Chapter # 4

Results And Discussions

4.1 Structural properties
MX2 is the chemical formula for monolayer transition metal dichalcogenides (TMDCs), which
have a hexagonal structure (M = Hf, Zr and X = S, Se). The metal atom M is bonded to six neighboring
X chalcogen atoms. In other words, metal atoms are sandwiched between double layers of
chalcogen atoms that are covalently bonded, while the individual layers are bonded through van-der
Wall interactions. The single layer MX2 can be found in two phases: 2H-phase (shown in fig. 1(a, b)
with top and side views) and 1T-phase (shown in fig. 1(c, d) with top and side views). The chalcogen
atoms are in different positions in both of these monolayers. In the 2H phase (as shown in Fig. 1b), X
atoms are stacked on top of one another, whereas in the 1T phase, the X atom shifts from its normal
position (as shown in Fig. 1d). According to the literature, these single layer materials have a
semiconductor nature in the 2H phase and a metallic behavior in the 1T phase, as well as being
unstable at room temperature. Due to its high stability at room temperature and various
technological applications in designing electronic and photonic devices, the 2H phase with
semiconducting behavior is of great interest [46].
 Fig. 1. The top and side view of 2H-phase (a,b) and 1T-phase (c,d) respectively.

For the convergence of forces and energy, we optimised the lattice constant
and relaxed the atomic positions, which agrees with previous theoretical findings
[107]. We then applied a tensile/compressive strain of 1%, 2%, and 3%, and relaxed
the atomic positions once more. The variation in lattice constant increases under
tensile strain while decreasing under compressive strain, which is in excellent
agreement with theoretical data [47]. Compounds' M-X bond length increases as
tensile strain increases and decreases as compressive strain increases. Without strain,
the M-X bond length closely resembles that of ref. [48]. The X-X bond length
decreases gradually as tensile strain increases and increases as compressive strain is
applied.

4.2 Electronic properties

4.2.1 Electronic structure

The Electronic band structure of compounds is very necessary for investigating

electronic properties. In crystalline solids, electron wave diffraction shapes the band
structure. The band structure's energy gap distinguishes between occupied and
unoccupied states. On the basis of Brillion zone symmetry points, materials' band
structures are classified as direct or indirect band gape. The symmetry points of the
first Brillion zone are at the same position of the valance band maxima and
conduction band minima in a direct band gap, whereas the symmetry points are at
different positions of the valance band maxima and conduction band minima in an
indirect band gap. The band structure of monolayer MX2 is calculated using the
GGA approximation in this present work. The unstrained MX2 monolayer are found
to be semiconductor with indirect band gap with 1.23 eV, 0.85 eV, 1.10 eV, and 0.80
eV respectively, which shows a well agreement with available theoretical and
experimental data [50, 51].
It is known that there is difference in Brillouin zones of bulk structures and monolayer
structures. Hence, the Brillouin zones with high symmetry k-points used in band structure
calculations are illustrated in Fig. 2.

The electronic structure of the monolayer IVB-VIA TMDs obtained by PBE method. It can be found
that they all belong to indirect band gap semiconductors, which are identical to the band gaps of
bulk structures. This feature is different from some other TMDs such as MoS2.

the values of the band gap of bulk crystal by hybridization functional theories are in good agreement
with experimental data, whereas the band gaps of some monolayer structures are overestimated to
some extent by hybridization functional theory It can also be found that from sulfur to selenium in
Group VIA, the band gaps decrease in both bulk and monolayer structures. Besides, in the case of
monolayer structures, the fundamental band gaps of HfS2 and HfSe2 are greater than that of ZrS2
and ZrSe2, respectively, while the band gaps for the bulk structures of ZrS2 and ZrSe2 are greater
than that of HfS2 and HfSe2, respectively. The change between bulk structures and monolayer
structures could be related to the electronegativity of bonded atoms and the interaction between
layers. Duffy et al. reveal the relationship between band gap and electronegativity of bonded atoms .
If the anion remains the same, the value of band gap is inversely proportional to the
electronegativity of cation. The layer–layer interaction also affects the states of bonded atoms and
cause the decrease of band gaps of bulk structures finally . The above two aspects may cause the
difference of band gaps between bulk structures and monolayer structures [49].

Figure 2 Brillion zone with high symmetry k-points used in band structure calculations of (a)
bulk structures and (b) monolayer structures.

The valance band maxima (VBM) and conduction band (CBM) are located at
K-point of Brillion zone. The VBM is due to the px , orbital with the minor
contribution of pz orbital, whereas in CBM is due to the main contribution of dxy
orbital and with the minor contribution dx2 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 2, 4, 6, 8, 10 percent compressive and tensile strain the bond M-X
bond length decreases and indirect band gap reduces due to the weakens of
coupling between X dxy and M p orbitals of the HfS2 monolayer. Applying 2%, 4%,
6%, 8% and 10% compressive strain the band gap of MX2 reduces from 1.23 eV to
0.96 eV, 0.88 eV, 0.86 eV, 0.82 eV and 0.70 eV correspondingly. Applying 2%, 4%,
6%, 8% and 10% tensile strain the band gap changes from 1.23 eV to 0.92 eV to 0.90
eV, 0.82 eV, 0.72eV, and 0.68 eV respectively.

new graph

Fig. 3 band structure of monolayer HfS2 (1st row compressive strain) and (2nd row
tensile strain).

New graph

When we apply 2, 4, 6, 8, 10 percent compressive and tensile strain the bond M-X
bond length decreases and indirect band gap reduces due to the weakens of
coupling between X dxy and M p orbitals of the HfSe2 monolayer. Applying 2%, 4%,
6%, 8% and 10% tensile strain the band gap of MX2 reduces from 0.85 eV to 0.82 eV,
0.78 eV, 0.74 eV, 0.72 eV and 0.62 eV correspondingly. Applying 2%, 4%, 6%, 8% and
10% compressive strain changes the band gap from 0.85 eV to 0.83 eV, 0.81eV,
0.74eV, 0.66 eV and 0.51 eV respectively.

Fig. 4 band structure of monolayer HfSe2 (1st row compressive strain) and (2nd row
tensile strain).

New graph

When we apply 2, 4, 6, 8, 10 percent compressive and tensile strain the bond M-X
bond length decreases and indirect band gap reduces due to the weakens of
coupling between X dxy and M p orbitals of the ZrS2 monolayer. Applying 2%, 4%,
6%, 8% and 10% compressive strain the band gap of MX2 reduces from 1.10 eV to
0.96 eV, 0.92eV, 0.88eV, 0.84 eV and 0.76 eV correspondingly. Applying 2%, 4%, 6%,
8% and 10% tensile strain changes the band gap from 1.10 eV to 0.88 eV, 0.80 eV, 0.76
eV, 0.54 eV and 0.50 eV respectively.

Fig. 5 band structure of monolayer ZrS2 (1st row compressive strain) and (2nd row
tensile strain).

New graph

When we apply 2, 4, 6, 8, 10 percent compressive and tensile strain the bond M-X
bond length decreases and indirect band gap reduces due to the weakens of
coupling between X dxy and M p orbitals of the ZrSe2 monolayer. Applying 2%, 4%,
6%, 8% and 10% compressive strain the band gap of MX2 reduces to 0.78 eV, 0.72 eV,
0.64 eV, 0.60 eV and 0.56 eV correspondingly. By applying 2%, 4%, 6%, 8% and 10%
tensile strain the band gap changes from 0.80 eV to 0.72 eV, 0.68 eV, 0.60 eV, 0.58 eV
respectivily.

Fig. 6 band structure of monolayer ZrSe2 (1st row compressive strain) and (2nd row
tensile strain).

New table

Lattice Minimum Band DSi-X DM-X

Monolayer constants energy gap (A) (M=Hf,Zr,X=S,Se) Geometry
(A) (RY) (ev) (A)
HfS2 a=b=3.63,c=2 -829.12 2.01 2.45 2.58 Buckle
5
HfSe2 a=b=3.75,c=2 -1075.14 1.23 - 2.70 Buckle
5
ZrS2 a=b=3.65,c=2 -440.09 0.85 - 2.60 Buckle
5
ZrSe2 a=b=3.77,c=2 -686.12 1.10 - 2.72 Buckle
5
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
information about the contribution of different energy states in conduction and
valance band formation. In figures thee negative energy of DOS represents valance
band while the positive energy represent the conduction band.

The MX2 unstrained monolayers are all indirect band gap semiconductors
nature with VBM and CBM at k-point of the first Brillion zone. The main
contribution for conduction of the monolayer HfS2, ZrS2, Hf’s and Zr’s dxy state and S’s px
state for valance band corresponded with blue and black colours accordingly. For the monolayer
HfSe2, ZrSe2 main contribution for the conduction band is by virtue of Hf’s and Zr’s d xy state and Se’s
px state for valance band corresponded with blue and black colours accordingly.

The monolayers HfS2, HfSe2, ZrS2 and ZrSe2 are all indirect band gap semiconductors with an
energy gap 1.23, 0.85, 1.10, and 0.23 at room temperature. In the indirect band structure the
valence band maximum (VBM) and conduction band minimum (CBM) are located at different
symmetry points in the Brillouin zone. On the other hand, for a direct band gap semiconductors the
VBM and CBM stay at the same symmetry point of the Brillouin zone. Due to these differences, the
two band structures differ in electron excitation recombination properties In the case of a direct
band gap semiconductor, a photon with similar energy to the band gap can be absorbed by the
system directly, while exciting a valence band electron to the conduction band. The reverse process
is also apt to happen. A photon is emitted when an electron in the conduction band falls back and
recombines with a hole in the valence band. On the other hand, for electron excitation of indirect
band gap materials, simultaneous absorption of a photon and a phonon (i.e. field quantum of lattice
vibration) is required for excitation. It lowers the efficiency of light absorption, and consequently the
recombination process is deferred greatly in comparison to the case of direct gap materials. band
structures of the monolayers HfS2, HfSe2, ZrS2 and ZrSe2 figure. Due to the aforementioned
characteristics of band structures, semiconductors with a direct band gap are featured in
applications such as light emitting diodes (LEDs) and laser diodes. Applications of indirect band gap
materials are limited by the temperature dependency in the excitation process. Silicon, however, is
an exception and establishes the current realm of field-effect transistors (FET) thanks to its moderate
band gap, native oxide layer, and abundance on earth
Figure band structure of the monolayers HfS 2, HfSe2, ZrS2 and ZrSe2

New graph
(TDOS )

In the total density of states we relate the band gap with the electronic band gap of
the HfS2,ZrS2,HfSe2 and ZrSe2 monolayers. In total density of state the band gap
matching with the electronic band gap of HfS2,ZrS2,HfSe2 and ZrSe2 monolayers so
the band gap of HfS2,ZrS2,HfSe2 and ZrSe2 monolayers is correct.
Fig. 7 total density of states of unstrained HfS2, ZrS2, HfSe2 and ZrSe2
PDOS

Figure (x) shows the partial density of states HfS2, ZrS2, HfSe2 and ZrSe2. In case of
the monolayer HfS2 (PDOS) indicate that the maximum contribution in valance band
is due to the S-px (black) state while the conduction band maximum is due to Hf-d xy
(blue) state.

In ZrS2 monolayer case (PDOS) indicate that the maximum contribution in valance
band is due to the S-px (black) state while the conduction band maximum is due to
Zr-dxy (blue) state.

In the third HfSe2 monolayer case (PDOS) indicate that the maximum contribution in
valance band is due to the Se-px (black) state while the conduction band maximum is
due to Hf-dxy (blue) state.

And in the fourth ZrSe2 monolayer case (PDOS) indicate that the maximum
contribution in valance band is due to the Se-px (black) state while the conduction
band maximum is due to Zr-dxy (blue) state respectivily.
Fig. 8 Partial density of states of unstrained HfS2, ZrS2, HfSe2 and ZrSe2
3.5. Photocatalytic properties
Hydrogen fuel cell technology is currently being researched for its potential as a pollution-
free source of energy. As a result, determining the capacity of materials for photocatalytic water
splitting is simple. It is thought to be a photocatalytic process in which the water molecule decouples
in a photoelectrochemical cell. Water's contribution is based on its renewable and cost-effective
nature. The valance and conduction band edge potentials (EVBM and ECBM), which are derived from
Mulliken electronegativity, are EVBM = - Eelec + 0.5Eg and ECBM = EVBM – Eg, respectively. On the
hydrogen scale, Eelec represents the standard electrode potential of 4.5 V, whereas represents the
geometric mean of component atoms. It's 0.5 times the sum of individual atoms' electron affinity
and first ionisation energy. 5.44 eV (SiS), 4.87 eV (Ti2CO2), 4.83 eV (Zr2CO2), 4.91 eV (Hf2CO2), 4.99
eV (SiS-Zr2CO2), and 5.05 eV (SiS-Zr2CO2) are the calculated values (SiS-Hf2CO2). It makes the world
a better place by meeting the world's energy needs.
[0000] Abid, Aqsa, M. Idrees, Haleem Ud Din, Qaisar Alam, Bin Amin, and Muhammad Haneef.
"Structural, electronic, optical, thermoelectric and photocatalytic properties of SiS/MXenes
van der Waals heterostructures." Materials Today Communications (2020): 101702.

The most important role for the development of modern society is energy storage and
conversion. Our reliance on fossil fuels, which are a finite and limited energy resource, has prompted
scientists to look for alternatives. Furthermore, these fuels emit energy, which contributes to
environmental pollution and climate change as the world's population grows. As a result of this
situation, we are looking for renewable and natural energy sources as long-term alternatives to our
current reliance on finite fossil fuels [1]. Water and sunlight must be used to produce hydrogen
through electrochemical or photocatalytic processes to meet rising global energy demands [1-2]. It's
worth noting that hydrogen is one of the most efficient energy carriers for storing and transporting
energy.

Dahl et al. [3] and Maeda et al. [4] have proposed that photocatalytic water splitting can be
used to generate clean hydrogen fuel. There must be 1.23 eV potential differences between the
anode and cathode during the electrochemical decomposition of water. Visible radiation, on the
other hand, has a slightly higher energy than the potential difference. To efficiently utilise solar
energy and split H2O to H2, a meaningful photocatalyst must have electronic band positions that
straddle the redox potentials, i.e. hydrogen evolution reaction (HER) and oxygen evolution reaction
(OER), and a gap less than 1.6 eV. The photocatalyst material is used in the photocatalysis process[5-
6].

Materials synthesis as photocatalysts can be divided into three generations. Metals show
ultraviolet-only absorption in the first generation, visible light absorption in the second generation,
and extended visible light absorption in the third generation for two-dimensional (2D) metals/non-
metals [2-4]. The first generation has a significant disadvantage in that its photon absorption window
is restricted to UV light only, implying low solar-to-hydrogen (STH) conversion efficiencies.

The efficiency of the second generation photocatalysts is poor due to inefficient charge
transfer kinetics, high recombination rate of photo-generated carriers, and instability in the
acidic/alkaline medium [7-12]. The oxides, sulphides, and nitride of titanium, cadmium, tungsten,
and other metals make up the first and second generations of photocatalysts. 3rd of 20 pages
Science and Technology of Catalysis Science and Technology of Catalysis Manuscript Accepted On
June 23, 2016, this article was published. University of California - Santa Barbara downloaded this on
the 24th of June, 2016 at 18:15:37. DOI: 10.1039/C6CY01172A4 DOI: 10.1039/C6CY01172A4
dichalcogenides of transition metals (TMDs). Because metal-based photocatalysts are toxic and
corrosive, they can only be used in the presence of precious metal co-catalysts (Pt, Au, Ag, etc.) [13].
Alternative elemental and compound photocatalysts have been investigated to overcome this
problem, with red-P, alpha-sulfur, and boron being reported as potential photocatalysts by
researchers [14-16]. Water splitting has been demonstrated experimentally on a titanium oxide
electrode [5, 17-18], and theoretical studies of layered transition metal dichalcogenides such as
MoS2, MoSe2, and TaS2 are being considered as potential candidates for catalysing solar water
splitting [19-22]. Furthermore, Zhuang and Hennig's theoretical study predicted that the monolayer
of group-III monochalcogenides would have ideal band edges for solar water splitting [23].

A significant advancement in research in this area has prompted us to look for materials that
are only a few atomic layers thick but are highly functional when compared to their bulk
counterparts. The structural, electronic, and electro-optical properties of two-dimensional materials
are abnormal [24-26]. Using first-principles calculations based on density functional theory, we
investigated the electronic, vibrational, and photocatalyst properties of hexagonal (1H) and trigonal
(1T) phases of HfS2 in this paper (DFT). On the standard hydrogen electrode (SHE) potential scale,
we determined the band position of edge energies and presented their relevance and suitability as
photocatalysts for water splitting in terms of water redox potentials.

[131313] Singh, Deobrat, Sanjeev K. Gupta, Yogesh Sonvane, Ashok Kumar, and Rajeev Ahuja. "2D-
HfS 2 as an efficient photocatalyst for water splitting." Catalysis Science & Technology 6, no. 17
(2016): 6605-6614.