Chapter 1

Introduction

Material classification

Based on the ability of various materials to conduct current, the materials are
classified as conductors, insulators and the semiconductors.

a) Conductors:- These are those materials whose electrical conductivity is very high.
Conductors conduct charges very easily . For super-conductor , the value of electrical
conductivity is infinite.

Examples. Copper, Silver, Aluminium , Tungsten etc.

(b) Semiconductors:- They are those materials whose electrical conductivity lies in
between insulators and conductors . Semiconductors can conduct charges but not so
easily as in case of conductivity.

Examples. Germanium.Silicon etc.

(c) Insulators:- These are those materials whose electrical conductivity is either very
very small or nil. Insulators do not conduct charges.

Examples. Glass, Rubber, Wood etc

Nanoscience and nanotechnology:

The word Nanoscience refers to the study, manipulation and engineering of matter,
particles and structures on the nanometer scale . Important properties of materials, such
as the electrical, optical, thermal and mechanical properties, are determined by the way
molecules and atoms assemble on the nanoscale into larger structures. Moreover, in
nanometer size structures these properties often different then on macroscale, because
quantum mechanical effects become important.

Nanotechnology is the application of nanoscience leading to the use of new

nanomaterials and nanosize components in useful products. Nanotechnology will
eventually provide us with the ability to design custom-made materials and products
with new enhanced properties, new nanoelectronics components, new types of “smart”
medicines and sensors, and even interfaces between electronics and biological systems.

Semiconducting Nanomaterials:
Nanomaterials (diameters in range 1-20 nm) with extremely small feature size has the
potential for wide-ranging industrial, biomedical, and electronic applications. In the
case of bulk materials, relatively small percentage of atoms will be at or near a surface
or interface a relatively small percentage of atoms will be at or near a surface or
interface whereas in nanomaterials, the small feature size ensures that many atoms,
perhaps half or more in some cases, will be near the interfaces. Surface properties like
energy levels, electronic structure and reactivity can be quite different from interior
states and give rise to unique material properties.In recent years more interest is been
observed in the preparation, characterization and application of semiconductor
nanoparticles in new technologies. When the size of semiconductor materials is reduced
to nanoscale, their physical and chemical properties changes due to their large surface
area or quantum size effect. The conductivity of the semiconductor and its optical
properties (absorption coefficient and refractive index) can be varied.They are
promising wide applications in field like solar cells, nanoscale electronic devices, light-
emitting diodes, laser technology, waveguide, chemical and biosensors, packaging
films, superabsorbents….. Semiconductor devices include the various types of
transistors, solar cells, many kinds of diodes including the light-emitting diode, the
silicon controlled rectifier, and digital and analog integrated circuits. Some of the
semiconductor nanomaterials such as Si-Ge, GaAs, AlGaAs, InP, InGaAs, GaN,
AlGaN, SiC, ZnS, ZnSe, AlInGaP, CdSe, CdS,ZnMn2O4,ZnO etc., exhibit excellent
application in computers, palm pilots, laptops, cell phones, pagers, CD players, TV
remotes, mobile terminals, satellite dishes, fiber networks, traffic signals, car taillights,
and air bags. Semiconductor nanocrystals are made from a different compounds. They
are referred to as II-VI, III-V or IV-VI semiconductor nanocrystals, based on the
periodic table groups into which these elements are formed.

Classification Of Semiconducting Nanomaterials

Schematic drawing to show the concept of system dimensionality:

(a) bulk semiconductors (3D); (b) thin film, layer structure, quantum
well (2D); (c) linear chain structure, quantum wire (1D); (d) cluster,
colloid, nanocrystal, quantum dot (0D). In the bottom, the
corresponding density of states[Δ(E)] versus energy (E) diagram (for
ideal cases)

In nanocrystalline materials, the electrons are confined to regions having one, two or
three dimensions ,when the relative dimension is comparable with the de Broglie
wavelength. For a semiconductor like CdSe, the de Broglie wavelength of free electron
is around 10 nm. The nanostructures of semiconductor crystals having the zdirection
below this critical value (thin film, layer structure, quantum well) are defined as two
dimensional(2D) nanostructures. When the dimension both in the x and z direction is
below this critical value (linear chain structure, quantum wire) the nanostructures are
defined as one dimensional(1D) and when the y direction is also below this threshold
(cluster, colloid, nanocrystal, quantum dot) it is referred to as zero dimensional(0D).(by
Sagadevan Suresh, Semiconductor Nanomaterials, Methods and Applications: A
Review, Nanoscience and Nanotechnology, Vol. 3 No. 3, 2013, pp. 62-74)

Compound Semiconductors

Compound semiconductors are semiconductors that are made from two or more
elements.Most of them are combinations of elements from GroupIII and GroupV of the
Periodic Table of the Elements (GaAs, GaP, InP and others). Other compound
semiconductors are made from Groups II and VI (CdTe, ZnSe and others). It is also
possible to use different elements from within the same group (IV), to make compound
semiconductors .Potential characteristics of compound semiconductors are high speed
operation(high electron mobility, ability to generate high frequency (microwave)
signal,low voltage operation (for lighter & longer lasting, low voltage batteries used for
portable devices),light emission (both visible and infrared light, for lasers and
LEDs),sensitivity to light (for photodetectors),sensitivity to magnetism (useful in sensor
applications),resistance to heat and radiation (useful in space applications, such as solar
cells for satellites).

ZnMn2O4 Nanomaterials

Literature Reviewss

XRD

XRD analysis provided in different journals give us information that the particle size of
ZnMn2O4 is observed within the range 24 nm – 90 nm, all the diffraction peaks appears
at 2o equal to 32.9420,54.4300,56.7380,60.8280 which is exclusively indexed to that of
tetragonal phase and the lattice constants a=b comes in the range 5.71749 A0 – 5.762 A0
and c in the range 9.23527 A0 – 9.470 A0.

Williamson-Hall analysis:

Assuming both size and strain broadening are lorentzian, the integral breadths of both
components are additive

β*=β cosθ∕λ =1/D + 2ed*

where β is integral breadth, λ is wavelength, θ is Bragg’s angle, D is volume weighted

main domain size, d*=1/d, reciprocal lattice spacing. by plotting β* v/s d*, fitting the
datapoints wit a straight line yield the crystallite size from the intercept and microstrain
from the slope of line.

Theoretical density

Theoretical density is an important parameter used to estimate the porosity of materials

after sintering, especially if the requirements for the materials’ densities are strict.

From XRD data, we can obtain the unit cell parameters. Using the unit cell parameters,
a,b,c, you can get the unit cell volume. Based on the crystal structure of the material,
we can find how many molecular units are present in every unit cell. Chemical
structure give us information about molecular weight. Using all these data and using
the formula given below we will be able to calculate the theoretical density.

Theoretical density = (Molecular weight x No. of molecules per unit cell)

(Volume of unit cell x Avogardo's number)
ρ=nA/vcNA

n=atoms/unit cell

A= molar mass

Vc= vol/unit cell

NA= avogadro’s no (6.023*1023 atoms/mol)

FTIR

According to the stretching and bending vibrations of surface hydroxyl and adsorbed
atmospheric moisture on the surface of the nanomaterial, the samples are having IR
Bands in the high frequency region of 3400 cm-1 and 1370 cm-1. The sample shows the
prominent IR band at 507cm-1 and 630 cm-1 which can be attributed to the stretching
vibration of Mn3+ species in Octahedral and Tetrahedral sites. A shoulder at 710cm-1
shows the asymmetric vibration of Mn-O band in an Octahedral environment. The
shoulder disappeared and an additional peak emerged at 423cm-1 which can be ascribed
to the stretching vibration of Zn-O.

UV

The Optical property of the ZnMn2O4 nanorods can be observed by the UV-visible
diffuse reflectance spectroscopy. In previous studies the spectra of ZnMn2O4 nanorods
at different temperatures. All the samples have strong absorption between 300nm and
500nm. The absorption edges of these samples are around 700nm from the UV-spectra
.It is clear that the absorbance decreases with increase in wavelength.This decrease in
absorption indicates the presence of optical band gap in the material.The optical band
gap could be determined from the tauc plot between (𝛼ℎʋ)2 versus hʋ curve of
ZnMn2O4 nanorods calcined at different temperatures.From the previous studies the
optical band gaps were calculated as 1.2,1.34 and 1.45eV for the samples calcined at
500,650 and 800℃ respectively.

Dielectric property

Dielecric constant analysis in various journals gives the idea that real and imaginary
dielectric constant decrease gradually with increase in frequency at low frequency
region and in high frequency region it is almost indepent of frequency .From dielectric
loss analysis it is noted that at low frequency region the value of dielectric loss is high
and as frequency increases dielectric loss tends to become zero,independent of
frequency.From real part impedence (Z) analysis we came to know that Z remains
constant at low frequency region and it emerges with increase of frequency;Z decreades
with increase in temperature.From the information provided in journals about imaginary
part impedence (Z’) we observed that Z’ peak decreases and shift towards higher
frequency with increase in temperature.

The dielectric parameters such as real part of dielectric constant (ε`), the imaginary part
of dielectric constant (ε``) and ac-conductivity were calculated using the equation given
below:
𝐶𝑑
ε`=
𝐴𝜀₀`

𝜎𝑎𝑐 =2𝜋𝑓𝜀`𝜀 0 𝑡𝑎𝑛𝛿

𝜎𝑎𝑐
𝜀`` =
𝜀 0 𝜔`
Where C capacitance in farad, d is the thickness of the pellet in mm, A is the cross
sectional area of the pellet in 𝑚2 ,ε₀ is constant of permittivity in free space , 𝜔 = 2𝜋𝑓 is
angular frequency and tan 𝛿 is dielectric loss.

CAPACITANCE

In different journals the capacitance of ZnMn2O4 is mentioned as :Li/ZnMn2O4 half

cell battery cycling showed that the nanoparticles give a high capacity of
430 mAh g−1 when cycled 100 time, ZnMn2O4 microspheres exhibit a reversible
capacity of 800 mAh g−1at 500 mA g−1 over 300 cycles,even at 2 A g−1,
ZnMn2O4 microspheres deliver a capacity of 395 mAh g−1, higher than the theoretical
capacity of graphite,the ZnMn2O4 nanoparticle electrode delivered an initial charge
capacity of 666.1 mAh g−1 and exhibited a capacity retention of ∼81%
(539.4 mAh g−1) after 50 cycles,the pure ZnMn2O4 electrode showed initial discharge
capacity of about 820 mAh g−1 and 57% of initial capacity retention after 50 cycles at a
rate of C/10.
REFERENCES
 CHAPTER 2

Combustion Synthesis

Combustion synthesis or self-propagating high temperature synthesis is an

effective, low cost method for production of various industrially useful materials.

3 types of combustion synthesis are; i)Conventional combustion synthesis of nanoscale

materials, that is, initial reactants are in solid state ii)solution combustion
synthesis(SCS) of Nano sized powders, that is, initial reaction medium is aqueous
solution iii)Gas phase combustion, synthesis of nanoparticle in flame.

Procedure

We decided to do combustion synthesis of ZnMn2O4. First we collected all the required

chemicals which are the compounds of Zn and Mn. Calculations are done and weighed
chemicals accordingly. Mixed the chemicals in a proper way in a beaker one after
another then we add citric acid to the beaker. To do combustion synthesis beaker is kept
on a hot plate and placed in a fume chamber. Observations are noted. Then we decided
to heat the prepared sample of ZnMn2O4. .the sample is collected and heated at 6500c
for half an hour in furnace to remove the inorganic impurities. XRD, UV and FTIRof
the Prepared sample ZnMn2O4 and heated ZnMn2O4 are taken. After that our heated
sample is converted into pellet. PVA is added as a binding agent before pelletising.
Sample in a paste form is kept to dry and after that fine power of sample converthed to
pellet.
Combustion synthesis

Compound name Molecular weight Required weight Weighing amount

Zn(NO3)2.6H2O 297.49 297.49 4.788

Mncl2.4H2O 161.87 323.74 5.2112
X- RAY DIFFRACTION

XRD is the most common characterization and a non-destructive technique used to

determine the structure and orientation of crystal. Besides that, composition, quality,
lattice parameters, defects strain and stress in semiconductor materials can be
estimated. Average spacing between layers of atoms also can be calculated from the
XRD profile. The SIEMENS D5000 with Cu-Kα probe beam at a wavelength of λ =
1.5406 Ǻ was used for all measurements. The phenomenon of x-ray diffraction by
crystalline materials results from a scattering process in which x-rays are scattered by
the electrons of atoms without any changes in wavelength. A diffracted beam is
produced by coherent or Bragg scattering only when certain geometrical conditions are
satisfied. Bragg concluded that the path difference between the two x-rays diffracted
from two consecutive lattice planes is 2dsinθ and it leads to Bragg’s law, which states
that the condition for diffraction of x-rays for a crystalline material is nλ= 2dsinθ. The
θ is the angle of incidence and λ is the wavelength of the x-rays, n is an integer and it
is the order of reflection, and d is the distance between the lattice planes. The
interatomic distance in solids is several Armstrong and the energy corresponds to this
distance can be 58 calculated as E= hc/λ for λ equals to 1 Å. Therefore, E
approximately equals to 12×103 eV. If the structure of the solid is to be probed by
electromagnetic waves then these waves should have energy at least equal to the
interatomic distance energies. X-rays have approximately same energy (keV) as the
interatomic distance energies of solids.

X-ray Powder Diffraction (XRD) Instrumentation

X-ray diffractometers consist of three basic elements: an X-ray tube, a sample holder,
and an X-ray detector.
X-rays are generated in a cathode ray tube by heating a filament to produce electrons,
accelerating the electrons toward a target by applying a voltage, and bombarding the
target material with electrons. When electrons have sufficient energy to dislodge inner
shell electrons of the target material, characteristic X-ray spectra are produced. These
spectra consist of several components, the most common being Kα and Kβ. Kα consists,
in part, of Kα1 and Kα2. Kα1 has a slightly shorter wavelength and twice the intensity as
Kα2. The specific wavelengths are characteristic of the target material (Cu, Fe, Mo, Cr).
Filtering, by foils or crystal monochrometers, is required to produce monochromatic
X-rays needed for diffraction. Kα1and Kα2 are sufficiently close in wavelength such
that a weighted average of the two is used. Copper is the most common target material
for single-crystal diffraction, with CuKα radiation = 1.5418Å. These X-rays are
collimated and directed onto the sample. As the sample and detector are rotated, the
intensity of the reflected X-rays is recorded. When the geometry of the incident X-rays
impinging the sample satisfies the Bragg Equation, constructive interference occurs
and a peak in intensity occurs. A detector records and processes this X-ray signal and
converts the signal to a count rate which is then output to a device such as a printer or
computer monitor.The geometry of an X-ray diffractometer is such that the sample
rotates in the path of the collimated X-ray beam at an angle θ while the X-ray detector
is mounted on an arm to collect the diffracted X-rays and rotates at an angle of 2θ. The
instrument used to maintain the angle and rotate the sample is termed a goniometer.
For typical powder patterns, data is collected at 2θ from ~5° to 70°, angles that are
preset in the X-ray scan.

FTIR SPECTROSCOPY

Fourier transform infra-red spectroscopy is a technique used to obtain an infra-red

spectrum of absorption or emission of a solid, liquid or gas. When IR radiation is
passed through a sample, some radiation is absorbed by the sample and some passes
through (is transmitted). The resulting signal at the detector is a spectrum representing
a molecular ‘fingerprint’ of the sample. The usefulness of infrared spectroscopy arises
because different chemical structures (molecules) produce different spectral finger
print.When a material is irradiated with infrared radiation, absorbed IR radiation
usually excites molecules into a higher vibrational state. The wavelength of light
absorbed by a particular molecule is a function of the energy difference between the
at-rest and excited vibrational states. The wavelengths that are absorbed by the sample
are characteristic of its molecular structure.