Chapter # 4

4.1 Structural properties

The monolayer transition metal dichalcogenides (TMDCs) chemical formula is MX 2
where (M=Mo, W and X=S, Se, Te) exhibit hexagonal structure. The metal atom M is
bonded to six neighboring X chalcogen atoms. In other words the metal atoms are
sandwich between double layers of chalcogen atoms, which are covalently bonded,
while the individual layers are bonded through the van-der Walls interaction. The
single layer MX2 are basically found in two different phases, 2H-phase as displayed
in fig. 1 (a, b) with top and side view, and 1T-phase as depicted in fig. 1(c, d) with
top and side view. Both of these monolayers have different positions of chalcogen
atoms. In 2H phase, X atoms are located on top of other X atom (as shown in Fig. 1b)
whereas in 1T-phase, the X atom shifts from its normal position (as shown in Fig.
1d). It is further noted from literature that these single layer materials exhibit
semiconductor nature in 2H phase and metallic behavior in 1T phase and unstable at
room temprature. The 2H phase with semiconducting behavior is of great interest
due to its high stability at room temperature and various technological applications
in designing electronic and photonic devices [106].

Fig. 1. The top and side view of 2H-phase (a,b) and 1T-phase (c,d) respectively.
We optimized the lattice constant and relaxed the atomic positions for the
convergence of forces and energy, which agrees with previous theoretical findings
[107]. Further we apply 1% 2% 3% tensile/compressive strain and again relaxed the
atomic positions. The variation in lattice constant increases under the tensile while
decreases under compressive strain simultaneously, which is a very good agreement
with available theoretical data [20]. The M-X bond length of compounds increase
with the increase of tensile strain and decreases with the compressive strain. For
without strain the M-X bond length well agrees with ref. [107]. The X-X bond length
decreases gradually due to increase in tensile strain and increase with the
application of compressive strain.
4.2Electronic properties

4.2.1 Band structure

For investigation of electronic properties the band structure information of

compounds is very necessary. The band structure is shaped due to the electron wave
diffraction in crystalline solids. The energy gap of band structure differentiates
between the occupied and unoccupied states. The band structure of materials are
categorized in direct and indirect band gape on the basis of symmetry points of
Brillion zone. When the symmetry points of first Brillion zone lies at same position of
valance band maxima and conduction band minima, so this types of band structure
is called direct band gap, whereas in indirect band gap the symmetry points lies at
different position of valance band maxima and conduction band Maxima.

In present work the band structure is calculated for monolayer MX2 under the GGA
approximation. The band structure of MX2 monolayers are shown in Fig. 2,3,4 and 5.
The unstrained MX2 monolayer are found to be semiconductor with direct band gap
of 1.626 eV, 1.344 eV, 0.966 eV, 1.596 eV 1.27 eV and 0.791 eV respectively, which
shows a well agreement with available theoretical and experimental data [50, 107].
The valance band maxima (VBM) and conduction band (CBM) are located at K-point
of Brillion zone. The VBM is due to the M dx2y2, and dxy orbitalswith the minor
contribution of M dz2 and X p orbitals, whereas in CBM is due to the main
contribution of M dz2 orbital, which is shown in fig. 2 and 3.

In common the relaxation of structure under strain altered the bond angle/bond
length, which modifies the coupling power of orbitals, resulting the modification in
band structure. In general, under tensile strain the band are shrink of most
semiconductor because of increase in bond length and extended the band gap under
the compressive strain due to decrease in bond length. Which produce the variation
in coupling and result the splitting between the orbitals.

When we apply 1, 2, 3 percent tensile strain the bond M-X bond length increases and
direct band gap reduces due to the weakens of coupling between X p and M d z2
orbitals. At 1%tensile strain the band gap of MX2 reduces to 1.5 eV, 1.26 eV, 0.890 eV,
1.469 eV, 1.169 eV and 0.690 eV correspondingly. The reduction in band gap at 2
percent tensile strain is 1.330 eV, 1.177 eV, 0.823 eV, 1.350 eV, 1.05 eV and 0.605 eV
respectively. We also noted the reduction of band gap at 3 percent tensile strain
which is mention in table 2.

Fig. 2 band structure of MoS2 (1st row) MoSe2 (2nd row) and MoTe2 (3rd row) with 1, 2,
3 percent tensile strain.
Fig.3 Band structure of WS2 (1st row) WSe2 (2nd row) and WTe2 (3rd row) with
unstrained, 1, 2 and 3 percent tensile strain.

As the M-X bond length decreases under the compressive strain (1, 2, 3 percent),
which enhance the coupling of orbitals, result the splitting between the orbitals at K-
point point, but diminishes it alongside of Г-K direction. In case of 1% compressive
strain the band gap of MoS2, MoSe2 and MoTe2 increases to 1.696 eV, 1.427 eV and
1.050 eV respectively along k-point, whereas the WS2, WSe2 and WTe2, band gap
reduces to 1.558 eV, 1.250 eV, and 0.875 eV along Г-K direction, which indicate the
transition from a direct to an indirect band gap. At 2 % compressive strain the MoS 2,
MoSe2, and MoTe2 also make a transition from direct to an indirect, the indirect band
gap of MX2 reduces to 1.696 eV, 1.380 eV, 1.040 eV, 1.496 eV, 1.207 eV and 0.837 eV
respectively along the Г-K point. At 3% compressive the band gap of MX 2 more and
more reduces to 1.628 eV, 1.328 eV, 0.987 eV,1.451 eV 1.169 eV, 0.798 eV along Г-K
point. These all variation in case of compressive strain are shown in fig. 3, 4.
Fig. 3 band structure of MoS2 (1st row) MoSe2 (2nd row) and MoTe2 (3rd row) with 1, 2,
3 percent compressive strain.
Fig.4 band structure of WS2 (1st row) WSe2 (2nd row) and WTe2 (3rd row) with 1, 2, 3
percent compressive strain.

The mobility μ=eτ/meff is determined with using the relaxation time of 1 ×10−13 s [110]
for MoS2,5.7 ×10−15 s [59] for MoSe2, 3.72 ×10−14 s for WS2 [57], 1.6 ×10−13 s for WSe2
[59] and 1.9 ×10−13 s for WTe2 [20]. Under the tensile/compressive strain the variation
in mobility is also noted. The calculated mobility yielding from 0.005 m 2V-1s-1 to
0.477m2V-1s-1, which summarized in table 2.

Compression unstraine Tensile

d
3% 2% 1% 0% 1% 2% 3%
MoS2 Eg 1.628 1.696 1.743* 1.626* 1.500 1.330 1.110
μ 0.092 0.087 0.083 0.092 0.097 0.109 0.135
MoSe2 Eg 1.328 1.380 1.427* 1.344* 1.265 1.177 1.080
μ 0.005 0.005 0.005 0.005 0.006 0.006 0.007
MoTe2 Eg 0.987 1.040 1.050* 0.966* 0.890 0.823 0.755
μ
WS2 Eg 1.451 1.496 1.558 1.596* 1.469 1.350 1.178
Μ 0.038 0.036 0.034 0.034 0.036 0.040 0.046
WSe2 Eg 1.169 1.207 1.250 1.275* 1.169 1.056 0.957
μ 0.187 0.187 0.175 0.165 0.187 0.216 0.046
WTe2 Eg 0.798 0.837 0.875 0.791* 0.690 0.605 0.526
μ 0.303 0.303 0.278 0.303 0.371 0.417 0.477

Table 2. Band gap (in eV), Eg represent indirect accepted those marked with star (*),
and mobility μ (in m2V-1s-1).

4.2.2 Density of states (DOS)

The density of states (DOS) of a compound is the amount of accessible electron states
per unit energy. The DOS is responsible for the electronic nature of materials. The
MX2 DOS plots are shown in figure 6,7,8,9. Which provide us the information about
the contribution of different energy states in conduction and valance band
formation. In figures the negative energy of DOS represents valance band while the
positive energy represent the conduction band.

The MX2 unstrained monolayer are all direct band gap semiconductor nature with
VBM and CBM at k-point of the first Brillion zone. The main contribution to the DOS
is the d (black) orbital of M atom and p (magnita) orbital of X atom. Considering the
partial density of states (PDOS), we conclude that VBM and CBM are essentially due
to the dz2 (red) and dx2y2 + dxy (green) orbital of d-block M atoms (Mo and W) and p
(magnita) orbital of p block X atoms (S, Se, and Te). While the d xy+dyz orbital of M
atom do not take any part to the edges of band structure due to the strong coupling
with the p (magnita) orbital of X atom which is clearly shown in figures of DOS.

In fig. 6 and 7 the first column shows unstrained density of states of MX 2, in which
the valance band maxima occur due to dx2y2 +dxy (green), with the miner contribution
of dz2 (red) and p (magnita) orbitals along k-point. While the CBM is due to the main
contribution of dz2 orbital along k-point. At 1 percent tensile strain the M-X bond
length increases, which modulate the DOS of MX 2 shown in fig. 6,7 2nd column. The
1% tensile strain weakens the coupling between X-p and M-d z2 orbitals, which
reduce the splitting between bonding and antibonding states at k-point of first
Brillion zone. At 2 and 3 percent tensile strain the bond length decreases
respectively, which produce the more and more weakness in coupling of X-p and M-
dz2 orbitals, result the reduction in bonding and antibonding states K direction
respectively, which is summarized in fig. 6,7 by 3rd and 4th column.
Fig. 6 Partial density of states of unstrained MoS2, MoSe2 and MoTe2 with 1, 2 and 3
percent.
Fig. 7 Partial density of states of unstrained WS2, WSe2 and WTe2 with 1, 2 and 3
percent tensile strain.

In fig. 8 and 9 the 1 first column are already explained in above figures. At 1 percent
compressive strain (2nd column) the bond length decreases which modulate the DOS
of MX2. From figures the coupling between X-p and M-dz2 orbitals become stronger,
which enhance the splitting between the bonding and antibonding states along K-
point, while the coupling between X-p and M-dx2y2 + dxy become weaker, which
reduces the splitting between bonding and antibonding along Г-K direction, which is
responsible for the phase transition from direct to indirect band gap of WS 2, WSe2
and WTe2, while the MoS2, MoSe2 and MoTe2 are direct band gap nature. At 2 and 3
percent compressive strain (3rd and 4th column) the coupling between X-p and M-dz2
orbitals more and more become stronger which enhance the splitting among the
bonding and antibonding states at k-point. On the other hand the coupling between
the X-p and M- dx2y2 + dxy orbital becomes weaker and weaker, which reduces the
splitting among bonding and antibonding states along Г-K direction, due to which
MoS2 and MoSe2 MoTe2 are also make phase transition from direct to indirect at 2
and 3 percent respectively.
Fig. 8 Partial density of states of unstrained MoS2, MoSe2 and MoTe2 with 1, 2 and 3
percent compressive strain.

Fig. 9 Partial density of states of unstrained WS2, WSe2 and WTe2 with 1, 2 and 3
percent compressive strain.