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1 - 28 - The Electronic Properties of Graphene - Castroneto2009 PDF
1 - 28 - The Electronic Properties of Graphene - Castroneto2009 PDF
F. Guinea
Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, E-28049 Madrid, Spain
N. M. R. Peres
Center of Physics and Department of Physics, Universidade do Minho, P-4710-057,
Braga, Portugal
This article reviews the basic theoretical aspects of graphene, a one-atom-thick allotrope of carbon,
with unusual two-dimensional Dirac-like electronic excitations. The Dirac electrons can be controlled
by application of external electric and magnetic fields, or by altering sample geometry and/or topology.
The Dirac electrons behave in unusual ways in tunneling, confinement, and the integer quantum Hall
effect. The electronic properties of graphene stacks are discussed and vary with stacking order and
number of layers. Edge 共surface兲 states in graphene depend on the edge termination 共zigzag or
armchair兲 and affect the physical properties of nanoribbons. Different types of disorder modify the
Dirac equation leading to unusual spectroscopic and transport properties. The effects of
electron-electron and electron-phonon interactions in single layer and multilayer graphene are also
presented.
what is accepted today. In 1968, Schroeder et al. distances of the order of micrometers in graphene 共No-
共Schroeder et al., 1968兲 established the currently ac- voselov et al., 2004兲. The sources of disorder in graphene
cepted location of electron and hole pockets 共McClure, are many and can vary from ordinary effects commonly
1971兲. The SWM model has been revisited in recent found in semiconductors, such as ionized impurities in
years because of its inability to describe the van der the Si substrate, to adatoms and various molecules ad-
Waals–like interactions between graphene planes, a sorbed in the graphene surface, to more unusual defects
problem that requires the understanding of many-body such as ripples associated with the soft structure of
effects that go beyond the band-structure description graphene 共Meyer, Geim, Katsnelson, Novoselov, Booth,
共Rydberg et al., 2003兲. These issues, however, do not et al., 2007a兲. In fact, graphene is unique in the sense
arise in the context of a single graphene crystal but they that it shares properties of soft membranes 共Nelson et
show up when graphene layers are stacked on top of al., 2004兲 and at the same time it behaves in a metallic
each other, as in the case, for instance, of the bilayer way, so that the Dirac fermions propagate on a locally
graphene. Stacking can change the electronic properties curved space. Here analogies with problems of quantum
considerably and the layering structure can be used in gravity become apparent 共Fauser et al., 2007兲. The soft-
order to control the electronic properties. ness of graphene is related with the fact that it has out-
One of the most interesting aspects of the graphene of-plane vibrational modes 共phonons兲 that cannot be
problem is that its low-energy excitations are massless, found in 3D solids. These flexural modes, responsible
chiral, Dirac fermions. In neutral graphene, the chemical for the bending properties of graphene, also account for
potential crosses exactly the Dirac point. This particular the lack of long range structural order in soft mem-
dispersion, that is only valid at low energies, mimics the branes leading to the phenomenon of crumpling 共Nelson
physics of quantum electrodynamics 共QED兲 for massless et al., 2004兲. Nevertheless, the presence of a substrate or
fermions except for the fact that in graphene the Dirac scaffolds that hold graphene in place can stabilize a cer-
fermions move with a speed vF, which is 300 times tain degree of order in graphene but leaves behind the
smaller than the speed of light c. Hence, many of the so-called ripples 共which can be viewed as frozen flexural
unusual properties of QED can show up in graphene but modes兲.
at much smaller speeds 共Castro Neto et al., 2006a; It was realized early on that graphene should also
Katsnelson et al., 2006; Katsnelson and Novoselov, present unusual mesoscopic effects 共Peres, Castro Neto,
2007兲. Dirac fermions behave in unusual ways when and Guinea, 2006a; Katsnelson, 2007a兲. These effects
compared to ordinary electrons if subjected to magnetic have their origin in the boundary conditions required for
fields, leading to new physical phenomena 共Gusynin and the wave functions in mesoscopic samples with various
Sharapov, 2005; Peres, Guinea, and Castro Neto, 2006a兲 types of edges graphene can have 共Nakada et al., 1996;
such as the anomalous integer quantum Hall effect Wakabayashi et al., 1999; Peres, Guinea, and Castro
共IQHE兲 measured experimentally 共Novoselov, Geim, Neto, 2006a; Akhmerov and Beenakker, 2008兲. The
Morozov, et al., 2005a; Zhang et al., 2005兲. Besides being most studied edges, zigzag and armchair, have drastically
qualitatively different from the IQHE observed in Si different electronic properties. Zigzag edges can sustain
and GaAlAs 共heterostructures兲 devices 共Stone, 1992兲, edge 共surface兲 states and resonances that are not present
the IQHE in graphene can be observed at room tem- in the armchair case. Moreover, when coupled to con-
perature because of the large cyclotron energies for ducting leads, the boundary conditions for a graphene
“relativistic” electrons 共Novoselov et al., 2007兲. In fact, ribbon strongly affect its conductance, and the chiral
the anomalous IQHE is the trademark of Dirac fermion Dirac nature of fermions in graphene can be used for
behavior. applications where one can control the valley flavor of
Another interesting feature of Dirac fermions is their the electrons besides its charge, the so-called valleytron-
insensitivity to external electrostatic potentials due to ics 共Rycerz et al., 2007兲. Furthermore, when supercon-
the so-called Klein paradox, that is, the fact that Dirac ducting contacts are attached to graphene, they lead to
fermions can be transmitted with probability 1 through a the development of supercurrent flow and Andreev pro-
classically forbidden region 共Calogeracos and Dombey, cesses characteristic of the superconducting proximity
1999; Itzykson and Zuber, 2006兲. In fact, Dirac fermions effect 共Heersche et al., 2007兲. The fact that Cooper pairs
behave in an unusual way in the presence of confining can propagate so well in graphene attests to the robust
potentials, leading to the phenomenon of Zitter- electronic coherence in this material. In fact, quantum
bewegung, or jittery motion of the wave function 共Itzyk- interference phenomena such as weak localization, uni-
son and Zuber, 2006兲. In graphene, these electrostatic versal conductance fluctuations 共Morozov et al., 2006兲,
potentials can be easily generated by disorder. Since dis- and the Aharonov-Bohm effect in graphene rings have
order is unavoidable in any material, there has been a already been observed experimentally 共Recher et al.,
great deal of interest in trying to understand how disor- 2007; Russo, 2007兲. The ballistic electronic propagation
der affects the physics of electrons in graphene and its in graphene can be used for field-effect devices such as
transport properties. In fact, under certain conditions, p-n 共Cheianov and Fal’ko, 2006; Cheianov, Fal’ko, and
Dirac fermions are immune to localization effects ob- Altshuler, 2007; Huard et al., 2007; Lemme et al., 2007;
served in ordinary electrons 共Lee and Ramakrishnan, Tworzydlo et al., 2007; Williams et al., 2007; Fogler,
1985兲 and it has been established experimentally that Glazman, Novikov, et al., 2008; Zhang and Fogler, 2008兲
electrons can propagate without scattering over large and p-n-p 共Ossipov et al., 2007兲 junctions, and as “neu-
II. ELEMENTARY ELECTRONIC PROPERTIES OF where ai, 共ai,† 兲 annihilates 共creates兲 an electron with
GRAPHENE spin 共 = ↑ , ↓ 兲 on site Ri on sublattice A 共an equiva-
lent definition is used for sublattice B兲, t共⬇2.8 eV兲 is the
A. Single layer: Tight-binding approach nearest-neighbor hopping energy 共hopping between dif-
ferent sublattices兲, and t⬘ is the next nearest-neighbor
Graphene is made out of carbon atoms arranged in
hopping energy1 共hopping in the same sublattice兲. The
hexagonal structure, as shown in Fig. 2. The structure
energy bands derived from this Hamiltonian have the
can be seen as a triangular lattice with a basis of two
form 共Wallace, 1947兲
atoms per unit cell. The lattice vectors can be written as
a1 = 共3, 冑3兲, a2 = 共3,− 冑3兲, E±共k兲 = ± t冑3 + f共k兲 − t⬘f共k兲,
a a
共1兲
2 2
where the plus sign applies to the upper 共*兲 and the FIG. 4. 共Color online兲 Cyclotron mass of charge carriers in
minus sign the lower 共兲 band. It is clear from Eq. 共6兲 graphene as a function of their concentration n. Positive and
that the spectrum is symmetric around zero energy if t⬘ negative n correspond to electrons and holes, respectively.
= 0. For finite values of t⬘, the electron-hole symmetry is Symbols are the experimental data extracted from the tem-
perature dependence of the SdH oscillations; solid curves are
broken and the and * bands become asymmetric. In
the best fit by Eq. 共13兲. m0 is the free-electron mass. Adapted
Fig. 3, we show the full band structure of graphene with
from Novoselov, Geim, Morozov, et al., 2005.
both t and t⬘. In the same figure, we also show a zoom in
of the band structure close to one of the Dirac points 共at
the K or K⬘ point in the BZ兲. This dispersion can be 1. Cyclotron mass
obtained by expanding the full band structure, Eq. 共6兲, The energy dispersion 共7兲 resembles the energy of ul-
close to the K 共or K⬘兲 vector, Eq. 共3兲, as k = K + q, with trarelativistic particles; these particles are quantum me-
兩q 兩 Ⰶ 兩K兩 共Wallace, 1947兲, chanically described by the massless Dirac equation 共see
E±共q兲 ⬇ ± vF兩q兩 + O关共q/K兲2兴, 共7兲 Sec. II.B for more on this analogy兲. An immediate con-
sequence of this massless Dirac-like dispersion is a cy-
where q is the momentum measured relatively to the clotron mass that depends on the electronic density as its
Dirac points and vF is the Fermi velocity, given by vF square root 共Novoselov, Geim, Morozov, et al., 2005;
= 3ta / 2, with a value vF ⯝ 1 ⫻ 106 m / s. This result was Zhang et al., 2005兲. The cyclotron mass is defined, within
first obtained by Wallace 共1947兲. the semiclassical approximation 共Ashcroft and Mermin,
The most striking difference between this result and 1976兲, as
冋 册
the usual case, ⑀共q兲 = q2 / 共2m兲, where m is the electron
mass, is that the Fermi velocity in Eq. 共7兲 does not de- 1 A共E兲
m* = , 共10兲
pend on the energy or momentum: in the usual case we 2 E E=EF
have v = k / m = 冑2E / m and hence the velocity changes
substantially with energy. The expansion of the spectrum with A共E兲 the area in k space enclosed by the orbit and
given by
around the Dirac point including t⬘ up to second order
in q / K is given by E2
A共E兲 = q共E兲2 = 共11兲
冉 冊
.
9t⬘a2 3ta2 vF2
E±共q兲 ⯝ 3t⬘ ± vF兩q兩 − ± sin共3q兲 兩q兩2 , 共8兲
4 8 Using Eq. 共11兲 in Eq. 共10兲, one obtains
where EF kF
共12兲
冉 冊
m* = = .
q vF2 vF
q = arctan x 共9兲
qy The electronic density n is related to the Fermi momen-
is the angle in momentum space. Hence, the presence of tum kF as kF2 / = n 共with contributions from the two
t⬘ shifts in energy the position of the Dirac point and Dirac points K and K⬘ and spin included兲, which leads to
breaks electron-hole symmetry. Note that up to order 冑
共q / K兲2 the dispersion depends on the direction in mo- m* = 冑n. 共13兲
vF
mentum space and has a threefold symmetry. This is the
so-called trigonal warping of the electronic spectrum Fitting Eq. 共13兲 to the experimental data 共see Fig. 4兲
共Ando et al., 1998, Dresselhaus and Dresselhaus, 2002兲. provides an estimation for the Fermi velocity and the
ρ(ε)
tence of massless Dirac quasiparticles in graphene 共No- 2
0.1
ρ(ε)
2. Density of states 0.6 0.2
0.4
The density of states per unit cell, derived from Eq. 0.1
0.2
共5兲, is given in Fig. 5 for both t⬘ = 0 and t⬘ ⫽ 0, showing in
0 0
both cases semimetallic behavior 共Wallace, 1947; Bena -2 0
ε /t
2 -0.8 -0.4 0
ε /t
0.4 0.8
共E兲 =
4 兩E兩 1
F ,
2 t 2 冑Z 0 2
冉 冑 冊 Z1
Z0
,
density of states close to the neutrality point of one electron
per site. For the case t⬘ = 0, the electron-hole nature of the
spectrum is apparent and the density of states close to the
neutrality point can be approximated by 共⑀兲 ⬀ 兩⑀兩.
冉 冏 冏冊
冦 冧
E 2
关共E/t兲2 − 1兴2
1+ − , −t艋E艋t
t 4
冏冏
Z0 =
E
4 , − 3t 艋 E 艋 − t ∨ t 艋 E 艋 3t,
t
冏冏
冦 冧
E
4 , −t艋E艋t
t
共14兲
冉 冏 冏冊
Z1 =
E 2
关共E/t兲2 − 1兴2
1+ − , − 3t 艋 E 艋 − t ∨ t 艋 E 艋 3t,
t 4
2Ac 兩E兩 1
冑N c 兺 共16兲
−ik·Rn
共E兲 = , 共15兲 an = e a共k兲,
vF2 k
where Ac is the unit cell area given by Ac = 3冑3a2 / 2. It is where Nc is the number of unit cells. Using this transfor-
worth noting that the density of states for graphene is mation, we write the field an as a sum of two terms,
different from the density of states of carbon nanotubes coming from expanding the Fourier sum around K⬘ and
共Saito et al., 1992a, 1992b兲. The latter shows 1 / 冑E singu- K. This produces an approximation for the representa-
larities due to the 1D nature of their electronic spec- tion of the field an as a sum of two new fields, written as
trum, which occurs due to the quantization of the mo-
mentum in the direction perpendicular to the tube axis. an ⯝ e−iK·Rna1,n + e−iK⬘·Rna2,n ,
From this perspective, graphene nanoribbons, which
also have momentum quantization perpendicular to the
ribbon length, have properties similar to carbon nano-
bn ⯝ e−iK·Rnb1,n + e−iK⬘·Rnb2,n , 共17兲
tubes.
where the index i = 1 共i = 2兲 refers to the K 共K⬘兲 point. binding Hamiltonian and expanding the opera-
These new fields, ai,n and bi,n, are assumed to vary tors up to a linear order in ␦. In the derivation, one
slowly over the unit cell. The procedure for deriving uses the fact that 兺␦e±iK·␦ = 兺␦e±iK⬘·␦ = 0. After some
a theory that is valid close to the Dirac point con- straightforward algebra, we arrive at 共Semenoff,
sists in using this representation in the tight- 1984兲
H⯝−t 冕 dxdy⌿̂†1共r兲 冋冉 0
− 3a共1 + i冑3兲/4
3a共1 − i冑3兲/4
0
冊 冉
x +
0
− 3a共i − 冑3兲/4
3a共− i − 冑3兲/4
0
冊册
y ⌿̂1共r兲
+ ⌿̂†2共r兲 冋冉 0
− 3a共1 − i冑3兲/4
3a共1 + i冑3兲/4
0
冊 冉
x +
0
− 3a共− i − 冑3兲/4
3a共i − 冑3兲/4
0
冊册y ⌿̂2共r兲
±,K共k兲 =
1
冉 冊
e−ik/2
冑2 ±eik/2 共20兲
helicity. Equation 共23兲 implies that has its two eigen-
values either in the direction of 共⇑兲 or against 共⇓兲 the
momentum p. This property says that the states of the
for HK = vF · k, where the ⫾ signs correspond to the system close to the Dirac point have well defined chiral-
eigenenergies E = ± vFk, that is, for the * and bands, ity or helicity. Note that chirality is not defined in regard
respectively, and k is given by Eq. 共9兲. The wave func- to the real spin of the electron 共that has not yet ap-
peared in the problem兲 but to a pseudospin variable as-
tion for the momentum around K⬘ has the form
sociated with the two components of the wave function.
冑 冉 冊
1 eik/2 The helicity values are good quantum numbers as long
±,K⬘共k兲 = −i /2 共21兲 as the Hamiltonian 共18兲 is valid. Therefore, the existence
2 ±e k
of helicity quantum numbers holds only as an
for HK⬘ = vF* · k. Note that the wave functions at K and asymptotic property, which is well defined close to the
K⬘ are related by time-reversal symmetry: if we set the Dirac points K and K⬘. Either at larger energies or due
origin of coordinates in momentum space in the M point to the presence of a finite t⬘, the helicity stops being a
of the BZ 共see Fig. 2兲, time reversal becomes equivalent good quantum number.
to a reflection along the kx axis, that is, 共kx , ky兲
→ 共kx , −ky兲. Also note that if the phase is rotated by
2, the wave function changes sign indicating a phase of
1. Chiral tunneling and Klein paradox
共in the literature this is commonly called a Berry’s
phase兲. This change of phase by under rotation is char- In this section, we address the scattering of chiral elec-
acteristic of spinors. In fact, the wave function is a two- trons in two dimensions by a square barrier 共Katsnelson
component spinor. et al., 2006; Katsnelson, 2007b兲. The one-dimensional
A relevant quantity used to characterize the eigen- scattering of chiral electrons was discussed earlier in the
functions is their helicity defined as the projection of the context on nanotubes 共Ando et al., 1998; McEuen et al.,
momentum operator along the 共pseudo兲spin direction. 1999兲.
The quantum-mechanical operator for the helicity has We start by noting that by a gauge transformation the
the form wave function 共20兲 can be written as
Energy
D I共r兲 =
1
冑2 冉 冊 1
se i ei共kxx+kyy兲 +
r
冑2 冉 se
1
i共−兲 冊 ei共−kxx+kyy兲 ,
V0 共25兲
E
x with = arctan共ky / kx兲, kx = kF cos , ky = kF sin , and kF
the Fermi momentum. In region II, we have
y D
冑 冉 冊 冑 冉 冊
I II III a 1 b 1
II共r兲 = i ei共qxx+kyy兲 + i共−兲 ei共−qxx+kyy兲 ,
φ
2 s ⬘e 2 s ⬘e
θ
φ 共26兲
x
with = arctan共ky / qx兲 and
FIG. 6. 共Color online兲 Klein tunneling in graphene. Top: sche-
matic of the scattering of Dirac electrons by a square potential. qx = 冑共V0 − E兲2/共vF2 兲 − k2y , 共27兲
Bottom: definition of the angles and used in the scattering
and finally in region III we have a transmitted wave only,
formalism in regions I, II, and III.
t
冉 冊 1
冉 冊
III共r兲 = ei共kxx+kyy兲 , 共28兲
1 1 冑2 sei
K共k兲 = . 共24兲
冑2 ±eik
with s = sgn共E兲 and s⬘ = sgn共E − V0兲. The coefficients r, a,
We further assume that the scattering does not mix the b, and t are determined from the continuity of the wave
momenta around K and K⬘ points. In Fig. 6, we depict function, which implies that the wave function has to
the scattering process due to the square barrier of width obey the conditions I共x = 0 , y兲 = II共x = 0 , y兲 and II共x
D. = D , y兲 = III共x = D , y兲. Unlike the Schrödinger equation,
The wave function in the different regions can be writ- we only need to match the wave function but not its
ten in terms of incident and reflected waves. In region I, derivative. The transmission through the barrier is ob-
we have tained from T共兲 = tt* and has the form
cos2 cos2
T共兲 = . 共29兲
关cos共Dqx兲cos cos 兴2 + sin2共Dqx兲共1 − ss⬘ sin sin 兲2
This expression does not take into account a contribu- 1. Similar calculations were done for a graphene bilayer
tion from evanescent waves in region II, which is usually 共Katsnelson et al., 2006兲 with the absence of tunneling in
negligible, unless the chemical potential in region II is at the forward 共ky = 0兲 direction its most distinctive behav-
the Dirac energy 共see Sec. IV.A兲. ior.
Note that T共兲 = T共−兲, and for values of Dqx satisfy- The simplest example of a potential barrier is a square
ing the relation Dqx = n, with n an integer, the barrier potential discussed previously. When intervalley scatter-
becomes completely transparent since T共兲 = 1, indepen- ing and the lack of symmetry between sublattices are
dent of the value of . Also, for normal incidence 共 neglected, a potential barrier shows no reflection for
→ 0 and → 0兲 and any value of Dqx, one obtains T共0兲 electrons incident in the normal direction 共Katsnelson et
= 1, and the barrier is again totally transparent. This re- al., 2006兲. Even when the barrier separates regions
sult is a manifestation of the Klein paradox 共Calogeracos where the Fermi surface is electronlike on one side and
and Dombey, 1999; Itzykson and Zuber, 2006兲 and does holelike on the other, a normally incident electron con-
not occur for nonrelativistic electrons. In this latter case tinues propagating as a hole with 100% efficiency. This
and for normal incidence, the transmission is always phenomenon is another manifestation of the chirality of
smaller than 1. In the limit 兩V0 兩 Ⰷ 兩E兩, Eq. 共29兲 has the the Dirac electrons within each valley, which prevents
following asymptotic form: backscattering in general. The transmission and reflec-
cos2 tion probabilities of electrons at different angles depend
T共兲 ⯝ . 共30兲 on the potential profile along the barrier. A slowly vary-
1 − cos2共Dqx兲sin2 ing barrier is more efficient in reflecting electrons at
In Fig. 7, we show the angular dependence of T共兲 for nonzero incident angles 共Cheianov and Fal’ko, 2006兲.
two different values of the potential V0; it is clear that Electrons moving through a barrier separating p- and
there are several directions for which the transmission is n-doped graphene, a p-n junction, are transmitted as
0.4
V0 = 200 meV sample.
V0 = 285 meV The scattering of electrons near the Dirac point by
0.2
graphene-superconductor junctions differs from An-
0
-90 -75 -60 -45 -30 -15 0 15 30 45 60 75 90 dreev scattering process in normal metals 共Titov and
1 Beenakker, 2006兲. When the distance between the Fermi
0.8 energy and the Dirac energy is smaller than the super-
conducting gap, the superconducting interaction hybrid-
0.6
T(φ)
冕
There is much progress in the measurement of transport
d 2k
properties of graphene ribbons with additional top gates
that play the role of tunable potential barriers 共Han et
共r,t兲 = 兺 ␣a,ka,K共k兲e−ia共k·r+vFkt兲 ,
共2兲2 a=±1
共32兲
al., 2007; Huard et al., 2007; Lemme et al., 2007; Özyil-
maz et al., 2007; Williams et al., 2007兲. where ␣±,k are Fourier coefficients. We can rewrite Eq.
A magnetic field and potential fluctuations break both 共31兲 in terms of Eq. 共32兲 by inverse Fourier transform
the inversion symmetry of the lattice and time-reversal and find that
symmetry. The combination of these effects also breaks ␣±,k = 冑we−k
2w2/2
±,K
†
共k兲 . 共33兲
the symmetry between the two valleys. The transmission
coefficient becomes valley dependent, and, in general, Note that the relative weight of positive energy states
electrons from different valleys propagate along differ- with respect to negative energy states 兩␣+ / ␣−兩, given by
ent paths. This opens the possibility of manipulating the Eq. 共20兲 is 1, that is, there are as many positive energy
valley index 共Tworzydlo et al., 2007兲 共valleytronics兲 in a states as negative energy states in a wave packet. Hence,
way similar to the control of the spin in mesoscopic de- these will cause the wave function to be delocalized at
vices 共spintronics兲. For large magnetic fields, a p-n junc- any time t ⫽ 0. Thus, a wave packet of electronlike states
tion separates regions with different quantized Hall con- has holelike components, a result that puzzled many re-
EeV
1
0.8
0.6
0.4
0.2
Π k ya 3
0.2
2 FIG. 9. 共Color online兲 Lattice structure of bilayer graphene, its
respective electronic hopping energies, and Brillouin zone. 共a兲
FIG. 8. 共Color online兲 Energy spectrum 共in units of t兲 for a Lattice structure of the bilayer with the various hopping pa-
graphene ribbon 600a wide, as a function of the momentum k rameters according to the SWM model. The A sublattices are
along the ribbon 共in units of 1 / 冑3a兲, in the presence of confin- indicated by darker spheres. 共b兲 Brillouin zone. Adapted from
ing potential with V0 = 1 eV, = 180a. Malard et al., 2007.
searchers in the early days of QED 共Itzykson and Zuber, The tight-binding Hamiltonian for this problem can
2006兲. be written as
Consider the tight-binding description 共Peres, Castro
Neto, and Guinea, 2006b; Chen, Apalkov, and Ht.b. = − ␥0 兺 共am,i,
†
bm,j, + H.c.兲
Chakraborty, 2007兲 of Sec. II.A when a potential Vi on 具i,j典
site Ri is added to the problem, m,
H e = 兺 V in i , 共34兲 − ␥1 兺 共a1,j,
†
a2,j, + H.c.兲,
i j,
oscillations. This is how Zitterbewegung could manifest where 共ignoring ␥4 for the time being兲
itself in magnetotransport.
冢 冣
−V v Fk 0 3␥3ak*
C. Bilayer graphene: Tight-binding approach v Fk * −V ␥1 0
HK ⬅ , 共38兲
0 ␥1 V v Fk
The tight-binding model developed for graphite can
be easily extended to stacks with a finite number of 3␥3ak 0 v Fk * V
graphene layers. The simplest generalization is a bilayer
共McCann and Fal’ko, 2006兲. A bilayer is interesting be- and k = kx + iky is a complex number; we have added V,
cause the IQHE shows anomalies, although different which is here half the shift in electrochemical potential
from those observed in a single layer 共Novoselov et al., between the two layers 共this term will appear if a poten-
2006兲, and also a gap can open between the conduction tial bias is applied between the layers兲, and
and valence band 共McCann and Fal’ko, 2006兲. The bi- ⌿k† = „b†1共k兲,a†1共k兲,a†2共k兲,b†2共k兲… 共39兲
layer structure, with the AB stacking of 3D graphite, is
shown in Fig. 9. is a four-component spinor.
FIG. 10. 共Color online兲 Band structure of bilayer graphene of FIG. 11. 共Color online兲 Band structure of bilayer graphene for
V = 0 and ␥3 = 0. V ⫽ 0 and ␥3 = 0.
冢 冣
point. For small momenta, and V Ⰶ t, the energy of the
vF2 k2
0 + 3␥3ak* conduction band can be expanded,
␥1
HK ⬅ . 共40兲 ⑀k ⬇ V − 2VvF2 k2/t⬜ + vF4 k4/2t⬜
2
V. 共42兲
vF2 共k*兲2
+ 3␥3ak 0 The dispersion for the valence band can be obtained by
␥1
replacing ⑀k by −⑀k. The bilayer has a gap at k2
⬇ 2V2 / vF2 . Note, therefore, that the gap in the biased
The hopping ␥4 leads to a k-dependent coupling be- bilayer system depends on the applied bias and hence
tween the sublattices or a small renormalization of ␥1. can be measured experimentally 共McCann, 2006; Mc-
The same role is played by the inequivalence between Cann and Fal’ko, 2006; Castro, Novoselov, Morozov, et
sublattices within a layer. al., 2007兲. The ability to open a gap makes bilayer
For ␥3 = 0, Eq. 共40兲 gives two parabolic bands, ⑀k,± graphene interesting for technological applications.
⬇ ± vF2 k2 / t⬜, which touch at ⑀ = 0 共as shown in Fig. 10兲.
The spectrum is electron-hole symmetric. There are two D. Epitaxial graphene
additional bands that start at ±t⬜. Within this approxi-
mation, the bilayer is metallic, with a constant density of It has been known for a long time that monolayers of
states. The term ␥3 changes qualitatively the spectrum at graphene could be grown epitaxially on metal surfaces
low energies since it introduces a trigonal distortion, or using catalytic decomposition of hydrocarbons or carbon
warping, of the bands 关note that this trigonal distortion, oxide 共Shelton et al., 1974; Eizenberg and Blakely, 1979;
unlike the one introduced by large momentum in Eq. Campagnoli and Tosatti, 1989; Oshima and Nagashima,
共8兲, occurs at low energies兴. The electron-hole symmetry 1997; Sinitsyna and Yaminsky, 2006兲. When such sur-
is preserved but, instead of two bands touching at k = 0, faces are heated, oxygen or hydrogen desorbs, and the
we obtain three sets of Dirac-like linear bands. One carbon atoms form a graphene monolayer. The resulting
graphene structures could reach sizes up to a microme-
Dirac point is at ⑀ = 0 and k = 0, while the three other
ter with few defects, and they were characterized by dif-
Dirac points, also at ⑀ = 0, lie at three equivalent points
ferent surface-science techniques and local scanning
with a finite momentum. The stability of points where
probes 共Himpsel et al., 1982兲. For example, graphene
bands touch can be understood using topological argu-
grown on ruthenium has zigzag edges and also ripples
ments 共Mañes et al., 2007兲. The winding number of a
associated with a 共10⫻ 10兲 reconstruction 共Vázquez de
closed curve in the plane around a given point is an
Parga et al., 2008兲.
integer representing the total number of times that the Graphene can also be formed on the surface of SiC.
curve travels counterclockwise around the point so that Upon heating, the silicon from the top layers desorbs,
the wave function remains unaltered. The winding num- and a few layers of graphene are left on the surface
ber of the point where the two parabolic bands come 共Bommel et al., 1975; Forbeaux et al., 1998; Coey et al.,
together for ␥3 = 0 has winding number +2. The trigonal 2002; Berger et al., 2004; Rollings et al., 2006; Hass,
warping term ␥3 splits it into a Dirac point at k = 0 and Feng, Millán-Otoya, et al., 2007; de Heer et al., 2007兲.
winding number −1, and three Dirac points at k ⫽ 0 and The number of layers can be controlled by limiting time
winding numbers +1. An in-plane magnetic field, or a or temperature of the heating treatment. The quality
small rotation of one layer with respect to the other, and the number of layers in the samples depend on the
splits the ␥3 = 0 degeneracy into two Dirac points with SiC face used for their growth 共de Heer et al., 2007兲 共the
winding number +1. carbon-terminated surface produces few layers but with
The term V in Eq. 共38兲 breaks the equivalence of the a low mobility, whereas the silicon-terminated surface
two layers, or, alternatively, inversion symmetry. In this produces several layers but with higher mobility兲. Epi-
case, the dispersion relation becomes taxially grown multilayers exhibit SdH oscillations with
order in terms of seven parameters: ␥0, ␥1, ␥2, ␥3, ␥4, ␥5,
K
H33 = ⌬ + 2␥5 cos共2kz/c兲,
and ⌬. The parameter ␥0 describes the hopping within
each layer, and it has been considered previously. The K
H34 = vF共kx + iky兲,
coupling between orbitals in atoms that are nearest
neighbors in successive layers is ␥1, which we called t⬜
earlier. The parameters ␥3 and ␥4 describe the hopping
K
H44 = 2␥2 cos共2kz/c兲, 共43兲
between orbitals at next nearest neighbors in successive
layers and were discussed in the case of the bilayer. The where c is the lattice constant in the out-of-plane direc-
couplings between orbitals at next-nearest-neighbor lay- tion, equal to twice the interlayer spacing. The matrix
ers are ␥2 and ␥5. Finally, ⌬ is an on-site energy that elements of HK⬘ can be obtained by replacing kx by −kx
reflects the inequivalence between the two sublattices in 共other conventions for the unit cell and the orientation
each graphene layer once the presence of neighboring of the lattice lead to different phases兲. Recent ARPES
layers is taken into account. The values of these param- experiments 共Ohta et al., 2006; Zhou, Gweon, and Lan-
eters, and their dependence with pressure, or, equiva- zara, 2006; Zhou, Gweon, et al., 2006; Bostwick, Ohta,
lently, the interatomic distances, have been extensively Seyller, et al., 2007兲 performed in epitaxially grown
studied 共McClure, 1957, Nozières, 1958; Dresselhaus and graphene stacks 共Berger et al., 2004兲 confirm the main
Mavroides, 1964; Soule et al., 1964; Dillon et al., 1977; features of this model, formulated on the basis of Fermi
Brandt et al., 1988兲. A representative set of values is surface measurements 共McClure, 1957; Soule et al.,
shown in Table I. 1964兲. The electronic spectrum of the model can also be
The unit cell of graphite with Bernal stacking includes calculated in a magnetic field 共de Gennes, 1964; Nakao,
two layers, and two atoms within each layer. The tight- 1976兲, and the results are also consistent with STM on
binding Hamiltonian described previously can be repre- graphite surfaces 共Kobayashi et al., 2005; Matsui et al.,
sented as a 4 ⫻ 4 matrix. In the continuum limit, the two 2005; Niimi et al., 2006; Li and Andrei, 2007兲, epitaxially
inequivalent corners of the BZ can be treated separately, grown graphene stacks 共Mallet et al., 2007兲, and optical
and the in-plane terms can be described by the Dirac measurements in the infrared range 共Li et al., 2006兲.
equation. The next terms of importance for the low-
energy electronic spectrum are the nearest-neighbor
couplings ␥1 and ␥3. The influence of the parameter ␥4 F. Surface states in graphene
on the low-energy bands is much smaller, as discussed
below. Finally, the fine details of the spectrum of bulk So far we have discussed the basic bulk properties of
graphite are determined by ⌬, which breaks the graphene. Nevertheless, graphene has very interesting
electron-hole symmetry of the bands preserved by ␥0, ␥1, surface 共edge兲 states that do not occur in other systems.
and ␥3. It is usually assumed to be much smaller than the A semi-infinite graphene sheet with a zigzag edge has a
other terms. band of zero-energy states localized at the surface
We label the two atoms from the unit cell in one layer 共Fujita et al., 1996; Nakada et al., 1996; Wakabayashi et
as 1 and 2, and 3 and 4 correspond to the second layer. al., 1999兲. In Sec. II.H, we discuss the existence of edge
Atoms 2 and 3 are directly on top of each other. Then, states using the Dirac equation. Here we discuss the
the matrix elements of the Hamiltonian can be written same problem using the tight-binding Hamiltonian. To
as see why these edge states exist, we consider the ribbon
geometry with zigzag edges shown in Fig. 14. The ribbon
K
H11 = 2␥2 cos共2kz/c兲, width is such that it has N unit cells in the transverse
cross section 共y direction兲. We assume that the ribbon
has infinite length in the longitudinal direction 共x direc-
K
H12 = vF共kx + iky兲,
tion兲.
We rewrite Eq. 共5兲, with t⬘ = 0, in terms of the integer
3 ␥ 4a indices m and n, introduced in Fig. 14, and labeling the
K
H13 = 共1 + eikzc兲共kx + iky兲,
2 unit cells,
A a1
0 = ␣共k,N − 1兲. 共55兲
n
a2 B Equations 共52兲 and 共53兲 are easily solved, giving
n+1 ␣共k,n兲 = 关− 2 cos共ka/2兲兴nei共ka/2兲n␣共k,0兲, 共56兲
y
x
n+2 共k,n兲 = 关− 2 cos共ka/2兲兴N−1−n
m−1 m m+ 1 m+ 2 ⫻e−i共ka/2兲共N−1−n兲共k,N − 1兲. 共57兲
FIG. 14. 共Color online兲 Ribbon geometry with zigzag edges. Consider, for simplicity, a semi-infinite system with a
single edge. We must require the convergence condition
兩−2 cos共ka / 2兲兩 ⬍ 1 in Eq. 共57兲 because otherwise the
H=−t 兺
m,n,
关a† 共m,n兲b共m,n兲 + a† 共m,n兲b共m − 1,n兲 wave function would diverge in the semi-infinite
graphene sheet. Therefore, the semi-infinite system has
+ a† 共m,n兲b共m,n − 1兲 + H.c.兴. 共44兲 edge states for ka in the region 2 / 3 ⬍ ka ⬍ 4 / 3, which
corresponds to 1 / 3 of the possible momenta. Note that
Given that the ribbon is infinite in the a1 direction, one the amplitudes of the edge states are given by
冑
can introduce a Fourier decomposition of the operators
leading to 2 −n/共k兲
兩␣共k,n兲兩 = e , 共58兲
共k兲
H=−t 冕 dk
兺 关a† 共k,n兲b共k,n兲 + eikaa† 共k,n兲b共k,n兲
2 n,
冑 2 −共N−1−n兲/共k兲
兩共k,n兲兩 = e , 共59兲
+ a† 共k,n兲b共k,n − 1兲 + H.c.兴, 共45兲 共k兲
where the penetration length is given by
where c† 共k , n兲兩0典 = 兩c , , k , n典 and c = a , b. The one-
particle Hamiltonian can be written as 共k兲 = − 1/ln兩2 cos共ka/2兲兩. 共60兲
A
B
A2
B2
n
a1
A1 y
B1
a2 n+1 x
armchair edge
y
m- 1 m m+ 1 m+ 2
G. Surface states in graphene stacks FIG. 16. 共Color online兲 A piece of a honeycomb lattice dis-
playing both zigzag and armchair edges.
Single-layer graphene can be considered a zero gap
semiconductor, which leads to the possibility of midgap zero energy is the surface states living near the edge of
states, at ⑀ = 0, as discussed in the previous section. The the graphene ribbon. More detailed ab initio calcula-
most studied such states are those localized near a tions of graphene nanoribbon spectra show that interac-
graphene zigzag edge 共Fujita et al., 1996; Wakayabashi tion effects can lead to electronic gaps 共Son et al., 2006b兲
and Sigrist, 2000兲. It can be shown analytically 共Castro, and magnetic states close to the graphene edges, inde-
Peres, Lopes dos Santos, et al., 2008兲 that a bilayer zig- pendent of their nature 共Son et al., 2006a; Yang, Cohen,
zag edge, like that shown in Fig. 15, analyzed within the and Louie, 2007; Yang, Park, Son, et al., 2007兲.
nearest-neighbor tight-binding approximation described From the experimental point of view, however,
before, has two bands of localized states, one completely graphene nanoribbons currently have a high degree of
localized in the top layer and indistinguishable from roughness at the edges. Such edge disorder can change
similar states in single-layer graphene, and another band significantly the properties of edge states 共Areshkin and
that alternates between the two layers. These states, at White, 2007; Gunlycke et al., 2007兲, leading to Anderson
⑀ = 0, have finite amplitudes on one-half of the sites only. localization and anomalies in the quantum Hall effect
These bands, as in single-layer graphene, occupy one- 共Castro Neto et al., 2006b; Martin and Blanter, 2007兲 as
third of the BZ of a stripe bounded by zigzag edges. well as Coulomb blockade effects 共Sols et al., 2007兲. Such
They become dispersive in a biased bilayer. As graphite effects have already been observed in lithographically
can be described in terms of effective bilayer systems, engineered graphene nanoribbons 共Han et al., 2007;
one for each value of the perpendicular momentum kz,
bulk graphite with a zigzag termination should show one 1 0.2
surface band per layer.
energy / t
0 0
H. The spectrum of graphene nanoribbons
冉 冊冉 冊 冉 冊
zag and armchair edges directly from the Dirac equa-
tion. This was originally done both with and without a 0 kx − y A共y兲 A共y兲
magnetic field 共Nakada et al., 1996; Brey and Fertig, = ⑀˜ , 共70兲
kx + y 0 B共y兲 B共y兲
2006a, 2006b兲.
with ⑀˜ = ⑀ / vF and ⑀ the energy eigenvalue. The eigen-
problem can be written as two linear differential equa-
1. Zigzag nanoribbons tions of the form
In the geometry of Fig. 16, the unit-cell vectors are 共kx − y兲B = ⑀˜ A ,
a1 = a0共1 , 0兲 and a2 = a0共1 / 2 , 冑3 / 2兲, which generate the
unit vectors of the BZ given by b1 共kx + y兲A = ⑀˜ B . 共71兲
冑 冑 冑
= 4 / 共a0 3兲共 3 / 2 , −1 / 2兲 and b2 = 4 / 共a0 3兲共0 , 1兲. From
these two vectors, we find two inequivalent Dirac points Applying the operator kx + y to the first of Eqs. 共71兲
given by K = 共4 / 3a0 , 0兲 = 共K , 0兲 and K⬘ leads to
= 共−4 / 3a0 , 0兲 = 共−K , 0兲, with a0 = 冑3a. The Dirac Hamil- 共− 2y + k2x兲B = ⑀˜ 2B , 共72兲
tonian around the Dirac point K reads in momentum
space with A given by
HK = vF 冉 0
px + ipy
px − ipy
0
冊 , 共61兲
1
A = 共kx − y兲B .
⑀˜
共73兲
and around the K⬘ as The solution of Eq. 共72兲 has the form
H K⬘ = v F 冉 0
px − ipy
px + ipy
0
冊 . 共62兲
B = Aezy + Be−zy , 共74兲
leading to an eigenenergy ⑀˜ 2 = k2x − z2. The boundary con-
The wave function, in real space, for the sublattice A is ditions for a zigzag edge require that A共y = L兲 = 0 and
given by B共y = 0兲 = 0, leading to
where A and B are the components of the spinor wave which leads to an eigenvalue equation of the form
function of Hamiltonian 共61兲 and A ⬘ and B⬘ have iden- kx − z
tical meaning but relative to Eq. 共62兲. Assume that the e−2zL = . 共76兲
kx + z
edges of the nanoribbons are parallel to the x axis. In
this case, the translational symmetry guarantees that the Equation 共76兲 has real solutions for z, whenever kx is
spinor wave function can be written as positive; these solutions correspond to surface waves
冉 冊
共edge states兲 existing near the edge of the graphene rib-
A共y兲
共r兲 = eikxx , 共65兲 bon. In Sec. II.F, we discussed these states from the
B共y兲 point of view of the tight-binding model. In addition to
and a similar equation for the spinor of Hamiltonian real solutions for z, Eq. 共76兲 also supports complex ones,
共62兲. For zigzag edges, the boundary conditions at the of the form z = ikn, leading to
edge of the ribbon 共located at y = 0 and y = L, where L is kn
the ribbon width兲 are kx = . 共77兲
tan共knL兲
⌿A共y = L兲 = 0, ⌿B共y = 0兲 = 0, 共66兲
The solutions of Eq. 共77兲 correspond to confined modes
leading to in the graphene ribbon.
If we apply the same procedure to the Dirac equation determined from Eq. 共73兲. The solutions of Eq. 共72兲 have
around the Dirac point K⬘, we obtain a different eigen- the form
value equation given by
B = Aeiknx + Be−iknx , 共88兲
kx + z
e−2zL = . 共78兲 B⬘ = Ceiknx + De−iknx . 共89兲
kx − z
This equation supports real solutions for z if kx is nega- Applying the boundary conditions 共86兲 and 共87兲, one ob-
tive. Therefore, we have edge states for negative values tains
kx, with momentum around K⬘. As in the case of K, the 0 = A + B + C + D, 共90兲
system also supports confined modes, given by
kn 0 = Aei共kn+K兲L + De−i共kn+K兲L + Be−i共kn−K兲L + Cei共kn−K兲L .
kx = − . 共79兲 共91兲
tan共knL兲
One should note that the eigenvalue equations for K⬘ The boundary conditions are satisfied with the choice
are obtained from those for K by inversion, kx → −kx. A = − D, B = C = 0, 共92兲
We finally note that the edge states for zigzag nano-
ribbons are dispersionless 共localized in real space兲 when which leads to sin关共kn + K兲L兴 = 0. Therefore, the allowed
t⬘ = 0. When electron-hole symmetry is broken 共t⬘ ⫽ 0兲, values of kn are given by
these states become dispersive with a Fermi velocity ve n 4
⬇ t⬘a 共Castro Neto et al., 2006b兲. kn = − , 共93兲
L 3a0
and the eigenenergies are given by
2. Armchair nanoribbons
⑀˜ 2 = k2y + kn2 . 共94兲
We now consider an armchair nanoribbon with arm-
No surface states exist in this case.
chair edges along the y direction. The boundary condi-
tions at the edges of the ribbon 共located at x = 0 and x
= L, where L is the width of the ribbon兲, I. Dirac fermions in a magnetic field
⌿A共x = 0兲 = ⌿B共x = 0兲 = ⌿A共x = L兲 = ⌿B共x = L兲 = 0.
We now consider the problem of a uniform magnetic
共80兲 field B applied perpendicular to the graphene plane.2
Translational symmetry guarantees that the spinor wave We use the Landau gauge: A = B共−y , 0兲. Note that the
function of Hamiltonian 共61兲 can be written as magnetic field introduces a new length scale in the prob-
冉 冊
lem,
A共x兲
共r兲 = eikyy
B共x兲
, 共81兲
ᐉB = 冑 c
eB
, 共95兲
and a similar equation for the spinor of the Hamiltonian
共62兲. The boundary conditions have the form which is the magnetic length. The only other scale in the
problem is the Fermi-Dirac velocity. Dimensional analy-
⬘ 共0兲,
0 = eikyyA共0兲 + eikyyA 共82兲 sis shows that the only quantity with dimensions of en-
ergy we can make is vF / ᐉB. In fact, this determines the
⬘ 共0兲,
0 = eikyyB共0兲 + eikyyB 共83兲 cyclotron frequency of the Dirac fermions,
c = 冑2
vF
⬘ 共L兲,
0 = eiKLeikyyA共L兲 + e−iKLeikyyA 共84兲 共96兲
ᐉB
⬘ 共L兲,
0 = eiKLeikyyB共L兲 + e−iKLeikyyB 共85兲 共the 冑2 factor comes from the quantization of the prob-
and are satisfied for any y if lem, see below兲. Equations 共95兲 and 共96兲 show that the
cyclotron energy scales like 冑B, in contrast with the non-
共0兲 + ⬘ 共0兲 = 0 共86兲 relativistic problem where the cyclotron energy is linear
and in B. This implies that the energy scale associated with
the Dirac fermions is rather different from the one
eiKL共L兲 + e−iKL⬘ 共L兲 = 0, 共87兲 found in the ordinary 2D electron gas. For instance, for
fields of the order of B ⬇ 10 T, the cyclotron energy in
with = A , B. It is clear that these boundary conditions
the 2D electron gas is of the order of 10 K. In contrast,
mix states from the two Dirac points. Now we must find
the form of the envelope functions obeying the bound-
ary conditions 共86兲 and 共87兲. As before, the functions B 2
The problem of transverse magnetic and electric fields can
and B⬘ obey the second-order differential equation 共72兲 also be solved exactly. See Lukose et al. 共2007兲 and Peres and
共with y replaced by x兲, and the functions A and A ⬘ are Castro 共2007兲.
for the Dirac fermion problem and the same fields, the
cyclotron energy is of the order of 1000 K, that is, two
orders of magnitude larger. This has strong implications
for the observation of the quantum Hall effect at room
temperature 共Novoselov et al., 2007兲. Furthermore, for
B = 10 T the Zeeman energy is relatively small, gBB
⬇ 5 K, and can be disregarded.
We now consider the Dirac equation in more detail.
Using the minimal coupling in Eq. 共19兲 共i.e., replacing
−iⵜ by −i ⵜ + eA / c兲, we find
ជ · 共− i ⵜ + eA/c兲兴共r兲 = E共r兲,
v F关 共97兲
vF 冋 0
− y − k + Bey/c
y − k + Bey/c
0
册
共y兲 = E共y兲,
冋 册
tion of one Landau level. Note that the sequence is not inter-
0 O rupted when passing through the Dirac point, between elec-
c † 共兲 = E共兲, 共99兲 trons and holes. The period of oscillations is ⌬n = 4B / ⌽0,
O 0
where B is the applied field and ⌽0 is the flux quantum 共No-
or equivalently voselov, Geim, Morozov, et al., 2005兲.
1
N,±共兲 = N−1共兲 丢 兩 ⇑ 典 ± N共兲 丢 兩 ⇓ 典 = 冉 N−1共兲
冊
± N共 兲
,
O† =
冑2 共− + 兲, 共102兲 共107兲
and their energy is given by 共McClure, 1956兲
which obey canonical commutation relations 关O , O†兴 = 1.
The number operator is simply N = O†O. E±共N兲 = ± c冑N, 共108兲
First, we note that Eq. 共100兲 allows for a solution with where N = 0 , 1 , 2 , . . . is a positive integer and N共兲 is the
zero energy, solution of the 1D harmonic oscillator 关explicitly, N共兲
共O+ + O†−兲0 = 0, 共103兲 = 2−N/2共N!兲−1/2 exp兵−2 / 2其HN共兲, where HN共兲 is a Her-
mite polynomial兴. The Landau levels at the opposite
ជ is of dimen-
and since the Hilbert space generated by Dirac point K⬘ have exactly the same spectrum and
sion 2, and the spectrum generated by O† is bounded hence each Landau level is doubly degenerate. Of par-
from below, we just need to ensure that ticular importance for the Dirac problem discussed here
is the existence of a zero-energy state N = 0, which is
O0 = 0, responsible for the anomalies observed in the quantum
Hall effect. This particular Landau level structure has
−0 = 0, 共104兲 been observed by many different experimental probes,
from Shubnikov–de Haas oscillations in single layer
in order for Eq. 共103兲 to be fulfilled. The obvious zero- graphene 共see Fig. 18兲 共Novoselov, Geim, Morozov, et
mode solution is al., 2005; Zhang et al., 2005兲, to infrared spectroscopy
where E is the total energy of the system. The localized + e−i共⌽/⌽0兲na† 共m,n兲b„m − 1,n − 共1 − z兲/2…
states do not respond to changes in ⌽, only the delocal-
ized ones. When the flux is changed by a flux quantum + ei共⌽/⌽0兲n关共z−1兲/2兴a† 共m,n兲b共m,n − z兲 + H.c.兴,
␦⌽ = ⌽0 = hc / e, the extended states remain the same by 共113兲
0.5 0.5
energy / t
0 0
-0.5 -0.5
-1 -1
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
0.4 0.4
µ
0.2 0.2
µ
energy / t
0 0
-0.2 -0.2
-0.4 -0.4
2 3 4 5 6 0.5 1 1.5 2
momentum ka momentum ka
冋 册
k,n,
⌽ ka
+ e−i共⌽/⌽0兲neikaa† 共k,n兲b„k,n − 共1 − z兲/2… E,k共k,N − 1兲 = − 2te−ika/2 cos 共N − 1兲 −
⌽0 2
+ ei共⌽/⌽0兲n关共z−1兲/2兴a† 共k,n兲b共k,n − z兲 + H.c.兴.
⫻␣共k,N − 1兲. 共118兲
We now consider the case of zigzag edges. The eigen-
problem can be rewritten in terms of Harper’s equations Similar equations hold for a graphene ribbon with arm-
共Harper, 1955兲, and for zigzag edges we obtain 共Rammal, chair edges.
1985兲 In Fig. 21, we show 14 energy levels, around zero en-
冋 冉 冊
ergy, for both the zigzag and armchair cases. The forma-
⌽ ka tion of the Landau levels is signaled by the presence of
E,k␣共k,n兲 = − t eika/22 cos n− 共k,n兲
⌽0 2 flat energy bands, following the bulk energy spectrum.
册
From Fig. 21, it is straightforward to obtain the value of
+ 共k,n − 1兲 , 共114兲 the Hall conductivity in the quantum Hall effect regime.
We assume that the chemical potential is in between two
Landau levels at positive energies, shown by the dashed
冋
E,k共k,n兲 = − t e−ika/22 cos 冉 ⌽
⌽0
n−
ka
2
冊
␣共k,n兲
line in Fig. 21. The Landau level structure shows two
zero-energy modes; one of them is electronlike 共hole-
册
like兲, since close to the edge of the sample its energy is
shifted upwards 共downwards兲. The other Landau levels
+ ␣共k,n + 1兲 , 共115兲 are doubly degenerate. The determination of the values
for the Hall conductivity is done by counting how many
where the coefficients ␣共k , n兲 and 共k , n兲 show up in energy levels 共of electronlike nature兲 are below the
Hamiltonian’s eigenfunction 兩共k兲典 written in terms of chemical potential. This counting produces the value
lattice-position-state states as 2N + 1, with N = 0 , 1 , 2 , . . . 共for the case of Fig. 21 one has
M. Diamagnetism
冉 冊
eycomb lattice using the theory introduced by Wallace
e2 e2 1 共1947兲, a calculation he later generalized to three-
xy = ± 2 共2N + 1兲 = ± 4 N+ . 共119兲
h h 2 dimensional graphite 共McClure, 1960兲. For the honey-
Equation 共119兲 leads to the anomalous integer quantum comb plane, the magnetic susceptibility 共in units of
Hall effect discussed previously, which is the hallmark of emu/g兲 is
single-layer graphene.
=−
0.0014 2
T
␥0 sech2 冉 冊
2kBT
, 共120兲
L. Landau levels in graphene stacks
where is the Fermi energy, T is the temperature, and
The dependence of the Landau level energies on the kB is the Boltzmann constant. For graphite, the magnetic
Landau index N roughly follows the dispersion relation susceptibility is anisotropic and the difference between
FIG. 23. 共Color online兲 Relative spectral strength of the low energy optical transitions between Landau levels in graphene stacks
with Bernal ordering and an odd number of layers. The applied magnetic field is 1 T. Left: 3 layers. Middle: 11 layers. Right: 51
layers. The large circles are the transitions in a single layer.
the susceptibility parallel to the principal axis and that ⑀F and zero temperature, the magnetic susceptibility is
perpendicular to the principal axis is −21.5 given by
⫻ 10−6 emu/ g. The susceptibility perpendicular to the
g vg s 2 2 W
principal axis is equal to about the free-atom suscepti- 共 ⑀ F兲 = − e ␥0 . 共122兲
bility, −0.5⫻ 10−6 emu/ g. In the 2D model, the suscepti- 3 兩 ⑀ F兩
bility turns out to be large due to the presence of fast In the clean limit, the susceptibility is given by 共Mc-
moving electrons, with a velocity of the order of vF Clure, 1956; Safran and DiSalvo, 1979; Koshino and
⯝ 106 m / s, which in turn is a consequence of the large Ando, 2007兲
value of the hopping parameter ␥0. In fact, the suscepti-
bility turns out to be proportional to the square of ␥0. g vg s 2 2
共 ⑀ F兲 = − e ␥0␦共⑀F兲. 共123兲
Later Sharma et al. extended the calculation of McClure 6
for graphite by including the effect of trigonal warping
and showed that the low-temperature diamagnetism in-
creases 共Sharma et al., 1974兲. N. Spin-orbit coupling
Safran and DiSalvo 共1979兲, interested in the suscepti-
bility of graphite intercalation compounds, recalculated, Spin-orbit coupling describes a process in which an
in a tight-binding model, the susceptibility perpendicular electron changes simultaneously its spin and angular
to a graphite plane using Fukuyama’s theory 共Fuku- momentum or, in general, moves from one orbital wave
yama, 1971兲, which includes interband transitions. The function to another. The mixing of the spin and the or-
results agree with those by McClure 共1956兲. Later, Saf- bital motion is a relativistic effect, which can be derived
ran computed the susceptibility of a graphene bilayer from Dirac’s model of the electron. The mixing is large
showing that this system is diamagnetic at small values in heavy ions, where the average velocity of the elec-
of the Fermi energy, but there appears a paramagnetic trons is higher. Carbon is a light atom, and the spin orbit
peak when the Fermi energy is of the order of the inter- interaction is expected to be weak.
layer coupling 共Safran, 1984兲. The symmetries of the spin-orbit interaction, however,
The magnetic susceptibility of other carbon-based ma- allow the formation of a gap at the Dirac points in clean
terials, such as carbon nanotubes and C60 molecular sol- graphene. The spin-orbit interaction leads to a spin-
ids, was measured 共Heremans et al., 1994兲 showing a dia- dependent shift of the orbitals, which is of a different
magnetic response at finite magnetic fields different sign for the two sublattices, acting as an effective mass
from that of graphite. Studying the magnetic response of within each Dirac point 共Dresselhaus and Dresselhaus,
nanographite ribbons with both zigzag and armchair 1965; Kane and Mele, 2005; Wang and Chakraborty,
edges was done by Wakabayashi et al. using a numerical 2007a兲. The appearance of this gap leads to a nontrivial
differentiation of the free energy 共Wakabayashi et al., spin Hall conductance, similar to other models that
1999兲. From these two systems, the zigzag edge state is study the parity anomaly in relativistic field theory in 2
of particular interest since the system supports edge + 1 dimensions 共Haldane, 1988兲. When the inversion
states even in the presence of a magnetic field, leading to symmetry of the honeycomb lattice is broken, either be-
very high density of states near the edge of the ribbon. cause the graphene layer is curved or because an exter-
The high-temperature response of these nanoribbons nal electric field is applied 共Rashba interaction兲, addi-
was found to be diamagnetic, whereas the low- tional terms, which modulate the nearest-neighbor
temperature susceptibility is paramagnetic. hopping, are induced 共Ando, 2000兲. The intrinsic and
The Dirac-like nature of the electronic quasiparticles extrinsic spin-orbit interactions can be written as
in graphene led Ghosal et al. 共2007兲 to consider in gen- 共Dresselhaus and Dresselhaus, 1965; Kane and Mele,
eral the problem of the diamagnetism of nodal fermions, 2005兲
冕
and Nakamura to study the orbital magnetism of Dirac
fermions in weak magnetic fields 共Nakamura, 2007兲. Ko- HSO;int ⬅ ⌬so d2r⌿̂†共r兲ŝzˆ zˆ z⌿̂共r兲,
shino and Ando considered the diamagnetism of disor-
dered graphene in the self-consistent Born approxima-
tion, with a disorder potential of the form U共r兲 = 1ui␦共r
− R兲 共Koshino and Ando, 2007兲. At the neutrality point HSO;ext ⬅ R 冕 d2r⌿̂†共r兲共− ŝxˆ y + ŝyˆ xˆ z兲⌿̂共r兲, 共124兲
and zero temperature, the susceptibility of disordered
graphene is given by where ˆ and ˆ are Pauli matrices that describe the sub-
lattice and valley degrees of freedom and ŝ are Pauli
gvgs 2 2 2W matrices acting on actual spin space. ⌬so is the spin-orbit
共0兲 = − e ␥0 , 共121兲
32 ⌫0 coupling and R is the Rashba coupling.
The magnitude of the spin-orbit coupling in graphene
where gs = gv = 2 is the spin and valley degeneracies, W is can be inferred from the known spin-orbit coupling in
a dimensionless parameter for the disorder strength, de- the carbon atom. This coupling allows for transitions be-
fined as W = niu2i / 4␥20, ni is the impurity concentration, tween the pz, px, and py orbitals. An electric field also
and ⌫0 = ⑀c exp关−1 / 共2W兲兴, with ⑀c a parameter defining a induces transitions between the pz and s orbitals. These
cutoff function used in the theory. At finite Fermi energy intra-atomic processes mix the and bands in
冕
al., 2007兲.
v The problem of structural order of a “free-floating”
ES = d2r关s共r兲 − h共r兲兴2 , 共128兲
2 graphene sheet can be fully understood from the exis-
tence of the flexural modes. Consider, for instance, the
where v characterizes the strength of the interaction po- number of flexural modes per unit of area at a certain
tential between substrate and graphene. temperature T,
First, consider the free floating graphene problem
共126兲 that we can rewrite in momentum space as
Nph = 冕 d 2k
共2兲 2 nk =
1
2
冕
0
⬁
dk
e
k
冑/k2
−1
, 共136兲
E0 = 兺 k4h−khk .
2 k
共129兲 where nk is the Bose-Einstein occupation number 共
= 1 / kBT兲. For T ⫽ 0, the above integral is logarithmically
We now canonically quantize the problem by introduc- divergent in the infrared 共k → 0兲 indicating a divergent
ing a momentum operator Pk that has the following number of phonons in the thermodynamic limit. For a
commutator with hk: system with finite size L, the smallest possible wave vec-
tor is of the order of kmin ⬃ 2 / L. Using kmin as a lower
关hk,Pk⬘兴 = i␦k,k⬘ , 共130兲 cutoff in the integral 共136兲, we find
and we write the Hamiltonian as
冉 1
冊 共137兲
再 冎
Nph = 2 ln 2 2 ,
LT 1 − e−LT/L
P−kPk k 4
H=兺 + h−khk , 共131兲 where
2 2
冉冊
k
2 1/4
where is graphene’s 2D mass density. From the LT = 共138兲
Heisenberg equations of motion for the operators, it is
冑k B T
trivial to find that hk oscillates harmonically with a fre- is the thermal wavelength of flexural modes. Note that
quency given by when L Ⰷ LT, the number of flexural phonons in Eq.
冉冊
共137兲 diverges logarithmically with the size of the sys-
1/2
flex共k兲 = k2 , 共132兲 tem,
冉 冊
2 L
which is the long-wavelength dispersion of flexural Nph ⬇ ln , 共139兲
LT2 LT
modes. In the presence of tension, it is easy to see that
the dispersion is modified to indicating that the system cannot be structurally ordered
at any finite temperature. This is nothing but the crum-
共k兲 = k 冑 2 ␥
k + ,
共133兲
pling instability of soft membranes 共Chaikin and Luben-
sky, 1995; Nelson et al., 2004兲. For L Ⰶ LT, one finds that
Nph goes to zero exponentially with the size of the sys-
indicating that the dispersion of flexural modes becomes tem indicating that systems with finite size can be flat at
linear in k, as k → 0, under tension. That is what happens sufficiently low temperatures. Note that for ⬇ 1 eV,
in graphite, where the interaction between layers breaks ⬇ 2200 kg/ m3, t = 3.4 Å 共 ⬇ 7.5⫻ 10−7 kg/ m2兲, and T
the rotational symmetry of the graphene layers. ⬇ 300 K, we find LT ⬇ 1 Å, indicating that free-floating
Equation 共132兲 also allows us to relate the bending graphene should always crumple at room temperature
energy of graphene with the Young modulus Y of graph- due to thermal fluctuations associated with flexural
ite. The fundamental resonance frequency of a macro- phonons. Nevertheless, the previous discussion involves
scopic graphite sample of thickness t is given by 共Bunch only the harmonic 共quadratic part兲 of the problem. Non-
et al., 2007兲 linear effects such as large bending deformations 共Peliti
and Leibler, 1985兲, the coupling between flexural and Hdd = 兺 Vi共a†i ai + b†i bi兲, 共140兲
in-plane modes 关or phonon-phonon interactions 共Le i
Doussal and Radzihovsky, 1992; Bonini et al., 2007兲兴, and
the presence of topological defects 共Nelson and Peliti, where Vi is the strength of the disorder potential on site
1987兲 can lead to strong renormalizations of the bending Ri, which is diagonal in the sublattice indices and hence,
rigidity, driving the system toward a flat phase at low from the point of view of the Dirac Hamiltonian 共18兲,
temperatures 共Chaikin and Lubensky, 1995兲. This situa- can be written as
tion has been confirmed in numerical simulations of free
graphene sheets 共Adebpour et al., 2007; Fasolino et al.,
2007兲.
Hdd = 冕 d 2r 兺
a=1,2
Va共r兲⌿̂†a共r兲⌿̂a共r兲, 共141兲
The situation is rather different if the system is under which acts as a chemical potential shift for the Dirac
tension or in the presence of a substrate or scaffold that fermions, it that is, shifts locally the Dirac point.
can hold the graphene sheet. In fact, static rippling of Because the density of states vanishes in single-layer
graphene flakes suspended on scaffolds has been ob- graphene, and as a consequence the lack of electrostatic
served for single layer as well as bilayers 共Meyer, Geim, screening, charge potentials may be rather important in
Katsnelson, Novoselov, Booth, et al., 2007; Meyer, Geim, determining the spectroscopic and transport properties
Katsnelson, Novoselov, Obergfell, et al., 2007兲. In this 共Ando, 2006b; Adam et al., 2007; Nomura and Mac-
case the dispersion, in accordance with Eq. 共133兲, is at Donald, 2007兲. Of particular importance is the Coulomb
least linear in k, and the integral in Eq. 共136兲 converges impurity problem, where
in the infrared 共k → 0兲, indicating that the number of
flexural phonons is finite and graphene does not e2 1
Va共r兲 = , 共142兲
crumple. We should note that these thermal fluctuations ⑀0 r
are dynamic and hence average to zero over time, there-
with ⑀0 the dielectric constant of the medium. The solu-
fore the graphene sheet is expected to be flat under
tion of the Dirac equation for the Coulomb potential in
these circumstances. Obviously, in the presence of a sub-
2D has been studied analytically 共DiVincenzo and Mele,
strate or scaffold described by Eq. 共128兲, static deforma-
1984; Biswas et al., 2007; Novikov, 2007a; Pereira, Nils-
tions of the graphene sheet are allowed. Also, hydrocar-
son, and Castro Neto, 2007; Shytov et al., 2007兲. Its so-
bon molecules that are often present on top of free
lution has many of the features of the 3D relativistic
hanging graphene membranes could quench flexural
hydrogen atom problem 共Baym, 1969兲. As in the case of
fluctuations, making them static.
the 3D problem, the nature of the eigenfunctions de-
Finally, one should note that in the presence of a me-
pends strongly on graphene’s dimensionless coupling
tallic gate the electron-electron interactions lead to the
constant,
coupling of the phonon modes to the electronic excita-
tions in the gate. This coupling could be partially re- Ze2
sponsible for the damping of the phonon modes due to g= . 共143兲
⑀ 0v F
dissipative effects 共Seoanez et al., 2007兲 as observed in
graphene resonators 共Bunch et al., 2007兲. Note that the coupling constant can be varied by either
changing the charge of the impurity Z or modifying the
dielectric environment and changing ⑀0. For g ⬍ gc = 21 ,
IV. DISORDER IN GRAPHENE
the solutions of this problem are given in terms of Cou-
lomb wave functions with logarithmic phase shifts. The
Graphene is a remarkable material from an electronic local density of states 共LDOS兲 is affected close to the
point of view. Because of the robustness and specificity impurity due the electron-hole asymmetry generated by
of the sigma bonding, it is very hard for alien atoms to the Coulomb potential. The local charge density decays
replace the carbon atoms in the honeycomb lattice. This like 1 / r3 plus fast oscillations of the order of the lattice
is one of the reasons why the electron mean free path in spacing 关in the continuum limit this gives rise to a Dirac
graphene can be so long, reaching up to 1 m in the delta function for the density 共Kolezhuk et al., 2006兲兴. As
existing samples. Nevertheless, graphene is not immune in 3D QED, the 2D problem becomes unstable for g
to disorder and its electronic properties are controlled ⬎ gc = 21 leading to supercritical behavior and the so-
by extrinsic as well as intrinsic effects that are unique to called fall of electron to the center 共Landau and Lifshitz,
this system. Among the intrinsic sources of disorder, 1981兲. In this case, the LDOS is strongly affected by the
highlight are surface ripples and topological defects. Ex- presence of the Coulomb impurity with the appearance
trinsic disorder can come about in many different forms: of bound states outside the band and scattering reso-
adatoms, vacancies, charges on top of graphene or in the nances within the band 共Pereira, Nilsson, and Castro
substrate, and extended defects such as cracks and Neto, 2007兲 and the local electronic density decays
edges. monotonically like 1 / r2 at large distances.
It is easy to see that from the point of view of single Schedin et al. 共2007兲 argued that without a high
electron physics 关that is, terms that can be added to Eq. vacuum environment, these Coulomb effects can be
共5兲兴, there are two main terms to which disorder couples. strongly suppressed by large effective dielectric con-
The first one is a local change in the single site energy, stants due to the presence of a nanometer thin layer of
absorbed water 共Sabio et al., 2007兲. In fact, experiments A共r兲 = Ax共r兲 + iAy共r兲. 共149兲
in ultrahigh vacuum conditions 共Chen, Jang, Fuhrer, et
al., 2008兲 display scattering features in the transport that In terms of the Dirac Hamiltonian 共18兲, we can rewrite
can be associated with charge impurities. Screening ef- Eq. 共146兲 as
fects that affect the strength and range of the Coulomb
interaction are rather nontrivial in graphene 共Fogler,
Novikov, and Shklovskii, 2007; Shklovskii, 2007兲 and,
Hod = 冕 ជ 共r兲⌿̂ 共r兲 + 共r兲⌿̂†共r兲⌿̂ 共r兲兴,
d2r关⌿̂†1共r兲 · A 1 1 1
冉冊
fined. A trajectory around the pentagon after a closed
␥ 1/2
circuit has to change the sublattice index.
ᐉt = ,
v The boundary conditions imposed at the edges of a
disclination are shown in Fig. 26, identifying sites from
ᐉc = 冉冊
v
1/4
. 共153兲
different sublattices. In addition, the wave functions at
the K and K⬘ points are exchanged when moving around
the pentagon.
Equation 共152兲 gives the height configuration in terms of Far away from the defect, a slow rotation of the spino-
the substrate profile, and ᐉt and ᐉc provide the length rial wave function components can be described by a
scales for elastic distortion of graphene on a substrate. gauge field that acts on the valley and sublattice indices
Hence, disorder in the substrate translates into disorder 共González et al., 1992, 1993b兲. This gauge field is techni-
in the graphene sheet 共albeit restricted by elastic con- cally non-Abelian, although a transformation can be de-
straints兲. This picture has been confirmed by STM mea- fined that makes the resulting Dirac equation equivalent
surements on graphene 共Ishigami et al., 2007; Stolyarova to one with an effective Abelian gauge field 共González et
et al., 2007兲 in which strong correlations were found be- al., 1993b兲. The final continuum equation gives a reason-
tween the roughness of the substrate and the graphene able description of the electronic spectrum of fullerenes
1 1 1 1 1 1 1 1 1
1 1 1 1 1 1 1
limit as elas
−1
⯝ ⑀ F.
1 1 1 1 1 1 1
1 1 1 1 1 1 1
1 1 1 1 1 1 1
1
1
1
1
1
1
1
1
1
1
1
1
The Dirac equation allows for localized solutions that
1
1
1
1
1
1
1
1
1
1
1
1
1
1 satisfy many possible boundary conditions. It is known
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1 that small circular defects result in localized and semilo-
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
calized states 共Dong et al., 1998兲, that is, states whose
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1 1 1 1 1 1 1 1 1 1 1
FIG. 26. 共Color online兲 Sketch of the boundary conditions as- model with unitary scatterers such as vacancies 共Pereira
sociated to a disclination 共pentagon兲 in the honeycomb lattice. et al., 2006兲. In the continuum, the Dirac equation 共19兲
for the wave function 共r兲 = „1共r兲 , 2共r兲… can be written,
for E = 0, as
with different sizes 共González et al., 1992, 1993b兲, and
other structures that contain pentagons 共LeClair, 2000; w1共w,w*兲 = 0,
Osipov et al., 2003; Kolesnikov and Osipov, 2004, 2006;
Lammert and Crespi, 2004兲. It is easy to see that a hep-
tagon leads to the opposite effective field. w*2共w,w*兲 = 0, 共157兲
An in-plane dislocation, that is, the inclusion of a
semi-infinite row of sites, can be considered as induced where w = x + iy is a complex number. These equations
by a pentagon and a heptagon together. The non- indicate that at zero energy the components of the wave
Abelian field described above is canceled away from the function can only be either holomorphic or antiholomor-
core. A closed path implies a shift by one 共or more兲 phic with respect to the variable w 关that is, 1共w , w*兲
lattice spacing. The wave functions at the K and K⬘ = 1共w*兲 and 2共w , w*兲 = 2共w兲兴. Since the boundary con-
points acquire phases, e±2i/3, under a translation by one ditions require that the wave function vanishes at infin-
lattice unit. Hence, the description of a dislocation in the ity, the only possible solutions have the form ⌿K共rជ兲
continuum limit requires an 共Abelian兲 vortex of charge ⬀ „1 / 共x + iy兲n , 0… or ⌿K⬘共rជ兲 ⬀ „0 , 1 / 共x − iy兲n…. The wave
±2 / 3 at its core. Dislocations separated over distances functions in the discrete lattice must be real, and at large
of the order of d lead to an effective flux through an distances the actual solution found near a vacancy tends
area of perimeter l of the order of 共Morpurgo and to a superposition of two solutions formed from wave
Guinea, 2006兲 functions from the two valleys with equal weight, in a
way similar to the mixing at armchair edges 共Brey and
d Fertig, 2006b兲.
⌽⬃ , 共156兲
k Fl 2 The construction of the semilocalized state around a
vacancy in the honeycomb lattice can be extended to
where kF is the Fermi vector of the electrons. other discrete models, which leads to the Dirac equation
In general, a local rotation of the honeycomb lattice in the continuum limit. One particular case is the
axes induces changes in the hopping which lead to mix- nearest-neighbor square lattice with half flux per
ing of the K and K⬘ wave functions, leading to a gauge plaquette, or the nearest-neighbor square lattice with
field like the one induced by a pentagon 共González et al., two flavors per site. The latter has been extensively stud-
2001兲. Graphene samples with disclinations and disloca- ied in relation to the effects of impurities on the elec-
tions are feasible in particular substrates 共Coraux et al., tronic structure of d-wave superconductors 共Balatsky et
2008兲, and gauge fields related to the local curvature are al., 2006兲, and numerical results are in agreement with
then expected to play a crucial role in such structures. the existence of this solution. As the state is localized on
The resulting electronic structure can be analyzed using one sublattice only, the solution can be generalized for
the theory of quantum mechanics in curved space 共Bir- the case of two vacancies.
rell and Davies, 1982; Cortijo and Vozmediano, 2007a,
2007b; de Juan et al., 2007兲.
D. Localized states near edges, cracks, and voids
0.06
Electrostatic potential
0.04 0.5
Charge density
0.02 0.5005
0.45
0
0.4
-0.02 0 10 20
-0.04 0.5
0 100 200 300 400 500
Position
0.0005
0.0004
Doping
0.0003
0.0002
0.0001
K K
0
0 200 400 600 800 1000 1200 1400
Width
K’ K’
FIG. 28. 共Color online兲 Displaced electronic charge close to a
graphene zigzag edge. Top: self-consistent analysis of the dis-
placed charge density 共in units of number of electrons per car-
FIG. 29. 共Color online兲 Gauge field induced by a simple elastic
bon兲 shown as a continuous line, and the corresponding elec-
strain. Top: the hopping along the horizontal bonds is assumed
trostatic potential 共in units of t兲 shown as a dashed line, for a
to be changed on the right-hand side of the graphene lattice,
graphene ribbon with periodic boundary conditions along the
defining a straight boundary between the unperturbed and per-
zigzag edge 共with a length of L = 960a兲 and with a circumfer-
turbed regions 共dashed line兲. Bottom: the modified hopping
ence of size W = 80冑3a. Inset: The charge density near the
acts like a constant gauge field, which displaces the Dirac
edge. Due to the presence of the edge, there is a displaced
cones in opposite directions at the K and K⬘ points of the
charge in the bulk 共bottom panel兲 that is shown as a function of
Brillouin zone. The conservation of energy and momentum
width W. Note that the displaced charge vanishes in the bulk
parallel to the boundary leads to a deflection of electrons by
limit 共W → ⬁兲, in agreement with Eq. 共161兲. Adapted from
the boundary.
Peres, Guinea, and Castro Neto, 2006a.
from them. The potential at the edge induced by a con- mix the two inequivalent valleys. As shown earlier, per-
turbations that hybridize the two sublattices lead to
stant doping ␦ per carbon atom is ⬃共␦e2 / a兲W / a 共␦e2 / a is
terms that change the Dirac Hamiltonian from vF · k to
the Coulomb energy per carbon兲, and W the width of the
vF · k + · A. Hence, the vector A can be thought of as
ribbon 共W / a is the number of atoms involved兲. The
if induced by an effective gauge field A. In order to
charge transfer is stopped when the potential shifts the
preserve time-reversal symmetry, this gauge field must
localized states to the Fermi energy, that is, when t⬘
have opposite signs at the two Dirac cones AK = −AK⬘.
⬇ 共e2 / a兲共W / a兲␦. The resulting self-doping is therefore
A simple example is a distortion that changes the hop-
t ⬘a 2 ping between all bonds along a given axis of the lattice.
␦⬃ , 共161兲 We assume that the sites at the ends of those bonds
e 2W
define the unit cell, as shown in Fig. 29. If the distortion
which vanishes when W → ⬁. is constant, its only effect is to displace the Dirac points
We treat the Hamiltonian 共159兲 within the Hartree ap- away from the BZ corners. The two inequivalent points
proximation 共that is, we replace HI by HM.F. = 兺iVini, are displaced in opposite directions. This uniform distor-
where Vi = 兺jUi,j具nj典, and solve the problem self- tion is the equivalent of a constant gauge field, which
consistently for 具ni典兲. Numerical results for graphene rib- does not change the electronic spectrum. The situation
bons of length L = 80冑3a and different widths are shown changes if one considers a boundary that separates two
in Fig. 28 共t⬘ / t = 0.2 and e2 / a = 0.5t兲. The largest width domains where the magnitude of the distortion is differ-
studied is ⬃0.1 m, and the total number of carbon at- ent. The shift of Dirac points leads to a deflection of the
oms in the ribbon is ⬇105. Note that as W increases, the electronic trajectories that cross the boundary, also
self-doping decreases indicating that, for a perfect shown in Fig. 29. The modulation of the gauge field
graphene plane 共W → ⬁兲, the self-doping effect disap- leads to an effective magnetic field, which is of opposite
pears. For realistic parameters, we find that the amount sign for the two valleys.
of self-doping is 10−4 − 10−5 electrons per unit cell for We have shown in Sec. IV.B how topological lattice
sizes 0.1– 1 m. defects, such as disclinations and dislocations, can be de-
scribed by an effective gauge field. Those defects can
only exist in graphene sheets that are intrinsically
F. Vector potential and gauge field disorder curved, and the gauge field only depends on the topol-
ogy of the lattice. Changes in the nearest-neighbor hop-
As discussed in Sec. IV, lattice distortions modify the ping also lead to effective gauge fields. We next consider
Dirac equation that describes the low-energy band struc- two physical processes that induce effective gauge fields:
ture of graphene. We consider here deformations that 共i兲 changes in the hopping induced by hybridization be-
change slowly on the lattice scale, so that they do not tween and bands, which arise in curved sheets, and
TABLE II. Estimates of the effective magnetic length, and potential is generated for nearest-neighbor hopping 共u
effective magnetic fields generated by the deformations. The
= ␦ជ 兲 共Eun-Ah Kim and Castro Neto, 2008兲,
ab
intrinsic curvature entry also refers to the contribution from
topological defects.
3Eaba2 2 2
A共h兲
x =− 关共xh兲 − 共2yh兲2兴,
B 共T兲 8
lB h = 1 nm, l = 10 nm, a = 0.1 nm
冉冊
3Eaba2 2
l A共h兲
y = 共xh + 2yh兲xhyh, 共165兲
Intrinsic curvature l 0.06 4
h
where the coupling constant Eab depends on microscopic
Extrinsic curvature l 冑 t l3
E ah2
0.006 details 共Eun-Ah Kim and Castro Neto, 2008兲. The flux of
effective magnetic field through a ripple of lateral di-
冑
mension l and height h is given by
Elastic strains 1 al 6
l
 h2 Eaba2h2
⌽⬇ , 共166兲
v Fl 3
冉 冊
relative orientation of neighboring orbitals at some po-
1 ui uj
sition ri in the graphene sheet. The value of i depends uij = + 共168兲
on the local curvature of the layer. The relative angle of 2 xj xj
rotation of two pz orbitals at position ri and rj can be
is the strain tensor 共x1 = x and x2 = y兲.
written as cos共i − j兲 = Ni · Nj, where Ni is the unit vector
There are many types of static deformation of the
perpendicular to the surface, defined in Eq. 共125兲. If rj
honeycomb lattice that can affect the propagation of
= ri + uij, we can write Dirac fermions. The simplest one is due to changes in
Ni · Nj ⬇ 1 + Ni · 关共uij · ⵜ兲Ni兴 + 21 Ni · 关共uij · ⵜ兲2Ni兴, the area of the unit cell due to either dilation or contrac-
tion. Changes in the unit-cell area lead to local changes
共162兲 in the density of electrons and, therefore, local changes
where we assume smoothly varying N共r兲. We use Eq. in the chemical potential in the system. In this case, their
共125兲 in terms of the height field h共r兲 关N共r兲 ⬇ z effect is similar to the one found in Eq. 共148兲, and we
− ⵜh共r兲 − 共ⵜh兲2z / 2兴 to rewrite Eq. 共162兲 as have
␦ជ ab
sible instabilities that may occur, can be found in Guinea
␦ui = · 关uA共Ri兲 − uB共Ri + ␦ជ ab兲兴. 共170兲 et al. 共2008兲.
a
The local displacements of the atoms in the unit cell can 3. Random gauge fields
be related to u共r兲 by 共Ando, 2006a兲
The preceding discussion suggests that the effective
共␦ជ ab · ⵜ兲u = −1共uA − uB兲, 共171兲 fields associated with lattice defects can modify signifi-
cantly the electronic properties. This is the case when
where is a dimensionless quantity that depends on mi- the fields do not change appreciably on scales compa-
croscopic details. Changes in the bond length lead to rable to the 共effective兲 magnetic length. The general
changes in the hopping amplitude, problem of random gauge fields for Dirac fermions has
been extensively analyzed before the current interest in
tij
tij ⬇ t0ij + ␦ui , 共172兲 graphene, as the topic is also relevant for the IQHE
a 共Ludwig et al., 1994兲 and d-wave superconductivity
and we can write 共Nersesyan et al., 1994兲. The one-electron nature of this
two-dimensional problem makes it possible, at the Dirac
␦u共r兲 energy, to map it onto models of interacting electrons in
␦t共ab兲共r兲 ⬇  , 共173兲
a one dimension, where many exact results can be ob-
tained 共Castillo et al., 1997兲. The low-energy density of
where
states 共兲 acquires an anomalous exponent 共兲
t共ab兲 ⬀ 兩兩1−⌬, where ⌬ ⬎ 0. The density of states is enhanced
= . 共174兲 near the Dirac energy, reflecting the tendency of disor-
ln共a兲
der to close gaps. For sufficiently large values of the
Substituting Eq. 共170兲 into Eq. 共173兲 and the final result random gauge field, a phase transition is also possible
into Eq. 共147兲, one finds 共Ando, 2006a兲 共Chamon et al., 1996; Horovitz and Doussal, 2002兲.
Perturbation theory shows that random gauge fields
A共s兲
x = 4 共uxx − uyy兲,
3
are a marginal perturbation at the Dirac point, leading
to logarithmic divergences. These divergences tend to
A共s兲
y = 2 uxy .
3
共175兲 have the opposite sign with respect to those induced by
We assume that the strains induced by a ripple of dimen- the Coulomb interaction 共see Sec. V.B兲. As a result, a
sion l and height h scale as uij ⬃ 共h / l兲2. Then, using renormalization-group 共RG兲 analysis of interacting elec-
trons in a random gauge field suggests the possibility of
 / vF ⬇ a−1 ⬃ 1 Å−1, we find that the total flux through a
nontrivial phases 共Stauber et al., 2005; Aleiner and Efe-
ripple is
tov, 2006; Altland, 2006; Dell’Anna, 2006; Foster and
h2 Ludwig, 2006a, 2006b; Nomura et al., 2007; Khvesh-
⌽⬇ . 共176兲 chenko, 2008兲, where interactions and disorder cancel
al
each other.
For ripples such that h ⬃ 1 nm and l ⬃ 20 nm, this esti-
mate gives ⌽ ⬃ 10−1⌽0, in reasonable agreement with the
estimates by Morozov et al. 共2006兲. G. Coupling to magnetic impurities
The strain tensor must satisfy some additional con-
Magnetic impurities in graphene can be introduced
straints, as it is derived from a displacement vector field.
chemically by deposition and intercalation 共Calandra
These constraints are called Saint-Venant compatibility
and Mauri, 2007; Uchoa et al., 2008兲, or self-generated
conditions 共Landau and Lifshitz, 1959兲,
by the introduction of defects 共Kumazaki and
uij ukl uil ujk Hirashima, 2006, 2007兲. The energy dependence of the
Wijkl = + − − = 0. 共177兲 density of states in graphene leads to changes in the
x k x l x i x j x j x k x i x l
formation of a Kondo resonance between a magnetic
An elastic deformation changes the distances in the crys- impurity and the graphene electrons. The vanishing of
tal lattice and can be considered as a change in the met- the density of states at the Dirac energy implies that a
ric, Kondo singlet in the ground state is not formed unless
the exchange coupling exceeds a critical value, of the
gij = ␦ij + uij . 共178兲
order of the electron bandwidth, a problem already
The compatibility equations 共177兲 are equivalent to the studied in connection with magnetic impurities in
condition that the curvature tensor derived from Eq. d-wave superconductors 共Cassanello and Fradkin, 1996,
共178兲 is zero. Hence, a purely elastic deformation cannot 1997; Polkovnikov et al., 2001; Polkovnikov, 2002; Fritz
induce intrinsic curvature in the sheet, which only arises et al., 2006兲. For weak exchange couplings, the magnetic
from topological defects. The effective fields associated impurity remains unscreened. An external gate changes
with elastic strains can be large 共Morozov et al., 2006兲, the chemical potential, allowing for a tuning of the
leading to significant changes in the electronic wave Kondo resonance 共Sengupta and Baskaran, 2008兲. The
functions. An analysis of the resulting state, and the pos- situation changes significantly if the scalar potential in-
duced by the magnetic impurity is taken into account. materials with strong spin-orbit coupling, as the spin di-
This potential that can be comparable to the bandwidth rection changes along the path of the electron 共Berg-
allows the formation of midgap states and changes the man, 1984; Chakravarty and Schmid, 1986兲. Hence, if
phase shift associated with spin scattering 共Hentschel scattering between valleys in graphene can be neglected,
and Guinea, 2007兲. These phase shifts have a weak loga- one expects a positive magnetoresistance, i.e., weak an-
rithmic dependence on the chemical potential, and a tilocalization. In general, intravalley and intervalley
Kondo resonance can exist, even close to the Dirac en- elastic scattering can be described in terms of two differ-
ergy. ent scattering times intra and inter, so that if intra
The RKKY interaction between magnetic impurities Ⰶ inter, one expects weak antilocalization processes,
is also modified in graphene. At finite fillings, the ab- while if inter Ⰶ intra, ordinary weak localization will take
sence of intravalley backscattering leads to a reduction place. Experimentally, localization effects are always
of the Friedel oscillations, which decay as sin共2kFr兲 / 兩r兩3 strongly suppressed close to the Dirac point but can be
共Ando, 2006b; Cheianov and Fal’ko, 2006; Wunsch et al., partially or, in rare cases, completely recovered at high
2006兲. This effect leads to an RKKY interaction at finite carrier concentrations, depending on a particular single-
fillings, which oscillate and decay as 兩r兩−3. When interval- layer sample 共Morozov et al., 2006; Tikhonenko et al.,
ley scattering is included, the interaction reverts to the 2008兲. Multilayer samples exhibit an additional positive
usual dependence on distance in two dimensions 兩r兩−2 magnetoresistance in higher magnetic fields, which can
共Cheianov and Fal’ko, 2006兲. At half filling extended de- be attribued to classical changes in the current distribu-
fects lead to an RKKY interaction with an 兩r兩−3 depen- tion due to a vertical gradient of concentration 共Moro-
dence 共Vozmediano et al., 2005; Dugaev et al., 2006兲. zov et al., 2006兲 and antilocalization effects 共Wu et al.,
This behavior is changed when the impurity potential is 2007兲.
localized on atomic scales 共Brey et al., 2007; Saremi, The propagation of an electron in the absence of in-
2007兲, or for highly symmetrical couplings 共Saremi, tervalley scattering can be affected by the effective
2007兲. gauge fields induced by lattice defects and curvature.
These fields can suppress the interference corrections to
H. Weak and strong localization the conductivity 共Morozov et al., 2006; Morpurgo and
Guinea, 2006兲. In addition, the description in terms of
In sufficiently clean systems, where the Fermi wave- free Dirac electrons is only valid near the neutrality
length is much shorter than the mean free path kFl Ⰷ 1, point. The Fermi energy acquires a trigonal distortion
electronic transport can be described in classical terms, away from the Dirac point, and backward scattering
assuming that electrons follow well-defined trajectories. within each valley is no longer completely suppressed
At low temperatures, when electrons remain coherent 共McCann et al., 2006兲, leading to further suppression of
over long distances, quantum effects lead to interference antilocalization effects at high dopings. Finally, the gra-
corrections to the classical expressions for the conduc- dient of external potentials induces a small asymmetry
tivity, the weak-localization correction 共Bergman, 1984; between the two sublattices 共Morpurgo and Guinea,
Chakravarty and Schmid, 1986兲. These corrections are 2006. This effect will also contribute to reduce antilocal-
usually due to the positive interference between two ization, without giving rise to localization effects.
paths along closed loops, traversed in opposite direc- The above analysis has to be modified for a graphene
tions. As a result, the probability that the electron goes bilayer. Although the description of the electronic states
back to the origin is enhanced, so that quantum correc- requires a two-component spinor, the total phase around
tions decrease the conductivity. These interferences are a closed loop is 2, and backscattering is not suppressed
suppressed for paths longer than the dephasing length l 共Kechedzhi et al., 2007兲. This result is consistent with
determined by interactions between the electron and en- experimental observations, which show the existence of
vironment. Interference effects can also be suppressed weak localization effects in a bilayer 共Gorbachev et al.,
by magnetic fields that break down time-reversal sym- 2007兲.
metry and add a random relative phase to the process When the Fermi energy is at the Dirac point, a replica
discussed above. Hence, in most metals, the conductivity analysis shows that the conductivity approaches a uni-
increases when a small magnetic field is applied 共nega- versal value of the order of e2 / h 共Fradkin, 1986a, 1986b兲.
tive magnetoresistance兲. This result is valid when intervalley scattering is ne-
Graphene is special in this respect, due to the chirality glected 共Ostrovsky et al., 2006, 2007; Ryu et al., 2007兲.
of its electrons. The motion along a closed path induces Localization is induced when these terms are included
a change in the relative weight of the two components of 共Aleiner and Efetov, 2006; Altland, 2006兲, as also con-
the wave function, leading to a new phase, which con- firmed by numerical calculations 共Louis et al., 2007兲. In-
tributes to the interference processes. If the electron teraction effects tend to suppress the effects of disorder.
traverses a path without being scattered from one valley The same result, namely, a conductance of the order of
to the other, this 共Berry兲 phase changes the sign of the e2 / h, is obtained for disordered graphene bilayers where
amplitude of one path with respect to the time-reversed a self-consistent calculation leads to universal conductiv-
path. As a consequence, the two paths interfere destruc- ity at the neutrality point 共Nilsson, Castro Neto, Guinea,
tively, leading to a suppression of backscattering 共Suz- et al., 2006; Katsnelson, 2007c; Nilsson et al., 2008兲. In a
uura and Ando, 2002a兲. Similar processes take place in biased graphene bilayer, the presence of impurities leads
to the appearance of impurity tails in the density of nel at the Dirac energy. The other two-thirds are semi-
states due to the creation of midgap states, which are conducting, with a gap of the order of vF / W, where W is
sensitive to the applied electric field that opens the gap the width. This result is a consequence of the additional
between the conduction and valence bands 共Nilsson and periodicity introduced by the wave functions at the K
Castro Neto, 2007兲. and K⬘ points of the Brillouin zone, irrespective of the
We point out that most calculations of transport prop- boundary conditions.
erties assume self-averaging, that is, one can exchange a A wide graphene ribbon allows for many channels,
problem with a lack of translational invariance by an which can be approximately classified by the momentum
effective medium system with damping. This procedure perpendicular to the axis of the ribbon, ky. At the Dirac
only works when the disorder is weak and the system is energy, transport through these channels is inhibited by
in the metallic phase. Close to the localized phase this the existence of a gap ⌬ky = vFky. Transport through
procedure breaks down, the system divides itself into these channels is suppressed by a factor of the order of
regions of different chemical potential and one has to e−kyL, where L is the length of the ribbon. The number
think about transport in real space, usually described in of transverse channels increases as W / a, where W is the
terms of percolation 共Cheianov, Fal’ko, Altshuler, et al., width of the ribbon and a is a length of the order of the
2007; Shklovskii, 2007兲. Single electron transistor 共SET兲 lattice spacing. The allowed values of ky are ⬀ny / W,
measurements of graphene show that this seems to be where ny is an integer. Hence, for a ribbon such that
the situation in graphene at half filling 共Martin et al.,
W Ⰷ L, there are many channels that satisfy kyL Ⰶ 1.
2008兲.
Transport through these channels is not strongly inhib-
Finally, we point out that graphene stacks suffer from
ited, and their contribution dominates when the Fermi
another source of disorder, namely, c axis disorder, energy lies near the Dirac point. The conductance aris-
which is due to either impurities between layers or rota- ing from these channels is given by 共Katsnelson, 2006b;
tion of graphene planes relative to each other. In either Tworzydlo et al., 2006兲
case, the in-plane and out-of-plane transport is directly
affected. This kind of disorder has been observed ex-
perimentally by different techniques 共Bar et al., 2007;
Hass, Varchon, Millán-Otoya, et al., 2008兲. In the case of
G⬃
e2 W
h 2
冕 dkye−kyL ⬃
e2 W
h L
. 共179兲
the bilayer, the rotation of planes changes substantially The transmission at normal incidence ky = 0 is 1, in
the spectrum restoring the Dirac fermion description agreement with the absence of backscattering in
共Lopes dos Santos et al., 2007兲. The transport properties graphene, for any barrier that does not induce interval-
in the out-of-plane direction are determined by the in- ley scattering 共Katsnelson et al., 2006兲. The transmission
terlayer current operator ĵn,n+1 = it 兺 共cA,n,s
†
cA,n+1,s of a given channel scales as T共ky兲 = 1 / cosh2共kyL / 2兲.
− cA,n+1,scA,n,s兲, where n is a layer index and A is a ge-
†
Equation 共179兲 shows that the contribution from all
neric index that defines the sites coupled by the inter- transverse channels leads to a conductance that scales,
layer hopping t. If we only consider hopping between similar to a function of the length and width of the sys-
nearest-neighbor sites in consecutive layers, these sites tem, as the conductivity of a diffusive metal. Moreover,
belong to one of the two sublattices in each layer. the value of the effective conductivity is of the order of
In a multilayer with Bernal stacking, these connected e2 / h. It can also be shown that the shot noise depends on
sites are the ones where the density of states vanishes at current in the same way as in a diffusive metal. A de-
zero energy, as discussed above. Hence, even in a clean tailed analysis of possible boundary conditions at the
system, the number of conducting channels in the direc- contacts and their influence on evanescent waves can be
tion perpendicular to the layers vanishes at zero energy found in Robinson and Schomerus 共2007兲 and Schom-
共Nilsson, Castro Neto, Guinea, and Peres, 2006; Nilsson erus 共2007兲. The calculations leading to Eq. 共179兲 can be
et al., 2008兲. This situation is reminiscent of the in-plane extended to a graphene bilayer. The conductance is,
transport properties of a single-layer graphene. Similar again, a summation of terms arising from evanescent
to the latter case, a self-consistent Born approximation waves between the two contacts, and it has the depen-
for a small concentration of impurities leads to a finite dence on sample dimensions of a 2D conductivity of the
conductivity, which becomes independent of the number order of e2 / h 共Snyman and Beenakker, 2007兲, although
of impurities. there is a prefactor twice as big as the one in single-layer
graphene.
The calculation of the conductance of clean graphene
I. Transport near the Dirac point in terms of transmission coefficients, using the Landauer
method, leads to an effective conductivity that is equal
In clean graphene, the number of channels available to the value obtained for bulk graphene using diagram-
for electron transport decreases as the chemical poten- matic methods, the Kubo formula 共Peres, Guinea, and
tial approaches the Dirac energy. As a result, the con- Castro Neto, 2006b兲, in the limit of zero impurity con-
ductance through a clean graphene ribbon is at most centration and zero doping. Moreover, this correspon-
4e2 / h, where the factor of 4 stands for the spin and val- dence remains valid for the case of a bilayer without and
ley degeneracy. In addition, only one out of every three with trigonal warping effects 共Koshino and Ando, 2006;
possible clean graphene ribbons has a conduction chan- Cserti, Csordés, and Dévid, 2007兲.
冋冉 冊册
voselov et al., 2004; Novoselov, Geim, Morozov, et al.,
2005; Novoselov, Jiang, Schedin, et al., 2005兲, except very
close to the neutrality point 共see Fig. 30兲. Since the gate −
f 0共 ⑀ k兲
⑀k
vk · −
⑀k −
T
冊 冉 1
rT + e E − r
e
冏 冏
potential depends linearly on the electronic density n,
one has a conductivity ⬀ n. As shown by Shon and fk
=− + vk · rgk + e共vk ⫻ H兲 · kgk . 共182兲
Ando 共1998兲, if the scatterers are short ranged, the dc t scatt
conductivity should be independent of the electronic
density, at odds with the experimental result. It has been The second approximation has to do with the form of
shown 共Ando, 2006b; Nomura and MacDonald, 2006, the scattering term. The simplest approach is to intro-
2007兲 that, by considering a scattering mechanism based duce a relaxation-time approximation,
on screened charged impurities, it is possible to obtain
from a Boltzmann equation approach a conductivity
varying linearly with the density, in agreement with the
− 冏 冏
fk
t scatt
→
gk
k
, 共183兲
冏 冏
dependence of the conductivity upon the electronic den-
fk sity agrees with experimental data. The Boltzmann
− vk · rf共⑀k兲 − e共E + vk ⫻ H兲 · ⵜkf共⑀k兲 = − . equation is certainly not valid at the Dirac point, but
t scatt
since many experiments are performed at finite carrier
共181兲
density, controlled by an external gate voltage, we ex-
The solution of the Boltzmann equation in its general pect the Boltzmann equation to give reliable results if an
form is difficult and one needs, therefore, to rely upon appropriate form for k is used 共Adam et al., 2007兲.
We compute the Boltzmann relaxation time k for two tential is one possible mechanism of producing a scatter-
different scattering potentials: 共i兲 a Dirac delta function ing rate of the form 共188兲, but we do not exclude that
potential and 共ii兲 an unscreened Coulomb potential. The other mechanisms may exist 关see, for instance, Katsnel-
relaxation time k is defined as son and Geim 共2008兲兴.
1
k
= ni 冕 冕 d
k⬘dk⬘
共2兲2
S共k,k⬘兲共1 − cos 兲, 共184兲
K. Magnetotransport and universal conductivity
where ni is impurity concentration per unit of area, and
The description of the magnetotransport properties of
the transition rate S共k , k⬘兲 is given, in the Born approxi-
electrons in a disordered honeycomb lattice is complex
mation, by
because of the interference effects associated with the
1 Hofstadter problem 共Gumbs and Fekete, 1997兲. We sim-
S共k,k⬘兲 = 2兩Hk⬘,k兩2 ␦共k⬘ − k兲, 共185兲 plify our problem by describing electrons in the honey-
vF
comb lattice as Dirac fermions in the continuum ap-
where vFk is the dispersion of Dirac fermions in proximation, introduced in Sec. II.B. Furthermore, we
graphene and Hk⬘,k is defined as focus only on the problem of short-range scattering in
冕
the unitary limit since in this regime many analytical
Hk⬘,k = drk* 共r兲US共r兲k共r兲, 共186兲 results are obtained 共Kumazaki and Hirashima, 2006;
⬘
Pereira et al., 2006; Peres, Guinea, and Castro Neto,
with US共r兲 the scattering potential and k共r兲 is the elec- 2006a; Skrypnyk and Loktev, 2006, 2007; Mariani et al.,
tronic spinor wave function of a clean graphene sheet. If 2007; Pereira, Lopes dos Santos, and Castro Neto, 2008兲.
the potential is short ranged 共Shon and Ando, 1998兲 of The problem of magnetotransport in the presence of
the form US = v0␦共r兲, the Boltzmann relaxation time is Coulomb impurities, as discussed, is still an open re-
given by search problem. A similar approach was considered by
Abrikosov in the quantum magnetoresistance study of
4vF 1 nonstoichiometric chalcogenides 共Abrikosov, 1998兲. In
k = . 共187兲
niv20 k the case of graphene, the effective Hamiltonian describ-
ing Dirac fermions in a magnetic field 共including disor-
On the other hand, if the potential is the Coulomb po-
der兲 can be written as H = H0 + Hi, where H0 is given by
tential, given by US共r兲 = eQ / 4⑀0⑀r for charged impuri-
Eq. 共5兲 and Hi is the impurity potential given by 共Peres,
ties of charge Q, the relaxation time is given by Guinea, and Castro Neto, 2006a兲
vF
k = k, 共188兲 Ni
u20 Hi = V 兺 ␦共r − rj兲I. 共192兲
where u20 = niQ2e2 / 16⑀20⑀2. As argued below, the phenom- j=1
gk = −
f 0共 ⑀ k兲
⑀k
ekvk · E, 共189兲 ⌿共r兲 = 兺
k
冉 冊
eikx
冑L
0
0共y兲
ck,−1
兺冑 冉 冊
and the electric current reads 共spin and valley indexes eikx n共y − klB2 兲
included兲 + ck,n,␣ , 共193兲
2L n+1共y − klB兲
2
n,k,␣
4
J= 兺 e v kg k .
A k
共190兲
where ck,n,␣ destroys an electron in band ␣ = ± 1, with
2
energy level n and guiding center klB ; ck,−1 destroys an
Since at low temperatures the following relation electron in the zero Landau level; the cyclotron fre-
−f0共⑀k兲 / ⑀k → ␦共 − vFk兲 holds, one can see that assum- quency is given by Eq. 共96兲. The sum over n = 0 , 1 , 2 , . . . is
ing Eq. 共188兲 where k is measured relatively to the Dirac cut off at n0 given by E共1 , n0兲 = W, where W is of the
point, the electronic conductivity turns out to be order of the electronic bandwidth. In this representa-
e2 2 e2 vF2 tion, H0 becomes diagonal, leading to Green’s functions
xx = 2 = 2 n, 共191兲 of the form 共in the Matsubara representation兲
h u20 h u20
where u0 is the strength of the scattering potential 共with 1
G0共k,n, ␣ ;i兲 = , 共194兲
dimensions of energy兲. The electronic conductivity de- i − E共␣,n兲
pends linearly on the electron density, in agreement with
the experimental data. We stress that the Coulomb po- where
E共␣,n兲 = ␣c冑n
ωc = 0.14 eV, B = 12 T
共195兲 0.008
ωc = 0.1 eV, B = 6 T
0.008
1. The full self-consistent Born approximation (FSBA) ni = 0.001
冋兿 冕 册
Ni in the top panel show the position of the renormalized Landau
levels 共see Fig. 32兲 given by the solution of Eq. 共202兲. Adapted
= L−2Ni drj
j=1
from Peres, Guinea, and Castro Neto, 2006a.
G共p,− 1; + 0+兲 = 关 − ⌺2共兲兴−1 , 共198兲 Due to the importance of scattering at low energies, the
where solution to Eq. 共202兲 does not represent exact eigen-
states of the system since the imaginary part of the self-
⌺1共兲 = − ni关Z共兲兴−1 , 共199兲 energy is nonvanishing. However, these energies do de-
termine the form of the density of states, as discussed
⌺2共兲 = − ni关gcG共p,− 1; + 0+兲/2 + Z共兲兴−1 , 共200兲 below.
In Fig. 32, the graphical solution to Eq. 共202兲 is given
Z共兲 = gcG共p,− 1; + 0+兲/2 for two different energies 关E共−1 , n兲, with n = 1 , 2兴. It is
clear that the renormalization is important for the first
+ gc 兺 G共p,n, ␣ ; + 0+兲/2, 共201兲 Landau level. This result is due to the increase in scat-
n,␣
tering at low energies, which is already present in the
and gc = Ac / 2lB
2
is the degeneracy of a Landau level per case of zero magnetic field. The values of satisfying
unit cell. One should note that the Green’s functions do Eq. 共202兲 show up in the density of states as the energy
not depend upon p explicitly. The self-consistent solu- values where the oscillations due to the Landau level
tion of Eqs. 共197兲–共201兲 gives the density of states, the quantization have a maximum. In Fig. 31, the position of
electron self-energy, and the change of Landau level en- the renormalized Landau levels is shown in the top
ergy position due to disorder. panel 共marked by two arrows兲, corresponding to the
The effect of disorder on the density of states of Dirac bare energies E共−1 , n兲, with n = 1 , 2. The importance of
fermions in a magnetic field is shown in Fig. 31. For this renormalization decreases with the decrease in the
reference, we note that E共1 , 1兲 = 0.14 eV for B = 14 T, number of impurities. This is clear in Fig. 31, where a
ni=0.001 ni = 0.001
20 20
B = 12 T
0.8
B=6T 0.4
15 B = 12 T 15 B = 10 T
-Im Σ1(ω) / ωc
Re Σ1(ω) / ωc
2
0.6 0.2
π KB(ω) h / e
0 10 10
0.4
-0.2
0.2 ω−E(-1,1) -0.4 5 5
ω−E(-1,2)
0
-6 -4 -2 0 2 4 6 -6 -4 -2 0 2 4 6 0 0
-0.4 -0.2 0 0.2 0.4 -0.4 -0.2 0 0.2 0.4
0.8
20 20
0.4
0.6 ω
Re Σ2(ω) / ωc
-Im Σ2(ω) / ωc
2
π KB(ω) h / e
0.4 0
10 10
-0.2
0.2
-0.4 5 5
0
-6 -4 -2 0 2 4 6 -6 -4 -2 0 2 4 6
ω / ωc ω / ωc 0 0
-0.4 -0.2 0 0.2 0.4 -0.4 -0.2 0 0.2 0.4
ω (eV) ω (eV)
FIG. 32. 共Color online兲 Imaginary 共right兲 and real 共left兲 parts
of ⌺1共兲 共top兲 and ⌺2共兲 共bottom兲, in units of c, as a function FIG. 33. 共Color online兲 Conductivity kernel K共兲 共in units of
of / c. The right panels also show the intercept of e2 / h兲 as a function of energy for different magnetic fields
− E共␣ , n兲 with Re⌺共兲 as required by Eq. 共202兲. Adapted from and ni = 10−3. The horizontal lines mark the universal limit of
Peres, Guinea, and Castro Neto, 2006a. the conductivity per cone 0 = 2e2 / h. The vertical lines show
the position of the Landau levels in the absence of disorder.
Adapted from Peres, Guinea, and Castro Neto, 2006a.
visible shift toward low energies is evident when ni has a
small 10% change, from ni = 10−3 to ni = 9 ⫻ 10−4.
Neto, 2006a; Tworzydlo et al., 2006兲. This result was ob-
Studying of the magnetoresistance properties of the
tained previously by Ando and collaborators using the
system requires calculation of the conductivity tensor.
second-order self-consistent Born approximation 共Shon
We compute the current-current correlation function,
and Ando, 1998; Ando et al., 2002兲.
and from it the conductivity tensor is derived. The de-
Because the dc magnetotransport properties of
tails of the calculations are presented in Peres, Guinea,
graphene are normally measured with the possibility of
and Castro Neto 共2006a兲. If, however, we neglect the real
tuning its electronic density by a gate potential 共No-
part of the self-energy, assume for Im ⌺i共兲 = ⌫ 共i = 1 , 2兲 a voselov et al., 2004兲, it is important to compute the con-
constant value, and consider that E共1 , 1兲 Ⰷ ⌫, these re- ductivity kernel, since this has direct experimental rel-
sults reduce to those of Gorbar et al. 共2002兲. evance. In the case → 0, we write the conductivity
It is instructive to consider first the case , T → 0, xx共0 , T兲 as
which leads to 关xx共0 , 0兲 = 0兴
冋 冕 ⬁
e2 4 Im ⌺1共0兲/Im ⌺2共0兲 − 1 e2 f共⑀兲
0 = xx共0,T兲 = d⑀ KB共⑀兲, 共206兲
h 1 + 关Im ⌺1共0兲/c兴2 h −⬁ ⑀
+
n0 + 1
n0 + 1 + 关Im ⌺1共0兲/c兴2
, 册 共203兲 where the conductivity kernel KB共⑀兲 is given in the Ap-
pendix of Peres, Guinea, and Castro Neto 共2006a兲. The
where we include a factor of 2 due to the valley degen- magnetic field dependence of kernel KB共⑀兲 is shown in
eracy. In the absence of a magnetic field 共c → 0兲, the Fig. 33. One can observe that the effect of disorder is the
above expression reduces to creation of a region where KB共⑀兲 remains constant be-
冋 册
fore it starts to increase in energy with superimposed
e2 4 关Im ⌺1共0兲兴2 oscillations coming from the Landau levels. The same
0 = 1− , 共204兲
h 共vF⌳兲2 + 关Im ⌺1共0兲兴2 effect, but with the absence of the oscillations, was iden-
tified at the level of the self-consistent density of states
where we have introduced the energy cutoff vF⌳. Either plotted in Fig. 31. Together with xx共0 , T兲, the Hall con-
when Im ⌺1共0兲 ⯝ Im ⌺2共0兲 and c Ⰷ Im ⌺1共0兲 关or n0 ductivity xy共0 , T兲 allows the calculation of the resistivity
Ⰷ Im ⌺1共0兲 / c, c = E共0 , 1兲 = 冑2vF / lB
2
兴 or when ⌳vF tensor 共109兲.
Ⰷ Im ⌺1共0兲, in the absence of an applied field, Eqs. 共203兲 We now focus on the optical conductivity xx共兲
and 共204兲 reduce to 共Peres, Guinea, and Castro Neto, 2006a; Gusynin et al.,
4 e2 2007兲. This quantity can be probed by reflectivity experi-
0 = , 共205兲 ments in the subterahertz to midinfrared frequency
h range 共Bliokh, 2005兲. This quantity is shown in Fig. 34
which is the so-called universal conductivity of graphene for different magnetic fields. It is clear that the first peak
共Fradkin, 1986a, 1986b; Lee, 1993; Ludwig et al., 1994; is controlled by E共1 , 1兲 − E共1 , −1兲, and we have checked
Nersesyan et al., 1994; Ziegler, 1998; Yang and Nayak, that it does not obey any particular scaling form as a
2002; Katsnelson, 2006b; Peres, Guinea, and Castro function of / B. On the other hand, as the effect of
ni = 0.001
1
冑2 共uA − uB兲, 共207兲
3
B = 12 T B = 10 T uop =
3
2
π σ(ω) h / e
c
2.5
2.5 b
a that is, the bond length deformation vector. To calculate
the coupling to electrons, we can proceed as previously
2 2 and compute the change in the nearest-neighbor hop-
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7 ping energy due to the lattice distortion through Eqs.
ω / ωc ω / ωc
共172兲, 共173兲, 共170兲, and 共207兲. Once again the electron-
2.7 phonon interaction becomes a problem of coupling elec-
2.6 trons with a vector potential as in Eq. 共150兲, where the
2
2.5
π σ(ω) h / e
2.5
2.4 components of the vector potential are
B=6T
2.3
冑
2.2 B = 12 T
2 2.1 B = 10 T
3  op
A共op兲
B=6T
2 x =− u ,
0 1 2 3 4
ω / ωc
5 6 7 0.22 0.24
1/2
0.26
1/2
0.28
2 a2 y
ω / B (eV/ T )
冑
FIG. 34. 共Color online兲 Frequency-dependent conductivity per
cone 共兲 共in units of e2 / h兲 at T = 10 K and ni = 10−3, as a 3  op
A共op兲 =− u , 共208兲
function of the energy 共in units of c兲 for different values of y
2 a2 x
the magnetic field B. The vertical arrows in the upper left
panel, labeled a, b, and c, show the positions of the transitions
between different Landau levels: E共1 , 1兲 − E共−1 , 0兲, E共2 , 1兲 where  = t / ln共a兲 was defined in Eq. 共174兲. Note that
− E共−1 , 0兲, and E共1 , 1兲 − E共1 , −1兲, respectively. The horizontal we can write A ជ op = −冑3 / 2共 / a2兲ជ ⫻ u . A similar expres-
op
continuous lines show the value of the universal conductivity. ជ replaced by −A
sion is valid close to the K’ point with A ជ.
The lower right panel shows the conductivity for different val-
ues of magnetic field as a function of / 冑B. Adapted from Optical phonons are important in graphene research
Peres, Guinea, and Castro Neto, 2006a. because of Raman spectroscopy. The latter has played
an important role in the study of carbon nanotubes
共Saito et al., 1998兲 because of the 1D character of these
scattering becomes less important, high-energy conduc- systems, namely, the presence of van Hove singularities
tivity oscillations start obeying the scaling / 冑B, as in the 1D spectrum leads to colossal enhancements of
shown in the lower right panel of Fig. 34. the Raman signal that can be easily detected, even for a
single isolated carbon nanotube. In graphene, the situa-
tion is different since its 2D character leads to a much
smoother density of states 共except for the van Hove sin-
V. MANY-BODY EFFECTS
gularity at high energies of the order of the hopping
energy t ⬇ 2.8 eV兲. Nevertheless, graphene is an open
A. Electron-phonon interactions surface and hence is readily accessible by Raman spec-
troscopy. In fact, it has played an important role because
In Secs. IV.F.1 and IV.F.2, we discussed how static de- it allows the identification of the number of planes 共Fer-
formations of the graphene sheet due to bending and rari et al., 2006; Gupta et al., 2006; Graf et al., 2007;
strain couple to the Dirac fermions via vector potentials. Malard et al., 2007; Pisana et al., 2007; Yan et al., 2007兲
and the study of the optical phonon modes in graphene,
Just as bending has to do with the flexural modes of the
particularly the ones in the center of the BZ with mo-
graphene sheet 共as discussed in Sec. III兲, strain fields are
mentum q ⬇ 0. Similar studies have been performed in
related to optical and acoustic modes 共Wirtz and Rubio,
graphite ribbons 共Cancado et al., 2004兲.
2004兲. Given the local displacements of the atoms in
We consider the effect of Dirac fermions on the opti-
each sublattice uA and uB, the electron-phonon coupling cal modes. If one treats the vector potential, electron-
has essentially the form discussed previously for static phonon coupling, Eqs. 共150兲 and 共208兲 up to second-
fields. order perturbation theory, its main effect is the
Coupling to acoustic modes is the most straightfor- polarization of the electron system by creating electron-
ward one, since it already appears in the elastic theory. If hole pairs. In the QED language, the creation of
uac is the acoustic phonon displacement, then the rela- electron-hole pairs is called pair 共electron-antielectron兲
tion between this displacement and the atom displace- production 共Castro Neto, 2007兲. Pair production is
ment is given by Eq. 共171兲, and its coupling to electrons equivalent to a renormalization of the phonon propaga-
is given by the vector potential 共175兲 in the Dirac equa- tor by a self-energy that is proportional to the polariza-
tion 共150兲. tion function of the Dirac fermions.
For optical modes, the situation is slightly different The renormalized phonon frequency is given by
since the optical mode displacement is 共Ando, 2006a, 共Ando, 2006a, 2007b; Lazzeri and Mauri, 2006; Castro
2007b兲 Neto and Guinea, 2007; Saha et al., 2007兲
22
⍀0共q兲 ⬇ 0 − 共q, 0兲, 共209兲
a 2 0 0.5
∆Ω0 ΛΩ0
electron-phonon polarization function is given by -0.5
共q, 兲 = 兺
s,s⬘=±1
冕 2
dk f关Es共k + q兲兴 − f关Es⬘共k兲兴
共2兲 0 − Es共k + q兲 + Es⬘共k兲 + i
2 , -1
-1.5
共210兲
0 0.5 1 1.5 2
(a) ΜΩ0
where Es共q兲 is the Dirac fermion dispersion 共s = + 1 for
the upper band and s = −1 for the lower band兲, and f关E兴
is the Fermi-Dirac distribution function. For Raman
spectroscopy, the response of interest is at q = 0, where
only the interband processes such that ss⬘ = −1 共that is,
processes between the lower and upper cones兲 contrib-
ute. The electron-phonon polarization function can be
calculated using the linearized Dirac fermion dispersion
共7兲 and the low-energy density of states 共15兲,
共0, 0兲 =
6冑3
vF2
冕 vF⌳
0
dEE共f关− E兴 − f关E兴兲
冉 冊
(b)
1 1
⫻ − , 共211兲
0 + 2E + i − 2E + i FIG. 35. Kohn anomaly in graphene. Top: the continuous line
is the relative phonon frequency shift as a function of / 0,
where we have introduced the cutoff momentum ⌳ and the dashed line is the damping of the phonon due to
共⬇1 / a兲 so that the integral converges in the ultraviolet. electron-hole pair creation. Bottom: 共a兲 electron-hole process
At zero temperature T = 0 we have f关E兴 = 共 − E兲 and that leads to phonon softening 共0 ⬎ 2兲, and 共b兲 electron-hole
we assume electron doping ⬎ 0, so that f关−E兴 = 1 共for process that leads to phonon hardening 共0 ⬍ 2兲.
the case of hole doping, ⬍ 0, obtained by electron-hole
symmetry兲. The integration in Eq. 共211兲 gives
冋
change in behavior depending on whether is larger or
6冑3 smaller than 0 / 2. For ⬍ 0 / 2, there is a decrease in
共0, 0兲 = v F⌳ −
vF2 the phonon frequency implying that the lattice is soften-
+
0
4
冉冏
ln
0/2 +
0/2 −
冏
+ i共0/2 − 兲 冊册 ,
ing, while for ⬎ 0 / 2, the lattice hardens. The interpre-
tation for this effect is also given in Fig. 35. On the one
hand, if the frequency of the phonon is larger than twice
共212兲 the chemical potential, real electron-hole pairs are pro-
where the cutoff-dependent term is a contribution com- duced, leading to stronger screening of the electron-ion
ing from the occupied states in the lower band and interaction, and hence to a softer phonon mode. At the
hence is independent of the chemical potential value. same time, the phonons become damped and decay. On
This contribution can be fully incorporated into the bare the other hand, if the frequency of the phonon is smaller
value of 0 in Eq. 共209兲. Hence the relative shift in the than twice the chemical potential, the production of
phonon frequency can be written as electron-hole pairs is halted by the Pauli principle and
␦0
0
⬇−
4
−
0
冉
+ ln
0/2 +
0/2 −
冏 冏
+ i共0/2 − 兲 , 冊 only virtual excitations can be generated, leading to po-
larization and lattice hardening. In this case, there is no
damping and the phonon is long lived. This result has
共213兲 been observed experimentally by Raman spectroscopy
where 共Pisana et al., 2007; Yan et al., 2007兲. Electron-phonon
coupling has also been investigated theoretically for a
36冑3 2 finite magnetic field 共Ando, 2007a; Goerbig et al., 2007兲.
= 共214兲
8Ma20 In this case, resonant coupling occurs due to the large
is the dimensionless electron-phonon coupling. Note degeneracy of the Landau levels, and different Raman
that Eq. 共213兲 has a real and an imaginary part. The real transitions are expected as compared with the zero-field
part represents the actual shift in frequency, while the case. The coupling of electrons to flexural modes on a
imaginary part gives the damping of the phonon mode free-standing graphene sheet was discussed by Mariani
due to pair production 共see Fig. 35兲. There is a clear and von Oppen 共2008兲.
B. Electron-electron interactions
冕
leads to a logarithmic renormalization of the Fermi velocity.
H ⬅ − ivF d2r⌿̂†共r兲 · ⵜ⌿̂共r兲
+
e2
冕 d rd r⬘
2 2 1
ˆ 共r兲ˆ 共r⬘兲, 共218兲
⌺HF共k兲 =
␣
4
k ln 冉冊
⌳
k
, 共220兲
2⑀0 兩r − r⬘兩
where ⌳ is a momentum cutoff which sets the range of
validity of the Dirac equation. This result remains true
where
even to higher order in perturbation theory 共Mish-
chenko, 2007兲 and is also obtained in large N expansions
ˆ 共r兲 = ⌿̂†共r兲⌿̂共r兲 共219兲 共Rosenstein et al., 1989, 1991; Son, 2007兲 共where N is the
number of flavors of Dirac fermions兲, with the only
is the electronic density. One can observe that the Cou- modification the prefactor in Eq. 共220兲. This result im-
lomb interaction, unlike in QED, is assumed to be in- plies that the Fermi velocity is renormalized toward
stantaneous since vF / c ⬇ 1 / 300 and hence retardation ef- higher values. As a consequence, the density of states
fects are very small. Moreover, photons propagate in 3D near the Dirac energy is reduced, in agreement with the
space whereas electrons are confined to the 2D general trend of repulsive interactions to induce or in-
graphene sheet. Hence, the Coulomb interaction breaks crease gaps.
the Lorentz invariance of the problem and makes the This result can be understood from the RG point of
many-body situation different from the one in QED view by studying the effect of reducing the cutoff from ⌳
共Baym and Chin, 1976兲. Furthermore, the problem de- to ⌳ − d⌳ and its effect on the effective coupling. It can
pends on two parameters: vF and e2 / ⑀0. Under a dimen- be shown that ␣ obeys 共González et al., 1994兲
sional scaling, r → r , t → t , ⌿ → −1⌿, both parameters
remain invariant. In RG language, the Coulomb interac- ␣ ␣2
⌳ =− . 共221兲
tion is a marginal variable, whose strength relative to the ⌳ 4
kinetic energy does not change upon a change in scale. If Therefore, the Coulomb interaction becomes marginally
the units are chosen such that vF is dimensionless, the irrelevant. These features are confirmed by a full relativ-
value of e2 / ⑀0 will also be rendered dimensionless. This istic calculation, although the Fermi velocity cannot sur-
is the case in theories considered renormalizable in pass the velocity of light 共González et al., 1994兲. This
quantum field theory. result indicates that strongly correlated electronic
The Fermi velocity in graphene is comparable to that phases, such as ferromagnetism 共Peres et al., 2005兲 and
in half-filled metals. In solids with lattice constant a, the Wigner crystals 共Dahal et al., 2006兲, are suppressed in
total kinetic energy per site 1 / ma2, where m is the bare clean graphene.
mass of the electron, is of the same order of magnitude A calculation of higher-order self-energy terms leads
as the electrostatic energy e2 / ⑀0a. The Fermi velocity for to a wave-function renormalization, and to a finite qua-
fillings of the order of unity is vF ⬃ 1 / ma. Hence, siparticle lifetime, which grows linearly with quasiparti-
e2 / ⑀0vF ⬃ 1. This estimate is also valid in graphene. cle energy 共González et al., 1994, 1996兲. The wave-
Hence, unlike in QED, where ␣QED = 1 / 137, the cou- function renormalization implies that the quasiparticle
pling constant in graphene is ␣ ⬃ 1. weight tends to zero as its energy is reduced. A strong-
Despite the fact that the coupling constant is of the coupling expansion is also possible, assuming that the
order of unity, a perturbative RG analysis can be ap- number of electronic flavors justifies an RPA expansion,
plied. RG techniques allow us to identify stable fixed keeping only electron-hole bubble diagrams 共González
points of the model, which may be attractive over a et al., 1999兲. This analysis confirms that the Coulomb
broader range than the one where a perturbative treat- interaction is renormalized toward lower values.
ment can be rigorously justified. Alternatively, an RG The enhancement in the Fermi velocities leads to a
scheme can be reformulated as the process of piecewise widening of the electronic spectrum. This is consistent
integration of high-energy excitations 共Shankar, 1994兲. with measurements of the gaps in narrow single-wall
This procedure leads to changes in the effective low- nanotubes, which show deviations from the scaling with
energy couplings. The scheme is valid if the energy of R−1, where R is the radius, expected from the Dirac
the renormalized modes is much larger than the scales of equation 共Kane and Mele, 2004兲. The linear dependence
interest. of the inverse quasiparticle lifetime with energy is con-
The Hartree-Fock correction due to Coulomb interac- sistent with photoemission experiments in graphite, for
tions between electrons 共given by Fig. 37兲 gives a loga- energies larger with respect to the interlayer interactions
rithmic correction to the electron self-energy 共González 共Xu et al., 1996; Zhou, Gweon, and Lanzara, 2006; Zhou,
et al., 1994兲, Gweon, et al., 2006; Bostwick, Ohta, Seyller, et al., 2007;
Sugawara et al., 2007兲. Note that in graphite, band- 1. Screening in graphene stacks
structure effects modify the lifetimes at low energies
The electron-electron interaction leads to the screen-
共Spataru et al., 2001兲. The vanishing of the quasiparticle
ing of external potentials. In a doped stack, the charge
peak at low energies can lead to an energy-dependent
tends to accumulate near the surfaces, and its distribu-
renormalization of the interlayer hopping 共Vozmediano
tion is determined by the dielectric function of the stack
et al., 2002, 2003兲. Other thermodynamic properties of in the out-of-plane direction. The same polarizability de-
undoped and doped graphene can also be calculated scribes the screening of an external field perpendicular
共Barlas et al., 2007; Vafek, 2007兲. to the layers, similar to the one induced by a gate in
Nonperturbative calculations of the long-range inter- electrically doped systems 共Novoselov et al., 2004兲. The
action effects in undoped graphene show that a transi- self-consistent distribution of charge in a biased
tion to a gapped phase is also possible, when the number graphene bilayer has been studied by McCann 共2006兲.
of electronic flavors is large 共Khveshchenko, 2001; From the observed charge distribution and self-
Luk’yanchuk and Kopelevich, 2004; Khveshchenko and consistent calculations, an estimate of the band-structure
Shively, 2006兲. The broken symmetry phase is similar to parameters and their relation with the induced gap can
the excitonic transition found in materials where it be- be obtained 共Castro, Novoselov, Morozov, et al., 2007兲.
comes favorable to create electron-hole pairs that then In the absence of interlayer hopping, the polarizability
form bound excitons 共excitonic transition兲. of a set of stacks of 2D electron gases can be written as
Undoped graphene cannot have well-defined plas- a sum of the screening by the individual layers. Using
mons, as their energies fall within the electron-hole con- the accepted values for the effective masses and carrier
tinuum, and therefore have a significant Landau damp- densities of graphene, this scheme gives a first approxi-
ing. At finite temperatures, however, thermally excited mation to screening in graphite 共Visscher and Falicov,
quasiparticles screen the Coulomb interaction, and an 1971兲. The screening length in the out-of-plane direction
acoustic collective charge excitation can exist 共Vafek, is of about two graphene layers 共Morozov et al., 2005兲.
2006兲. This model is easily generalizable to a stack of semimet-
Doped graphene shows a finite density of states at the als described by the 2D Dirac equation 共González et al.,
Fermi level, and the long-range Coulomb interaction is 2001兲. At half filling, the screening length in all direc-
screened. Accordingly, there are collective plasma inter- tions diverges, and the screening effects are weak.
actions near q → 0, which disperse as p ⬃ 冑兩q兩, since the Interlayer hopping modifies this picture significantly.
system is 2D 共Shung, 1986a, 1986b; Campagnoli and To- The hopping leads to coherence 共Guinea, 2007兲. The
satti, 1989兲. The fact that the electronic states are de- out-of-plane electronic dispersion is similar to that of a
scribed by the massless Dirac equation implies that P one-dimensional conductor. The out-of-plane polariz-
⬀ n1/4, where n is the carrier density. The static dielectric ability of a multilayer contains intraband and interband
constant has a continuous derivative at 2kF, unlike in the contributions. The subbands in a system with Bernal
case of the 2D electron gas 共Ando, 2006b; Wunsch et al., stacking have a parabolic dispersion, when only the
2006; Sarma et al., 2007兲. This fact is associated with the nearest-neighbor hopping terms are included. This band
suppressed backward scattering in graphene. The sim- structure leads to an interband susceptibility described
plicity of the band structure of graphene allows analyti- by a sum of terms like those in Eq. 共228兲, which diverges
cal calculation of the energy and momentum depen- at half filling. In an infinite system, this divergence is
dence of the dielectric function 共Wunsch et al., 2006; more pronounced at k⬜ = / c, that is, for a wave vector
Sarma et al., 2007兲. The screening of the long-range Cou- equal to twice the distance between layers. This effect
lomb interaction implies that the low-energy quasiparti- enhances Friedel-like oscillations in the charge distribu-
cles show a quadratic dependence on energy with re- tion in the out-of-plane direction, which can lead to the
spect to the Fermi energy 共Hwang et al., 2007兲. changes in the sign of the charge in neighboring layers
One way to probe the strength of the electron- 共Guinea, 2007兲. Away from half filling, a graphene bi-
electron interactions is via the electronic compressibility. layer behaves, from the point of view of screening, in a
Measurements of the compressibility using a single- way very similar to the 2DEG 共Wang and Chakraborty,
electron transistor 共SET兲 show little sign of interactions 2007b兲.
in the system, being well fitted by the noninteracting
result that, contrary to the two-dimensional electron gas
共2DEG兲 共Eisenstein et al., 1994; Giuliani and Vignale, C. Short-range interactions
2005兲, is positively divergent 共Polini et al., 2007; Martin
et al., 2008兲. Bilayer graphene, on the other hand, shares In this section, we discuss the effect of short-range
characteristics of the single layer and the 2DEG with a Coulomb interactions on the physics of graphene. The
nonmonotonic dependence of the compressibility on the simplest carbon system with a hexagonal shape is the
carrier density 共Kusminskiy et al., 2008兲. In fact, bilayer benzene molecule. The value of the Hubbard interaction
graphene very close to half filling has been predicted to among electrons was, for this system, computed long
be unstable toward Wigner crystallization 共Dahal et al., ago by Parr et al. 共1950兲, yielding U = 16.93 eV. For com-
2007兲, just like the 2DEG. Furthermore, according to parison purposes, in polyacetylene the value for the
Hartree-Fock calculations, clean bilayer graphene is un- Hubbard interaction is U ⯝ 10 eV and the hopping en-
stable toward ferromagnetism 共Nilsson et al., 2006a兲. ergy is t ⬇ 2.5 eV 共Baeriswyl et al., 1986兲. These two ex-
amples show that the value of the on-site Coulomb in- 共Lee and Lee, 2005兲 关as originally proposed by Pauling
teraction is fairly large for electrons. As a first guess 共1972兲 in 1956兴 since mean-field calculations give a criti-
for graphene, one can take U to be of the same order as cal value for U to be of the order of U / t ⯝ 1.7. Whether
for polyacethylene, with the hopping integral t ⯝ 2.8 eV. this type of ground state really exists and whether quan-
Of course in pure graphene the electron-electron inter- tum fluctuations push this value of U toward larger val-
action is not screened, since the density of states is zero ues is not known.
at the Dirac point, and one should work out the effect of
Coulomb interactions by considering the bare Coulomb
potential. On the other hand, as shown before, defects
induce a finite density of states at the Dirac point, which 1. Bilayer graphene: Exchange
could lead to an effective screening of the long-range The exchange interaction can be large in an unbiased
Coulomb interaction. We assume that the bare Coulomb graphene bilayer with a small concentration of carriers.
interaction is screened in graphene and that Coulomb It was shown that the exchange contribution to the elec-
interactions are represented by the Hubbard interaction. tronic energy of a single graphene layer does not lead to
This means that we must add to the Hamiltonian 共5兲 a a ferromagnetic instability 共Peres et al., 2005兲. The rea-
term of the form son for this is a significant contribution from the inter-
HU = U 兺 关a†↑共Ri兲a↑共Ri兲a†↓共Ri兲a↓共Ri兲
band exchange, which is a term usually neglected in
Ri
doped semiconductors. This contribution depends on
the overlap of the conduction and valence wave func-
+ b†↑共Ri兲b↑共Ri兲b†↓共Ri兲b↓共Ri兲兴. 共222兲 tions, and it is modified in a bilayer. The interband ex-
The simplest question one can ask is whether this system change energy is reduced in a bilayer 共Nilsson et al.,
shows a tendency toward some kind of magnetic order 2006b兲, and a positive contribution that depends loga-
driven by the interaction U. Within the simplest rithmically on the bandwidth in graphene is absent in its
Hartree-Fock approximation 共Peres et al., 2004兲, the in- bilayer. As a result, the exchange energy becomes nega-
stability line toward ferromagnetism is given by tive, and scales as n3/2, where n is the carrier density,
similar to the 2DEG. The quadratic dispersion at low
2 energies implies that the kinetic energy scales as n2,
U F共 兲 = , 共223兲
共兲 again as in the 2DEG. This expansion leads to
冕 冉冑 冊
sible 共Doretto and Morais Smith, 2007兲.
1 ⌳
共qជ , 兲 ⬀ d 2k ⬀ ln , Interactions modify the edge states in the quantum
兩qជ 兩⬍⌳ − 共vF2 /t兲兩k兩2 t/vF2 Hall regime. A novel phase can appear when the n = 0 is
共228兲 the last filled level. The Zeeman splitting shifts the elec-
tronlike and holelike chiral states, which disperse in op-
where ⌳ ⬃ 冑t2 / vF2 is a high momentum cutoff. These posite directions near the boundary of the sample. The
logarithmic divergences are similar to the ones that resulting level crossing between an electronlike level
show up when the Fermi surface of a 2D metal is near a with spin antiparallel to the field, and a holelike level
saddle point in the dispersion relation 共González et al., with spin parallel to the field, may lead to Luttinger-
1996兲. A full treatment of these divergences requires a liquid features in the edge states 共Fertig and Brey, 2006;
RG approach 共Shankar, 1994兲. Within a simpler mean- Abanin, Novoselov, Zeitler, et al., 2007兲.
field treatment, however, it is easy to note that the diver-
gence of the bilayer susceptibility gives rise to an insta-
VI. CONCLUSIONS
bility toward an antiferromagnetic phase, where the
carbon atoms that are not connected to the neighboring Graphene is a unique system in many ways. It is truly
layers acquire a finite magnetization, while the magneti- 2D, has unusual electronic excitations described in terms
zation of atoms with neighbors in the contiguous layers of Dirac fermions that move in a curved space, is an
remains zero. A scheme of the expected ordered state is interesting mix of a semiconductor 共zero density of
shown in Fig. 38. states兲 and a metal 共gaplessness兲, and has properties of
soft matter. The electrons in graphene seem to be almost
D. Interactions in high magnetic fields insensitive to disorder and electron-electron interactions
and have very long mean free paths. Hence, graphene’s
The formation of Landau levels enhances the effect of properties are different from what is found in usual met-
interactions due to the quenching of the kinetic energy. als and semiconductors. Graphene has also a robust but
This effect is most pronounced at low fillings, when only flexible structure with unusual phonon modes that do
the lowest levels are occupied. New phases may appear not exist in ordinary 3D solids. In some sense, graphene
at low temperatures. We consider here phases different brings together issues in quantum gravity and particle
from the fractional quantum Hall effect, which has not physics, and also from soft and hard condensed matter.
been observed in graphene so far. The existence of new Interestingly enough, these properties can be easily
phases can be inferred from the splitting of the valley or modified with the application of electric and magnetic
spin degeneracy of the Landau levels, which can be ob- fields, addition of layers, control of its geometry, and
served in spectroscopy measurements 共Sadowski et al., chemical doping. Moreover, graphene can be directly
2006; Henriksen, Tung, Jiang, et al., 2007兲, or in the ap- and relatively easily probed by various scanning probe
pearance of new quantum Hall plateaus 共Zhang et al., techniques from mesoscopic down to atomic scales, be-
2006; Abanin, Novoselov, Zeitler, et al., 2007; Giesbers et cause it is not buried inside a 3D structure. This makes
al., 2007; Goswami et al., 2007; Jiang, Zhang, Stormer, et graphene one of the most versatile systems in
al., 2007兲. condensed-matter research.
Interactions can lead to new phases when their effect Besides the unusual basic properties, graphene has
overcomes that of disorder. An analysis of the competi- the potential for a large number of applications 共Geim
tion between disorder and interactions has been found and Novoselov, 2007兲, from chemical sensors 共Chen, Lin,
by Nomura and MacDonald 共2007兲. The energy splitting Rooks, et al., 2007; Schedin et al., 2007兲 to transistors
of the different broken symmetry phases, in a clean sys- 共Nilsson et al., 2006b; Oostinga et al., 2007兲. Graphene
tem, is determined by lattice effects, so that it is reduced can be chemically and/or structurally modified in order
by factors of order a / lB, where a is a length of the order to change its functionality and henceforth its potential
of the lattice spacing and lB is the magnetic length 共Ali- applications. Moreover, graphene can be easily obtained
from graphite, a material that is abundant on the Earth’s Valery Kotov, Alessandra Lanzara, Leonid Levitov, Al-
surface. This particular characteristic makes graphene lan MacDonald, Sergey Morozov, Johan Nilsson, Vitor
one of the most readily available materials for basic re- Pereira, Philip Phillips, Ramamurti Shankar, João Lopes
search since it frees economically challenged research dos Santos, Shan-Wen Tsai, Bruno Uchoa, and Maria
institutions in developing countries from the depen- Vozmediano. N.M.R.P. acknowledges financial support
dence of expensive sample-growing techniques. from POCI 2010 via project PTDC/FIS/64404/2006. F.G.
Many of graphene’s properties are currently subject of was supported by MEC 共Spain兲 Grant No. FIS2005-
intense research and debate. Understanding the nature 05478-C02-01 and EU Contract No. 12881 共NEST兲.
of the disorder and how it affects the transport proper- A.H.C.N was supported through NSF Grant No. DMR-
ties 共a problem of fundamental importance for applica- 0343790. K.S.N. and A.K.G. were supported by EPSRC
tions兲, the effect of phonons on electronic transport, the 共UK兲 and the Royal Society.
nature of electron-electron interactions, and how they
modify its physical properties are research areas that are
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