SYNTHESIS AND CHARACTERISATION OF

Ti3C2Tx MXene THIN FILM

PROJECT REPORT

In partial fulfillment of the requirement for the sixth semester course of

Integrated M.Sc. in Sciences (Physics)
submitted by
ALEENA TOMY
REGISTER NO: 35220001

Under the supervision of

Dr. ASHA A S
Associate Professor, Department of Physics
Cochin University of Science And Technology
Kochi-22, Kerala, India

DEPARTMENT OF PHYSICS
COCHIN UNIVERSITY OF SCIENCE AND TECHNOLOGY
KOCHI-22, KERALA, INDIA
July 2023

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 CERTIFICATE

This is to certify that the Minor Project work entitled “SYNTHESIS AND
CHARACTERIZATION OF Ti3C2TX MXene THIN FILM” is the bonafide
work done by ALEENA TOMY (Register No: 35220001), at Cochin
University Of Science and Technology under the supervision of Dr. ASHA A S,
in partial fulfilment of the requirement for the sixth semester course of
Integrated M.Sc. in Sciences (Physics).

Dr. ASHA A S Prof. TITUS K MATHEW

Supervising Guide Head of the Department
Associate Professor Department Of Physics
Department of Physics CUSAT
CUSAT

2
 DECLARATION

I ALEENA TOMY hereby declare that the thesis entitled “SYNTHESIS AND
CHARACTERIZATION OF Ti3C2TX MXene THIN FILM” is the work
done by me under the guidance of Dr. ASHA A S, Associate Professor,
Department of Physics, Cochin University of Science and Technology.

Kochi-22 Aleena Tomy

3-July-2023 Integrated M.Sc. in Physics
Centre For Integrated Studies
CUSAT

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 ACKNOWLEDGEMENT

The "SYNTHESIS AND CHARACTERIZATION OF Ti3C2Tx MXene

THIN FILM" project work was completed at the Department of Physics,
Cochin University Of Science & Technology, under the supervision of Dr.
ASHA A S. I would like to use this occasion to express my gratitude to
everyone who helped me finish this work.

My supervisor and adviser, Dr. ASHA A S, Associate professor in the

Department of Physics at Cochin University of Science and Technology, has
been a tremendous help to me during my work. I would like to offer my
heartfelt thanks to her for her valuable guidance and thoughtful advice.

I embrace Prof. Titus K Mathew, Head of the Physics Department at Cochin

University of Science and Technology, for being supportive and for providing
the essential infrastructure resources.

I am appreciative of the opportunity and the support I have received from Dr.
Manoj N, Coordinator of the Centre for Integrated Studies at CUSAT, and Dr.
Prasad V V, Course Coordinator.

For their huge support, assistance, and encouragement throughout my work, I

would like to thank Ms. Anamika Ashok and Ms. Varsha Vijayan, Research
Scholars, Nanomaterials for Emerging Solid State Technology Research
Laboratory, Department of Physics, CUSAT.

I sincerely appreciate the collaboration and assistance of all of my lab mates.

In particular, I want to thank my parents and all of my friends and well-wishers

for their support and affection throughout my academic career.

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 CONTENTS
Abstract 7

List Of Figures 8

Chapter 1: Introduction

1.1: Nanomaterials 9
1.2: Classification Of Nanomaterials 9
1.3: Two Dimensional Nanomaterials 10
1.4: MXene 10
1.5: MAX Phase 10
1.6: General Properties of MXene 11
1.6.1: Structural Properties
1.6.1.1: MAX Phase
1.6.1.2: MXene
1.6.2: Electrical Properties
1.6.3: Optical Properties
1.7: Synthesis Of MXene 15
1.7.1: Top Down Approach
1.7.1.1: Etching
1.7.1.2: Washing and Exfoliation
1.7.2: Bottom Up Approach
1.7.3: Fabrication of Thin Films
1.7.3.1 : Spray Coating Method
1.9: Applications of MXene thin films 19
1.9.1: Memristors
1.9.2: Transparent Conducting Thin Films
1.9.3: EMI Shielding
1.10: Objective of the Present Study 21
1.11: Conclusion 21
1.12: References 22

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Chapter 2: Synthesis & Characterization

2.1: Introduction 26
2.2: Synthesis of Ti3C2Tx MXene 26
2.3: Thin Film Fabrication 28
2.3.1: Spray Coating Technique
2.3.2: Fabrication of MXene thin film
2.4: Characterization Technique 31
2.4.1: X-Ray Diffraction
2.4.2: UV-Visible NIR Spectroscopy
2.4.3: Field Emission Scanning Electron Microscopy
2.4.4: Stylus Profilometry
2.4.5: Cross Sectional SEM
2.4.6: Two Probe Method
2.5: References 40

Chapter 3: Result & Discussion

3.1: Introduction 43
3.2: Morphological Analysis 43
3.3: Structural Characterization 44
3.4: Optical Characterization 47
3.5: Electrical Analysis 48
3.6: Summary and Conclusion 52

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 ABSTRACT

The transparent conducting thin films are of growing interest in the field of flat panel
displays, solar cells, touch panels owing to their good electrical conductivity and light
emission. The most widely used transparent conducting oxides is ITO. The ongoing efforts to
replace ITO had met many other competitors. Among them, 2D transition metal carbides and
nitrides also known as MXenes which exhibit brilliant optoelectronic properties is a potential
contender. In the current study, an in situ HF etching technique is used to create Ti3C2Tx
MXene. Spray coating was used to deposit the delaminated stable colloids produced by
ultrasonication and centrifugation onto a glass substrate. Thin films are prepared by varying
the synthesis parameters like spray rate and deposition time. The optoelectronic properties of
thin films were investigated and the morphology was studied. For the fabricated MXene thin
films, with increasing deposition time and spray rate sheet resistance increased while the
figure of merit increased with increasing thickness and then decreased with further increase.
Thus optoelectronic properties of MXene thin films can be tuned by varying the preparation
conditions.

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 LIST OF FIGURES

1.1 : Unit cells of a) 211, b) 312 and c) 413 phases.

1.2: Views from the top and sides of the (a) pristine, (b)model 2 and (c) model 4 MXenes.
1.3: The colloidal solutions of Ti2C, Ti3C2
1.4: Synthesis pathway using different etchants.
2.1: Products after centrifugation
2.2: Diagrammatic representation of the mass flow controller, injection pump, and atomizing
nozzle for the automated spray coating system.
2.3: A - Nozzle head, B - Coating Fluid, C - Atomization through collision with air
2.4: Schematic diagram of spray coating technique and the image of fabricated thin film
2.5: a) Condition for constructive interference in XRD. Red and green circles represent
scattering centers for X-rays. b) Schematic Diagram of X-Ray Diffractometer
2.6: Schematic diagram of HR-XRD
2.7: Schematic diagram of UV-Visible spectrophotometer
2.8: Schematic representation of working of FE-SEM
2.9: Schematic diagram of Stylus Profilometer
2.10: Diagram of two-probe method
3.1: SEM image of a) MXene powder and b) MXene thin film
3.2: a) XRD pattern of Ti3AlC2 MAX phase and Ti3C2Tx MXene . b) XRD pattern of Ti3C2Tx
MXene thin film fabricated at two different spray rates.
3.3: Variation of grain size with deposition time for the MXene thin films prepared at a spray
rate of 1 ml/min and 2 ml/min
3.4: Transmittance spectra of MXene thin film fabricated at varying duration at a spray rate
of a) 1 ml/min & b) 2 ml/min respectively.
3.5: I-V plot of fabricated MXene thin films.
3.6: Variation of sheet resistance with the duration of spray.
3.7: Variation of figure of merit with duration of spray.

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 CHAPTER 01
INTRODUCTION

1.1 NANOMATERIALS
Nano is a millionth of a millimeter or billionth of a meter [1]. Nanomaterials are said to be
those substances for which at least one dimension is less than approximately 100 nanometres.
Due to their small-scale dimension, nanomaterials have unique optical, magnetic and
electrical properties [2]. They show an extremely large surface-to-volume ratio than their
bulk counterparts. This property together with the quantum confinement alter their physical
properties appreciably [3]. Phenomenally, they can show unique character when their size and
shape are modified at the nanoscale level [4].

1.2 CLASSIFICATION OF NANOMATERIALS

Nanomaterials are ranked into many categories depending on their size, composition, form,
origin, dimension, etc. Nanomaterials should be categorized precisely based on their
dimensionality [5]; because at the nanoscale the properties of a material change significantly
as a function of size and dimension[6].

According to their dimensions, they are categorized as follows:

(i) Zero-dimensional nanomaterials (0-D): The nanomaterials having all their

three dimensions in the nanoscale range, eg. Fullerenes and Quantum Dots.
(ii) One-dimensional nanomaterials (1-D): The nanomaterials having one
dimension outside the nanoscale range, eg. Nanotubes and Nanorods.
(iii) Two-dimensional nanomaterials (2-D): The nanomaterials having two
dimensions outside the nanoscale range, eg. Nanosheets and Nanolayers.
(iv) Three-dimensional nanomaterials (3-D): The nanomaterials having no
dimensions confined to the nanoscale range, eg. Bulk powders, Dispersion of
nanoparticles, etc[7].

1.3 TWO-DIMENSIONAL NANOMATERIALS

2D nanomaterials possess a layered structure with strong in-plane bond but the Van der Waal
force of attraction between the layers is weak. The high aspect ratio or surface area to volume

9
ratio is one of their characteristics and hence they have more atoms on their surface which
leads to a change in the behaviour of 2D nanomaterials [8]. In contrast to 0D, 1D, and 3D
nanomaterials, the electronic characteristics of 2D nanomaterials may be accurately
controlled by manipulating their thickness[9]. There has been a lot of interest in 2D materials
since the discovery of graphene. Graphene has a huge specific surface area, good optical
transparency, outstanding thermal conductivity, extremely high carrier mobility at ambient
temperature, and many other unusual characteristics.

1.4 MXENE

Two-dimensional (2D) materials have been extensively studied since the discovery of unique
characteristics of single-layer graphene. This curiosity sparked a new wave of research on 2D
materials already known to exist, like metal dichalcogenides and boron nitride, as well as the
identification of numerous novel 2D materials. These latter include the rapidly expanding
class of 2D materials known as MXenes (pronounced "maxenes"), which consists of
transition metal carbides and nitrides [10]. MXenes was discovered in 2011.
Two-dimensional (2D) transition metal carbides, nitrides and carbonitrides are collectively
called MXenes. The structure of MXene can be written as Mn+1XnTx, where:

● M is an early transition metal (Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W)
● X is a carbon or/and nitrogen
● Tx represents the surface terminations such as O, OH, F, or Cl and x in Tx gives the
number of surface functionalities
● The n in the equation can be from 1-4 [11].

MXenes are usually synthesized by chemical etching from their parent phase known as MAX
phase.

1.5 MAX PHASES

MAX phases were a contender for energy storage before MXenes. The father of MAX phases
is Prof. Michel W. Barsoum. MAX phases are known as the precursors of MXenes given by
the formula Mn+1AXn . The M in the formula denotes the early transition metal, A denotes
elements mostly such as In, Al, S, Si, Cd, P, Ga, As, Ge, Sn, and Pb, and X gives carbon
or/and nitrogen [11]. The several stoichiometries of MAX phases are indicated as 211 (n=1),
312 (n=2), 413 (n=3) etc. Closely packed layers of metal atoms and layers of pure group

10
A-element are interspersed in each unit cell of the 211, 312, and 413 phases, with X-atoms
filling the octahedral positions between the former[12].

While the M-X layers are covalent linked, M-A bonds in the MAX phase are entirely metallic
in nature. Because the covalent connections between M-X layers are typically stronger than
those between M-A layers, selective etching of A layers is feasible. Thus, by eliminating A
layer from the bulk 3D MAX phase, 2D MXene can be created[13].

1.6 GENERAL PROPERTIES OF MXENES

1.6.1 Structural properties

1.6.1.1 The MAX phase

MAX phases reside in the space group D46h-P63/mmc, with two formula units per unit cell.
They possess a layered hexagonal structure. The unit cells of the 211, 312, and 413 phases are
contrasted in Figures 1(a), (b), and (c), respectively [14].

Figure 1.1 : Unit cells of a) 211, b) 312 and c) 413 phases. Vertical arrows marked with the letter "c"
separate the unit cells. The horizontal dashed line is drawn through the centers of the unit cells [14].

The difference in the number of M layers between the A layers is what distinguishes the 211,
312, and 413 phases. The unit cells are made up of layers of A elements interspersed between
M6X octahedra, such as Ti6C. The MX layers are twinned with respect to one another in the

11
MAX phases, and the A layer serves as a mirror plane to separate them. The Al-based MAX
phase is the most widely utilised.

Ti3AlC2 is the MAX phase employed throughout thepresent investigation. It has the
hexagonal structure and the lattice parameters as; a = 3.07 Å, c =18.58 Å and theoretical
density 4.5 g/cm3[16]. It only took around 2 years to establish MXenes as a unique class of
2D materials in their own right because the A layers can be selectively erased from the MAX
phases to generate MXene[17].

1.6.1.2 MXene

From their parent MAX antecedents, MXenes inherit hexagonal symmetry with the P63/mmc
space group. As contrary to the M-Al bond, which is metallic, the in-plane M-X bond in the
Al-containing MAX phases has a mixed covalent, metallic, and ionic character, making it
easy to selectively remove the Al layer from the MAX phases and transform them into
MXenes. Following etching, surface terminations of O, OH, F, and/or Cl are bonded to the
outer transition metal layers.[16].

It is proper to presume that the transition metals in MXenes make six chemical bonds with
the nearby X atoms and the associated chemical groups on the surfaces since the coordination
number of a transition metal ion is frequently six. In the structure of MXene, the X element
atoms are located in the octahedral interstitial sites, while the transition metal (M) atoms are
organised in a relatively close-packed arrangement. On the surface of the M2X type of
MXenes, there are three potential locations for surface terminations: hollow site A and
hollow site B.

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 Figure 1.2: Views from the top and sides of the (a) pristine, (b)model 2 and (c) model 4 MXenes. A
and B stand for different kinds of hollow sites that are mentioned. Transition metal, C/N, and the
associated chemical groups (F, O, or OH) are indicated by the letters M, X, and T, respectively[17].

Hollow site A: The site under which there is no X atom between transition metal layers.

Hollow site B: The site under which there is an X atom between transition metal layers.

1.6.2 Electronic Properties

The pure MXenes are identical to the MAX phases in that they are completely metallic.
However, several of the MXenes exhibit semiconductivity after surface functionalization.
Non-terminated (bare) MXenes have a high density of states (DOS) at the Fermi level and are
metallic[18].

The d-electrons of the transition metals dominate the DOS (density of states) for the majority
of MXenes close to the Fermi level, whereas the p-electrons of the X atoms form energy
bands between -3 and -5 eV below the Fermi level. The states close to the Fermi level for
Mn+1Xn (n = 1, 2, 3 or 4) MXenes are mostly controlled by the d-electrons of the metal atoms
on the surface.

13
The surface functionalization of the metal surfaces can have an impact on the electronic
structure, which is a major factor in the electronic characteristics of MXenes. Following the
termination of the metal surface, the Fermi level drops lower as new bands develop below it.
A large reduction in DOS of the surface transition metal at the Fermi level is caused by
surface functionalization, and this is because electrons from the transition metal are
transferred to the surface terminations that are electronegative [19].

As an illustration, pure Ti3C2 MXene exhibited metallic properties; however, when -OH, -F,
and -I functional groups were added to the material's surface, semiconductivity was
discovered. Furthermore, it has been shown that the electrical conductivity of MXenes is
inversely related to the number of layers. And, the electrical conductivity shown by the
MXene flakes are generally between 850 - 9880 S/cm-1[20].

1.6.3 Optical Properties

In studies of MXene-light interaction, the first step is often UV-vis-NIR spectroscopy, which
can be performed on colloidal solutions and thin films. The absorption of light by MXene in
the visible and near-infrared ranges is caused by electronic transitions and plasmonic
processes. MXene's coloration (diluted Ti3C2Tx aqueous solutions are green) is due to the
distinctive plasmonic peak at roughly 780 nm. On the other hand, the thinner Ti2CTx MXene
exhibits a plasmonic peak at 550 nm, giving its solution a vining shade [21].

Figure 1.3: The colloidal solutions of Ti2C, Ti3C2

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Surface plasmons and bulk plasmons are two ways to categorise MXene's plasmonic
characteristics. The electrons in metal atoms collectively oscillate when MXene is
illuminated, producing an electrical dipole moment. Surface plasmons are the electronic
oscillations that arise at the MXene-dielectric contact, whereas bulk plasmons form further
inside the MXene[22].

In the case of Ti3C2Tx, the MXene powder is black while its corresponding precursor, i.e,
Ti3AlC2 powder is ash in colour. It has a plasmonic peak around 780 nm. The optical
absorption for this compound is found at 1.7 eV and is associated with the transversal surface
plasmon, while the absorption is found at 0.8 eV which is interconnected with dipole surface
plasmon.

Ti3C2Tx is 93% transparent in bulk form when it is 4 nm thick. This qualifies it as a possible
material for transparent electrodes and conductors.

1.7 SYNTHESIS OF MXENES

Top-down and bottom-up methods are the two main strategies used to create 2D Mxenes.
While the bottom-up strategy focuses on the development of MXenes from atoms or
molecules, the top-down method relates to the exfoliation of huge crystal amounts into
single-layered MXene sheets. As of now, a large portion of the synthesis of MXene includes
wet application of an etching method followed by phase exfoliation [23]. Usually, MXenes
are synthesized from MAX phases. During the synthesis, the A layer is removed from the
MAX phase by the selective etching method coming under the top down approach.

1.7.1 Top Down Approach

In almost all top down processes for producing (2D) materials, exfoliation from bulk layered
materials is an important method. Since the first effective selective separation of Al from
Ti3AlC2 to produce Ti3C2, top-down synthesis methods have been the most common method
for creating MXenes [24].

1.7.1.1 Etching

The first stage in the synthesis of MXene is the selective etching of the A layer from the
MAX phase. The various terminal groups Tx, such as hydroxyl (-OH), oxygen (-O), or
fluorine (-F), always replace the etched layers. After etching, Mn+1XnTx multilayers are held

15
together by weaker van der Waals bonds. Several types of etching methods are available to
extract Ti3C2Tx from its MAX phase Ti3AlC2. For the etching process, we use “in-situ HF”
which is a powerful etching agent. However it is highly corrosive.

There are four categories of etching techniques: HF, HF-forming, HF-containing (mixed acid)
etchants, and alkaline and/or hydrothermal treatments[25].

i) Direct etching using HF

The first technique for weakening the M-A metallic bindings while maintaining the strength
of the M-X bonds involves exposing a layered precursor (such as Ti3AlC2) to concentrated
aqueous HF, which will eventually result in the selective etching of A layer from various
Mn+1AXn systems [26]. In this method, Ti3AlC2 is mixed with HF of high concentration
(about 48 wt.%) for 5 hours. Different concentrations of HF with different etching time can
also be used for this process. Due to the evolution of hydrogen gas, an open accordion
structure will result from using 48wt.% HF as an etchant. Hydrogen evolution likewise
diminishes when the concentration of HF rises[25].

ii) Etching by In-Situ HF Formation

To selectively remove aluminium from Ti3AlC2, concentrated HF has frequently been the
preferred etchant. Since HF is a highly corrosive chemical that can penetrate skin, muscle
tissue and bones; the method of in-situ preparation of HF for etching is more suitable. The
intercalation of Li+ ions, which simplifies the etching process, is a significant advancement of
this technique[27].

When LiF and HCl are mixed, the fluoride salt serves as a limiting reagent [13]. The MXene
created in this way exhibited a wider interlayer spacing than the one created using only HF
because cations from fluoride or bifluoride salts were intercalated into the etchants. This
approach commonly contains unetched MAX phase even if delamination takes less time [28].

iii) HF containing Etching

Acid mixtures containing lower concentrations of HF can be used as etchants in the MXene
synthesis. Using HF/HCl etchants, Shahzad et al. synthesised Mo2TiC2 and Mo2Ti2C3 from the
Mo2TiAlC2 and Mo2Ti2AlC3 MAX phases, respectively. Stable colloidal MXene solutions
were produced by intercalating tetrabutylammonium hydroxide (TBAOH), and then manually
shaking and rinsing the intercalants [29].

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iv) Alkaline and/or Hydrothermal Treatments

The binding capacity of aluminium with alkali is strong. Hence the alkaline etchants can be
used extensively to etch Ti3AlC2 or any other layered precursors. Fluoride-free etchants are
also suggested, using a combination of alkali and hydrothermal treatments, such as sodium
hydroxide (NaOH) followed by H2SO4 hydrothermal treatment [30].

1.7.1.2 Washing & Exfoliation

After etching, the solution that contains MXene multilayers is acidic in nature. Therefore,
they are rinsed multiple times to achieve a pH balance and to get rid of any synthesis
by-products. The conversion of multilayered into single or few layered MXene is known as
delamination or exfoliation.

Figure 1.4: Synthesis pathway using different etchants [31].

The multilayers formed can accommodate many types of cations and organic compounds. In
LiF/HCl etching, the process of sonication alone can lead to delamination. But in HF etching
an additional process named intercalation is required to achieve exfoliation. Some
intercalants used for this purpose are: Dimethyl Sulphoxide (DMSO), tetrabutylammonium
hydroxide (TBAOH), tetramethylammonium hydroxide (TMAOH) etc[31].

1.7.2 Bottom Up Approach

Bottom-up methods effectively construct the materials atom by atom, one layer at a time.
This means that it has the ability to create materials that are almost flaw free, with certain
orientations revealed, or to create materials or structures that won't naturally form. Physical
vapour deposition and chemical vapour deposition are the two main strategies for bottom-up

17
synthesis. Although there have been numerous recent developments in these methods that
have reduced the cost and produced larger crystals, these methods are expensive and have a
limited potential to scale[32].

1.7.3 Fabrication of MXene thin film

Fabrication of thin films from various 2D materials opened up a new channel in the research
development. Depending on the needs, many thin film fabrication techniques are utilised,
such as magnetic assemblies, chemical/physical vapour deposition, electrodynamic
atomization, dip coating, spin coating, and spray coating. Gold nanoparticles, graphene,
carbon nanotubes, and black phosphorus have all attracted a lot of attention as thin films of
2D materials, but the difficulty of thin film fabrication and unsatisfactory stripping strategies
limit their use for advanced applications[33].

MXene, a new class of 2D transition metal carbides or nitrides, has exhibited properties like
metallic conductivity, hydrophilicity, high mechanical strength and the ability to act as an
intercalant host agent. Among the several materials under consideration for transparent
conductive thin film applications, due to its exceptional characteristics, 2D MXene has
perhaps received the most attention recently. The thin film fabrication is mainly done through
chemical vapor deposition (CVD) process or solution-processed methods.
Solution-processing techniques involves spray coating, spin coating, and dip coating.
However, the high sheet resistance (Rs) of the transparent films made using such techniques is
mostly caused by defects (functional groups) and inter-flake resistance. After the
delamination during the synthesis, the formed MXene colloidal solution contains huge
amount of ≅1 nm thick 2D flakes with lateral dimensions of up to several micrometres. This
makes it a better candidate for solution-processing [34].

1.7.3.1 Spray Coating Method

For large-area processing methods, spray coating is regarded as the best choice. It is
recognized as one of the fastest methods for fabrication of thin films, and when compared to
spin coating methods, it is helpful on an industrial scale.

In spray coating technique, thin and homogenous layers can be accomplished by repeatedly
washing the substrate and spraying it with MXene solution. The spray flow, spray speed,
substrate type, and spray cycles all have an impact on the property of MXene thin films. For

18
instance, using the spray-coating technique, Gogotsi et al. produced Ti3C2 MXene thin films
with thicknesses ranging from 5 to 70 nm[35].

1.8 APPLICATION OF MXENE THIN FILMS

MXene have drawn a lot of attention in research because of their distinctive properties, which
include superior electrical conductivity, high volumetric-electrochemical capacitance, tunable
plasmonic features and work function, optical transparency, high thermal stability, good
mechanical strength, and the ability to form highly stable colloidal solutions in a variety of
polar solvents, particularly alcohols and water. Due to their appealing properties, MXenes
have been used in a number of industries, including energy storage, electronics and are used
as structural components, and for environmental cleaning. The most extensive use of MXenes
to date was for energy storage, but it has subsequently been expanded to encompass
supercapacitors and all kinds of batteries [36].

Nowadays, transparent conducting electrodes and thin films are essential components in
many electronic devices. Indium tin oxide is now the preferred transparent conductive
electrode because of its good optoelectronic characteristics. However, continuing initiatives
are being made to other materials including conducting polymers, metal, and carbon-based
nanostructures such as “MXene '' in its stead. Some emerging studies and applications of 2D
MXene are found in memristors, transparent conducting thin film, EMI shielding etc[35].

1.8.1 Memristors

Memristors—artificial synapses based on diverse 2D materials—have been developed in

order to overcome the von Neumann bottleneck and Moore's law constraints, for
neuromorphic and data storage technologies with low power, great scalability, and high
speed. Having configurable device resistance, they are a nonlinear electrical component. In
2008, the HP research lab at California, physically created the first memristor, which was
made up of a sandwich-like Pt/TiO2/Pt structure. The sandwich-like construction of
memristor devices, which have an electrode, active material, and electrode arrangement, is
radiation- and energy-resistant. MXene are being considered as a viable material for synthetic
synapses. Because of their extremely high conductivity, quick charge response, great stacking
density, and high hydrophilicity, 2D MXenes have a significant potential for use in
memristors [38].

19
1.8.2 Transparent Conducting Thin Films

Indium tin oxide (ITO) is now the preferred transparent conducting electrode because of its
superior optoelectronic characteristics. However, there are ongoing initiatives to replace it
with substitutes like conducting polymers, metal, and carbon-based nanostructures. High
transmittances (>85%) in the visible and ultraviolet spectrums, as well as low sheet
resistances (Rs) in the range of 0.01 to 1 kΩ sq-1, are necessary characteristics of innovative
transparent electrode materials. The new materials also need to be strong mechanically for
applications using flexible touch screens and organic light-emitting diodes. Added to good
mechanical and optoelectronic characteristics, affordable production costs, unit area and the
viability of large-scale manufacturing are crucial determinants of their industrial achievement
[35].

MXene with its extravagant optoelectronic and structural properties, proved that they were a
good choice for the competing candidate against ITO. Ti3C2Tx MXene thin films produced by
spray coating method are cost efficient and feasible for large scale production. These
transparent conducting and flexible thin films processed by spray coating find its application
in the field of transistors, memory devices, integrated circuits, solar cells and many more
[40].

1.8.3 EMI shielding

Unwanted noise or interference in an electrical route or circuit brought on by an external

source is known as electromagnetic interference (EMI).The performance of electronic
devices are affected by electromagnetic interference. An increase in EMI in gadgets has the
ability to seriously harm both the health of people and the devices themselves. To minimise
this EMI effect, a shielding material with strong, accurate, highly conductive, and
electromagnetic radiation absorption qualities is always needed.

Numerous 2-D materials have been investigated to block EMI, including metals, polymer
matrices, and composite materials, however their drawbacks hinder their direct application in
electronic devices. Due to their superior conductivity, flexibility, and simplicity of binding
with other polymers, MXene thin films are potential candidates for EMI shielding.
Controlling the concentration of MXene and thickness of the shield stronger EMI shielding
effect can be produced. The thick film architecture and high conductivity of Ti3C2Tx MXene
had a significant impact in providing increased shielding effect [34].

20
1.9 OBJECTIVE OF THE PRESENT STUDY

The objective of the current study is to prepare titanium carbide MXene from equivalent
MAX phase Ti3AlC2 through in-situ HF forming etching method. Then to fabricate
transparent and conducting MXene thin films using the spray coating technique. And the
investigation of the optoelectronic properties with the variation in preparation conditions.

1.10 CONCLUSION

The structure, properties and synthesis methods of 2D transition metal carbides and nitrides
are overviewed. Fabrication of these materials into thin films using spray coating techniques
and their application are briefly discussed. The structure and characteristics of MXene can be
varied by the synthesis process as well as by varying the thin film production techniques.

21
1.11 REFERENCES

1. Introduction to nanomaterials and nanotechnology,

https://www.agc.ac.in/resources/Introduction_to_Nanomaterials_and_Nanotechnolog
y.pdf
2. A, Alagarasi,. (2011). Chapter - INTRODUCTION TO NANOMATERIALS.
3. Quevedo AC, Guggenheim E, Briffa SM, Adams J, Lofts S, Kwak M, Lee TG,
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13. Berdiyorov, Golibjon. (2016). Optical properties of functionalized Ti3C2T2 (T = F, O,

OH) MXene: First-principles calculations. AIP Advances. 6. 055105.
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14. Michel W. Barsoum, The MN+1AXN phases: A new class of solids:

Thermodynamically stable nanolaminates, Progress in Solid State Chemistry, Volume
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15. Eklund, Per & Rosén, Johanna & Persson, Per. (2017). Layered ternary Mn+1AXn
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16. Hantanasirisakul, K., Gogotsi, Y., Adv. Mater. 2018, 30, 1804779.
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17. Anasori, Babak & Gogotsi, Yury. (2019). 2D Metal Carbides and Nitrides (MXenes)
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Applications. Molecules 2022, 27, 4925. https://doi.org/10.3390/molecules27154925

35. Hantanasirisakul, Kanit & Zhao, Meng-Qiang & Urbankowski, Patrick & Halim,
Joseph & Anasori, Babak & Kota, Sankalp & Ren, Chang & Barsoum, Michel &
Gogotsi, Yury. (2016). Fabrication of Ti3C2Tx MXene Transparent Thin Films with
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(2022). Emerging MXene‐Based Memristors for In‐Memory, Neuromorphic
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film fabrication by electrohydrodynamic atomization technique. J Mater Sci: Mater

Electron 27, 5440–5445 (2016). https://doi.org/10.1007/s10854-016-4447

25
 CHAPTER 02

SYNTHESIS & CHARACTERIZATION

2.1 INTRODUCTION

In comparison to other 2D materials, MXene thin films have aroused scientific interest due to
its unique opto-electronic properties. The initial stage in the preparation of thin film is the
synthesis of MXene powder from its MAX phase precursor. The surface terminations that are
added during synthesis can vary, leading to rich surface characteristics that have a significant
impact on its properties. In the present study, spray coating technique is employed to fabricate
MXene thin films. The structural, optical and morphological characterisation of the prepared
thin films are carried out using various techniques.

2.2 SYNTHESIS OF Ti3C2TX MXene

Using the top-down liquid phase exfoliation approach, Ti3C2Tx MXene is synthesized. The
in-situ HF forming etching route uses a LiF/HCl based etchant. To create Ti3C2Tx Mxene, the
Al layer of the MAX phase precursor is exfoliated during the etching procedure[1]. The
following are the main steps in the synthesis process:

i) Etching using in-situ HF formation (LiF/HCl):

In light of the hazardous nature of hydrofluoric acid (HF), a moderate etchant solution
including a mixture of lithium fluoride (LiF) and hydrochloric acid (HCl) was used to
accomplish the selective etching. In this process, 1.6g of LiF is added to the HCl solution
(5ml DI water + 15 ml HCl) at room temperature. The HCl solution used is 35-37 wt%. This
mixture yields HF with a low concentration (3-5%) according to the following equation:

LiF(aq) + HCl(aq) = HF(aq) + LiCl(aq) [2] (2.1)

1g of Ti3AlC2 is then slowly added into the LiF + HCl etchant solution under magnetic
stirring for 24 h maintained at 200 rpm (rotations per minute). The reaction mechanism that
leads to the formation of Ti3C2 is given below:

2Ti3AlC2 + 6LiF + 6HCl ⟶ 2Ti3C2 + Li33AlF6 + AlCl3 + 3LiCl+ 3H2 (2.2)

26
ii) Centrifugation

The etched solution will have an acidic pH less than 1. To make the synthesized solution
alkaline in nature, the solution is diluted using deionized water. The diluted solutions are
poured into 4 centrifugation tubes respectively, which is centrifuged for 30 minutes under
8000 rpm. This process is repeated till the pH is above 6 [3]. All of the further reaction
by-products (supernatant) are eliminated during centrifugation.

Figure 2.1: Products after centrifugation[4]

For the subsequent stages of synthesis, the pellets or precipitate are utilised.

iii) Extraction of multilayer MXene

The precipitates are once again diluted, and the resulting solution is vacuum filtered to
produce multilayered MXene. The process of vacuum filtration is done using the help of a
PVDF membrane or polyvinyl difluoride membrane. The membrane has a pore size of about
0.22 µm. The resulting filtrate is stored in the desiccator until it is dried and then crushed
with mortar to obtain the MXene powder.

iv) Preparation of solution for thin film fabrication ( sonication & centrifugation)

0.5g of MXene powder is weighed and diluted using 100 ml of DI water. To thoroughly mix
the components, the solution is ultrasonicated five times at intervals of ten minutes. After
that, the mixture is centrifuged for an hour at 2500 rpm. The supernatant form is used for the
thin film fabrication.

2.3 THIN FILM FABRICATION

27
The spray coating technique is used to fabricate thin films of MXene. Spray coating can bring
out the most defect free and uniform thin films. The colloidal solution containing delaminated
Ti3C2Tx MXene solution ( 0.5 g in 100 ml of deionized water) is used for the preparation of
thin films. Flow rate or liquid infusion rate (1 and 2 ml/min) and duration of spray coating
(5,10,15,20 and 25 min) are the parameters varied and optimized so as to achieve a
transparent conducting thin film. Parameters such as concentration (0.5 g in 100 ml) and
substrate temperature (100 ℃) are kept constant.

2.3.1 Spray Coating Technique

Spray coating is the process of atomising the solution and depositing them on a substrate. The
spraying nozzle is used to disperse the coating liquid into tiny droplets[5]. There are different
types of spray methods: pneumatic spray method, ultrasonic spray method and electrostatic
spray method [6]. For the thin film fabrication of Ti3C2Tx MXene thin film in the present
study, an air spray coating head is used. The machine used is an ‘ADVANCED SPRAY
COATER’, model - SprayPyAtm 302 of ‘Delgado coatings & technology solutions Pvt.
Ltd.’.

Working & Instrumentation:

Aerosol spray is generated using a pneumatic nozzle. The spray is made to fall on the
substrate kept at 100 ℃. The fluid will get adhered to the surface, leaving behind a dry
uniform film.

Figure 2.2: Schematic representation of the mass flow controller, injection pump, and atomizing
nozzle for the automated spray coating system. Robotics can control the X- and Y-direction
autonomously[7].

28
As shown in figure 2.2, the atomization of the coating fluid is achieved with the help of high
pressure air that passes through the spray nozzle.

A clear view of atomization of droplets is depicted in the following diagram:

Figure 2.3: A - Nozzle head, B - Coating Fluid, C - Atomization through collision with air

The resultant film’s properties will be decided by: viscosity and surface energy of the
solution, the spray rate, the distance between substrate and the spray head, the duration of
spray coating[8]. All these parameters can be optimized to obtain a transparent conducting
thin film with good optoelectronic properties.

2.3.2 Fabrication of MXene thin film

The MXene thin films were fabricated using a spray coating method under varying synthesis
parameters. The synthesis parameters varied to achieve transparent conducting thin film were
the spray rate (1 ml/min, 2 ml/min) and deposition time or duration (5,10,15 & 20 minutes).
All the thin films were fabricated on glass substrate. Figure 3.1 depicts the schematic diagram
of the fabrication process.

Figure 2.4: Schematic diagram of spray coating technique and the image of fabricated thin film

29
The thickness of all the fabricated thin films were measured using a stylus profilometer and
confirmed using cross-sectional SEM.

Grain Size: The crystallinity of the thin film is determined by calculating the grain size using
the Debye-Scherrer equation given by:

𝐷 = 𝐾 λ / β 𝐶𝑜𝑠θ (2.3)

where: D is the crystalline size or the grain size, K is the Scherrer constant (0.98), λ is the
wavelength (1.54 nm), β denotes the full width at half maximum (FWHM).

The variation of grain size with spray duration is given in table 2.1. The grain size is found to
increase with the spray duration.

Table 2.1: Grain size of MXene thin films with varying deposition time and spray rate

Duration (min) Grain Size(nm)

Spray rate (1 ml/min) Spray rate (2 ml/min)

5 0.37 0.40

10 0.52 0.65

15 0.58 0.80

20 0.92 0.97

2.4 CHARACTERIZATION TECHNIQUES

2.4.1 X- Ray Diffraction (XRD)

The most common procedure for examining a material's structural characteristics is by using
X-ray diffraction (XRD). We employ HR (high resolution) - XRD to study the structural
properties of the fabricated Ti3C2Tx MXene thin films. XRD can give us a lot more of
information about:

● what kind of crystallites exist in the sample

● what proportion of the sample is made up of these crystallites
● how the crystals are oriented in the sample

30
X-ray diffraction is widely used as a tool in the identification of crystal samples and in the
investigation of lattice modifications in the annealed samples[9].

Principle:

When X-rays and a crystalline sample interact constructively, diffraction occurs. When the
wavelength of given X-rays are in a matching level with the spacing between atoms in the
sample, it results in a diffraction pattern. The pattern is examined using Bragg's Law, which is
applied in the measuring of crystals and their phases[11].

The X-Ray’s in the X-Ray diffraction is formed by the collision of high energy electrons on
copper (Cu) target which produces a monochromatic beam of Cu-Kɑ radiation. X-rays are
diffracted by the crystal's planes when they strike crystalline materials. According to Bragg's
rule, a diffraction peak can only occur when the distance that the rays travel after reflecting
from different crystal surfaces differs by an integral multiple of wavelengths. Bragg’s
equation is given by:

2𝑑 𝑠𝑖𝑛 θ  =  𝑛λ (2.4)

where, n is the order of diffraction, d is the interplanar spacing, θ is the incidence angle, and λ
is the incident X-rays' wavelength.

The term d is said to be the interplanar spacing between Bragg planes. The planes that consist
of these constructively diffracting atoms are known as Bragg planes. The d value is equal to
the magnitude of one of the lattice parameters. And usually these lattice parameters, say
(a,b,c) are equal to the spacing between neighbouring atoms in most inorganic compounds.
The below diagram gives a schematic view of the Bragg planes and that of the X-Ray
diffractometer[9]. ◻

31
 (b)

Figure 2.5: a) Condition for constructive interference in XRD. Red and green circles represent
scattering centers for X-rays. α is X-ray incidence angle, δ is X-ray exit angle. d is the separation
between Bragg (reflecting) planes, and s is half the path difference between two rays. Bragg planes
are indicated by thick orange lines[9]. b) Schematic Diagram of X-Ray Diffractometer[10].

Working & Instrumentation:

X’Pert Pro HR-XRD was used to record the XRD pattern of MXene thin films. The device
mainly consists of a sample stage, X-Ray source and a detector. The X-ray is produced by the
cathode ray tube with the help of high speed electrons that collide with a target. The target
used is of the element Copper(Cu). The characteristic X-ray, Cu-Kɑ X-Ray formed is used to
diffract the sample. The detector that rotates at 360° captures the scattered rays. The intensity
of scattered rays are recorded and stored in the computer. A plot of angle (2θ) v/s intensity is
employed which is then compared to the known database[12].

Figure 2.6: Schematic diagram of HR-XRD

32
2.4.2 UV-Visible NIR Spectroscopy

UV-Visible NIR spectroscopy is a method used to inspect the absorption and transmission of
the sample in the ultraviolet(UV)-visible region of electromagnetic spectrum. This method is
used in a wide range of fields determining the electronic structure of a compound [13].

Principle:

When UV light is absorbed, electrons are excited from their ground state to a higher energy
state. This results in a spectrum that may be used to identify the material. The visible zone
falls between 400-800 nm while the UV range is between 400-200 nm[13].

UV-Visible spectroscopy works on Beer-Lambert's law. Beer-Lambert’s law states that:

absorbance of a material sample is directly proportional to its thickness (path

length).absorbance of a material sample is directly proportional to its thickness (path
length).

Working & Instrumentation:

Figure 2.7: Schematic diagram of UV-Visible spectrophotometer[15].

JASCO V-570 FLH 466 spectrophotometer is used to record the UV-Vis spectra.. The
primary components of the device comprises a light source, monochromator, sample holders,
detectors, amplifiers and recorder. When deuterium or hydrogen is electrically excited at low
pressures, a continuous UV spectrum is created. The visible light source is a tungsten
filament bulb. This lamp has a wavelength range of 350 to 2500 nm. To choose a certain
wavelength range, the generated beam is sent via the monochromator. With the use of a
half-mirror splitter, light is split into two before it reaches the sample, each of comparable

33
intensity. The first beam passes through MXene thin film deposition and the second beam, or
the reference beam, passes through a glass substrate devoid of any thin film. The transmitted
or absorbed light intensity is detected, and recorded [16].

2.4.3 Field Emission Scanning Electron Microscopy (FESEM)

SEM (scanning electron microscope) and TEM ( transmission electron microscope) are the
two major types of electron microscopes. FESEM is a type of scanning electron microscope
that utilises electrons instead of light, where the electrons are produced using a field emission
source[18]. FESEM is used to examine the structure of materials smaller than 1 nm and
provides topographic information about the sample's surface.

In the case of MXene thin film, FESEM gives valuable information regarding:

● the formation of ‘accordion’ structure in MXene

● oxidation of nanoparticles on the outer layer
● qualitative information when coupled with EDS technique

● thickness of the thin film[17].

Principle:

The FESEM follows the same method of a conventional scanning electron microscope. The
specimen's surface is scanned by an electron beam focussed by electromagnetic lenses, and
the reflected and interacting electrons provide a picture of the sample's surface and
topography. In FESEM the electron generation system uses a field emission gun as the
electron source while in the case of SEM the electrons are generated by thermionic
emission[18].

Working & Instrumentation:

The device used belonged to the Zeiss Sigma field emission SEM. The schematic
representation of the device is given in Figure 2.8.

34
 Figure 2.8: Schematic representation of working of FE-SEM[19].

The electron beam focussed to a small diameter using the electron column is used to scan the
specimen. The specimen holder lies at the bottom of the column. The generated electron
beam is emitted using a field emission gun after which it passes through the anode where the
condenser lens converges the beam to pass it through the focal point. The beam interacts with
the sample on the specimen stage after undergoing a zig-zag motion. The signal produced by
the sample after the interaction is collected by detectors and converted into images by
electronic detectors. [20].

2.4.4 Stylus Profilometer

The stylus profilometer is the most widely used tool for measuring surface roughness. The
probe, which is directed by the reference surface of the device, acts as the basis for its
effective design. On the surface to be measured, the stylus records height variations. The
thickness of the thin film to be studied can be determined using the height differences[21].

Principle:

In a stylus profilometer, a diamond stylus is moved laterally and vertically while remaining in
touch with the sample for a certain period of time. It accurately determines minute differences
in stylus displacement in relation to position. This method measures the sample's surface
height or thickness directly[22].

Working & Instrumentation:

35
A profilometer operates on a very simple theory. Moving along the X axis is a tiny point that
is in contact with the surface. The surface relief causes the tip's vertical movement to be
caught and magnified. The stylus can be placed above the component to be measured because
the profilometer is often mounted on a Z column. The traverse unit moves the stylus
perpendicular to the Z axis, along the X axis. The granite base supports the parts being
measured as well as acting as a reference plane. A motor drives a reference bar on which the
sensor slides. The bar acts as a standard for internal straightness. It enables the stylus to
capture every feature of the surface texture, including roughness, waviness, form deviations,
and even the form itself[21].

Figure 2.9: Schematic diagram of Stylus Profilometer[23].

2.4.6 Two- Probe Method

By measuring the voltage drop across the wire caused by the passage of known current
supplied by the battery through two probes, it is possible to determine the resistivity of the
thin film. A voltmeter can be used to determine the potential difference (V) between the two
contacts at either end of the bar. As a result, the wire's resistivity(ρ) is given by:

ρ = 𝑉. 𝐴/𝐼. 𝐿 [26] (2.7)

The inverse of resistivity gives conductivity(𝛔), i.e,

σ = 1/ρ (2.8)

36
Working & Instrumentation:
The KEITHLEY 4200-SCS was used to measure conductivity. The value of resistance is
obtained by taking the I-V characteristic plot and calculating the slope. This can be used to
calculate the resistivity, whose reciprocal yields the conductivity value. The following
equation is used to calculate resistivity:
⍴ = 𝑉𝐴/ 𝐼𝐿 (2.9)
The equation for thin films is as follows:
ρ = 𝑅(𝑙 * 𝑡) / 𝑑 (2.10)
where;
R is the film's resistance
The length of the electrode is l.
t is the film's thickness, and D is the distance between the electrodes.

Figure 2.10 shows the image of the device employed for the two probe method.

Figure 2.10: Diagram of two-probe method[27].

37
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limitation (2023) Microbiology Note – Online Biology Notes. Available at:
https://microbiologynote.com/uv-vis-spectroscopy/ (Accessed: 24 June 2023).
14. Granite, S. by (2023) Beer Lambert law: Transmittance & Absorbance, Edinburgh
Instruments. Available at: https://www.edinst.com/blog/the-beer-lambert-law/
(Accessed: 24 June 2023).
15. P. Senthil Kumar, K. Grace Pavithra, Mu. Naushad, Chapter 4 - Characterization
techniques for nanomaterials, Nanomaterials for Solar Cell Applications, Elsevier,
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https://doi.org/10.1016/B978-0-12-813337-8.00004-7.
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17. Mikhail Shekhirev, Christopher E. Shuck, Asia Sarycheva, Yury Gogotsi,
Characterization of MXenes at every step, from their precursors to single flakes and
assembled films, Progress in Materials Science, Volume 120, 2021, 100757, ISSN
0079-6425, https://doi.org/10.1016/j.pmatsci.2020.100757.
18. Information on the FESEM (field-emission scanning electron microscope) - ru.
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(Accessed: 24 June 2023).
19. Field Emission Scanning Electron Microscopy (Fesem) with a very big future in
pharmaceutical research - IJPBS. Available at:
https://www.ijpbs.com/ijpbsadmin/upload/ijpbs_60f7bc8470dc4.pdf (Accessed: 24
June 2023).
20. M. Kannan, Scanning Electron Microscopy: Principle, Components and Applications,
Scanning Electron Microscopy: Principle, Components and Applications (2018).
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(Accessed: 25 June 2023).

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22. Measurement of thickness of thin film - nplindia.org. Available at:
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2111003010241 ) (no date) Studocu. Available at:
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 CHAPTER 03

RESULT AND DISCUSSIONS

3.1 INTRODUCTION

This study aims to achieve transparent conducting thin film using Ti3C2Tx titanium carbide
MXene prepared by in-situ HF forming etching method. Initially, multilayer MXene powder
was synthesized from its precursor, the MAX phase. The XRD analysis of MXene and MAX
phase was carried out to confirm the etching and formation of Ti3C2 from Ti3AlC2. For the
preparation of transparent conducting thin film, spray coating technique was employed. The
thin film samples were fabricated using the prepared MXene powder after further
ultrasonication and centrifugation. The optimization of various synthesis parameters was
done to achieve transparent and conducting thin film. The synthesis parameters kept fixed
during the fabrication were: concentration (0.5g in 100 ml), substrate temperature (100 ℃)
and pressure (0.25 Bar). The parameters varied and optimized were: spray rate (1 ml/min, 2
ml/min) and duration of coating (5,10,15 & 20 minutes). The structural, optical, electrical
and morphological features of the thin films were analysed using various characterization
techniques. The suitability of these films for transparent conducting thin film application
were analysed by considering the transmittance spectra, sheet resistance and the figure of
merit.

3.2 MORPHOLOGICAL ANALYSIS

SEM analysis provides information about the morphology of the samples. The SEM image of
a Ti3C2Tx MXene powder and MXene thin film fabricated for 10 min at a spray rate of 1
ml/min is shown in figure 3.1.

41
 a) b)

Figure 3.1: SEM image of a) MXene powder and b) MXene thin film ( Spray rate: 1 ml/min,
Deposition time: 10 min)

The image demonstrates that the MXene powder has a layered structure with open
accordion-like morphology while the fabricated MXene thin film has been deposited
uniformly along the glass substrate. The thin film is composed of tiny flake-like features
arranged uniformly over the substrate.

3.3 STRUCTURAL CHARACTERISATION

The structural characterization of MXene was done through XRD analysis. The XRD pattern
of MAX phase, multilayer MXene powder and the fabricated MXene thin films were
recorded using Rigaku Miniflex 600 X-Ray diffractometer. The interlayer spacing and the
lattice parameters can be found from the XRD pattern.

Figure 3.2 shows the XRD pattern of MAX phase and MXene formed after the etching
process along with the XRD pattern of fabricated MXene thin film for 20 min at a spray rate
of 1 ml/min.

42
 a) b)

Figure 3.2: a) XRD pattern of Ti3AlC2 MAX phase and Ti3C2Tx MXene . b) XRD pattern of Ti3C2Tx
MXene thin film fabricated at two different spray rates.

The diffraction peak of aluminium at 2θ = 39° corresponding to the plane (014) in the MAX
phase has less intensity in the XRD pattern of MXene indicating the partial etching of
aluminium during the synthesis process. The MXene sample had the characteristic (002)
plane diffraction peak of MXene at 2θ = 6.95°. The MAX phase had the diffraction peak at
2θ = 9.3°. Thus the MXene samples had a larger interlayer spacing compared to the
corresponding MAX phase. In the XRD pattern of MXene thin films at two different spray
rates, the diffraction peak corresponding to all other planes except the plane (002) has
completely disappeared due to delamination by sonication and centrifugation before the thin
film fabrication.

The interplanar distance between two successive planes is represented by d. Interplanar

spacing is given by the equation of Bragg’s law:

43
 2𝑑 𝑠𝑖𝑛 θ  =  𝑛λ (3.1)

Using d, the lattice parameters a and c can be found. Lattice parameters are the physical
dimensions and angles that determine the geometry of a unit cell in a crystal lattice. MXenes
have hexagonal crystal structure. The a lattice parameter gives the spacing between two
transition metal elements in a layer and on the other hand the c lattice parameter gives the
interlayer spacing. The equation for calculating lattice parameter is given by:

where, (hkl) are the miller indices, and d is the interplanar spacing. The lattice parameters of
MAX phase and MXene are given as follows:

Table 3.1: The a and c lattice parameters of MAX phase and the prepared MXene powder

Sample a-L.P c-L.P

MAX 3.08Å 19.02Å

phase (2θ-60.08°) (2θ-9.3°)

MXene 3.04Å 25.5Å

(2θ-60.78°) (2θ-6.95°)

Here, the interlayer spacing in MXene has increased when compared to that of its parent
MAX phase due to the removal of aluminium layer during the synthesis process. In the case
of MXene thin film the lattice parameter has increased further to a value of 28.37Å, due to
sonication and centrifugation assisted delamination in the colloidal solution used for thin film
fabrication.

Fig 3.3 gives the variation of grain size with deposition time for the thin films prepared at
spray rate of 1 ml/min and 2 ml/min. The grain size was found to increase with the duration
in both cases.

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Figure 3.3: Variation of grain size with deposition time for the MXene thin films prepared at a spray
rate of 1 ml/min and 2 ml/min

3.4 OPTICAL CHARACTERIZATION

Electronic transitions and plasmonic absorption in the produced materials can be found by
analysing NIR UV-Visible spectra. The transmittance spectra is analysed for the wavelength
within a range from 200 nm to 2000 nm. The delaminated Ti3C2Tx MXene thin film shows a
characteristic plasmonic peak at 780 nm in the absorption spectra due to the surface
plasmonic effect.

a) b)

Figure 3.4: Transmittance spectra of MXene thin film fabricated at varying duration at a spray
rate of a) 1 ml/min & b) 2 ml/min respectively.

45
The transmittance spectra of the MXene thin films indicate that the thin films are more
transparent at the near IR region. These thin films also show comparable transparency in the
visible region and can be of greater interest for TCO applications. The transparency at both
IR and visible regions decreases with the increasing thickness of the thin film. The MXene
thin film fabricated at 1 ml/min of flow rate for 5 mins shows higher transparency compared
to other films in both the visible and IR region. Hence, by varying the synthesis parameters
such as flow rate and deposition time, we can tune the transparency of the Ti3C2Tx MXene
thin films.

3.5 ELECTRICAL ANALYSIS

Figure 3.5 shows the I-V characteristics of MXene thin film fabricated at two different spray
rates. The I-V plot of MXene thin films fabricated at different spray rates were ohmic in
nature.

Figure 3.5: I-V plot of fabricated MXene thin films.

From the slope of this I-V graph we can obtain the resistance (R) offered by the thin films.
The resistance can give the resistivity (ρ) of the films by the formula:

𝑅(𝑙.𝑡)
ρ = 𝑑
(3.2)

where l is the length of the electrodes, t is the thickness of the thin films and d is the distance
between the electrodes. The inverse of resistivity gives the conductivity(𝛔).

46
 1
i.e, σ = ρ
(3.3)

In the case of thin films, we consider sheet resistance (Rs). The resistance of a square piece
of a thin material is known as sheet resistance. It enables an easy comparison between
different thin film samples. Sheet resistance is given by the formula:

𝑅
𝑅𝑠 = 𝑙.𝑑
(3.4)

where, R is the resistance, l is the length of the electrode and d is the distance between
electrodes.

Table 3.2: Conductivity and sheet resistance of MXene thin films fabricated at varying flow rate and
deposition time.

Sample Resistance (Ω) Conductivity Sheet resistance(Ω

(S/cm) per sq)

1 ml/min & 5 min 508.36 234.17 677.81

1 m/min & 10 min 207.09 201.19 276.13

1 ml/min & 15 min 128.35 247.33 171.13

1 ml/min & 20 min 100.64 212.31 134.19

2 ml/min & 5 min 250.87 207.61 334.49

2 ml/min & 10 min 137.11 127.27 182.82

2 ml/min & 15 min 82.56 139.21 110.08

2 ml/min & 20 min 49.81 168.11 66.42

47
 Figure 3.6: Variation of sheet resistance with the duration of spray.

From figure 3.6, we can elucidate that as the deposition time and spray rate increases the thin
films offer less resistance. The sheet resistance of the thin film decreases gradually as the
deposition time increases.

Figure of Merit: Figure of merit is a quantity used to denote the performance or quality of
substance or a material. In the case of MXene thin film, the figure of merit is calculated to
understand the performance of fabricated thin films. High value of the figure of merit
corresponds to the quality of the film. Figure of merit is given by the equation:

FoM = Electrical conductivity (𝞂DC) / Optical conductivity (𝞂opt) (3.5)

Since we are looking on to the TCO applications we consider the transparency level and
transmittance at the visible range of the spectrum. Figure of merit can be calculated using
sheet resistance and transmittance given by the formula:

(3.6)

where, Z0 is the free space impedance (377Ω), T is the transmittance and Rs is the sheet
resistance. In the present study the T% at 550 nm was taken in each film, as it corresponded

48
to the wavelength at which the T% was maximum in the visible region. By solving the above
equation, we get:

(3.7)

Table 3.3: Tabulation of figure of merit of different MXene thin films fabricated

Duration Spray rate 1 ml/min Spray rate 2 ml/min

T% Rs FOM T% Rs FOM

(Ω/𝑠𝑞𝑢𝑎𝑟𝑒) (Ω/𝑠𝑞𝑢𝑎𝑟𝑒)

5 48.00 677.81 0.63 31.79 334.49 0.73

10 30.78 276.13 0.85 18.01 171.13 0.81

15 11.98 182.82 0.55 9.87 134.19 0.64

20 3.03 110.08 0.36 0.94 66.42 0.30

49
 Figure 3.7: Variation of figure of merit with duration of spray.

As the deposition time increases, sheet resistance decreases. However, the trend in the figure
of merit for the thin films prepared at a spray rate of 1 ml/minute, increases with duration and
then steadily falls with the further increase. The highest figure of merit value is 0.85 Ω-1, for
the thin film fabricated for a duration of 10 minutes at a flow rate of 1 ml/min. In the case of
thin films prepared at a spray rate of 2 ml/min, the figure of merit was found to decrease with
the duration due to the decrease in transmittance with duration.

3.6 SUMMARY AND CONCLUSION

Multilayer Ti3C2Tx MXene powder was synthesized by using liquid phase exfoliation by in
situ HF forming etching mechanism. MXene thin films were fabricated by spray coating
technique. The structural, optical and morphological properties of the fabricated Ti3C2Tx
MXene thin films were investigated. XRD pattern revealed that the MXene thin film had an
increased interlayer spacing than its precursor. The grain size of each thin film increased as
the spray rate and deposition time increased. The transmittance at the IR and visible region
decreased with increasing the deposition time. The fabricated thin films were all uniformly
deposited along the surface of the glass substrate. The sheet resistance of the thin films
decreased with increasing deposition time and spray rate. The MXene thin film with a grain
size of 0.52 nm and thickness of 80 nm fabricated at a flow rate of 1 ml/min for 10 minutes

50
exhibited the highest FoM value of 0.85 Ω-1.The optical and electrical properties of the
as-prepared Ti3C2Tx films can be tuned by optimizing the synthesis parameters.

51