Unit 4 Lecture Notes
Unit 4 Lecture Notes
Course Outcomes
At the end of the course the student will be able to.
Apply the knowledge of nanotechnology for societal applications
Introduction to nanotechnology:
The prefix ‘nano’ is referred to a Greek prefix meaning ‘dwarf’ or something very small and
depicts one thousand millionth of a meter (10−9 m).
As a comparison, a single human hair is 80,000 nm diameter and the DNA has a radius of 1
nm.
Nanoscale: 1-100 nm. A nanometer (10-9m) is one billionth of a meter, roughly the width of
three or four atoms. The diameter of average human hair is about 80 μm (80,000 nanometers)
Nanomaterials: Materials in which a single unit is between 1 and 100 nm (in at least one
dimension). These materials can be synthesized to play a specific role making them useful in
various industries, from healthcare and cosmetics to environmental preservation and air
purification.
Origin of Nanotechnology
The idea of nanotechnology was first discussed in 1959 by Richard Feynman in his talk
“There's Plenty of Room at the Bottom”, in which he described the possibility of synthesis via
direct manipulation of atoms.
The term "nano-technology" was first used by Taniguchi in 1974. Inspired by Feynman's
concepts, Drexler used the term "nanotechnology" in his 1986 book Engines of Creation: The
Coming Era of Nanotechnology. Also in 1986, Drexler co-founded “The Foresight Institute”
to help increase public awareness and understanding of nanotechnology concepts.
Surface area to volume ratio (SA/V)
The Surface Area /volume (SA/V) ratio increases as side length reduces (particle size
decreases).
There is change in properties of materials due to increased surface area to volume ratio.
Reactions take place at the surface of a material. A particle with a high surface area has a
greater number of reaction sites than a particle with low surface area, and thus, results in higher
chemical reactivity.
6𝑎2 6
SA/V ratio of cube = =𝑎
𝑎3
4𝜋𝑟 2 3
SA/V ratio of Sphere = 4 =𝑟
𝜋𝑟 3
3
2𝜋𝑟 2 +2𝜋𝑟ℎ 2 2
SA/V ratio of cylinder = =𝑟+ℎ
𝜋𝑟 2 ℎ
Numerical examples:
1.
SA/V = 2
Reduce side to 1 cm
6
SA/V = 1
SA/V = 6
As the cube side reduced from 3cm to 1 cm, the SA/V ratio increased from 2 to 6.
Examples:
Carbon-based materials: These are composed of carbon, taking the form of hollow spheres,
ellipsoids or tubes etc.
3-D carbon-based material: Graphite is a crystalline form of the element carbon with its
atoms arranged in a hexagonal structure.
Uses of graphite:
• Pencil lead
• Lubricant
• Electrodes in batteries
• Brake linings for heavy vehicles
1-D Carbon-based material: Carbon nanotubes (CNTs) are cylindrical molecules that
consist of rolled-up sheets of single-layer carbon atoms (graphene). They can be single-walled
(SWCNT) with a diameter of less than 1 nm or multi-walled (MWCNT), with diameters more
than 100 nm and length several micrometers or even millimeters.
Carbon nanotubes rope together via van der Waals forces, and form ultra-high strength, low-
weight materials that possess highly conductive electrical and thermal properties. This makes
them highly attractive for numerous applications.
CNT Applications:
Quantum dots can increase the efficiency of solar cells. In normal solar cells, a photon of
light generates one electron. Experiments with both silicon quantum dots and lead sulfide
quantum dots can generate two electrons for a single photon of light. Therefore, using
quantum dots in solar cells could significantly increase their efficiency in producing electric
power.
• Single-electron transistors
• solar cells
• LEDs
• Lasers
• quantum computing
• medical imaging.
Quantum Confinement
Two-dimensional electrons
nz
2D confinement: carriers are free to move in one direction e.g. Quantum Wire
ny
Confined in 2 Directions: Quantum wire
One-dimensional electrons nz
3D-confinement: carriers are confined in all directions e.g. C-60
Quantum confinement influences the nanomaterial properties such as electrical, optical and
mechanical behaviour of material.
Nanomaterials-Synthesis
There are two ways to produce nanomaterials.
Top-down approach: To start with a bulk material and then break it into smaller pieces using
mechanical, chemical or other form of energy. Top-down approach refers to slicing or
successive cutting of a bulk material to get nano sized particle. Example: Attrition or Ball
Milling.
Bottom-up approach: To synthesize the material from atomic or molecular species via
chemical reactions, allowing particles to grow in size. Bottom-up approach refers to the buildup
of a material from the bottom: atom by atom, molecule by molecule or cluster by cluster.
Example: colloidal dispersion, sol-gel processing, Chemical vapor deposition, atomic layer
deposition, Electrodeposition and electroless deposition, Pulsed laser deposition.
Bottom-up methods
Sol-Gel method
The process starts with a chemical solution which acts as the precursor for a gel of particles.
Precursors are raw materials which undergo various forms reactions. The sol evolves towards
the formation of a gel-like system containing both a liquid phase and solid phase.
Fluid may be removed by allowing time for sedimentation to occur, and then pouring off the
remaining liquid. Centrifugation can also be used to accelerate the process of phase separation.
Removal of the remaining liquid requires a drying process. Afterwards, final sintering, a
thermal treatment is necessary to enhance mechanical properties, for densification and grain
growth. One of the advantages of using this method is that densification is achieved at a much
lower temperature.
Precipitation
Precipitation is the formation of a solid in a solution during a chemical reaction. When the
reaction occurs in a liquid, the solid formed is called the precipitate, and the liquid remaining
above the solid is called the supernate. Powders derived from precipitation are also known as
flowers.
During chemical reactions, precipitation occurs if an insoluble substance is introduced into a
solution and the density happens to be greater. With soluble substances, precipitation is
accelerated once the solution becomes supersaturated.
An important stage of the precipitation process is the onset of nucleation. Nucleation is the first
step in the formation of a new structure via self-assembly.
Methods of precipitation include settling or sedimentation, where solid forms over a period of
time due to gravity or centrifugation.
Finally, the solution is filtered and the resultant nano-powder is calcined.
Combustion
In the physical vapour deposition method atoms transfer from a target to vapour to substrate.
Top-Down method
Ball milling
A ball mill, a type of grinder, is a cylindrical device used in grinding and mixing materials.
Ball mills rotate around a horizontal axis, partially filled with the material to be ground plus
the grinding medium. Ceramic balls or stainless steel balls are used as media. An internal
cascading effect reduces the material to a fine powder. The smaller the media particles, the
smaller the particle size of the final product.
In ball milling, also called mechanical crushing, small steel balls are allowed to rotate
around the inside of a drum and then fall on a solid with gravitational force and crush the solid
into nanoparticles. The grinding is also carried out with different fluids like ethylene glycol,
xyline, butanol and water with surface active agent (surfactant). The size of the nanoparticle
obtained in this process depends on many factors like grinding hours, the weight ratio of the
steel balls, fluid media etc. Ball milling can be used to prepare a wide range of elemental and
oxide powders. Ball milling is the preferred method for preparing metal oxides.
There are certain disadvantages with ball milling method. The nanoparticles prepared
with ball milling are contaminated with the material of the balls. Most of the cases it is difficult
to obtain uniform particle size. These problems can be overcome with bottom-up approach.
Characterization techniques:
Characterization refers to the study of material’s features such as its composition, structure,
particle size, etc. Example of characterization techniques are X-Ray Diffraction (XRD),
Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM).
XRD works by illuminating a material with incident X-rays and then measuring the
intensities and scattering angles of the X-rays that leave the material.
Crystal atoms scatter incident X-rays through interaction with the atoms’ electrons. A regular
array of atoms produces a regular array of spherical waves. These waves add constructively
when Bragg’s law is satisfied.
Where d is the spacing between diffracting planes, θ is the incident angle, n is an integer, and
λ is the wavelength of x-ray.
X-ray diffractometers consist of three basic elements: an X-ray tube, a sample holder, and an
X-ray detector.
When the geometry of the incident X-rays striking the sample satisfies the Bragg Equation,
constructive interference occurs and a peak in intensity occurs. A detector records this X-ray
signal.
𝑘𝜆
Scherrer Formula: D=
𝛽𝐶𝑜𝑠 𝜃
Where, D = Average Crystallite size, β = Width at half maxima, θ = Bragg angle, λ = X-Ray
wavelength and k is a constant (called the shape factor) depending on the shape of the
sample. If particles are spheres :k: 0.89, if cubes : k: 0.91
Applications
1. X-ray powder diffraction is most widely used for the identification of unknown
crystalline materials
2. characterization of crystalline materials and determine crystal structures
3. identification of fine-grained minerals such as clays and mixed layer clays that are
difficult to determine optically
4. determination of unit cell dimensions
5. measurement of sample purity
6. determining the thickness, roughness and density of the film
Strengths
1. Powerful and rapid (< 20 min) technique for identification of an unknown mineral
2. it provides an unambiguous mineral determination
3. Minimal sample preparation is required
4. Data interpretation is relatively straight forward
Limitations
Secondary and backscattered electrons are used to produce an image. The secondary
electrons are emitted from the specimen detect the topography of the material while the
backscattered electrons show the composition of the elements of the material.
Construction:
The electrons are emitted from the electron source and allowed to move in a fast motion to
the anode, which is a positive charge plate.
Scanning by this microscope is attained by tapering a beam of electrons back and forth over a
thin section of the microscope.
The beam of electrons interacts with the specimen to produce signals that give information
about the surface topography and composition of the specimen.
When the secondary electrons reach and enter the detector, they emit flashes of light which
get converted into an electric current by a photomultiplier, sending a signal to the cathode ray
tube. This produces an image that looks like a television picture that can be viewed and
photographed.
The quantity of secondary electrons that enter the detector is defined by the nature of the
specimen i.e raised surfaces to receive high quantities of electrons, entering the detector
while depressed surfaces have fewer electrons reaching the surface and hence fewer electrons
enter the detector. Therefore, raised surfaces will appear brighter on the screen while
depressed surfaces appear darker.
Applications of the Scanning Electron Microscope (SEM)
Limitations
This is a powerful electron microscope that uses a beam of electrons to focus on a specimen
producing a highly magnified and detailed image of the specimen.
The magnification power is over 2 million times better than that of the light microscope,
producing the image of the specimen which enables easy characterization of the image in its
morphological features and compositions.
TEM uses a beam of electrons to focus on the specimen, to produce an image. TEM can be
used to detail the internal structures of the smallest particles.
1. Electron gun
2. Image producing system
3. Image recording system
Electron gun
This is the part of the Transmission Electron Microscope responsible for producing electron
beams. It also has two condenser lens system which focus the electron beam on the specimen.
It’s made up of the objective lens, a movable stage to hold the specimen and projector lenses.
They function by focusing the passing electrons through the specimen forming a highly
magnified image.
The objective has a short focal length of about 1-5mm and it produces an intermediate image
from the condenser which are transmitted to the projector lenses for magnification.
Image-Recording System
It’s made up of the fluorescent screen used to view and to focus on the image. They also have
a digital camera that permanently records the images.
Working:
Electron gun produces electrons that get focus on the specimen by the condenser lenses.
Magnetic lenses are used to focus the beam of electrons of the specimen. By the assistance
offered by the column tube of the condenser lens into the vacuum creating a clear image, the
vacuum allows electrons to produce a clear image without collision with any air molecules
which may deflect them.
On reaching the specimen, the specimen scatters the electrons focusing them on the magnetic
lenses forming a large clear image, and if it passes through a fluorescent screen it forms a
polychromatic image.
• It has a very powerful magnification of about 2 million times that of the Light
microscope.
• It can be used for a variety of applications ranging from basic Biology to
Nanotechnology, to education and industrial uses.
• It produces very efficient, high-quality images with high clarity.
• It can produce permanent images.
• It is easy to train and use the Transmission Electron Microscope
Applications
Disease and ill health are caused largely by damage at the molecular and cellular level.
Nanotechnology involves manipulating properties and structures at the nanoscale, involving
dimensions that are just tiny fractions of the width of a human hair. One area of nanotechnology
application providing great benefits in the future is in medicine
1. Drug Delivery
3. Therapy Techniques
Buckyballs may be used to trap free radicals generated during an allergic reaction and block the
inflammation that results from an allergic reaction. Nanoshells may be used to concentrate the heat
from infrared light to destroy cancer cells with minimal damage to surrounding healthy cells.
4. Providing oxygen
Another application would be to provide metabolic support in the event of impaired circulation. Poor
blood flow, caused by a variety of conditions, can result in serious tissue damage. A major cause of
tissue damage is inadequate oxygen. A simple method of improving the levels of available oxygen
despite reduced blood flow would be to provide an "artificial red blood cell." A simple design: a sphere
with an internal diameter of 0.1 microns (100 nanometers) filled with high pressure oxygen at ~1,000
atmospheres (about 10^8 pascals). The oxygen would be allowed to trickle out from the sphere at a
constant rate.