Chapter II

INTRODUCTION

The prefix (nano) in the word nanochemistry means

a billionth (1 x 10-9 m). Atoms are very small and the
diameter of a single atom can vary from 0.1 to 0.5 nm. It
deals with various structures of matter having dimensions
of the order of a billionth of meter.
 BASICS OF NANOCHEMISTRY

1. Nanoparticles
 Nanoparticles are the particles, the size of which ranges from 1-50 nm.
 Generally they are obtained as colloids.
 The colloidal particles have a tendency to remain single crystal and hence are called as
nanocrystals.
 A large percentage of atoms in nanocrystals are present on the surface, nanocrystals possess
electronic, magnetic and optical properties.
 Since the nanoparticles exhibit an electronic behavior (Electronic devices control the flow of
electrons in order to perform a task), governed by the quantum physics, they are also called as
quantum dots.
QUANTUM DOTS are man-made nanoscale crystals that that can transport electrons.
When UV light hits these semiconducting nanoparticles, they can emit light of various
colours. These artificial semiconductor nanoparticles that have found applications in
composites, solar cells and fluorescent biological labels.
DISTINCTION BETWEEN NANO PARTICLES, MOLECULES AND BULK MATERIALS

1. The size of nanoparticles are less than 100 nm in diameter, molecules are in the range of
picometers, but bulk materials are larger in micron size.

2. Molecule is a collection of atoms, nanoparticles are collection of few molecules that is less
than 100 nm but bulk materials contains thousands of molecules.

3. Surface area of nanoparticles is more than the bulk materials.

4. Nano particles possesses lower melting point than the bulk materials.
Example:
Gold nanoparticles melt at lower temperature (3000C) for 2.5 nm, but Gold slab melts at
10640C.
5. Nano particles possesses size dependent properties, but bulk materials possess constant physical
properties.

6. Corrosion resistance is more than the bulk materials, hence localised corrosion in nanomaterials is
stopped.

7. Behavior of bulk materials can be changed, but cannot enter inside the nano particles.

8. Nano particles, due to its size, possess unexpected optical (visible) properties.

a. Gold nano particles appear deep red to black colour in solution compared to yellow colour with Gold.

b. ZnO nano particles possesses superior UV blocking property compared to bulk material.

c. Absorption of solar radiation in photovoltaic cell containing nano particles are higher than the film (bulk
material).
9. Sintering of nanoparticles takes place at lower temperature and in short time than
the bulk materials.
10. Electrical properties, resistivity of nanoparticles are increased by 3 times.
11. Suspension of nanoparticles is possible, because nanoparticles possess high surface
area, but bulk materials cannot.
12. The wear resistance of nanoparticles are 170 times higher than the bulk materials.
2. Nanomaterials

 Nanomaterials are the materials having components with size less than 100 nm
at least in one dimension.
 Nanomaterials, in one dimension, are layers such as a thin films or surface
coatings.
 Nanomaterials, in two dimension, are tubes such as nanotubes and
nanowires.
 Nanomaterials, in three dimension, are particles like precipitates, colloids
and Quantum dots.
3. Nanochemistry (or) Nanoscience
 Nanoscience is defined as the study of phenomena and manipulation of
materials at atomic, molecular and macromolecular scales.
4. Nanotechnology
 Nanotechnology is defined as the design, characterization, production
and applications of structures, systems and devices by controlling size and shape
at 10-9 m scale or the single-atomic level.
Table 7.1 Comparison of atom/molecule, nano
particles/cluster, bulk materials

NOTE:
Aspect ratio of a geometric shape is the
ratio of its size in different dimensions.
(length divided by width for nanorods)
SIZE DEPENDENT PROPERTIES
 Nearly all the properties as shown in following figure 2.1 like hardness,
strength, ductility, melting point and density, change for nanomaterials. These
behaviors vary so significantly by a mere reduction in grain size.
 Nanomaterials are composed of grains and grain boundaries (The individual crystals
are called"grains." In any one grain, all atoms are arranged with one particular orientation and
one particular pattern. The juncture between adjacent grains is called a "grain boundary.“) The
grain boundary is a transition region in which some atoms are not exactly aligned with
either grain..

 Nanometresized grains contains only a few thousands of atoms with in each grain.
 A large number of atoms reside at the grain boundaries.
 As the grain size decreases, there is a significant increase in the volume fraction of
grain boundaries or interfaces.
 The properties of the materials are bound to be governed to a large extent by defect
configurations. Hence the mechanical and chemical properties of nanomaterials are
significantly altered due to defect dynamics.
 The elastic property of nanomaterials are different from that of bulk alloys due to the
presence of increased fraction of defects.
Example

Fig 2.1 Shows how different properties change in the nano-materials

 SYNTHESIS OF NANO - MATERIALS
Nano-materials are synthesised in two methods
Top-down (or) Physical (or) Hard methods
It involves conversion of larger particles into smaller particles of nano-scale
structure.

Bottom-up (or) Chemical (or) Soft methods (or) Small to Big methods
It involves building-up of materials from the bottom by atom by atom (≈ 0.1
nm), molecule by molecule or cluster by cluster.
 Top-down (or) Physical (or) Hard methods
1. Laser ablation
2. Chemical Vapour Deposition (CVD)
3. Electro-deposition

1. Laser Ablation
In laser ablation, high-power laser pulse is used to
evaporate the matter from the target. The stoichiometry of the
material is preserved in the interaction. The total mass ablated from
the target per laser pulse is referred to as the ablation rate.
Reaction Setup
A typical laser ablation setup in shown in the following figure.2.2 Fig 2.2 Laser ablation chamber
equipped with a rotating target holder
 When a beam of laser is allowed to irradiate the target, a
supersonic jet of particles is evaporated from the target surface.
Simultaneously, an inert gas such as argon, helium is allowed into the
reactor to sweep the evaporated particles from the furnace zone to the
colder collector.
 The ablated species condense on the substrate placed opposite
to the target.
 The ablation process takes place in vacuum chamber,
either in vacuum or in the presence of some background gas.
Disadvantage: This process is not economical. It is costly.
Chemical Vapor Deposition. CVD is a widely used technique to make 2D nanomaterials
and thin films on solid substrates. In this technique, the precursors, gas or vapor, can
react or decompose on the preselected substrate at high temperature and vacuum in a
chamber, as shown in Fig.

E ample
E ample
1. Solvothermal Process
2. Sol-Gel Method
Solvothermal Synthesis

Solvothermal synthesis involves the use of solvent under high temperature

(between 1000C to 10000C) and moderate to high pressure (1 atm to 10,000 atm) that
facilitate the interaction of precursors during synthesis.

Method
A solvent is mixed with certain metal precursors and the solution mixture is placed
in an autoclave kept at relatively high temperature and pressure in an oven to carry out the
crystal growth. The pressure generated in the vessel, due to the solvent vapour, elevates the
boiling point of the solvent.
Solvothermal synthesis of zinc oxide
Zinc acetate dihydrate is dissolved in 2-propanol at 50 0C. Subsequently, the solution is
cooled to 00C and NaOH is added to precipitate ZnO. The solution is then heated to 65 0C to allow
ZnO growth for some period of time before a capping agent (1-dodecanethiol) is injected into the
suspension to arrest the growth. The rod shaped ZnO nano-crystal is obtained.
Uses
1. Many geometries including thin film, bulk powder,
single crystals can be prepared.
2. Thermodynamically stable novel materials can also
be prepared easily.
Electrospinning is a manufacturing technique involving
electrostatic driven process used to create electrospun fibers. The
diameter of these fibers typically ranges between tens of
nanometers to a few micrometers.
PROCESS:

Ultrafine fibers are defined as fibers finer than silk, and are also called nanofibers. In
addition to conventional thermoplastic polymers, ceramic nanofibers such as alumina,
zirconium oxide, and titanium oxide are also being produced. Nanofibers are used in a
wide range of fields such as filters, high-performance masks, protective clothing, and
regenerative medicine.
One of the methods of nanofiber production is electrospinning. Electrospinning can be
used to spin various materials such as polymers into nanofibers. Electrospinning can
produce ultra-fine fibers with diameters of 50 to 500 nm, and is characterized by its easy
operation.
In field spinning, a polymer solution or molten polymer is placed in a syringe, and the
polymer solution is injected while applying a high voltage. When the voltage exceeds a
threshold value, the repulsive force of the electric charge overcomes the surface tension
of the polymer droplets, and a jet of charged material is generated. By accumulating
these jets, ultra-fine polymer fibers are formed.
The elongation and thinning of the fiber resulting from this bending instability
leads to the formation of uniform fibers with nanometer-scale diameters.
DC high-voltage power supplies with positive polarity output of about 10 kV to 30 kV can
generally be used. Depending on the polymer solution you want to static electricity,
thickness of the fiber, and speed to fly the fiber to the target electrode, the higher voltage
such as up to 50 kV or more, DC high voltage with negative polarity, and a high-voltage
amplifier can also be required.
BLOCK DIAGRAM
Electron microscope

Electron microscope uses a beam of electrons to illuminate the object and form an enlarged
image. Electrons have much shorter de Broglie wavelengths compared to the wavelengths
of the visible light and hence a beam of electrons facilitates a much higher resolution. The
resolving power of electron microscopes is much greater, about 2 million times as
compared to 2000 times of light microscopes and hence details at atomic levels can be
obtained.

The primary beam of electrons passes through the sample depending on its thickness and
density without suffering any energy loss. The primary electron beam on its interaction
with sample gives various detectable signals like Back scattered electrons, Secondary
electrons, Transmitted electrons, Auger electrons, X-rays, Photons..
Block diagram of electron microscope Electron microscope image of carbon nano particles
 The transmitted electrons provide the two dimensional image of the object.
 The primary electrons can be backscattered on elastic collision with the atoms of the
sample. The intensity of backscattering increases with the atomic number.
 Hence heavier atoms can be distinguished with the help of backscattered electrons.
 Secondary electrons are emitted from the sample due to inelastic collision of the primary
electrons. Thus secondary electrons gives topographical information of the sample.
 X-rays and Auger electrons are emitted by the relaxation of core-ionised atoms, Which
provides the chemical composition of the sample.
 The electrons diffracted by the particles in the object provides the crystallographic
information of the sample.
 Thus, from these detectable signals, we can able to get topography, morphology, chemical
composition and crystallographic structure of the sample.
 CHARACTERISTIC INFORMATION
• TOPOGRAPHY – surface features of an object (hardness. Reflectivity, etc.,)
• MORPHOLOGY – shape and size of the particles ( ductility, strength, shape,
etc.,)
• COMPOSITION – The elements and compounds that the object is composed
of and the relative amounts of them.
• CRYSTALLOGRAPHIC INFORMATION – how the atoms are arranged in
the object.
There are four basictypes of electronmicroscope,
 Analytical Electron Microscope (AEM)
 Transmission Electron Microscope (TEM)
 Scanning Electron Microscope (SEM)
 Scanning Tunnelling Electron Microscope (STEM)
Transmission Electron Microscope
This technique gives a two dimensional image of the sample when a fine beam of electrons of
wavelength 0.1 to 0.01 nm is transmitted over a ultra thin sample, interacting with the sample
as it passes through the sample.
TEM allows one to read the inner structure of the sample as the high energetic electron
travels through the sample.
It provides the size, shape, topography, chemical composition, arrangement of particles in the
sample.
The sample used in TEM should be ultra thin and conductive.
A transmission electron microscope consists of electron source, condenser lens with
aperture, sample compartment, objective lens with aperture, projector lens and fluorescent
screen or photographic plate.
The specimen is mounted on sample holder after suitable sample preparation procedures.
The tungsten filament cathode inside the electron gun produces a beam of electrons on a
application of high voltage (Thermionic emission).
The electron beam is accelerated by anode and focused as a fine spot by a set of electrostatic
and magnetic lenses (condenser lens)
 The fine electron beam is partly transmitted through the thin section of sample and
partly scattered.
 The information on the structure of the sample contained in the emerging beam is
magnified by the objective lens.
 The image projected on the fluorescent screen is of several thousand times in
magnification.
 The image produced can be either a bright field or dark field image.
 In regions of the objects, where the electron beam encounter atoms with heavier
nucleus, they rebound. (Dark field image)
 In the regions where the object consists of lighter atoms, the electrons can able to pass
through.(Bright field image)
 As a result a contrasted image is formed on the fluorescent screen or photographic
plate.
APPLICATIONS

a) The main application of a transmission electron microscope is to provide high

magnification images of the internal structure of a sample.
b) It is an important diagnostic tool in medicine especially in the studies of tumour
cell.
c) It is used to study the impact of environmental pollution on biological organisms.
d) It is exclusively used in the study of semiconductors, nanomaterials, ceramics,
polymers..
Scanning Electron Microscope

A scanning electron microscope is a type of electron microscope that images the

sample by scanning it with a high- energy beam of electrons in a raster pattern.

The electrons on its interaction with the sample produces various detectable signals.

Mostly SEM detects the signals like secondary electrons, backscattered electrons, X-ray
photons , diffracted electrons , which provides the topography, morphology, chemical
composition and structural information's of the sample.

The components of scanning electron microscope are electron gun, anode, electromagnetic
lenses, scanning coils, sample stage and detector.
SCANNING ELECTRON MICROSCOPE: SEM

PRINCIPLE:
• The basic principle is that a beam of electrons is generated by a suitable source,
typically a tungsten filament or a field emission gun.
• The electron beam is accelerated through a high voltage and pass through a system a
apertures and electromagnetic lenses to produces a thin beam of electrons.
• Then the beam scans the surface of the specimen. Electrons are emitted from the
specimen by the action of the scanning beam and collected by a suitably positioned
detector.
The sample analysed in SEM should be solid ,electrically conducting and stable under vacuum.

The surface of non conducting sample may be coated with a thin layer of gold, platinum or graphite
to make the surface as electrically conducting.

The tungsten cathode in electron gun is electrically heated to emit electrons. The emitted electrons
are focused with the help of anode towards the condensing lenses which are electromagnetic in
nature.

The condensing lenses colliminates the fine beam of electrons towards the scanning coils. the
scanning coil faciliates the scanning of electron spot in a raster pattern (horizontal & vertical
scanning) over the sample surface.

As the electrons strike and penetrate the sample surface (depth about 100nm-5 micrometer), a variety
of interactions can occur within this volume, resulting in various signals.
 These signals are detected with the help of suitable detectors.
 The secondary electron detector is a scintillator - photomultiplier
system. Ṭhe electrical signal output from the photomultiplier tube
gives the topographical image of the sample which can be stored.
 Scintillator or semiconducting devices can be used to detect
backscatterd electrons and diffracted electrons, which helps in
identifying heavier elements distribution and crystallographic pattern.
 The signals from Auger electron & X-ray detector provides the
chemical composition of the sample.
Applications

 SEM have variety of applications in various scientific and industrial fields especially
in analysing solid materials. In addition to morphology , topography and crystal
structure, it can be used for examining surface contamination, spatial variation,
microstructural and qualitative analysis.
 SEM can be as essential research tool in fields such as life science, biology,
gemology, medical and forensic science, metallurgy.
 It is an important tool for analysing optical and electronic properties of
semiconductor devices and microchips in computers.
 TEM SEM
• Electron beam passes through the thin sample. • Electron beam scans over the surface of the sample.
• Specially prepared thin samples are mounted on the • Sample of any thickness can be analysed.
sample holder. • Sample stage is placed at the bottom of the column.
• Sample stage is placed in the middle of the column. • SEM detects the secondary electrons and
• TEM detects the transmitted electrons. backscattered electrons.
• It provides the detailed information about internal • It focuses on the sample surface and its composition.
structure of the sample. • SEM gives the three dimensional image of the object.
• TEM gives the two dimensional image of the object.
• The magnification of SEM is 2 million times.
• The magnification level of TEM is 50 million times.
• The resolution of SEM is 0.2 nm
• It has a high resolution of 0.5 Angstron.
TYPES OF NANOMATERIALS

1. NANOPARTICLES
2. NANOWIRES
3. NANORODS
4. NANOCLUSTERS
5. NANOTUBES
Nanoparticles

 Nanoparticles are the particles, the size of which ranges from 1-50 nm.
 Generally they are obtained as colloids.
 The colloidal particles have a tendency to remain single crystal and
hence are called as nanocrystals.
 A large percentage of atoms in nanocrystals are present on the surface,
nanocrystals possess electronic, magnetic and optical properties.
 Since the nanoparticles exhibit an electronic behavior, governed by the
quantum physics, they are also called as quantum dots.
NANO-WIRES
Nano-wire is a material having an aspect ratio i.e., length to width
ratio greater than 20. Nano-wires are also referred to as “quantum wires”.

1. Nano-wires of metals : Au, Ni, Pt.

2. Nano-wires of semiconductors : InP, Si, GaN

3. Nano-wires of Insulators : SiO2, TiO2

4. Molecular nanowires : DNA

Characteristics of Nano-wires

1. Nano-wires are one-dimensional material.

2. Conductivity of a nano-wire is less than that of the corresponding bulk materials.

3. It exhibits distinct optical, chemical, thermal and electrical properties due to this
large surface area.

4. Silicon nano-wires show strong photo luminescence characteristics.

Synthesis of Nano-wires
Nanowires can be synthesised by any one of the following
methods.

1. Template-assisted synthesis
Template assisted synthesis of nanowires is simple way to fabricate
nanostructures. These templates contain very small cylindrical pores or voids
within the host material and the empty spaces are filled with the chosen material
to form nanowires.
Examples for templates

Alumina (Al2O3), nano-channel glass, mica films, ion track-edged

polymers.
Applications of Nano-wires

1. Nanowires are used for enhancing mechanical properties of composites.

2. It is also used to prepare active electronic components such as p/n junction
and logic gates.
3. Semiconductor nanowire crossings are expected to play a important role in
future of digital computing.
4. Nanowires find applications in high-density data storage either as magnetic
read heads or as patterned storage media.
NANO-RODS
Nano-rod is a material having an aspect ratio in the range 1 to 20
with short dimension of the material being 10-100 nm.

Characteristics of Nano-rods
1. Nano-rods are one-dimensional materials.
2. It also exhibits optical and electrical properties
Synthesis
Nano-rods are produced by direct chemical synthesis. A
combination of ligands act as shape control agents and bond to
different facets of the nano-rods with different strength.
Applications
It finds applications in display technologies and micromechanical
switches
NANO CLUSTER
 Nano clusters constitute an intermediate state of matter between
molecules and bulk materials.
 These are fine aggregates of atoms or molecules. They are
bound by forces, which may be metallic, covalent, ionic,
hydrogen bond or Vander Waals force in character.
 The size of nanocluster ranges from sub-nanometer to 10 nm in
diameter. It has been found that clusters of certain critical size
(clusters with a certain number of atoms in the group) are more
stable than others.
 Nanoclusters consisting of up to a couple of hundred atoms, but
larger aggregates containing 10 3 or more atoms are called
nanoparticles.
 In some materials, certain collections of atoms are more preferred due to energy
minimization and exhibiting stable structures and providing unique properties to
the materials.
 These collections of atom providing stable structures to the materials are called
as MAGIC NUMBER.
 Magic number: The number of atoms in the clusters of critical sizes with higher
stability.
 For example, one of the combination of 55 atoms of gold provides stable
structure and hence its magic number is 55.
 For this combination, surface area is minimized. By further adding/removing any
atom leads to the increase in surface to volume ratio. So, in this sense, gold
prefers to form a clusters of 55 atoms which is a stable geometrical structures
due to local minimum. This is called as magic number and is arbitrary number.
 These crystals have certain unique properties and can be used for certain specific
applications.
Production of Nano Cluster

Fig 7.7 Production of nano clusters from atoms or

molecules or from bulk materials
 Clusters can be produced from atomic or molecular constituents or
from the bulk materials as shown in the figure. Atomic clusters or
molecular clusters are formed by nucleation of atoms or molecules
respectively. Clusters of the same type may be obtained by top down
process also.
Sources of Clusters
There are many kinds of cluster sources. Two of them are
1. Supersonic nozzle source
2. Gas-aggregation source