Tunable electron and hole doping in FeCl3

intercalated graphene
Cite as: Appl. Phys. Lett. 100, 213112 (2012); https://doi.org/10.1063/1.4722817
Submitted: 21 March 2012 • Accepted: 12 May 2012 • Published Online: 24 May 2012

James Nathaniel and Xiao-Qian Wang

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Appl. Phys. Lett. 100, 213112 (2012); https://doi.org/10.1063/1.4722817 100, 213112

© 2012 American Institute of Physics.

 APPLIED PHYSICS LETTERS 100, 213112 (2012)

Tunable electron and hole doping in FeCl3 intercalated graphene

James Nathaniel and Xiao-Qian Wanga)
Department of Physics and Center for Functional Nanoscale Materials, Clark Atlanta University, Atlanta,
Georgia 30314, USA

(Received 21 March 2012; accepted 12 May 2012; published online 24 May 2012)
We have studied the electronic characteristics of FeCl3 intercalated bilayer graphene under a
perpendicularly applied electric bias. Evolution of the electronic structure of FeCl3 intercalated
bilayer graphene as a function of the applied electric bias is performed using first-principles
density-functional theory including interlayer van der Waals interactions. The calculation results
demonstrate that the hole-doped graphene layers associated with the high electronegativity of
FeCl3 transform into electron-doped layers tuned by the applied bias. The implications of
controllable electronic structure of intercalated graphene for future device applications are
C 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4722817]
discussed. V

Graphene, a monolayer of sp2 -hybridized carbon net-
work, has attracted considerable attention in the fields of
optoelectronics, sensors, and hydrogen storage.1–3 Among a
variety of graphene-based materials, graphene intercalation
compounds (GICs) are formed by insertion of molecular
layers with various chemical species between graphite
layers.4,5 A host of potential applications using different
intercalants has been proposed. Weak van der Waals (vdW)
binding between graphene and intercalant layers makes
GICs versatile and allows for tunable electronic properties.
As the interlayer distance of graphite is dramatically
increased due to the presence of intercalants, the modified
layer distance strongly affects the electronic coupling
between graphene sheets.6 As a result, the electrical, thermal,
and magnetic properties can be tailored by simply choosing
from various intercalantes.4,7,8 Consequently, intercalation
of graphene-based compounds represents an efficient
approach to modify the properties of graphene.
In virtually all potential applications of graphene, an
in-depth understanding of the electronic characteristics is
pivotal to the integration of graphene into future nanoelec-
tronic devices.7–12 In this regard, interlayer interactions in
GIC play an crucial role in determining the electronic struc-
ture properties. Recent experimental advances have demon-
strated the preparation of ferric chloride (FeCl3) intercalated
few-layer graphene by two-zone vapor transport method.5,13
While the FeCl3 intercalation effectively decouples the adja-
cent graphene layers, the intrinsic hole-doping may lead to
graphene oxidization and constrain the electrical properties.
To explore the feasibility of a controlled doping, herein we
employ a dispersion-corrected density-functional theory
(DFT) that incorporates interlayer vdW interactions to inves-
tigate the corresponding electronic structure.19 The calcu-
lated dependence of the electronic structure on the applied
electric bias reveals that there is a notable change of the na-
ture of doping from hole doping to electron doping. As such,
the intercalation can be utilized for graphene-based devices.
Since DFT is deficient in treating long-range interac-
tions,14,15 it is necessary to take into account the dispersion
corrections associated with vdW forces. This is particularly
a)
Electronic mail: xwang@cau.edu.
the case for FeCl3 intercalated graphene under the influence
of an electric field. Our first-principles calculations are based
on dispersion-corrected DFT with general gradient approxi-
mation (GGA) for exchange-correlation potential for which
Perdew, Burke, and Ernzerhof (PBE) exchange-correlation
functional16 was used as implemented in DMol3 package.17
We employed the dispersion correction with GGA using the
Tkatchenko-Scheffler (TS) scheme,14 which exploits the
relationship between polarizability and volume. The TS dis-
persion correction accounts for the relative variation in dis-
persion coefficients of differently bonded atoms by
weighting values taken from the high-quality first-principles
database with atomic volumes derived from partitioning of
the self-consistent electronic density.
To facilitate the calculation of an electric field, the Ham-
iltonian has been extended to include not only the potential
arising from the nuclear charges as external potential but
also the static potentials arising from an externally applied
electric field. The static potentials were constructed by inves-
tigating the dissociation of molecules in strong electric fields
and subsequently fitting the bond length and vibrational fre-
quency as a function of the field all the way up to the dissoci-
ation limit by analytical formula. In our calculations, a static
electric field was applied perpendicular to the graphene layer
plane,17 and electric bias was varied from 0 to 2.06 V/Å.
FIG. 1. Crystal structure of two layers of graphene intercalated with FeCl3.
The graphene layers sandwich FeCl3. Cl and Fe atoms are represented with
light and dark grey, respectively.

0003-6951/2012/100(21)/213112/3/$30.00 100, 213112-1 C 2012 American Institute of Physics

V
213112-2 J. Nathaniel and X.-Q. Wang
FIG. 2. Calculated band structures of two layers of graphene intercalated
with FeCl3: (a) no electric bias, (b) 1.03 V/Å electric bias, (c) 1.54 V/Å elec-
tric bias, and (d) 2.06 V/Å electric bias, respectively.
Shown in Fig. 1 is the optimized structure of double layer
of graphene intercalated by FeCl3. A supercell with lattice
constants a ¼ b ¼ 12:12 Å periodic in the xy plane was con-
structed, which amounts to combining 2  2 unit cells of
FeCl3 and 5  5 cells of graphene as suggested by previous
works.4,13 The stacking sequence of the bilayer graphene is
the AA type with the graphene atoms in different layers sit-
ting on top of each other.4 It is worth clarifying that the char-
acteristic AA stacked adjacent layers is promoted by FeCl3
intercalation, in contrast to the Bernal (AB) stacking in graph-
ite.4 A vacuum of 10 Å was used to avoid the interactions
between replicas. The unit cell has P31m (D3d ) symmetry.4,13
The double numerical plus polarization basis set
was employed, along with a kinetic energy change of
3  104 eV in the orbital basis. Appropriate Monkhorst-
Pack k-point grids of 4  4  1 for FeCl3 intercalated bilayer
graphene was sufficient to converge with the integration of
the charge density. The optimization of the atomic positions
proceeds until the change in energy is less than 5  105 eV
per cell.14,18 The optimized geometry yields an interlayer
distance of 9.405 Å between graphene layers and 4.689 Å
between FeCl3 and graphene layers. The calculated results
are in excellent agreement with experimental observations
based on an x-ray diffraction study of an interlayer distance
Appl. Phys. Lett. 100, 213112 (2012)
of 9.37 Å between graphene layers and a distance of 4.69 Å
from the FeCl3 and graphene layers.11,13 It is worth mention-
ing that although the local density approximation (LDA)
approach provides qualitatively correct pictures and remains
the popular choice for investigations of electric-field effects,
our calculations reveal that dispersion corrected GGA leads
to substantial improvements over the LDA results regarding
the layer distances. The dispersion-correction method,
coupled to suitable density functional, has been shown to
account for the long-range dispersion forces with remarkable
accuracy,18 particularly in rectifying the considerable weak
bonding in the GGA approach.19
We illustrate in Fig. 2 the evolution of band structures
of FeCl3 intercalated graphene with perpendicularly applied
electric fields. In the absence of an electric bias, the FeCl3
layer serves as an acceptor.9,10,12 The FeCl3 layer sand-
wiched between two graphene layers accepts electrons from
both the layers, leading to hole-doped graphene. The upward
shift of the Dirac point of 1 eV is reminiscent of the heavy
hole doping. The extracted upshift of the Dirac point for pris-
tine FeCl3-intercalated graphene is in very good agreement
with previous theoretical calculation result,13 and is in good
conformity with experimental observations.5 As seen in Fig.
2, the FeCl3 intercalated layer displays flat bands in the elec-
tronic band structure. These dispersionless bands are con-
nected to the d-orbital of Fe, which can facilitate
photoexcited transition between energy levels with the assis-
tance of optical phonons.20
Upon the application of an electric bias, the band struc-
ture undergoes profound modifications. With the increase
of the electric field magnitude, the corresponding electronic
band structures display monotonic downward shifting of
the the Dirac point (the crossing at K). As readily observ-
able in Fig. 2, the Dirac point shifts to the Fermi level (at
0 eV) at an electric field of 1.03 V/Å. Downward shifts of
the Dirac point to 1 eV and 2 eV are observed with
increasing the electric field to 1.54 and 2.06 V/Å, respec-
tively. However, when the electric bias is further increased,
FIG. 3. Extracted charge density distribution for near-gap
states at the band center of the conduction band maximum
(CBM) and valence band minimum (VBM) in the absence of
electric bias.
213112-3 J. Nathaniel and X.-Q. Wang
TABLE I. Calculated electric bias () induced change in distance between
graphene layer and FeCl3 (d0 ), along with that between graphene layers (d1 ),
respectively. The corresponding Mulliken charges in FeCl3 and Fe are also
listed.
 (V/Å) d0 (Å) d1 (Å) FeCl3 (e)
0 4.689 9.405 1.49
1.028 4.683 9.416 1.81
1.543 4.682 9.423 1.60
2.057 4.677 9.426 2.61
the Dirac point shifts back towards the Fermi level, along
with changes of the number of flat bands above the Fermi
level.
Closer scrutiny of the band structure characteristics
reveals that the shift of the Dirac point is attributed to the
charge transfer associated with flat bands near the Fermi
level. We show in Fig. 3 the extracted charge density of
near-gaps states, which correspond to flat bands in the band
structure. As seen in Fig. 3, the electronic charges are con-
fined at Fe or Cl sites. Specifically, the hybridization of
graphene-based dispersed bands and FeCl3-based flat bands
leads to charge transfer between graphene layers and FeCl3,
and between Fe and Cl.
We summarize in Table I the changes in the layer dis-
tances, along with the extracted Mulliken charges of various
components. As shown in Table I, the FeCl3 intercalants
accept electrons from graphene layers. As there is a symme-
try for the bilayer intercalated graphene system, each gra-
phene layer donates half of the charge as FeCl3 receives. It is
worth noting that with the application of an electric bias, the
charge transfer takes place not only between FeCl3 and gra-
phene but also between Fe and Cl. As a consequence, the flat
bands originated from the FeCl3 can shift and contract as the
electric bias increases in magnitude. This is in conformity
with the corresponding changes of the band structure in that
the ferric chloride flat bands upshifts higher as the graphe-
ne’s Dirac point shifts downwards. Overall, the electric bias
can be used to control the hole doping of the FeCl3 intercala-
tion. With the application of the electric bias, the hole-doped
graphene layers can turn into n-type doping ones. It is worth
noting that the grouping of flat bands with the increase of the
applied electric bias. The FeCl3 stretches to move closer to
the graphene layers, resulting an effective repelling of the
graphene sheets from each other. In the case of electric-field-
induced electron doping, the shifted Dirac point opens a
small gap ED ’ 0:1eV.11
Appl. Phys. Lett. 100, 213112 (2012)
In summary, we have investigated the evolution of band
structure of FeCl3-intercalated graphene layers with the
application of an electric field. Our results demonstrate that
the hole-doped pristine GIC can transform into electron-
Fe (e) doped with the electric bias. The tunable doping is of partic-
ular importance to the optical responses as the band filling
1.17
and electron-hole interactions lead to enhanced excitonic
1.19
effect on the optical absorption.21As the tailoring of doping
1.56
0.30
plays an important role in graphene-based electronics devi-
ces and optoelectronics, we hope the advocated tunable dop-
ing with electric bias can promote future experimental
studies in this direction.
This work was supported by the National Science Foun-
dation under Grant No. DMR-0934142 and the Air Force
Office of Scientific Research under Grant No. FA9550-10-1-
0254.
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