Chemical Physics 527 (2019) 110499

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Chemical Physics
journal homepage: www.elsevier.com/locate/chemphys

Tuning the electronic structure of 2D materials by strain and external T

electric field: Case of GeI2 monolayer
D.M. Hoata,b, , Tuan V. Vuc,d, Mohammed M. Obeide, Hamad R. Japporf
⁎

a
Computational Optics Research Group, Advanced Institute of Materials Science, Ton Duc Thang University, Ho Chi Minh City, Viet Nam
b
Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, Viet Nam
c
Division of Computational Physics, Institute for Computational Science, Ton Duc Thang University, Ho Chi Minh City, Viet Nam
d
Faculty of Electrical and Electronics Engineering, Ton Duc Thang University, Ho Chi Minh City, Viet Nam
e
Department of Ceramic, College of Materials Engineering, University of Babylon, 51002 Hilla, Iraq
f
Department of Physics, College of Education for Pure Sciences, University of Babylon, Hilla, Iraq

ARTICLE INFO ABSTRACT

Keywords: Strain and external electric field effect on electronic structure of GeI2 monolayer has been investigated using first
GeI2 monolayer principles calculations. The obtained results indicate that GeI2 monolayer is an indirect semiconductor with band
Strain engineering gap value of 2.188 eV. With biaxial strain, the band gap of considered material increases slightly with com-
External electric field pression up to −6% and then it decreases and shows abrupt drop for strain −9% to −12%, whereas it just
Electronic structure
shows decreasing trend with tensile strain. In case of uniaxial strain, the band gap value increases nearly linearly
under the effect of considered strain range. The weak external electric field has no significant effect on the band
gap of GeI2 monolayer, while with E = ± 0.6 (eV/Å/e), the band gap decreases considerably as I-6s state in
conduction band moves to the lower energy levels.

1. Introduction bulk layered-structure compounds have been widely employed to iso-

Perhaps, one of the most memorable and important milestone of the
science is the successful exfoliation of graphene, a two-dimensional
(2D) sheet of sp2 -hybridized carbon, in 2004 by Novoselov and colla-
borators [1]. Graphene possesses exceptional chemical and physical
properties but the unexpected zero-gap semiconductor nature has lim-
ited so much its technological applications [2,3]. Therefore, geat effort
of scientific community has been devoted to the band gap opening of
graphene by different methods in order to make it more suitable for
applications [4,5]. Parallelly, the discovery of graphene also has
aroused interest in 2D materials which have received huge attention. So
far, some wide band gap semiconductor 2D materials have been ex-
tensively investigated, for examples, metal dichalcogenides and
monodichalcogenides [6–10].
Germanium (II) iodide was experimentally synthezided by E. Urgiles
et al. [11]. It was reported to crystallize in hexagonal layered-structure,
space group P3m1 (No. 164). H. Ozisik et al. [12] studied the structural,
elastic, and lattice dynamical properties of GeI2, they found that this
compounds is mechanical and thermodynamically stable, and it has
direct band gap of 1.72 eV. The mechanical and liquid exfoliation of
late two-dimensional materials. [13,14]. The layered semiconducting
GeI2 shows low cleavage energy (0.16 J/m2) which is lower than that of
the graphite, thus the isolation of monolayer GeI2 could be experi-
mentally feasible. The monolayer GeI2 can be appropriate for operation
at high temperature due to its thermally stable at high temperature
(600 K). Furthermore, the light absorption of GeI2 monolayer in the
spectral range between 240 and 650 nm makes it potential candidate in
the future electronic and ultraviolet optoelectronic devices, that em-
ployed under ultraviolet and blue light [15]. Recently, Chun-Sheng Liu
et al. [16] predicted theoretically the dynamic, electronic and optical
properties of GeI2 monolayer which could be exfoliated from its bulk
counterpart. It was reported that this 2D material is dynamically stable,
a semiconductor with band gap of 2.59 eV and can be promising can-
didate for application in optoelectronic devices. The authors also found
that the semi-hydrogenation on the GeI2 surface motivate the trans-
formation from semiconductor (nonmagnetic) to ferromagnetic half-
metal, which makes it promising material for spintronic applications.
Based on both experimental and theoretical studies, it has been de-
monstrated that the electronic properties of 2D materials can be con-
siderably tuned by the strain and external electric field engineering

Corresponding author at: Computational Optics Research Group, Advanced Institute of Materials Science, Ton Duc Thang University, Ho Chi Minh City, Viet Nam.
⁎

E-mail addresses: dominhhoat@tdtu.edu.vn (D.M. Hoat), vuvantuan@tdtu.edu.vn (T.V. Vu), m.obeid8686@gmail.com (M.M. Obeid),
hrjms@yahoo.com (H.R. Jappor).

https://doi.org/10.1016/j.chemphys.2019.110499
Received 29 April 2019; Received in revised form 9 June 2019; Accepted 15 August 2019
Available online 17 August 2019
0301-0104/ © 2019 Elsevier B.V. All rights reserved.
D.M. Hoat, et al. Chemical Physics 527 (2019) 110499

[17–21]. However, to the best of our knowledge, the effect of these two
factors on the electronic properties of GeI2 monolayer has not been
studied well, so far.
In this work, we systematically investigate the electronic properties
of GeI2 monolayer under applied strain and external electric field using
DFT calculations. The structure of the paper is as follow: In Section 2,
the employed method and computational parameters are briefly de-
scribed. In Section 3, the obtained results are presented and discussed in
details. Finally, remarkable results are summarized in Section 4.

2. Methodology and computational parameters

First principles calculations based on the pseudopotential plane-

wave method [22], as implemented in the Cambridge Serial Total En-
ergy Package (CASTEP) [23], have been carried out for investigating
the electronic properties of GeI2 monolayer under different strains and (a) Top-view
external electric fields. To avoid the interation between layers, a va-
cumm of 15 (Å) was used. Generalized gradient approximation with
Perdew-Burke-Ernzerhof (GGA-PBE) scheme [24] was adopted for the
treatment of exchange-correlation potential. Moreover, the ion-electron
interaction was treated with the norm-conserving pseudopotential.
Weak van der Waals interactions were described with the empirical
(b) side-view
dispersion correction DFT-D method as proposed by Grimme et al. [25].
3d10 4s 2 4p2 and 4d105s 25p5 were treated as valence states for Ge and I Fig. 1. Top- and side-view of atomic structure of GeI2 monolayer (Gray balls:
atoms, respectively. Cut-off energy for the expansion of plane waves Ge; Blue balls: I).
was set to be 500 (eV). Tolerance for total energy was selected as
2 × 10 7 eV/atom.
Theoretically, it is well known that GGA-PBE functional under-
estimates the band gap of solids. In this work, we focus our study
mainly on the variation trend of electronic structure of GeI2 monolayer
under applied strain and external electric field. Therefore, the PBE
functional was employed for all calculations because it has been proven
that this functional describes very well the band structure profile of
crystalline solids.

3. Results and discussion

GeI2 monolayer has hexagonal symmetry belonging to the P3m1

space group (No. 164). Its structure consists of a stacking of three
atomic layers I-Ge-I. In Fig. 1, its atomic structure is displayed. The
optimized lattice parameters of studied material are a = b = 4.179 (Å)
and its thickness is d = 3.527 (Å) which agree well with the previously
obtained theoretical results [16]. At equilibrium, the interatomic dis-
tance Ge-I is 2.988 (Å). The phonon dispersion relations are used for
examining the dynamical stability of materials, those with soft phonons
modes possess the dynamical stability and vice verse. In Fig. 2, the
phonon dispersion spectrum of GeI2 monolayer is illustrated which
confirms that this material is dynamically stable as there are not ima-
ginary phonon modes in the plot. The effect of biaxial xy and uniaxial z
strain was investigated by varying the lattice constant of the monolayer
a and its thickness d, respectively, which is definied as:
a a0
xy = × 100
a0 (1)
d d0
z = × 100
d0 (2)
Here subscript “0” indicates the parameters at equilibrium. The studied
range is from −12% to 12% with step of 3%. Theoretical studies have
proven that the 2D monolayers can bear high strains [26]. Previous
studies have indicated that the maximum strains which iodides can take
are ranging between −20% to 20% [27–29]. Our discussion is within
this range. By measuring the interatomic distance Ge-I, we observe that
this parameter increases as increasing the strain value being
2.760(2.869) (Å) and 3.227(3.118) (Å) at xy ( z ) = −12% and
xy ( z ) = 12%, respectively. Our obtained results do obey the well
Fig. 2. Phonon dispersion curve of GeI2 monolayer.
known strain-dependence of bond length in 2D materials [30]. It seems
that the Ge-I bond length is more affected by the compressive biaxial
strain than by tensile biaxial and uniaxial strains.
Fig. 3 shows the electronic band structure, total and partial density
of states (TDOS and PDOS) of the unstrained GeI2 monolayer. The band
structure is calculated in high symmetry direction M K of
Brillouin zone (See Fig. 3). The profile of obtained band structure im-
plies that considered material is an indirect semiconductor as the
maximum of valence band is located at K -path, while the minimum of
conduction band is found at point. The calculated band gap is
2.188 eV which is consistent with the previously estimated value [16].
From the figure, it can be seen that in the energy range from −6.5 eV to
6.5 eV, the valence band is dominated mainly from I atom with a small
contribution from Ge atom, while both atoms contribute to the con-
duction band. Specifically, the upper part of valence band is dominated
mainly by the I-5p, while the lowest partition of conduction band is
generated mainly from the Ge-4p state. One can see that the higher
partition is constructed from the unoccupied I-6s orbital. It seems that
there is a slight hybridization between Ge-4p and I-5p orbitals as they

2
D.M. Hoat, et al. Chemical Physics 527 (2019) 110499

Fig. 3. Selected k-path in Brillouin zone; Band structure and density of states of GeI2 monolayer without strain and external electric field.

(a) xy-strained

(b) z-strained

(c) Electric field

Fig. 4. Band structure of GeI2 monolayer under strain and applied electric field.

3
D.M. Hoat, et al. Chemical Physics 527 (2019) 110499

appear at almost same energies in both valence and conduction bands.
Fig. 4a and b show the band structure of GeI2 monolayer under the
effect of different bi- and uniaxial strains −12%, −6%, 6%, 12%. It is
important to note that in all cases, the maximum of valence band is
located at K -path, while the minimum of conduction band occurs at
point similar to that of the unstrained one, with only one exception
when the biaxial strain equal to −12%, the bottom of conduction band
is situated at K -path. The band gap values Eg are strongly varied by
the applied strains. Fig. 6 shows the strain dependence of this para-
meter as function of both biaxial and uniaxial. One can see that Eg in-
creases for compressive biaxial strains up to −6% where its maximum
value reaches 2.260 eV, from this strain it shows a decreasing trend,
and an abrupt drop is observed from xy = −9% (Eg = 2.225 eV) to
xy = −12% (Eg = 1.802 eV).Theses results show very similar trend to
those of PbI2 monolayer, which can be attributed to the elastic and
mechanical unstability of the monolayer at compressive strains higher
than −10% [27]. However, our results show that the electronic band
gap of GeI2 still can be effectively modulated with the biaxial strain
from −10% to 10%. With biaxial strain range between [−6% – 12%],
Eg decreases almost linearly and under applied xy = 12%, Eg value is
2.041 eV. A similar trend has been found for PbI2 monolayer [31]. On
the other hand, the band gap of GeI2 monolayer increases linearly
under uniaxial strain from −12% (Eg = 1.762 eV) to 12%
(Eg = 2.523 eV), which presents change of −19.47% and 15.31% as
compared to the unstrained GeI2 sheet. It seems that band gap of GeI2
mono-sheet shows higher dependence on uniaxial strain than on biaxial
one. In Fig. 5a and Fig. 5b, the TDOS and PDOS of GeI2 monolayer
under strains are displayed. In general, the contribution of each state
aforementioned is similar as compared with case of unstrained studied
material. But we can observe three clear strain-dependent behaviors: (i)
the spreading energy range of valence band increases according rising
the strain values, for example, from −6.5(-4.75) eV to 0 eV in case of
xy ( z ) = −12%, and from −2.5(-3.8) eV to 0 eV if xy ( z ) = 12%, it
seems that the biaxial strain shows more significant role on spreading
range of valence band than uniaxial; (ii) the density of states of each
constituent state increases with increasing the strain value and (iii) the
upper part of conduction band, which is formed mainly from I-6s state,
moves to the lower energy range as strain is varied from −12% to 12%,
this result shows the increasing trend of hybridization between I-6s and
Ge-4p states if the bond length Ge-I is reduced.
Now, we study the effect of external electric field E on electronic
structure of unstrained GeI2 monolayer. The applying dirrection is
perpendicular to the xy-plane (parallel to z-axis). Positive value of E
indicate that electric field direction is along z-axis and negative value
implies the opposite orientation. The obtained band structures of GeI2
monolayer under external electric field are given in Fig. 4c. Their
profile shows that there are no decisive change on the position of the
valence band maxima and the conduction band minima as compared to
that of pristine GeI2 monolayer in the absence of the electric field, that
is, they occur at K -path and point, respectively. In Fig. 6, the band
gap values Eg are plotted as a function of E. It can be noted that Eg
varies trivially for E range between −0.5 (eV/Å/e) (Eg = 2.177 eV) and
0.5 (eV/Å/e) (Eg = 2.177 eV). On the other hand, Eg decreases con-
siderably down to 2.110 eV and 2.020 eV under the effect of E = −0.6

(a) xy-strained

(b) z-strained

(c) Electric field

Fig. 5. Total and partial density of states of GeI2 monolayer under strain and applied electric field.

4
D.M. Hoat, et al.
Fig. 6. Variation of electronic band gap of GeI2 monolayer under applied strain
and external electric field.
(eV/Å/e) and E = 0.6 (eV/Å/e), respectively. This result demonstrates
that the electronic structure of GeI2 monolayer is not significantly af-
fected by weak electric field, while strong one can shorten its electronic
forbidden energy range, which is the well known behavior of 2D ma-
terials, for example silicene [32]. It is well known that van der Waals
(vdW) coupling in heterostructures has a significant impact on the band
shift where it can cause semiconductor-to-metal transitions under the
effect of electric field [33]. In our case, it is evident that vdW coupling
has trivial effect of the band gap shift. One may also observe that the
positive electric field is more effective than the negative one, therefore,
we can expect that semiconductor-to-metal transition may occur at
higher positive electric field (1.0 eV/Å/e). The plots of TDOS and PDOS
of GeI2 monolayer under applied E are given in Fig. 5c. In general, the
profile and energy range of constituent states are similar as compared to
the case of the absence of external electric field E, while the band gap
significantly decreases as I-6s state in conduction band shifts to lower
energy levels under the effect of stronger E. It seems that the mentioned
state is strongly affected by the applied external electric field and this is
the reason why the band gap drops rapidly for strong E (-0.6 and 0.6).
4. Conclusions
In summary, the electronic properties of GeI2 monolayer under
applied strain and external electric field have been studied using first
principles calculations based on the pseudopotential plane-wave
method. Our results indicates that this 2D material is an indirect
semiconductor with band gap of 2.188 eV and it is dynamically stable.
In the energy range from −6.5 eV to 6.5 eV, the Ge-4p, I-5p and I-6s
states are main contributor to the valence and conductions band. All
mentioned states are strongly affected by the biaxial and uniaxial
strains, while just I-6s state is influenced by the presence of external
electric field. The band gap of GeI2 monolayer shows strong depen-
dence on the applied strain, particularly, the uniaxial one. The obtained
band gap values slightly vary with the weak electric field between −0.5
to 0.5 (eV/Å/e), whereas an abrupt drop of this parameter has been
observed under the impact of a strong electric field (−0.6 and 0.6 (eV/
Å/e)). We hope that the obtained results in this work will be helpful for
future experimental and nanoelectronic practices.
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