Unit I:

Basics and Scale of Nanotechnology

Introduction and scientific revolutions, Time and length scale in structures, Definition of a Nano
system, Dimensionality and size-dependent phenomena, Surface to volume ratio, Fraction of surface
atoms and surface energy, Surface stress and surface defects, Properties at the nanoscale – optical &
mechanical, Properties at nanoscale – electronic & magnetic.

Introduction to Nanotechnology Definitions

• Nanoscience is the study of phenomenon and manipulation of materials at atomic, molecular
and macro-molecule scales, where properties differ significantly from those at large scale.
• Nanotechnology is the branch of science and engineering which deals with creation of
materials, devices and systems through the manipulation of individual atoms and molecules.
• Nanotechnologies are the design, characterization, production and application of structures,
devices and systems by controlling shape and size at nanometer scale
• The goal of nanotechnology is to control individual atoms and molecules to create computer
chips and other devices that are thousands of times smaller than current technologies limit.
Nanotechnology involves the understanding and control of matter at the nanometer-scale. The
so-called nanoscale deals with dimensions between approximately 1 and 100 nanometers.
The prefix “Nano” is derived from the Greek word which means “Dwarf”. • One nanometer is
equal to one billionth of meter (10-9).
Nanometre Scale:
A nanometre (nm) is 10⁻⁹ metres, which is one-thousandth of a micrometre, or one-billionth of a
metre. This is the scale at which we measure atoms and the molecules they make
Nanoscience and nanotechnology are the study and application of extremely small things and
can be used across all the other science fields, such as chemistry, biology, physics, materials
science, and engineering.
Here are a few illustrative examples:

 There are 25,400,000 nanometers in an inch

 A sheet of newspaper is about 100,000 nanometers thick
 On a comparative scale, if a marble were a nanometer, then one meter would be the size
of the Earth
The chart starts with objects that can be seen by the unaided eye, such as an ant, at the top of the
chart, and progresses to objects about a nanometer or less in size, such as the ATP molecule used
in humans to store energy from food.
Now that you have an idea of how small a scale nanotechnologists work with, consider the
challenge they face. Think about how difficult it is for many of us to insert thread through the
eye of a needle. Such an image helps you imagine the problem scientists have working with
nanoparticles that can be as much as one millionth the size of the thread. Only through the use of
powerful microscopes can they hope to ‘see’ and manipulate these nano-sized particles.
Nano meter scale:

• At the nanoscale, the physical, chemical, and biological properties of materials differ in
fundamental and valuable ways from the properties of individual atoms and molecules or bulk
matter
. • Nanoscale science and technology i.e. Nanotechnology is a young and burgeoning field that
encompasses nearly every discipline of science and engineering.
• Nanotechnology is truly a multidisciplinary, interdisciplinary and multifunctional field. Today,
chemists, physicists, medical doctors, engineers, biologists and computer scientists are working
and collaborating for the development of Nanotechnology
Applications of Nanotechnology:
Nanotechnology is helping to considerably improve, even revolutionize, many technology and
industry sectors: information technology, homeland security, medicine, transportation, energy,
food safety, and environmental science, among many others

History of nanotechnology:
The first ever concept was presented in 1959 by the famous professor of physics Dr. Richard P.
Feynman.about Nanotechnology.
Richard Feynman’s famous presentation “There’s Plenty of Room at the Bottom” was in the
1959 at the American Physical Society. Here he asked:
•Why can’t we manipulate materials atom by atom?
• Why can’t we control the synthesis of individual molecules?
•Why can’t we write all of human knowledge on the head of a pin?
•Why can’t we build machines to accomplish these things?
• The term “Nano-technology” had been coined by Norio Taniguchi in 1974
• Feynman solicit the Physicists in 1959 “to make the electron microscope 100 times better”.
This was achieved about 22 years later.
 Invention of the scanning tunneling microscope in 1981 and the discovery of
fullerene(C60) in lead to the emergenceof nanotechnology

• Not only seeing the atoms but also their manipulation became a reality in 1981 when Gerd
Binnig and Heinrich Rohrer of IBM, Zurich Research Laboratory invented the Scanning
Tunneling Microscope (STM) for which they were awarded Noble Prize in 1986.
• In 1985 Binnig along with Gerber and Quate invented the Atomic Force Microscope (AFM)
which did not require the specimen to be conducting. At very small sizes physical properties
(magnetic, electric and optical) of materials can change dramatically.
.The early 2000s also saw the beginnings of commercial applications of nanotechnology,
although these were limited to bulk application of nanomaterials.
Silver nano platform for using silver- nanoparticles as an antibacterial agent , nanoparticle-based
transparent sunscreens, and carbon nanotubes for stain-resistant textiles.
What is nanomaterial?
• Is defined as any material that has unique or novel properties, due to the nanoscale ( nano
metre- scale) structuring.
• These are formed by incorporation or structuring of nanoparticles.
• They are subdivided into nanocrystals, nano powders, and nanotubes: A sequence of nanoscale
of C60 atoms arranged in a long thin cylindrical structure Nanomaterial properties can be ‘tuned’
by varying the size of the particle (e.g. changing the fluorescence colour so a particle can be
identified)
Examples of Nanomaterials
•Examples:
• Amorphous silica fume (nano-silica) in Ultra High Performance Concrete – this silica is
normally thought to have the same human risk factors as non-nano non-toxic silica dust
• Nano platinum or palladium in vehicle catalytic converters - higher surface area to volume of
particle gives increased reactivity and therefore increased efficiency
• Crystalline silica fume is used as an additive in paints or coatings, giving e.
Dimensionality and size-dependent phenomena
Classification is based on the number of dimensions, which are not confined to the nanoscale
range (¡100nm)
1) Zero dimensional (0-D)
2) One- dimensional (1-D)
3) two-dimensional (2-D)
4) Three dimensional (3-D)
Zero dimensional nanomaterials
Materials wherein all the dimensions are measured within the nanoscale • The most common
representation of zero dimensional nanomaterilas are nano dots
One dimensional nanomaterials
• One dimension is outside the nanoscale and other two dimensions are in the nanoscale • This
leads to needle like-shaped nanomaterials
• 1-D materials include nanotubes, nanorods and nanowires.
• 1-D nanomaterials can be
• Amorphous or crystalline
• Single crystalline or poly crystalline
• Chemically pure or impure
• Metallic, ceramic or polymeric.
Two dimensional materials
One dimension lies in the nanometer range and other two dimensions are not confined to the
nanoscale
• 2D nanomaterials exhibit plate like shapes
• Two dimensional nanomaterials include nanofilms, nanlayers and nanocoatings.
Three dimensional materials
Three dimensional materials are not confined in the nanoscale in any dimension.
These materials are thus characterized by having three arbitrarily dimensions above 100nm
• Materials possess a nanocrystalline structure or involve the presence of features at the
nanoscale
Nanomaterials’ Characteristics

Category of nanomaterials example

One- dimensional Nanomaterial layers, multi-layers, thin films,
platelets and surface coatings. They
have been developed and used for
decades, particularly in the electronics
industry.
Two -dimensional Nanomaterial nanowires, nanofibres made from a
variety of elements other than carbon,
nanotubes and, a subset of this group,
carbon nanotubes.
Three- dimensional Nanomaterial are known as nanoparticles and
include precipitates, colloids and
quantum dots (tiny particles of
semiconductor materials), and
Nanocrystalline materials

Quantum effects
• The overall behavior of bulk crystalline materials changes when the dimensions are reduced to
the nanoscale.
• For 0-D nanomaterials, where all the dimensions are at the nanoscale, an electron is confined
in 3D space. No electron delocalization (freedom to move) occurs.
• Fr 1D nanomaterials, electron confinement occurs in 2D whereas delocalization takes place
along the long axis of then nanowirenanorod/nanotube
 • In the case of 2D nanomaterials, the conduction electrons will be confined across the thickness
but delocalized in the plane of the sheet
Electrons confinement
• For 0D nanomaterials the electrons are fully confined.
• For 3D nanomaterials the electrons are fully delocalized
• In 1D and 2D nanomaterials, electron confinement and delocalization coexist.
• The effect of confinement on the resulting energy states can be calculated by quantum
mechanics as the particle in the box problem. A electron is considered to exist inside of an
infinitely deep potential well from which it cannot escape and is confined by the dimensions of
the nanostructure
Manipulation of Atoms
• Feynman solicit the Physicists in 1959 “to make the electron microscope 100 times better”.
This was achieved about 22 years later.
• Not only seeing the atoms but also their manipulation became a reality in 1981.
when Gerd Binnig and Heinrich Rohrer of IBM, Zurich Research Laboratory invented the
Scanning Tunneling Microscope (STM) for which they were awarded Noble Prize in 1986.
• In 1985 Binnig along with Gerber and Quate invented the Atomic Force Microscope (AFM)
which did not require the specimen to be conducting
Benefits of Nanotechnology
• “The power of nanotechnology is rooted in its potential to transform and revolutionize multiple
technology and industry sectors, including aerospace, agriculture, biotechnology, homeland
security and national defense, energy, environmental improvement, information technology,
medicine, and transportation. Discovery in some of these areas has advanced to the point where
it is now possible to identify applications that will impact the world we live in.

Approaches to Nanotechnologies can be:

Top-down:
which enables us to control the manufacture of smaller, more complex objects, as illustrated by
micro and nanoelectronics;
• Etching a block of material down to the desired shape
• Chips and processors
Bottom-up:
which enables us to control the manufacture of atoms and molecules, as illustrated by
supramolecular chemistry. The traditional world has come together with the quantum world.
Sectors that were once separate are now coming together. The natural world is of interest to
physicists as well as to computer scientists and mathematicians. The divisions between the
different disciplines are disappearing and paving the way for new paradigms. These approaches
come together in the nanometric domain.
• Building materials atom by atom.
• Nanoparticles such as C60, carbon nanotubes, quantum dot
Surface Area to Volume Ratio

The smaller something is, the larger its surface area is compared to its volume.
Surface Area the exposed size of an object is measured in m2.
Example: The surface area of a cube is equal to the sum of the areas of each of its sides.
 All four cubes have the same volume

By breaking the cube into multiple cubes the amount of surface exposed increases
 Suppose you broke the block into 1 nm squares. How much surface area would be
exposed?

1 nm = 1/1,000,000,000 m
6 x (1/1,000,000,000 m)2 x 10729=6,000,000,000 m2 = 1,482,632 acres1260,000 m2 = 14.8 acres
 On a macro scale, the properties remain the same even if the size decreases

Ex: Sugar cubes and powdered sugar both dissolve in water

 On a nano scale, the properties change .Nano sugar may not dissolve at al.

For a nano sample: more atoms are at the surface because more of the sample is surface..
For a macro sample: Just as many atoms can be inside as are on the surface

For example, fine powders offer greater reaction speed because of the increased surface area.
Nanoscale particles maximize surface area, and therefore maximize possible reactivity
Fraction of surface atoms and surface energy, Surface stress and surface defects:
The surface stress originates from an elastic deformation and thus from bonds stretching. It is an excess
of stress in the surface (double arrows).
Surface energy originates from a cleaving process and thus from breaking bonds.

Fraction of surface atoms

The term "fraction of atoms in the surface" refers to the proportion of atoms in a nanoparticle
that are located on the surface of the particle, as opposed to being located within the interior of
the particle.

In a nanoparticle, the surface-to-volume ratio is much higher than in bulk materials. This means
that a larger fraction of the atoms in a nanoparticle are exposed at the surface, and therefore are
available for chemical reactions and interactions with the environment.

The fraction of atoms in the surface of a nanoparticle can have a significant impact on its
properties, such as reactivity, stability, and solubility. For example, surface atoms may be more
reactive than interior atoms due to their exposure to the environment, and they may also play a
role in determining the stability of the nanoparticle by interacting with the surrounding solvent or
other materials.

The fraction of atoms in the surface of a nanoparticle can be influenced by various factors, such
as the size and shape of the particle, the synthesis method used to make the particle, and the
processing conditions used to form and stabilize the particle. Understanding and controlling the
fraction of atoms in the surface is an important aspect of nanoparticle research and development,
as it can impact the performance and behavior of nanoparticles in various applications.
Surface Defects
 Surface defects are the boundaries or planes that separate a material into regions, with
each region having the same crystalline structure but a different orientation.
 Surface defects are usually formed by surface finishing methods like embossing or by
degradation caused by weathering or environmental stress cracking.
 Defects may also be produced during the processing of and use of metals in service.
 Surface defects are the boundaries, or planes, that separate a material into regions, each
region having the same crystal structure but different orientations.
 There are different kinds of surface defects, some of which are described:

(1) Material Surface

The exterior dimensions of the material represent surfaces at which the lattice abruptly
ends. Each atom at the surface no longer has the proper coordination number and atomic
bonding is disrupted. The exterior surface may also be very rough, may contain tiny
notches, and may be much more reactive than the bulk of the material.

(2) Grain Boundaries

The microstructure of most materials consists of many grains. the orientation of the atom
arrangement, or crystal structure, is different for each adjoining grain.
 (3) Tilt boundary
Tilt boundaries are formed when dislocations of the same polarity get aligned. This
produces a low energy orientation and splits the parent grain lattice to subgrains.

(4) Twist boundary:

Twist boundaries are similar to tilt boundaries but are twisted in a direction normal to the
boundary plane.

Physical properties
• At very small sizes physical properties (magnetic, electric and optical) of materials can change
dramatically

SIZE DEPENDENT PROPERTIES OF NANOMATERIALS

The various properties, which get tremendously altered due to the size reduction in at least one
dimension are:
a) Chemical properties: Reactivity; Catalysis.
b) Thermal property: Melting point temperature.
c) Electronic properties: Electrical conduction.
d) Optical properties: Absorption and scattering of light.
e) Magnetic properties: Magnetization.
 Chemical Properties

 Based on the surface area to volume effect, nanoscale materials have:

a) Increased total surface area.
b) Increased number of atoms accessible on the surface.
c) Increased catalytic activity of those large number surface atoms.
d) Different/tunable surface catalytic properties by the change in shape, size and composition.
 Hence, nanoscale catalysts can increase the rate, selectivity and efficiency of various chemical
reactions.

 Thermal Properties
 The melting point of a material directly correlates with the bond strength. In bulk
materials, the surface to volume ratio is small and hence the surface effects can be
neglected. However, in nanomaterials the melting temperature is size dependent and it
decreases with the decrease particle size diameters.
 The reason is that in nanoscale materials, surface atoms are not bonded in direction
normal to the surface plane and hence the surface atoms will have more freedom to move.
 Electronic Properties
 In bulk materials, conduction of electrons is delocalized, that is, electrons can move
freely in all directions.
 When the scale is reduced to nanoscale, the quantum effect dominates. For zero
dimensional nanomaterials, all the dimensions are at the nanoscale and hence the
electrons are confined in 3-D space. Therefore no electron delocalization (freedom to
move) occurs
.  For one dimensional nanomaterial, electrons confinement occurs in 2-D space and
hence electron delocalization takes place along the axis of nanotubes/nanorods/nanowires
.  Due to electron confinement, the energy bands are replaced by discrete energy states
which make the conducting materials to behave like either semiconductors or insulators.

Optical Properties Because of the quantum confinement in nanomaterials, the emission

of visible light can be tuned by varying the nanoscale dimensions. It is observed that the
size reduction in nanomaterials shifts the emission of peak towards the shorter
wavelength (blue shift).

Magnetic Properties
 The size of magnetic nanoparticles also influences the value magnetization. The figure
illustrates the effect of particle size on the saturation magnetization of zinc ferrite. The
magnetization increases significantly below a grain size of 20nm. Hence, by decreasing
the particle size of a granular magnetic material it is possible to improve the quality of
magnets fabricated from it.
Properties of Nanoparticles
(i) As the particle size decreases, surface area increases. This enhances the catalytic
activity of the nanoparticles.
(ii) Reduction of particle size from micron to nanometer scale influences their optical
properties. For Example: CdS in micron size appear as red, 6nm size appear
orange in colour, 4nm size is yellow coloured and 2nm size appear as white.
(iii) Reduction of particle size from micron to nanometer scale influences the thermal
properties like melting point and thermal conductivity.

Applications of Nanoparticles
a) Silver nanoparticles have good antibacterial properties, and are used in surgical
instruments, refrigerators, air-conditioners, water purifiers etc.
b) Gold nanoparticles are used in catalytic synthesis of silicon nano wires, sensors
carrying the drugs and in the detection of tumors.
c) ZnO nanoparticles are used in electronics, ultraviolet (UV) light emitters, piezoelectric
devices and chemical sensors.
d) TiO2 nanoparticles are used as photocatalyst and sunscreen cosmetics (UV blocking
pigment).
e) Antimony-Tin-Oxide (ATO), Indium-Tin-Oxide (ITO) nanoparticles are used in car
windows, liquid crystal displays and in solar cell preparations.