PHYSICAL REVIEW B 86, 075411 (2012)

Thermoelectricity in graphene: Effects of a gap and magnetic fields

Aavishkar A. Patel1 and Subroto Mukerjee2

1
Department of Physics, Indian Institute of Technology, Kanpur, India
2
Department of Physics, Indian Institute of Science, Bangalore, India
(Received 30 August 2011; revised manuscript received 28 May 2012; published 3 August 2012)
We calculate the thermopower of monolayer graphene in various circumstances. We consider acoustic
phonon scattering which might be the operative scattering mechanism in freestanding films and predict that
the thermopower will be linear in any induced gap in the system. Further, the thermopower peaks at the same
value of chemical potential (tunable by gate voltage) independent of the gap. We show that in the semiclassical
approximation, the thermopower in a magnetic field saturates at high field to a value which can be calculated
exactly and is independent of the details of the scattering. This effect might be observable experimentally. We also
note that a Yukawa scattering potential can be used to fit experimental data for the thermopower for reasonable
values of the screening length parameter.

DOI: 10.1103/PhysRevB.86.075411 PACS number(s): 72.80.Vp

I. INTRODUCTION where the cyclotron frequency is high and oscillations have

been seen indicative of the formation of Landau levels.5–7,12
Graphene has become one of the most studied electronic
However, not much attention has been paid to the effect of a
systems in recent years. The interest in this system stems from
magnetic field at higher values of filling when the cyclotron
the existence of a relativistic band structure which gives rise to frequency is low and semiclassical physics can apply at
several interesting electrical properties.1 Very high values of reasonable temperatures. We show that in such a situation
electron mobility combined with robust mechanical properties the thermopower can saturate at high field, an effect that might
make graphene a promising candidate for use in several devices be observable experimentally.
and technologies. Two recent developments have proven very In this paper, we consider semiclassical transport in
significant in this regard: the ability to introduce a tunable graphene taking into account the effects of a band gap, various
gap in single sheets of graphene2,3 and the fabrication of scattering mechanisms, and magnetic fields. We consider the
free standing sheets.4 The former, in principle, enables one case of scattering due to acoustic phonons, which might be
to fabricate electronic devices using single sheets of graphene the dominant scattering mechanism in freestanding films due
while the latter is an important step towards increasing the to the near absence of impurity effects from the substrate.
mobility of electrons by eliminating scattering effects from Here, we predict that the thermopower is proportional to the
the substrate. band gap and obtain an exact expression in the limit of small
An enhanced mobility (and hence electrical conductivity) is gaps. This is quite distinct from what happens in the presence
important for thermoelectric applications as well. In addition of substrates and might be used to characterize the band gap.
to the technological significance of the phenomenon of Finally, we calculate the effect of magnetic fields and find that,
thermoelectricity, the thermopower of a system is often used in the semiclassical limit, the thermopower saturates to a value
to shed light on various properties of the elementary charge at high field, which can be calculated exactly, independent of
carriers. These include the sign of their charge, the principle the details of scattering. We show that for reasonable values
scattering mechanism, and, in certain limits, their entropy. of various parameters this saturation can occur at a few tesla
Thus, the thermopower in graphene has also been studied of field, making it relevant experimentally.
extensively in the last few years both experimentally5–7 and
theoretically.8–14 Interesting behavior such as the violations II. TRANSPORT FORMALISM
of the Mott formula at high temperatures have been found Graphene has a hexagonal Brillouin zone. At the six corners
and attributed to the nondegenerate behavior of carriers. Most of the zone, the dispersion is given by E(k) = ±h̄vf |k|, where
theoretical calculations have focused on monolayer graphene vf is the Fermi velocity. The density of states is
without a gap, with screened impurities being the dominant
source of scattering. This is indeed the situation for graphene 2|E|
g(E) = . (1)
on substrates of SiO2 on which most experiments have π h̄2 vf2
been carried out. However, with the two new developments
mentioned in the previous paragraph, it has become important In linear response response theory the transport coefficients
to consider the effect of a gap and other scattering mechanisms, are defined by the following expression
which is one of the objectives of this paper.  
e 11 1
A magnetic field can have interesting effects on thermo- Ji = − Lij ∇j φ + Lij ∇j 12
, (2)
T T
electricity. It can produce oscillations7,12 or steps15 in the  
thermopower under suitable circumstances which can provide e 1
JiQ = − L21 ij ∇ j φ + L 22
ij ∇ j , (3)
information about the energy levels of the carriers of the T T
system. The effect of magnetic fields on the thermopower of where Ji and JiQ are the ith components of the charge and heat
graphene has also been studied, mainly at low carrier densities, currents, respectively, φ is the electrostatic potential, T is the

1098-0121/2012/86(7)/075411(5) 075411-1 ©2012 American Physical Society

AAVISHKAR A. PATEL AND SUBROTO MUKERJEE PHYSICAL REVIEW B 86, 075411 (2012)

temperature, and e is the charge of the electron. In the above positive,

expressions, there is a summation over repeated indices. The   
∞
diagonal electrical conductivity e2 1 ∂f
L12
xx ∝ E (E − μ) − dE
π h̄2 0 E ∂E
e2 11   
σ = L ,  −∞
T xx −1 ∂f
+ E (E − μ) − dE , (7)
0 E ∂E
and the diagonal Peltier conductivity
giving
e2 12
α= L .  ∞  
T xx ∂f
L12
xx ∝ (E − μ) − dE = 0, (8)
In the semiclassical approximation, the transport coefficients −∞ ∂E
relevant to thermoelectricity are given by
since the integrand is an odd function of E − μ. The
   thermopower is identically zero with acoustic phonon scatter-
e2 ∂f
L11
ij = τ [E(k)] − vi vj dk, ing independent of the chemical potential (and hence carrier
2π 2 ∂E(k)
   density).20 To demonstrate the effect of a band gap, we assume
−e ∂f a massive Dirac particle dispersion of the form
L12
ij = [E(k) − μ]τ [E(k)] − vi vj dk. (4)
2π 2 T ∂E(k)
where vi is the ith component of the velocity, μ is the E(k) = ± h̄2 vf2 |k|2 + 2. (9)
chemical potential, and f is the Fermi function. The thermo-
power The magnitude of the velocity now picks up an energy
α L12 dependence:
S= = xx
. (5)
σ L11
xx
2
v(E) = vf 1 − . (10)
The momentum integrals are carried out in the vicinity of all E2
six corners of the Brillouin zone. The carrier density ρ can be Note that vf here is not the magnitude of the physical velocity
related to μ through the expression of the carriers (which is given by |∇E(k)|),  but is just a
 ∞  0 mathematical parameter which must have the same numerical
ρ= g(E)f (E) dE − [1 − f (E)]g(E) dE. (6) value to give the correct expression when = 0. The relation
0 −∞ EdE = h̄2 vf2 kdk still holds. The density of states is calculated
from (factor of 2 for spin degeneracy, and an angular range of
ρ is the excess carrier concentration over the completely filled 4π from six corners of the hexagonal Brillouin zone)
lower band and μ = 0 when ρ = 0.
1 4π k(E  )
g(E  ) = . (11)
III. ACOUSTIC PHONON SCATTERING AND BANDGAPS 2π 2 | dE |
dk E=E


Acoustic phonon scattering is likely to be relevant for Since dE/dk is the same as in the ungapped case, g(E) is still
freestanding graphene films of the sort that have been fab- given by Eq. (1) and ρ can be calculated in terms of μ to yield
ricated recently due to greatly reduced impurity scattering
2kB2 T 2
(which arises from impurities present in the substrate). It ρ= {Li2 [−e−(μ+ )/kB T
] − Li2 [−e(μ− )/kB T
]}
can be shown from the Fermi golden rule that the relaxation π h̄2 vf2
time τ (E) ∝ 1/g(E) and hence 1/|E| for scattering from 2kB T 1 + e(μ− )/kB T
in-plane acoustic phonons.16–18 Incidentally, this is also the + ln , (12)
π h̄2 vf2 1 + e(−μ− )/kB T
energy dependence of τ (E) for localized impurity scatter-
ing. Scattering by flexural (transverse) acoustic phonons in where Li2 (x) is the second polylogarithmic function. The
freestanding sheets is dominant only at lower temperatures integrand in the expression for L12 xx is no longer an odd
(T < Tx ), where Tx ≈ 70K and the temperature dependence function of E − μ. Further, the limits of integration also
of the carrier scattering rate is T 5/2 lnT as opposed to T 4 for change. However, the form of τ (E) stays the same for in-plane
in-plane phonons.19 Thus at significantly higher temperatures acoustic phonon scattering due to g(E) not changing.18 The
(such as room temperature) only the effect of in-plane phonons resultant integration gives a nonzero value of the thermopower.
needs to be considered. In the absence of a gap, as is shown The electrical conductivity and Peltier conductivity are given
below, the energy dependence of the product of the density by
of states with the square of the velocity in the integrals for  
∞ 2 
αβ
Lxx is exactly canceled by that coming from τ (E). In the e2 ∂f
Lxx ∝
11
1− 2 − dE
lower band, τ ∝ −1/E, and in the upper band, τ ∝ 1/E. k π h̄2 E ∂E
must run from 0 to ∞ on both bands. Therefore, noting that  −  
2 
E = h̄ vf k on one band and E = −h̄ vf k on the other, so that ∂f
+ 1− 2 − dE , (13)
EdE = h̄2 vf2 kdk in both cases and that τ ∝ 1/|E| must be −∞ E ∂E

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THERMOELECTRICITY IN GRAPHENE: EFFECTS OF A . . . PHYSICAL REVIEW B 86, 075411 (2012)

2
2
−0.2 1.5

S(kB /e)
−0.4 1
1
−0.6
0.5
S(kB /e)

−0.8 0

S(kB /e)
0 1 2
µ = 0.1kB T Δ/kB T
−1 0
µ = 0.5kB T Δ = 0.1kB T
−1.2 −0.5
µ = kB T Δ = 0.2kB T
−1.4 µ = 5kB T −1 Δ = 0.5kB T
−1.6 µ = 10kB T Δ = kB T
−1.5
−1.8 Δ = 2kB T
0 0.5 1 1.5 2
Δ/kB T −2
−5 −4 −3 −2 −1 0 1 2 3 4 5
µ/kB T
FIG. 1. (Color online) Thermopower as a function of band gap
for acoustic phonon scattering. The different curves correspond to FIG. 2. (Color online) Thermopower for different values of chem-
different values of chemical potential. ical potential evaluated numerically for acoustic phonon scattering.
 The different curves correspond to different values of the gap. It can be
∞  2  seen that the peak occurs at approximately μ = 1.5kB T , independent
−e ∂f
L12
xx ∝ (E − μ) 1 − 2 − dE of the value of the gap. Inset: The peak value of the thermopower as
π h̄2 T E ∂E a function of the gap.
 
 − 2 
∂f
+ (E − μ) 1 − 2 − dE . (14) low Fermi energies where oscillations have been observed as a
−∞ E ∂E function of the field consistent with quantization of energy
levels.5,7 Here we focus on semiclassical transport in the
The expression for the thermopower S = L12 11
xx /Lxx can then be presence of a magnetic field which is relevant to experiments
found. The value can be obtained analytically in the limit of at higher temperatures and higher Fermi energies. The field B
small gaps, with  μ ≈ kB T , giving is assumed to be perpendicular to the plane of the sheet. We
consider the effect of magnetic fields in the absence of a gap.
kB 4 μ e−μ/kB T
S=− . (15) The semiclassical equation of motion of the wave vector k is
e kB T kB T (1 + e−μ/kB T )2
−e ∂E
h̄k˙ = 
× B. (16)
The thermopower can also be calculated numerically for h̄ ∂ k
larger values of the gap. The results are shown in Fig. 1
Defining β = evf2 B and ω = β/E, the solutions are
from which it can be seen that the thermopower is roughly
linear to reasonably large values of the gap. The thermopower E
as a function of chemical potential is shown in Fig. 2. A kx = cos(ω t + θ ),
h̄vf
curious fact is that the maximum appears at a value of
E
μ/kB T = 1.54, roughly independent of the band gap. This ky = sin(ω t + θ ). (17)
can be seen directly for very low band gaps from Eq. (15) but h̄vf
holds more generally for larger gaps as well. The maximum Here θ is the inital phase angle of the wave vector k.  These
value of the thermopower can be seen to be of the order of kB /e describe orbits in which the energy of the electron is a
for sufficiently large values of the gap and is shown in the inset constant. The linear response formulas, Eqs. (4), then have
of Fig. 2. It can also be seen that this peak thermopower is also to be modified to include the average of the velocities along
linear in the gap up to far large values of the gap. Thus, the these orbits. Operationally, this involves replacing one of the
thermoelectric properties of a gapped freestanding graphene velocity operators by its average value in an orbit given by21,22
sheet are likely to be quite different from those of a sheet on  0 t/τ (E)
a substrate. In particular, the linear relation between the gap  = e 
v¯ (k) v[k(t)]dt, (18)
and the peak thermopower in the former case might provide a −∞ τ (E)
method to estimate the size of the gap. Also, the thermopower
is not affected if the two bands are shifted horizontally with These average velocities are
respect to each other after introducing the gap, as the Jacobian vf cos θ/τ (E) + ω sin θ
of the coordinate transform k = k + a is 1. v¯x = ,
τ (E) 1/τ (E)2 + ω2
(19)
IV. MAGNETOTHERMAL TRANSPORT vf sin θ/τ (E) − ω cos θ
v¯y = .
We now focus our attention on the case of magnetothermal τ (E) 1/τ (E)2 + ω2
transport. The thermopower of graphene has been measured where τ (E) is the relaxation time. It can be shown after
in the presence of a magnetic field at low temperature and evaluating the modified transport integrals that the following

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AAVISHKAR A. PATEL AND SUBROTO MUKERJEE PHYSICAL REVIEW B 86, 075411 (2012)

relations result for the various transport coefficients when τ (E) 0

explicitly depends on |E|:23 Acoustic Phonon
Unscreened Coulomb
 Saturation
−e2 ∞ ∂f dE
L11
xx = 2
E 2 + β 2 /E 2 ]
, −50
π h̄ −∞ ∂E τ (E)[1/τ (E)


S (µV/K)
e2 β ∞ ∂f d|E|
xy =
L11 ,
π h̄ −∞ ∂E 1/τ (E)2 + β 2 /E 2
2
 ∞ −100
e ∂f dE
xx =
L12 E(E − μ) ,
2
π h̄ T −∞ ∂E τ (E)[1/τ (E)2 + β 2 /E 2 ]
 ∞
−eβ ∂f d|E|
xy =
L12 (E − μ) . (20)
2
π h̄ T −∞ ∂E 1/τ (E)2 + β 2 /E 2 −150
−6 −4 −2 0
10 10 10 10
Note that while the integrals over the two bands for the diagonal B (T)
αβ
coefficients Lxx add, the ones for the off-diagonal coefficients
αβ FIG. 3. (Color online) Thermopower as a function of magnetic
Lxy subtract. This is due to the fact that the sense of rotation
field for T = 300 K and μ/kB T = 3, for acoustic phonon scattering
of the orbits is opposite in the two bands. We have verified that and unscreened Coulomb scattering. For acoustic phonon scattering,
the above integrals for unscreened Coulomb scattering yield the deformation potential for graphene was taken to be 18 eV, the
values of conductivity and hall resistance as functions of μ that velocity of LA phonons 2.1 × 106 cm/s and mass density 7.6 × 10−7
show good qualitative agreement with the experimental data of Kg/m2 . For unscreened Coulomb scattering, the impurities were
αβ αβ αβ αβ
Ref. 24. The Onsager relations Lxx = Lyy and Lxy = −Lyx assumed to have a charge of e and a concentration of 0.1 ppm.
can also be shown to hold. The thermopower in the presence
of a magnetic field is given by the formula An analytic expression can be obtained for the saturation
value of the thermopower at large magnetic fields:
xx Lxx + Lxy Lxy
L12 11 12 11
S= 2 2
. (21)
L11
xx + L12
xy

1 4μkB2 T 2 Li2 (−eμ/kB T ) − 12kB3 T 3 Li3 (−eμ/kB T ) − 2μkB2 T 2 π 2 /3

Sxx = , (22)
eT 4kB2 T 2 Li2 (−eμ/kB T ) + μ2 + kB2 T 2 π 2 /3

where Li3 (x) is the third polylogarithmic function. For For a Yukawa potential of the type V (r) = eqe−r/ξ /4π 0 r,
different scattering mechanisms, the field dependence of the relaxation time with impurity density ρi can be shown
the thermopower has to be calculated numerically. This to be
is shown for two scattering mechanisms, acoustic phonon  
1 qe 2 ρi ξ 2 k 1 + 2k 2 ξ 2 − 1 + 4k 2 ξ 2
scattering and unscreened Coulomb scattering, in Fig. 3 for = . (23)
realistic values of the relevant parameters. The thermopower τ (k) 20 2h̄2 vf 2k 4 ξ 4
approaches the value given by Eq. (22) for large enough Calculations of the peak thermopower with respect to chemical
fields in both cases. The saturation value is independent of potential or gate voltage using this scattering potential can be
the scattering mechanism as can be seen from Eqs. (20). For used to obtain a very good agreement with the experimental
sufficiently large fields, β/E dominates the factor 1/τ (E) data of Ref. 7 for reasonable values of the screening length
where the value of the integrand is appreciable. In this limit, parameter ξ (8.5–10 nm) over a fairly large range of
S ∼ L12 11
xy /Lxy , which can be shown to be equal to Eq. (22). temperatures (180–300 K).
For the parameters used, the saturation field is of the order
of a tesla as can be seen from Fig. 3, which could make
the effect experimentally observable. For the relatively large
carrier densities [O(1012 /cm2 )] and temperatures around
ACKNOWLEDGMENTS
room temperature considered, the semiclassical calculations
are applicable at these fairly low magnetic fields, and effects We thank Arindam Ghosh for helpful discussions. We
of the quantization of states due to formation of Landau would like to acknowledge financial support from the Depart-
levels need not be considered. Effects of Zeeman splitting of ment of Science and Technology (DST) of the government of
the electrons can be neglected here since the corresponding India especially through the Kishore Vigyan Protsahan Yojna
energy is extremely small compared to the Fermi energy. (AAP) and the Ramanujan Fellowship (SM).

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(2007). 10.1103/PhysRevB.86.075411 for [brief description].

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