PHYSICAL REVIEW B 83, 115436 (2011)

Spin-orbit interaction in curved graphene ribbons

D. Gosálbez-Martı́nez,1 J. J. Palacios,1,2 and J. Fernández-Rossier1

1
Departamento de Fı́sica Aplicada, Universidad de Alicante, San Vicente del Raspeig, Spain
2
Departamento de Fı́sica de la Materia Condensada, Universidad Autónoma de Madrid, Spain
(Received 1 December 2010; revised manuscript received 14 January 2011; published 16 March 2011)
We study the electronic properties of electrons in flat and curved zigzag graphene nanoribbons using a
tight-binding model within the Slater Koster approximation, including spin-orbit interaction. We find that a
constant curvature across the ribbon dramatically enhances the action of the spin-orbit term, strongly influencing
the spin orientation of the edge states: Whereas spins are normal to the surface in the case of flat ribbons, this is
no longer the case for curved ribbons. This effect is very pronounced, the spins deviating from the normal to the
ribbon, even for very small curvature and a realistic spin orbit coupling of carbon. We find that curvature results
also in an effective second neighbor hopping that modifies the electronic properties of zigzag graphene ribbons.
We discuss the implications of our findings in the spin Hall phase of curved graphene ribbons.

DOI: 10.1103/PhysRevB.83.115436 PACS number(s): 81.05.ue, 71.70.Ej

I. INTRODUCTION from the small size of spin-orbit and hyperfine nuclear

coupling.35 Thus, some mechanism enhancing the strength
The electronic structure of graphene depends both on
of spin-orbit interaction must be at play in these samples. A
its structure at the atomic scale, determined by the sp2
possible candidate could be curvature7,36 induced by ripples
hybridization, and on its structure at a much larger length scale,
and adatoms.37,38 Curvature has been shown to enhance the
determined the shape of the sample.1,2 Thus, the electronic
effect of spin-orbit coupling in the case of carbon nanotubes,
properties of flat graphene differ in subtle but important ways
for which recent experimental work has reported zero field
from rippled graphene3 and the properties of carbon nanotubes
splittings induced by spin-orbit coupling splittings in the range
are fully determined by the way they fold.1 Curvature is be-
of 200 μeV.36
lieved to affect the transport,4,5 magnetic,6 and spin relaxation
The recently reported fabrication of curved graphene
properties of graphene.7 In a wider context, the interplay
ribbons by unzipping carbon nanotubes39–41 opens the way
between mechanical deformations and electronic properties,
toward the experimental study of the effect of curvature
the so-called flexoelectronics, is giving rise to a new branch
on the edge states of graphene ribbons. Here we study
in nanotechnology. Whereas conventional electronics devices
this system from the theoretical point of view and we
are based on the capability to tune their working properties by
compare the spin properties of a graphene ribbon both for
application of external perturbations in the form of electric and
flat and curved ribbons. In flat graphene the π bands are
magnetic fields, mechanical deformation can have a major im-
decoupled from the σ bands, unless spin-orbit coupling is
pact on the properties of nanoelectronic devices. This results in
considered. However, the effect of spin-orbit coupling on
a wide range of new effects, like piezoelectric nanogenerators8
π bands occurs only via virtual transition to higher energy
and field effects induced by piezoelectric effects9 in ZnO
σ bands.
nanowires, and stress driven Mott transitions in VO2
In the case of flat graphene, it has been verified that the effect
nanowires.10
of spin-orbit on the π bands can be properly described by an
The spintronic and magnetic properties of graphene are
effective spin dependent second neighbor hopping between
intriguing. From the theory side, there are two bold predictions.
First, graphene should display a quantum spin Hall phase the π orbitals. This is the so called Kane and Mele model,11,12
with spin-filtered states in the zigzag edges.11,12 Second, the which predicts that graphene is a quantum spin Hall insulator
same edges should have ferromagnetic order.13–22 The striking with a spin and valley dependent gap and peculiar spin-filter
progress in the fabrication of atomically precise graphene zigzag edge states.11,12 In the case of curved graphene, π and
ribbons is starting to provide experimental evidence for the σ orbitals are coupled, and to the best of our knowledge the
existence of stable zigzag edges.23–25 On the other hand, validity of the Kane-Mele model has not been tested. This is
several groups have reported the observation of ferromagnetic why we adopt a different strategy7,31,42–45 and use a four-orbital
order in graphene and graphite,26–30 in most instances in tight-binding model, which includes both the π orbitals and
samples that contain many flakes or structural disorder, or the s, px , and py orbitals.
have been irradiated. The rest of this paper is organized as follows. In Sec. II
The observation of the spin Hall phase in flat graphene we describe the tight-binding method used in our calculations
would require reducing the temperature below the spin-orbit and review some general results about the spin properties of
induced gap, which is smaller than 10 μeV.31–33 From this the system. In Sec. III we present results for the electronic
point of view it would be desirable to increase the strength structure of flat zigzag graphene ribbons and compare with
of spin-orbit interaction in graphene. Hints of how this could those of the Kane-Mele model. In Sec. IV we address the main
be achieved come from experiments. On one side, the spin point of this work, the electronic structure of edge states in
relaxation time of graphene, as measured in lateral spin valves, curved graphene zigzag ribbons. In Sec. V we discuss our
is in the range of 100 ps,34 much shorter than expected results.

1098-0121/2011/83(11)/115436(8) 115436-1 ©2011 American Physical Society

D. GOSÁLBEZ-MARTÍNEZ et al. PHYSICAL REVIEW B 83, 115436 (2011)

II. FORMALISM †
second quantization operators cI,σ that create one electron in
In this section we briefly comment on the two different the atomic site I with spin σ :
tight-binding approximations used to calculate the electronic  †
structure and we provide some theory background. H0 = TI σ,J σ  cI,σ cJ,σ  . (2)
I,J,σ,σ 
A. Slater Koster approximation
In most of the calculations in this work we use a multiorbital The Hamiltonian matrix is the sum of four terms:
approach, taking into account the four valence orbitals of
the carbon atom, s,px ,py , and pz , similar to what was used
(1)
TI σ,J σ  = tδσ,σ  NI,J + t  δσ,σ  NI,J
(2)

in previous work.31,42–45 Thus, counting the spin, the single + itKM τσ,σ  · (d1 × d2 )NI,J
(2)
. (3)
particle basis has 8 elements per carbon atom. In addition, we
passivate the edge carbon atoms with a single hydrogen atom (1) (2)
for which a single s orbital, with the corresponding spin degen- The elements of the matrix NI,J (NI,J ) are equal to 1 when I
eracy, is included. The matrix elements of the Hamiltonian are and J are first (second) neighbors, and zero everywhere else.
computed according to the Slater Koster approach considering Thus, the first two terms are the spin independent first and
only first neighbor hoppings. For simplicity we approximate second neighbor hoppings. The third term is the Kane-Mele
the overlap matrix as the unit matrix. We model both the spin-orbit model.11,12 It is a spin dependent second neighbor
carbon-carbon and carbon-hydrogen hoppings of graphene hopping between sites I and J which have a common first
with a set of tight-binding parameters derived by Kaschner neighbor C. The unit vector along the bond between sites I and
et al.46 from comparison with density functional calculations. C (C and J ) is denoted by d1 (d2 ). In the Kane-Mele spin-orbit
We show these parameters in Table I. model the spin dynamics is linked to the bond orientation.
Spin-orbit coupling is treated as an intra-atomic potential: Thus, in flat graphene and graphene ribbons, the bonds lie in a
 plane so that the Kane-Mele spin-orbit conserves the spin along
VSO = λS · I ,
L (1) the normal to the plane. This is in contrast to the curved ribbons
I and nanotubes considered below, for which the bond vectors
where λ is the spin-orbit coupling parameter, S is the spin are not restricted to a plane and no component of the spin
 i is the orbital angular momentum operator operator is conserved. In the rest of this paper we calculate the
operator, and L
band structure of graphene based one-dimensional structures
acting on the atomic orbitals of site I . The representation of
using the four-orbital Slater Koster model and compare with
this operator in the basis px ,py , and pz is provided in the
the results of the one-orbital model defined by Eqs. (2) and (3).
Appendix. Whereas there is no consensus regarding the value
Whereas the one-orbital model gives results very similar to
of the atomic spin-orbit coupling in carbon, the values reported
those of the flat ribbon, this is not so in the case of curved
in recent work range between λ = 4 and λ = 8 meV.31,32,36 In
ribbons.
this work we always discuss our results for values of λ in that
range and, when some physical insight is gained by so doing,
for values of λ much above the realistic range.
C. Some general results

B. One-orbital tight-binding model

We study one-dimensional ribbons formed repeating a
crystal unit cell. Taking advantage of the crystal symmetry, the

The low energy physics of most graphene based nanostruc- Hamiltonian can be written as Hn,m (k)  where the indexes n
tures can be described with a tight-binding model with a single and m run over the single-particle spin orbitals of the unit cell.
orbital per atom, which can be taken as a l = 1 atomic orbital For the one-dimensional structures considered below, the unit
projected along the local normal direction to the graphene cell is shown in Fig. 1. The period of the crystal is given by the
surface, the so-called π orbitals. From the discussion above, graphene lattice parameter a, k is given by a scalar k, and the
it is apparent that the atomic spin-orbit operator mixes orbital Brillouin zone can be chosen in the interval −π/a and π/a.
states in the same atom with different values of m. However, The eigenstates of the crystal are labeled with the band index
in some instances it is still possible to describe the low energy
sector of graphene with an effective Hamiltonian governed by
the π orbitals in which spin-orbit gives rise to spin dependent
hopping terms.11,12 We express the effective Hamiltonian using

TABLE I. Slater-Koster parameters and on-site energies involving

the same atoms, carbon-carbon interaction, and two different atoms,
carbon-hydrogen interaction. All the values are in eV.

V ssσ V spσ Vppσ Vppπ

C-C −7.76 8.16 7.48 −3.59 FIG. 1. (Color online) (a) Perspective view of a curved graphene
C-H −6.84 7.81 ribbon with edge atoms passivated with hydrogen. (b) Section of
εsC = −8.8 εpC = 0.0 εsH = −2.5 a curved ribbon. (c) Scheme of the procedure to generate curved
ribbons.

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ν and their crystal momentum k. They are linear combination 16 × 16 matrix, corresponding to the two atoms A and B of the
of the atom I with quantum numbers n = l,m: unit cell.31 At zero spin-orbit the 16 bands are two copies (one
 per spin) of three bonding-antibonding pairs of σ bands and
νk (N,r ) = eikNa Cνk (I,n,s)φn (r − rI )χs , (4) one bonding-antibonding pair of the π orbitals which compose
I,n,s the states of the bands at the Fermi energy and are decoupled
where N is an integer that labels the unit cell, and φn (r − rI ) from the σ bands. The Fermi surface is composed of two points
is the atomic orbital with orbital quantum numbers n (which K and K  where the gap between the two π bands vanishes.
encodes l and m) in the atom I of the unit cell. The eigenstate In the neighborhood of both K and K  points the two π bands
of the spin operator along the z axis is denoted by χs , where are linear and the k · p theory is formally identical to that of
s can take values ± 12 . Because of the spin-orbit coupling it is massless two-dimensional Dirac electrons. Spin-orbit couples
important to specify the positions of the atoms with respect to the σ and π orbitals, producing anticrossings away from the
the spin quantization axis. Fermi energy and opening a gap at the K and K  points.
Due to time reversal symmetry, every state with energy Within the one-orbital approach the Hamiltonian of
ν (k) must have the same energy as its time reversal partner, graphene reads
ν  (−k), where ν and ν  label states related by time reversal  x 1 + G(k)s
H = F (k)σ  z σz , (7)
symmetry. In systems with inversion symmetry the bands
satisfy ν (k) = ν  (k) so that, in the same k point, there are where the σ operators act on the sublattice space A and B, 1 is
at least two degenerate states. In systems without inversion the unit matrix in the spin space, and sz = ±1 labels the spin.
symmetry, like the curved ribbons considered below, a twofold The first neighbor hopping function reads
degeneracy at a given k point is not warranted. In this  
 = t(1 + ei k·a1 + ei k·a2 ),
nondegenerate situation we can compute, without ambiguity, F (k) (8)
the spin density associated with a given state with quantum with a1 = a(1,0) and a2 = a(cos π3 , sin π3 ). The Kane-Mele
numbers ν,k as second neighbor spin-orbit coupling yields
   
Sν,k (I ) ≡ ∗
Ck,ν (I,n,s)Ck,ν (I,n,s  )Ss,s  , (5)  = itKM (ei k·a1 − ei k·a2 + ei k·(a2 −a1 ) − h.c.).
G(k)
i,n,s,s   vanishes
At the Dirac points K and K  , the function F (k)
where Sσ,σ  are the Pauli spin 1/2 matrices. in contrast with the the √ spin-orbit term, which is given by
In the cases with inversion symmetry, like the flat ribbon G(K  a) = −G(Ka) = 3 3tKM . Thus, the energy levels of
considered below, for a given k point there are at least two graphene at the Dirac points are governed by the following
degenerate bands. Thus, any linear combination of states Hamiltonian:11
of the degenerate pair νk and ν  k is also the eigenstate h = SO τz σz sz , (9)
of the Hamiltonian and has different spin density. In these
instances, we include an infinitesimally small magnetic field √ τz = ±1 labels the valley quantum number and SO =
where
in the calculation which breaks the degeneracy and permits 3 3tKM . Thus, for a given spin orientation sz = ±1, spin-
us to attribute a given spin density to a given state. When the orbit opens a gap that takes a valley dependent value 2| SO |.
calculated spin densities so obtained are independent of the This spin and valley dependent gap would make graphene a
orientation of the infinitesimally small magnetic field, they peculiar type of insulator which could not be connected with
can be considered intrinsic properties of the spin states. As a standard insulator by smooth variation of a parameter in the
we discuss below, this is the case of the spin filter states in Hamiltonian,11,12 i.e., a quantum spin Hall insulator.
flat spin ribbons, which point perpendicular to the ribbon and
have a strong correlation between spin orientation, edge, and B. Flat ribbons
velocity, as predicted by Kane and Mele.11,12 We now discuss the electronic structure of flat graphene
In order to characterize the properties of a given state it will ribbons with zigzag edges. The unit cell that defines the
also be convenient to calculate their sublattice polarization: zigzag ribbon has N carbon atoms and two hydrogen atoms
 z   that passivate the dangling bonds in the edges of the ribbon.
σν,k = |Ck,ν (I,n,s)|2 σz (I ), (6)
I,n,s
These structures were proposed by Nakada et al.47 Using the
one-orbital tight-binding model, without spin-orbit coupling,
where σz (I ) = +1 when I is an A site and σz (I ) = −1 when they found that zigzag ribbons have almost flat bands at the
I is a B site. Fermi energy, localized at the edges. An important feature
of zigzag edges is the fact that all the atoms belong to the
III. FLAT GRAPHENE ZIGZAG RIBBONS same sublattice. Since the honeycomb lattice is bipartite, a
semi-infinite graphene plane with a zigzag termination must
A. Two-dimensional graphene have zero energy edge states48 whose wave function decays
The spin properties and electronic structure of the flat exponentially in the bulk, with full sublattice polarization.
ribbons considered below can be related to those of the two- In finite width zigzag ribbons, the exponential tails of the
dimensional graphene crystal. We briefly recall the spin-orbit states of the two edges hybridize, resulting in a bonding-
physics of two-dimensional graphene as described within the antibonding pair of weakly dispersing bands.17 The bands
Slater Koster model.31 Within this approach, the electronic of the zigzag ribbon can be obtained by folding from those
structure of two-dimensional graphene is described by a of two-dimensional graphene, either with real or imaginary

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D. GOSÁLBEZ-MARTÍNEZ et al. PHYSICAL REVIEW B 83, 115436 (2011)

transverse wave vector, and the longitudinal wave vector

varying along the line that joins the two valleys K and K  .
Thus, the valley number is preserved in zigzag ribbons.
Spin-orbit coupling, described with the one-orbital model,
has a dramatic effect on the (four) edge bands.11,12 The second-
neighbor hopping makes the single edge band dispersive and
overcomes the weak interedge hybridization. Interestingly the
quantum numbers connect well with those at the Dirac points,
which are described by the effective Hamiltonian (9). Thus,
as we move from valley K to K  (positive velocity bands)
the spin ↑ (↓) states of the edge with sublattice A (B) must
change from the top of the valence band to the bottom of the
conduction band. The roles of spin and sublattice are reversed
when considering the two bands that start at K  and end at K.
Thus spin ↑ electrons move with positive velocity in one edge
and negative velocity in the other.
FIG. 3. Properties of the edge state valence band. (a) Square of the
This scenario is confirmed by the four-orbital model and is
Wave function for valence states with k = πa − 0.01. The sublattice
expected based on the fact that 2D graphene with spin-orbit polarization is apparent. (b) Spin density for states with k = πa −
coupling is a quantum spin Hall insulator. In Fig. 2 we show the 0.01. (c) Spin density of time reversal symmetric state with k = − πa +
bands of a flat ribbon with N = 20 carbon atoms. In Fig. 2(a) 0.01. The spin density of the four states is polarized perpendicular to
we show the bands calculated without spin-orbit coupling. the sample.
The calculation shows both the edge and confined π bands
as well as some σ bands higher in energy. The rather flat
band at +7 eV comes from the hydrogen s orbitals hybridized can use m to quantify the effect of spin-orbit coupling on the
with the carbon edge σ orbitals. In the inset we zoom on the edge states. Figure 2(d) shows that for flat ribbons, we can fit
edge states to show that they are almost dispersionless except m = αλ2 with α  24 Å . eV2
when k gets close to the Dirac point. In Fig. 2(b) we show the Since the flat ribbons have inversion symmetry, the bands
same edge states, calculated with SO coupling, both within the have a twofold degeneracy. In order to avoid numerical spin
four-orbital and the one-orbital model. For this particular case mixing of the degenerate states we apply a tiny magnetic field
we have taken λ = 500 meV and tKM = 0.42 meV. Figure 2(c) (always less than 2 × 10−4 T) to split the states. As long
shows a slightly different slope for valence and conduction as the associated Zeeman splitting is negligible compared to
bands for the four-orbital case. This electron-hole symmetry the spin-orbit coupling, the direction of the field is irrelevant.
breaking can not be captured with the one-orbital Kane-Mele By so doing, we can plot the spin density of the edge states
model. without ambiguity. In Fig. 3 we show both the spin density
It is apparent that the edge states acquire a linear dispersion of the four edge states with k = πa − 0.01 and the square of
 = mk. The slope m of the edge states dispersion increases the wave function for valence states, calculated with the four-
linearly with the size of the gap at the Dirac points, which in orbital model. In agreement with the one-orbital Kane-Mele
turn scales quadratically with λ (and linearly with tKM ). We model, the spin densities are peaked in the edge, oriented
perpendicular to the plane of the ribbon. We have repeated the
calculation rotating the plane of the ribbon and obtained the
10
(a) (b) same result. From inspection of Figs. 2(b) and 3, it is apparent
E-EF(meV)

1
that the valence bands correspond to the edge states and display
0
the spin filter effect; i.e., in a given edge right goers and left
-1 goers have opposite spin.
-π/a -1.2 -1.13 -1.05
-1
k(Å )
5
IV. CURVED GRAPHENE ZIGZAG RIBBONS
E(eV)

E(meV)

(c) (d)
0 0
6 The calculation of the previous section, using the four-
|m|(meV/ů¹)

-5
-π/a orbital model, backs up the conclusions of the Kane-Mele one-
4 orbital model for the spin filter effect in graphene. However,
the bandwidth of the edge states is less than 0.1 μeV for the
2 accepted values43 of λ = 5 meV. Thus, the effect is very hard
to observe in flat graphene ribbons. This leads us to consider
0
0 0.1 0.2 0 0.2 0.4 ways to enhance the effect of spin-orbit. For that matter, we
-10
-π/a Γ
2 2
λ (eV ) tKM(meV) calculate the edge states in a curved graphene zigzag ribbon,
similar to those reported recently,39,40,49 using the four-orbital
FIG. 2. (Color online) (a) Bands for flat ribbon without SO. Inset: model. In contrast to flat ribbons, the properties of the edge
Zoom of the edge bands for case (a). (b) Edge bands with SO (λ = states of a curved ribbon cannot be inferred from those of a
500 meV) and tKM = 0.42 meV. (c) Slope vs λ2 . (d) Slope vs tKM . parent two-dimensional compound, because it is not possible

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SPIN-ORBIT INTERACTION IN CURVED GRAPHENE RIBBONS PHYSICAL REVIEW B 83, 115436 (2011)

10 20 0
0 -0.5 10
(a) (b) (c) (a) (c)

ΔE(μeV)
0
-1 -1 -1
10
0.3

|m|(meVÅ)
-20
-π/a -1.20 -1.13 -1.05 0.2

|m|(meVÅ)
E(meV)
-1 -2
-2 -1.5
E(eV)

k(Å ) 10
0 (e)
(d) 15
(b) 0.1
0
-2

|m|(meVÅ)
10
-1 -3 0
10 0 0.25 0.5 0.75
-1
-4 1/R(nm )
5
-2

-3 -6 0 10 0
-4
-π/a -1.16 -1.05 -π/a -1.16 -1.05 0 0.1 0.2 0.3 0.4 0.5 0.6 0.5 1 1.5 2 2.5
-10 -1 λ(eV) -1
-π/a Γ k(Å ) 1/R(nm )

FIG. 4. Electronic structure of curved zigzag ribbon with R = FIG. 5. (a) Differential energy bands [see Eq. (10)] for ribbons
4.1 nm. (a) Bands for curved ribbon without SO. (b)–(e) Zoom of with N = 20, R = 4.1 nm, and λ = 5 meV. It is apparent that for
the edge bands for λ = 0 (b), λ = 5 meV (c), λ = 50 meV (d), and small k they are linear, with slope m. (b) Slope of the differential
λ = 500 meV (e). energy bands as a function of λ, for R = 4.1 nm. (c) Slope of the
differential energy bands as a function of κ = R −1 , both in linear and
to define a two-dimensional crystal with a finite unit cell and logarithmic scale, for λ = 5 meV. A 100-fold enhancement of the
constant curvature. slope occurs in a very narrow range of small curvatures.
The unit cell of the curved ribbons is obtained as fraction
of a (n,n) nanotube, with radius R (see Fig. 1). For a given the edge bands as a function of λ, obtained with the procedure
nanotube we can obtain a series of curved ribbons with the just described, for the same ribbon discussed before (N = 20,
same curvature R −1 and different widths W or different R = 4.1 nm). It is apparent that the slope m is no longer
numbers of carbon atoms N . We can also study ribbons with linear in λ2 , in contrast to the case of flat ribbons. Even
the same N and different curvatures R using a parent nanotube more interesting, in Fig. 5(c) we plot the slope m for a fixed
with different n. Our curved ribbons are thus defined by W and value of λ = 5 meV, as a function of the curvature κ = R −1 .
R or, more precisely, by n and N . We find a dramatic 100-fold increase at small κ. This result
is consistent with the effective k · p Hamiltonian for carbon
A. Energy bands nanotubes.7,50
The curvature induced enhancement of the spin-orbit effect
The energy bands of curved ribbons is shown in Fig. 4 on the edge states of the curved ribbon can be understood
for a ribbon with N = 20 and R = 4.1 nm. There are three as follows. In flat graphene the Dirac bands are linear
main differences with the flat ribbon. First, the edge states are combinations of atomic π orbitals with quantum numbers l =
dispersive even with λSO = 0, as seen in Fig. 4(b). This effect 1, m = 0. The effect of atomic spin-orbit coupling λL  · S can
can be reproduced, within the one-orbital model, including be understood perturbatively. To first order, spin-orbit coupling
an effective second-neighbor hopping (t   −1.5 meV). This has no effect on the product states |σ  × |l = 1,m = 0.
dispersion breaks electron-hole symmetry and competes with Second order coupling, via intermediate states with with
the one induced by SO coupling, as seen in panels (c), (d), and respect to the Dirac point and orbital quantum numbers
(e) of Fig. 4, with λSO = 5, 50, and 500 meV, respectively. l = 1, m = ±1, results in an effective spin-orbit Hamiltonian
Second, curvature enhances the effect of spin-orbit cou- 2
acting on the π orbitals, with strength λ , which conserves
pling, as expected. In order to separate the effect of spin-orbit
Sz . Curvature changes this situation, because it mixes the
from the effect induced by curvature, we define the differential
π orbitals with the l = 1,m = 0 orbitals, resulting in a spin-
bands as the energy bands of the curved ribbon at finite λSO ,
orbit Hamiltonian for the electrons at the Fermi energy7,50
subtracting the bands without spin-orbit:
linear in the spin-orbit coupling λ.
˜ν (k) ≡ ν (k) − ν (k,λSO = 0). (10) The third difference with the flat ribbon is apparent for the
bands away from the zone boundary: They are not degenerate.
In Fig. 5(a) we plot the differential bands for the ribbon with This is shown in Fig. 6(a), which is a zoom of Fig. 4(b),
N = 20 and R = 4.1 nm. They are two doubly degenerate including states at both sides of the Brillouin zone boundary.
linear bands with opposite velocities in the Brillouin zone The lack of degeneracy is originated by the lack of the inversion
boundary. Thus, when the effect of curvature alone is sub- symmetry of the curved ribbon. Interestingly, the degree of
tracted, the dispersion edge states look pretty much like those sublattice polarization σz , shown in Fig. 6(b), anticorrelates
of the flat ribbons in the region close to the Brillouin zone with the splitting. In other words, the states strongly localized
boundary. Thus, we can also characterize them by the slope at the edges are insensitive to the lack of the inversion of the
of the linear bands, m. In Fig. 5(b) we plot that the slope of structure, which is nonlocal property.

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FIG. 6. (Color online) Detail of the edge states for curved ribbon
with R = 4.1 nm and λ = 5 meV. (a) Dispersion of the edge states.
(b) Sublattice polarization σz as a function of k for the two lowest
energy bands.
FIG. 8. (Color online) Spin densities for states with k = − πa +
B. Electronic properties 0.01 [panels (a) and (b)] and k = πa − 0.01 [panels (c) and (d)]
We now discuss the spin properties of the edge states in in almost flat ribbon, R −1 = 3.7 × 10−3 nm−1 . Note that curvature
the curved ribbons. Note that due to the lack of inversion cannot be appreciated.
symmetry, there is no degeneracy at a given k so that the spin
The effect is even more striking in the case of an almost
density is an intrinsic property of the state. In Fig. 7 we plot the
flat ribbon, shown in Fig. 8 for which the spin quantization
magnetization density Sν,k (I ) for the two lowest energy edge
direction is clearly not perpendicular to the ribbon plane.
bands with momentum k = πa + 0.01 (upper panels) and k =
Thus, a very small curvature is enough to change the spin
− πa − 0.01 (lower panel), for a ribbon with R = 4.1 nm and
quantization direction of the edge states. This is better
λ = 5 meV. Whereas the correlation between the velocity, the
seen in Fig. 9, where we plot the angle formed between the
spin orientation, and the edge is the same as in flat ribbons, it is
spin quantization axis and the local normal in the edge atom.
apparent that the quantization axis is no longer parallel to the
In Fig. 9(a) we show the evolution of the angle for the states
local normal direction. The spin of the edge states lies almost
with k = − πa + 0.01 for the two lowest energy edge bands.
perpendicular to the normal direction. Thus, this is different
from the case of nanotubes, where the spin quantization axis For flat ribbons R −1 = 0, the angles are 0◦ and 180◦ , i.e.,
is parallel to the tube main axis, and different from the flat the quantization axis is perpendicular to the ribbon plane. In
ribbon. the opposite limit, for large curvature, the spin quantization
angle lies perpendicular to the normal, i.e., tangential, but

FIG. 9. (Color online) (a) Angle θ formed by the edge spin density
and the local normal as a function of curvature κ = R −1 for λ = 5
meV. (b) Detail of (a) for small κ. Inset: derivative of the angle with
FIG. 7. (Color online) Spin densities for states with k = − πa + the curvature. Note the extremely large dκ dθ
for a very narrow region
0.01 [panels (a) and (b)] and k = πa − 0.01 [panels (c) and (d)]. of small curvatures.

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SPIN-ORBIT INTERACTION IN CURVED GRAPHENE RIBBONS PHYSICAL REVIEW B 83, 115436 (2011)

always in the plane perpendicular to the ribbon transport direction is independent of curvature and perpendicular to both
direction. the normal and the ribbon direction. The strong sensitivity of
The transition between the two limits is far from smooth. the spin orientation of edge states on the curvature suggests
Even for the less curved ribbon that we have considered, that flexural phonons can be a very efficient mechanism for
with R = 271 nm, we have θ  70◦ . This is better seen in spin relaxation in graphene.
Fig. 9(b), where we show the low curvature region only for Note added: During the final stages of this work a related
one of the bands. The dramatic effect of curvature on the preprint was posted.52
spin orientation of the edge states is quantified in the inset
dθ
of Fig. 9(b), where we show dκ as a function of curvature
κ. For small curvatures the derivative blows up exponentially. ACKNOWLEDGMENTS
Thus, the spin orientation of the edge states is very sensitive to We acknowledge fruitful discussions with David Soriano,
moderate buckling deformation of the ribbon. This sensitivity A. S. Núñez, and S. Fratini. This work has been financially
is especially important for the small values of λ adequate supported by MEC-Spain (MAT07-67845, FIS2010-21883-
for carbon. Larger values of λ reduce the effect. We have C02-01, and CONSOLIDER CSD2007-00010) and Generali-
verified that the single-orbital model with the generalized tat Valenciana (ACOMP/2010/070).
Kane-Mele Hamiltonian is not sufficient to capture the
effect.
APPENDIX: ATOMIC ORBITAL BASIS AND
MATRIX ELEMENTS
V. DISCUSSION AND CONCLUSIONS
In this appendix we give the expressions for the atomic
We are now in position to discuss whether or not the orbitals and the corresponding angular momentum matrix
spin filter effect could be more easily observed in curved elements, necessary to compute the spin-orbit matrix. In
graphene ribbons. One side, the bandwidth of the edge states is our formalism, the atomic orbitals are described in terms
dramatically increased. For moderate curvatures (R = 4.1 nm) of the Cartesian basis, s,px ,py ,pz , which is related to the
the bandwidth of the edge states is 20 μeV, and it can reach basis of the eigenstates of L2 and Lz , through the following
60 μeV for R  1 nm, to be compared with 0.1 μeV for flat transformation:51
ribbons. Thus, experiments done at 100 mK could resolve the
edge band of curved ribbons. On the other hand, the curvature- |s = |l = 0,m = 0, (A1)
induced second-neighbor hopping breaks the electron-hole
symmetry [see Fig. 6(a)], so that now there are four edge bands 1
|px  = − √ (|l = 1,m = 1 − |l = 1,m = −1, (A2)
at the Fermi energy. At each edge there would be left goers and 2
right goers with the same spin orientation, although slightly
different k. Taken at face value, this would imply that there is no i
|py  = √ (|l = 1,m = 1 + |l = 1,m = −1, (A3)
spin current in the ground state and backscattering would not be 2
protected.
In conclusion, we have studied the interplay of spin-orbit |pz  = |l = 1,m = 0. (A4)
coupling and curvature in the edge states of graphene zigzag
ribbons. Our main conclusions are as follows: The spin-orbit Hamiltonian operator reads,
(1) In the case of the flat graphene ribbon, the microscopic  
L̂+ ŝ− + L̂− ŝ+
four-orbital model yields results identical to those of the Kane- VSO = λ + L̂z ŝz , (A5)
Mele one-orbital model. In particular, the edge states have the 2
spin filter property11,12 and the spin is quantized perpendicular which only affects the l = 1 subspace. The matrix elements of
to the sample. this operator in the Cartesian basis read,
(2) Curved graphene ribbons also have spin-filtered edge
|px , ↑ |py , ↑ |pz , ↑ |px , ↓ |py , ↓ |pz , ↓
states. The bandwidth of the edge bands of curved ribbons is
increased by as much as 100 for moderate curvatures and is |px , ↑ 0 −iλ/2 0 0 0 λ/2
proportional to the curvature, for fixed spin-orbit coupling. |py , ↑ iλ/2 0 0 0 0 −iλ/2
(3) Curvature induces a second neighbor hopping which
|pz , ↑ 0 0 0 −λ/2 iλ/2 0
modifies the dispersion of the edge states and, in this sense,
competes with their spin-orbit induced dispersion. |px , ↓ 0 0 −λ/2 0 iλ/2 0
(4) The spin of the edge states is not quantized along the |py , ↓ 0 0 −iλ/2 −iλ/2 0 0
direction normal to the ribbon. For moderate curvature, their
|pz , ↓ λ/2 −iλ/2 0 0 0 0
quantization direction depends very strongly on the curvature
of the ribbon. Above a certain curvature, the quantization (A6)

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