Page |1

Chapter 1: General Introduction

We are living in an age where science and technology are speeding themselves to the peak of
advancement. From the mid-19th century till today we are advancing every day and the credit
goes to scientific research and advanced technology. Technology has always revolutionized our
world and it’s a contentious process. We are already in the process of adopting the 4th industrial
revolution and that’s why we need to focus on various aspects of science deeply to find
something new which will help humanity and solve their existing problems. [1,3]

Among a hundred thousand new technologies, thin film technology is a well-recognized and
miraculous one that has drawn the attention of scientists in the field of research. Advances in thin
film deposition techniques during the 20th century have enabled a wide range of technological
breakthroughs in areas such as magnetic recording media, electronic semiconductor
devices, Integrated passive devices, LEDs, optical coatings (such as antireflective coatings), hard
coatings on cutting tools, and for both energy generation (e.g. thin-film solar cells) and storage
(thin-film batteries). [1,3]

1.1 Some theoretical aspects of thin film

The film means a layer of coating of material onto another material (called the substrate) which
is non-reactive except for sufficient adhesion. The solid material is said to be a "Thin film" when
it is built up as a thin layer on a solid support, called substrate, by a controlled condition of the
individual atomic, molecular, or ionic species either directly by a physical process or via a
chemical or electrochemical reaction. [7,8]

The word "Thin" gives a relative measurement of any dimension but not any absolute value and
"Film" means a coating. The term thin as it applies to thin films is quite ambiguous. It is used to
define a layer of thickness that is comparable with the mean free path (MPF) of conduction
electrons. Typically thin films are considered from 10nm to 100nm based on their characteristics.
Depending on the specific FR tool configuration, the thickness of thin and thick, single layer and
multi-layer, supported and free-standing, transparent and semi-transparent, uniform and non-
uniform films is measured using FR tools in the 1nm to 1000nm range. The FR-Mapper module
is an improvement on the FR-Basic tool that uses scanning to automatically characterize a single
 Page |2

film or stack of films over huge areas or preselected spots. More than 1-micrometer thickness is
considered thick films. Films are made by depositing them on a specific substrate such as glass
or quartz. [8]

Depending on the technique used and the deposition parameters, such as substrate temperature,
deposition rate, pressure, and alignment of vapor stream with substrate, different and
sophisticated chemical reactions take place throughout the deposition process, giving rise to a
diversity of microstructures. The resulting microstructure defines the physical and chemical
characteristics of the film hence it is imperative to regulate these variables adequately to achieve
the desired film qualities. Microstructures that come from this process might be amorphous,
polycrystalline, or epitaxial. [10,11]

1.2 Amorphous thin film:

The development of amorphous film materials can occur by several different processes,
including direct deposition of glassy material, deposition at low temperatures that prevent the
formation of crystalline structures (high rate of thermal quenching), ion bombardment of high-
modulus materials during deposition, deposition of materials with hydrogen-bonds that are
partially saturated, and ion bombardment of films after deposition that may cause them to
amorphized. On the surface of a substrate, amorphous films of alternating layers can be
generated using a wide range of techniques. These films can have a completely different
composition from the deposited layer. Deposition technologies essentially employ three
components:

1. The location where the substance to be deposited, or one of its components, is concentrated
(crucible, metal plate, gas bottle, etc.), as well as the place where fundamental physical processes
such as the dispersion of the substance into atoms, ions, molecules, and clusters occur (group of
atoms or molecules).

2. The medium in which material transfer processes manifest themselves between the source and
the substrate A reactive gas, for instance, and the atoms of the substance to be deposited may be
having a chemical reaction there.

3. The surface on which a condensation phenomenon occurs. [2,5]

 Page |3

1.3 Polycrystalline thin film:

Polycrystalline thin films can be created using a number of thin-film deposition procedures, such
as chemical vapor deposition, physical vapor deposition, and sputter deposition. Microscopic
(usually around 0.1.m) chemical microcrystals, or "grains," make up the domains of
polycrystalline thin films and are separated by grain boundaries. It is probably not unexpected
that many of the material characteristics of polysilicon thin films approach those of bulk
crystalline material as polycrystalline is really composed of tiny domains containing crystalline
material. [11,12]

1.4 Epitaxial thin film:

Epitaxial films are described as thin films that follow their substrates, which act as seed crystals,
in highly organized configurations. Since ferroelectric and ferroelastic domain structures
correspond to a single orientation or a twinned structure, epitaxial films exhibit these properties.
Ferroelectric epitaxial films have displayed excellent performance among the epitaxial films
made of diverse materials [1,5]. Epitaxial films should provide good contact between the film
and the substrate, and their homogenous characteristics are a result of their almost uniform
orientation: Important properties for applications involving semiconductor devices, such as
ferroelectric memory systems. [4]

1.5 Some notable applications of thin film

First off, there were just a few uses for thin films, such as reflectors in optical instruments such
as mirrors and plating equipment. However, throughout time, research into the electrical,
thermal, optical, and magnetic properties of thin film structures successfully presented some
remarkable deeds in the realm of microelectronics to the scientific community. Films have
shown incredible properties that have put them in the driving seat of electronic components and
sensor development. Transparent conductors (TCs) have gained popularity significantly,
enabling them an indispensable tool for some exciting transparent electronics applications such
as thin-film transistors, light-emitting diodes (LEDs), and flat-panel displays, and more. [3]
 Page |4

Chapter 2: Thin film deposition techniques

In general thin films are designed to provide special qualities, including electrical, optical,
mechanical, and chemical characteristics, to meet the demands of particular applications. The
resulting film structure, which is strongly impacted by the deposition technique, film material,
and substrate choices determines the desired attributes. The most frequently used deposition
methods, from the numerous that have been created or refined to optimize the film properties in
line with the vast range of uses for thin films, are covered in this section. These three major steps
are followed by the plurality of deposition techniques:

1. Synthesis of the deposition species,

2. Conveyance from source to substrate,

3. Deposition and adhesion of the source onto the substrate and subsequent film growth.

Broadly thin film deposition methods are categorized into two categories

(i) Physical vapor deposition methods (PVD)

(ii) Chemical vapor deposition methods (CVD)

2.1 Physical deposition methods (PVD)

Physical deposition methods are usually referred as to physical vapor deposition methods (PVD)
because the process entails the generation of vapor. PVD essentially consists in removing growth
species from a source or target material via evaporation, then this vapor is transported to the
substrate surface, and eventually, it solidifies on the surface, forming the film. [1,2,7]

The physical Vapor Deposition method is the most sought-after technique and has gathered a ton
of variations and improvements in the last few decades, researchers are thriving to improve the
attributes of coatings and the testimony rate [8,9]. There are two main processes by which the
particle can be obtained from the material-based of which PVD has generally divided i.e.
evaporation and sputtering. The evaporation technique, for the most part, offers lower nuclear
 Page |5

vitality, fewer adsorbed gases into the coating, a substantially more directional nature, bigger
molecules moving with higher mass, progressively arranged molecules, a lower attachment to the
substrate with higher testimony rates than the faltering procedure. In this manner, the dissipation
procedure is generally progressively reasonable for mechanical applications and forms films
ranging from medium to thick, as surface morphology is not a primary quality necessity among
certain applications [10]. Contaminant particles are situated in the cauldron and can be directed
to the parts to be coated, and in long run diminished the immaculateness of the coatings acquired.
This sputtering process is also known as arc PVD in which material is vaporized from the
cathode using an electric arc. This vaporized material then reverts back to its original state to
form a thin film coating. When quality requirements like grain size, roughness, and
stoichiometry are of greater significance than the deposition rate, the sputtering process is used.

2.2 Chemical deposition methods (CVD)

The chemical deposition method (CVD) is a deposition method where a volatile compound of a
pre-established substance is introduced into a reactor, usually along with inert gas, to induce a
chemical reaction that produces a solid thin film onto a substrate at an elevated temperature. In
this technique, unlike PVD, the reaction does not have to be produced under vacuum conditions.
Due to its versatility to work with a broad range of reactants and precursors, this technique
enables the deposition of a variety of structures, including metal alloys and compound
semiconductors with excellent control of purity and doping (stoichiometric film) [13]. Compared
to PVD, this technique offers higher deposition rates, better conformance in rough substrates,
easy deposition onto complex surfaces, and high throughput.

The CVD processes can be classified based on the type of source employed to initiate the
chemical reaction, the range of pressure under which the deposition is carried out, and the type of
reactant used. The thermal activated CVD is the most conventional method where the thermal
energy produced inside the reactor triggers the chemical reactions. Two variants are noticeable
within this process concerning the pressure range under which the deposition materializes,
namely atmospheric pressure CVD (APCVD), and low-pressure CVD (LPCVD) [14]. Both
variants essentially comprise the same chemical reactions which overall consist of the creation of
 Page |6

vapor from reactants; then these vapor species are directed into the reactor, where depending on
the deposition parameters, homogeneous chemical reactions take place in the gas phase while
heterogeneous reactions occur near the substrate surface. Finally, the crystallization of a solid
film occurs on the substrate surface. An alteration of the rate-limiting process occurs when the
pressure is reduced in LPCVD by about 1000-fold for the atmospheric pressure CVD [13].

2.3 Plasma-enhanced CVD

A plasma is a state made up of neutral and charged particles like atoms, molecules, positive and
negative ions, electrons, and possibly most or all of them. Plasma is typically electrically neutral
because any imbalance in the charges would yield electric fields that would tend to redistribute
the charges in a way that would eliminate the imbalance. As a result, the density of positively
charged ions will be equal to the sum of the electron density and the negative ion density (1).
The degree of ionization, which is the % of the primordial neutral species (atoms and/or
molecules) that have become ionized, is a crucial plasma parameter. Weakly ionized plasmas are
those that have levels of ionization that seem to be significantly lower than unity. This kind of
plasma will behave in a way that is dominated by the existence of a significant number of neutral
entities. The degree of ionization in completely ionized plasmas is nearly unity, and neutral
particles have little to no impact.

To create the necessary ionization to generate and maintain a plasma, an energy source is
needed. When the plasma is in a steady state, recombination, diffusion, and convection losses of
ions and electrons from the plasma volume must be balanced by an increase in the rate of
ionization. Since plasma is created by adding energy (heat) to a gas, it is frequently referred to as
the fourth state of matter. However, the transition from a neutral gas to plasma is more
continuous and does not include a clear phase change.

CVD (PECVD) is one of the most frequently employed CVD variants [4]. This approach
enhances the dissociation of the reactive gases by incorporating plasma energy in addition to
 Page |7

thermal energy. When the energy in the form of an electric field—is injected into the reactor,
which shelters the reacting gases in the area between two electrodes, plasma is generated. Then,
under decreased pressures, complicated chemical processes occur in the plasma, creating
energetic ions and radicals that flow towards the substrate, bombarding its surface and
accelerating reactions that result in a solid coating. In contrast to APCDV or LPCDV, this
variation permits the deposition of arcuate films at lower temperatures (200-400 K). The
activation of plasma by radiofrequency fields (RF = 13.56 MHz) and microwave frequency fields
(2.45 GHz), which use the effect of electron cyclotron resonance (ECR) to lower the pressure,
has improved this deposition technique. The latter's higher frequency enables larger energy and
concentration of electrons in the plasma, increasing the degree of ionization by up to a factor of
1000 over that achieved with the RF field [16]. In the fields of photochromic coatings,
microelectronics, optoelectronic devices, and transistors, PECVD is a well-known deposition
technique. [1,9]
 Page |8

Chapter 3: Synthesis of CuI thin films by PE-CVD method

3.1 Introduction
The zincblende copper iodide (CuI) is a wide band gap highly transparent native p-type binary
compound semiconductor [13,14]. The direct band gap of CuI thin films is 3.1 eV and they show
high transparency >80%, hole mobility >40 cm2V-1s-1, and conductivity >150 S/cm [13-18]. The
high p-type conductivity of CuI thin film arises due to small hole effective mass (0.3m0) and its
conductivity can further be improved by iodine doping that plays the role of electron acceptor
creating holes in the valance band [13-14, 18]. Transparent conductors (TCs) such as indium tin
oxide (ITO), aluminium zinc oxide (AZO), and highly doped GaN are n-type wide-bandgap
semiconductors and are well known for their extensive use as transparent electrodes for solar
cells, flat-panel displays, and light-emitting diodes. Copper iodide (CuI) can be a potential
candidate to be used as a transparent hole transport layer. So far, CuI is a low-cost and highly
promising p-type TC with a decent energy band gap.

CuI thin film has a wide range of applications such as CuI electrode in organic electronics,
thermoelectric, hole conductor in CuI/n-Si heterojunction, organic, polymer and perovskite solar
cells [19-26].

Literature reports indicate that different techniques have been deployed for the deposition of CuI
thin films such as reactive sputtering, thermal evaporation, spin coating, drop-casting, vapour-
phase iodination of Cu thin films, a spraying method, epitaxy, CBD and SILAR methods etc.
[13-14, 27-36]. Among the methods, spin coating is a very simple, low-temperature and low-cost
technique for the fabrication of CuI thin films, in fact, recent work on liquid phase iodination
during spin coating shows potential in increasing the conductivity of CuI thin films to be used as
an electrode [14]. However, the film discontinuity and roughness are very high although the
liquid phase iodine doping slightly decreases the roughness. This will hamper the carrier
transport in the CuI thin films. Therefore, an alternative low-cost solution processes deposition
technique is indispensable for the deposition of CuI thin films.

Here, we report the deposition of CuI thin films by a low-cost high pressure (HP) plasma
enhanced chemical vapor deposition (HP-PECVD) method. The HP-PECVD deposition system
is simple and it can be used to deposit high-quality CuI thin films. The synthesized CuI thin films
 Page |9

were characterized by XRD SEM and FTIR. The optical properties of the films were also
studied.

3.2 Experimental set-up

3.2.1 Materials and preparation of CuI thin films

The CuI, and acetonitrile (ACN) chemicals were acquired from Sigma-Aldrich. The CuI powder
was dissolved in ACN at a rate of 1 mg/ml and mixed by a magnetic stirrer. Then the resultant
solution was filtered using a nylon filter having a pore diameter of 0.45 µm. The glass substrates
were first cleaned by piranha-solution to dispel the gross contaminants. Then they were cleaned
with acetone and distilled water and dried by an air blower prior to film deposition. The CuI thin
films were deposited on glass substrates by a simple HP-PECVD deposition system.

Fig.1(a) shows the schematic of the experimental setup used for the preparation of Cu film and
fig 1 (b) shows the produced films. The setup contains a vacuum chamber, rotary pump, high
voltage power supply, high voltage probe and current probe, digital oscilloscope, two
spectrophotometers, ceramic substrate stand and substrate holder, and cylindrical glass tube. The
CuI solution was kept in a conical flask whose outlet was connected to the deposition chamber
by a flexible tube.

Seat: There were five orifices at the steel seat and used as inlet and outlet ports. Two stainless
steel tubes (inner diameter 9mm, length 50mm) were welded to two of the side orifices of the
steel seat for connecting the rotary pump for lowering the inside pressure of the bell jar and gas
intel. Power and neutral high voltage wires were inserted through the remaining two side
orifices. A pyrex glass tube was inserted through the centre orifice and was used C 2H3N-CuI
vapour inlet channel. One of the two tubular (height 10mm, inner diameter 9mm, thickness
2mm) stainless electrodes were used as high voltage electrodes. The powered electrode was
placed at the top of the ceramic stands while the grounded electrode was placed at the bottom.
Pyrex glass substrate was placed at the axial centre of the two electrodes as well as on the upper
surface of the power electrode. Distance between two electrodes was 58mm. A pyrex cylindrical
glass tube (height 58 mm, inner diameter 18mm) was used both as active plasma discharge
 P a g e | 10

channel as well as acetonitrile (C2H3N)-CuI vapor flow channel. There was a circular window
(diameter 12mm) at the top ceramic base plate in order to penetrate the CuI solution for the
deposition as film.

Bell Jar
Glass substrate
Window
SS power
electrode
Glass
cylinder
Ceramic
stand
SS seat
SS ground
electrode
Ar inlet
Pump inlet
C2H3N-CuI
vapor inlet

(i) (ii) (iii)

Fig. 1: (a) The HP-PECVD machine (b) Produced CuI thin films (i) 5 min (ii) 7 min (iii)
10 min [Deposition rate 0.75mL/min]
 P a g e | 11

Film preparation: A 40mm×25mm pyrex glass substrate was placed at the substrate holder and
the setup was enclosed with a bell jar. The inside pressure of the bell jar was reduced five times
and argon gas was allowed to insert within the bell jar in order to reduce air from the vacuum
chamber. The rotary pump was allowed to operate during the whole film preparation period. A
15kV, 50Hz power supply was connected across the electrodes and plasma was produced
between the electrodes enclosed with a cylindrical pyrex glass tube for the confinement of
plasma within the glass tube. The inside pressure of the bell jar was maintained at 60 torrs.
C2H3N-CuI solution started to evaporate due to opening the stop cock of the container because
lowering the inside pressure of the container and the C2H3N-CuI vapor started to flow into the
discharge region at a rate of 0.75mL/min. Subsequently, the plasma discharge color was changed
due to the presence of C2H3N-CuI vapor in the discharge zone as shown in Fig. 1(b).

3.2.2 Thin film characterization

The thickness of the CuI thin films were measured by Bruker Dektak XTL thickness profiler.
The generic characteristics which are taken into concern are thickness, optical properties, X-Ray
diffraction characterization, and Surface morphology by Scanning electron microscope (SEM)
technique and Fourier transform infrared (FTIR) spectroscopy for identification of unknown
materials and confirmation of production materials. The CuI thin film thickness was 125, 165
and 250nm relatively for deposition times 5min, 7 min and 10 min. The transmittance and
absorbance data were obtained by UV-VIS spectrophotometer (UV-1650 PC, Shimadzu
Corporation, Japan).

The XRD data were taken by X’Pert-Pro, Philips, Japan XRD Diffractometer with
monochromatized CuKα radiation (λ =1.54056 Å). The SEM and EDS studies were carried out
by Carl Zeiss, Model: EVO-18 Research SEM systems.
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Chapter 4: Results and discussion

4.1 Diagnostics of CuI chemical vapor

4.1.1 Current voltage characteristics

Discharge voltage and current were measured with a high voltage and current probe in the
combination of an oscilloscope, shown in Fig. 2, in order to determine plasma discharge power.
Two spectrophotometers were used. The electrical power (𝑤) deposited in the discharge was
determined by integrating the voltage (𝑣(𝑡)) and current (𝑖(𝑡)) over a period (𝑇) using the
1 𝑇
following equation: 𝑤 = (𝑇) ∫0 𝑣(𝑡)𝑖(𝑡)𝑑𝑡. The absorbed powers were 7.83W for air and

13.60W for C2H3N-CuI vapor.

2.5
4
2.0
Current (air)
Voltage (air) 3
1.5

2
1.0

Current (mA)
1
Voltage (kV)

0.5

0.0 0
Current (CuI)
-0.5 Voltage (CuI) -1

-1.0
-2

-1.5
-3
-2.0
-4
-2.5
0 100 200 300 400
Time (ms)

Fig 2: Plasma discharge current and voltage

 P a g e | 13

4.1.2 Optical characteristics

A spectrophotometer (AvaSpec-2018, slit length 10μm, grating 2400 lines/mm, optical

resolution 0.07nm) was used to identify species produced in air and CuI discharges shown in Fig.
3. Optical emission spectroscopic (OES) data were fitted with MassiveOES software to
determine rotational (𝑇𝑟 ) and vibrational (𝑇𝑣 ) temperatures of the heavy species, shown in Fig. 4.
Fitted data revealed that 𝑇𝑟 were in CuI plasmas. Whereas, 𝑇𝑣 was 2315 ± 73𝐾 in CuI plasmas,
respectively.

Fig. 3 The experimental data of the N2 (C- B) band simulated with MassiveOES simulation
software to determine Trot and Tvib [Air+Ar plasma]
 P a g e | 14

40

Intensity (10 x a.u)

N2 (C-B) (a) Ar/ Air Plasma
32 (0,0)

3
(0,1)
24 +
N2 (B-X)
16 (0,0) (0,1)
(0,1) (1,2) (0,2)
8 (2,1)
(1,3)
(2,5)
(2,3) (2,4) (1,4) (0,3)
0
60 CN(B-X)
Intensity (10 x a.u)

0,0
48 (b) Ar/Air plasma + CuI sample
3

36 N2 (C-B)
24 CN(B-X)
12
0
300 320 340 360 380 400
Wavelength (nm)

Fig. 4: Optical emission spectra of (a) Ar/Air (b) Ar/air+CuI plasmas [Gas flow rate:
0.75mL/min, electrode gap: 58 mm, applied voltage: 15 kV, and frequency: 50 Hz]

Optical emission spectroscopy (OES) is a useful tool for species identification as well as
atmospheric pressure plasma diagnostics. Figure 4 (a) shows the typical emission spectrum of
plasma with Ar/Air and 4(b) with Ar/Air+CuI maintaining the flow rate of 0.75mL/min and
supply voltage 15kV and frequency 50 Hz.

The FTIR spectra reveal that CuI, CO, CH, and CN were deposited onto the glass substrate.
Therefore, their production mechanisms in plasmas will be shortly described. Due to direct
electron impact of CH3 NC, atomic C+ , H + , N+ and molecular CH3 CN+ , CH2 N+ , C2 H2 N+ ,
CH3 N+ , CH + , CH2+ , CH3+ and so on can be produced in the plasma system. Besides, 𝐶H2 CN− ,
CHCN− , CCN− , CN− and CH3− can also be produced in the plasma system through dissociative
electron attachment processes. However, elemental analysis of 10 min deposited CuI thin film
prepared by HP-PECVD reveals that the film contains C (76.9 wt%), N (21.8 wt%), Cu (0.3
wt%) and I (1.1 wt%). The following pathways can be considered for the production of CuI, CO,
CH and CN in HP-PECVD system. In the laser assisted plasmas, CH3 CN+ , CH2 CN+ , CHCN+ ,
CCN+ , CH2+ , C + and CN are produced. In the HP-PECVD CuI- CH3 CN plasmas, strong UV
radiation was produced and thereby the above acetonitrile species can be considered to produce
in the plasma system.
 P a g e | 15

𝐶H3 CN + nhν → CH3 CN + + e− (R1)

CH3 CN + nhν → CH2 CN+ + H + e− (R2)

CH2 CN + nhν → CHCN+ + H + e− (R3)

CH2 CN + nhν → CCN+ + H2 + e− (R4)

CH2 CN + nhν → CH2+ + CN + e− (R5)

CCN + + nhν → C+ + CN + e− (R6)

Dissociation of CH3 CN2+ can follow the following pathways

CH3 CN2+ → CNH +∗ + CH2+ → CN+ + H + CH2+ (R7)

CH3 CN2+ → CN+ + CH3+∗ → CN + + H + CH2+ (R8)

CH3 CN2+ → CN+ + H + CH2+ (R9)

CH3 CN2+ → CH2 CN2+∗ + H → CN+ + H + CH2+ (R10)

Dissociative attachment of low energy electrons to acetonitrile can follow the following
pathways

e− + CH2− → CH2 (R11)

e− + CH3− → CH3 (R12)

Besides, low energy dissociative electron attachment may also take place

e− + CH3 CN → H2 + CHCN− (R13)

e− + CH3 CN → CH3 + CN− (R14)

Due to the presence of a certain amount of air within the plasma discharge zone, the following
product molecules can be produced in the plasma system

N2+ + CH3 CN → CH3 CN+ + N2 (R15)

N2+ + CH3 CN → CH2 CN+ + H + N2 (R16)

 P a g e | 16

N2+ + CH3 CN → CHCN+ + H2 + N2 (R17)

CO+ + CH3 CN → CH3 CN + + CO (R18)

CO+ + CH3 CN → CH2 CN + + H + CO (R19)

CO+ + CH3 CN → CH3 CN + + CO2 (R20)

Inside rotational temperature (considered as gas temperature) of the HP-PECV reactor is 𝑇𝑟 ≈

1479𝐾. The structure of the CuI thin films depends [6] on reactor temperature, such as it takes
zinc blend structure (γ − CuI) when the temperature below 663𝐾, wurtzite structure (β − CuI) in
the temperature range (663 − 713)𝐾 and cubic structure (α − CuI) for the temperature above
713𝐾. Therefore, one may consider that the CuI thin films can be of cubic structure because the
gas temperature within the plasma discharge zone was ~1479𝐾. Besides, one can also consider
that such high temperature may affect species kinetics within the reactor and the discussion
concerning this phenomenon is beyond the scope of this work.
 P a g e | 17

4.2 Study to obtain CuI thin film properties

4.2.1 XRD studies of PH- PECVD CuI thin films

Fig. 5: XRD spectra of HP-PECVD deposited CuI thin films.

Fig. 5 depicted the XRD spectra of CuI thin films deposited by HP-PECVD method. It is
observed from the figure that the film deposited for 5 min shows a peak at 52.2° that correspond
to the 222 plane and the film deposited for 10 min shows three peaks at 25.4, 42.2 and 52.4°
those correspond to 111, 220 and 222 according to the ASTM ref. PDF 01-076-0207. These
results indicate a zinc blend face-centred cubic γ-CuI phase [14,37-38]. Therefore, it can be
concluded that CuI thin films deposited by the HP-PECVD technique using CAN solvent are
polycrystalline in nature.

The size of crystallites has been calculated from Debye-Scherrer’s formula [27]

0.94𝜆
D = 𝛽𝑐𝑜𝑠𝜃 ………………………………………………………………………………………..(1)

where λ denotes the X-ray wavelength, β denotes the FWHM in radians of different planes.
 P a g e | 18

4.2.2 Surface morphology of PH- PECVD CuI thin films

(a)

(b)
 P a g e | 19

(c)

Fig.6: SEM images of CuI thin films deposited for (a) 5 min, (b) 7 min and (c) 10 min by HP-
PECVD method.

Fig 6 shows the surface morphology of high pressure plasma enhanced CuI thin film. The images
were taken by scanning electron microscope where the film deposition time were 5 min, 7 min
and 10 min where the film deposition rate was 0.75mL/min. From the images, we can clearly see
that the CuI molecules are increasing with increased deposition time.
 P a g e | 20

4.2.3 EDS Mapping

(a) (b)

(c) (d)

Fig. 7: EDS mapping of CuI thin film showing the presence of (a) C, (b) N, (c) Cu and (d) I,
respectively for the deposition time of 5 min.
 P a g e | 21

Table 1: The elemental composition of CuI thin films deposited by HP-CVD method

Sample Carbon (wt%) Nitrogen (wt%) Copper (wt%) Iodine (wt%)

5 min 73.4 23.1 0.7 2.8

7 min 71.9 25.3 0.5 2.4

10 min 76.9 21.8 0.3 1.1

Table 1 describes the energy dispersive spectrometry (EDS) of CuI thin films. The film
deposition rate was 0.75mL/min. The table shows that most of the atoms found in the film were
Carbon. With increasing deposition time, the carbon % gradually increased from 73.4% to 76.9%
for 5 and 10 min deposition. Nitrogen comes in the second position with 23.1% for 5 min, 25.3%
for 7 min and 21.8% for 10 min deposition. The Copper % has gradually decreased from 0.7%,
0.5% and 0.3% as well as Iodine where Iodine % was 2.8% for 5 min, 2.4% for 7min and 1.1%
for 10 min deposition.

4.2.4 FTIR studies of CuI thin films

Fig. 8 shows the FTIR spectra of CuI thin films deposited by the HP-PECVD method in the
range of 300-1800 cm-1. The absorption peak in the range of 549-670 cm-1 indicates the
characteristic peak for CuI stretching vibration [40-41]. It is observed from the figure, that other
peaks arrive at ~1080, 1400, and 1592 cm-1 can be attributed to C-O, C-H and C=N stretching
vibration bonds, respectively [40-41]. No other peaks were detected in the range of 2000-4000
cm-1, therefore, not shown in the figure. There HP-PECVD method shows a potential technique
for the deposition of highly pure CuI thin films.
 P a g e | 22

Fig. 8: The FTIR spectra of CuI thin films deposited by HP-PECVD method

4.2.5 Optical properties of PH-PECVD CuI thin films

The optical properties of the synthesized CuI thin films have been studied by measuring UV-Vis
spectra. Fig. 9 shows the transmittance and absorbance spectra of CuI thin films deposited by the
HP-PECVD method. It was visualized from the figures that the transmittance of the film was
over 80-85% in the range of 700-1100 nm for the 5 min film. The film deposited for 7 min shows
a transmittance over 70-80% in the range of 800-1100 nm which is consistent with earlier reports
[14,42]. As the deposition time increases the transmittance of the films decreases which is
expected as the thickness of the film increases with deposition time.

Likewise, the absorbance of the CuI films is lower for the film deposited for 5 min. After that,
the absorbance of the films increases with deposition time due to the increase in film thickness.
 P a g e | 23

(a) (b)

Fig. 9: The (a) transmittance and (b) absorbance spectra of CuI thin films.

Fig. 10: The Tauc plot of CuI thin films fabricated by HP-PECVD method.
 P a g e | 24

The optical band gap of the synthesized CuI thin films have been measured from the Tauc plot
[30]

(αhν)2 = 𝐴(hν − 𝐸𝑔 )…………………………………………………………………………..(2)

where α represents the absorption coefficient, A denotes a constant depending on the transition
probability, Eg stands for the optical band gap, respectively.

Fig. 10 reveals the optical band gap of the CuI thin films synthesized by the HP-PECVD method.
The band gap of the films varies in the range of 3.14, 2.87, and -2.71 eV depending on the
deposition time i.e. the thickness of the film. These results are consistent with previous reports
[41].
 P a g e | 25

Chapter 5: Conclusion

From the performed experiment I have found the plasma characteristics and structural and
optical properties of CuI thin film. The thin film deposition time has played a vital role in this
experiment affecting the transmittance, absorbance and optical band gap energy where the
transmittance is found 80-85% in the range of 700-1100 nm for the 5 min film and the film
deposited for 7 min shows a transmittance over 70-80% in the range of 800-1100 nm. The band
gap of the films varies in the range of 3.14, 2.87, and -2.71 eV depending on the deposition time.
The FTIR spectra of CuI thin films were found in the range of 300-1800 cm-1 where the
absorption peak found in the range of 549-670 cm-1 indicates the characteristic peak for CuI
stretching vibration. The EDS mapping confirms that the thin film mostly consisted of Carbon
followed by Nitrogen, Iodine and Copper respectively. The SEM images showed the Cu
presence, increasing with deposition time. From the XRD observation, it is observed from the
figure that the film deposited for 5 min shows a peak at 52.2° corresponding to the 222 plane
and the film deposited for 10 min shows three peaks at 25.4, 42.2 and 52.4° corresponding to
111, 220 and 222 according to the ASTM ref. PDF 01-076-0207. From the optical emission
spectroscopy of the plasma, Optical emission spectroscopic (OES) data were further fitted with
MassiveOES software to determine rotational (𝑻𝒓 ) and vibrational (𝑻𝒗 ) temperatures of the
heavy species. Fitted data revealed that 𝑻𝒓 were 𝟏𝟏𝟖𝟓 ± 𝟑𝟒𝑲 in air CuI plasmas and 𝑻𝒗 was
𝟐𝟑𝟏𝟓 ± 𝟕𝟑𝑲 in CuI plasmas, respectively. I have found the presence of Nitrogen atoms
dominating Ar/Air and CN in Ar/Air + Cu vapor composition via the species identification
method. The current and voltage figure (fig 1) revealed the power consumption of the plasma
which was 7.83W for air and 13.60W for C2H3N-CuI vapor. Overall the optical and structural
properties of high-pressure plasma enhanced CuI thin film was obtained along with the
characterization of CuI-CH3CN vapor in plasma.
 P a g e | 26

References

[1] Edwin Acosta, in “Thin Films/Properties and Applications”

[2] B. L. Zink in “Thermal Conductivity and Specific Heat of Thin-Film Amorphous Silicon”
[3] Sushil Kumar D. K. Aswal in “Recent Advances in Thin Films”
[4] IVREJOIU, DHESSE and MALEXE in “Single crystalline PZT films and the impact of
extended structural defects on the ferroelectric properties” <epitaxial>
[5] Musgraves Hu Calvez, in “Springer Handbook of glass” <amorphous>
[6] Copper(I)_iodide, in Chemeurope.com
[7] R. J. Bunsen, Prakt Chem; 56(1852) 53.
[8] W.R. Grove, Phil. Trans. Royal. Soc. London, 147 (1851) 345.
[9] M. Faraday ., Phil. Trans. Roy. Soc. London, 147 (1857) 145.
[10] R. Nahrwold, Wied. Ann., 31 (1887) 467.
[11] A. Kundt, Ann. Physik, 31 (1888) 473.
[12] J.J. Thomson, Proc. Cambridge Phil. Soc., 11(1901) 120.
[13] K. Fuchs, Proc. Cambridge Phil. Soc., 34 (1938) 100.
[14] F.H. Sondheimer, Phys. Re., 80 (1950) 401.
[15] A.F. Mayadas, and M. Shatzkes, Phys. Rev., B1 (1970) 1382.
[16] K.L. Chopra, in "Thin Film Phenomena" Published by McGraw-Hill Book Company New
york 1969
[13] C. Yanga, M. Kneiβ, M. Lorenza, M. Grundmanna, Room-temperature synthesized copper
iodide thin film as degenerate p-type transparent conductor with a boosted figure of merit, PNAS
113 (2016) 12929–12933.

[14] M. Rahman, M. A. Newaz, B. K. Mondal, A. Kuddus, M. M. Rashid, M. A. Karim, Mirza

H. K. Rubel and J. Hossain, Unraveling the electrical properties of solution-processed copper

iodide hole conducting thin films for CuI/n-Si heterojunction solar cells, Mater. Res. Bull. 118

(2019) 110518.
 P a g e | 27

[15] M. Grundmann, F.-L. Schein, M. Lorenz, T. Böntgen, J. Lenzner, H. von Wenckstern,

Cuprous iodide: A p-type transparent semiconductor, history, and novel applications, Phys.
Status Solidi A 210 (2013) 1671-1703.

[16] J. Wang, J. Li, S.-S. Li, Native p-type transparent conductive CuI via intrinsic defects, J.
Appl. Phys. 110 (2011) 054907.

[17] D. Chen, Y. Wang, Z. Lin, J. Huang, X. Chen, D. Pan, F. Huang, Growth strategy and
physical properties of the high mobility p-type CuI crystal, Cryst. Growth Des. 10 (2010) 2057-
2060.

[18] M.N. Amalina, M. Rusop, Investigation on the I2:CuI thin films and its stability over time,
Microelectron. Eng. 108 (2013) 106-111.

[19] Lee JH, Leem DS, Kim JJ (2009) High performance top-emitting organic light-emitting
diodes with copper iodide-doped hole injection layer. Org Electron 9:805–808.

[20] R. Mulla, M.K. Rabinal, Defect controlled copper iodide: A promising and eco-friendly
thermoelectric material, Energy Technol. 6 (2018) 1178-1185.

[21] P. Li, S. Wang, Y. Jia, Z. Li, C. Ji, L. Zhang, H. Li, E. Shi, Z. Bian, C. Huang, J. Wei, K.
Wang, H. Zhu, D. Wu, A. Cao, CuI–Si heterojunction solar cells with carbon Nanotube Films as
Flexible Top-Contact Electrodes, Nano Res. 4 (2011) 979-986.

[22] H. Iimori, S. Yamane, T. Kitamura, K. Murakoshi, A. Imanishi, Y. Nakato, High

photovoltage generation at minority-carrier controlled n-Si/p-CuI heterojunction with
morphologically soft CuI, J. Phys. Chem. C 112 (2008) 11586-11590.

[23] L. Zhang, Y. Lei, X. Yang, J. Cheng, C. Wang, H. Jia, Z. Zheng, A facile room temperature
iodination route to in-situ fabrication of patterned copper-iodide/silicon quasi-bulk-
heterojunction thin films for photovoltaic application, Dalton Trans. 44 (2015) 5848-5853.

[24] W. Sun, H. Peng, Y. Li, W. Yan, Z. Liu, Z. Bian, C. Huang, Solution-processed copper
iodide as an inexpensive and effective anode buffer layer for polymer solar cells, J. Phys. Chem.
C 118 (2014) 16806-16812.
 P a g e | 28

[25] K. Takahashi, Y. Suzuki, Perovskite solar cells with CuI inorganic hole conductor, Jpn. J.
Appl. Phys. 56 (2017) 08MC04.

[26] L. Cattin, J. C. Berne`de, Y. Lare, S. Dabos-Seignon, N. Stephant, M. Morsli, P. P. Zamora,

F. R. Diaz, M. A. del Valle, Improved performance of organic solar cells by growth optimization
of MoO3/CuI double-anode buffer, Phys. Status Solidi A 210, 802–808 (2013)

[27] M. Xia, M. Gu, X. Liu, B. Liu, S. Huang, C. Ni, Electrical and luminescence properties of
Zn2+ doped CuI thin films, J. Mater. Sci.: Mater. Electron. 26 (2015) 2629-2633.

[28] L.A. DeSilva, J. Harwell, A. Gaquere-Parker, U.A.G. Perera, K. Tennakone, Thin films of
copper (I) iodide doped with iodine and thiocyanate, Phys. Status Solidi A 214 (2017) 1700520.

[29] K. Tennakone, G.R.R.A. Kumara, I.R.M. Kottegoda, V.P.S. Perera, G.M.L.P. Aponsu,
K.G.U. Wijayantha, Deposition of thin conducting films of CuI on glass, Sol. Energy Mater. Sol.
Cells 55 (1998) 283-289.

[30] N. Yamada, R. Ino, Y. Ninomiya, Truly transparent p-type γ-CuI thin films with high hole
mobility, Chem. Mater. 28 (2016) 4971-4981.

[31] Y.-H. Yan, Y.-C. Liu, L. Fang, Z.-C. Lu, Z.-B. Li, S.-X. Zhou, Growth of CuI buffer layer
prepared by spraying method, Trans. Nonferrous Met. Soc. China 21 (2011) 359-363.

[32] C. Yang, M. Kneiß, F.-L. Schein, M. Lorenz, M. Grundmann, Room-temperature domain-

epitaxy of copper iodide thin films for transparent CuI/ZnO heterojunctions with high
rectification ratios larger than 109, Sci. Rep. 6 (2016) 21937.

[33] A.C. Nkele, U.K. Chime, A.C. Nwanya, D. Obi, R.U. Osuji, R. Bucher, P.M. Ejikeme, M.
Maaza, F.I. Ezema, Role of metallic dopants on the properties of copper (1) iodide nanopod-like
structures, Vacuum, 161 (2019) 306-313.

[34] R.N. Bulakhe, N.M. Shinde, R.D. Thorat, S.S. Nikam, C.D. Lokhande, Deposition of copper
iodide thin films by chemical bath deposition (CBD) and successive ionic layer adsorption and
reaction (SILAR) methods, Curr. Appl. Phys. 13 (2013) 1661-1667.
 P a g e | 29

[35] K.O. Ighodalo, D. Obi, A. Agbogu, B.N. Ezealigo, A.C. Nwanya, S.L. Mammah, R. Bucher,
M. Maaza, F.I. Ezema, The structural and optical properties of metallic doped copper (I) iodide
thin films synthesized by SILAR method, Mater. Res. Bull. 94 (2017) 528-536.

[36] N.P. Klochko, K.S. Klepikova, V.R. Kopach, I.I. Tyukhov, D.O. Zhadan, G.S. Khrypunov,
S.I. Petrushenko, S.V. Dukarov, V.M. Lyubov, M.V. Kirichenko, A.L. Khrypunova,
Semitransparent p-CuI and n-ZnO thin films prepared by low temperature solution growth for
thermoelectric conversion of near-infrared solar light, Solar Energy, 171 (2018) 704-715.

[37] W. Sun, H. Peng, Y. Li, W. Yan, Z. Liu, Z. Bian, C. Huang, Solution-processed copper
iodide as an inexpensive and effective anode buffer layer for polymer solar cells, J. Phys. Chem.
C 118 (2014) 16806-16812.

[38] S. Inudo, M. Miyake, T. Hirato, Electrical properties of CuI films prepared by spin coating,
Phys. Status Solidi A 210 (2013) 2395-2398.

[39] B.D. Cullity, “Elements of X-Ray Diffraction”, Addison-Wesley, Reading, MA, p.102
(1972).

[40] Z. Ghasemi, S. Shojaei, A. Shahrisa, Copper iodide nanoparticles supported on magnetic

aminomethylpyridine functionalized cellulose: a new heterogeneous and recyclable
nanomagnetic catalyst for facile access to N-sulfonylamidines under solvent free conditions,
RSC Adv. 6 (2016) 56213-56224.

[41] H. R. Humud, S. Hussein, Characterization of cupper iodine thin films fabricate by spin
coating from nanoparticles produced by exploding Cu wire in Iodine solution, Int. J. ChemTech
Research 10 (2017) 1109-1116.

[42] D.K. Kaushik, M. Selvaraj, S. Ramu, A. Subrahmanyam, Thermal evaporated Copper

Iodide (CuI) thin films: A note on the disorder evaluated through the temperature dependent

electrical properties, Sol. Energy Mater. Solar Cells 165 (2017) 52–58.