Nanotechnology

There is Plenty of Room at the Bottom…

Richard Phillips Feynman

 Nanotechnology

Nano size: Generally 1-100 nm

Nanoscale was seen to range from 1 to 1000 nm

Particle size classification

• 1 nm Chemical drug
• 5 nm Protein
• 10 nm DNA
• 20-50 nm Blood vessel pore
• 50 nm Carbon nanotube
• 100-500 nm Liposome nanoparticle
• 1000 nm (1 µm) bacteria
• 10 µm Cell
• 50 µm Human hair
Introduction
• Nanoscience which deals with building up complex materials and machines
using fine control on the matter at the nano meter scale
• Study of materials and their properties at the length scale of few nano
meters is called nanoscience
Nanotechnology
The techniques involved in the preparation, characterization and use of
the properties of nano materials in different applications are collectively
called as Nanotechnology
Significance of nano scale
At nano scale, optical, thermal, mechanical, electrical, magnetic, dynamic
properties of the material changes

Property change is due to:

1. Surface to volume ratio
2. Quantum confinement
3. Dominance of electromagnetic forces
Surface to volume ratio
• Nanoparticles of a material show different properties
compared to larger particles of the same material
• Forces of attraction between surfaces can appear to be
weak on a larger scale, but on a nano scale they are strong
Quantum Confinement
• Quantum effect dominates at nano scale affecting the optical, electrical and
magnetic behaviour of materials
• This effect is observed when diameter of a material is of the same magnitude as
the de Broglie wavelength of the electron wave function

Structure Quantum No. of free

Confinement dimensions
Bulk 0 3
Quantum 1 2
Well
Quantum 2 1
Wire
Quantum 3 0
Dot
Quantum Confinement
• Quantum effect dominates at nano scale affecting the optical, electrical and
magnetic behaviour of materials
• This effect is observed when diameter of a material is of the same magnitude as
the de Broglie wavelength of the electron wave function

Structure Quantum No. of free

Confinement dimensions
Bulk 0 3
Quantum 1 2
Well
Quantum 2 1
Wire
Quantum 3 0
Dot
 Quantum confinement effect-an overview
The most popular term in the nano world is quantum confinement effect which is
essentially due to changes in the atomic structure as a result of direct influence of
ultra-small length scale on the energy band structure.

The length scale corresponds to the regime of quantum confinement ranges from 1
to 25 nm for typical semiconductor groups of IV, III-V and II-VI. In which the spatial
extent of the electronic wave function is comparable with the particle size.

As a result of these “geometrical” constraints, electrons “feel” the presence of the

particle boundaries and respond to changes in particle size by adjusting their energy.
This phenomenon is known as the quantum-size effect.

where ε is the dielectric constant of the

material, m* is the mass of the particle, m
is the rest mass of the electron, and aо is
the Bohr radius of the hydrogen atom.
Based on free dimensions
 Quantum
confinement

A particle behaves as if it were free when the confining dimension is large

compared to the wavelength of the particle. During this state, the bandgap remains
at its original energy due to a continuous energy state.
However, as the confining dimension decreases and reaches a certain limit,
typically in nanoscale, the energy spectrum turns to discrete.
What happens when the size of the of the nanoparticle becomes
smaller than the radius of the orbit of the electron – hole pair (exciton)
Two situations : weak and strong confinement

Weak confinement :
The particle radius is larger than the radius of the electron hole pair. But the
range of the motion of the exciton is limited causing a blue shift in the
absorption spectrum
rp > re,h
Strong confinement:
When the radius of the particle is smaller than the orbital radius of the
electron hole pair, the motion of the electron hole pair becomes
independent and the exciton does not exist. The hole and the electron have
their own energy levels.
rp < r e,h
Quantum confinement in semiconductors
If the electron and hole are constrained further, then the semiconductor's
properties change. This effect is a form of quantum confinement, and it is a
key feature in many emerging electronic structures.

Quantum confined semiconductors include:

• quantum wells, which confine electrons or holes in one dimension

and allow free propagation in two dimensions.

• quantum wires, which confine electrons or holes in two spatial

dimensions and allow free propagation in the third.

• quantum dots, which confine electrons in all three spatial

dimensions
 Structure Quantum confinement Number of free
dimensions
Quantum well Quantum well 1 2

Quantum wells are formed in semiconductors by having a material, like gallium

arsenide sandwiched between two layers of a material with a wider bandgap,
like aluminium arsenide.

Quantum well infrared photodetectors are also based on quantum wells, and are
used for infrared imaging.
 Structure Quantum confinement Number of free
dimensions
Quantum wire
Quantum wire 2 1

Quantum wires, which confine electrons or holes in two spatial dimensions and
allow free propagation in the third.

Carbon nanotubes is an excellent example of quantum wires.

The advantages of making wires from carbon nanotubes include their high
electrical conductivity (due to a high mobility), light weight, small diameter, low
chemical reactivity, and high tensile strength.
 Structure Quantum confinement Number of free
dimensions
Quantum dot 3 0

Quantum dots
A quantum dot is a semiconductor whose excitons are confined in all three spatial
dimensions. As a result, they have properties that are between those of bulk
semiconductors and those of discrete molecules.

An immediate optical feature of colloidal quantum dots is their coloration.

While the material which makes up a quantum dot defines its intrinsic energy
signature, the quantum confined size of the nanocrystal is more significant at
energies near the band gap. Thus quantum dots of the same material, but with
different sizes, can emit light of different colors. The physical reason is quantum
confinement effect.

The larger the dot, the redder (lower energy) its fluorescence spectrum.
Conversely, smaller dots emit bluer (higher energy) light. The coloration is directly
related to the energy levels of the quantum dot.
Properties of nanoparticles or specialty of nanotechnology
Why so special?

Very high surface to volume ratio compared to bulk

Surface free energy is changed and chemical potential is modified.
Quantum effect of the charge particles

Examples of some improvement of material properties

Quantum confinement in semiconductor nanoparticles increases the band gap and
as a result different fluorescent colors comes from such nanoparticles for different
band gap
Using one dimensional confinement in semiconductor nanoparticles quantum well
laser brings much more efficient laser
Pd being nanoparticles can occlude huge volume of hydrogen which is very
significant for hydrogen storage devices
Gold particles being nano in nature the thermodynamic properties is influenced
greatly and the melting temperature reduces
The storage capacity in computer hard disk has been increased using ferromagnetic
nanoparticles
Optical Properties
• When light is incident on the material, it can be
absorbed or scattered
• If size of material is less than 20 nm, absorption is
significant and if the size greater than 100 nm,
scattering is significant
• Therefore, by designing the nanoparticle of different
sizes, optimal amount of absorption or scattering can
be achieved
• This may result into different colour for the particles
of different sizes
 Opaque substances at the bulk level, become
transparent at nano level (copper)
 Gold nanoparticles of 50 nm are green in colour
and 100 nm particles appear orange in colour
Electrical Properties
• Electrical conductivity of material is altered when it reduced to nano size
• It is possible to invent nanomaterials having desired conductivity

Ex.
• In ceramics, electrical conductivity increases with decrease nanoparticle
size
• In metals, electrical conductivity decreases with decrease in nanoparticle
size
• In semiconductor, electrical conductivity of nanomaterials improves at nano
scale. For eg. Graphene, Si nano wire, CNT
Magnetic Properties
• Nano material are more magnetic than bulk material
• Even non magnetic solids are found to show magnetic properties
when reduced to nano level

Ex.
• Sodium, Potassium which are paramagnetic at the bulk level become
ferromagnetic at the nano level
• Iron, Nickel, Cobalt which are ferromagnetic at the bulk level become
super paramagnetic at the nano level
Structural Properties
• In nanomaterials, surface to volume ratio is very large
• Many atoms (more than half) are at the interfaces. Force of attraction
between surfaces is very strong
• Surface properties such as energy levels, electronic structure and
reactivity can be quite different from interior states
• This may lead to different surface morphology, change in crystal
structure etc.
Mechanical Properties
• At nano scale, strength of metals enhances
• The mechanical properties like hardness, elasticity, adhesion, friction
improve as the material size is reduced to nano scale
• Lubrication improves at the nano scale
• Ductility of nanomaterials may be high at high temperatures
• Carbon nanomaterials such as graphene, fullerenes, carbon nanotubes
show better mechanical properties than metals
Applications of Nanomaterials
• Electronics industry
• Medicine
• Food processing
• Automobiles
• Paint technology
• computer technology
• Robotics
• Nanoprobes and sensors
• Field emitting devices
• Space technology
Production Techniques

Nano scale
Particles
Top Down Approach
• Top down approach is a
physical process
• In this approach, a large scale
object is progressively reduced
in dimensions
• It consist of ultra fine micro
machining of materials using
lithography, epitaxy and
etching
• This method is time consuming
and relatively costly
Bottom Up Approach
• This is a chemical process
• In bottom up approach, different
materials and devices are
constructed from molecular
components on their own which do
not require any external agent to
assemble them
• They chemically assemble
themselves by recognising the
molecules of their own type
• This approach starts by collection
and combination of atoms and
molecules to build complex
structures
Methods to Synthesize Nanomaterials

• Ball Milling method (Mechanical method)

Physical Vapour Deposition (PVD)
• Vapour Deposition Thermal evaporation, Electron beam, Sputtering

Chemical Vapour Deposition (CVD)

Thermal CVD, Plasma CVD, Hot-wire CVD
• Solgel (Chemical method)
Scanning Electron Microscope
“Microscopes that uses electrons rather than light
are called as electron microscopes”

• Secondary electrons gives topographical

information of the sample
• Back scattered electrons (BSE) give chemical
composition of sample along with topographical
information
• X-rays give elemental composition of the sample
 Due to very narrow electron beam, SEM micrographs
have a large depth of field giving structure of the
sample

Advantages
• SEM can produce highly magnified image of
resolution between 10 Å to 100 Å
Disadvantages:
• SEM can produce image of surface only few nano
meter deep
• The sample should conductive in nature
otherwise a thin coating of conducting material is
SEM Layout Diagram applied on the sample before analysis
Transmission Electron Microscopy
TEM is an extremely useful tool for material
characterization. The resolution of TEM is
about 0.2 nm

Various Components of TEM are

1. Electron Gun
2. Condenser lens
3. Objective lens
4. Fluorescent screen

 These lenses are electromagnetic whose focal

lengths are varied to obtained optimize images.
All these are housed in a chamber having
vacuum 10-5 torr
Working:
• TEM sample preparation is a skilful
and tedious job
• TEM require sample thickness <300
nm, so that sufficient electrons need
to be transmitted through the sample
• Powder samples (<300 nm) can be
held on a some metal (usually Cu) grid
coated with thin carbon film (~ 5nm)
• In TEM The waveform diffraction
pattern can be obtained to analyse
crystal structure of the sample
Advantages:
• TEM offers most powerful magnification
• A three dimensional image obtained gives more information of the
specimen (surface features, shape, size and structure)
• Very small amount of specimen is required for the analysis

Disadvantages:
• TEM systems is large and very expensive
• Samples are need to electron transparent and special preparations
Beata Turoňová et al. In situ structural analysis of SARS-CoV-2 spike reveals flexibility mediated by
three hinges Science , published on 18 August 2020
https://cen.acs.org/articles/98/i37/Cryo-electron-microscopy-reaches-resolution.html
Tunnel Effect
• Classically a particle with energy E<Vo can not
penetrate a barrier and it must rebound from the
barrier

• The quantum mechanical penetration of particle

through the potential barrier even when the
energy is less than the height of the barrier is
called tunnel effect
Application of Tunnel Effect

1. The emission of alpha particles from a radioactive element

2. The electrical breakdown of insulators

3. The switching action of a tunnel diode

4. The field emission of electrons from a metallic surface

 Scanning Tunnelling Microscope (STM)
Scanning Tunnelling Microscope (STM)
• STM is used for imaging surfaces at the atomic level. For an STM,
good resolution is considered to be 0.1 nm of lateral and 0.01 nm
of depth resolution
• The STM relies on the quantum tunneling effect and applicable
to the conducting samples only

STM image showing surface

topography at an atomic level

material STM tip

~ 1 nm
material
STM tip
Modes of Operations
1. Constant Height Mode
2. Constant Current Mode

Uses:
1. Surface Roughness

2. Observing surface defects

3. Size determination
 Application: Tunneling Microscopy
 Due to the quantum effect of “barrier x Metal
penetration,” the electron density of a tip
material extends beyond its surface:

One can exploit this material STM tip

to measure the
electron density on a ~ 1 nm
material’s surface:
material
STM tip
Real STM tip

Iron atoms DNA Double

Copper Helix:
surface

STM images

http://www.quantum-physics.polytechnique.fr/en/
LT-STM
In the above slide, the material is applied with negative potential and the tip is
applied with positive potential. Hence the electron tunnels from the electron
cloud of the material to the tip surfaces.

It can be vice versa also…………..

Tip can be with negative potential and the sample can be applied with positive
potential……. In that case tunneling will take from right side to left side.

1. Constant height mode

2. Constant current mode