bend to the middle layer symmet-
rically, as shown in Figure 5(a). The magnetic order of
ground state is AA (intra-layer antiferromagnetic ordering
and inter-layer antiferromagnetic ordering). (Note that the
final magnetic order converges to AA when starting with
initial magnetic order of AF, 120 order, or 90 order.)
The magnetic moment of atom 1 is 0.021 B , which is the
same as that of atom 5. The magnetic moment of atom 3
is much smaller with only −0.003 B . Here the negative
sign only means the direction of the magnetic moment of
atom 3 is opposite to that of atoms 1 and 5. The magnetic
moment of atoms 2, 4, and 6 are −0.043 B , 0.011 B , and
−0.043 B , respectively. The magnetic moments of edge
atoms for middle layer are much smaller than that for the
other two layers. This is because the wave functions of the
edge states, which are responsible to the magnetization,
are mainly distributed on the top and bottom layers. All
layers in the T-ZGNR with -alignment edges keep almost
flat, as shown in Figure 5(b). It has a magnetic ground
state with non-collinear but coplanar order (denoted as CP
in Table II). The direction of magnetic moments of atoms
1, 3, and 5 are coplanar and they are in an angel of 162 ,
36 , 162 with each other. (Note that atom 3 is not the
most edge atom but has the same x-coordinate with atoms
Zhang et al. Structural and Magnetic Instability of Bilayer and Trilayer Zigzag Graphene Nanoribbons

Table II. The optimized energies from different initial magnetic orders in T-ZGNRs.

Initial magnetic orders PP AF FF AA FA 90 order 120 order

Final magnetic orders () PP AA AA AA AA AA AA
Final energy (eV) () −503.943 −503.950 −503.950 −503.950 −503.949 −503.951 −503.950
Final magnetic orders () PP AF FF AA FF CP CP
Final energy (eV) () −503.614 −503.668 −503.663 −503.659 −503.663 −503.677 −503.677

1 and 5). However, the magnetic moments of atoms 2, 4,
and 6 are in an angle of 105 , 150 , 105 . The intra-layer
magnetic order is always antiferromagnetic. The magnetic
moments of most edge atoms 1, 3 , and 5 have almost the
same magnitude of 0.097, 0.106, 0.097 B , respectively,
while those of most edge atoms 2 , 4, and 6 are 0.116,
0.110, 0.116 B , respectively.
In Figure 5(a), the structural deformation of the
T-ZGNR with -alignment edges is significant. The rea-
son is similar to the case of B-ZGNRs. However, in the
T-ZGNR only the top and bottom layers bend inward; the
middle layer keeps flat due to the cancelation of the forces
from the top and bottom layers. In Figure 5(b), all lay-
ers of the T-ZGNR with -alignment edges remain almost
flat, similar to the case of B-ZGNRs. However, the sym-
metry of magnetic moments of the ground state is mirror
symmetry about the middle layer, which is different from
that of B-ZGNRs. The difference is determined by the odd
spatial symmetry of the T-ZGNR.
Finally, we plot the band structures of T-ZGNRs with
different edge alignments near Fermi energy in Figure 6.
Figure 6(a) presents the band structures of the T-ZGNR
with -alignment edges by non-spin-polarized calculations.
There are flat energy bands at Fermi energy even with
the edge bending. So, unlike the case of B-ZGNRs, struc-
tural deformation alone is not enough to get stable elec-
tronic structure of the T-ZGNR with -alignment edges.
Further magnetization is needed to remove those flat bands
at Fermi energy to lower the total energy, as shown in
Figure 6(b). Figure 6(c) is the band structures of the
T-ZGNR with -alignment edges by non-spin-polarized
calculations. As expected, there are energy bands at Fermi
energy. When including spin-polarization in calculations,
those energy bands become magnetic and move away from
Fermi energy. The non-collinear magnetic moments in the
T-ZGNR may lead to non-trivial phenomena in electron
transport, such as Berry phase effects of spin,15 and need
to be studied further.
4. CONCLUSIONS
We investigate both structural and magnetic instability of

RESEARCH ARTICLE
B-ZGNRs and T-ZGNRs with different edge alignments
(a) (b) and get the following conclusions:
(1) Edge states at Fermi energy are unstable which may
lead to structural deformation or magnetization, or both, at
the edges of layered ZGNRs;
(2) structural deformation only happens in layered ZGNRs
with -alignment edges; the ground state of the B-ZGNR
with -alignment edges is nonmagnetic; while that of the
T-ZGNR with -alignment edges is magnetic even with
structural deformation;
(3) layered ZGNRs with -alignment edges are always flat
and have magnetic ground states;
(c) (d) (4) the intra-layer magnetic order in a layered ZGNR is
always antiferromagnetic near each edge regardless of edge
alignment and number of layers, as long as its ground state
is magnetic;
(5) with the increasing of the number of layers, the mag-
netic order of the ground states can be complex and non-
collinear.
Though our conclusions are based on studies of B-ZGNRs
and T-ZGNRs, most of them are determined only by spatial
symmetry (odd or even) and edge interactions, thus will be
still valid when studying layered ZGNRs with more than
three layers.
Fig. 6. Band structures of T-ZGNRs with (a) -alignment edges without
spin-polarization; (b) -alignment edges with spin-polarization; (c) -
alignment edges without spin-polarization; and (d) -alignment edges Acknowledgments: Yongjin Jiang is grateful for the
with spin-polarization. financial support from the Natural Science Foundation of

J. Comput. Theor. Nanosci. 8, 1–6, 2011 5

 Structural and Magnetic Instability of Bilayer and Trilayer Zigzag Graphene Nanoribbons
Zhejiang Province (No. Y7080383) and the Program for
Innovative Research Team in Zhejiang Normal University.
JQL acknowledges the start-up support from the Institute
for Functional Nanomaterials, University of Puerto Rico.
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