A generic tight-binding model for monolayer,

bilayer and bulk MoS2

Cite as: AIP Advances 3, 052111 (2013); https://doi.org/10.1063/1.4804936
Submitted: 28 March 2013 . Accepted: 29 April 2013 . Published Online: 08 May 2013

Ferdows Zahid, Lei Liu, Yu Zhu, Jian Wang, and Hong Guo

COLLECTIONS

Paper published as part of the special topic on Chemical Physics, Energy, Fluids and Plasmas, Materials Science and
Mathematical Physics

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AIP Advances 3, 052111 (2013); https://doi.org/10.1063/1.4804936 3, 052111

© 2013 Author(s).
 AIP ADVANCES 3, 052111 (2013)

A generic tight-binding model for monolayer, bilayer

and bulk MoS2
Ferdows Zahid,1,a Lei Liu,2 Yu Zhu,2 Jian Wang,1 and Hong Guo3
1
Department of Physics, The University of Hong Kong, Pok Fulam Road,
Hong Kong SAR, China
2
Nanoacademic Technologies Inc., Brossard, Quebec, J4Z 1A7, Canada
3
Centre for the Physics of Materials and Department of Physics, McGill University,
Montreal, PQ, H3A 2T8, Canada
(Received 28 March 2013; accepted 29 April 2013; published online 8 May 2013)

Molybdenum disulfide (MoS2 ) is a layered semiconductor which has become very

important recently as an emerging electronic device material. Being an intrinsic semi-
conductor the two-dimensional MoS2 has major advantages as the channel material in
field-effect transistors. In this work we determine the electronic structures of MoS2
with the highly accurate screened hybrid functional within the density functional
theory (DFT) including the spin-orbit coupling. Using the DFT electronic structures
as target, we have developed a single generic tight-binding (TB) model that accu-
rately produces the electronic structures for three different forms of MoS2 - bulk,
bilayer and monolayer. Our TB model is based on the Slater-Koster method with
non-orthogonal sp3 d5 orbitals, nearest-neighbor interactions and spin-orbit coupling.
The TB model is useful for atomistic modeling of quantum transport in MoS2 based
electronic devices.  C 2013 Author(s). All article content, except where otherwise

noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

[http://dx.doi.org/10.1063/1.4804936]

Molybdenum disulfide (MoS2 ) belongs to a family of layered transition metal dichalcogenides

(TMDC) in which the layers are held together by weak van der Waals forces, and it can be ex-
foliated mechanically to a single layer thickness. In its bulk form MoS2 is an indirect band gap
semiconductor which turns into a direct band gap semiconductor for monolayer structure.1 This
intrinsic semiconducting nature of MoS2 is a major advantage over graphene (which has no intrinsic
band gap) as a two-dimensional (2D) channel material in field-effect transistors (FET). Indeed, FET
devices based on MoS2 monolayer and bilayer have already been fabricated in the experimental
labs and demonstrated to have useful device performances.2, 3 Several theoretical studies of MoS2
FET devices4–6 based on simplified description of the electronic structures within an effective mass
model have also been reported recently.
Due to the complex nature of the layered TMDC materials and the great interests in the
electronics community for its applications in emerging devices, a more reliable, accurate, and
atomistic treatment of the electronic structures of TMDC is desired. Since ab initio models are
computationally expensive and often intractable for realistic device structures having large number
of atoms, a widely applied intermediary option is the tight-binding (TB) model. TB models are
atomistic full-band yet computationally efficient due to the small number of basis orbitals and the
rigid nature of the Hamiltonian. Properly parameterized TB models have been extensively applied
to predict reliable results for a diverse range of devices including the resonant tunneling diodes,7
quantum dots,8 Si nanowireFET,9 and compound semiconductor heterostructures.10
In this study, we report a generic TB model with non-orthogonal sp3 d5 orbitals including the
nearest-neighbour interactions and spin-orbit coupling, that accurately determines the electronic

a Electronic mail: [email protected]

2158-3226/2013/3(5)/052111/6 3, 052111-1 
C Author(s) 2013
052111-2 Zahid et al. AIP Advances 3, 052111 (2013)

structures of bulk, monolayer and bilayer MoS2 . A reliable and accurate target band structure is
the primary requirement for a successful tight-binding modeling. For the calculations of the target
band structures we employ density functional theory (DFT) with the screened hybrid functional of
Heyd, Scuseria, and Ernzerhof11 (HSE) that has been shown in the literature12–14 to produce accurate
band gaps and reasonable effective masses for a wide range of semiconductors. Our calculated band
structures of MoS2 from the self-consistent DFT-HSE shows excellent agreement with the available
experimental data and compare well with other theoretical studies.15–17 Even though an accurate
target band structure is obtained by DFT-HSE, it is nontrivial to develop a generic TB model which
can accurately capture electronic structures and effective masses of not only bulk MoS2 but also its
double-layer and single-layer forms. For the layered TMDC structures there is a thickness dependent
interlayer interaction that significantly affects the electronic properties, the TB model must capture
these effects so as to be applicable to devices made of different layer thicknesses. As shown below,
our generic TB model accurately produces the band structures for three different forms of MoS2 :
bulk, monolayer and bilayer. The reported TB model can be easily extended to other MoS2 structures
of higher number of layers as well as other layered TMDC materials such as WS2 , WSe2 , and MoSe2 .
The accuracy of our TB model is validated by comparing the band gaps and effective masses with
our calculated ab initio results.
In our study, all the DFT-HSE calculations are performed using the projector augmented-wave
(PAW) pseudopotential plane-wave method as implemented in the VASP software package.18 A
Monkhorst-Pack scheme is adopted for the sampling of the Brillouin zone with k-point meshes of
7 × 7 × 2 for the bulk and 9 × 9 × 1 for the two-dimensional (2D) structures. An energy cutoff of
280 eV is used in a plane wave basis set. We also included the spin-orbit coupling self-consistently.
Due to the presence of van der Waals interaction which determines the interlayer distance in MoS2 ,
geometry optimization becomes quite tricky and complicated. Without the van der Waals intereaction
the lattice parameter c (vertical length of the unit cell) is overestimated by a large margin. However,
it is not yet possible to include van der Waals interaction in the HSE calculations, and it is an area of
active research. We therefore optimize the bulk crystal structure using the Perdew-Burke-Ernzerhof
(PBE) functional19 for which the van der Waals interaction can be included explicitly by adopting the
DFT-D2 method.20 We then use this optimized structure for the HSE calculations. The values of our
optimized lattice parameters for bulk MoS2 are: a = 3.179 Å and c = 12.729 Å with a layer thickness
of 3.135 Å (S-S vertical distance). Although the value of c parameter improves significantly with
the DFT-D2 method, it is still overestimated by around 3.6% compared to the experimental value.
It is a well-known fact that DFT within the local density approximation (LDA) or the generalized
gradient approximation (GGA) underestimates band gaps of semiconductors due to factors such as
the self interactions. This error can be minimized in the HSE scheme of hybrid functional method11
by incorporating 25% short-range (SR) exact Hartree-Fock (HF) exchange with the PBE functional.
A screening parameter μ defines the range separation, and is empirically set to 0.2 Å−1 (HSE06
scheme) for both the HF and PBE parts. In our calculations for MoS2 we observe that the band gap
energies vary significantly with the screening parameter for both the bulk and the 2D structures. We
therefore decided to adjust the value of μ to fit the experimental band gap, and an optimize value
for μ is found to be 0.4 Å−1 which corresponds to an interaction range of π /μ = 7.85 Å for the
SR nonlocal exchange. Note that a single value of μ is used for all the three structures of MoS2 :
bulk, double-layer and single-layer, namely the HSE results presented here were all obtained using
μ = 0.4 Å−1 .
Our calculated band structure results for MoS2 are plotted in Fig. 1. As observed in previous
studies15, 16, 21 we also notice from our DFT-HSE calculations that the monolayer MoS2 has a direct
band gap at the K point whereas an indirect band gap opens up due to the presence of interlayer
interactions in the bilayer and the bulk structures. Although both bulk and bilayer MoS2 have indirect
band gaps the conduction band minima (CBM) are located at different points: for bulk it is at 
point (midpoint of  and K points) and for bilayer it is at K point. Similar behavior is observed
in a previous theoretical study.15 For monolayer MoS2 the splitting of the valence band maximum
(VBM) at K point is solely due to the spin-orbit coupling (SOC) whereas a combination of SOC
and interlayer interactions is responsible for the VBM splitting in bulk and bilayer MoS2 . With
the self-consistent calculations of the spin-orbit effects within the DFT-HSE model we obtain a
052111-3 Zahid et al. AIP Advances 3, 052111 (2013)

1L 2L

Bulk

FIG. 1. Band structures for monolayer (1L), bilayer (2L), and bulk MoS2 using screened hybrid density functional theory
(blue lines) and our tight-binding fitting (red dots). The zero in the energy axis is set at the Fermi level as shown by the dashed
line. Spin-orbit coupling is included in the calculations self-consistently.

TABLE I. Band gap energies obtained by DFT-HSE and our TB model. The fifth column is the deviation between the HSE
and the TB values. Experimental data is shown in the sixth column, taken from Ref. 22 (for bulk) and Ref. 1 (for monolayer
and bilayer). All the energies are in the unit of eV. Subscripts v and c stand for valence band and conduction band, respectively.
The splitting of the valence band maximum at K point is given by Kv1 (top) and Kv2 (bottom), whereas  is the midpoint of
the line joining the  and the K points.

Structure Gap HSE (target) TB (fitted) Deviation (%) Exp.

Monolayer Kv1 to Kc 1.786 1.805 1.06 1.90

Kv2 to Kc 1.974 1.969 0.24 2.05
Bilayer v to Kc 1.480 1.516 2.41 1.60
Kv1 to Kc 1.779 1.792 0.76 1.88
Kv2 to Kc 1.980 1.987 0.35 2.05
Bulk v to  c 1.328 1.331 0.22 1.29
Kv1 to Kc 1.776 1.749 1.46 1.88
Kv2 to Kc 1.960 2.009 2.46 2.06

split-off value of 188 meV for the VBM at K point for monolayer MoS2 , which is comparable to
the experimental value of 150 meV. The splitting of CBM due to SOC is minimal (around 5 meV).
The calculated band gap energies for different transitions are presented in Table I. Our DFT-HSE
results show good agreement with the experimental data. The values of effective masses at different
band edges along different directions as presented in Table II also compare well with other available
theoretical studies.15, 17
With the calculated DFT-HSE band structures as target, we employed the Nanoskif23 software
package to obtain a set of TB parameters for the on-site energies, the Slater-Koster energy integrals,
052111-4 Zahid et al. AIP Advances 3, 052111 (2013)

TABLE II. Values of effective masses at various band edges in the unit of free electron mass (m0 ) calculated using the HSE
method and our tight-binding model. The subscripts l and t refer to the masses calculated at the point along the longitudinal
and the transversal directions of the line connecting the  point and that point, respectively.

Electron Hole
Structure Point HSE (target) TB (fitted) Deviation (%) HSE (target) TB (fitted) Deviation (%)

Monolayer Kl 0.407 0.430 4.58 0.485 0.463 4.54

Kt 0.404 0.426 5.45 0.480 0.458 4.58
Bilayer  1.039 1.321 27.91
Kl 0.430 0.457 6.28
Kt 0.423 0.454 7.33
Bulk  0.785 0.917 16.82
l 0.574 0.712 24.04
t 0.819 0.999 21.98

TABLE III. Tight-binding parameters for MoS2 using non-orthogonal model with sp3 d5 orbitals, nearest-neighbour interac-
tions, and spin-orbit coupling: on-site energies (E), spin-orbit splitting (λ), Slater-Koster energy integrals (E1 for intra-layer
and E2 for inter-layer interaction) and overlap integrals (O1 for intra-layer and O2 for inter-layer interaction). The energies
are in the unit of eV.

Es Ep Ed λSO
S 7.6595 −2.1537 8.7689 0.2129
Mo 5.5994 6.7128 2.6429 1.0675
E1 (S,Mo) E1 (S,S) E2 (S,S) E1 (Mo,Mo) O1 (S,Mo) O1 (S,S) O2 (S,S) O1 (Mo,Mo)

ssσ −0.0917 0.3093 0.3207 0.1768 0.0294 −0.0532 −0.1430 −0.0575

spσ 0.6656 −0.9210 −0.1302 1.0910 0.1042 0.0240 0.0196 0.0057
psσ −1.6515 0.1765
ppσ 1.4008 0.7132 0.7053 −0.3842 −0.1865 0.0478 −0.0486 0.0296
ppπ −0.4812 −0.1920 −0.0980 0.5203 0.0303 −0.0104 0.0117 0.0946
sdσ 0.2177 −0.2016 0.1164 −0.5635 −0.0480 0.0946 0.0297 −0.1082
dsσ −1.0654 −0.1432
pdσ −2.8732 −0.5204 −0.0334 −0.2316 0.0942 0.0724 −0.0087 0.0212
dpσ 2.1898 0.2002
pdπ 0.7739 −0.1203 −0.0370 0.0582 0.0132 0.0772 −0.0031 −0.0448
dpπ −1.9408 −0.2435
ddσ −3.1425 0.8347 −0.2300 0.3602 0.0273 0.1849 0.0060 −0.0216
ddπ 2.4975 0.7434 0.0050 0.0432 0.1940 −0.0429 −0.0378 −0.0285
ddδ −0.3703 −0.1919 −0.1104 0.1008 0.1261 −0.0333 0.0007 0.0432

overlap integrals,24 and the spin-orbit splitting.25 In our TB model we adopted a non-orthogonal basis
set of sp3 d5 orbitals considering only the nearest neighbour interactions. The effects of spin-orbit
coupling is included through a split-off energy term. A set of 96 parameters are optimized through
the automated process built in Nanoskif.23 The root-mean-square deviation of the fitting is within 25
meV. The optimized TB parameters are listed in Table III. Note that this single set of TB parameters
is capable of producing accurate band structures of all three different forms of MoS2 .
The band structures obtained from our TB model are plotted in Fig. 1 along with those obtained
from DFT-HSE. The agreement in energies around both VBM and CBM for all three structures of
MoS2 is excellent. Fig. 2 shows the energy contours around the valence band maximum (VBM)
and the conduction band minimum (CBM) for the monolayer MoS2 . Again, we observe excellent
agreement in the shape of the energy contours from DFT-HSE and TB fitting. The band gap energies
for different transitions and the effective mass values at different symmetry points obtained from
the DFT-HSE and the TB model are presented in Table I and Table II respectively. For the band gap
energies a fitting accuracy of less than 2.5% is achieved. On the other hand, for the effective masses,
in most cases the deviations between the DFT-HSE and the TB values are less than 10% which is
052111-5 Zahid et al. AIP Advances 3, 052111 (2013)

VBM CBM

FIG. 2. Contour plots of the energies around the valence band maximum (VBM) and conduction band minimum (CBM) for
monolayer MoS2 from screened hybrid density functional theory (blue solid lines) and our tight-binding model (red dashed
lines). The contour lines are associated with E = ± 30
1
, ± 15
1
, ± 10
1
eV, respectively and the kx and the ky are in the unit
2π
of a , where a is the unit cell length.

quite acceptable. In four cases (excluding the monolayer structure) the deviations are higher with
the worst situation at ∼27.9%. Given that just a single set of TB parameters is used to produce the
band structurues of all three different forms of the material, this level of quantitative consistency is
rather satisfactory.
In conclusion, we have developed a generic TB model for accurately calculating the band
structures of bulk, monolayer and bilayer MoS2 . Our TB model is based on the Slater-Koster
method. For the optimization of the TB parameters, accurate target band structures are obtained
using the screened hybrid DFT method. The accuracy of our TB model is verified by comparing
the band gaps for different transitions and the effective masses at different band edges against the
ab initio band structures. One main feature of our TB model is that with only one set of parameters
it can reproduce the band structures of MoS2 of different structural configurations: from bulk
to 2D structures. Our tight-binding model can be easily extended to other TMDC materials that
show electronic characteristics similar to MoS2 . The TB model reported in this paper is useful for
simulations of quantum transport in nanoelectronic devices based on the TMDC materials.

ACKNOWLEDGMENTS
This work is supported by the University Grant Council (Contract No. AoE/P-04/08) of the
Government of HKSAR (FZ, JW), NSERC (HG) and IRAP (LL, YZ) of Canada. F.Z. would like to
thank Dr. Ji Wei and Mr. Darshana Wickramaratne for useful discussions on the VASP calculations.

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