Electrons near a graphene edge

V. A. Volkov and I. V. Zagorodnev

Citation: Low Temperature Physics 35, 2 (2009); doi: 10.1063/1.3064694

View online: http://dx.doi.org/10.1063/1.3064694
View Table of Contents: http://scitation.aip.org/content/aip/journal/ltp/35/1?ver=pdfcov
Published by the AIP Publishing

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
148.217.201.2 On: Tue, 11 Mar 2014 17:14:20
 LOW TEMPERATURE PHYSICS VOLUME 35, NUMBER 1 JANUARY 2009

Electrons near a graphene edge

V. A. Volkova兲 and I. V. Zagorodnev
V. A. Kotelnikov Institute of Radio Engineering and Electronics of the Russian Academy of Sciences,
ul. Mokovaya 11, korp. 7, Moscow 125009, Russia
共Submitted July 29, 2008兲
Fiz. Nizk. Temp. 35, 5–9 共January 2009兲

To describe the behavior of a 2D electron near a graphene edge, one needs to know the bound-
ary conditions for the effective 共envelope兲 wave function, which obeys an equation of the Weyl–
Dirac type. These conditions, which are deduced from general arguments, amount to a linear re-
lation on the components of the spinor comprised of the envelope functions. In neglect of the
intervalley interaction, the boundary conditions depend only on one real parameter, which con-
tains a boundary of the general type. The spectrum of electronic edge states for the linear bound-
ary is obtained. © 2009 American Institute of Physics. 关DOI: 10.1063/1.3064694兴

I. INTRODUCTION sample.5,6 To solve this problem it is necessary to solve the

Graphene, a monoatomic plane layer of carbon atoms at boundary-value problem for the envelope functions at the
sites of a 2D hexagonal lattice 共see Fig. 1兲, is a building edge of the sample. This was the task of the present study.
block for the formation of 3D graphite, 1D nanotubes, and Envelope functions in graphene obey the Weyl–Dirac
0D fullerenes. The crystal lattice consists of two equivalent equation:7
sublattices: A and B. The electrons in graphene have a gap-
Ĥ␺ = E␺ , 共1兲
less energy spectrum which is linear in the 2D momentum,
twofold degenerate with respect to spin and twofold with where the Hamiltonian

冉 冊
respect to valley number 共see Fig. 2兲, the valence band and
conduction band touching at points K and K⬘. Graphene ␴ · p̂ 0
Ĥ = ␥ , 共2兲
lamellae in the free state have been obtained quite recently.1,2 0 ␴ · p̂⬘
The surprising properties demonstrated by graphene in the
p̂ = 共p̂x , p̂y , 0兲 is the two-dimensional momentum operator,
first experiments have given rise to an upsurge in the number
p̂⬘ = 共p̂x , −p̂y , 0兲, ␴ = 共␴1 , ␴2 , ␴3兲 is the vector of Pauli matri-
of papers 共see, e.g., the reviews2–4兲.
ces in the standard representation, ␥ = 106 m / s is the velocity
Initially the interest in graphene was in connection with
of the electrons on the Fermi surface 共an analog of the speed
the ultrarelativistic form of the single-particle electron spec-
of light in the relativistic Weyl equation兲, and the coordinates
trum. The envelope wave functions of the electrons in each
axis are chosen as shown in Fig. 1. In this representation the
valley are described by a two-component Weyl equation,
Hamiltonian operates on a column of envelope wave func-
which is usually applied to description of the neutrino. This
tions 共␺A , ␺B , ␺A⬘ , ␺B⬘ 兲T, and the total wave function of the
equation can be obtained by transforming the four-
electron in graphene in the tight-binding model has the form
component Dirac equation after letting the mass 共i.e., the
band gap兲 go to zero. It is often said, therefore, that the
electrons in graphene obey the Dirac 共or Weyl–Dirac, or sim-
兺A 共␺AeiK·R 兲 + 共␺A⬘ eiK⬘·R 兲␹共r − Ra兲 + 兺B 共− ␺BeiK·R
a a b

ply Weyl兲 equation and have a massless Dirac spectrum in

the form of a pair of cones. For the description of a number
of effects, including the anomalous quantum Hall effect, re-
vealed in the first experimental studies, it is necessary to
know the behavior of the electron or hole near an edge of the
+ ␺B⬘ eiK⬘·Rb兲␹共r − Rb兲, 共3兲
where ␹共r兲 is the wave function of the pz orbital of the car-
bon atom, Ra and Rb are the positions of atoms of types A
and B, and the summation is over all atoms of the sublattice.
Henceforth the 2 ⫻ 2 unit matrix is denoted as ␴0 and the
origin is chosen such that K⬘ = −K.
Applying the unitary transformation

FIG. 1. Crystal lattice of graphene. FIG. 2. Energy spectrum of electrons in graphene near the points K and K⬘.

1063-777X/2009/35共1兲/4/$30.00 2 © 2009 American Institute of Physics

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
148.217.201.2 On: Tue, 11 Mar 2014 17:14:20
 Low Temp. Phys. 35 共1兲, January 2009 V. A. Volkov and I. V. Zagorodnev 3

U= 冉 ␴0 0
0 i␴2
冊 共4兲
Thus the boundary condition written above for the armchair
boundary is an entangling boundary condition.
The goal of this paper is to answer the question of what
to the Hamiltonian 共2兲, we obtain another representation of boundary conditions satisfying the general requirements
it: 共Hermiticity and time-reversal symmetry of the problem兲

冉 冊
are, in principle, possible. We consider the boundary in the
␴ · p̂ 0
Ĥ = ␥ . 共5兲 absence of intervalley coupling 共the spinor components cor-
0 − ␴ · p̂ responding to different valleys are not mixed at the bound-
ary兲. It is shown that in this case the problem of possible
This is the representation that will be used in this paper.
boundary conditions at a graphene edge described by the
Henceforth we shall set ␥ = 1.
Hamiltonian 共5兲 reduces to finding the boundary condition
We now discuss the question of the boundary conditions
for a single Weyl equation, and the spectrum for graphene
at the edges of a graphene sample. In Ref. 8 a “rather strong”
can be obtained using symmetry arguments. In Sec. II it is
delta function clamped to an infinitely high barrier was in-
shown that from only the Hermiticity of the problem11,12 one
troduced to obtain for Hamiltonian 共5兲 the general boundary
can obtain a boundary condition that couples two compo-
condition for a hard wall:
nents of the spinor at the edge of the system and depends on
兩共1 − M兲␺兩S = 0, 共6兲 only one parameter characterizing the boundary. Using the
boundary condition found, it is easy to solve the 2D Weyl
where M is a 4 ⫻ 4 matrix satisfying the following condi- equation on a half plane and find the spectrum of edge states
tions: on a rectilinear boundary. In Sec. III the symmetry of the
M 2 = 1, problem with respect to time reversal is used 共together with
Hermitianity兲 to obtain the boundary condition and the spec-
M+ = M , trum of edge states in graphene. It is shown that the band of
edge states is linear in momentum, chiral, and has dispersion
兵n ⫻ ⌺,M其 = 0, depending on a parameter characterizing the boundary. In
Sec. IV the results obtained for graphene in Sec. III are com-

⌺= 冉 ␴ 0
0 −␴
, 冊 共7兲
pared with the known results for the massless Dirac
equation.11

and n = 共nx , ny , 0兲 is the vector normal to the boundary S.

II. BOUNDARY CONDITIONS FOR THE 2D WEYL EQUATION
In Ref. 9 the additional requirement that the matrix M
commute with the time reversal operator was imposed. In We consider the Weyl Hamiltonian
that case the matrix M appearing in the boundary condition
Hw = ␴ · p. 共11兲
共6兲 is determined by the two unit vectors ␯ , m, m ⬜ n 共three
parameters in all兲: We require Hermiticity of the Hamiltonian 共11兲 in a re-
gion with boundary S and vector normal to the boundary n
M = 共␯ · ␴兲 丢 共m · ␴兲, m ⬜ n, 共8兲
= 共cos ␣ , sin ␣兲, i.e., for any pair of spinors ␸ = 共␸1 , ␸2兲, ␺
where 丢 is the direct product of matrices. = 共␺1 , ␺2兲 the following must hold:
In Ref. 10 the two types of boundaries, “armchair” and
“zigzag” 共see Fig. 1兲 were considered in the nearest-neighbor
approximation 共tight-binding model兲. The following bound-
具␸兩Hw兩␺典 = 冕V
␸+共r兲Ĥw␺共r兲d3r = 具␺兩Hw兩␸典*

ary conditions were proposed for the two types of bound-

aries:
armchair:
− iបc 冕
S
␸+共r兲␴ · n␺共r兲dS = 具␺兩Hw兩␸典* . 共12兲

兩共␺AeiK·r + ␺A⬘ e−iK·r兲兩S = 0, Hence it follows that

兩␸+共r兲␴ · n␺共r兲兩S = 0, 共13兲
兩共− ␺Be iK·r
+ ␺B⬘ e −iK·r
兲兩S = 0, 共9兲
from which we obtain the boundary condition
zigzag for a boundary of type A atoms:
兩共␺1 + iae−i␣␺2兲兩S = 0, 共14兲
兩␺A兩S = 0,
where a is a real parameter that completely specifies the
boundary. The boundary condition can be written in the form

冏冉 冊冉 冊冏
兩␺A⬘ 兩S = 0. 共10兲
1 iae−i␣ ␺1
We note that representation 共2兲, generally speaking, is = 0. 共15兲
0 0 ␺2 S
valid in slowly varying 共on interatomic scales兲 external
fields, and therefore the external potentials must be smooth We solve the Weyl equation on a half plane with bound-
and not mix envelopes belonging to different valleys. In the ary specified by the vector normal n, for a particle with
case of the sharp change of the potential at the boundary, the specified momentum k along a boundary with some value of
boundary conditions can mix envelopes belonging to differ- the parameter a. At an infinite distance from the boundary we
ent valleys. Such boundary conditions are called entangling. assume
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the that
termsthe
at: wave function is finite. Among theDownloaded
http://scitation.aip.org/termsconditions. solutions to IP:
148.217.201.2 On: Tue, 11 Mar 2014 17:14:20
 4 Low Temp. Phys. 35 共1兲, January 2009 V. A. Volkov and I. V. Zagorodnev

b⬘ = 冉 1 ide−i␣
0 0
冊 . 共21兲

The time reversal operator 共corresponding to complex

conjugation of the total wave function兲 in our chosen repre-
sentation 共5兲 is

T̂ = 冉 0
␴1
␴1
0
冊K̂0 , 共22兲

where K̂0 is the complex conjugation operator.

From the symmetry of the boundary condition with re-
spect to time reversal one can obtain a relation between the
coefficients a and d in Eqs. 共20兲 and 共21兲 and the final ex-
pression for the matrix ⌫ˆ :

冢 冣
1 iae−i␣ 0 0
FIG. 3. Electron spectrum E共k兲 for the 2D Weyl equation on a half plane.
The shaded region corresponds to the continuous spectrum 共bulk solutions兲,
0 0 0 0
⌫ˆ = . 共23兲
the thick lines to edge states, which decay exponentially away from the 0 0 1 ie−i␣/a
boundary. The edge states exist in different quadrants, depending on the
parameter ␤: ␤ 苸 共␲ / 2 , ␲兲 共a兲, ␤ 苸 共0 , ␲ / 2兲 共b兲, ␤ 苸 共−␲ / 2 , 0兲 共c兲, ␤ 0 0 0 0
苸 共−␲ , −␲ / 2兲 共d兲.
We solve the Schrödinger equation 共1兲 for Hamiltonian
共5兲 on a graphene half plane whose lateral boundary is speci-
fied by a 2D vector normal n, for a particle with specified
will be those corresponding to the bulk spectrum of the Weyl momentum k along the boundary. As in Sec. II, among the
equation 共the shaded region in Fig. 3兲, and the solutions cor- solutions are solutions corresponding to the bulk spectrum
responding to the edge states 共the thick line兲. The edge states 共shaded in Fig. 4兲 and solutions corresponding to edge states
are described by the dispersion equation 共the heavy line兲. Also as in Sec. II, we introduce the bound-
1 − a/E共冑k2 − E2 + k兲 = 0. 共16兲 ary parameter ␤ and obtain the following solutions for the
edge states:
This implies the following dispersion relation: in one valley:
2a E = k sin ␤ ,
E= k, k共1 − a2兲 艌 0. 共17兲
a2 + 1
k cos ␤ 艋 0, 共24兲
The spectrum 共17兲 can be written in another form by
introducing a new parameter ␤: sin ␤ = 2a / 共a2 + 1兲, and stipu- and in the other valley:
lating that ␤ = 0 at a = ⬁ and ␤ = ␲ at a = 0. Then instead of E = − k sin ␤ ,
Eq. 共17兲 we get
E = k sin ␤ , k cos ␤ 艋 0. 共18兲 k cos ␤ 艌 0. 共25兲

The spectrum of edge states is presented in Fig. 3. De- A comparison of Figs. 3 and 4 shows that the spectrum
pending on the value of the parameter ␤, the edge states exist of edge states in graphene, if the intervalley coupling is ne-
in different quadrants of the 共E , k兲 plane: ␤ 苸 共−␲ , −␲ / 2兲 in glected, is a natural generalization of the spectrum of edge
Fig. 3d, ␤ 苸 共−␲ / 2 , 0兲 in Fig. 3c, ␤ 苸 共0 , ␲ / 2兲 in Fig. 3b, and states for the Weyl Hamiltonian.
␤ 苸 共␲ / 2 , ␲兲 in Fig. 3a.
IV. DISCUSSION OF THE RESULTS. CONCLUSION
Let us compare our results for the edge states with the
III. BOUNDARY CONDITIONS FOR GRAPHENE known results. The results for graphene have been obtained
If intervalley coupling is neglected, the general boundary
condition for graphene can be written in terms of a 4 ⫻ 4
boundary matrix ⌫ˆ acting on a bispinor comprising an eigen-
vector of the Hamiltonian 共5兲:

冏 冉 冊冏 冏冉 冊冉 冊冏
⌫ˆ
␺
␺⬘ S
=
b
0 b⬘
0 ␺
␺⬘ S
= 0, 共19兲

where b and b⬘ are unknown 2 ⫻ 2 matrices.

From the Hermiticity of the Hamiltonian 共5兲, as in Sec.
FIG. 4. Electron spectrum E共k兲 for a graphene half plane x = 0, Ky and K⬘y
II, we obtain the following expressions for b and b⬘:

冉 冊
are the projections of the valley centers on the y axis. The shaded region
1 iae−i␣ corresponds to the continuous spectrum, and the thick lines to edge states.
b= , 共20兲 The slope of the spectrum of edge states with respect to the axes is deter-
0 0 as indicated in the article. Reuse of AIP content is subject
This article is copyrighted mined by the
to the boundary
terms parameter ␤.
at: http://scitation.aip.org/termsconditions. Downloaded to IP:
148.217.201.2 On: Tue, 11 Mar 2014 17:14:20
 Low Temp. Phys. 35 共1兲, January 2009 V. A. Volkov and I. V. Zagorodnev 5

in the nearest-neighbor approximation 共tight-binding model兲.

It has been shown3,4,9,10 that such states exist for a boundary
of the zigzag type, which corresponds to n = 共1 , 0兲. The band
of such states E共k兲 = 0 is dispersionless and connects the cen-
ters of the two valleys. This band can be obtained from our
spectrum in the particular case ␤ = 0 共a = ⬁兲.
In Ref. 11 the boundary condition and edge state spec-
trum were obtained for the 3D Dirac equation on a half
space. The Hermiticity of the 4 ⫻ 4 Dirac Hamiltonian and
the invariance of the problem with respect to time reversal
were used. It is important to note that in the massless limit,
the Dirac equation can be reduced to a pair of Weyl equa- FIG. 5. Electron spectrum of edge states 共heavy lines兲 E共k兲 for the Dirac
equation on a half space in the massless limit.
tions, and here the time reversal operator has the form

冉 i␴2
冊
再 冎
0
Ŝ = K̂0 . 共26兲
0 i␴2 ␤ 苸 共− ␲/2, ␲/2兲, k 艋 m sin ␤ ,
共32兲
Let us present the main results of Ref. 11 in a form ␤ 苸 共␲/2,3␲/2兲, k 艌 m sin ␤ .
convenient for comparison with the results obtained in the
In the massless limit the spectrum of edge states for the
present paper. We write the Dirac equation in the form
Dirac equation are illustrated in Fig. 5. It can be obtained

冉 冊冉 冊 冉 冊
from the spectrum of edge states in graphene 共Fig. 4兲 as the
␴ · p̂ m ␺c ␺c
=E , 共27兲 intervalley distance tends toward zero.
m − ␴ · p̂ ␺v ␺v
where ␺c and ␺v are spinors comprised of the envelopes of
the wave function of the conduction band 共c兲 and valence a兲
Email: VoVA@cplire.ru
band 共v兲 with the spin-orbit coupling taken into account. In
the 2D case in the massless 共gapless兲 limit m = 0, the Hamil-
tonian of Eq. 共27兲 reduces to the Hamiltonian 共5兲. 1
K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V.
The boundary condition obtained in Ref. 11 is trans-
Dubonos, I. V. Gregorieva, and A. A. Firsov, Science 306, 666 共2004兲.
formed in this representation to 2
A. K. Geim and K. S. Novoselov, Nature Mater. 6, 183 共2007兲.
3
A. H. Castro Neto, F. Guinea, N. M. R. Peres, K. S. Novoselov, and A. K.
兩共␺c + ei␤·␴n␺v兲兩S = 0, 共28兲 4
Geim, arXiv:0709.1163v1 共2007兲.
C. W. J. Beenakker, arXiv:0710.3848 共2007兲.
where ␤ is a parameter characterizing the boundary. The 5
D. A. Abanin, P. A. Lee, and L. S. Levitov, Phys. Rev. Lett. 96, 176803
spectrum of edge states has the form 共2006兲.
6
D. A. Abanin, K. S. Novoselov, U. Zeitler, P. A. Lee, A. K. Geim, and
E = m cos ␤ − k sin ␤ , 共29兲 7
L. S. Levitov, Phys. Rev. Lett. 98, 196806 共2007兲.
T. Ando, J. Phys. Soc. Jpn. 74, 777 共2005兲.
8
if E. McCann and V. I. Fal’ko, J. Phys.: Condens. Matter 16, 2371 共2004兲.

再 冎
9
A. R. Akhmerov and C. W. J. Beenakker, Phys. Rev. B 77, 085423
␤ 苸 共− ␲/2, ␲/2兲, k 艌 − m sin ␤ , 共2008兲.
共30兲 10
L. Brey and H. A. Fertig, Phys. Rev. B 73, 195408 共2006兲.
␤ 苸 共␲/2,3␲/2兲, k 艋 − m sin ␤ . 11
V. A. Volkov and T. N. Pinsker, Fiz. Tverd. Tela 共Leningrad兲 23, 1756
共1981兲 关Sov. Phys. Solid State 23, 1022 共1981兲兴.
and 12
M. V. Berry and R. J. Mondragón, Proc. R. Soc. London, Ser. A 412, 53
E = m cos ␤ + k sin ␤ , 共31兲 共1987兲.

if Translated by Steve Torstveit

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
148.217.201.2 On: Tue, 11 Mar 2014 17:14:20