1

Acknowledgements

I am greatly thankful to my supervisor, Prof. R Thangavel, for his invaluable guidance, support, and
encouragement throughout my research journey. His expertise and insights have greatly enriched
my understanding of Condensed Matter Physics.

I am particularly indebted to Miss Ankita Dey for her kind and sincere support, without which this
thesis would have been an impossible task. Her willingness to assist me whenever I faced difficulties
or had questions about my research has been truly invaluable.

Lastly, I extend my heartfelt thanks to my family and friends for their unwavering support and
encouragement during this endeavor. Their belief in me has been a source of strength.

Thank you all for being an integral part of my academic journey.

 2

Abstract

The limitations of charge-based electronics have driven interest in spintronics, where control of
electron spin enables faster, energy-efficient devices. Realizing spintronic functionality requires
materials with strong spin-orbit coupling, tunable electronic structure, and low-dimensional
confinement. Two-dimensional transition metal dichalcogenides (TMDs), particularly MoS₂, meet
these criteria through their semiconducting behavior, atomic-scale thickness, and pronounced spin–
valley coupling.

This thesis reports the hydrothermal synthesis and systematic characterization of MoS₂ nanostructures
optimized for spintronic applications. Two synthesis conditions were studied: a 1:5 and a 1:8 Mo:S
molar ratio at 190 °C and 200 °C, respectively. Structural and chemical analysis using XRD, XPS,
Raman, FESEM, and UV–Vis spectroscopy revealed that the optimized 1:8 synthesis yielded phase-
pure MoS₂ with improved crystallinity (crystallite size ~9.5 nm), minimal oxidation, and uniform
nanoflower morphology.

The results demonstrate the critical role of synthesis parameters in tailoring the structural and
electronic quality of MoS₂. The optimized material offers a viable platform for future spintronic
architectures and lays the foundation for doping, heterostructure engineering, and device integration.
 3

List of Content
1. Introduction
1.1 The emergence of low-dimensional materials
1.2 The two-dimensional materials
1.3 Transition metal dichalcogenides
1.4 Applications of TMDs in different fields
1.5 Materials of Interest
2. Experimental Technique
2.1 Hydrothermal Synthesis Method
2.2 Definition and conceptual foundations
2.3 Working principle and process flow
2.4 Instrumentation
2.5 Advantages
2.6 Applications
3. Characterization Techniques
3.1 XRD
3.2 XPS
3.3 RAMAN
3.4 UV-VIS
3.5 FESEM
4. Synthesis of Sample 1
4.1 Experimental Procedure
4.2 Characterization Techniques
4.2.1 XRD
4.2.2 XPS
4.2.3 Raman
4.2.4 FESEM
4.2.5 UV-VIS
4.3 Conclusion
5. Synthesis of Sample 2
5.1 Experimental Procedure
5.2 Characterization Techniques
5.2.1 XRD
 4

5.2.2 Raman
5.2.3 XPS
5.2.4 UV-VIS
5.3 Conclusion
6. Summary
 5

List of Figures
1. Different dimensions of Nano structures
2. The Elemental ZOO of Two-dimensional materials
3. Structure of MoS2
4. Various applications of two-dimensional materials
5. Electronic structure of MoS2
6. Flowchart of evolution of Hydrothermal Process
7. Schematic diagram for Autoclave
8. Hydrothermal method process flow
9. Application fields of Hydrothermal method
10. X-Ray Diffraction process
11. High Resolution X-Ray Diffractometer (HRXRD) at iRh IIT ISM
12. Working principle of XPS, XRF and Auger
13. XPS Analyzer at iRh IIT ISM
14. Raman Scattering Phenomena
15. Micro Raman Spectroscopy at iRh IIT ISM
16. UV-VIS-NIR Spectrophotometer at iRh IIT ISM
17. FESEM Set-up at iRh IIT ISM Dhanbad
18. XRD Pattern of the sample compared with standard JCPDS Data
19. Elemental XPS Scan for Mo
20. Elemental XPS Scan for S
21. Survey scan for elemental composition
22. Raman Shift of the sample
23. FESEM Images of the sample
24. Tauc’s plot for band gap calculation of the material
25. XRD Pattern of the sample compared with standard JCPDS Data
26. Raman Shift of the sample
27. Elemental XPS Scan for (a) Mo and (b) S
28. Survey scan for elemental composition
29. Tauc’s plot for band gap calculation of the material
 6

CHAPTER 1

Introduction
1.1 Emergence of Low-Dimensional Materials

In recent decades, there has been a significant shift due to new nanostructured systems, materials
science technologies. One such system, low-dimensional materials, has been developed into advanced
materials due to their unique physical and chemical properties and electrical characteristics, which
are very distinct from their bulk material counterparts. These materials are categorized based on the
level of their dimensions confined to the nanoscale, which is generally below one hundred
nanometres. Classifications encompass quantum dots or nanoparticles perceived as zero-dimensional
(0D), one-dimensional (1D) nanowires or nanotubes, two-dimensional (2D) sheets or monolayers,
and three-dimensional (3D) bulk materials. By reducing the dimensionality of a system, we open a
window of advantages, including quantum confinement effects, increased surface area, and enhanced
volume, which all benefit nanotechnology, and many other fields of study can be used to take
advantage of this dimension reduction. These benefits provide possible avenues to real-world
applications, including electronics, photonics, energy storage, catalysis, and spintronics.

Fig 1. Different dimensions of Nano Structures (1)

 7

1.2 Two-Dimensional Materials

The fundamental physics of low-dimensional materials arises from the reduced dimensionality, which
leads to quantum confinement. When one or more dimensions of a material are reduced to the
nanoscale, the movement of electrons is restricted. This effect is prominently evident in two-
dimensional materials where electrons are free to move in the x-y plane but are confined in the z-
direction. The confinement gives rise to unique layer-dependent band gaps and a unique coupling to
both spin and valley, along with better light and matter interaction. This makes them well-suited for
applications in nanoelectronics, optoelectronics, photonics, and energy storage. (4)

Another fascinating characteristic of 2D materials is the van der Waals (vdW) interactions between
the layers, in contrast to the strong covalent or ionic bonding within the layers. These weak interlayer
interactions enable simple mechanical or chemical exfoliation of individual sheets and the creation
of vdW heterostructures where the 2D materials can be stacked without lattice-matching limitations.
This heterostructure allows us to have a custom-designed material platform with possibly tailored
properties that can be utilized in the next generation of transistors, tunnelling devices, and quantum
wells. (5)

Low-dimensional materials have already found applications in various fields like Flexible and
transparent electronics, Photodetectors and photovoltaics, Catalytic processes (especially HER),
Supercapacitors and batteries, Field-effect transistors (FETs), and Spintronic devices. (5) In just one
decade, two-dimensional (2D) materials have transformed many fields of modern science and
technology, both by extensive fundamental work and through the first commercial uses

Fig 2: Elemental ZOO of Two-Dimensional Materials

 8

1.3 Transition Metal Dichalcogenides

The discovery of graphene in 2004 as a single layer of carbon atoms organized into a 2D hexagonal
lattice was a remarkable milestone. This opens up a new field of research for researchers to delve into
other two-dimensional materials with equivalent or improved properties. Graphene has some unique
properties among other 2D materials: high mechanical strength, carrier mobility, flexibility, and
transparency, but it still has limitations due to a lack of natural bandgap preventing it from being used
in an alternate related field, digital electronics, which rely on the presence of a bandgap allowing
switching to take place in transistors. (3)

To overcome this drawback, researchers began investigating a new group of 2D materials called
transition metal dichalcogenides (TMDs), which can exhibit semiconducting, metallic, or insulating
characteristics depending on their composition and crystal structure. TMDs have a general formula
of AB₂, with A denoting a transition metal (Mo, W, V, or Ti) and B being a chalcogen (S, Se, or Te).
They can crystallize in nature in a layered structure consisting of one atomic plane of metal
sandwiched between two atomic planes of chalcogen atoms. Within a layer, the atoms are firmly held
together with covalent bonds, while adjacent layers are held together by relatively weak van der Waals
(vdW) attractions. These materials can be easily mechanically or chemically exfoliated into
monolayers or few-layer sheets, like graphene, which can be mechanically or chemically exfoliated
from graphite. (3)

One of the most remarkable features of TMDs is their ability to exist in multiple polymorphic crystal
structures, each having different electronic properties. The three most common phases of TMDs are
1T, 2H, and 3R.

1. The 1T phase has tetragonal symmetry with octahedrally coordinated metal atoms; it is often
"metastable" (though metal-like).

2. The 2H phase of TMDs (the phase with hexagonal symmetry trigonal prismatic coordination
and is stable, semiconducting, and quite often the preferable phase in natural MoS₂) is the
most typical expected phase.

3. The 3R phase has rhombohedral symmetry and semiconducting properties but is less common
than 2H.
 9

These polymorphs can significantly impact optical, electrical, and magnetic properties; thus, phase
control is an important area of research on TMDs.

Crystal and Electronic Structure:

A key characteristic is the presence of strong spin–orbit coupling (SOC), particularly for heavier
TMDs such as MoS₂ and WS₂. SOC breaks the degeneracy of the valence band at the K-point in the
Brillouin zone, producing spin-split bands. This makes TMDs promising in the field of spintronics,
referring to the effort to also control the spin degree of freedom (in addition to charge) as a viable
means of transforming data into alternate states for more efficient data processing in terms of speed
and efficiency. (6)

Fig 3: Structure of MoS2 (1)

1.4 Applications of TMDs in different fields

In recent decades, the progressive downscaling of silicon-based electronics has reached fundamental
physical and technological limits, giving rise to finding new materials to enable future
nanoelectronics breakthroughs. Two-dimensional (2D) semiconductors, particularly transition metal
dichalcogenides (TMDs), are most attractive due to their high electrostatic control, intrinsic bandgaps,
 10

and atomically thin profiles. These properties (as well as a few others) make TMDs promising
candidates for next-generation thin-film transistors (TFTs) and flexible electronic devices.

During this period of intense global research, diverse studies and review articles have continually
provided chronologically oriented accounts of the significant experimental advances in the synthesis,
fabrication, and characterization of 2D materials. Demonstrating superior thin-film transistors (TFTs)
utilizing synthesized MoS₂ has moved forward significantly. The layered structures bound by weak
van der Waals forces provide abundant sites for ion accommodation during charge-discharge
processes while remaining intact and with a certain flexibility under repeated electrochemical
stresses. Due to its sheet-like morphology, MoS2 displays EDLC (electrical double-layer capacitance)
and pseudo capacitance due to molybdenum in several oxidation states (Mo²⁺ to Mo⁶⁺). These
properties allow MoS₂ to facilitate rapid and reversible redox reactions, leading to enhanced energy
and power densities.

TMDs such as MoS₂, WS₂, and WSe₂ have proven to be the best materials for sensor development
due to their increased surface-to-volume ratio. An increased surface-to-volume ratio means greater
interaction between target analytes and sensor material. This structure allows ultrasensitive detection,
rapid response and recovery, and low-power operation, making TMDs attractive as sensors in
portable, real-time applications.

Thus far, most TMD sensors have used mechanically exfoliated and/or LPE MoS₂ flakes.
Mechanically exfoliated flakes are ideal for prototype development and performance benchmarking,
where defect-free monolayers are needed. At the same time, LPE provides a large-scale, low-cost way
to prepare TMDs in suspension for thin-film device fabrication. Numerous TMDs have been used in
gas sensing, biosensing, and chemical detection to advance human welfare. (1)

Catalysis is another area where TMDCs excel, particularly with the hydrogen evolution reaction
(HER). Specific engineering methods can improve the catalytic activity profile through modified
design, such as introducing defects or doping foreign atoms. These changes increase the active site
density and improve conductivity and reaction kinetics (4). The two-dimensional transition metal
dichalcogenides (2D TMDs) are a promising new class of materials for biosensing. Their ultrathin
and high surface area ensures a maximum degree of packing of immobilized biomolecules, which is
desirable for biosensors to achieve high sensitivity and efficiency.
 11

Fig 4: Various Applications of two-dimensional materials (1)

TMDs can access their surfaces more than bulk 3D materials and 1D nanostructures such as silicon
nanowires and carbon nanotubes (CNTs), yielding stronger analyte interactions with lower detection
limits and greater signal responses. (1)
 12

In conclusion, TMDs are outstanding materials with several benefits in electronics, optoelectronics,
energy storage, and sensing applications. Their tunability, availability, large surface area, and
compatibility with flexible devices make them attractive candidates across many applications for
next-generation technologies.

1.5 Materials of Interest

Molybdenum Disulfide

As part of the large family of two-dimensional (2D) materials, molybdenum disulfide (MoS₂) has
gained notoriety in the materials field due to its remarkable electrical, optical, mechanical, and
catalytic properties. MoS₂ belongs to the transition metal dichalcogenide (TMD) family and is
structured as a layered hexagonal crystal, with a single layer of Mo atoms sandwiched between two
layers of S atoms via weak van der Waals forces [1]. The layered structure provides a means of
mechanically exfoliating MoS₂ down to monolayers in a similar way to graphene while also providing
tunable properties via layer thickness modification.

Bulk MoS₂ has a bandgap of ~1.2 eV and becomes a direct bandgap semiconductor (~1.8 eV) in
monolayer form. This has created significant interest in using MoS₂ for optoelectronics,
photodetectors, and valleytronics. MoS₂ has semiconductor properties compared to graphene, which
has no bandgap and cannot be used in field-effect transistors (FETs) and other nanoelectronic devices.
Furthermore, MoS₂ has attracted considerable interest in sensing and catalysis owing to the abundance
of active edge sites.

MoS2 has a unique ability to modify its properties through doping, inducing strain, creating defects,
and creating heterostructures and nanocomposites, making it attractive for research today. In
particular, MoS2 has been studied in spintronics and shows good prospects in external electric and
magnetic fields; monolayer spin-orbit coupling effects have also been demonstrated . These properties
suggest exploring future spin-based devices. It can be said that, overall, MoS₂ is situated at the
interface of physics, materials science, and nanotechnology and is a solid predecessor platform on
which one can conceptualize and develop a basic understanding and its broader potential. Its
interesting electronic tunability, layered structure, and multifunctional nature validate its interest as a
"material of the future."
 13

Fig 5: Optimized electronic structure of MoS2, (the red and

yellow spheres represent the Mo and S, respectively) (2)
 14

CHAPTER 2

Experimental Techniques
2.1 Hydrothermal Synthesis Method

Think of a pressure cooker in the kitchen — an enclosed vessel that uses pressurized steam to expedite
and elevate food preparation. Hydrothermal synthesis operates in parallelly, creating functional
nanomaterials with high-temperature, high-pressure water. This analogy might appear too simple, but
it reflects the nature of the process: Inside a sealed autoclave, aqueous chemical reactions under
controlled thermodynamic conditions result in the formation of highly crystalline, phase-pure, and
occasionally complex materials. The technique originates from natural geological structures like
quartz crystals in Earth's crust, where mineral formation occurs under conditions of deep pressure and
temperature over millions of years. The lab-based version of this process provides scientists with a
handy tool for synthesizing nanostructured materials, specifically transition metal dichalcogenides
(TMDs), for use in catalysis, electronics, and spintronics.

2.2 Definition and Conceptual Foundations

Hydrothermal synthesis is a solution-based materials synthesis through chemical reactions in a sealed,

high-pressure, and high-temperature environment, usually in an autoclave. The reaction medium is
an aqueous solution, which can dissolve and transport otherwise insoluble materials. It is highly suited
to synthesizing crystalline materials like oxides, sulfides, and other nanostructures. The word
"hydrothermal" is a combination of hydro (water) and thermal (heat), and anything that deals with
water under high temperature and pressure. The origin of this process is naturally occurring geological
structures such as quartz crystals in the Earth's crust, where the growth of minerals occurs over
millions of years, with high temperatures and high pressure. The laboratory simulates these conditions
using a Teflon-lined autoclave placed within an oven with desired pressure and temperature
conditions.

Historically, the method became popular during the early twentieth century when scientists tried to
grow large quartz crystals in a laboratory environment. Since then, it has also been a general synthesis
method for inorganic compounds such as oxides, silicates, sulfides, phosphates, and even zeolites.
 15

Over the last 20 years, its application to synthesize nanomaterials has become increasingly common
due to its environmental compatibility, energy efficiency, and capability of controlling the material's
morphology. Hydrothermal synthesis is often used to create well-characterized, high-purity
nanoparticles and nanostructures, especially those that are otherwise difficult to form at atmospheric
pressure. Autogenous pressure — internally developed through heating the solvent above its boiling
point within an enclosed system — is a critical feature of the method. High-temperature water has
some peculiar physical properties: it is less polar and can dissolve many insoluble compounds at room
temperature. Such solubility variations are crucial to controlling nucleation and growth kinetics, and
thereby, scientists can cultivate crystals with extremely well-characterized shape, size, and surface
properties. Consequently, hydrothermal synthesis has proved highly useful in synthesizing two-
dimensional and layered materials such as MoS₂, WS₂, and VS₂, which are at the center of current
energy storage, catalysis, and spintronic applications research (7,8)

Fig 6: Flow chart of the evolution of hydrothermal method

 16

2.3 Working Principle and Process Flow

The hydrothermal synthesis includes synthesizing a precursor solution, sealing in a Teflon-lined

stainless-steel autoclave, heating at a constant temperature for a given time, and subsequent cooling
and recovery of the product synthesized. The key steps are as follows:

Preparation of the Precursor Solution

The initial precursor (metal salts, oxides, or sulfides) is dissolved in a polar solvent or deionized
water. Surfactants, mineralizers, or pH regulators can yield particle shape control.

Sealing the Reaction Mixture in the Autoclave

The precursor solution is subjected to a Teflon-lined autoclave, and the autoclave is closed. Teflon is
employed to avoid corrosion and contamination. The fill ratio (usually 60–80%) is essential since it
affects pressure buildup.

Heating and Reaction

The autoclave is then subjected to an oven and heated to the desired temperature (typically 120–
220 °C). The pressure inside the Teflon increases due to vaporization, which promotes solubility
alteration, ion migration, and recrystallization. This causes nucleation and crystal growth.

Cooling and Product Gathering

The autoclave is allowed to cool naturally or rapidly after the reaction time. The solid products are
filtered, washed with ethanol or water, and dried for characterization. The main thermodynamic
parameters — i.e., temperature, pressure, concentration, and time — control the end product size,
crystallinity, and phase [1]. For instance, increasing the temperature causes grain growth at larger
sizes, and decreasing the reaction time yields nanostructures. Temperature-controlled solubility of
materials in hydrothermal conditions offers the prospect of insoluble materials under normal
conditions dissolving and re-crystallizing under controlled conditions. Autogenous pressure within
the autoclave is another non-mechanical driving force for reaction and growth.
 17

2.4 Instrumentation

The effective execution of hydrothermal synthesis is dependent to a large extent on highly specialized
equipment aimed at maintaining and controlling high-temperature and high-pressure conditions
within a sealed environment. The primary equipment usually includes a Teflon-lined autoclave, a
steel pressure vessel, an oven with temperature control, and, in sophisticated systems,
temperature/pressure sensors for real-time observation.

Fig 7: Schematic Diagram for Hydrothermal Method Equipment

The above figure shows a simplified diagram of hydrothermal synthesis equipment. The precursor
solution is kept in a Teflon beaker (liner), which is sealed in a stainless-steel autoclave reactor. This
assembly is kept in a laboratory oven where the temperature can be accurately controlled. The close
sealing of the autoclave allows the internal vapor pressure to develop as temperature increases,
allowing dissolution, nucleation, and crystal growth of nanomaterials in the solution.
 18

Since hydrothermal processing frequently uses high temperatures and pressures, it is important that
the reaction vessel, generally referred to as an 'autoclave,' should have the ability to withstand such
extreme conditions without structural or compositional degradation.

The design of a hydrothermal reaction vessel requires careful attention to the following parameters:

• Any oxidizing agent interacting with the vessel is strictly not allowed.

• During its operational life, the vessel should demonstrate leak resistance and the ability to withstand
maximum pressures and temperatures.

• Under extended exposure to high temperatures and pressures, the vessel's material composition and
structural integrity should be able to withstand such conditions.

In addition, the container should maintain stability without requiring any treatment or machining after
every experimental run. Autoclaves are often made of high-strength quartz cylinders and alloys to
meet such demands.

Fig 8: Hydrothermal Method Process Flow

 19

2.5 Advantages

In recent years, hydrothermal synthesis has been used increasingly; it can have numerous benefits:

1. Ability to Control Morphology Control particle shape, size, and crystallinity with the method by
simply changing the reaction conditions like pH, temperature, and concentration of precursors [2].

2. Energy Efficient and Low Temperature

Compared to solid-state synthesis, the hydrothermal routes use cooler temperatures that cut down on
energy bills and keep the layered structures intact.

3. Environmental-friendly

By using water as a solvent, this approach sticks to green chemistry principles to cut back on harmful
organic solvents and toxic waste.

4. Top-Quality Products

The sealed setting limits contamination, resulting in highly pure and phase-selective nanocrystals.

5. Scalable and Cost-Effective

The process can be scaled to industrial manufacturing in large autoclaves and utilized on devices
useful for energy and electronics applications.

These benefits render hydrothermal synthesis a desirable method in spintronic material synthesis,
such as 2D transition metal dichalcogenides, with high crystalline quality and phase control
requirements.

2.6 Applications

The Hydrothermal Method finds applications in various fields.

1. Material Science

Hydrothermal synthesis is important in materials science for creating nanomaterials with controlled
morphology, crystallinity, and particle size distribution. The ability to control these parameters is
important for relating these materials to optical, electronic, and catalytic applications. Under
 20

hydrothermal conditions, well-defined material forms from metals like ZnO, TiO₂, and Fe₂O₃
nanoparticles are created. These materials include applications in photocatalysis, gas sensing, and
supercapacitors

2. Chemistry

The hydrothermal method provides a framework for inorganic and coordination chemistry to create
oxide crystals and zeolites and even hybrid organic-inorganic frameworks under mild conditions.
Reactions that may be slow or not feasible at standard atmospheric conditions can proceed in an
autoclave under pressure and temperature due to increased solubility of the reactants. Hydrothermal
conditions support the principles of green chemistry primarily by the reduced need for harmful
solvents and reductants.

3. Physics

Hydrothermal synthesis is used in physics, especially in solid-state physics and photonics, to

fabricate materials with a precise bandgap and defect density. This is important in optoelectronic
devices. In addition to the ability of the hydrothermal synthesis technique to tune defect states and
dopants, it is ideal for investigating magnetoresistance and piezoelectric effects.

4. Earth Science

Within earth sciences, hydrothermal synthesis mimics natural geological processes, allowing
researchers to develop experimental setups to explore mineral formation under sub-surface
conditions. Hydrothermal synthesis aids in growing synthetic analogs of minerals such as beryl,
quartz, or tourmaline and can mimic deep-sea hydrothermal vents in ocean science.

5. Metallurgy

Hydrothermal processing is being adopted increasingly in metallurgy to create nano-metallic alloys,

metal sulfides, and metallic oxides of uniform size and phase for use mainly as precursors for
sintering, catalyst, or electrocatalyst in various industrial operations.

6. Biology

The hydrothermal method has produced biocompatible and biodegradable nanostructures in countless
drug delivery systems, imaging, and tissue engineering applications. For example, hydrothermally-
 21

synthesized hydroxyapatite nanocrystals---the main mineral compound found in bones---are

employed in orthopedic implants and bone grafting. Furthermore, hydrothermally synthesized
nanostructured ZnO and TiO₂ coatings have highly surface reactive component features and are
designed for antibacterial coatings and biosensors for their safe biological profile.

Fig 9: Application fields of Hydrothermal

 22

CHAPTER 3

Characterization Techniques
Characterization constitutes a fundamental component of materials science, functioning as the critical
interface between the processes of synthesis and their corresponding applications. It entails the
methodical investigation of a material's structural attributes, morphological characteristics,
compositional elements, and performance metrics, aimed not solely at validating the efficacy of the
synthesis methodology but also at elucidating the intrinsic mechanisms that govern its operational
behaviour. Without complete characterization of the synthesized material, its nature remains
unknown, and therefore, correlating its structure to its performance in target applications is
impossible. Especially in low-dimensional materials and nanostructures, where properties are
incredibly size- and phase-dependent, accurate characterization is essential for tailoring materials to
specific technological applications such as spintronics, optoelectronics, and catalysis. Therefore, a
complete set of techniques is used to obtain qualitative and quantitative information about the
material.

3.1 X-Ray Diffraction (XRD)

X-ray diffraction (XRD) is a technique for examining a material's composition and how X-rays
interact with it, especially in crystalline substances. It is among the key methods for examining
materials' crystallographic structure and phase purity. It is beneficial for nanomaterials, where minor
alterations in structure and lattice strain are crucial in defining their characteristics. It is one of the
most important techniques in investigating materials' crystallographic structure and phase purity.

XRD provides a non-destructive method to study various structural features of crystalline materials.
It helps determine whether the target material has been synthesized successfully or not and whether
secondary or impurity phases exist. It also enables one to estimate the crystallite size, microstrain,
unit cell dimensions, and preferred orientation, which are extremely important in correlating structure
with physical and electronic properties.
 23

Fig 10: X-Ray Diffraction Process

X-ray diffraction represents a phenomenon wherein the atomic constituents of a crystal engage in
interference with the incident waves of an X-ray beam due to their periodic arrangement. The
interaction of the crystal's atomic planes with the X-rays is analogous to the interaction observed
between a uniformly ruled diffraction grating and a light beam. An X-ray beam impinges upon a
crystal at a specific angle of incidence denoted as θ. At this identical angle θ, the beam is subsequently
reflected from the atomic structure of the crystal. Atomic planes within the crystal that are delineated
by a spacing ‘d’ are responsible for the reflection of the X-rays. To establish an interference pattern,
the X-rays reflecting off two separate planes must undergo constructive interference; otherwise, if
constructive interference does not occur, destructive interference prevails, resulting in the absence of
a discernible pattern. For constructive interaction to transpire, the beams reflecting off two atomic
planes must exhibit a path length difference equivalent to an integral multiple (n) of wavelengths (λ),
expressed as nλ. This requirement is encapsulated by the Bragg law, nλ = 2d sin θ. Peaks identified
at varying 2θ values correspond to reflections stemming from distinct structural planes within the
crystal. (11)
 24

Next, the standard XRD pattern from the International Centre for Diffraction Data (ICDD) is
compared with these peaks. This comparison allows us to determine whether the intended phase is
present in the synthesized sample. Additionally, one can estimate the arrangement of atoms or
molecules within the crystal by using the position of the peaks in the pattern obtained from the XRD.

Fig 11: High Resolution X-Ray Diffractometer (HRXRD) at iRh IIT ISM

3.2X-ray Photoelectron Spectroscopy (XPS)

As material systems scale down to the nano regime, surface properties play a more important role in
defining a device's or functional material's overall behavior. X-ray Photoelectron Spectroscopy
(XPS)is a strong surface-sensitive measurement method. It is also known as electron spectroscopy
chemical analysis (ESCA). It mainly helps find out the composition of elements, simple formulas,
chemical state, and electronic state of the parts in a material. Since it was made in the 1960s, XPS
has turned into an important tool for studying the surface chemistry of solid materials.
 25

XPS is essential for knowing the parts that make up something and how they are changed and stick
together. It helps check if tiny materials are made right, the amounts of added stuff, and if there are
any dirty spots or layers on the surface.

XPS can identify not just the elemental content of a material's surface but also the present elements'
chemical state. This type of understanding is essential in nanomaterials, where surface behavior
dominates over bulk behavior. Non-destructive and surface-sensitive, XPS can supply information
from the upper 1–10 nm of the material's surface, providing insights that are out of reach to methods
probing more deeply into the bulk. XPS thus becomes critical not only in fundamental
characterization but also in optimizing materials for application-specific behavior. (12)

Theoretical Background and Working Principle

XPS relies basically on the photoelectric effect. When an irradiated material is subjected to X-rays of
adequate energy (usually 1000–1500 eV), electrons at the core level in the material's atoms will
capture the energy and be ejected from the atomic orbitals. Ejected electrons are referred to as
photoelectrons, while the photoelectrons' kinetic energy (Eₖ) is quantified with an electron energy
analyzer. Given the energy of the incident photon (hν) and the kinetic energy of photoelectrons
emitted, the binding energy (BE) of electrons may be determined from the equation.

BE =hν−KE−ϕ

where hν is the incident photon's energy (e.g., Al Kα = 1486.6 eV), KE represents the electron's
kinetic energy, and ϕ represents the material's work function, including energy losses during electron
transport. Binding energy is particular to every element and electron orbital.

XPS is surface-sensitive by nature, with an analysis depth of ~5–10 nm, depending on the density of
the sample and photoelectron escape depth.
 26

Fig 12: Working principle of (a) XPS, (b) XRF, and (c) Auger

While plotting the intensity of emitted electrons against their binding energies, a photoelectron
spectrum is obtained, which is composed of sharp peaks typical of the elements and their electronic
surroundings. These peaks are attributed to certain electronic transitions like Mo 3d, V 2p, S 2p, etc.,
and can also provide information regarding oxidation states, chemical bonding, and even molecular
structure. (13,14)

XPS spectra can show not only the presence of specific elements but also variations in chemical state
through binding energy shifts

Instrumentation:

An X-ray photoelectron spectroscopy (XPS) system typically comprises the following essential
components:

1. X-ray source:

Produces monochromatic X-rays, predominantly Al Kα or Mg Kα.

 27

2. Ultra-high vacuum chamber:

Sustains vacuum conditions ranging from 10⁻⁹ to 10⁻¹⁰ Torr to mitigate any interference with the
trajectory of photoelectrons.

3. Electron energy analyzer:

Conventionally, a hemispherical analyzer that assesses the kinetic energies of the emitted electrons.

4. Detector:

Quantifies the number of electrons exhibiting a specific kinetic energy.

5. Sample stage:

Facilitates the manipulation and inclination of the sample.

The preparation of samples is of paramount importance in XPS. The surface must be pristine, devoid
of adsorbed contaminants, and flat at the nanoscale. Generally, samples are affixed to conductive
stubs and may necessitate surface cleaning (via ion sputtering) before the measurement.

Fig 13: XPS Analyzer at iRh IIT ISM

 28

3.3 Raman Spectroscopy

The presentation of Raman spectra is usually depicted as the intensity of Raman scattering versus
Raman shift (change in frequency between the incident and dispersed radiation), where every peak
corresponds to a molecular vibration. Raman spectroscopy is a dispersive method that is capable of
being used to detect vibrational, rotational, and other low-frequency vibrations. This technique is
highly selective, non-destructive, and takes minimal effort to prepare the samples.

In contrast to IR spectroscopy, which relies on a dipole moment change, Raman spectroscopy is

sensitive to a change in molecular polarizability. Because of this complementarity, vibrational modes
can be identified as inactive in IR but active in Raman, thus offering a more complete vibrational
profile of a material.

Fig 14: Raman Scattering Phenomena (15)

Instrumentation

The main parts of the Raman spectrometer include a monochromatic laser source, a sampling
interface, and a detector. Attributes such as narrow linewidth, low power consumption, stable output,
etc., are the primary reasons to use a laser as the source of a spectrometer. The fiber-optic probe is
generally employed as the sampling interface due to high flexibility, high-optical-density Raman cut-
offs, etc. Charge-coupled devices (CCD) and photomultiplier tubes (PMT) are the detectors to
observe the Raman spectra for visible and UV excitations, respectively. A typical indium gallium
arsenide (InGaAs) array is used for NIR excitation. For the present thesis work, measurements have
been monitored through the LabRAM HR Evolution (HORIBA Scientific) Raman Microscope.
 29

Fig 15: Micro Raman Spectroscopy IIT ISM iRh

UV-VIS Spectroscopy

Ultraviolet-visible (UV-VIS) spectroscopy is an extensively used analytical method that interrogates

the response of matter to electromagnetic radiation over the ultraviolet (200–400 nm) and visible
(400–800 nm) parts of the electromagnetic spectrum. It quantifies a sample's absorption of light
against wavelength, providing information on its electronic transitions, energy band structure, and
optical band gap.

Instrumentation and Measurement

A conventional UV-VIS spectrophotometer comprises several primary. The light source generally
consists of a deuterium lamp for the ultraviolet spectrum (200–400 nm) and a tungsten-halogen lamp
for the visible spectrum (400–800 nm), generating a broad and continuous light spectrum. The light
is directed through a monochromator that isolates the desired wavelength, usually employing
diffraction gratings or prisms. This beam is transmitted through the sample and kept in the holder.
Due to their transparency in the UV range, liquid samples are kept in quartz cuvettes, while solid-
state substances such as thin films or powders are affixed to transparent substrates or formed into
pellets. Upon interaction with the sample, the transmitted or reflected light is subsequently detected
by a photodiode array (PDA) or photomultiplier tube (PMT), which converts the light intensity into
an electrical signal. Finally, the signal is analysed and displayed as a spectrum of transmittance or
 30

absorbance with respect to wavelength. This integrated configuration permits the accurate assessment
of a material's optical characteristics, which is instrumental in characterizing semiconducting
nanomaterials and thin films.

Once the sample holder is loaded with the sample, the spectrophotometer is calibrated with a blank
reference to account for background absorption. The instrument is then operated to scan over a
specified wavelength range (usually 200–800 nm), measuring the absorbance or reflectance of the
sample. The resulting absorbance values are fundamental in calculating the optical band gap via the
Tauc method, which entails the plotting of (αhν)n against hν, where α represents the absorption
coefficient and hν denotes the energy of the photon. N is a function of the type of electronic
transition—n=1/2 in the case of direct allowed and n=2 for indirect allowed transitions. The linear
section of the Tauc plot is extrapolated to cut the energy axis to estimate the material's optical band
gap, which is of prime importance for assessing its suitability for optoelectronic and spintronic
applications. (16)

Fig 16: UV-VIS-NIR Spectrophotometer at iRh IIT ISM

 31

FESEM (Field Emission Scanning Electron Microscopy).

Among the several microscopy methods, FESEM is unique because of its unmatched resolution and
surface sensitivity. FESEM supplements spectroscopic methods by providing nanoscale surface
imaging, particularly important in two-dimensional material research and their composites.

Unlike conventional optical microscopy, which is limited by the wavelength of visible light, FESEM
avoids the diffraction limit because it employs electrons rather than photons, enabling imaging at
resolutions below 1 nm. Such an ability is particularly vital in studying nanostructured materials
where structural properties such as flake size, stacking, edges, and grain boundaries might
substantially influence physical, optical, and electrical properties. (17)

Fundamentals of Electron Microscopy

The visible light wavelength limits Optical microscopes' resolution to ~200 nm. Electron microscopy
uses beams of accelerated electrons to image specimens at a much higher resolution than visible light.
Since electrons have shorter wavelengths, the resolving power increases.

By comparison, high-voltage accelerated electrons (e.g., 1–30 kV) have a wavelength of 0.005–0.01
nm, allowing for resolutions below 1 nm. A considerable gradient in the electric field induces the
expulsion and subsequent acceleration of electrons from a field emission source within a field
emission scanning electron microscope (FESEM). (18)

Fig 17: FESEM Set-up at iRh IIT ISM Dhanbad

 32

In a high vacuum environment, electronic lenses concentrate and redirect the primary electron beams,
thereby generating a highly intense and focused beam aimed at the target specimen. The interaction
of this beam with the specimen engenders the production of secondary electrons. The surface
morphology of the object is manifested in the velocities and angular distributions of these secondary
electrons. A detector captures the secondary electrons, which subsequently generate an electrical
signal
 33

CHAPTER 4

Synthesizing Molybdenum Disulfide

4.1 Experimental Procedure:

Hydrothermal synthesis technique was utilized to synthesize MoS2. Sodium molybdate dihydrate
(Na₂MoO₄·2H₂O) and thiourea (CH₄N₂S) were chosen as precursors for Molybdenum and sulfur,
respectively. First, 0.1M of sodium molybdate was dissolved in 50 ml of DI and kept on magnetic
stirring at 600 rpm. This stirring was performed for 30 minutes. The stirring mixed the molybdate
ions thoroughly (to ensure the dissolution of the compound). The thiourea was gradually added until
the final concentration was 0.5 M (~0.025 mol), maintaining a 1:5 molar ratio of Mo:S source.
Afterward, the solution was stirred for another 30 minutes to ensure adequate mixing and reaction.

The final homogeneous solution was poured into a 100 mL Teflon-lined stainless-steel autoclave, and
the autoclave was sealed tightly and placed into the hot air oven at 190°C for 24 hours. After 24 hours,
the autoclave was cooled without any intervention in the oven to prevent thermal shock.

Centrifugation at 7000 rpm was used to collect the resulting black precipitate, which was repeatedly
cleaned with ethanol and DI water to eliminate any unreacted species and contaminants. It was then
dried in an oven at 80°C for 10 hours. With this technique, MoS₂ powder was successfully formed.

A molar ratio 1:5 of sodium molybdate dihydrate to thiourea was selected to use an excess sulfur
during the synthesis step. By doing so, we could regularly sulfurize the molybdenum ions and
minimize the formation of oxidative species, such as molybdenum oxides, by having an excess sulfur
species. It is critically important in these instances to excess sulfur species if the ultimate goal is to
produce high purity MoS₂ with adequate crystallinity and stoichiometry for its potential applications
regarding electronics and spintronics. (22)

4.2 Characterizations:

4.2.1 XRD Analysis

X-ray diffraction (XRD) techniques scrutinized the synthesized material's phase composition and
crystallinity. The analytical procedure utilized a Rigaku Smartlab diffractometer equipped with Cu
 34

Kα radiation (λ = 1.5406 Å). The resultant diffraction patterns were obtained over a 2θ interval
spanning from 10° to 80° at a scanning rate of 2°/min.

The experimental XRD pattern, in conjunction with the standard reference JCPDS card (No. 01-075-
1539), which pertains to the hexagonal phase of molybdenum disulfide (MoS₂), is illustrated in
Figure. A broad diffraction peak, centered at approximately 13.74°, was detected, corresponding to
the (002) plane of the layered MoS₂ structure. Nonetheless, considerable broadening and diminished
intensity were observed compared to the distinct peaks of the reference JCPDS pattern. Additional
weak and broadened peaks emerged within the range of 30° to 80°, which can be associated with the
(102), (110), and (200) planes of MoS₂.

For the prominent diffraction peak observed at 2θ=13.74º, the FWHM was measured to be 2.82.
After converting the values to radians and applying them in the Scherrer equation, the calculated
crystallite size was found to be approximately 2.84 nm. The small crystallite size corroborates the
broad nature of the diffraction peaks observed in the XRD pattern, further indicating that the
synthesized material is highly nanocrystalline or possesses poor long-range crystallinity.

The noted discrepancies between the experimental diffraction pattern and the standard JCPDS
reference may be ascribed to various factors:

Low Crystallinity: The broad peaks and diminished intensity suggest inadequate long-range order
within the crystal lattice, often linked to hydrothermally synthesized materials wherein lower
temperatures and abbreviated reaction times are employed.

Possible Amorphous Content: The occurrence of partial amorphization during the synthesis process
can further exacerbate peak broadening and augment background noise in the XRD pattern.

Strain Effects: Internal lattice strain induced during growth may result in slight peak displacements
and broadening.

These observations indicate that the synthesized MoS₂ predominantly exhibits a nanocrystalline and
disordered layered configuration.
 35

Fig 18: XRD pattern of sample compared with standard JCPDS data

4.2.2 XPS (X-Ray Photoelectron Spectroscopy)

In this study, XPS was employed to investigate the chemical composition and bonding states of the
synthesized molybdenum disulfide (MoS₂) sample prepared via the hydrothermal route. High-
resolution spectra were recorded for Mo 3d, S 2p, and O 1s regions to evaluate the presence of Mo–
S bonding and possible oxidation or stoichiometric deviations.

Al Kα X-ray source (1486.6 eV) was used for measurements. The pass energy was set to 280 eV.
High-resolution spectra and a wide-scan survey spectrum were collected for Mo 3d, S 2p, and O 1s
core levels. The acquired spectra were background-corrected using the Shirley method and fitted with
pseudo-Voigt (mixed Gaussian-Lorentzian) profiles using the XPSPEAK41 software.
 36

Survey Spectrum:

The survey spectrum confirmed the presence of Mo, S, O, C, and a trace amount of Bi. The atomic
percentages derived from the survey are:

Element Atomic %

O 1s 38.8
C 1s 29.8µµ
Mo 3d 15.6
S 2p 14.2
Bi 4f 1.5

Interpretation: The sulphur content is lower than expected for stoichiometric MoS₂ (S: Mo = 2:1),
suggesting a sulphur-deficient structure likely represented as Mo(S₂₋ₓ)Oₓ. High oxygen content
further suggests the incorporation of oxygen either during synthesis or due to post-synthesis
oxidation.

Summary Table of Peak Fitting Results

Binding Energy FWHM Peak Area

Element Peak Assigned State Comments
(eV) (eV) (a.u.)

Mo 3d 3d₅/₂ 227.305 1.067 5057 Mo⁴⁺ (MoS₂) Primary MoS₂ peak

Mo 3d 3d₃/₂ 231.466 2.907 12455 Mo⁴⁺ (MoS₂) Spin-orbit pair

Mo⁶⁺ (MoO₃-
Mo 3d 3d₅/₂ 228.323 1.325 4125 Indicates oxidation
like)

Mo⁶⁺ (MoO₃-
Mo 3d 3d₃/₂ 235.249 1.981 2306 Oxidized state
like)
 37

Binding Energy FWHM Peak Area

Element Peak Assigned State Comments
(eV) (eV) (a.u.)

S 2p 2p₃/₂ 160.58 2.01 2685 S²⁻ (MoS₂) Main sulfur peak

S 2p 2p₁/₂ 161.79 2.75 2901 S²⁻ (MoS₂) Spin-orbit component

SOₓ (oxidized Suggests sulfur

S 2p 2p₃/₂ 167.90 2.53 2051
sulfur) oxidation

Lattice O (Mo– Metal oxide formation

O 1s 1s 530.85 3.13 3888
O) (Mo6+)

Surface OH / Surface Adsorbed

O 1s 1s 530.60 2.39 9546
H₂O Species

Mo 3d Core-Level Spectrum

Fig 19: Elemental XPS scan for Mo

 38

The Mo 3d region exhibits four distinct peaks:

• The primary doublet at 228.323 eV and 227.305 (3d₅/₂) and 231.466 eV (3d₃/₂) corresponds
to Mo⁴⁺ species in MoS₂. (19)

• Additional peaks at 233.3 eV and 236.4 eV indicate the presence of Mo⁶⁺, typically associated
with MoO₃.

Conclusion: The co-existence of Mo⁴⁺ and Mo⁶⁺ states confirm partial oxidation of molybdenum,
consistent with a mixed phase of MoS₂ and molybdenum oxide, Mo(S₂₋ₓ)Oₓ.

S 2p Core-Level Spectrum

Fig 20: Elemental XPS scan for S

 39

Peak Binding Energy (eV) Area FWHM (eV) %GL Comment

1 160.58 2685 2.01 0% S²⁻ (S 2p₃/₂ of MoS₂)

3 161.79 2901 2.75 0% S²⁻ (S 2p₁/₂ of MoS₂)

2 167.90 2051 2.53 6% Oxidized S (e.g. SO₄²⁻, SO₃²⁻)

Interpretation:

• The main S 2p doublet is present, so Mo–S bonds exist.

• But a strong oxidized sulfur peak (~168 eV) confirms partial sulfur oxidation.

• S 2p₃/₂ at 160.6 eV is slightly lower than the standard 162.0 eV, which could be due to charge
correction or electronic environment shifts. (20)

Conclusion: The intensity reduction in the prominent S 2p peaks and the presence of oxidized sulfur
suggest sulfur loss or oxidation during synthesis, supporting the formation of Mo(S₂₋ₓ)Oₓ.

O 1s Core-Level Spectrum

Two components are observed in the O 1s region

Interpretation:

• A significant oxygen bond in metal–oxygen (Mo–O) form.

• The broader FWHM of lattice O and strong OH/H₂O signal support oxidation of Mo and
surface adsorption.

Conclusion: The oxygen signals support the presence of molybdenum oxides and surface adsorbates,
confirming significant oxygen incorporation.
 40

Survey Scan

Fig 21: Survey Scan of the elemental composition

Final Remarks

"XPS analysis of the S 2p region revealed two prominent peaks at 160.6 eV and 161.8 eV,
corresponding to the spin-orbit doublet of S²⁻ species in MoS₂. An additional peak at 167.9 eV
indicated the presence of oxidized sulphur (e.g., SO₄²⁻), suggesting partial sulphur oxidation.
Similarly, the O 1s spectrum showed strong contributions from lattice oxygen (530.85 eV) and
adsorbed –OH/H₂O species (530.60 eV), confirming significant oxygen incorporation into the
structure. These results collectively confirm that the synthesized material is the oxidized phase best
described as Mo(S₂₋ₓ)Oₓ." This deviation is essential in engineering the material's electronic and
catalytic properties, and future synthesis should aim at enhancing sulfurization and reducing
oxidation.
 41

4.2 3 Raman Spectroscopy

Fig. shows the Raman spectra of MoS2 nanocrystals over a cleaned glass substrate. The observed
peaks at 377.277 and 403.224 cm−1 correspond to the E1 2g and A1g phonon modes of MoS2,
respectively. The hexagonal structure of all the MoS2 thin film samples is confirmed by peaks near
377.277 and 403.224 cm−1, which are related to the E1 2g and A1g phonon modes. The E1 2g mode
represents the in-plane vibration of molybdenum and sulphur atoms. In contrast, the A1g mode
involves the out-of-plane vibration of sulphur atoms, indicating the edge-terminated structure of
MoS2. (21)

Fig 22: Raman shift of sample

 42

4.2.4 FESEM

The FESEM images of the synthesized sample reveal the presence of partially formed nanoflower-
like structures, although the overall morphology lacks the uniformity and definition typical of well-
developed MoS₂ nanoflowers. In some regions, particularly in images S10_00 and S10_01, loosely
packed nanosheets and layered textures suggest the early stages of flower-like assembly. However,
the structures appear incomplete, with irregular stacking and non-uniform growth. Image S10_02
highlights a large central void surrounded by disordered material, possibly indicating solvent
evaporation effects or incomplete crystallization. Image S10_03 also shows non-uniform features and
some aggregated or amorphous domains. These results suggest that while nanoflower formation has
initiated, the synthesis conditions may have been insufficient to fully support the self-assembly
process, likely due to factors such as sulfur deficiency, oxygen incorporation, or suboptimal reaction
parameters. (20)

Fig 23: FESEM Images of the Sample

 43

4.2.5 UV-VIS Spectroscopy

The UV-VIS DRS (Diffusive Reflectance Spectroscopy) was performed to calculate the band gap of
the compound. The spectrum was recorded over a wavelength of 200-800 nm. To determine the band
gap, a Tauc plot was plotted to take (F(R) hv)1/2 versus photon energy by assuming the indirect
allowed electronic transition.

The band gap we obtained through extrapolation of the linear portion of the curve to the energy axis
comes out to be 2.53 eV.

The value obtained is significantly higher than the literature-reported value, i.e., 1.2 eV. This deviation
indicates that the synthesized material may possess a possible surface disorder. (21)

Fig 24: Tauc’s plot for calculation of band gap of material

 44

4.3 Conclusion
In this chapter, the structural, chemical, and morphological characterization of MoS₂ synthesized
through the hydrothermal method was performed using a suite of advanced techniques, including
XRD, XPS, Raman spectroscopy, FESEM, and UV-Vis spectroscopy. The X-ray diffraction (XRD)
analysis confirmed the formation of MoS₂ with a layered hexagonal structure. However, the
diffraction peaks were significantly broadened and showed reduced intensity, suggesting that the
obtained material possessed nanocrystalline characteristics with low long-range order. The crystallite
size, calculated using the Scherrer equation, was ~2.84 nm, confirming poor crystallinity of the
sample.

The X-ray photoelectron spectroscopy (XPS) study revealed key insights into the chemical states
present in the sample. While the Mo 3d and S 2p peaks corresponding to Mo⁴⁺ and S²⁻ were present
and consistent with MoS₂, additional peaks indicating Mo⁶⁺ and oxidized sulphur species such as
SO₄²⁻ were also observed. This suggested that during or after synthesis, partial oxidation of both
molybdenum and sulphur had occurred, possibly due to atmospheric exposure or incomplete reaction
pathways. The presence of oxygen was significant, and the composition was estimated to be
Mo(S₂₋ₓ)Oₓ, indicating that the stoichiometry was not ideal and further optimization was necessary.

Raman study confirmed the MoS₂ structure by detecting the characteristic E₂g and A₁g phonon modes.
However, the slight deviation in their positions suggested the presence of strain or defects within the
crystal lattice.

FESEM imaging highlighted morphological inconsistencies. Although some nanoflower-like

structures began to form, the images predominantly showed loosely packed nanosheets and irregular
textures, lacking the uniformity usually expected from well-formed nanostructures.

While a larger bandgap may benefit specific optoelectronic applications, it also suggests that the
material is structurally and chemically modified from its ideal form.

Overall, the findings from this chapter emphasize the importance of precisely controlling
hydrothermal reaction parameters to avoid oxidation and to achieve high-purity, stoichiometric, and
crystalline MoS₂.
 45

CHAPTER 5
Synthesis of MoS2

5.1 Experimental Procedure:

For the synthesis of MoS2 nanostructures, sodium molybdate dihydrate (Na2MoO4·2H2O) and
thiourea (CH4N2S) were used as the Mo and S sources, respectively. A stoichiometric amount of
sodium molybdate was dissolved in 35 mL of deionized (DI) water via magnetic stirring.
Subsequently, thiourea was added while maintaining a controlled molar ratio of Mo to S at 1:8. After
thoroughly mixing the solution for 1 h under magnetic stirring, the homogeneous solution was
transferred to a 100 mL Teflon-lined stainless-steel autoclave. The sealed autoclave was then
subjected to a hydrothermal reaction at 200 °C for 24 h. The as-obtained powder was centrifuged
several times using DI water and then dried at 180 °C for 2 hours, ensuring the formation of MoS2
nanostructures.

5.2 Characterizations

5.2.1 XRD Analysis

The X-ray diffraction (XRD) pattern of MoS2 powder is analysed to verify the single-phase formation
of MoS2 in the sample. Data collection is carried out across a 2θ range from 10º to 80º, with each
measurement taken at intervals of 0.02º. The results are shown in Fig., where the observed diffraction
peaks closely match those listed in the standard JCPDS card no. 01-075-1539. This agreement
confirms that the MoS2 has a hexagonal crystal structure. A significant peak is observed at 14.16º,
which corresponds to the (002) Miller indices. The prominent peaks in the XRD pattern show that the
synthesized material has the anticipated orientation and structure.
 46

Fig 25: XRD pattern of sample compared with standard JCPDS data

For the prominent diffraction peak observed at 2θ=14.08º, the FWHM was measured to be 0.84.
After converting the values to radians and applying them in the Scherrer equation, the calculated
crystallite size was found to be approximately 9.53 nm. This relatively large crystallite size indicates
good crystallinity of the synthesized material, suggesting well-defined crystal domains and minimal
lattice imperfections. Such enhanced crystallinity is often desirable in nanostructured materials,
particularly for electronic and spintronic applications, as it can lead to improved charge transport and
reduced defect-induced scattering.

5.2.2 Raman Analysis

Fig. shows the Raman spectra of MoS2 nanocrystals over a cleaned glass substrate. The observed
peaks at 373.109 and 401.43 cm−1 correspond to the E1 2g and A1g phonon modes of MoS2,
respectively. The hexagonal structure of all the MoS2 thin film samples is confirmed by peaks near
373.109 and 401.43 cm−1, which are related to the E1 2g and A1g phonon modes. The E1 2g mode
represents the in-plane vibration of molybdenum and sulphur atoms. In contrast, the A1g mode
involves the out-of-plane vibration of sulfur atoms, indicating the edge-terminated structure of MoS2.
(21)
 47

Fig 26: Raman shift of sample

5.2.3 XPS Analysis

The survey spectrum confirmed the presence of Mo, S, O, C, and a trace amount of Bi. The atomic
percentages derived from the survey are:

Element Atomic %

C 1s 34.8

S 2p 29.1

Mo 3d 21.8

O 1s 14.2
 48

High-resolution XPS analysis of the Mo 3d region reveals two dominant peaks at 228.05 eV and
231.21 eV, corresponding to the Mo 3d₅/₂ and Mo 3d₃/₂ components of Mo⁴⁺, respectively. These
values are consistent with stoichiometric MoS₂ and indicate the absence of higher oxidation states
such as Mo⁶⁺, which would otherwise appear at ~233–236 eV. The S 2p spectrum displays the
expected spin–orbit doublet for sulfide species, with peaks at 162.0 eV (2p₃/₂) and 163.2 eV (2p₁/₂).
No peaks were observed at higher binding energies, confirming the absence of oxidized sulphur
species such as SO₄²⁻. Together, these results confirm the successful synthesis of MoS2 with minimal
oxidation or sulphur deficiency. (23)

Mo 3d XPS Scan S 2p XPS Scan

Fig 27: Elemental XPS Scan of (a) Mo and (b) S

 49

Survey Scan of the elemental composition

Fig 28: Survey Scan of the elemental

composition

5.2.4 UV-VIS Spectroscopy

The UV-VIS DRS (Diffusive Reflectance Spectroscopy) was performed to examine the band gap of
the compound. The spectrum was recorded over a wavelength of 200-800 nm. The recorded spectrum
was converted into Kubelka-Munk function F(R) = (1-R)2/2R, where R is the Reflectance. To
determine the band gap, a Tauc plot was plotted to take (F(R).hv)1/2 versus photon energy by
assuming the indirect allowed electronic transition.

The band gap we obtained through extrapolation of the the linear portion of the curve to the energy
axis comes out to be 2.59 Ev.

The value obtained is significantly higher than the literature-reported value, i.e., 1.2 eV. This deviation
indicates that the synthesized material may possess a possible surface disorder. Such deviations have
usually been reported in some modified samples. Also, these enhance the potential performance in
applications where higher band gaps are favorable for wide-spectrum light absorption. (21)
 50

Fig 29: Tauc’s plot for band gap calculation of the material

5.3 Conclusion

This chapter describes the synthesis and characterization of MoS₂ with improved hydrothermal
parameters, i.e., increased sulfur content (1:8 molar ratio) and increased reaction temperature of
200°C for 24 hours. The aim was to rectify defects of previous synthesis, i.e., sulfur deficiency,
partial oxidation, and low crystallinity. The characterization confirms a significant improvement in
structural quality and phase purity. XRD analysis showed sharper peaks, indicating crystallinity and
long-range structural order improvement. High-resolution XPS confirmed the improved chemical
purity of the sample, with no sign of oxidized states. Raman spectra showed peaks at 373.1 cm⁻¹ and
401.4 cm⁻¹, indicating less strain and fewer structural defects. UV-VIS spectroscopy revealed a band
gap of 2.59 eV. This indicates that the deviation is primarily due to nanoscale phenomena rather than
disorder or oxidation effects. The enhanced synthetic methodology has achieved superior structural,
morphological, and electronic characteristics of MoS₂.
 51

CHAPTER 6
This thesis systematically investigated the synthesis, characterization, and optimization of
molybdenum disulfide (MoS₂), a two-dimensional transition metal dichalcogenide (TMD), using
hydrothermal techniques. The work was conducted in the broader context of enabling low-
dimensional materials for future applications in electronics, optoelectronics, catalysis, and
spintronics. Two separate synthesis routes were explored, each followed by comprehensive material
characterization using XRD, XPS, Raman spectroscopy, FESEM, and UV-Vis spectroscopy to assess
structural, chemical, and functional properties.

In Chapter 4, the initial synthesis employed a 1:5 molar ratio of Mo:S and a reaction temperature of
190 °C. While the XRD pattern confirmed the presence of MoS₂, the broad peaks and low crystallite
size (~2.84 nm) suggested poor crystallinity. XPS and Raman spectroscopy revealed partial oxidation
and sulfur deficiency, likely due to insufficient sulfur supply and suboptimal temperature. The
FESEM images displayed non-uniform morphologies, and UV-Vis spectroscopy indicated a
significantly large bandgap (~2.59 eV). These results highlighted the need for more controlled
reaction conditions to promote phase purity.

In contrast, Chapter 5 demonstrated the benefits of an optimized synthesis route, increasing the sulfur
ratio to 1:8 and the temperature to 200 °C. These adjustments yielded substantial improvements in all
key parameters: crystallinity was enhanced (crystallite size ~9.53 nm), oxidation was minimized
(absence of Mo⁶⁺ and oxidized S), and morphology showed better uniformity. Raman spectra aligned
well with literature values, and UV-Vis again showed a bandgap of 2.59 eV. However, in this case, it
could be primarily attributed to the nanoscale nature of the material rather than the disorder. These
enhancements strongly support the idea that hydrothermal synthesis can be finely tuned to engineer
2D materials with desired properties.

The thesis highlights the necessity of precise control over the precursor ratios, temperature, and time
in getting the phase-pure and stoichiometric MoS₂ nanomaterials. It provides a replicable
methodology for improving material quality and offers a roadmap for optimizing 2D materials for
specific functionalities. Future research directions include doping MoS₂ with transition metals,
forming heterostructures, addressing scalability, and incorporating synthesized MoS₂ into FETs,
photodetectors, or supercapacitor electrodes.
 52

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Thesis 12.pdf
ORIGINALITY REPORT

7 %
SIMILARITY INDEX
4%
INTERNET SOURCES
4%
PUBLICATIONS
2%
STUDENT PAPERS

PRIMARY SOURCES

1
www.mdpi.com
Internet Source 1%
2
Xiaoqiang Fan, Xiaopeng Li, Zhuang Zhao,
Zhaofan Yue, Peng Feng, Xiaoliang Ma, Hao Li,
1%
Xiangyuan Ye, Minhao Zhu. "Heterostructured
rGO/MoS2 nanocomposites toward
enhancing lubrication function of industrial
gear oils", Carbon, 2022
Publication

3
Saurav Lahiri, Manish Kumar, Thangavel R. "
An ab initio and monte carlo study of MS /VS
1%
(M=Mo, W) ferromagnetic bilayer with
negative magnetoresistance in MoS /VS
heterostructure ", Physica Scripta, 2024
Publication

4
Submitted to University of Witwatersrand
Student Paper 1%
5
www.researchsquare.com
Internet Source <1%
6
d.docksci.com
Internet Source <1%
7
escholarship.org
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8
iris.unitn.it
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9
diva-portal.org
Internet Source <1%
10
Submitted to University of Kent at Canterbury
Student Paper <1%
11
cyberleninka.org
Internet Source <1%
12
digital.csic.es
Internet Source <1%
13
iopscience.iop.org
Internet Source <1%
14
Reza Khazaeinezhad, Sahar Hosseinzadeh
Kassani, Tavakol Nazari, Hwanseong Jeong et
<1%
al. "Saturable optical absorption in MoS2
nano-sheet optically deposited on the optical
fiber facet", Optics Communications, 2015
Publication

15
circuitgenerator.com
Internet Source <1%
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mimp.materials.cmu.edu
Internet Source <1%
17
umpir.ump.edu.my
Internet Source <1%
18
J.-K. Guo, J. Li, H.-M. Kou. "Advanced Ceramic
Materials", Elsevier BV, 2017
<1%
Publication

19
Xu, Mingsheng, Tao Liang, Minmin Shi, and
Hongzheng Chen. "Graphene-Like Two-
<1%
Dimensional Materials", Chemical Reviews,
2013.
Publication

20
chinamanufacturer.law.blog
Internet Source <1%
21
Mingcai Yin, Fangfang Jia, Fangfang Qiao,
Pengfei Zheng, Wenli Zhang, Yaoting Fan.
<1%
"Facile wet-chemical synthesis and efficient
photocatalytic hydrogen production of
amorphous MoS 3 sensitized by Erythrosin B",
Materials Characterization, 2017
Publication
22
Submitted to University of Massachusetts -
Amherst
<1%
Student Paper

23
Keerthana Muthusamy, Aqib Muzaffar,
Basheer Ahamed M.. "Synthesis and
<1%
characterization of Fe(NO3)2-NiO composite
as a photocatalyst for degradation of
methylene blue dye under UV-irradiation",
Optik, 2019
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24
Rita Elena Serda. "Mass Transport of
Nanocarriers", Pan Stanford, 2019
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