2023 - 24 — Semester-I CSD-B — Nanoscience

Nanoscience

1 Introduction

Nanotechnology is the use of matter on an atomic, molecular, and supramolecular scale for
industrial purposes. Nanotechnology may be able to create many new materials and devices
with a vast range of applications, such as in nanomedicine, nanoelectronics, biomaterials
energy production, and consumer products.
Nanomaterials are the nanostructured materials having a characteristic length less than
100nm. Nanomaterials can exist in zero dimension (e.g. clusters), one dimension (e.g.
thin films, surface coatings), two dimensions (e.g. nanowires and nanotubes) and three
dimensions (e.g. quantum dots, nanocrystalline materials). In nano regime, two principal
factors cause the properties of nanomaterials to differ significantly from other materials.
These are:

1. Increased Relative Surface Area

2. Quantum Confinement Effect

2 Surface area to Volume ratio

Nanomaterials have a relatively larger surface area, when compared to the same volume.
Let us consider a sphere of radius ‘r’.
Surface Area = 4πr2
Volume = 43 πr3
Hence, the surface to volume ratio for a sphere will be

S 4πr2 3
= 4 3 = (1)
V 3
πr r

The smaller the radius/size of any material, higher the surface area. Thus nanoparticles
have a much greater surface area as compared with larger particles. It makes materials
more chemically reactive. This affects their strength or electrical properties hence they are
used mainly in sensors.
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A characterization parameter for the effectiveness of a nanoparticle is the ratio of its

surface area to its volume. Explain with example of a cube.
Let us consider an example. For a one cubic volume shown in figure, the surface area is
6m2 . When it is divided into eight pieces its surface area becomes 12m2 . When the same

volume is divided into 27 pieces its surface area becomes 18m2 . Thus when given volume
is divided into smaller pieces, the surface area increases. Hence as particle size decreases,
a greater proportion of atoms are found at the surface compared to those inside. Thus
nanoparticles have a much greater surface area compared with larger particles

3 Quantum Confinement effect

When atoms are isolated the energy levels are discrete. However, when very large numbers
of atoms are closely packed to form a solid, the energy levels form bands. Nanomaterials
represent intermediate stage.
When size of dimensions of the nano material comes in the range of 1-10 nm, which
is same as that of deBroglie wavelength of electrons, quantum confinement effect will
come into picture. Quantum confinement is change of electronic and optical properties
when the material samples is of sufficiently small size - typically 10 nanometers or less.
This results splitting of energy levels in quantum dots. Semiconductor band gap increases
with decrease in size of the nanocrystal. Quantum confinement of electronic particles in
nanocrystals produces unique optical and electronic properties that have the potential to
enhance the power conversion efficiency of solar cells for photovoltaic.

4 Synthesis of Nanomaterials
There are various ways to synthesize nanomaterials. Each method has its own set of
processes, advantages and disadvantages. The method can be as simple as spin or dip
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Figure 1: Quantum confinemtn effect in quantum dots

coating method to complicated such as Molecular Beam epitaxy, Pulse Laser deposition.
Discussing all type of deposition method is out of scope of this syllabus. We will discuss
the following popular methods to synthesize nanomaterials.

1. Top-Down fabrication methods

• Ball Milling method

• Chemical Vapour Deposition

2. Bottom-up fabrication methods

• Sol-Gel Method

• Combustion method

4.1 Ball milling (Top Down) method

Ball milling, also called mechanical crushing is a popular method to synthesize nanopowders
of various solid materials. This comes under Top-Down approach of nanomaterial synthesis.
The following is the process flow to synthesize nanomaterial by ball milling method.
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Figure 2: Ball milling method

• It consist of a drum which can rotate coaxially. The materials in raw form (big
particle size) which need to be grinded into the nanoform has to be taken inside the
drum.

• The grinding medium is usually iron balls or zirconia beads. They come with various
diameter.

• A mixing medium is also required in most of the cases. Usually Ethyl Alcohol,
Acetone, Distilled water is used for this purpose.

• The milling machine connected to a motor which will rotate the drum containing raw
powder, beads at high RPM, which results formation of nanopowder.

• Ball milling takes typically much time (8 hours - 24 hours) in order to obtain fine
nanopowder.

• By changing the RPM, duration of milling, size of zirconia bead, we can control the
average particle size in nanopowder.

Advantages

• Ease of synthesis

• Low cost
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• Non-toxic

• Loe temperature processing

Disadvantages

• Time consuming

• Loss of materials

• Chances of contamination is more

• Non-uniform particle size distribution

4.2 Chemical vapour deposition (Top Down)

Chemical Vapor Deposition (CVD) is a chemical process is a whereby a thin solid film is
deposited onto a substrate through chemical reactions of the gaseous species. For structural
component applications, the deposition typically takes place at a temperature of around
1000o C.
Figure 3 gives a typical example of a CVD system, where reactant gases, normally
called precursor gases of CH3SiCl3 and H2, are delivered into a reaction chamber at a
suitably determined temperature. As they pass through the reactor these gases come into
contact with a heated substrate; they then react and form a solid SiC layer deposited onto
the surface of a substrate. Usually, an inert gas, such as Ar, is used as a diluent gas.
The depositing temperature and pressure are the critical parameters in this process. After
the reactions, the exhaust gases containing HCl species are trapped by NaOH and then
condensed by liquid N2 trap before being released into the atmosphere.

Advantages

• Versatile- any element or compound can be deposited

• High purity can be obtained

• High density – nearly 100% of the theoretical value

• Economical in production, since many parts can be coated at the same time.
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Figure 3: Chemical vapour deposition

Disadvantages

• High deposition temperatures (usually greater than 600o c)

• Restrictions on the kind of substrates that can be coated.

• Chemical and safety hazards caused by the use of toxic, corrosive, explosive precursor.

4.3 Sol-gel (Bottom Up) Method

The sol–gel process represents the chemical transformation of a system from a liquid “sol”
(mostly a colloidal suspension of particles) into a gelatinous network “gel” phase with sub-
sequent post-treatment and transition into solid oxide material. This sol-gel process is well
adapted for composite nanopowder (NP) synthesis, and oxide NPs Certain experimental
conditions are required in the Sol-Gel method such as specific reaction time, temperature,
solution concentration, stoichimetry. Figure 4 shows the step by step process to synthesize
nanomaterials.

• We start with reactants of suitable stoichiometry. The solution is mixed well in a

magnetic stirrer.

• For a uniform mixture the stirring process may take few hours.

• The solution is kept for ageing, inorder to deposit thin film by dip or spin coating
method.

• In order to synthesize nanopowders, suitable combustion source is added to the so-

lution. Usually Glycin, Urea are used.
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• The solution is heated at suitable temperature in order to get NP ashes. The ashes
are collected, grinded in mortar and pestle in order to get the desired nanopowder.

• Typical sizes of particles produced by this method are 5-30 nm

Figure 4: Process flow of sol-gel method

Advantages

• Less time consuming as compared to ball milling method

• Uniform size distribution

• Doping is easy

• Low temperature densification

Disadvantages

• Toxic gasses evolves in some reaction

• Cost of raw materials can be high

• Chances of contamination is more

• Non-uniform particle size

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4.4 Combustion method (Bottom Up)

Combustion synthesis (CS), or self-propagating high-temperature synthesis (SHS), is an

effective, lowcost method for production of various oxide materials. Recently, CS has
become a very popular approach for preparation of nanomaterials. Combustion synthesis is
a method for producing both inorganic and organic compounds by exothermic combustion
reactions in solids of different nature. Reactions can occur between a solid reactant coupled
with either a gas, liquid, or other solid. If the reactants, intermediates, and products are
all solids, it is known as a solid flame. If the reaction occurs between a solid reactant
and a gas phase reactant, it is called infiltration combustion. Since the process occurs at
high temperatures, the method is ideally suited for the production of refractory materials
including powders, metallic alloys, or ceramics.
The classification of CS processes is generally based on the physical nature of the initial
reaction medium:

• Conventional CS used as initial reactants in solid state (condensed phase combustion)

• SCS is processing where the initial reaction medium is aqueous solution.

• Synthesis of nanoparticles in flame is known as gas-phase combustion

5 Characterization techniques

5.1 X-ray diffraction

X-ray diffraction (XRD) is a non-destructive type of analytical technique which provides

valuable insight about the lattice structure of a crystalline substance like unit cell dimen-
sions, bond angles, chemical composition and crystallographic structure of natural and
manufactured materials. XRD is based on the principle of constructive interference of
x-rays by crystalline materials which is the sample concerned. The x-rays which are gen-
erated by a cathode ray tube (CRT) are filtered, collimated and then directed towards
the sample. The interaction of the incident rays with the sample produces constructive
interference of diffracted rays when conditions satisfy the Bragg’s Law as given by

2dsinθ = nλ (2)
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where d is the spacing between diffracting planes, θ is the incident angle (or diffraction
angle), n is an integer, and λ is the beam wavelength.

Figure 5: Schematic representation of Bragg’s law conditions.

Consider a crystal with crystal lattice planar distances d. Where the travel path length
difference between the ray paths 1P1’ and 2Q2’ is an integer multiple of the wavelength,
constructive interference will occur for a combination of that specific wavelength, crystal
lattice planar spacing and angle of incidence.
The path difference can be written as from the Fig 5,

SQ + QT = nλ (3)

Where SQ = dsinθ and QT = dsinθ. Hence the final the equation becomes

2dsinθ = nλ (4)

The Bragg’s law relates the wavelength of electromagnetic radiation to the diffraction
angle and the lattice spacing in a crystalline sample. These diffracted X-rays are then
detected, processed and counted. By changing the geometry of the incident rays, the
orientation of the centered crystal and the detector, all possible diffraction directions of
the lattice should be attained.
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5.2 Application of X-ray diffraction

1. Determine the structural properties

• Lattice parameters

• Grain size

• Strain

• Phase composition

2. Measure thickness of thin films and multi-layers

3. Identify crystalline phases and orientation

6 Scanning Electron Microscopy

The Scanning Electron Microscope (SEM) is an electron microscope that uses high energy
accelerating electrons instead of light (photons) to form an image of a sample by scanning
the surface with a focused beam of electrons. In SEM, 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 fields and lenses, which focus the beam down toward the sample shown in
Fig 6. Once the beam hits the sample, electrons and X-rays are ejected from the sample.
Actually, the electrons-sample interaction creates signals in the form of secondary electrons,
backscattered electrons and various rays that are characteristic of the sample.
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Figure 6: Scanning Electron Microscope

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Figure 7: Interaction of electrons with the sample

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 final image. The secondary electrons are emitted from the specimen play
the primary role of detecting the morphology and topography of the specimen while the
backscattered electrons show contrast in the composition of the elements of the specimen.

6.1 Applications of the SEM

1. Obtain the microstructural informatipn and surface/bulk chemical analysis.

2. Determine causes of failures in wide variety of materials.

3. Inspection of semiconductors

4. Eliminate backlogs with rapid analysis of drugs, trace evidence, explosives and etc.
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7 Transmission Electron Microscopy

Transmission electron microscope (TEM) has three essential components: (1) an electron
gun, which produces the electron beam, and the condenser system, which focuses the beam
onto the object, (2) the image-producing system, consisting of the objective lens, movable
specimen stage, and intermediate and projector lenses, which focus the electrons passing
through the specimen to form a real, highly magnified image, and (3) the image-recording
system, which converts the electron image into some form perceptible to the human eye.

Figure 8: Transmission Electron Microscope

Electrons can interact with the samples in two ways: scattering elastically or inelas-
tically. Elastic scattering produces back-scattered electrons (BSE) whereas inelastic pro-
duces secondary electrons (SE). BSEs are incidentally scattered by the specimen atoms,
and typically deflect in larger angles with little energy loss. SEs are ejected from the
specimen atoms in smaller angles and less energy as kinetic energy is transferred to the
specimen atoms. The major difference is that BSEs come from the microscope electron
beam, whereas SEs come from the sample itself. BSEs are used for elemental composition
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contrast, and SEs for topographic contrast. A vacuum environment is required in a TEM
because collisions between high-energy electrons and air molecules significantly absorb elec-
tron energy. Other issues include phonon scattering from the atomic lattice vibrations, and
the inner shell electrons being ejected (called Auger-electrons). Same theory can be found
in the SEM in different wording, and schematic diagram.
The image produced by the TEM, called a micrograph, is seen through projection
onto a screen that is phosphorescent. TEM can be used to observe particles at a much
higher magnification and resolution than can be achieved with a light microscope because
wavelength of an electron is much shorter than that of a photon. Resolution in microscopy is
limited to about 1/2 of the wavelength of the illumination source (photon/electron beam)
used to image the sample. Because our eyes can only detect photons with wavelengths
greater than ∼400 nm, the best resolution that can be achieved by light microscopes is
about ∼200 nm.

7.1 Applications of TEM

1. Microstructural analysis of metals and alloys using high-resolution images.

2. Study of the structure and texture of crystals and metals at molecular level.

3. Identification of flaws, fractures and damages to micro sized objects.

8 Applications of nano materials

1. Next-Generation Computer Chips

2. Kinetic Energy Penetrators with Improved Lethality

3. Better Insulation Materials

4. Phosphors for High-Definition TV

5. Low-Cost Flat-Panel Displays

6. Tougher and Harder Cutting Tools

7. Elimination of Pollutants
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8. High Energy Density Batteries

9. High-Power Magnets

10. High-Sensitivity Sensors

11. Automobiles with Greater Fuel Efficiency

12. Aerospace Components with Enhanced Performance Characteristics

13. Better and Future Weapons Platforms

14. Longer-Lasting Satellites

15. Longer-Lasting Medical Implants

16. Ductile, Machinable Ceramics

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1. Why light scattered by different sized nanoparticles appear different in colour?

As the bandgap of nanoparticles depends on their size (i.e., Eg is inversely propor-
tional to particle size), they scatter light of different colours.

2. Why nanomaterials show different physical and chemical properties than its bulk
form?
Because of finite size effect and high surface to volume ratio of nanomaterials com-
pared to its bulk form.

3. What are the two important characteristics of nanomaterials?

Finite size effect and high surface to volume ratio.

4. Does interatomic distance of a material changes upon reduction of size to nano scale?
No, as atomic separation scale (Å=10 nm) is one order smaller than nano meter scale

5. Which category/approach includes Sol-gel method for nanomaterial synthesis?

A) Ball Milling
B) Top Down
C) Bottom Up
D) Up-Down

6. Why resolving power of electron microscope is more compared to optical microscope?

Because according to deBroglie hypothesis the wavelength of high energy electrons
is less compared to visible light. (λ=h/mv)

7. Find out which cell has greater S/V ratio if Cell Y has a surface area of 40 µm2 , and
a volume of 8 µm3 , while, Cell Z has a surface area of 72 µm2 and a volume of 12
µm3 ?
S/V=40/8=5 µm−1 and S/V=72/12=6 µm−1

8. Find the condition for Bragg’s law?

A) nλ = 2d sin θ
B) nλ = 2d sin 2θ
C) nλ = 2d cos θ
D) nλ = 2d cos 2θ
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9. Write down the S/V for cube?

Surface are of the cube: 6a2
Volume of the cube: a3
S/V for cube: 6/a

10. What is quantum confinement effect?

When the size of nanoparticles comes in the range of 1-10 nm, which is same as
that of deBroglie wavelength of electrons, quantum confinement effect will come into
picture.

11. What is the difference between XRD and TEM?

XRD provides information about the crystal structure, lattice parameters, and phase
composition of the sample, but it does not provide direct information about the size
or shape of individual particles.
TEM can provide detailed information about the size, shape, and distribution of
particles, and morphology of the material and defects in the material.

12. What parameters are influencing the depth of the transmission electron microscope?
Depending on the energy of the electron beam and the properties of the sample being
studied.

13. Define the centrifugal force and Coriolis force? Centrifugal force is a force that
appears to act on an object moving in a circular path. The Coriolis force is a force
that appears to act on objects that are in motion relative to a rotating reference
frame

14. What is the particle size in ball milling and sol-gel method?
Around 0.2 -1 µm and 5 - 30 nm

15. Write down the techniques for top-down and bottom-up strategy?
Top-Down: Ball milling
Bottom-up: Sol-gel

16. Why are X-rays not deflected by electric and magnetic field?
Since X-rays do not contain any charged particles, they do not deflect these beams.
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17. Define X-rays?

X-rays are an electromagnetic wave with wavelengths from 0.1 Å to 100 Å called
X-rays.

18. Write the examples of 1D, 2D and 3D nano materials?

1D – Nano wires and Nano tubes
2D – Thin film
3D – Polycrystals

19. Why are TEM images in black and white/grey scale?

The electron microscope has a beam of monochromatic electrons with an extremely
short wavelength; there are no visible wavelength colors to visualize. Color images
from electron microscopes have been pseudo-colored using computer software to in-
crease contrast or to help the viewer study the image.