Preparation of Molybdenum Oxide (MoO3)

Thin Films by Thermal Evaporation Method and Study of

its Optical Properties

By
Himanshu Phukan

Department of Physics
Jagannath Barooah College(Autonomous)
 CERTIFICATE

This is to certify that the short term project entitled “PREPARATION OF MOLYBDENUM

TRIOXIDE THIN FILMS BY THERMAL EVAPORATION METHOD AND STUDY OF ITS

OPTICAL PROPERTIES” submitted for partial fulfilment for the Bachelor Degree in Science (Physics

honours) by HIMANSHU PHUKAN, student of Jagannath Barooah College(Autonomous), Jorhat under

my supervision. I wish him every success in life.

(Dr Ranjit Sarma)

Associate Professor & Head

Department of Physics

Jagannath Barooah College(Autonomous), Jorhat

Annexure II

Approval Sheet

The thesis entitled “……………………………………….” by Name of the student(Student ID) is

approved for the degree of BACHELOR OF SCIENCE.
 __________________
Examiner 1

__________________
Examiner 2

_________________________ __________________________
Supervisor Co-Supervisor (if any)

__________________________

HOD, Department of Physics

Jagannath Barooah College
Date:
Place:
 Annexure III

Declaration of Academic Integrity

"I declare that this written submission (“…………………title of the

work…………………………………….”) represents my ideas in my own words and where others ideas
or words have been included, I have adequately cited and referenced the original sources. I also declare
that I have adhered to all principles of academic honesty and integrity and have not misrepresented or
fabricated or falsified any idea/data/fact/source in my submission. I understand that any violation of the
above will be cause for disciplinary action as per the rules and regulations of the Institute."

Sincerely,

Place: Name:

Date: Students ID:

 Annexure IV

CERTIFICATE

This is to certify that the Thesis entitled “…………Title of the Thesis………” submitted to the
Department of Physics, Jagannath Barooah College in partial fulfillment for the award of the degree of
Bachelor of Science in Physics is a record of work carried out by ……Name of the student…… under my
supervision and guidance.

All helps received from various sources have been duly acknowledged.

__________________________
(Supervisor)

Name:
Designation:
Affiliation:
Date:
Place:
 Annexure V

CERTIFICATE

This is to certify that the Thesis entitled “…………Title of the Thesis………” submitted to the
Department of Physics, Jagannath Barooah College in partial fulfillment for the award of the degree of
Bachelor of Science in Physics is a record of work carried out by ……Name of the student…… under my
supervision and guidance.

All helps received from various sources have been duly acknowledged.

__________________________
(Co-Supervisor)

Name:
Designation:
Affiliation:
Date:
Place:
 ACKNOWLEDGEMENT

I would like to express my deepest appreciation to all those who provided me the possibility to

complete this report. First of all, I would like to convey my gratitude to Dr Ranjit Sarma, Head of

Department of Physics, Jagannath Barooah College(Autonomous), Jorhat for allowing me to complete

my project work in this laboratory.

I am highly indebted to our guide, Mrs. B. D. Baruah Madam sir for her constant supervision as

well as for providing necessary informaton regarding the project and also for their support in completng

the project.

Thanking all

Himanshu Phukan

Department of Physics, J.B. College (Autonomous)

 Abstract

We have reported the preparation and study of optical properties of Molybdenum Oxide (MoO3)

thin film. The Molybdenum Oxide (MoO3) thin films were deposited on glass substrates using thermal

evaporation method under high vacuum atmosphere. Optical properties of these thin films have been

studied using Ultraviolet-visible (UV-VIS) spectrometer. The bandgap energy value of these thin films

has been calculated from its UV absorption spectrum, which was found to be 2.9594 eV. The

transmittance spectrum of the films has also been observed.

Chapter 1

Introduction
Nanomaterials are being adapted into several applications across multiple domains such as

cosmetics, optical components, biology, physics, chemistry, polymer science, pharmaceutical drug

manufacture, toxicology, and mechanical engineering. Molybdenum trioxide is a transition metal oxide

having several optical properties.Lampert(1984) reviewed numerous inorganic and organic

electrochromic material in the context of developing a film-based optical shutter for energy-efficient

windows. Thin films of MoO3 can be used in electronic information displays and colour memory

devices. The last decade saw extensive electrical and optical investigation of electrochromic material.

Molybdenum trioxide is a wide band gap semiconductor. It is n-type semiconductor which has

distinctive electrochromic, thermochromic and photochromic properties. It has been widely

investigated as a smart material for catalysis, sensors lubricants, lithium battery, organic solar cells and

display materials. It is realized that the purity of phase MoO 3 depends on the manufactured technique

and experimental conditions. Impressive advances have been accomplished recently for the size and

phase controlled synthesis of MoO3 with enhanced catalyst properties.

Material:
 This Project discusses the properties and applications of molybdenum oxide nanoparticles.

Molybdenum is a Block D, Period 5 element, while oxygen is a Block P, Period 2 element. Molybdenum

does not occur naturally as a free metal on Earth.

Molybdenum oxide nanoparticles are graded as harmful and can affect the skin and eyes. It may

also cause cancer. Molybdenum oxide nanoparticles appear in a powder form.

Chemical Properties:

The chemical properties of molybdenum oxide nanoparticles are outlined in the following table.

Chemical Data

Chemical symbol MoO3

CAS No. 1313-27-5

Group Molybdenum 6

Oxygen 16Electronic configuration Molybdenum [Kr] 4d5 5s1

Oxygen [He] 2s2 2p4

Chemical Composition

Element Content (%)

Molybdenum 66.65

Oxygen 33.32

Physical Properties

The physical properties of molybdenum oxide nanoparticles are given in the following table.

Properties Metric Imperial

Density 4.70 g/cm3 0.170 lb/in3

Molar mass 143.94 g/mol -

Thermal Properties

The thermal properties of molybdenum oxide nanoparticles are provided in the table below.

Properties Metric Imperial

Melting point 795°C 1460°F

Boiling point 1155°C 2111°

Chapter 2
Methodology

This project contains a brief introduction to the evaporation sources along with details discussion of the

experimental procedure for the fabrication of the thin film by using different patternable shadow masks,

thermal vacuum evaporation.

2.1 Introduction to evaporation sources

For evaporation of material in a vacuum, a source is required that will supply heat of vaporization in

addition to supporting the evaporant. To avoid contamination of the deposit, the support material itself

must have negligible vapour and dissociation pressure at the operating temperature. The two types of

support material used are refractory metals and oxides, nitrides, etc.

The metallic evaporation sources consist of either metal wire, or metal foils/wire sources are used for the

evaporator, which sticks to the filament, by surface tension, on melting. Metal foils are usually designed

into open boats of various shapes. Metals like tantalum, tungsten, and molybdenum are commonly used

for such evaporation sources. For flash-evaporation techniques various arrangement are available. One

such arrangement is called the dispenser. In this technique, a finely divided powder of the evaporator is

made to fall slowly on a very hot tungsten strip, from a vibrating dispenser. On being in contact with the

hot tungsten strip, the material evaporates immediately. Non-metallic crucible having high thermal

conductivity are also used as evaporation sources. Wire coils heat these electrically non-conducting
crucibles wound around them or by placing them on heated metal foil structure. For preparing a very

pure film, one has to resort to the electron beam heating technique. In this process, a stream of electrons

accelerated up to 10 KV, is focussed on the surface of the evaporator. This causes the evaporation of the

material. Reactive evaporation is used to obtain oxide thin –films. In this method, metals under

relatively high oxygen pressure are evaporated, and the oxide of metals is deposited on the substrates.

2.2 Method of preparation of the thin film

The thin film is defined as the uniform layer of materials whose thickness are ranging from nanometer

(10-9) to several micrometres (10-6). Now a day’s fabrication of thin film is considered as a fundamental

step for many applications. For example, thin metallic coating on the back side of a glass sheet to form a

reflective interface and hard coatings on cutting tools and also for energy generation and storage

devices. In addition to this thin film also play an important role in the improvement and study of

materials with new and exclusive properties.

Physical vapour deposition method and spin coating techniques are the only effective method which is

broadly used for the preparation of thin films. Physical methods include the deposition techniques,

which depend on the evaporation or physical ejection of the materials from a source. The most widely

used methods, such as vacuum evaporation and sputtering fall in this group. The physical methods are

thought to produce films of good quality, purity, and resolution.

2.2.1 Vacuum evaporation

This is a widely used method. In this method, the material is heated in a vacuum to its gaseous state and

then condensed on the substrate. Because of reduced pressure, the melting point of the material is

sufficiently lowered, the tendency to form oxides is considerably reduced, the number of impurities in

the deposited film is minimum, and the evaporated material from the source to substrate follows the
straight-line path, which ultimately aids in producing the good quality films. The temperature of the

material may be raised either by resistive heating or electron bombardment heating. In the resistive

heating process, the material is heated to its evaporation temperature either by slowly increasing the

source temperature or by allowing the material to fall in a source maintained at its evaporation

temperature. The later method requires the flash evaporation facilities for instant evaporation. In electron

bombardment heating a stream of the electron is accelerated through high voltage and focused on to the

evaporator surface. Sometimes oxygen or nitrogen gas is introduced into the chamber, allowing reaction

with the evaporant to obtain films of controlled composition. This technique is called reactive

evaporation. There are two processes of obtaining more than one deposition by vacuum evaporation,

namely (i) single pump down procedure (SPD) and (ii) multiple pump down procedure (MPD).

2.2.1.1 SPD Procedure

In the SPD method, the step-by-step deposition of the different materials is done in one pump down of

the vacuum system, i.e., without breaking the vacuum. The masks required to obtain different

geometries of the films on the substrates are positioned at various suitable places inside the vacuum

chamber. For deposition at various suitable places inside the vacuum chamber of different layers, the

substrates are shifted from the mask to mask with the help of suitable levers operated from the outside.

Again proper positioning and uncovering of the different evaporation sources containing the evaporator

inside the chamber are also performed from the outside. The vacuum evaporation units having these

facilities involve large capital investment. Nevertheless, the procedure is advantageous because the

ambient contamination between the deposited layers is avoided, and it achieves high-quality devices

showing good performance.

2.2.1.2 MPD procedure

In this procedure, the vacuum is broken after each deposition step or in between some deposition steps.

The main advantage of the MPD method is that devices could be produced in bulk. Since one deposition

is usually done with a large mask or an array of identical masks covering the entire dimension of the

chamber could be used, thus enhancing the volume of production. Moreover, such units require far less

capital investment. Another advantage of this method is that it permits the use of mechanically obtained

shadow masks as well as a photolithographic process for the deposition of the electrodes of the devices.

The method of photolithography obtains the fine geometry required for the electrodes. High resolution is

achieved by this method for which it is widely used in the IC industry. Further, the computer-controlled

electron beam technique permits the highest resolution of the pattern.

2.3 Evaporation mask for vacuum deposition:

2.3.1 Fabrication of evaporation masks

For fabrication of Thin film by vacuum deposition procedure, the various selected materials were

evaporated on the substrates in suitable geometrical patterns which were achieved by the use of shadow

masks. For each desired deposition, the substrates were placed on the masks near allow deposition of the

film to the exposed substrate areas only. All the masks were processed mechanically. The different

structures of the masks used in the present investigation are described below:

2.3.2 Evaporation mask for the buffer layer deposition:

An aluminium foil thickness 0.03 cm was cut to the circular shape of diameter 23.5 cm to suit our

vacuum unit. A fine metal tip at first drew the desired geometrical patterns of the buffer layers, and then

the openings were using cutting and filing tools. With sufficient precaution, the patterns were kept

regular and mask plane and free of dents. The mask was then fixed over a rigid metal ring and

thoroughly cleaned by the procedure as described in our section 2.4. The complete buffer layer or hole
injection layer deposition mask is shown in the following the figure. Before every organic layer

deposition in successive use, the mask was thoroughly cleaned.

While fabricating the above masks, a great deal of precautions was taken to keep the plane of the

mask and dent free.

2.4 Cleaning of the evaporation masks:

The evaporation masks should be free from dust particles, scattered pieces of rubbing from the

cutting process, fibres and any other type of contaminants to avoid possible film contamination. For

cleaning the masks were treated with “Teepol” (a green-coloured detergent) and washed in running

tap water. These were then washed with acetone and dried in an electric oven. The masks were

finally cleaned with acetone and dried by blowing air hot air. During the investigation, the cleaning

of masks was a routine procedure and was undertaken before fabrication of a Thin Film.

2.5 Fabrication and Optical Properties testing of Thin Film of MoO3

In our work, A thin film of Molybdenum trioxide was prepared by the thermal vacuum deposition

technique. Therefore, the description of the thermal evaporation system and spectroscopy

techniques for checking the optical property will be discussed in this section.

2.5.1 Thermal Evaporator System: Model-VT-2015

The vacuum coating unit, Model-VT-2015, was used for the fabrication of Thin film. The whole unit

consists of three main parts, i.e., a vacuum chamber, the pumping system, and the electrical

connections. The vacuum chamber is a corning bell jar of 13-inch diameter placed on the metal base

plate. The chamber is evacuated using an oil diffusion pump backed by a double stage gas ballast

rotary pump having a suction capacity of 200litre/minute. The pump

alone could produce a rough vacuum of 2×10-3 Torr. The ultimate vacuum obtainable in the unit is

10×10-6 torr, which may be measured by using penning ionization gauge attached to the unit. The

rough vacuum of the chamber and the diffusion backing line is measured with the help of Pirani

gauge. There are seven well insulated and three earthed electrodes fitted to the base of the chamber.

Each electrode was coupled to the earthed electrode electrically connected to the base. Out of these

two-electrode were used for heating the evaporation source of the remaining electrode, two are for
 either the radiant heater or the substrates heater and one for HT discharge cleaning. In addition to

these, the base plate has provisions for fitting a movable shutter. The masks can be positioned with

the help of stand fitted on the base plate. The transformer and the corresponding electrical circuits

for passing current at required voltages through the various electrodes and gauges are contained in

the compact unit. All the switches, control knobs and meters for performing different operations are

fitted on the front panel of the instrument. The following figure shows the set up of the vacuum

evaporation unit.

Figure 2.5 (a): Vacuum coating set up under laboratory environment

 Figure 2.5.1 (b) :- Inside the vacuum deposition chamber

2.5.2 Cleaning of the vacuum unit and filaments:

Before every deposition, the corning bell jar cleaned by carbon tetrachloride and then finally by acetone.

The metal electrodes, base plate, a substrate holder, etc were cleaned using acetone. After cleaning all

the components were dried by using an air gun. The cleaning of the vacuum chamber was a routine work

performed before every evaporation step irrespective of evaporates. Moreover, for ensuring faultless

performances of the unit, normal checking of the vacuum points and the rotary pump oil level was

periodically undertaken.

All new filaments and boats were flash-cleaned in vacuum by passing a heavy current momentarily.

Flash-cleaning of filaments and boats are essentially for removal of contaminants adhering to them.

2.5.3 Substrates preparation:

In our work, we used commercially available glass as substrates for the fabrication. Then the glass is cut

into small square pieces. Here all substrates were properly cleaned with acetone, isopropanol and

deionized water for 15 minutes and then dried by an air gun before fabrication. This cleaning step is

used to remove the surface contaminants and to provide a clean surface to enhance the adhesion of the

layer onto the substrates. Therefore, initially, all substrates were cleaned for the better formation of layer

over it.

2.5.6 Evaporation of the material:

One of the common methods of Physical Vapor Deposition (PVD) is Thermal Evaporation. Physical

Vapor Deposition - also known as PVD Coating - refers to a variety of thin film deposition techniques

where solid metal is vaporized in a high vacuum environment and deposited on electrically conductive

materials as a pure metal or alloy coating.

As a process that transfers the coating material on a single atom or molecule level, it can provide

extremely pure and high-performance coatings which for many applications are much preferable to

electroplating. PVD Coating processes are an environmentally friendly process that can greatly reduce

the number of toxic substances that must be disposed of with more conventional types of coating that

involve fluid precursors and chemical reactions.

At the heart of every microchip and semiconductor device, PVD Coatings enable the solar panel

industry to make greener electricity as well as surgical and medical implants that require the highest

degrees of purity. It produces coatings with superior hardness, durability and resistance to wear. PVD

Coatings reduce friction for high performance moving parts, making them widely used in the aerospace

and automotive industry, and for cutting tools where long-lasting durability is the crucial success factor.
Physical Vapor Deposition Coatings are also highly resistant to tarnishing and corrosion, enabling them

to be used for a wide range of decorative finishes with colours that do not fade. PVD produces highly

brilliant finishes that make watches highly resistant to scratches and scrapes and is used in a wide

variety of optical applications ranging from glasses to self-cleaning tinted windows. Their resistance to

corrosion makes them widely used on household items such as door handles, plumbing fixtures and

marine fixtures.

PVD is fundamentally a vacuum coating technique vaporizing a metal to a plasma of atoms or molecules

and depositing them on a wide range of substrates. Carried out in a high vacuum chamber approximating

outer space at 10-2 to 10-4 millibar, the process usually takes place between 150 and 1500 Degrees C.

The material to be coated is secured in a fixture and placed in the vacuum deposition equipment

chamber. The equipment is pumped down to the optimum pressure depending upon the coating

materials, substrate and process used, and the object to be coated is often preheated and sputter cleaned.

Inside the vacuum, even a relatively low vapour pressure is enough to raise a vapour cloud inside the

chamber. This evaporated material now travels upward in the chamber, hits the substrate, condensed and

stick to it as a coating or film. Here, the fixture used is a molybdenum crucible. The crucible was

electrically heated, and it contained the material that is to be evaporated (Figure 2.5.4(a)). The

evaporation rate is determined by the vapour pressure of the source material at the evaporation

temperature. The Joule heating of typical molybdenum crucible allows to reach temperature of 2800 K.

It provides required vapour pressures for most of the metals. A deposition chamber under high vacuum

(<10-2 Pa) is necessary. Such a high vacuum is required to avoid oxidation of the source. The thermal

evaporation process is conventionally called vacuum deposition.

Of all of the benefits of the PVD Coating process that produce some of the toughest, most brilliant and

cutting edge technology of our time ranging from microchips to solar panels, none is more important
than the fact that PVD Coatings can be applied with no toxic residues or byproducts which degrade our

planet’s environment

Figure 2.5.4 (a): Molybdenum crucible

 Figure 2.5.4 (b): Thermal evaporation process

Chapter 3
2.6 Ultraviolet-visible (UV-Vis) spectroscopy:
Ultraviolet-visible (UV-Vis) spectroscopy is one of the most popular analytical techniques because it is

very versatile and able to detect nearly every molecule. With UV-Vis spectroscopy, the UV-Vis light is

passed through a sample, and the transmittance of light by a sample is measured. From the transmittance

(T), the absorbance can be calculated as A=-log (T). An absorbance spectrum is obtained that shows the

absorbance of a compound at different wavelengths. The amount of absorbance at any wavelength is due

to the chemical structure of the molecule.

UV-Vis can be used qualitatively, to identify functional groups or confirm the identity of a compound by

matching the absorbance spectrum. It can also be used quantitatively, as the concentration of the analyte

is related to the absorbance using Beer's Law. UV-Vis spectroscopy is used to quantify the amount of

DNA or protein in a sample, for water analysis, and as a detector for many types of chromatography.

Kinetics of chemical reactions are also measured with UV-Vis spectroscopy by taking repeated UV-Vis

measurements over time. UV-Vis measurements are generally taken with a spectrophotometer. UV-Vis is

also a very popular detector for other analytical techniques, such as chromatography, because it can

detect many compounds.

Typically, UV-Vis is not the most sensitive spectroscopy technique, because not a lot of light is absorbed

over a short path length. Other spectroscopy techniques such as fluorescence have higher sensitivity, but
they are not as generally applicable, as most molecules are not fluorescent. UV-Vis has a similar

sensitivity to other absorbance measurements, such as infrared spectroscopy.

PRINCIPLES

UV-Vis is often called a general technique because most molecules will absorb in the UV-Vis

wavelength range. The UV extends from 100–400 nm and the visible spectrum from 400–700 nm. The

100–200 nm range is called the deep UV. Light sources are more difficult to find for this range, so it is

not routinely used for UV-Vis measurements. Typical UV-Vis spectrometers use a deuterium lamp for

the UV that produces light from 170–375 nm and a tungsten filament lamp for visible, which produces

light from 350–2,500 nm.

When a photon hits a molecule and is absorbed, the molecule is promoted into a more exciting energetic

state. UV-visible light has enough energy to promote electrons to a higher electronic state, from the

highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). The

energy difference between the HOMO and the LUMO is called the band gap. Typically, these orbitals

are called bonding and anti-bonding. The energy of the photon must exactly match the band gap for the

photon to be absorbed. Thus, molecules with different chemical structures have different energy band

gaps and different absorption spectra. The most common transitions that fall in the UV-Vis range are π-

π* and n- π*. Pi orbitals arise due to double bonds, and n orbitals are for non-bonding electrons. Pi star

is anti-bonding pi orbitals. Thus, the best UV-Vis absorption is by molecules that contain double bonds.

Pi orbitals adjacent to each other that are connected, called conjugation, typically increases absorption.

Sigma-σ* transitions, associated with single bonds, are higher energy and fall in the deep UV, so they

are less useful for routine use. The appearance of broad bands or shoulders on the UV-Vis structure is
due to the numerous vibrational and rotational states of a molecule, which lead to separate energy band

gaps of slightly different energies.

For molecules with absorption in the visible region, the compounds will often appear coloured.

However, a common misconception is that the wavelength of peak absorption (λ max) for a compound is

the colour it appears. A compound that appears red does not have much absorption in the red region of

the spectrum. Instead, the λmax for a compound that looks red is green. The colour of a compound arises

because those wavelengths of light are selectively transmitted through the sample, and thus, they are not

absorbed. A colour wheel helps determine what colour a compound will absorb and what range the

λmax will be, as the colour directly across the wheel from the observed colour is the colour that is most

absorbed.

Absorption follows Beer's Law, A=εbC where ε is the molar attenuation coefficient, b is path length, and

C is concentration. The molar attenuation coefficient is the characteristic of an individual compound to

absorb at a given wavelength, and this property is due to functional groups, conjugation, etc. If a

compound does not have a high attenuation coefficient, it could be tagged with an appropriate group to

increase its absorbance. The path length is generally related to the size of the cuvette and is 1 cm in

standard spectrophotometers.

UV-Vis is performed on a variety of instruments, from traditional spectrophotometers to more modern-

day plate readers. The absorbance wavelength must be chosen, either using a filter or a monochromator.

A monochromator is a device that separates the wavelengths of light spatially and then places an exit slit

where the desired wavelength of light is. Monochromators can be scanned to provide a whole

absorbance spectrum. Alternatively, a diode-array instrument allows all colours of light to be transmitted

through the sample, then the light is separated into different wavelengths spatially and detected using
photodiodes. Diode-array instruments collect full spectra faster but are more complicated and more

expensive.

A spectrophotometer is made up of two instruments: a spectrometer and a photometer. The spectrometer

is to produce light of any wavelength, while the photometer is to measure the intensity of light. The

spectrophotometer is designed in a way that the liquid or a sample is placed between spectrometer and

photometer. The photometer measures the amount of light that passes through the sample and delivers a

voltage signal to the display. If the absorbing of light change, the voltage signal also changes.

Spectrophotometers come in a variety of shapes and sizes and have multipurpose uses to them. The

different types of spectrophotometers available are all different from one another, based on their

application and desired functionality. The most popular spectrophotometers are 45 degrees, sphere and

multi-angle spectrophotometers. Another closely related concept is Spectroscopy that simply measures

the absorption of light from its source and the intensity of light as well.

2.7 PARTS OF SPECTROPHOTOMETER:

There are seven essential parts of a spectrophotometer

Light source – In spectrophotometer, three different sources of light are commonly used to produce

light of different wavelength. The most common source of light used in the spectrophotometer for the

visible spectrum is a tungsten lamp. For Ultraviolet radiation, commonly used sources of are the

hydrogen lamp and the deuterium lamp. Nernst filament or globar is the most satisfactory sources of IR

(Infrared) radiation.

Monochromator – To select the particular wavelength, prism or diffraction grating is used to split the

light from the light source.

Sample holder – Test tube or Cuvettes are used to hold the coloured solutions. They are made up of

glass at a visible wavelength.

Beam splitter – It is present only in double beam spectrophotometer. It is used to split the single beam

of light coming from the light source into two beams.

Mirror – It is also present only and double beam spectrophotometer. It is used in the right direction to

the split light from the beam splitter.

Photodetector system – When light falls on the detector system, an electric current is generated that

reflects the galvanometer reading.

Measuring device – The current from the detector is fed to the measuring device – the galvanometer.
The meter reading is directly proportional to the intensity of light.
2.8 WORKING OF THE SPECTROPHOTOMETER

⇒ When using a Spectrophotometer, it requires being calibrated first, which is done by using the

standard solutions of the known concentration of the solute that has to be determined in the test solution.

For this, the standard solutions are filled in the Cuvettes and placed in the Cuvette holder in the

spectrophotometer that is similar to the colourimeter.

⇒ There is a ray of light with a certain wavelength that is specific for the assay is directed towards the

solution. Before reaching the solution, the ray of light passes through a series of the diffraction grating,

prism, and mirrors. These mirrors are used for navigation of the light in the spectrophotometer, and the

prism splits the beam of light into different wavelength, and the diffraction grating allows the required

wavelength to pass through it and reaches the Cuvette containing the standard or Test solutions. It

analyzes the reflected light and compares with a predetermined standard solution.

⇒ When the monochromatic light (light of one wavelength) reaches the Cuvette some of the light is

reflected, some part of the light is absorbed by the solution, and the remaining part is transmitted

through the solution which falls on the photodetector system. The photodetector system measures the

intensity of transmitted light and converts it into the electrical signals that are sent to the galvanometer.

⇒ The galvanometer measures the electrical signals and displays it in the digital form. That digital

representation of the electrical signals is the absorbance, or optical density of the solution analyzed.

⇒ If the absorption of the solution is higher than there will be more light absorbed by the solution and if

the absorption of the solution is low then more lights will be transmitted through the solution which

affects the galvanometer reading and corresponds to the concentration of the solute in the solution. By
putting all the values in the formula given in the below section, one can easily determine the

concentration of the solution.

⇒ In double beam spectrophotometers, the beam splitters are present which splits the monochromatic

light into two beams, one for the standard solution and the other for test solution. In this, the absorbance

of Standard and the Test solution can be measured at the same time, and any no. of test solutions can be

analyzed against one standard. It gives more accurate and precise results, eliminates the errors which

occur due to the fluctuations in the light output and the sensitivity of the detector.

2.9 Absorbance and Transmittance

From the Figure 2.6.3 (a), the amount of photons that go through the film and falls on the detector is dependent

upon the thickness of the film (l) and the concentration of the film. If the intensity of light, i.e. the number of

photons after it passes through the film, is known, then it can be used to calculate the transmittance (T).

Transmittance is the fraction of the incident light that passes through the film. This can be calculated using the

equation:

Transmittance (T) = It /Io ………………………………………………………………………… (1)

where It = the light intensity after the beam of light passes through the film

Io= the light intensity before the beam of light passes through the film

Transmittance can be related to absorption by the expression:

Absorbance (A) = -log(T) = -log(It /Io) ……………………………………(2)

Where absorbance stands for the number of photons of the incident beam that is being absorbed by the
film. [5]
 Figure 2.6.3 (a) :- Transmittance

2.9.1 Band gap energy

If some amount of light energy falls on a molecule, then the molecule can absorb that energy if it can be

used to promote electrons to higher energy levels. Different wavelengths of light have different energies.

Therefore, a molecule can absorb only certain wavelengths of light. The energy difference between the

top of the valence band and bottom of the conduction band is the band gap energy. As long as a specific

minimum amount of energy is provided to the electrons, they can jump from one band to another.

Based on the spectrum obtained from the spectrometer, the optical band gap can be calculated using the

Eq. (3). E.g. represents the optical band gap expressed in eV and λa.e. denotes the absorption edge

wavelength or cut off wavelength expressed in nm.

The absorption edge wavelength can be obtained from the offset wavelength derived from the low

energy absorption band as schematically represented in Figure 2.6.4 (a).

Eg (eV) = h × f = h × ……………………………………………………(3)
Where ,h = Planks constant = 6.626 × 10-34 Joules sec

c = Speed of light = 3.0 × 108 meter/sec

Figure 2.6.4 (a).

Chapter 3

Experimental Results and Discussion

3.1 The product

The fabricated thin film of Molybdenum Trioxide deposited by thermal evaporation technique in high

vacuum is shown in Figure 3.1 (a) below

Transmittance and Absorbance Spectra

3.2.1 Transmittance

Figures 3.2.1 (a) presents the spectral behaviour of transmittance(T) for Molybdenum trioxide film

fabricated by the thermal evaporation method. The thin film was scanned in the range 190-1100nm of

wavelength with scan step 0.5 nm. The Table-3.2.1(a) shows the transmittance of the thin film with the

corresponding wavelength.
 Table-3.2.1(a)

WAVELENGTH (nm) TRANSMITTANCE (T%)

200 1.085
250 0.260
300 0.441
350 0.867
520 100.39
540 101.20
560 103.40
580 102.23
600 99.93
650 102.70
700 100.70
750 101.19
800 104.38
850 103.21
900 102.22
950 103.86
1000 106.14
1050 106.38
1100 105.81
 Figures 3.2.1 (a)

From the spectrum, it is found that the Transmittance(T) of the thin film varies periodically with the

wavelengths. Multiple oscillations can be seen on the transmittance curve of the thin film. It is due to the

interferences among multiple reflected waves — the oscillation period of the characteristics changes as

the wavelength increases. Thus, the transmittance characteristics of the thin film are dependent on the

wavelength.
3.2.2 Absorbance

Figures 3.2.2 (a) presents the spectral behaviour of absorbance (Abs) for Molybdenum Trioxide thin

film fabricated by the thermal evaporation method. The thin film was scanned in the range 190-1100nm

of wavelength with scan step 0.5 nm. The Table-3.2.2(a) shows the absorbance of the thin film with the

corresponding wavelength

Table-3.2.2(a)

WAVELENGTH (nm) ABSORBANCE (Abs)

190 .9860
250 1.975
300 1.912
350 0.7142
400 0.3588
450 0.1637
500 0.1010
550 0.0801
600 0.0871
650 0.1010
700 0.1010
750 0.0731
800 0.0871
850 0.1010
900 0.1080
950 0.0592
1000 0.0452
1050 0.1149
1100 0.0004
 Figures 3.2.2 (a)

3.3 Calculations for energy band gap from absorption spectra

The resulting spectrum obtained on Molybdenum Trioxide is shown in Figure 3.3 (a). The spectral data
recorded showed the strong cut off at 419.375 nm; where the absorbance value is minimum (0.010453).
 Figure 3.3 (a).

Therefore the band gap energy is-

Eg (eV) = h × f = h ×
Where h × c = ( 6.626 × 10-34) J s × (3 × 108) m/s

= 1.988 × 10-25 J m

= (1.988 × 10-25 ) / (1.6 × 10-19) eV m ; 1 eV = 1.6 × 10-19 J

= (1.240 × 10-5) eV m

= 1240 eV nm

Therefore,

Eg (eV) = 1240 eV nm / 419.375 nm

= 2.9594eV

Hence, the energy band gap of Molybdenum Trioxide is found to be 2.9594 eV.

4.0 Discussions

The absorption edge wavelength is λa.e. = 419.375 nm, which corresponds to the band gap energy of

2.9594 eV. It indicates that the energy separation between the highest occupied molecular orbital

(HOMO) and the lowest unoccupied molecular orbital (LUMO) is 2.9594 eV, i.e. an electron requires

2.9594 eV amount of energy to jump from HOMO to LUMO.

The theoretical band gap energy = 3 eV

The experimental band gap energy = 2.9594 eV

Therefore, % error = × 100 % = 1.35 %

This deviation may be due to the improper handling of the sample. The samples were exposed to air for

several times due to which the thin film was contaminated by foreign substances. Such errors can be

avoided by performing the experiments in a clean room in a controlled environment that has a very low

level of pollutants. Also, the samples should be kept in an air tight vessel. While handling the samples,

gloves should be used.

Chapter 4

Conclusions

Molybdenum trioxide coatings were deposited on a glass substrate by thermal evaporation and

characterized by UV-visible absorbance and reflectance spectroscopy.

Here, the transmittance and absorbance of the material with wavelength was studied. The results showed

that the absorbance and transmittance are strongly dependent on the wavelength of the electromagnetic radiation,

which was used for this purpose.

The band gap energy of the material was also calculated from absorption characteristics and by using standard

relation.

Thus, we studied the optical characteristics of the thin film of MoO 3 from the corresponding graphs and
also the energy of the band gap calculated.