CHAPTER 1

INTRODUCTION

1.1. Introduction
First chapter is about brief introduction of nanotechnology, its application, nanowires, nanotubes
and nanoparticles, also detailed description about Iron Aluminum oxide, its all properties,
crystal structure and synthesis method.

1.2. Nanotechnology and science society

Nanotechnology has ability to observe measure and change things at nanometer level. A length
of nanometer is SI i-e 10-9 [1, 2]. The technology which measure thing at nano level is
Nanotechnology .Nanotechnology has vast present and future applications in our society and in
science. It is use in different fields such as medical field, agriculture, military applications,
sporting goods, car paints and car waxes, antibacterial cleanser, medical bandages, apparel
industry, sun screens and cosmetics, organic light emitting displays or OLEDS [3], diagnostics,
novel drugs, lightweight materials, advance computing, increased situation awareness, powerful
munitions, energy and water[4]. It is check and explain of material at the nano scale having
dimensions between 1 to 100 nanometer [5]. It enables wide range of distinctive applications
which might be not possible if working with materials of size even of single atoms or molecules.
Researchers looking to know about the basic property called nanoscience which paying attention
on effective use of the properties called nano engineering. At nano level, nanotechnology
involves imaging, measure, modeling, and manipulate of material.
Nanotechnology is progressing rapidly nowadays [3-6]. Researchers are learning vast amount of
knowledge about health benefits. The origin of nanotechnology is found to the ability of
innovative developments towards all science fields. The potential applications of nanotechnology
is too immense and various, but one of the greatest achievement of nanotechnology will be in the
field of effective medical dealing [1, 7-10]. By using nanotechnology, we can enhance the
medical quality including, the development of nanoparticles for drug, gene delivery and
diagnostics. By using these technologies we are able to make accurate diagnosis.
1.2.1 History of Nanotechnology
The width of hair of animal is about 80,000 nm while the width of a human blood cell is 7000
nm. Size of atoms is less than 1 nm, whereas many particles and some proteins are between 1 nm
and larger [11]. Its hypothetical basics were first introduced in 1959 by Richard Feynman,
2

theres abundance of room at the underside .Then nanotechnology term is used by Norio
Taniguchi to discuss the materials ability to engineer precisely at the nano scale. Initially
miniaturization was done by electronics industries that focus to create tools to develop smaller
electronic devices by using silicon chips. In 1970s, technique of e-beam lithography was used to
create very small nanostructures at IBM in US. Then, in 1981, G. Binning and H. Rohrer of
IBM Research Laboratory examined atom by STM first time in the history. At last, in 1985,
Robert F. Curl Jr., Harold W. Kroto and Richard E. found Bucky balls made up of carbon and
measuring roughly 0.7nm wide[12].

1.2.2 Nanotechnology Benefits for Society

Benefits are given below
1. By using nanotechnology, we can find out the diseased cell and drugs can be directly given to
the cancerous cell without harming the healthy cells.
2. By using nanotechnology, we can convert sunlight to electricity by using more reliable solar
panels that will be more economical for production of solar power in future era.
3. By the help of nanotechnology we are in the position to clean our drinking water i.e., by using
very small flecks of rust to eliminate arsenic from drinking water.
4. By the help of nanotechnology we can also have environmental cleanup.

1.3. Nanostructures
A nanostructure has size that is intermediate between microscopic and molecular structures. Its
physical dimension smaller than 100nm. Any physical substance with structural dimensions
between 1-100 nm can be defined as nanomaterials. Nanostructure materials are materials with a
microstructure characteristic length scale of which is on the order of a few nanometers.
1.3.1 Types of Nanostructures
In nanostructures it is necessary to distinguish between the numbers of dimensions at nano level.
Physical substance with structural dimensions between 1-100 nm can be defined as
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nanomaterials. Nanostructures materials may be grouped under nanoparticles, Nano

intermediates and Nano composites. They may be in or far away from thermodynamic
equilibrium.

1.4. Nanoparticles
Particle of less than 100nm in diameter are known as nanoparticles. Nanoparticles continue
living widely in todays time: for instance as the resulting product of volcanic and photochemical
activity, and created by algae and plants. Nanoparticles attain great intention because of their
unique properties as compared to bigger particles of like materials. Nanoparticles have a range of
applications like textiles, new cosmetics and paints. Nanoparticles can also be agreed into layers
on surfaces, owing to large surface area and the resulting enhanced activity nanoparticles find
wide range of applications as catalysts.
Nanoparticles are lesser cluster of atoms about 1 to 100nm long. Nanometer is billionth of meter
or 10-9m. Nanoparticles are superior or greater than individual atom or molecule but are smaller
than bulk solid. Hence, they obey neither supreme quantum chemistry nor laws of established
physics and have property that differs markedly from those predictable which is shown in fig1.1.
These differences are happening due two major phenomena.
As the size of the crystal abridged number of atoms at the outside of the crystal compared to
number of atom in the crystal itself increases. For example, 4nm diameter CdS nanoparticles
have about 150 atoms, of which about a third are on the surface. Properties which are usually
determined by molecular structure of bulk lattice now become more and more dominated by
imperfection arrangement of outside.

Figure 1.1: Diagram show schematic representation of different sizes [13]

Second phenomenon occurs only in metals and semiconductors it is called size quantization and
arises because size of nanoparticles is comparable to de-Broglie wavelength of its charge carrier
(i-e electrons and holes). Due to spatial confinement of charge carriers, edge of valance and
conduction band split into discrete, quantization and electronic level. These electronic levels are
similar to those in atoms or moles as shown in fig 1.2[13].

Figure 1. 2: In diagrams, conduction band and valance band in solid, Nanoparticles and atom
state of semiconductor (left) and a metal (above) are compared [13].
6

It can be seen here again that nanoparticles represent a state of matter in transition state between
bulk solids and individual atom.

1.5. Nanowires
A nanowire is defined as a wire of dimension of few nanometers. At nanometer level Quantummechanical effect is dominated so these wires are also called quantum wires.
1.5.1 Types of Nanowires

Metallic( Ni,Pt and Au nanowires)

Semiconductor ( InP,Si and GaN nanowires)

Insulator (SiO2 and TiO2 nanowires).

Organic or inorganic molecular nanowires can be produced by repeating molecular unit. Mostly
nanowire has large aspect ratio of 1000 or more. Nanowires have some unique properties that are
not rated to be observed in bulk material since at Nano scale level these shows quantum
confinement effect of electrons but in bulk scale these materials shows continues energy level.
Bulk material have large conductivity as compare to nanowire this is because when the width of
wire is below the free electrons mean free path of the bulk material there exist scattering from
the boundaries of wires. Nanowires also show many strange electrical properties due to quantum
size effect.

1.6. Nanotubes
For one element hollow cylindrical or toroid molecule are made. Nanotechnology is investigated
for uses in nanotubes. They have good thermal conductivity and extremely strong material. They
have possible use in Nano-electronic and Nano-mechanical devices. In several fields the
researcher and companies are using the properties of nanotubes. When the other molecules are
attached to the carbon nanotubes their electrical resistance varies. Most of the Companies are
7

using property to develop sensors which will detect chemical vapors for example carbon
monoxide or biological molecules. Due to quantum confinement effect in 2D, semiconductor
nanotubes reveal electronic and optical properties.

1.7. Iron
Iron is a chemical element of periodic table located in the eighth group and is represented by the
symbol Fe. This metal is present in first transition element series [15]. It is the fourth most
common element present in earths crust. Iron exists in wide range of oxidation states that ranges
from +2 to +6. The most common state is +2 and +3. Iron is very reactive with oxygen and
water. Fresh iron appears with silverish grey surface but it oxides with normal air and form iron
oxide which is commonly known as rust. When impurities, most commonly carbon is added into
iron by smelting process, then it converts into steel. Steel is 100 times harder than pure iron.
Chemical compounds of iron are also of wide use. Fig 1.3 below shows the physical appearance
of iron:

Figure 1.3 physical appearance of Iron metal [21].

1.7.1. Physical properties of Iron

The major physical properties of iron as given below in the table 1.1:
Table 1.1 Physical properties of Iron.
Color

Silver-gray metal

Malleability

Capable of being shaped or bent

Ductility

Easily pulled or stretched into a thin wire

Luster

Has a shine or glow

Conductivity

Good transmission of heat or electricity

Allotropy

It occurs in two or more crystalline forms in the same physical state

Tensile

It can be stretched without breaking

Ferromagnetic

Easily magnetized

1.7.2. Chemical properties of Iron

The chemical properties of iron are given below in the table 1.2.
Table 1.2Chemical properties of iron.

Chemical formula
Toxicity

Fe
Non Toxic

Reactivity with waterReacts with very hot water and steam to produce hydrogen gas
Oxidation
Solubility

Readily combines with oxygen in moist air which produces iron

oxide also known as rust
Dissolves in acids

1.7.3. Isotopes of Iron

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Isotopes of Iron are given below in the table 1.3

Table 1.3 isotopes of iron.
Isotope

Atomic mass

Natural abundance

Half life

( %)

(years)
>3.1x1022 years

Mode of decay

54

53.94

5.845

56

55.935

91.574

57

56.935

2.119

58

57.933

0.282

Fe
Fe
Fe
Fe

Ec-Ec

1.7.4. Crystal structure of Iron

Iron atoms are able to arrange themselves into both stable crystal structure that is body centered
cubic structure and face centered cubic structure. The body centered cubic structure of iron is
called Ferrite and it is stability occurs at two temperature ranges that are, 1665K or below and
1184K or above. The iron that is stable at first temperature is known as Alpha iron and the iron
that is stable at second temperature is known as iron. The face centered cubic structure of iron
is known as Austenite and is stable between the two above mentioned temperature and is referred
as Gamma iron. The crystal structure of iron is shown in the fig 1.4.

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Figure 1.4 Body centered and Face centered crystal structure of Iron [22]
1.7.5. Uses of Iron
Iron is one of the most widely used metal. Its extensive use in industry is due to its low cost and
high strength. It is used in industry in making various tools, metallurgical instruments and auto
mobiles. Iron plays a vital role in the field of biology. Many complexes are formed by iron with
oxygen in hemoglobin and hemoglobin in human body. Adult human have about one eighth of a
once that is about 3.5g of iron in their body. IDA that is Iron deficiency anemia is due to
deficiency of iron in human blood.

1.8. Aluminum
Aluminum is a silvery white metal in its pure form. Its symbol is Al and having atomic number
13. It is soft in nature and ductile element. After oxygen and silicon it is the most abundant
element found in the earths crust. Aluminum is nontoxic and nonmagnetic
use for decorative purposes.
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element. It is

1.8.1. Physical properties of aluminum

Table 1. 4 physical properties of aluminum
Atomic mass

26.98154 g.mol -1

Electro negativity according to Pauling

1.5

Density

2.7 g.cm -3 at 20 C

Melting point

660.4 C

Boiling point

2467 C

Vander Waals radius

0.143 nm

Ionic radius

0.05 nm

Isotopes

Artificial isotopes

16

Electronic shell

1s2 2s2 2p6 3s2 3p1

Energy of first ionization

577.4 kJ.mol -1

Energy of second ionization

1816.1 kJ.mol -

Energy of third ionization

2744.1 kJ.mol -1

Standard potential

- 1.67 V

1.8.2. Chemical properties of Aluminum

One of the most useful properties of aluminum is that in moist air it reacts slowly with oxygen
and forms a thin layer of aluminum oxide on the surface of the metal that prevents the element
from further reaction and corrosion. This thin layer of aluminum oxide can easily be seen on
aluminum outdoors. Aluminum is a highly reactive metal. It reacts with various hot acids. It also
reacts with hot water and alkalis. The powder form of aluminum catches fire quickly as it is
highly flame able.

1.9. Aluminum oxide

The common name of aluminum oxide is Alumina. It is basically the chemical compound of
oxygen and aluminum and represented by the symbol Al 2O4. Aluminum oxide is commonly used
to produce aluminum metal due to its high melting point and hardness. [16]. The physical
appearance of alumina is shown in fig below:
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Figure 1.5 physical appearance of aluminum oxide.

1.9.1. Physical properties of aluminum oxide

The physical properties of alumina are shown in table 1.5:
Table 1.5 physical properties of aluminum oxide
Molecular formula

Al2O4

Molar mass

101.96 g mol1

Appearance

white solid

Odor

Odorless

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Density

3.954.1 g/cm3

Melting point

2,072 C (3,762 F; 2,345 K)

Boiling point

2,977 C (5,391 F; 3,250 K)

Solubility in water

Insoluble

Solubility

Insoluble in diethyl ether

practically insoluble in ethanol.

Thermal conductivity

30 Wm1K1

1.9.2. Chemical properties of aluminum oxide

Aluminum oxide is insoluble in water.

It reacts with acids. Bases and alkalis.

It has high melting point.

It is beneficial as abrasive due to its hardness

It also acts as electrical insulator.

Aluminum oxide prevents the metal aluminum from further corrosion.

1.9.3. Crystal structure of aluminum oxide

The most common crystalline form of Al 2O3 is known as corundum. The crytal structure of
alumina exists in different modifications. The three most important crystalline forms of
alumina are:

Alpha (stable)

Kappa (metastable)

Gamma (metastable)
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a. Alpha alumina
It is the only stable state of alumina at all the temperatures. The structure of alpha alumina is
trigonal and it is explained as ABAB stacking of oxygen planes along c direction and aluminum
ions are present at 2/3 of the octahedral interstitial position.

Figure 1.6 Schematic drawing of the first layer in the alpha alumina structure [19]

b. Kappa alumina
Kappa alumina shows the orthorhombic structure. In this structure oxygen is closely packed in
ABAB stacking arrangement along the c direction. In this structure of the aluminum atoms
are present at tetrahedral position and remaining occupy the octahedral position.

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Figure 1.7 Schematic drawing of the first two layers in the kappa alumina structure. Octahedral
Al ions are black, tetrahedral are grey [19].
c. Gamma alumina
The structure of gamma alumina is cubic. In this structure oxygen is present in stacking position
of ABCABC and is based on fcc structure. This type of structure is often referred as defect
cubical spinel structure where vacancies are present at cation positions. In this structure
aluminum ions occupy both positions, octahedral and tetrahedral.

Figure 1.8 Schematic drawing of the first two layers in the gamma alumina structure [19].

1.9.4. Applications of aluminum oxide

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Aluminum oxide is one of the most versatile oxides and it has wide applications in various fields.
As aluminum oxide is a very good electric insulator so it is used as a substrate for integrated
circuits. It also uses as a tunnel barrier for the fabrication and synthesis of super conducting
devices such as single electron transistor. Aluminum oxide is also used in the manufacturing of
spark plug insulator. The major applications of aluminum oxide are as under:

Filter

Catalysis

Purification

Abrasive

Paint

Composite fiber

1.10. Techniques for the synthesis of nanostructures

There are two approaches for synthesis of the nanomaterial. One is the top-down approach and
the second one is the bottom-up approach.
1.10.1. Top-down Approach
In this approach the work is started from the top (from the bulk material) and ended at the bottom
(nanomaterial). So top-down means from top (larger) to bottom (smaller). This approach has the
same trend as for making the statue made of a stone. For example; the making of a statue is
started from the bulk level or a big piece of a stone, in the same way in the top-down approach,
bulk material is taken at the starting. Then the carving and cutting processes are involved to
achieve desired shape. The various top down techniques are as under:

Nanolithography

Dry etching techniques

Anodization

1.10.2. Bottom-up Approach

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This is the second one approach; in this approach the work is started from the bottom (at the
atomic level) and ended at the top (nanomaterial). The bottom-up means from the bottom
(smaller) to the top (larger). In this approach, a nano-metric structure is taken then this structure
is assembled without any external manipulation. This method is known as self- assembly. The
various bottom up techniques use for the synthesis of nanostructures are as under:

Sol-gel processing

Chemical vapor deposition

Self-assembly and bio assisted synthesis

Laser pyrolysis

Electrochemical deposition/ electroplating

Spraying synthesis

The fig 1.9 shows the pattern of both the techniques for the synthesis of nanomaterial.

Figure 1.9 top down and bottom up approaches [20].

1.10.3. Electrodeposition technique
Electrodeposition is the process of deposition of metals. It is the process in which electric current
is required to reduce cations of the desired material from the solution and to coat the desired
material on the conductive substrate in the form of thin film. Electrodeposition is used for the
variety of applications in nanotechnology, microelectronic optics and related fields. It is also
widely used in many industrial applications for the manufacturing of jewelry, tools, electronic
devices automobile and toy industry. [17]
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1.10.4. Types ofelectrodeposition

There are two types of electrodeposition
Electroplating
Electro-less plating
Electroplating
In electroplating process, we place our substrate in a liquid solution which is known as
electrolyte. By applying the electrical potential between a conduction area on the substrate and a
counter electrode in the liquid, a chemical process occurs and as a result a layer of material
deposit in the conductive substrate.

Electro-less plating
In this process, a complex chemical solution is used in which deposition happens spontaneously
on any surface which forms a high chemical potential with the solution.
The main difference between the two techniques is the requirement of external applied electric
voltage. In eletropalting we need an external applied voltage but in electro-less plating there is no
such requirement. The electroplating process is only for conductive substrates. By using this
technique we can grow the films with the thickness ranges up to tens of micrometer. Whereas,
the electro-less plating process can be used for the conductors and dielectrics but in this
technique it becomes difficult to control the thickness and uniformity of the film[18]
1.10.5. Benefits of electrodeposition
This process is considered to be best for the deposition of metals. It is less expensive technique
for the formation of well-defined nanostructure as compared to the other vacuum based
techniques. By using this technique we can grow the films with the thickness ranges from

19

1micrometer to 100 micrometer. The applied external electric potential helps to control the
thickness and uniformity of the deposited film.
1.10.6. Requirements for successful electrodeposition
The basic requirement for the successful deposition of material via electrodeposition is as under:
Good adhesion of resist is required because the plating presses against the resist during selective
area plating.
Cleaning of substrate, solution and equipment is another basic requirement because a little
amount of impurity can affect the quality of deposited film.
The plating solution has to be compatible with the substrate and the resist because various
plating solutions are caustic and reacts with the substrate and the resist.
1.10.7. Working principle of electrodeposition
Electrodeposition is also termed as electroplating. This method is referred to as bottom up
technique for the synthesis of nanostructures. Electrodeposition is mainly use for the synthesis of
nanostructure. By using this technique one can obtain designs with high density and high aspect
ratio. As in the lithographic technique, electrodeposition also requires polymer mask from which
the metal is deposited. Electrodepostion build the structure atom by atom and do not show the
problem of showing near interfaces and edges, as in the other techniques such as ion milling, RIE
and isotropic etching. This technique is restricted to the electrically conductive materials. By
using this method we can synthesis nanostructures with thickness having range from ~1m to
>100m. In this process a suitable substrate is placed in the liquid solution known as electrolyte.
During electrodeposition process we use electric current to reduce the cation of the desired
material present in the solution. As a result of this current these cations coats as a thin film of that
material on the conducting substrate surface. The thickness of the thin film on the substrate
depends on the timing of the plating. The longer the object remains in the operating plating bath
the thicker will be the layer of the electroplated thin film. The arrangement for the
electrodeposition process is shown in the fig below.

20

Figure 1.10 Setup for electrodeposition [18].

1.10.8. Properties of deposited film

The deposited film should have some properties that are listed below.

Adhesion:

The one of the major requirement of the electroplated film is good adhesion. The adhesion is
mainly depends on the substrate. For good adhesion the cleaning of the substrate should be
done properly. It should be free of any surface films. The substrate and the deposited film
should interfuse with interlocking grains to give a smooth surface.

Mechanical properties:

Mechanical properties of the electrodeposited film onto the substrate mainly rely on the
amount and the type of the growth inhibiting substances on the surface of the cathode. The
reason we use growth inhibiting substance is to obtain fine grain structure of the
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electrodeposited film. So that the grain boundaries act as the obstacle to dislocation motion.
As a result the deposited film has high yield strength and hard surface.

Brightness:

Brightness of the electroplated film is required for decoration purposes. The brightness of the
film mainly relies on the surface finish of the substrate material. In order to obtain a thicker
bright deposited film, an additional agent has to be added in the plating solution. These
additional agents eliminate the protrusions. Widely used additional agents includes organic
compounds such as lactose, dextrose,tartarates and formaline.
1.10.9. Applications of electroplating
The application of electroplating is mainly in the following four fields:

Decoration
This application includes forming a layer of an expensive metal on another metal base for
the decoration purpose. It is used in the formation of jewelry, furniture, hardware and
table ware.

Protection
To save material from corrosion. For example by coating chromium layer on auto
mobiles parts, by coating cadmium and zinc layer on electrical parts, Nuts, tools and
screws.

Electroforming
This application involves the manufacturing of record stampers, screens, moulds and
dies.

Enhancement
This application involves the coating of a material which has better electrical and thermal
conductivity as well as reflectivity and solders ability.

22

1.10.10. Factors affecting the electro-deposition technique

The factors that influence the coating quality and quantity in electro-deposition technique are as
below:

Current efficiency

Current density

Electrode potentials

Current efficiency
According to Faradays laws, the amount of chemical charge at an electrode is proportional to
total amount of electricity passing from electrode. Current efficiency can be define as total
percentage of electric current that is passing through the electrolytic cell for the required
chemical reaction. The current efficiency provided to cathode reaction is known as cathode
efficiency and that provided to anode is termed as anode efficiency.
Current density
The current per unit area of electrode is termed as current density and it is calculated in amperes.
The current density largely affects the properties of the coated film. Current will move at the
edges in order to minimize the solution resistance. For uniform current distribution the amount of
current has to be same at all point of the electrodes.
Electrode potential
The electric potential difference between the reference electrode and electrode is known as
electrodes potential. It is always referred to as an arbitrary zero point.

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1.11 Layout of the Thesis

In first chapter, I briefly introduce nanotechnology, its application, nanowires, nanotubes and
nanoparticles, also detailed description about element which I choose for my research work. I
also described the properties, crystal structure and synthesis methods. Thesis layout is also
included in this chapter.
In the second chapter, detailed description of the methods and process for the synthesis were
given. Also, mentioned the previous work done by various techniques.
Third chapter includes the experimental detail about the synthesis. The techniques used for the
characterization were also described. Third chapter also describes the preparation method of Iron
Aluminum Oxide.
The results of various characterization techniques and the discussion of these results are given in
this chapter. Also the conclusion on the basis of these results was in chapter 4.

24

1.12. References
1. Nanotechnology Basic Science and Emerging Technologies By M. Nilson,K.Kannangara,
M. Simmons and B. Raguse, Chapman and Hall, 2002.
2. Nanotechnology, Risk, Ethics and Law by G. Hunt and M. Mehta, Earth Scan, 2006.
3. Nanotechnology by John Mongillo, Greenwood, 2007.
4. Nanotechnology, Risk, Ethics and Law by G. Hunt and M. Mehta, Earth Scan, 2006.
5. Understanding of Nanoscience and Technology by P. Dutta and S.Gupta, Global Vision,
2006.
6. Nanotechnology by R. Booker and E.Boysen, Wiley, 2005.
7. Nanotechnology by John Mongillo, Greenwood, 2007.
8. Nanocomposites by Dr. P. Diwan and A. Bharadway, Pentagon, 2006.
9. Inorganic Chemistry by A. G. Sharpe, Pearson Education & Dorling Kindersley, 2007.
10. Zinc Oxide by D. B. Faloon, Van Nostrand, 1926.
11. Inorganic Chemistry by A. G. Sharpe, Pearson Education & Dorling Kindersley, 2007.
12. Nanotechnology by John Mongillo, Greenwood, 2007.

25

13. Nanomaterials and nanostructures by l. Costlow and A. P. Domi,Hyatt Regency

Downtown, 2003.
14. Understanding of Nanoscience and Technology by P. Dutta and S.Gupta, Global
15. "Alumina (Aluminum Oxide) The Different Types of Commercially Available Grades".
The A to Z of Materials. Retrieved 2007-10-27.Vision, 2006.
16. A.J Bard, L.R Faulkner. Electrochemical methods and applications, 2nd edition, John
Wiley and sons, New York, 2001
17. T.Osaka, T.Yokoshima, D.Shingha, K.Imai, K.Takashima, electrochem. Solid-State
Lett, 53-55, 2003
18. http://electroplating.wikispaces.com.
19. http://fy.chalmers.se/~f10mh/CVD/aluminaintro.html.
20. M. Imran, The Synthesis and Characterization of TiO 2 Nanoparticles. Centre of solid
state physics, University of the Punjab.
21. http://goldsilveralert.blogspot.com/2011_02_01_archive.html.
22. http://zappnews.com/series3-2.html.

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CHAPTER 2
Literature Review

27

2.1. Introduction
This chapter is based on the literature review of previous papers that has been written on the
synthesis of iron aluminum oxide nanostructures with various techniques. In my experimental
work Top down approach has been used for the synthesis iron aluminum oxide nanostructures.
We have use electro-deposition technique in our experiment. Iron and alumina is obtained from
different sources of iron and aluminum.

2.2 literature review

Paesano Jr. et al. [1] reported the synthesis of Fe.Al 2O3 nanocomposites by Arc melting
pellets of iron and aluminum powders. In this experiment two different nominal grades of
alumina was used for the synthesis of nanocomposites. The samples were characterized by x-ray
diffractometry, spectroscopy and magnetization. The results of the samples showed that spinel
Fe. Al2O3 and metallic iron were formed by this melting process. It could be seen from the results
that by increasing the iron contents in the initial powder, the chances of hercynite reaction also
increased. When the arc melted sample was annealed at 1200C in hydrogen atmosphere, it
showed a reduction in hercynite and phase separation of metallic iron. They also found that more
used of pure alumina, in started powder reduced the fraction of iron nano crystals.
28

Pradhan et al. [2] reported the synthesis of nancomposites of iron incorporated

mesoporous Al2O3. These nanocomposite were proved an efficient photo catalyst for hydrogen
production under visible light. They used the sol-gel process for the formation of
nanocomposites which is then followed by wetness impregnation method. These nanocomposites
were proved to be active photo catalyst for the evolution of hydrogen energy from water in the
presence of sacrificial agent. The factors that play part in the splitting of water are band gap
energy, small particle size, high surface area and mesoporous nature. The DRUV-vis spectra
measured the band gap. TEM is used to evaluate the particle size. The material is also
characterized by x-ray diffraction. The small particle size that is about 47.95nm, visible light
active band gap 1.90 eV were the factors that contributed in the high hydrogen production ability
of Fe.Al2O3. The mesoporus Al2O3 was synthesized by using sucrose as a substrate. Mesoporous
Al2O3-MCM-41 was synthesized by incorporating meso- Al 2O3 to the MCM-41. Iron with
different weight was then added in Al2O3-MCM-41 by using wetness impregnation method.
Ferrous Sulphate was used as the source of iron. After this the iron added Al 2O3-MCM-41
nanocomposites were calcined at 600C for 6h.
Shinde et al. [3] reported the synthesis of aluminum doped Fe 2O3 nanoparticles. They
studied their physical and photochemical properties in regard to solar energy conversion. In this
experiment they used the method of spray pyrolysis for the synthesis of aluminum doped Fe 2O3.
The samples were characterized by using X-ray diffraction technique, scanning electron
microscopy and impedance analyzer. The results showed that the aluminum doped iron oxide
thin film shows the deficiency of oxygen. The preparation parameters are controlled so that the
prepared thin film show good quality and adhesion with substrate. The deposited iron oxide film
showed single hematite phase. The crystal structure of nanoparticles was found polycrystalline
rhombohedra and the crystal size was 20-40nm. Al doped hematite showed better photocurrent as
compared to un-doped hematite. By using the spray pyrolysis technique, un-doped and Al doped
Fe2O3 were deposited on ultrasonically cleaned glass and fluorine doped tin oxide coated glass
substrate. Fe2O3 was obtained by adding 0.1 M ferric trichloride in the solution. Al doping was
obtained by adding Aluminum nitrate in the solution. This solution was sprayed on the preheated
substrate. The temperature of substrate was kept control at 623 K. spray rate was 5 cc/min,
nozzle diameter 0.05cm and the distance of substrate from nozzle was 33cm.

29

Tamboli et al. [4] reported the synthesis of nanostructure iron oxide thin film by electrodeposition method. Hematite was formed by using 3M NH 4Cl and 0.02M FeCl2.4H2O as reagents
with 99.95% purity. To adjust the reagent pH at 7.52, 1M NaOH was used. Ultra purely distilled
water was used to prepare all the solutions. The deposition process was occurred in conventional
three electrode cell. They had used Fluorine doped tin oxide glass plate as working electrode and
platinum plate as a counter electrode. The iron oxide film was prepared at different deposition
potentials and was annealed at different temperatures. In this paper they studied the effect of
deposition potential, Deposition time and annealing temperature on the photochemical properties
of iron oxide nanostructures. The characterization of the samples was done by x-ray diffraction
method. The results of x-ray diffraction showed the peaks (104) and (110). These peaks confirm
the Fe2O3 phase formation. As the annealing temperature varied from 400 C to 700 C so the
results showed the transition in the surface morphology from nano sheets to dumbbell shaped
nano particles. The variation in annealing temperature also resulted in the variation of optical
band gap. The increase in the photocurrent increases the thickness of the film.
Shwarsctein et al. [5] reported the synthesis of aluminum doped iron oxide by electrodeposition method. In this paper they showed that doping of iron oxide enhanced electronic
properties of iron oxide for the solar photochemical applications. Generally the non isovalent
doping of iron oxide enhances its electric conductivity but this paper showed that isovalent
doping of Al also improved the electric conductivity of iron oxide. The characterization of the
sample was done by x-ray diffraction technique. The surface morphology was analyzed by
scanning electron microscopy and the atomic composition of the sample was checked by ICP
mass spectrometer. The sample was synthesized by the electro-deposition of doped and un-doped
Al in a conventional three electrode cell. A quartz substrate with Ti/Pt adhesion layer was used as
counter electrode and fluorine doped tin oxide was used as working electrode. The electro
deposition solution consisted of 5mM FeCl3 + 5 mM KF +0.1 M KCl + 1 M H 2O2. Al doping is
obtain by adding AlCl3 solution. The applied voltage varied between 0.49V and 0.40V. After
deposition the film was washed by distilled water three times to remove any impurity. After this
calcination was done in air at 700 C for Ti/Pt doped quartz substrate and at 600 C for FTO
substrate.

30

Lokhande et al. [6] reported the synthesis of iron oxide by electro deposition method.
They studied the iron oxide nanostructure for their super capacitive application. The iron oxide
was deposited electrochemically on a stainless steel substrate. Ferric chloride aqueous solution of
0.1 M concentration was used as electrolyte. This solution was prepared using double distilled
water. The substrate was polished using a fine grade polishing paper, after this the polished
substrate was etched for 1 min in 3% HCl and then washed ultrasonically for 20 min with
distilled water. The stainless steel was used as working electrode. A constant voltage of 1.1 V
was applied. The deposited electrodes were then dried for 12hr and then annealed for 1hr at
different temperatures starting from 423K to 673K. Structural and morphological
characterization of the sample is done by using x-ray diffraction technique and scanning electron
microscopy.
Krifa et al. [7] reported the synthesis of iron aluminum copper alloy disordered
nanostructures. The iron aluminum copper alloy composition was formed by the mechanical
alloying of the elemental powders by ball milling process. The elemental powders of Fe, Al and
Cu with purity of 99.99% were mixed and mechanical alloying was done for 50hr. The process
of mechanical alloying was carried out in a high energy planetary ball mill, in argon atmosphere.
The diameter of stainless steel vials and balls was about 12mm, the ball to powder ratio was
about 12:1 and the rotation speed of the disk was 700. They used x-ray diffraction technique to
study the transformation, occurs in the material during the high energy ball milling process. They
found that by increasing the time of ball milling process all the atoms of al and Cu dissolved in
BCC Fe and the final product of mechanical alloying becomes nanocrystalline Fe (AL, Cu) solid
solution with a mean size of 9nm. Scanning electron microscopy was used to study the surface
morphology of the material as a function of milling time. The change in magnetic properties of
the material were also studied. Initially the material show soft ferromagnetic behavior Hc = 173
A/m, then during the early processing of alloy it showed hardening ferromagnetic behavior Hc =
15277A/m and for longer milling time the material again showed a slightly soften magnetic
behavior and became a semi hard ferromagnetic Hc = 5500A/m.
Siddique et al. [8] reported the effect of temperature on the modified alumina with Fe 2O3.
In this experiment they used transmission electron microscopy TEM for the study of the effect of
high temperatures on the material. And for the study of magnetic properties VSM was used. The
31

stability of the material was checked by heating it for 2hr in air with the temperatures ranging
from 400C to 1200C. The modified alumina with Fe 2O3 was used for the separation of
hydrocarbons such as alkenes and alkenes. The change in the phases of the material was
measured at the temperatures ranging from 400C to 1200C. From results, they found that high
spin F+3 were present at almost all temperatures in the form of FeAlO 3 but with different
concentrations. The material showed completely paramagnetic behavior at 400C. But at
temperatures higher than 400C it becomes partially paramagnetic. Above 400C the presence of
iron oxide along with Fe+3 can be seen. Finally Fe2O3 and Fe+3 were detected at 1200C. The
parameters showed that regarding to the stability of the material, 800C is the most important
temperature.
Bhujun et al. [9] reported the synthesis of aluminum doped transition metal ferrite
nanomaterial and study their properties as superconductor electrodes. The synthesis of aluminum
doped transition metal ferrite was carried out by using the sol-gel technique. Asymmetric
electrochemical capacitors were formed from nanostructured ferrite compounds and activated
carbon nanocomposit material. In this paper he synthesis different compounds such as
aluminum- nickel Fe2O4, aluminum-cobalt Fe2O4, aluminum copper Fe2O4. All these compounds
are formed using the sol gel technique. The characterization of the materials was done by x-ray
diffraction technique and scanning electron microscopy is used for study of surface morphology.
It was found that metal oxide compounds showed that they possess porous spinel structure. The
electrochemical performances of the electrode cells in 0.1M KOH was evaluated using cyclic
voltmeter and galvanometer. The results of the experiments showed that the transition metal
incorporation with the iron oxide enhances the capacitive abilities of super capacitors. The pore
size of the nanomaterial played an important role in enhancing the capacitive abilities of the
electrodes.
Li et al. [10] reported the synthesis of nanocrystalline Nickel iron alloy by the electrodeposition technique. This experiment studied the thermal stability and microhardness of the
sample material. The approximate grain size of the alloy was found 14nm. The electrodepostion
was carried out in conventional disk rotating cathode setup. The nickel iron alloy was deposited
on annealed Cu substrate with 35mm diameter. The stainless steel was used as working
electrode. Firstly the copper substrate was glued on this electrode by using silver epoxy. Then
32

substrate polishing was done in phosphoric acid solution, and activated in 20% H 2SO4, before its
deposition in the cell. The platinum foil served as anode. Nickel sulphamate solution was used as
electrolyte in this experiment. The other parameters of deposition were temperature 298K and
pH value of 2. After the deposition completed the samples were annealed for 90 mins in the
temperature ranges from 373-773 K. The results showed that grain grown started at 400k or
above annealed temperature. Two schemes of grain growth was seen in the results. The low grain
scheme at 575K can be controlled by grain boundaries diffusion whereas the high gran growth
was controlled by lattice diffusion. The characterization of the sample was done by X-ray
diffraction technique and by Microprobe analysis.
Lecina et al. [11] reported the synthesis of Ni/Al 2O3 nanocomposite coatings by using the
electro-deposition technique. These coating were obtained by the deposition of Al 2O3
nanoparticles from Nickel watts baths with the average grain size of 40-47nm. Different
concentrations of Al2O3 were used in the solution. In this paper comparison between the effects
of mechanical and ultrasonic string was analyzed on the properties of electrodeposited NI/ Al 2O3
coatings. The analysis showed that there was an increment of Al 2O3 in the composite coating and
this increment enhances the uniformity of particle distribution on Nickel matrix. The
incorporation of Al2O3 increases the surface morphology and tribiological properties of nickel
matrix. The characterization of the sample is done by using XRD, SEM and TEM.
Kim et al. [12] reported the synthesis of Cu/ Al 2O3 nanocomposities coating by using
electrodeposition technique. Later they studied the effect of ultrasonification on the Cu/ Al 2O3
nanocomposites during the electro-deposition process. In this paper nanocomposite were
synthesized by incorporating Al2O3 nanoparticles with size of 50nm. Silicon wafer was used as a
substrate. One side of the wafer was polished with surface roughness less than 3nm. This wafer
was then cut into pieces. After this a 5nm thick Cr and 5nm thick Au film was coated on the
substrate. High potential galvanostat was used to control the deposition parameters.
Ultrasonifiaction during the electro-deposition process reduced the agglomeration of
nanoparticle and efficiently reduced the grain size of Cu matrix. SEM is used for the
characterization of the prepared samples.
Thiemig et al. [13] reported the synthesis of Nickel alumina nanocomposites by the
electro-deposition method. In this experiment they studied the influence of hydrodynamics and
33

pulse plating parameters on the electro-deposition of these nanocomposits. Nickel alumina

composites were synthesized using two electrodes configuration i.e. a parallel plate electrode and
impinging jet electrode. The current modulations used in this experiments are direct current,
pulse plating and pulse reverse plating. Generally the nanocomposite show more hardness as
compared to pure Nickel coating. The enhancement in the hardness was due to Al 2O3
incorporation. The electro-deposition process was carried out by using an acidic nickel
sulphamate electrolyte containing

1.08M Ni (NH 2SO3)2, 0.04M NiCl2 6H2O and 0.65M

H3BO3. Double distilled water was used to form the solutions. The suspension was formed by
adding Al2O3 to the electrolyte. The diameter of alumina particles can be either 13nm or 50nm.
After this the solution was placed in a covered beaker and was stirred by a magnetic stirrer for 12
to 24 hr. The pH of the solution must be sustained at 4.3 with either NaHCO 3 or H2SO4. After
formation the samples were washed in distilled water for 10 min to remove the badly adhering
particles. The samples were characterized by using scanning electron microscopy. X-ray
diffraction was used to measure the crystal size of the sample.

34

2.3. References
1. A. Paesano , C.K. Matsudaa, J.B.M. da Cunhab, M.A.Z. Vasconcellosb, B. Hallouchec,
S.L.Silva. Synthesis and characterization of Fe-Al2O3 composites. Journal of
Magnetism and Magnetic Materials 264, 264274 (2003).
2.

Amaresh C. Pradhan, Satyabadi Martha, S.K. Mahanta, K.M. Parida . An efficient

photocatalyst for hydrogen production under visible light. International journal of
hydrogen energy 36, 12753 - 2760, (2 0 1 1).

3. S. S. Shinde, R. A. Bansode, C. H. Bhosale, and K. Y. Rajpure. Physical properties of

hematite -Fe2O3

: application to photoelectrochemical solar cells. Journal of

Semiconductors (2011).
4. Sikandar H. Tambolia, Gul Rahmana, Oh-Shim Jooa, Influence of potential, deposition
time and annealing temperature on photo electrochemical properties of electrodeposited
iron oxide thin films. Journal of Alloys and Compounds 520, 232 237 (2012).
5. Alan Kleiman-Shwarsctein, Muhammad N. Huda, Aron Walsh Yanfa Yan, Galen D.
Stucky,

Yong-Sheng

Hu,

Mowafak

35

M.

Al-Jassim,

and

Eric

W.

McFarland.Electrodeposited Aluminum-Doped r-Fe2O3 Photoelectrodes: Experiment

and Theory. Chem. Mater, 22, 510517, (2010)
6. B.J.Lokhande, R.C.Ambare, S.R.Bharadwaj. Thermal optimization and supercapacitive
application of electrodeposited Fe2O3 thin films. Measurement 47, 427432, (2014)
7. M. Krifa, M. Mhadhbi, L. Escoda, J. Saurina, J.J. Suol, N. Llorca-Isern, C. ArtiedaGuzmn, M. Khitouni. Phase transformations during mechanical alloying of Fe30%
Al20% Cu. Powder Technology 246, 117124, (2013).
8. M. Siddique, M.Riaz. Stability of modified alumina with Fe2O3 at high temperatures.
Physica B 405, 22382240, (2010).
9. Bhamini Bhujun, S. Anandan Shanmugam and Michelle tan. Study of aluminium doped
transition metal ferrite nanomaterials as supercapacitor electrodes. Journal of
Engineering Research and Design Vol. 2(1), 1-10, April, (2014).
10. H.Q. Li, F. Ebrahimi. An investigation of thermal stability and microhardness of
electrodeposited nanocrystalline nickel-21% iron alloys. Acta Materialia 51, 39053913,
(2003).
11. E. Garca-Lecina, I. Garca-Urrutia a, J.A. Dez a, J. Morgiel b, P. Indyka. A
comparative study of the effect of mechanical and ultrasound agitation on the properties
of electrodeposited Ni/Al2O3 nanocomposite coatings. Surface & Coatings Technology
206, 29983005, (2012).
12. Minho Kim, Fangfang Sun, Jaebeom Lee, Yang Ki Hyun., Dongyun Lee. Influence of
ultrasonication on the mechanical properties of Cu/Al2O3 nanocomposite thin films
during electrocodeposition. Surface & Coatings Technology 205, 23622368, (2010).
13. Denny Thiemiga, Andreas Bunda, Jan B. Talbot. Influence of hydrodynamics and pulse
plating parameters on the electrocodeposition of nickelalumina nanocomposite films.
Electrochimica Acta 54, 24912498, (2009).

36

CHAPTER 3
CHARACTERIZATION TECHNIQUES

37

3.1. Introduction
This chapter deals with the techniques for experimental investigation of iron aluminum oxide
deposited nanostructures by electro deposition technique on copper substrate. The deposition
potential and deposition time acts as the controlling parameters. Structural and magnetic
properties of iron aluminum oxide were analyzed by several techniques. The samples are
characterized by using vibrating sample magnetometer VSM, X-ray diffraction and scanning
electron microscopy SEM.

3.2. Types of growth

The growth of synthesized nanostructures can be carried out in two ways which are as under:
1. Template free growth

38

When large area growth is required then we normally use template free growth. For template free
growth substrate are required.
2. Template assisted growth
When the region of growth is defined, then the template assisted expansion is used for the
synthesis of nanostructure.
We have used template free growth for the synthesis of our nanostructures.

3.3. Experimental details

There are many steps involved for the growth of iron aluminum oxide nanostructures. The
essential deposition parameters for the growth of nanostructures are also discussed here. We have
started our work with the selection of suitable substrate. Substrate is often ignored or only
slightly referred although the substrate accompanies thin film from start till end. Ideally a
substrate must provide only the mechanical support and should not interact with the film except
for sufficient adhesion but unfortunately the ideal substrates dont exist. It exerts considerable
influence on the thin film characteristics. [1]

3.3.1 Substrate selection

The substrate only purpose is to give mechanical support and in electronic application it usually
serves as an insulator. For long term stability of thin film substrate it should not make any
chemical reaction with thin film which could change the properties of thin film. Thus it should
fulfill certain requirements: [2]

Mechanical strength

Sufficient adhesion of film to the substrate

High dielectric strength

Flat and smooth surface of the substrate

Commonly used substrates are as follows:

39

Glass slides

Polycrystalline ceramics

Single crystal substrates

Metal substrates

In our experiment we used copper substrate due to its several advantages over other electrodes.
Some important features of copper substrate are listed below:

It is easily available material.

Copper is strong and easy to shape material.

It shows good conducting properties without showing much loss of energy.

Due to its compatibility with transistorized and pulse type power supply, it is
considered to be suitable for metallic electrode material.

3.3.2 Substrate Cleaning

A completely cleaned substrate is a prerequisite for the preparation of nanostructures. Cleaning
techniques depend upon the nature of substrate, the type of contaminations, and the degree of
cleanliness required. Residues from manufacturing and packaging, finger prints, oil and grease
and dust particles are example of frequently encountered contaminants [1]. The substrate should
be cleaned thoroughly before mounting onto the chamber [3]. We will do chemical cleaning by
using appropriate solvents like acetone and isopropyl alcohol along with detergent. Ultrasonic
agitation is also applied during chemical cleaning.

3.3.3 Substrate etching

40

First of all copper substrate are etched by acidic solution HCl. The reason of etching with acid is
to remove the roughness of the surface at nano scale. 10% conc. HCl is often used for the etching
of copper substrate. We put copper substrate in HCL for 30 minutes and then washed out the
substrate with the D ionized water.
3.3.4 Chemical Cleaning of substrate
After etching, the substrates are cleaned by using the following chemicals:

Acetone (CH3)2CO
Isopropyl alcohol (IPA)

Cleaning was done by giving ultrasonic bath. Kerreys ultrasonic vibrator was used for this
purpose. Copper substrate was dipped in acetone and gives the ultrasonic bath for 20 min. After
this the substrate was dipped in IPA and giving the ultrasonic bath for 10 min. IPA increases the
adhesion property of substrate.

3.4 Sample preparation

We have prepared nanostructures of Fe.Al2O4 through the simple electrodeposition method. The
method is very simple and inexpensive. In this process a thin metallic layer is deposited by the
passage of electric current. The nanostructures of iron aluminum oxide were deposited as a
function of time and voltage. We have used copper substrate due to its unique qualities. A
conventional electrolytic cell was used in our experiment. Copper substrate was employed as
cathode. The deposition was done for series of time i.e. 5 min, 10 min, 15 min, 20 min, 25 min
and 30 min. the voltage is kept constant at 2v. We had prepare six series. In our experiment the
electrolyte constituents and their precise molarities are:

0.1M Al(NO3)3.9H2O
41

0.1M Fe(NO3)3.9H2O

2.0126g Boric acid

All these constituents were mixed in DI water to make the solution. The morality of above
mentioned constituents are adjusted by the following formula.

In the process of Electrodeposition, the metal ions from aqueous, organic or fused salt
electrolytes are reduced. We can represent this process in equation form as:
M+n

ne- ----------------------- M

The deposition is fulfill by the following two paths:

An external power supply to provide electrons for electrodeposition.

Autocatalytic deposition process that is also known as electro less plating in which
electrons are provided by the reducing agent present in the solution.

The electrodeposition comprises of following steps:

Metal solution interface as the locus of the deposition process.

Nucleation and growth process of the metallic lattice.

Structure and properties of the deposits.

The fig 3.1 shows the setup for electrodeposition process. After forming the series of six
samples, these samples were annealed at 300C for 1hr.

42

Figure 3.1: setup of Electrodeposition [14]

3.4.1 Annealing
Annealing is a heat treatment which is used for changing the properties of the material such as
strength and hardness. Annealing is used for the removal of the stresses, refines the structure by
making it homogeneous, improve the cold working properties, soften the material and induce
ductility. It is the process which produces the conditions by heating to above the re crystallization
temperature, maintain the suitable temperature and then cooling. Diffusion of atoms is occurring
during annealing within the material so the material progress towards its equilibrium state. Heat
is required to increase the rate of diffusion by giving the energy needed to break the bond.
The removal of stress is thermodynamically spontaneous process. At room temperature it is a
very slow process, but at high temperature at which annealing occurs serves to accelerate the
process.
3.4.1.1 Stages of annealing process
There are two stages of annealing process:

43

1. Recovery of phase which is causes of shifting the material by the removal of internal stress
and defects.
2. Re-crystalline the phase of material where new strain free grains nucleates and grows to
replace the internal stresses.
3.4.1.2 Principle of annealing
For the annealing process, a large oven is used. There is enough large space in the oven so that
the maximum area of our work pieces is exposed to the heated air. We have annealed our samples
for 1hr at 300C. Once the annealing is done, the samples are remaining placed in the oven so
that the oven cools down at normal room temperature. The samples are removed from the oven
after the temperature of oven is resumed to the room temperature.

3.5 Characterization Techniques

The synthesized Iron aluminum oxide was characterized with the following dissimilar
characterization techniques in order to explore its different properties i-e;

X-ray Diffraction (XRD)

Scanning Electron Microscopy (SEM)

Vibrating sample magnetometer (VSM)

3.5.1 X-Ray Diffraction

In 1895, Wilhelm Conrad Roentgen investigated some radiation and give them the name of Xrays. Initially these rays were unknown naturally but later on, due to further investigations, it was
found that these are actually electromagnetic radiations with wavelength range 0.01-10 . on the
basis of wavelength these rays are classified into two types, name as soft x-rays and hard x-rays.
The x-rays with wavelength less than 1 are term as hard x-rays and those having wavelength
longer than 1 are known as soft x-rays. [8]
1n 1912, it was concluded by three scientist M. Laue, Knipping and Friedrich that atomic crystal
and x-ray beam interaction possibly results into different diffraction patterns. In 1916, x-ray
diffraction phenomenon was firstly used to analyze the polycrystalline structure of different
samples. [9]
44

3.5.1.1 Diffraction
To understand the word diffraction one should be familiar of three phenomenon that are

Scattering

Interference

Diffraction

In scattering, the incident radiations fall on some material and then reemitted into various
directions. In interference, superposition occurs among different waves of same frequency and
consequently producing a single overlapping wave. The result of constructive interference
among various scattered waves from some object is termed as diffraction. [10]
3.5.1.2 Braggs Law and X-Ray Diffraction
X-ray diffraction is the characterization tool which is used to analyze various characteristics of a
material, such as identification of different material, crystal defects, lattice constants, preferred
orientation, stresses and geometry of the given structure. In x-ray diffraction, x-ray beam is the
collimated beam having wavelength range from 0.7 to 2 , and the crystalline phases are
responsible factors for its diffraction which is stated by Braggs law:

(1)

In the above equation, d represents the spacing in atomic planes which is the representation of dspacing. The lambda represents the wavelength of incoming x-ray and its value is 1.54 .
whereas n represents any integers with different values such as n = 0,1,2 .

45

Figure 3.2 Schematic diagram of Braggs Law [4]

The intensities related to the diffracted x-rays are investigated in sense of diffraction angle 2.
Braggs relation has two significant variable factors that are theta () and lambda (). By
changing any of these two variables, the conditions of Braggs law can be achieved [5]. A
schematic diagram of x-ray diffractometer is shown in the fig 3.3. It consists of a sample holder,
Detector and x-ray source. In this procedure x-ray source does not change it position but the
other two components change along their axis.
When sample is bombarded with x-rays then the sample as well as detector is in continuous
motion along their axis. It can be analyzed that the motion of -axis is grater in magnitude two
times the motion of -axis. This is reason we chose angle 2 in place of , in the case of
diffraction patterns. The detector collects the data from the diffracted x-rays and gives us the
information.
It is a nondestructive characterization technique. Various positions of peaks are analyzed with
XRD technique, due to which characterization of homogeneous and inhomogeneous strain
becomes easy. The size of the crystal D is calculated by using the Scherers formula [10]. The
Scherers formula is written as:

46

Figure 3.3 Schematic diagram of X-Ray Diffractrometer [4].

3.5.1.3 X-RAY Diffraction System
The X-ray diffractrometer system is an instrument for crystallographic study of resources. In this
method x-rays of known wavelength are worn [6].
It has three major parts;
1. X-Ray Generator
2. Goniometer
3. Counting and Recording Equipment.
3.5.1.4 Advantages of XRD

It provides information about the orientation of texture.

It gives quick response to find the unknown material.

Minimum sample preparation is required in this approach.

It is nondestructive technique.

3.5.1.5 Uses
47

It is used for the recognition of single phase resources, multiple phases in microcrystalline
mixtures and amorphous resources. It is also used to decide the phase work of art of a sample,
unit cell lattice parameters and bravais lattice symmetry, residual damage, crystal arrangement
and crystallite size and micro strain.

3.6. Scanning electron microscope

The SEM is technique to study the surfaces morphology of the material. We create image in the
same way as in TV by scanning with an electron beam that generated and focused the samples by
the operation of the microscope. The SEM has high depth of focus as compare with optical
microscope. So SEM can generate image having good representation of 3D sample. The
applications of SEM imaging encompass microstructural studies, microscopic feature
measurement, fracture and defect studies, thin coating evaluations and surface contamination
assessment etc.
3.6.1. Principle of SEM
In SEM, we use electrons instead of light to produce image. When heating the metallic filament,
beam of electrons is produced at the top. This electron beam follows vertical path through the
column of microscope. Then electron beam passes through electromagnetic lenses which focus
and down the beam direct towards the sample. Other electrons are ejected from the sample when
beam hits the sample. After collecting the secondary or backscattered electrons from the detector,
it changes them to a signal that is sent to a viewing screen as compare with our conventional
television, thus producing an image.
3.6.2. Working of SEM
At the top there are Virtual Source presents the electron gun which producing a stream of
monochromatic electrons. The stream of electrons is condensed by 1stcondenser lens. The main
purpose of condenser lens is to focus the beam. Condenser lens works with the condenser
aperture to eliminate the high-angle electrons from the beam. The second condenser lens forms
the thin and coherent beam electrons and controlled by the fine look into current knob. Highangle electrons eliminated by user selectable aperture from the beam. A set of coils then scan
48

or sweep the beam in a grid fashion, period of time is determined by the scan speed. The final
lens focused scanning beam onto the part of the specimen which is desired. When the beam
strike with sample, and is detected by different Instruments. Before the moving of beam, these
instruments count number of interactions and display pixel on a CRT whose strength is resolute.
Repeated this process until the grid scan is finished. The schematic diagram of SEM is shown in
fig3.4.

Figure 3.4 Schematic Diagram of Scanning Electron Microscope [11].

3.6.3. Electron beam/specimen interaction

While all these signals are in attendance in the SEM, not all of them are detected and used for
information. The suggestions that are mostly used are the Secondary Electrons, the Backscattered
Electrons and X-rays. Electron/Specimen Interaction is shown in Fig. 3.5.

49

Figure 3.5 Electron beam/specimen interactions [12]

50

3.6.4 Backscattered electrons (BSE)

When electron beam interact with sample atom by elastic collision, it generated a very high
energy electrons known as backscattered electrons because they travel in straight line and moves
very fast as shown in fig3.6. BSE is directly proportional to the atomic number of the sample
electron. A detector is located in their path in order to form an image with BSE. After hitting the
detector, a signal is shaped which is used to form the TV image. BSE also provides topographical
information.

Figure 3.6 Different sized nuclei of elements are shown [13]

3.6.5. Secondary electrons and detection

Sometimes beam of electrons interact with the electrons present in the atom and sometimes it
interact with nucleus. The secondary electrons are shown in fig3.7. The beam electron does not
attract sample electrons. The movement of beam electron is slow due to this interaction as it
repels the specimen electrons. The repulsion is so high which cause emission of specimen
electrons from the atom, these are called secondary electrons. When secondary electrons leave
the sample, they moved very slowly as compare with BSE.

51

Figure 3.7 Secondary Electrons [13].

Due to their slow movement they gets negative charge so they can attract by positively charged
detector. This attraction force attracts electrons from large area and especially from corners. The
ability of electrons attraction from around corners gives secondary electron image a 3dimensional look.
3.6.6. HITACHI S-3400 N SEM
In Centre of Excellence in Solid State Physics University of the Punjab, we have a very good
resolution Scanning Electron Microscope whose model is HITACHI S-3400 N SEM of SEM as
shown in fig3.8. It has voltage of 0.3 to 30V and has pressure of 6-270pa. It is user friendly. It
gives high scanning electrons and backscattered electron resolution. Backscattered electron
image has resolution of 4nm and secondary electron image has resolution of 3nm.

52

Figure 3.8 HITACHI S-3400 N SEM

3.7. Vibrating sample magnetometer

3.7.1 Working principle of VSM
A vibrating sample magnetometer VSM is used to measure the magnetic behavior of magnetic
materials. A (VSM) works on Faraday's Law of Induction, which states that a changing
magnetic field will produce an electric field. This electric field can be measured and through
this electric field we can get information about the changing magnetic field.

53

Figure 3.9 Working of VSM

The easiest method for manufacturing magnetization based on the change of flux through a coil
is the extraction magnetometer in which a sample placed at a center of a coil in the field is
quickly removed to a point far from coil.
The AC version of the extraction magnetometer is the Vibrating sample magnetometer VSM
also known as Foner balance after its inventor. Here sample is mounted on a vertical rod in
center of a set of coils and vibrated vertically. The coil arrangement based on whether the field
applied is vertical, as with superconducting solenoid, or horizontal as with an electromagnet. In
either case the coils are oppositely wound so that the emf induced in them may add by the
vibrating sample. Two pair of coils is used in a Quadra pole configuration for the horizontally
applied field to create a saddle point around which the sensitivity is independent of position of
sample.
The vibration frequency is typically in range 10-100 Hz and vibration amplitude which is of a
few tenths of mm can be controlled by a feedback loop. Sensitivity of a well-designed VSM is
better than 10-8 Am2 [7].
When the sample is mounted into the sample holder it is vibrated mechanically in presence of
magnetic field as shown in fig3.9. The vibration in magnetized sample causes changes in the flux
which in return produce electric field as suggested above due to Faraday Law of induction. This
54

induced electric field, sensed by the pickup coils, is proportional to the samples magnetic
moment.
3.7.2 LAKE SHORE 7400 VSM
The VSM used in Centre of Excellence for Solid State Physics is Lake Shore 7400 VSM shown
in fig3.10. It is the most sensitive VSM available today having sensitivity 0.5emu.The VSM is
calibrated using a sample of nickel with known magnetization before use. The nickel sample is
of very small size (500m2) and image charges on larger films are therefore, not effectively
calibrated. The film sample size tested in VSM is usually 510mm, image charges do influence
such data. Additionally, samples placed with long axis of the film transverse to the field direction
are not entirely within the strongest field and magnetization may not fully measure. This problem
was reduced by placing samples with their long axes in line with the magnetic field direction.
Samples were not cut or patterned to a smaller size, in order to allow their processing in to
devices. Powders, solids, liquids, single crystals, and nanostructures are accommodated in the
lake shore VSM.

Figure 3.10 Lake Shores 7407 VSM

55

3.8. Refrences
1.

L. I. Maissel, Hand book of thin film technology,McGraw-Hill, New York, 1970

2.

L.Eckertova. Physics of thin films 2nd edition, Plenum Press, 1986

3. L. Holland, Thin film microelectronics, Chapman and Hall Ltd. London, 1965.
4. Y. Waseda, E. Matsubara, K. Shinoda, X-Ray diffraction crystallography. Springer,
New York, 2011
5.

B.D.Cullity, Elements of X-Ray Diffraction, 2nd edition, Addison-Wesley publishing

company, 1978

6.

B.D.Cullity and S.R.Stock, Elements of X-Ray Diffraction, 3rd Edition, London, 2001

7.

B.D.Culity, Elements of XRD, 1st addition, Philippines: Addison-Wesley Publishing

company.Inc, 1978.

8. F. Yang, J. Hamilton, Modern Atomic and Nuclear Physics, World scientific publishing
Co. USA, 2010.
9. Rene, Guinebretiere, X-Ray diffraction by polycrystalline Materials, ISTE. Ltd, UK,
2007
10. C.Suryanarayana, M. Grant Norton, X-Ray Diffraction a Practical Approach, Plenum
Press, New York, 1998.
11. http://www.chm.bris.ac.uk/pt/diamond/jamespthesis/chapter2.htm
12. http://www.purdue.edu/ehps/rem/rs/sem.htm
13. http://www.mcswiggen.com/FAQs/FAQ_EF-2.htm.
14. I Mansoor, Y Liu, U O Hfeli and B. Stoeber. Arrays of hollow out-of-plane
microneedles made by metal electrodeposition onto solvent cast conductive polymer
structures. Journal of Micromechanics and Micro engineering.

56

CHAPTER NO. 4
RESULTS AND DISSCSIONS

57

4.1 Introduction
The literature of this chapter provides the brief explanation regarding the results, discussions and
comprehensive conclusion about the material. Nanostructures of iron aluminum oxide were
deposited on the copper substrate using the low cost electrodeposition process. Six different
samples had been prepared regarding to the oxidation time. Deposition was done on the copper
substatre for 5 min, 10 min, 15 min, 20 min, 25 min and 30 mins. Latter on all the six samples
were annealed at 300C for 1 hr. The structural analysis and magnetic properties were
investigated by using the X-ray diffraction and Vibrating sample magnetometer. The surface
morphology of the nanostructures was studied by using Scanning electron microscopy. The main
objective of this research work is to synthesis iron aluminum oxide nanostructures with the help
of simple electrodeposition process. Theses nanostructures are getting a huge deal of
contemplation due to wide exclusive characteristics and novel applications.

4.2 X-ray Diffraction Analysis for Iron Aluminum Oxide

The X-ray diffraction pattern of Iron aluminum oxide material were obtained by using X-ray
diffractometer and different structural properties of this material such as crystalline size, strain
etc. are extracted from these

XRD patterns. For this characterization technique, the

diffractometer used in Centre of Excellence in Solid State Physics is Bruker D8 Advance which
is equipped with the Cu K ( = 1.5405 ) radiations.

4.3 Scherers Formula for Crystalline Size Determination

The crystalline size of all samples was determined from the intense peak in the XRD pattern of
the samples by using simple Scherers formula that is given below:

Where
T is the crystalline size.

58

K is the Scherer constant and its value is 0.94

B is Full Width at half maximum (FWHM) of peaks.
is the Braggs angle.
is Cu K radiation with wavelength 1.5405 which is used to get the XRD graphs of the
sample.
Figure 4.1 shows the XRD pattern for iron aluminum oxide thin film that is prepared by the
conventional electrodeposition process. The pattern shows the diffraction peaks corresponding to
(311), (400),(331),(511) and (620) planes. These planes are located at angle 2theta = 36.8, 43.2,
50.1, 61.5, 74.05 respectively. No peak correspondence to aluminum oxide or iron oxide was
observes which indicates the successful compound formation of iron aluminum oxide.

59

Figure 4.1: XRD patterns for Iron aluminum oxide with variation in deposition time.

60

Table

Lattice
consta
nt
()

Unit
cell
volume
()3

X-ray
density
(g cm-3)

8.199

551.1663

15

8.20

551.1368

Depositio

Lattice

n time

(a), unit
volume

Crystal
line
size
(nm)

Disloca
tion
density
(1x1015
m-2)

5.121

15.7

4.06

5.119

24.7

1.64

(min)

4.1:
constant
cell
(Vcell),

30
8.21
553.3877
5.101
29
1.19
crystalline size (D), X-ray density (dx), and dislocation density () of as-deposited
nanostructures with varying the deposition time.

Crystalline size increases with the increase in deposition time from 5 min to 30 min. The increase
in crystalline size with deposition time shows the increases crystalinity of iron aluminum oxide
thin film. Crystalline size depends on two factors that are

Neighboring grain

Strain

Variation in lattice parameters

Lattice parameters a for all electrodeposited nanostructures of cubic iron aluminum oxide are
calculated using Braggs equation (Eq. 4.1).
a=d hkl h 2+ k 2 +l 2 (4.1)

The trend of lattice parameter variations with deposition time is shown in Figure 4.7. With the
increase in deposition time lattice parameter increases.

61

Figure 4.2: variation in lattice parameters with deposition time

Variation in Dislocation density

The dislocation density indicates the amount of defects in a crystal. It is defined as the length of
dislocation lines per unit volume of the crystal. It is calculated by using the equation 4.2.
=

1
2
D

(4.2)

Where, D is crystallite size. Higher value of dislocation density indicates lower crystallinity
levels of the nanostructures [1]. The dislocation density of all deposited nanoparticles with
varying deposition time is listed in Table 4.1. The effect of deposition time on the dislocation
density is shown in Figure 4.3. The presence of dislocations or defects during the deposition
process may be due to micro-strain present in the film [2].

62

.
Figure 4.3: variation in dislocation density with deposition time
Variation in crystalline size
The average crystallite size (D) were determined using Debye Scherrers formula (Eq. 4.3).
D=

0.9
cos

(4.3)

Where D is the average crystallite size of the phase under investigation, is the wavelength of
Cu K used in X-ray diffraction, the Full width at half maxima (FWHM), contribution to the
diffraction peak width due to small size of crystallites and must be taken in radians and is the
Braggs angle of diffraction [3].
The average crystallite sizes (D) of all the electrodeposited nanoparticles with varying the
deposition time are listed in Table 4.1. The trend of crystallite size of as-deposited nanoparticles

63

with the variation in deposition time is shown in Figure 4.4. The crystalline size increases with
the increase in deposition time.

Figure 4.4: variation of crystalline size with deposition time.

Variation in X-ray density
The X-ray density of nanostructures was estimated using Eq. 4.4.
=

1.66042 A
(4.4)
V

Where V is unit cell volume and A is atomic weigth of number of atoms or ions in a unit cell [8].
X-ray density of all the deposited nanostructures is shown in Table 4.1. The variation in x-ray
density with deposition time is shown in Figure 4.5. The trend of x-ray density decreses with the
increase in deposition time.

64

Figure 4.5: variation in x-ray density with deposition time.

4.4

Magnetic

analysis

of

as-deposited

iron

aluminum

oxide

Nanostructures
Figure 4.6 shows the room temperature M-H curve for as-deposited iron aluminum oxide
nanostructures. The presence of open hysteresis loop at low field strength indicates
ferromagnetic behavior but at high fields paramagnetic domains indicating that the particles
require further heat treatment.

65

(a)

(b)

66

(c)

(d)

67

(e)

(f)
Figure 4.6: M-H curve for As-deposited iron aluminum oxide nanostructures with deposition
time as (a) 5 min (b) 10 min (c) 15 min (d) 20 min (e) 25 min (f) 30 min

68

4.5 Magnetic analysis of 300C annealed iron aluminum oxide

nanostructures
Figure 4.7 shows the M-H curve for electrodeposited nanostructures after annealing at 300C in
the presence of magnetic field.

(a)

(b)
69

(c)

(d)

70

(e)

(f)
Figure 4.7: M-H curves for Iron aluminum oxide nanostructures annealed at 300 C with
deposition time as (a) 5 min (b) 10 min (c) 15 min (d) 20 min (e) 25 min (f) 30 min
71

4.6 Effect of deposition time and annealing on magnetic properties

Figure 4.8 shows the coercivity of iron aluminum oxide nanostructures as a function of
deposition time. This figure shows how the trend of coercivity changes with the change in
deposition time. The figure shows that coercivity increases at 5 and 10 min deposition and then
decreases for 15 and 20 min depositions. We see a further increase for 25 min deposition.

Figure 4.8: variation in coercivity with deposition time.

Figure 4.9 and 4.10 shows the variations in the magnetization and retentivity of iron aluminum
oxide nanostructures.

72

Figure 4.9: Magnetization of annealed iron aluminum oxide nanostructures

Figure 4.10: Retentivity of annealed iron aluminum oxide nanostructures

73

4.7 SEM results of Electrodeposited samples:

Fig 4.11 shows the SEM results for iron aluminum oxide nanostructures with 5 min, 10 min, 15
min, 20 min, 25 min and 30 min deposition time.

(a)

74

(b)

(c)
75

(d)

(e)
76

(f)
Figure 4.11: SEM images of Iron aluminum oxide Nanostructures with deposition time (a) 5 min,
(b) 10 min, (c) 15 min, (d) 20 min, (e) 25 min and 30 min.

As we can see from the figure 5 min deposition shows grain size of 100-120 nm, 10 min
deposition shows 200 nm, 15 min deposition time shows 50 nm, 20 min deposition shows 140180 nm, 25 min deposition shows grain size of 160-185 nm and 30 min deposition showed grain
size of 80-100 nm.

77

4.8 Conclusions

78

4.9 References
1. K. Usharani, A. R. Balu, G. Shanmugaval, M. Suganya and V. S. Nagarethinam,
International Journal of Scientific Research and Reviews, 2, 53-68, (2013).
2. J. M. Iwata, R. V. Chopdekar, F. Wrong, E. Areholz and Y. Suzuki, Applied Physics
Letters, 105, 905-911, (2009).
3. B. D. Cullity, Elements of X-ray Diffraction, Addison-Wesley Publishing Company,
USA, (1978).

79