PART A

1.1 Choice and introduction of field of research.

The choice of the topic for research is based on Electronic Properties of

Bulk and Monolayer Transition metal Dichalcogenides (TMDs)

Introduction of field of research

Transition metal dichalcogenides (MX2, M stands for transition metal and X stands
for chalcogen) are layered materials, which possess strong bonding in-plane and weak
bonding between planes (van der Waals). The first exploration of bulk transition metal
dichalcogenides (TMDs) was done decades ago. In the recent decades monolayers of
TMDs, as one kind of the representatives of two dimensional (2D) materials, have attracted
much attention owing to their rich physics and promising applications in nanoelectronics
and photonics. Significant amount of effort has been devoted to the synthesis of TMD
materials and as well to the exploration of their properties. Electronic properties of these
materials are of a great importance when it comes to applications. In general, the variation
of electronic properties of TMDs is determined by the variation of the band structure with
the transitions from bulk to monolayer.

Density functional theory (DFT) is a method of choice for theoretical exploration of

solids. The approximation of the exchange-correlation energy plays a key role in DFT
computations. So, various approximations of the exchange-correlation energy have been
developed starting with local density approximation (LDA) and generalized gradient
approximation (GGA), which allow accurate prediction of many ground state properties
including structural properties and stability. Unfortunately, the same is not always true for
the electronic properties, where the lack of correlation between experimental and theoretical
results could be found as the band gap could be significantly underestimated, and errors can
reach even 40%. The latter essentially complicates the theoretical search for new materials
with desired electronic properties
Transition metal dichalcogenides are promising materials for a wide range of applications

including energy storage, sensing, catalysis, and electronic devices such as field-effect

transistors. After exfoliation into mono or few-layers additional functionalities are created by

the spatial confinement of the electron system. For example, bulk MoS 2 and WS2 are indirect

band gap semiconductors, while monolayers show a direct band gap. Due to their distinct

electronic and optical properties, monolayers of MoS 2, MoTe2, WS2, and WS2 have already been

used in transistors, logic circuits, and memory cells. In addition, recent experiments confirm

that MoS2 and WTe2 can enhance catalytic activities. In general, strain is a useful tool to

improve device performances, because it changes the band gap as well as the effective mass and

mobility of the electrons.

Because 2D materials span the full range of electronic properties, they can be combined

to build various planar electronic devices with high performance, low power consumption, and

other desirable properties such as flexibility and transparency. Multilayered graphene is a

conductor, so it can replace bulk metals, such as aluminum and copper, in an integrated circuit.

In a bulk-metal wire carrying an AC signal, the current density is largest near the wire’s surface.

That so-called skin effect leads to power loss and heat dissipation. Theoretical analysis has

shown that the effect is diminished in multilayer graphene ribbons, which could be promising

for designing low-loss devices that can operate at ultrahigh frequencies and low power.

The semiconducting TMDs such as MoS2 and WSe2 have many desirable properties for low-

power devices; those properties include uniform thickness, atomically smooth surfaces without

dangling bonds, and relatively large bandgaps of 1–2 eV. Because the energy dispersions near

the band edges are parabolic in shape, a carrier transport in monolayer TMDs can be described

by effective-mass transport equations. Monolayer TMDs generally have larger effective carrier

masses than common bulk semiconductors do, so their density of states, which is proportional to
 the effective mass, is also large. As a result, monolayer TMDs have large mobile carrier

densities and thus can carry high currents.

1.2 Assumptions and techniques

Assumption

 The objective of this work is to study electronic properties of TMDs

such as MX2 (M=W; X=S/Se/Te)

 To determine the Band Structure, Density of states (DOS) and partial

density od states (PDOS)

 To study the carrier transport properties of TMDs such as MX2

(M=W; X=S/Se/Te)

 To understand and study the electronic and carrier transport

properties of bulk to monolayer TMDs

Techniques

Computational Details

The first principle density functional theory (DFT) calculations can be used in

QUANTUM ESPRESSO/VESTA/CASTEP/ package to calculate band structure, density of

states (DOS), projected density of states (PDOS) calculations and carrier transport

properties.

Density functional theory (DFT)

Basically it is computational quantum mechanical modelling method used to explore the

electronic structural properties of many body systems particularly in atoms, molecules and
of condensed phases (principally the ground states). Using DFT calculations we can
 determine the properties of various electron systems by implementing functionals. In DFT
calculations these functionals are dependent on the electron density which is a function of
space and time. By focusing on electron density one can possibly derive effective one
electron type Schrödinger equation.
Quantum ESPRESSO

Open source package used in the field of research in electronic structure, simulation and
optimization.

It is a computational quantum mechanical method implemented in Quantum ESPRESSO

package, used to investigate the electronic structure of elements with density of states
(DOS), projected density of states (PDOS), charge carrier effective mass (m*) can be
calculated using first principle DFT calculations at nanoscale.

List of following jobs can be done to predict various calculations,

1) Structural optimizations
2) Ground states calculations
3) Minimum energy paths and transition states
4) Spectroscopic properties
5) Ab initio molecular dynamics.

These calculations are based on density functional theory, plane waves, and pseudopotentials.

Pseudopotentials
The Pseudopotetials is an endeavour to supplant the complicated impacts on the
movement of core electrons which are basically non-valence electrons in a
particle and its core with successful potential so that the Schrödinger equation
contains an adjusted potential term rather than the coulombic potential term for
core electrons present within the Schrödinger equation. Potential made to built to
replace the nuclear electron potential so that the core states can be eliminated and
the valence electron are portrayed by pseudo-wavefunctions with significantly
less nodes.
 This allows us the psedopotentials to be shown with far less Fourier modes
therefore utilizing plane waves for the practical uses.
There are different types of pseudopotentials
1. Norm conserving
2. PAW pseudopotentials
3. ultra soft pseudopotentials.
1.3 Thesis appreciation

The selected thesis is very informative based on the topic of research and the
methodology which are explained was in detail.

The which are used in this particular field is well explained, the explaining
techniques are very useful and it is in detail.

The thesis is written and constructed in such a way that it can be easily
understandable. And by the list of content that they are mentioned are very clear and
understandable.

So that I can conclude after referencing to this thesis is that I is well designed in a
proper manner tool for studying.

1.4 Proposed title and aim

Proposed title:

Studying electronic structural and Carrier Transport properties of WSe2

and WSe2(1-x)Te2x

Proposed Aim:
 To study electronic structural and carrier transport properties of WSe2

and WSe2(1-x)Te2x using density functional theory(DFT)

PART B

2.1 Choice the specific topic of research and introduction

The choice of the specific topic of research is based on Electronic Structural and
Carrier Transport properties of WSe2 and WSe2(1-x)Te2x

Transition metal dichalcogenide (TMD) alloys have attracted great interest in recent
years due to their tuneable electronic properties and the semiconductor-metal phase
transition along with their potential applications in solid-state memories and thermoelectric
among others. However, the thermal conductivity of layered TMD alloys remains largely
unexplored despite that it plays a critical role in the reliability and functionality of TMD-
enabled devices. Intrigued by the unique electronic structures and the abundant phase
transition in MoTe2 and WTe2, MoTe2 or WTe2 based TMD alloys have also attracted
intensive research, especially on the manipulation of the physical properties through
controlling the phase transitions. . For example, the topological electronic states of W 2Mo1-
xTe2 can be effectively manipulated by the alloy composition. A hysteresis effect during the
1T’-to-Td phase transition of W2Mo1-xTe2 was observed, and the phase change can be tuned
to occur at room temperature. which makes it a promising material for phase change
memory devices.
Depending on the composition, WSe2(1-x)Te2x also exhibits a 2H-to-Td phase
transition, which can be used for bandgap tuning. Such phase transition in ternary TMD
alloys could be potentially exploited for optimizing thermoelectric performances. However,
there exists no study on how such a phase transition would affect the thermal transport
 properties along both the in-plane and cross-plane direction. WSe2(1-x)Te2x can be in both the
2H phase and the Td phase. When the Se atom occupies the majority of the chalcogen sites,
the TMD alloy shows a hexagonal 2H phase. A phase transition to the orthorhombic Td
phase would happen when the Te atom becomes the majority.

2.2 Collection of technical papers and justification of relevance of these

papers.

The articles which are selected are:

Article 1: Anisotropic thermal transport in van der Waals layered alloys

WSe2(1-x)Te2x [1](Qian et al., 2018)

Article 2: Tungsten Ditelluride: a layered semimetal [2](Lee et al., 2015)

Article 3: First-principles study of lattice thermal conductivity of Td-WTe2

[3](Liu et al., 2016)

Article 4 : Strain engineering of WS2, WSe2, and WTe2 [4](Amin et al., 2014)

Article 5: Pressure-induced Td to 1T' structural phase transition in WTe2

[5](Zhou et al., 2016)

Article 1 [1](Qian et al., 2018)

Justification:
The thermal conductivity of layered TMD alloys remains largely unexplored despite that it

plays a critical role in the reliability and functionality of TMD-enabled devices. A hysteresis
effect during the 1T’-to-Td phase transition of W2Mo1-xTe2 was observed, and the phase change
can be tuned to occur at room temperature which makes it a promising material for phase
change memory devices. Depending on the composition, WSe 2(1-x)Te2x also exhibits a 2H-to-Td
phase transition, which can be used for bandgap tuning.34 Such phase transition in ternary
TMD alloys could be potentially exploited for optimizing thermoelectric performances.
However, there exists no study on how such a phase transition would affect the thermal
transport properties along both the in-plane and cross-plane direction.

Article 2 [2](Lee et al., 2015)

Justification:
The physical and electronic properties of WTe 2 and other TMDs have been widely modeled for
their device performance as semiconductor materials based on a 2H structure, despite the fact
that experimental data and non-constrained geometry optimization using density functional
theory (DFT) provide strong evidence that WTe 2 has its lowest energy in a distorted 1T (Td)
structure, also called 1T’ Both 2H and Td structures have been reported in experimental studies
of WTe2, and recent reports have focused on the extraordinary magnetoresistance and
thermoelectric properties of Td-WTe2

Article 3 [3](Liu et al., 2016)

Justification:
The thermal transport properties are a key consideration to accelerate the application of
WTe2,
which are likely to demonstrate thermally limited performance. WTe2 is a semimetal which is
also a potential thermoelectric material and we can further improve its thermoelectric
performance by doping. The performance of thermoelectric materials depends on the figure of
merit ZT . One effective way to increase ZT is to reduce the thermal conductivity without
affecting electronic conductivity . Moreover, ultralow thermal conductivity is required to
prevent the back-flow of heat from the hot end to the cool one. Therefore, it is crucial to
search
for ultralow thermal conductivity materials in thermoelectric applications.

Article 4[4](Amin et al., 2014)

Justification:
Bulk MoS2 and WS2 are indirect band gap semiconductors, while monolayers show a direct
band
gap. Due to their distinct electronic and optical properties, monolayers of MoS2, MoTe2, WS2,
and2 have already been used in transistors, logic circuits, and memory cells. In addition, recent
experiments confirm that MoS2 and WTe2 can enhance catalytic activities. In general, strain is a
useful tool to improve device performances, because it changes the band gap as well as the
effective mass and mobility of the electrons. Hardening/softening of vibrational modes by strain
has been confirmed in two-dimensional materials by micro-Raman spectroscopy.
Article 5 [5](Zhou et al., 2016)

Justification:
The MX2 compounds can crystallize into various phases including 2H, 1T, 1T ′ and Td.
Accordingly, their physical properties are not only related to the sample thickness or
dimensions
but also determined by their crystalline structures. The well-studied hexagonal 2H phase
exhibits a transition from an indirect band gap to a direct one with thickness reduction down
to
monolayer, which can be applied in optoelectronic devices.

2.3 Review the three papers with own analysis/comments

Article 1: Anisotropic thermal transport in van der Waals layered alloys

WSe2(1-x)Te2x [1](Qian et al., 2018)

Assumptions:
This study focuses on the composition and temperature-dependent anisotropic thermal
conductivity of the van der Waals layered TMD alloys WSe2(1-x)Te2x in both the in-plane
direction (parallel to the basal planes) and the cross-plane direction (along the z-axis) using
time-
domain thermoreflectance measurements
Technique:
Author measured the anisotropic thermal conductivity of layered TMD alloys using a
femtosecond laser-based TDTR system . This system splits the femtosecond
laser into a pump beam and a probe beam. The pump beam is modulated by an electric-optical
modulator (EOM) at a typical frequency from 0.3 MHz to 10 MHz to create a periodic thermal
excitation on the surface of TMD alloy samples, where the surface of TMD alloy samples is
deposited with an aluminum metal thin film (75 nm).
Result:
They observed that the cross-plane thermal conductivity depends on the modulation
frequency
of the TDTR pump beam due to the non-equilibrium transport between different phonon
modes
in the cross-plane direction The in-plane thermal conductivity is then determined using a
tightly
focused laser spot with a radius of 4.2 lm. Both the in-plane and cross-plane thermal
conductivities are reduced at a higher alloy mixing level as the composition fraction x or (1–x)
in
WSe2(1-x)Te2x approaches 0.5.
Conclusion:
The temperature dependence of thermal conductivity for the TMD alloys becomes weaker
compared with the pristine 2H WSe 2 and Td WTe2 due to the atomic disorder. This work
serves
as an important starting point for exploring phonon transport physics in layered alloys.
Limitation:
The reason for the phase transition does not explain in the work

Article 2: Tungsten Ditelluride: a layered semimetal [2](Lee et al., 2015)

Assumption:
The focus of this paper is to work on experimental and theoretical investigation of the
structure, dynamics and electronic properties of Tungsten Ditelluride (WTe2).

Technique:
WTe2 crystals were grown by chemical vapor transport (CVT) using bromine (Br) as the
transport agent. The powder and bulk crystals were characterized by X-ray powder diffraction
(XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Raman
spectroscopy, and temperature-dependent current-voltage (I-V) measurements.
Results and conclusions:
 Authors studied Stable phase and electronic properties of WTe2 using DFT to model the
structure and based on atomic positions authors calculated XRD patterns of Td-WTe2
and from hypothetical 2H-WTe2 structure.
 Authors found that distorted 1T structure (Td) of bulk WTe2 has been experimentally
verified to be thermodynamically stable relative to the 2H polymorph and
experimentally verified that Td-WTe2 behaves as metal with an strong dependence of
resistivity on the thickness of multilayer.
Limitation:
This study does not talk about low dimensional phase of WTe2 and Dynamically stability has
not been clearly studied.

Article 3: First-principles study of lattice thermal conductivity of Td-WTe2

[3](Liu et al., 2016)
Assumption:
This paper focus on studying structural and thermal properties of bulk Td-WTe2 using first
principle calculations and their study focuses on applications of WTe2 in thermal insulation and
thermoelectric materials.
Technique:
The first-principles calculations are performed by using the density functional theory as
implemented in the Vienna ab initio simulation package . The Perdew–Burke–Ernzerh of
generalized gradient approximation (GGA) is chosen as the exchange-correlation functional
Results and conclusions:
  Authors found that the thermal conductivity of WTe 2 is anisotropic and the highest
thermal conductivity is 11.06 Wm-1K-1 at 300K temperature along y-axis and the lowest
conductivity is 1.04 Wm-1K-1 at 300K temperature along z-axis.
 van der Waals force plays an important role in the inter-layer interaction of WTe2.

Limitation:
2-D phase of WTe2 has not been studied in this literature and Size dependency of WTe 2 Td
phase
Does not explained.

Article 4 : Strain engineering of WS2, WSe2, and WTe2 [4](Amin et al., 2014)

Assumptions:
The focus of this paper to investigate the structural, electronic, and vibrational properties of
WS2, WSe2, and WTe2 considering compressive and tensile strain upto 2% and taking into
account the spin orbit coupling.
Technique:
They employed density functional theory using the PWSCF code and the generalized gradient
approximation used in the Perdew– Burke–Ernzerho flavor
Result and Conclusion:
 Transitions from a direct to an indirect band gap are observed for 1%, 1.5%, and 2%
compressive strain for WS2, WSe2, and WTe2, respectively, while the nature of the
band gap remains intact in the case of tensile strain.
 The band gap first grows and then shrinks under compressive strain, whereas it
decreases monotonically under tensile strain. Interestingly, the spin splitting of the
valence band remains very large under strain, which is promising for spintronics devices
based on transition metal dichalcogenides.
Limitations:
Microscopic understanding related to transport properties such as relaxation time is not
been clearly studied. Electronic lifetime 𝛕 has not been clearly understood using Boltzmann
transport theory.

Article 5: Pressure-induced Td to 1T' structural phase transition in WTe2

[5](Zhou et al., 2016)
Assumptions:
This paper is focus on the reporting results of high-pressure synchrotron X-ray diffraction
(XRD), Raman and electrical transport measurements on WTe2. Both the XRD and Raman
results reveal a structural transition upon compression, starting at 6.0 GPa and completing
above 15.5 GPa.
Technique:
The issues in WTe2 addressed by combining synchrotron X-ray diffraction and polarized
Raman scattering measurements. In situ high-pressure synchrotron X-ray diffraction
(XRD) measurements were performed with pressure up to 33.8 GPa.
Result:
The high-pressure lattice symmetry is monoclinic 1T ′ with space group of P21/m. This
transition is related to a lateral sliding of adjacent Te-W-Te layers and results in a collapse
of the unit cell volume by ∼20.5%. The structural transition also casts a pressure range with
the broadened superconducting transition, where the zero resistance disappears.
Conclusion:
By combining the high-pressure synchrotron XRD and Raman spectroscopy as well as the
electrical transport investigations in WTe2, they found that a pressure-driven structural
transition starts at around 6.0 GPa and completes above 15.5 GPa. The determined high-
pressure structure was the so-called 1T ′ phase via the layer sliding of the low-pressure Td
phase. On the other hand, the zero-resistance residing outside the structural transition
zone
indicated that both the Td and 1T ′ phases are superconducting in WTe2.

References
[1] Qian, X., Jiang, P., Yu, P., Gu, X., Liu, Z. and Yang, R., 2018. Anisotropic thermal
transport in van der Waals layered alloys WSe2 (1-x) Te2 x. Applied physics letters,
112(24), p.241901.
[2] Lee, C.H., Silva, E.C., Calderin, L., Nguyen, M.A.T., Hollander, M.J., Bersch, B., Mallouk,
T.E. and Robinson, J.A., 2015. Tungsten ditelluride: a layered semimetal. Scientific reports,
5(1), pp.1-8.
[3] Liu, G., Sun, H.Y., Zhou, J., Li, Q.F. and Wan, X.G., 2016. First-principles study of lattice
thermal conductivity of Td–WTe2. New Journal of Physics, 18(3), p.033017.
[4] Amin, B., Kaloni, T.P. and Schwingenschlögl, U., 2014. Strain engineering of WS 2, WSe
2, and WTe 2. Rsc Advances, 4(65), pp.34561-34565.
[5] Zhou, Y., Chen, X., Li, N., Zhang, R., Wang, X., An, C., Zhou, Y., Pan, X., Song, F.,
Wang, B. and Yang, W., 2016. Pressure-induced Td to 1T′ structural phase transition in
WTe2. Aip Advances, 6(7), p.075008.
[6] Gusakova, J., Wang, X., Shiau, L.L., Krivosheeva, A., Shaposhnikov, V., Borisenko, V.,
Gusakov, V. and Tay, B.K., 2017. Electronic properties of bulk and monolayer TMDs:
theoretical study within DFT framework (GVJ‐2e method). physica status solidi (a),
214(12), p.1700218.