2

CHAPTER 1

NANOSTRUCTURED MATERIAL-A
BRIEF INTRODUCTION

1.1. Nanotechnology and Nanomaterials : An introduction

The roots of Nanotechnology and Nanomaterials can be traced to a lecture delivered by Richard
Feymann(Nobel Laureate) in 1959 in a meeting of American physical society, when he speculated
this future scientists and engineers would build structures from atoms and molecules(1). He gave
a talk, "There's Plenty of Room at the Bottom," at an American Physical Society meeting at
caltech. Nanotechnology shortened to "nanotech", is the study of manipulating matter on an
atomic and molecular scale. Generally, nanotechnology deals with structures sized between 1 to
100 nanometre in at least one dimension, and involves developing materials or devices
possessing at least one dimension within that size. Quantum mechanical e/ects are very
important at this scale, which is in the quantum realm.The Greek word “nano” refers to a
dimension ,one thousand times smaller than a micron.
 3

Richard Feymann

Although nanotechnology is a relatively recent development in scienti3c research, the

development of its central concepts happened over a longer period of time. The emergence of
nanotechnology in the 1980s was caused by the convergence of experimental advances such as
the invention of the scanning tunneling microscope in 1981 and the discovery of fullerenes in
1985, with the elucidation and popularization of a conceptual. framework for the goals of
nanotechnology beginning with the 1986 publication of the book Engines of Creation.
The scanning tunneling microscope, an instrument for imaging surfaces at the atomic level, was
developed in 1981 by Gerd Binnig and Heinrich Rohrer at IBM Zurich Research Laboratory, for
which they received the Nobel Prize in Physics in 1986. Fullerenes were discovered in 1985 by
Harry Kroto, Richard Smalley, and Robert Curl, who together won the 1996 Nobel Prize in
Chemistry.
Around the same time, K. Eric Drexler developed and popularized the concept of nanotechnology
and founded the 3eld of molecular nanotechnology. In 1979, Drexler encountered Richard
Feynman's 1959 talk "There's Plenty of Room at the Bottom". The term "nanotechnology",
 4
originally coined by Norio Taniguchiin 1974, was unknowingly appropriated by Drexler in his 1986
book Engines of Creation:

One of the problems facing nanotechnology is the confusion about its

de3nition. Most de3nitions revolve around the study and control of phenomena and materials at
length scales below 100nm and quite often they make a comparison with a human hair, which is
about 80000nm wide. There has been much debate on the future implications of
nanotechnology. Nanotechnology has the potential to create many new materials and devices
with a vast range of applications, such as in medicine,electronics and energy production.

Nanomaterials is a 3eld that takes a materials science-based approach to nanotechnology. It

studies materials with morphological features on the nanoscale, and especially those that have
special properties stemming from their nanoscale dimensions. Nanoscale is usually de3ned as
smaller than a one tenth of a micrometer in at least one dimension, [2 ] though this term is
sometimes also used for materials smaller than one micrometer.

Nanomaterials (nanocrystalline materials ) are materials possessing grain sizes of the order of
a billionth of ammeter.A nanocrystalline material has grains of the order of 1-100 nm.The average
size of an atom is of the order of 1 to 2 Angstroms in radius. 1 nanometer comprises 10
Angstroms; hence in one nm there may be 3 to 5 atoms,depending on their radii. Nanocrystalline
materials are exceptionally strong,hard, and ductile at high temperatures,wear
resistant,corrosion resistant, erosion resistant & chemically very active.

1.2. Classification of nanomaterials.

1.2.1. On the basis of dimension

Nanostructured materials are Classified into four different categories
depending on their physical dimensions. They are:
 5
a. Nanomaterials in zero dimension(clusters)
This is the recent type of the nanostructured materials. The zero dimensional clusters
are being investigated to tailor optical properties. Solgel process has been commonly used to
generated clusters. The typical method of synthesis of the recent zero dimensional
nanostructured materials are the solgel process. They are also called quantum dots.

b. Nanomaterials in one dimension:

One dimensional nano structure has been called by a variety of names including
whiskers,3bres or 3brids,nanowires or nanorods. One dimensional nanostructured materials
there will be a layered structure or a lamellar structure. Vapour deposition, sputtering techniques
and electro deposition techniques have been used to synthesize the one dimensional layered
nanostructured materials. The magnitude of length & width are much greater than the thickness
of the layered nanocrystals. Monolayer’s(layers that are one atom or molecule) are also routinely
mace & used in chemistry.

c. Nanomaterials in two dimension:

In this nanostructured materials synthesized are 3lamentary in nature. The length
substancially larger than the width or dimeter in 3lamentary nanocrystals. Two dimensional
nanomaterials includes tubes & wires.Because of 3lamentary nature,this type of nanostructured
materials is referred to as two dimensional.The typical method of synthesis of two dimensional
nanostructured material is chemical vapour deposition.(CVD)

Nanowires

Nanowires are ultra3ne wires or linear arrays of dots,formed by self assembly.They can be
made from a wide range of materials.Semiconductor Nanowires made of silicon,gallium nitride &
indium phosphide have demonstrated remarkable optical,electronic & magnetic characteristics.
 6
d. Nanomaterials in three dimension
The nanostructured materials are basically in equiaxed in and are hence called as
nanocrystallites or three dimensional nanostructured.The methods commonlyemployed to
synthesis nanocrystalline phase in a variety of materials are gas condensation,mechanical alloying
& chemical precipitation and spray conversion prosessing technjques.

1) Nanoparticles.

Nanoparticles are sized between 1&100nms. Nanoprticles may or may not exhibit
size related properties that di/er signi3cantly from those observed in 3ne particles or bulk
materials.
Nanoclusters have atleast one dimension between 1&10nms and anarrow size
distribution.Nanopowders are agglomerates of ultra3ne Particles, nanoparticles or
nanoclusters.Nanometer sized single crystals,or single domain ultra3ne particles are often
referred to as nanocrystals . Nanoparticles research is currently an area of intense scienti3c
interest due to a wide variety of potential applications in biomedical,optical & electronic 3elds.

2) Fullerene
A fullerene is any molecule composed entirely of carbon, in the form of ahollow
sphere ,ellipsed,or tube.Spherical fullerenes are also called Carbon nanotubes or buckytubes.
Fullerenes are similar in structure to graphite,which is composed of stacked graphine sheets of
linked hexagonal rings .
 7

Fig.1.1 Fullerene

3) Den drimers
Den drimers are spherical polymeric molecules,formed through a nanoscale
,hierarchial self assembly process.There are many types of den drimers ; the smallest is several
nanometers in size. Den drimers are used inconventional applications such as coatings & links.

4) Quantum dots.
Nanoparticles of semiconductors(quantum dots) were theorized in the 1970s and
initially created in early 1980s.If semiconductors particles are made small enough, quantum
e/ects come into play ,which limit the energies at which electrons & holes can exist in the
particles.
Fig 1.2

Fig1.2. represents the schematic representation of the four di/erent types of nanostructured
materials.

1.2.2 Phase composition

According to phase composition nanostructured materials are classi3ed into 3
groups.They are

Single phase solids Crystalline ,amorphous particles &

 8
Layers etc.
Multi phase solids Matrix composites,coated particles
etc.
Multi phase systems Colloids,aerogels,ferro Kuids etc

Table 1.2.2.Classi3cation based on phase composition.

1.2.3 Manufacturing process

Gas phase reaction Flame

synthesis,condensation,CVD etc
Liquid phase reaction Solgel,precipitation,hydrothermal processing etc.
Mechanical procedures Ball milling,plasyic deformation etc
Table 1.2.3.Classi3cation based on manufacturing process.

1.3. Properties of Nanostructured Materials

Owing to the very 3ne grain size, nanostructured materials exhibit a variety of properties
that are di/erent and often considerably improved in comparison with those of conventional
coarser grained polycrystalline materials. If the size of the atomic ensemble becomes comparable
to or smaller than the typical length scale of a physical phenomenon, then the spatial
con3nement can a/ect any property. Some of the properties of nanostructured materials are
given below.

(a). Mechanical Properties

Elastic constants of nanocrytstalline materials have been reduced considerably compared
to those of bulk materials. This is due to the comparatively higher inter-atomic spacing in the
 9
boundary regions. The strength of nanocrystalline material increases considerably than that of
coarse-grained material. Hardness also increases with decreasing grain size in conventional
coarser grained materials. This relationship is called HallPetch relationship5. For nanocrystalline
materials hardness decreases with decrease in grain size. It is referred to as inverse Hall-Petch
e/ect. In some grains, direct relationship between Young’s modulus and hardness has been
established. Reducing the grain size can lower the ductile/brittle transition temperature. The
fracture stress of nanocrystalline material is lower than that of conventional coarse-grained
material. Grain size and shape, their distribution, pores and their distribution, surface condition,
all a/ect the mechanical behaviour of nanocrystalline materials.

(b).Thermal Properties
The thermal expansion coeNcient of nanocrystalline material is greatly enhanced due to
the presence of large amount of grain boundaries. The speci3c heat of a material is closely
related to the vibrational and con3gurational entropy of the material, which is directly related to
the nearest neighbour con3guration. The speci3c heat in nanocrystalline material is much higher
than that in the coarser grained material. The increase in speci3c heat in nanocrystalline material
is art attributed to the complicated structure of grain and phase boundaries. The enthalpy and
entropy of nanocrystalline material is very high.

(c). Electrical Properties

The electrical resistivity of nanocrystalline metal is higher than in both coarse-grained
polycrystalline metal and alloys. The residual resistivity of nanocrystalline metals of 0 0K decreases
with an increase in grain size. If the crystal size is smaller than the electron mean free path, grain
boundary scattering dominates and hence electrical resistivity as well as the temperature
coeNcient is increased. It has been shown that the AC conducting of nanocrystalline TiO 2 doped
with about 1% Pt is reversible with temperature. The magnitude of electrical resistivity and
hence the conductivity in composites can be changed by altering the size of the electrically
conducting component.

(d). Magnetic Properties.

 10
Magnetic Properties of nanocrystalline materials depend on the grain size. It was noted
that with increasing grain size d, the coercivity H c increases following d6 power law up to 50nm,
runs through maximum of the Hc 30A/cm and then decreases for grain sizes of about 50nm
decoding to the well known 1/d law for polycrystalline magnets. Nanostructured materials show
a reduction in the saturation magnetization and ferromagnetic transition temperature, due to the
deviations of inter-atomic spacing in the interfacial region.5
Nanocrystalline iron based alloys are used for soft magnetic applications due to their
speci3c characters like low coercivity, high permeability, zero magnetostriction, low core losses
due to high electrical receptivity and good thermal stability. Magnetic calori3c e/ect is another
important magnetic property of nanocomposites5. The magnetic property of nanosized particle
depends on the large surface to volume ratio. Unlike bulk materials consisting of multiple
magnetic domains, several small ferromagnetic particles can form single magnetic domains,
giving rise to supramagnetism. This behaviour opens the possibly for application in information
storage.

(e). Optical Properties

When the diameter of the nanostructured material is decreased, discrete electronic
energy states are formed. The exciton Bohr radius play the central role in the optical properties
of semiconductor nanostructures, when the size of nanostructure component approaches the
Bohr radius electronic and optical absorption changes and the integrated absorption can increase.
If the crystallite size of a nanocrystalline material becomes comparable or smaller than de-Broglie
wavelength of the charge carriers generated by the absorbed light, the con3nement increases
energy required for absorption. This energy increase shifts the absorption/luminescence spectra
towards shorter wavelength (blue). The blue shift is a quantum size e/ect. Example: Blue shift is
observed in the luminescence spectra of nanocrystalline ZnO as a function of crystal size.
Controlling particle size can change optical properties of nanostructure samples. By
controlling the cluster size of CdSe, Steigerwald and Burs (1989) were able to synthesize clusters
of very narrow size distributions and show that they indicate varying degrees of quantum
con3nement and di/erent band gaps. Clusters of 1.2-1.5nm diameter have a band gap of 3eV and
 11
those having diameter of 3.5nm have a band gap of 2.3eV while the bulk material have a band
gap of 1.8eV. Due to three dimensional con3nements, the mechanisms for resonant band edge
optical non-linearities in nano crystallites are di/erent from those in bulk materials. Optical and
infrared absorption measurements have been performed for nano crystalline Si 3lm at di/erent
temperatures. A pronounced red shift of the absorption was noticed with increasing
temperatures up to 3500C. If deposition temperature was increased to 400 0C blue shift was
observed which shows the relation between crystal size and deposition temperature

1.4 Characteristic features of nanostructured materials

In nanostructured materials, two types of atoms can be distinguished crystal atoms and
boundary atoms. Schematic representation of hard sphere model of an equiaxed nanocrystalline
metal is shown in Figure 1.3. and two types of atoms can be distinguished, of these the 3rst one
contains crystal atoms with nearest neighbor con3guration corresponding to the lattice and
boundary atoms with a variety of inter atomic spacing di/ering from boundary to boundary. A
nanocrystaline metal contains a large number of interfaces (~6*1025m-3)with random orientation
relationships and consequently a substantial fraction of atoms lie in the interfaces. Assuming that
grains have the shape of spheres or cubes the volume fraction of the nanocrystaline materials
associated with the boundary can be calculated as 3 ∆/d, where ∆ is the average grain boundary
thickness and d the average grain diameter. Thus the volume fraction of atoms in the grain
boundaries can be as much as 50% for 5nm grains and decrease to about 30% for 10nm grains
and 3% for 100nm grains.
 12

Figure 1.3

1.5 Applications of nanotechnology

With nanotechnology, a large set of materials and improved products rely on a change in
the physical properties when the feature sizes are shrunk. Nanoparticles, for example, take
advantage of their dramatically increased surface area to volume ratio. Their optical properties,
e.g. Kuorescence, become a function of the particle diameter. When brought into a bulk material,
nanoparticles can strongly inKuence the mechanical properties of the material, like sti/ness or
elasticity. For example, traditional polymers can be reinforced by nanoparticles resulting in novel
materials which can be used as lightweight replacements for metals. Therefore, an increasing
societal bene3t of such nanoparticles can be expected. Such nanotechnologically enhanced
materials will enable a weight reduction accompanied by an increase in stability and improved

functionality. There are many applicatons of nanotechnology, few of them are show here. a
Tissue engineering
Nanotechnology can help to reproduce or to repair damaged tissue. “Tissue engineering”
makes use of arti3cially stimulated cell proliferation by using suitable nanomaterial-based
sca/olds and growth factors. Tissue engineering might replace today’s conventional treatments
like organ transplants or arti3cial implants. Advanced forms of tissue engineering may lead to life
extension.

b Chemistry and environment

Chemical catalysis and 3ltration techniques are two prominent examples where
nanotechnology already plays a role. The synthesis provides novel materials with tailored features
 13
and chemical properties: for example, nanoparticles with a distinct chemical surrounding
(ligands), or speci3c optical properties. In this sense, chemistry is indeed a basic nanoscience. In a
short-term perspective, chemistry will provide novel “nanomaterials” and in the long run,
superior processes such as “self-assembly” will enable energy and time preserving strategies. In a
sense, all chemical synthesis can be understood in terms of nanotechnology, because of its ability
to manufacture certain molecules. Thus, chemistry forms a base for nanotechnology providing

tailor-made molecules, polymers, etcetera, as well as clusters and nanoparticles. c Catalysis

Chemical catalysis ben3ts especially from nanoparticles, due to the extremely large
surface to volume ratio. The application potential of nanoparticles in catalysis ranges from fuel
cell to catalytic converters and photocatalytic devices. Catalysis is also important for the
production of chemicals.

d Medicine
The biological and medical research communities have exploited the unique properties of
nanomaterials for various applications. Terms such as biomedical nanotechnology,
nanobiotechnology, and nanomedicine are used to describe this hybrid 3eld. Functionalities can
be added to nanomaterials by interfacing them with biological molecules or structures. The size
of nanomaterials is similar to that of most biological molecules and structures; therefore,
nanomaterials can be useful for both in vivo and in vitro biomedical research and applications.
Thus far, the integration of nanomaterials with biology has led to the development of diagnostic
devices, contrast agents, analytical tools, physical therapy applications, and drug delivery

vehicles. e Filtration

A strong inKuence of nanochemistry on waste-water treatment, air puri3cation and

energy storage devices is to be expected. Mechanical or chemical methods can be used for
e/ective 3ltration techniques. One class of 3ltration techniques is based on the use of membranes
with suitable hole sizes, whereby the liquid is pressed through the membrane. Nanoporous
membranes are suitable for a mechanical 3ltration with extremely small pores smaller than 10
nm (“nano3ltration”) and may be composed of nanotubes. Nano3ltration is mainly used for the
removal of ions or the separation of di/erent Kuids. On a larger scale, the membrane 3ltration
technique is named ultra3ltration, which works down to between 10 and 100 nm. One important
3eld of application for ultra3ltration is medical purposes as can be found in renal dialysis.
 14
Magnetic nanoparticles o/er an e/ective and reliable method to remove heavy metal
contaminants from waste water by making use of magnetic separation techniques. Using
nanoscale particles increases the eNciency to absorb the contaminants and is comparatively

inexpensive compared to traditional precipitation and 3ltration methods 6 f Information and

communication
Current high-technology production processes are based on traditional top down
strategies, where nanotechnology has already been introduced silently. The critical length scale of
integrated circuits is already at the nanoscale (50 nm and below) regarding the gate length of
transistors in CPUs or DRAM devices.

g Novel semiconductor devices

An example of such novel devices is based on spintronics.The dependence of the
resistance of a material (due to the spin of the electrons) on an external 3eld is called
magnetoresistance. This e/ect can be signi3cantly ampli3ed (GMR - Giant Magneto-Resistance)
for nanosized objects, for example when two ferromagnetic layers are separated by a
nonmagnetic layer, which is several nanometers thick (e.g. Co-Cu-Co). The GMR e/ect has led to a
strong increase in the data storage density of hard disks and made the gigabyte range possible.
The so called tunneling magnetoresistance (TMR) is very similar to GMR and based on the spin
dependent tunneling of electrons through adjacent ferromagnetic layers. Both GMR and TMR
e/ects can be used to create a non-volatile main memory for computers, such as the so called
magnetic random access memory or MRAM.

In 1999, the ultimate CMOS transistor developed at the Laboratory for Electronics and
Information Technology in Grenoble, France, tested the limits of the principles of the MOSFET
transistor with a diameter of 18 nm (approximately 70 atoms placed side by side). This was
almost one tenth the size of the smallest industrial transistor in 2003 (130 nm in 2003, 90 nm in
2004, 65 nm in 2005 and 45 nm in 2007). It enabled the theoretical integration of seven billion
junctions on a €1 coin. However, the CMOS transistor, which was created in 1999, was not a
simple research experiment to study how CMOS technology functions, but rather a
demonstration of how this technology functions now that we ourselves are getting ever closer to
working on a molecular scale. Today it would be impossible to master the coordinated assembly
 15
of a large number of these transistors on a circuit and it would also be impossible to create this

on an industrial level7. h Cosmetics

One 3eld of application is in sunscreens. The traditional chemical UV protection approach

su/ers from its poor long-term stability. A sunscreen based on mineral nanoparticles such as
titanium dioxide o/er several advantages. Titanium oxide nanoparticles have a comparable UV
protection property as the bulk material, but lose the cosmetically undesirable whitening as the

particle size is decreased. i Energy

The most advanced nanotechnology projects related to energy are: storage, conversion,
manufacturing improvements by reducing materials and process rates, energy saving and

enhanced renewable energy sources. j Reduction of energy consumption

A reduction of energy consumption can be reached by better insulation systems, by the
use of more eNcient lighting or combustion systems, and by use of lighter and stronger materials
in the transportation sector. Currently used light bulbs only convert approximately 5% of the
electrical energy into light. Nanotechnological approaches like light-emitting diodes (LEDs) or
quantum caged atoms (QCAs) could lead to a strong reduction of energy consumption for
illumination.

1.6Present Work
Nanomaterials have fascinated scienti3c community in recent past. Nanosized materials
are those which have particles-organic, inorganic or combinations that are of nanometer size.
These materials exhibit unusual properties compared to their bulk counterparts. The synthesis of
nanomaterials with uniform particle size is a subject of intensive research in recent times because
of their fundamental scienti3c interest as well as for technological importance.

Acid salts of metals (TMA salts) are obtained in amorphous and crystalline form. These
compounds have the general formula M(IV) (HXO4)2nH2O where, M(IV)=Ce,Zr,Th,Ti etc X=P,Mo,W
etc. The properties of the -OH group of above materials can be exchanged for several cations and
thus these materials are termed inorganic ion exchangers. A number of cation can be exchanged
with H+ due to which the material possess cation exchange properties depending on the
stoitiometry of the reagent used, temperature at which they are mixed, rate of addition, mode of
 16
mixing, PH etc. The resultant materials vary in water content, compostition and crystallinity.
Literature shows that these materials are well studied in crystalline and amorphous forms.

In the present work, nanoparticles of Cerium molybdoiodate and Cerium

molybdophosphate are synthesized by controlled chemical coprecipitation method using EDTA as
the organic templating agent. The as prepared samples are annealed at 500 0C for 2 hours. The
average crystalline size of both samples are determined from X-ray di:raction line broadening by
using Scherrer equation. The surface morphology and chemical composition of both samples are
obtained from SEM with EDAX techniques. The FTIR spectrum of both samples are recorded for
determining the di/erent stretching and bending frequencies of molecular groups in the samples.

1.7Reference

1. (H Gleiter,prog.Mater.Sci.33(1988)223.)

2.Cristina Buzea, Ivan Pacheco, and Kevin Robbie (2007). “Nanomaterials and Nanoparticles:
Sources and Toxicity”.

3.N. Taniguchi (1974). On the ‘Basic Concept of Nano-Technology’.

Proc. Intl. Conf. Prod. London, Part II British Society of Precision Engineering.

4.Kahn, Jennifer (2006). "Nanotechnology". National Geographic 2006 (June):

98–119.

5.Alivasatos A.P.Johnson K.P, Peng X, Wilson T E, Loweth C J, Schultz P G,

Nature, 382 (1996) 609.

6.Sergey P. Gubin (2009). Magnetic nanoparticles. Wiley-VCH.

 17

CHAPTER-2
CHARACTERIZATION
TECHNIQUES
2.1. Introduction

The nanomaterials can be investigated and characterized using di/erent techniques like X-
ray di/raction (XRD), UV-Visible Spectroscopy(UVVis),Infrared Spectroscopy(IR), Scanning Electron
Microscopy(SEM), Tunneling Electron Microscopy(TEM) etc. This chapter brieKy describes the
theory and instrumentation of X-ray di/raction analysis, SEM with EDAX technique and UV-visible
Spectroscopy.

2.2. X-Ray Di:raction

2.2(a).Introduction
X-ray Di/raction (XRD) is one of the most versatile and widely employed experimental
techniques for the structural characterization of crystalline materials 1-3. X-ray di/raction pattern of
the sample primarily give information about the di/erent crystalline phases present 4,5 . Therefore,
the 3rst step after synthesizing the crystalline sample is to record its X-ray di/raction pattern. X-ray
di/raction is the most convenient indirect method for the determination of average crystallite size
of nanocrystalline samples 6-

7 .

2.2(b).Theory and Instrumentation

X-ray powder di/raction has been used in two main areas, for the 3nger print
characterization of crystalline materials and for the determination of their structure. Each
crystalline solid has its unique characteristic X-ray powder pattern, which may be used as a
’3nger print’ for its identi3cation. X-ray crystallography can also be used to determine crystal
structure. The measurement of crystalline size of a polycrystalline specimens by means of X-ray is
 18
based on the broadening of di/raction lines when the crystallite size is very 3ne i.e., less than 10-
m 4,5 . The broadening of di/raction peak can be used to determine the size of the crystalline
7

sample using the Scherrer equation.

Scherrer equation is, t = 0.9*l/βhkl*Cos qhkl

Bragg’s law is given by,
2dsinθ = nλ …………………………….. (1)
For 3rst order di/raction,
2dsinθ = λ………………………………… (2)
Multiplying both sides by an integer m such that md =t, thickness of the crystal
2tsinθ =m λ…………………….......... (3)
Eqn(2), can also be interpreted as the m th order reKection from a set of planes with interplanar
distance’t’.
Differentiating both sides of (3), remembering m λ is a constant.
2tcosθ Δ θ +2sin θ Δ t =0………… (4)
Δ θ can be positive or negative. Considering magnitude only (4) leads to t=Δtsinθ/ Δ
θcosθ
Since the smallest increment in ‘t’ is d, using Δ t=d, and substituting λ/2 for dsinθ [from (2)], we
get
t= λ/2Δθcosθ……………………….. (5)
 19

1
.

Figure :2.1

Let θ1 = θ +Δ θ, be the highest possible angle that can be got before complete destructive
interference and let θ2=θ –Δ θ be lowest angle that can be got before complete destructive
interference. Now we can interpret 2Δθ as the angular width of the X-ray di/raction line.
In the X-ray di/ractometer what is recorded is the variation in intensity of the diffraction
lines with 2θ, so in the X-ray diffractogram we can see diffracted X-rays over all scattering angles
between 2θ1and2θ2. If we assume a triangular shape for the peak, the full width at half
maximum
(FWHM) will be,

β = (2θ1 - 2θ2 ) /2
= θ1-θ2
 20
= (θ +Δ θ) – (θ –Δ θ)
β = 2 Δ θ……………………………… (6)

Imax

Intensity

Imax/2. ….β….
2θ2 2θ 2θ1

Figure:2.2

Diffraction from finite thickness crystal, substituting β for 2Δθ on (5), we get t =
λ/β Cosθ…………………………….. (7)
This is essentially the Scherrer equation.
A more rigorous treatment (using a Gaussian function, rather than a triangular function) gives,

t = 0.9λ /β Cosθ………………… (8), for spherical crystal of

diameter t.
t = k*λ /βhkl *Cosθhkl

Here,t is the average crystallite size normal to the reKecting planes ,k is the shape factor, which
lies between 0.95 and 1.15 depending upon the shape of the grains in the wave length of X-ray
used and βhkl is the Full Width at Half Maximum(FWHM) of the diffraction in radians and θ hkl is the
Bragg angle corresponding to the di/raction line arising from the planes designated by the Miller
indices(hkl)7. Knowing the wave length (λ) of the X-ray and analyzing the spectrum, the
thickness’t’ of the crystalline sample can be determined. The instrument for taking X-ray
di/raction pattern is shown in Figure:2.3.
 21

Figure:2.3.Experimental set up for XRD

X-Ray di:ractometer
 22

2.3. Scanning Electron Microscope with EDAX 2.3.1. Introduction

SEM stands for scanning electron microscope. The SEM is a microscope that uses
electrons instead of light to form an image. Since their development in the early 1950's, scanning
electron microscopes have developed new areas of study in the medical and physical science
communities. The SEM has allowed researchers to examine a much bigger variety of specimens.
The scanning electron microscope has many advantages over traditional microscopes.
The SEM has a large depth of 3eld, which allows more of a specimen to be in focus at one time.
The SEM also has much higher resolution, so closely spaced specimens can be magni3ed at much
higher levels. Because the SEM uses electromagnets rather than lenses, the researcher has much
more control in the degree of magni3cation. All of these advantages, as well as the actual
strikingly clear images, make the scanning electron microscope one of the most useful
instruments in research today.

Figure:2.4

Morphological studies of the samples are done using scanning electron microscopy. SEM
is a very eNcient tool to study the surface textures of materials. Here the surface of the sample is
irradiated with a beam of accelerated electrons. Since electrons have shorter wavelengths
compared to photons, the resolution obtained in SEM is very high compared to that in
conventional optical microscopy. Furthermore, the depth of focus in SEM is much greater than
that achieved in optical microscopy. In addition to the above two factors, it has the advantage of
 23
greater magnifying power and hence SEM has become a very powerful technique to explore the
free surfaces of materials. The energy dispersive spectrum of the sample are also shown along
with the SEM image.
The SEM is an instrument that produces a largely magni3ed image by using electrons
instead of light to form an image. A beam of electrons is produced at the top of the microscope
by an electron gun. The electron beam follows a vertical path through the microscope, which is
held within a vacuum. The beam travels through electromagnetic 3elds and lenses, which focus
the beam down toward the sample. Once the beam hits the sample, electrons and X-rays are
ejected from the sample.

Figure:2.5
Detectors collect these X-rays, backscattered electrons, and secondary electrons and convert
them into a signal that is sent to a screen similar to a television screen. This produces the 3nal
image.
 24

2.3.2 .Instrumentation :

Figure:2.6

SEM opened sample chamber

The SEM micrographs of our samples are obtained with a Hitachi Model S-3000H electron
microscope. The electron beam is focused on selected areas of the samples according to the
requirements and at di/erent magni3cation. The kinetic energy acquired by electrons in an
electron column, when they are accelerated through an electric 3eld, is transferred to the sample
and its dissipation yields a variety of signals available for analysis of electron from the highest
occupied molecular orbital to the lowest available un3lled molecular orbital. In most of the cases,
several transitions occur resulting in the formation of several bands.
The most important property of a semiconductor nanostructure is its optical behavior to
crystallite size. Optical properties may be absorption, spectral response, photoluminescence,
photoluminescence excitation, electroluminescence and Raman scattering whose optical
properties respond to crystalline size. As the size is decreased, the electronic states are
discretized and results in widening of the band gap and increases the oscillator strength. The
radiative recombination life time of carrier is lowered from nanosecond to picoseconds. These
features known as quantum size e/ect (QSE) are observed in semiconductor nanocrystals.
 25

2.4. Fourier Transform Infrared Spectroscopy 2.4.1. Introduction

Spectroscopy is the study of interaction of electromagnetic radiation with matter. Infrared
Spectroscopy is one of the most powerful analytical techniques which o/er the possibility of
chemical identi3cation. One of the most important advantages of IR spectroscopy over the other
usual methods of structural analysis is that it provides useful information about the structure of
molecule quickly. This technique is based on the fact that a chemical substance shows selective
absorption in the infrared region. After absorption of IR radiation, the molecule of a chemical
substance vibrate at many rate of vibration giving rise to packed absorption band, called IR
absorption spectra. Various bands will correspond to the characteristic functional groups and
bond present in a chemical substance. Thus an IR spectrum of a chemical substance is 3ngerprint
for its identi3cation.
A molecule absorbs radiation only when the natural frequency of vibration of some part
of a molecule is the same as the frequency of the radiation. The molecules vibrate at increased
amplitude. This occurs at the expense of the energy of IR radiation which has been absorbed. In
Infra-red spectroscopy, the absorbed energy brings about predominant changes in the vibrational
energy which depend upon:
(a) Mass of the atom present in the molecule
(b) Strength of the bond
(c) The arrangement of atom within the molecule.
It has been found that no two compounds except the enantiomers can have similar Infra-
red spectra. When infra-red light is passed through sample, the vibrational and rotational
energies of the molecule are increased. Two types of fundamental vibrations are stretching and
bending. In stretching vibrations, the distance between the two atoms increases or decreases but
the atom remain in the same bond axis. But in bending vibrations the position of atoms changes
with respect to the original bond axis. There are two types of stretching vibrations. Also there
are four types of bending vibrations- scissoring, rocking, wagging and twisting.
Another condition for a molecule to absorb IR radiation is its electric dipole. A molecule
can only absorb IR radiation when its absorption causes a change in its electric dipole. A
molecule is said to have an electric dipole, when there is a slight positive charge and a slight
negative charge on its component atoms.
 26

2.4.2. Instrumentation
The apparatus for measuring infrared spectra is di/erent from that for visible and
ultraviolet regions because the optical materials like glass and quartz absorb strongly in the
infrared region. The main parts of an IR spectrometer are as follows. 10 a The IR radiation source. b
The monochromators. c The sample cells and sampling of substances. d Detectors.

Figure: 2.7

(a) The IR radiation source

The various popular sources of IR radiations are, i

Incandescent lamp
In the near infrared instruments an ordinary incandescent lamp is generally used, which
fails in the far infrared.

ii Nernst glower
It consist of a hollow rod which is about 2mm in diameter and 30mm in length, which is
non conducting at room temperature and must be heated by external means to bring it to a
conducting state. The main disadvantage of Nernst glower is that it emit IR radiation over wide
wavelength range, the intensity of radiation constant over long period of time.

iii Glower source

 27
It is a rod of sintered silicon carbide which is about 50mm in length and 4mm in
diameter. Unlike the Nernst glower it is self starting and more satisfactory. The main
disadvantage is that it is a less intense source than the Nernst glower.
(iv) Mercury arc

It is used in far infrared instrument.

(b) Monochromator
The radiation source emits radiation of various frequencies as the sampling electrons absorbs at
certain frequency. It is necessary to select desired frequency from the radiation source. This
selection is advised by monochromators, which are mainly of two types, prism monochromator
and grating monochromator.
(c) Sample cells and sampling of substances
Sample can be solid, liquid or gas. But it should be contained in a cell transparent to IR
radiation. Sample cells are usually made of alkali metal halides such as sodium chloride,
potassium bromide etc.
Sampling of solids
Four techniques are generally employed for preparing solid samples.
These are:
Solid run in solution
If the solution of solid can be prepared in a suitable solvent then the solution is run in one
of the cells for liquids. But this method cannot be used for all solids because suitable solvent are
limited in number and there is no single solvent which is transparent throughout the IR region.

(ii) Solid 3lms

If the solid is amorphous in nature, the sample is deposited on the surface of KBr or NaCl
cell by evaporation of a solution of the solid.
iv Mull technique
In this technique, the 3nely ground solid sample is mixed with nujol (mineral oil) to make
a thick paste which is then made to spread between IR transmitting windows. When IR spectrum
of a solid sample is taken in nujol mull, absorption bands of the sample that happen to coincide
with the absorption band of the nujol mull will be hidden, but others will be clearly seen in the IR
 28
spectrum. This method is good for qualitative analysis but not for quantitative analysis. v Pressed
Pellet technique
In this technique a small amount of 3nely ground solid sample is intimately mixed with
about 100 times its weight of powdered potassium bromide. The 3nely ground mixture is then
passed under very high pressure in a press to form a small pellet (about 1-2mm thick and 1cm in
diameter).
The resulting pellet is transparent to IR radiation and is run as such.
Advantages
1 KBr pellets can be stored for long period of time.
2 As the concentration of the sample can be suitably adjusted in the pellets, it can be used
for quantitative analysis.
3 The resolution of the spectrum in the KBr is superior to that obtained with mulls.
Disadvantages
1 The high pressure involved during the formation of pellets may bring about polymorphic
changes in crystallinity in the samples, which may cause complication in IR spectrum.
2 This method is not successful for some polymers which are diNcult to grind with KBr.
From the above discussion we knows that one may employ the Nujol method for running
crystalline compounds in the solid and may reserve the KBr pellet method for remaining solid
samples. d Detectors
Two main types are in common use, one sensing the heating e/ect of radiation, the other
depending up on photoconductivity. In the near infrared region photoconductivity cell is
generally used that is the radiation is allowed to fall on photo conducting material and
conductivity of material measured continuously by a bridge network. Usual IR detectors are
thermocouple, thermisters, golay cell, photoconductivity cell, bolo meters etc.

2.5. References

1. J S Blackmore, in Solid state Physics, Second Edition, Cambridge University Press, Cambridge
(1985).

2. J P Srivasthava, in Elements of Solid State physics-Prentice-Hall India, New Delhi (2001).

 29
3. C.Kittel, Introduction to solid state physics, Seventh Edition, John Wiley & Sons Inc., Singapore
(1995).

4. N F M Henry, H Lipson and W A bWooster, in Interpretation of X-ray di/raction Photographs,

Mac Milan & Co Ltd., London (1961).

5. B D Cullity, in Elements of X-ray di'raction, I Edition, Addison-Wesley

Company, Inc., Massachusetts (1978).

6. Suryanarayana C., Bull.Mat.Sci. 17 (1994) 307.

7. A Cervellnio, C Giannini, A Guagliardi and M Ladisa, Phy.Rev.B.72 (2005) 035412. (Electronic
version).
8. R Jamutowski,J.R.Ferraro, and D.C Lanski, Spectroscopy,7(1992) 22; I.R, Altemose,
J.Chem.Educ, 63 (1986) A216, A262.

9. Skoog, Holler and Nieman, in Principles of Instrumental Analysis, Fifth edition.