NS651: Physics at Nanoscale

Satyendra Singh
Email: satyambd@gmail.com
Contact No.: 9868370772
Important dates & information
Class:
Monday : 11 - 12
Wednesday : 11 - 12
Thursday : 11 - 12

Venue of Lectures: SCNS committee Room

Beginning of Lectures: July, 22

Ending of Lectures: December, 11

1st Mid-Sem/sessional Exam: Not later than 2nd week of September

2nd Mid-Sem/sessional Exam: Not later than 3rd week of October

End-Semester Examination: December, 12 -20

 Grades

Reg.  Enrol. Name 1st Mid- 2nd Mid- End  Total Grade 
No. No. Sem/sessional Sem/session (50) (100) Awarded
Exam (25) al Exam (25)
A A A B
B B B A+
C C C F
D D D C
E E E D
‐ ‐ ‐ ‐
‐ ‐ ‐ ‐
Course outline
Introduction to Nanoscience:
Introduction to Nanoscience and Nanotechnology, Different types of Nanomaterials,
Significance of Nanoscale (Surface Area; Quantum Confinement effect)

Structure of Matter:
Crystalline and noncrystalline materials, Unit Cells, Crystal Structures (Bravais
Lattices), Crystallographic Directions, Crystallographic Planes, Miller Indices, Linear
and Planar Densities, Close-Packed Crystal Structures, Bragg’s Law, Powder X-ray
Diffraction, Scherrer equation and Williamson-Hall plot

Chemical Bonding:
Bonding Forces and Energies, Types of bonding: Ionic, Covalent, Metallic and van der
Waals, Hydrogen bonding

Types of Material:
Different types of materials: Metals, Semiconductors, Composite materials, Ceramics,
Alloys, Polymers
Course outline
Introduction to Quantum Mechanics: Wave-particle duality, Schrödinger
equation and expectation values, Uncertainty principle.

Basics of Quantum Mechanics: Solutions of the one-dimensional Schrödinger

equation for free particle, particle in a box, particle in a finite well, linear
harmonic oscillator. Reflection and transmission by a potential step and by a
rectangular barrier.

Applications of Quantum Mechanics: Particle in a three dimensional box,

linear harmonic oscillator and its solution, density of states, free electron
theory of metals. Electrons in nanostructures and quantum effects.

Basics of nanoelectronics: Introduction: Recent, past, the present and its

challenges, Future, Overview of basic Nano electronics. Spintronics:
Introduction, Overview, History & Background, Generation of Spin
Polarization Theories of spin Injection, spin relaxation and spin dephasing,
Spintronic devices and applications. Various types of transducers.
Recommended Books
Introduction to Solid State Physics - C. Kittel
Publisher: Wiley India Pvt. Ltd.

Solid State Physics- A.J. Dekker,

Publisher: Macmillan India Ltd.

Materials Science & Engineering: An Introduction- William D.

Callister, Jr, Publisher: Wiley India Pvt. Ltd.

Solid State Chemistry and its applications -Anthony R. West,

Publisher: John Wiley & Sons.

Elements of X-ray Diffraction, B. D. CULLITY

An Introduction to Nanoscience and Nanotechnology, Alain Nouailhat

Chapter 1: Introduction to Nanoscience

Introduction to Nanoscience and Nanotechnology, Different types of

Nanomaterials, Significance of Nanoscale (Surface Area; Quantum
Confinement effect),
 What is Nano and Nanometer ?
 In day-today terminology, the term ‘nano’ is quite often loosely used.

 Nano – a prefix that means very, very, small !

 Question: How small is ‘Nano’ ?

 Answer: One Billionth of something = 0.000000001 = 10-9

 The term nano, by itself, is not a measure of length, mass, or time and
hence should be used as a prefix to standard units.

 A nanometer is one billionth of a meter.

 Nanoscale is actually Nanometer scale.

 Nanometer scale range from approximately 100 nm to 1 nm.

 How big is a nanometer (nm)?
milli 10-3 Latin micros  thousand
micro 10-6 Greek micros  small
nano 10-9 Greek nanos  dwarf
pico 10-12 Spanish pico  small quantity
femto 10-15 Danish/Norwegian femten  fifteen
atto 10-18 Danish/Norwegian atten  eighteen
“ NANO” is derived from the Greek word for “dwarf”.
 1 nanometer = 10-9 m

 It is approx width of 4-5 hydrogen atoms

 Thickness of a paper sheet : ~ 80,000 nm

 A human hair: ~ 80,000 - 100,000 nm wide
 How big is a nanometer (nm)?

A human fingernail grows A man’s beard grows 5

1 nanometer every second. nanometers every second.
 How big is a nanometer (nm)?
Bohr radius

 Bohr radius = 0.5292Å ≈ 0.05 nm

 C atom (VdW radius) = 0.17 nm
 In a 1nm line: 3 C atoms
 In a 1nm x 1nm surface: 9 C atoms
 In a 1nm x 1nm x 1nm cube: 27 C atoms
 In a 100 nm x 100 nm x 100 nm cube: 2.7 x 107 C atoms
 In a 1m x 1m x 1m cube: 2.7 x 1028 C atoms

Typical nanosystems may contain from hundreds to tens

of thousands of atoms.
 Nanomaterials
The term ‘nano-material’ usually implies that one or more of the
components (entities) which make up the material are nanosized.

Nanomaterials could be defined as the materials with at

least one of its dimensions in the range of a nanometer
(1 - 100 nm).

Thus the material need not be so small that it cannot be

seen, it can be a large surface or a long wire whose
thickness is in the scale of Nanometers.
Surface Bulk
related related
properties properties
 Nanosystems: % of Surface atoms
Example of Gold Nanoparticle:
 Sphere of radius 12.5 nm contains total approx. 480,000 atoms.
surface contains approx. 48,000 atoms.
So, approx. 10% atoms are on the surface.

 Sphere of radius 5 nm contains total approx. 32,000 atoms.

surface contains approx. 8000 atoms.
So, approx. 25% atoms are on the surface.

Surface atoms have unused

electrons – so very reactive
(can be used as catalysis)
 Nanoscience & Nanotechnology?

Processing
Performance

Characterization

Structure Properties

Processing  Structure  Properties  Performance

Nanoscience
Nanoscience is about the phenomena that occur in systems with
nanometer dimensions.

Top-down
Nanoscience

0.1 nm 1 nm 10 nm 100 nm 1 m 10 m

Bottom-up Size and shape dependent

properties
Nanoscience
Nanoscience deals with the scientific study of objects with
sizes in the 1 – 100 nm range in at least one dimension.

Nanoscience is the ‘study’ of the fundamental principles of

nanomaterials (molecules and structures with at least one
dimension between 1 and 100 nm).

Nanoscience is concerned with materials and systems whose

structures and components exhibit novel and significantly
improved physical, electronic, chemical and biological
properties, phenomena and processes, because of their small
nanoscale size.
 Nanotechnology
 In the broadest sense, nanotechnology is the application of the
principles of nanoscience into useful deliverables.
 This includes the application of nanomaterials into useful nanoscale
devices and components.
 Further, by tailoring (or manipulating) the concepts of nanoscience,
nanotechnology aims at improving the lifestyle of the human race.
 It must be pointed out that the applications include those, which
otherwise would not be possible with the use of conventional
technology. Processing
Performance

Structure Properties
Nanoscience & Nanotechnology
Up to 20th Century 21st Century
Physics Physics

SCIENCE SCIENCE

Biology Biology

Nanoscience & Nanotechnology- An interdisciplinary

area- all physics, chemistry, materials science,
engineering , biology
Nanomaterials: Classification
 Nanomaterials: Classification
Nanomaterials are defined as materials with at
least one external dimension in the size range
from approximately 1–100 nanometers
Classification is based on the number of dimensions, which are
bigger to the nanoscale range (<100 nm).

Zero-dimensional (0-D)

One-dimensional (1-D)
Two-dimensional (2-D)
Three-dimensional (3-D)
 Zero-dimensional Nanomaterials

All dimensions <100 nm (length , breadth and heights are

confined at single point.)
Nanoparticles, Nanoclusters, Nanocrystals, Quantum dot etc.
Nanoparticles: amorphous or semicrystalline nanostructures with dimensions larger
than 10 nm, and a relatively large size distribution (≥15%).

Nanoclusters: For amorphous / semicrystalline nanostructures smaller in size ( 1–10

nm), with a narrow size distribution, the term nanocluster is more appropriate.

Nanocrystals: any nanomaterial that is single crystalline should be referred to as a

nanocrystal.
If a particle exhibits only regions of crystallinity, it is better termed a nanoparticle or
nanocluster depending on its dimensions.

Quantum dots: A special case of nanocrystal that is comprised of a semiconductor is

known as a quantum dot. Typically, the dimensions of these nanostructures lie in the
range 1–30 nm.
No freely motion of conduction electrons, valence holes, in all three spatial directions.
 Zero Dimensional Nanomaterials
Gold Nanoparticles
Amorphous silica

Satyendra et al., Journal of Applied Physics, 111, 024314 (2012).

Zero Dimensional Nanomaterials
1 Dimensional Nanomaterials

Nanotube, Nanofiber, Nanowire, and Nanorod

Nanotube : polycrystalline
Nanofiber : amorphous
TiO2 Nanotubes

Nanotubes
ZnMgO nanorods

Alumina nanofibers
MW CNTs, formed from the folding (a) 5-,
(b) 2-, and (c) 7- stacked graphene sheets. TiO2 Nanowires
1 Dimensional Nanomaterials

Wall Thickness:  ~ 18 nm
PbZrO3 Nanotubes

PbZrO3 Nanotube 100 nm

BiFeO3 Nanotubes

Satyendra et al., Journal of Nanoscience and Nanotechnology, 8, 5757 (2008).

1μm Satyendra et al., Journal of Nanoscience and Nanotechnology, 8, 335 (2008).
Nanotubes for Memory Device Applications

Multiferroic Tester
Capacitor model
BF-PT NT arrays

Multiferroic Tester
Top electrode
NT arrays
BF-PT

Bottom electrode
Nanotubes for Memory Device application

Multiferroic Tester
& Impedance
Analyzer
 2 Dimensional Nanomaterials
 Two of the dimensions are not confined to the
nanoscale.
 2D nanomaterials exhibit plate-like shapes.
 2D nanomaterials include nanofilms, nanolayers,
and nanocoatings.

 2D nanomaterials can be:

 Amorphous or crystalline
 Made up of various chemical compositions
 Used as a single layer or as multilayer structures
 Deposited on a substrate
 Metallic, ceramic, or polymeric
 3 Dimensional Nanomaterials

 3D Nanomaterials are materials that are not confined to the

nanoscale in any dimension.
 These materials are thus characterized by having three arbitrarily
dimensions above 100 nm.
 Materials possess a nanocrystalline structure or involve the
presence of features at the nanoscale.
 In terms of nanocrystalline structure, bulk nanomaterials can be
composed of a multiple arrangement of nanosize crystals, most
typically in different orientations.
 With respect to the presence of features at the nanoscale, 3-D
nanomaterials can contain dispersions of nanoparticles, bundles of
nanowires, and nanotubes as well as multinanolayers.
3 Dimensional Nanomaterials

3D SnO2 nanostructures

3D ZnO nanostructures
Nanocrystalline materials
A nanocrystalline material is a polycrystalline material with a
crystallite size of only a few nanometers.
Nanocrystalline copper: the material itself is ‘bulk’, but is made up of
grains which are nano-sized.

R.Kumar, &S.Singh, Ceramics International, 764, 289-294 (2018).

Nano-composite
Nano-composite a composite of two materials, where at least one of
them is a nano-sized.
Often a synergistic enhancement in terms of properties is achieved on
the formation of a composite.

Nanoparticles of
alumina in a
bulk Ni matrix
Carbon nanotubes (CNTs)
reinforcing alumina (matrix) Nano-protein layer sandwiched between
Al2O3-4 wt.% CNT composite calcite layers in an abalone shell
 Nano-porous materials
Porous materials are a subset of hybrids called lattice structures, which are a
composite of matter and voids. The pores may be isolated or
interconnected.
If the porosity size is of the order of few nanometers, the material is termed
as a nano-porous material.
Anodized aluminum oxide templates with hexagonal arrayed nano-pores
Nano-pores in nano-filtration membrane to filter bacteria from water
Porous Alumina
 The Scale of Things -- Nanometers and More
Things Natural 10-2 m 1 cm Things Manmade
10 mm
Head of a pin
1-2 mm
1,000,000 nanometers = 21st Century
Ant 10-3 m 1 millimeter (mm) Challenge
~ 5 mm Micro Electro Mechanical devices
10 -100 m wide

Microwave
Dust mite
200 m 0.1 mm
10-4 m
100 m

Human hair Fly ash

Microworld
~ 80-100 m wide ~ 10-20 m
0.01 mm
The
10-5 m
10 m O
P
O O

Infrared
Red blood cells
O O O O

O O O O O O O O

with white cell 1,000 nanometers =

O O O O O O O O

~ 2-5 m 10-6 m 1 micrometer (m) Red blood cells

S S S S S S S S

Pollen grain
Visible

Zone plate x-ray “lens”

Outermost ring spacing
0.1 m
10-7 m ~35 nm Combine nanoscale building
100 nm
blocks to make novel
Ultraviolet

functional devices, e.g., a

The Nanoworld

photosynthetic reaction
center with integral
semiconductor storage
10-8 m 0.01 m
10 nm
DNA
~2-1/2 nm diameter
10-9 m 1 nanometer (nm)
Soft x-ray

Nanotube electrode Nanotube transistor

Carbon nanotube
10-10 m 0.1 nm ~2 nm diameter
Atoms of silicon
spacing ~tenths of nm
 History of NANO- First Example
4th century: The Lycurgus Cup
It was created in the 4th century AD in Italy,
now it is in the British Museum

When illuminated from the outside, the gold or

silver nanoparticles inside the glass cup scatter the
light, making the cup appear green.
However, when a light is placed inside the cup,
the absorption of the gold or silver nanoparticles
changes the cup’s apparent color to red.

Dichroic Effect
 History of NANO
Stained Glass
 As early as 500 AD, glass
artisans were making
stained glass windows with
vibrant reds and yellows.

 These colours were much

more luminous and durable
than dyes could produce.

 They were the products of

metal nanoparticles
imbedded in the glass.

Gold nanoparticles (20 nm): Red

Gold nanoparticles (80 nm): Orange
Now we call it Nanotechnology
 History of NANO
13th-18th C: Saber blades contained carbon nanotubes and cementite nanowires—
an ultrahigh-carbon steel formulation that gave them strength, resilience, the
ability to hold a keen edge.
 History of NANO
1857: Michael Faraday discovered colloidal “ruby” gold,
demonstrating that nanostructured gold under certain lighting
conditions produces different-colored solutions.
History of NANO

First TEM
1931:
Ernst Ruska and Max Knoll
built the first TEM

1938 : First scanning transmission electron microscope (M. von Ardenne)

1939: First commercial TEM by Siemens (Ruska, von Borries)
~1970: First HRTEM microscopes with a resolution better than 4 Å
1986: Nobel prize for E. Ruska (together with G. Binning and H. Rohrer,
who developed the Scanning Tunneling Microscope)
 History of NANO
1936: Erwin Müller, working at Siemens Research
Laboratory, invented the field emission microscope,
allowing near-atomic-resolution images of materials.

First all-metal atom-probe

field ion microscope

On Oct. 11, 1955, Pennsylvania State

University physics professor Erwin W.
Müller and Kanwar Bahadur, who at the
time was a Ph.D. student working with
Müller, made history by being the first
people to image individual atoms.
 History of NANO
The conceptual underpinning of nanotechnology
was first laid out in 1959 by the physicist Richard
Feynman, in his lecture.

“There’s plenty of room at the bottom”

Feynman
Feynman explored the possibility of manipulating material
at scale of individual atoms and molecules.

Everything is made up of atoms. But what is their size and

shape, and how do they stick together- will matter the most.
 History of NANO
Moore’s Law
In 1965, Gordon Moore observed that number of transistors per
integrated circuit is growing exponentially with time.
Doubling every 2 yrs (approximately)

Gordon Moore
Co-founder of Intel

Gordon E. Moore, “Cramming more components onto integrated circuits,” Electronics, 38(8), (19 Apr 1965).
 History of NANO
• 1981 : Invention of
Scanning Tunneling
Microscopy

Phys. Rev. Lett. 49, 57(1982)

The STM, an instrument for imaging surfaces at the atomic level, was
developed by Gerd Binnig and Heinrich Rohrer at IBM Zurich
Research Laboratory, for which they were awarded the Nobel Prize in
Physics in 1986.
 History of NANO

1985
A fullerene (C60) is composed
entirely of carbon, in the form of a
hollow sphere, ellipsoid or tube.
Spherical fullerenes have been
nicknamed “buckyballs”.

Fullerenes were engineered by Harry

Kroto, Richard Smalley, and Robert Curl,
who together won the 1996 Nobel Prize
in Chemistry.
 History of NANO
•1986 Invention of Atomic Force Microscopy

G. Binning, C.F. Quate and C. Berger

Atomic Force Microscopy, Phys. Rev. Lett. 56, 930-933 (1986)
 History of NANO
1989
This was the first
object assembled
atom by atom.

IBM researcher Don Eigler was the first to manipulate

atoms using a scanning tunneling microscope.
He used 35 Xenon atoms to spell out the IBM logo.

He shared the 2010 Kavli Prize in Nanoscience for this work.

 History of NANO
1991

A Carbon Nanotube

• 1991 Sumio Iijima wins the inaugural 2008 Kavli Prize in Nanoscience for his
creation of carbon nanotubes.
• Carbon nanotubes, some 1000 times smaller than conventional carbon fibers, have
tensile strengths 100x that of steel and conduct electricity like metals. They
promise a revolution in structural and electrical engineering.
 Real “Nanomotors”

“machine-like” nanoscale
behaviour

A tiny blade of gold attached to a

carbon “nanotube”, and an
electrical current allows it to spin.

Nature 2003 424, 408.

 Why Nano ?
At the nanoscale, the physical, chemical, and biological properties
of materials differ in fundamental and in valuable ways from the
properties of individual atoms and molecules or bulk matter.
One can control and manipulate the matter at atomic level to get
desired properties and functions, which may be useful for device
applications.
 Electronics
– Nanoelectronic  smaller faster transistors
– molecular scale electronics  build electronic circuits with
molecules
 Mechanics
– MEMS micro electromechanical systems
• accelerometers, nano-guitar
– NEMS nano electromechanical systems
• molecular motors
Moore’s Law
Doubling every 2 yrs (approximately)

Gordon Moore
Co-founder of Intel
Fundamental structure of a DRAM

DRAM Array Layout

Gate
MOSFET
Source Drain

Fixed
Fixed voltage
voltage
Requirements for DRAM Capacitor’s materials

 High dielectric constant

 Low leakage current

 Micromachinability

 Low diffusion into semiconductor substrate

 Low contamination during the fabrication process

Assignment 1.

Calculate the size of the square-shaped capacitor for 30 fF with a 50 nm

thick SiO2 film (Ɛ = 3.9)
∈ ∈𝑆
𝐶
𝑡
𝑆 43.4 10 [m2]
L = 6.6 µm
Assignment 2.
Calculate the size of the square-shaped capacitor for 30 fF with a 50 nm
thick SrTiO3 film (Ɛ = 220)

𝑆 0.77 10 [m2]

L = 0.88 µm
Properties of Nanomaterials
 Properties of a Material
A property describes how a material
acts under certain conditions.

• Types of properties:
 Optical (e.g. color).
 Electrical (e.g. conductivity).
 Physical (e.g. melting point).
 Chemical (e.g. reaction rate).

• Properties are usually measured by

looking at large (~1023) aggregations of
atoms or molecules.
Optical properties: The Lycurgus Cup
Optical properties of nanomaterials can be significantly different
from bulk crystals.
The Lycurgus Cup is an
excellent example of the
optical properties of gold.

When illuminated from

outside, it appears green.
However, when Illuminated
from within the cup, it glows
red.
Red color is due to very
small amounts of gold nano
powder (about 40 parts per
million)
 Optical Properties: Colour of Gold

Bulk gold appears yellow

Even with the gold layer only 0.1µm thick in
the gold leaf, it still maintains the properties of
bulk gold.
Nano sized gold appears red in colour.
12 nanometer gold clusters
of particles look red.
The particles are so small that electrons are not free to move about as
in bulk gold. Because this movement is restricted, the particles react
differently with light.
 Optical Properties: Nanoparticles
Depending on their size (1-100nm), gold particles can appear
red, blue or gold in colour.

Each of the different sized arrangement of gold atoms absorbs and

reflects light differently based on its energy levels, which are determined
by size and bonding arrangement.
It is quit difficult to make all nanoparticles of the same size.
Production of single sized nanoparticles is still a challenge today.
 Different Sizes of Collodial Gold Particles

The color of a gold nanoparticle solution depends on the size and

shape of the nanoparticles.
The volume and shape of a nanoparticle determines how it interacts
with light.
Accordingly, this determines the color of a nanoparticle solution.
 Band gap

The band gap is

increases with reducing
the size of the particles

Semiconductors : ZnO, CdS, and Si, the band gap changes with size

 Bandgap is the energy needed to promote an electron from the valence band to the
conduction band

When the band gaps lie in the visible spectrum, changing

band gap with size means a change in color
 Physical Properties of Nanomaterials
Crystal structure of Nanomaterials is same as bulk structure
with different lattice parameters.

The inter atomic spacing decreases with size and this is due to
long range electrostatic forces and the short range core-core
repulsion.

The Melting point of Nanomaterials decreases with size.

Transition Temperature in Nanomaterials may vary with size.

 Physical Property: Melting Point of a Substance
Melting Point (microscopic definition)
– Temperature at which the atoms, ions, or molecules in a
substance have enough energy to overcome the
intermolecular forces that hold the them in a “fixed”
position in a solid
– Surface atoms require less energy to
In contact with 4 atoms
move because they are in contact with
fewer atoms of the substance.
In contact with 7 atoms
The Melting point of Nanoparticles decreases with size.
It should be noted that the melting
point of bulk gold is 1,064◦C

The melting point of gold particles

decreases dramatically as the particle
size gets below 5 nm.
 Surface Area

The total surface area (or)

the number of surface atom
increases with reducing size
of the particles
 Chemical Properties of Nanomaterials
• Nanoparticles are very small in size and hence they react are
very quick.

• Very large surface area to volume ratio

• The Electronic structure of Nanoparticles is dependent on its

size and the ability of Nano cluster to react, depends on
cluster size.

The large surface area to volume

ratio, the variations in geometry and
the electronic structure of
Nanomaterials have a strong effect
on catalytic properties.
Electrical properties of Nanomaterials
Nanomaterials of different sizes will have different electronic
structures and different energy level separations which is
different from its bulk material.
The density of the energy states in the conduction band
changes.
When the energy spacing between two energy levels is more
than KBT , energy gap is created.
Electrical conductivity decreases with a reduced
dimension due to increased surface scattering.
The Ionization potential at Nano sizes are higher than that
for the bulk materials.
 Magnetic Properties
The Magnetic Moment of Nanomaterials is found to be very less when compared
them with its bulk size.
Ferromagnetism may disappear and transfers to superparamagnetism in the
nanometer scale due to the huge surface energy.
Nanoparticles of metal oxides shows ferromagnetic behavior at room-temperature
(universal properties).

The origin of ferromagnetism may be the exchange interactions between localized

electron spin moments resulting from oxygen vacancies at the surfaces of nanoparticles
 Mechanical Properties
• Grain boundaries are
barriers to slip.

• Barrier "strength” increases with

increasing angle of misorientation.

• Smaller grain size: more barriers to slip.

Hall-Petch equation:

 y  0  k y d
o and ky are constants for particular material,
d is the average grain diameter.
o = a friction stress below which dislocations will not
move in the material in the absence of grain boundaries
Mechanical properties of Nanomaterials
Hall-Petch Plot for Cu
Grain size d d-1/2 (nm)-1/2
(nm)
1600 0.025
1000 0.031
400 0.1
25 0.2
10 0.32
With grain sizes of several tens of nanometres the Hall-Petch equation,
to a certain extent, is not observed, giving way to the so-called inverse
Hall-Petch effect, whose mechanisms are not well understood yet.

Meyers et al. Progress in Materials Science 51 (2006) 427–556

 Mechanical properties of Nanomaterials

Processing flaws like porosity and incomplete bonding among the

grains can mask and/or distort mechanical properties of nanocrystalline
materials.

Young’s modulus as a function of

porosity for nanocrystalline Pd and Cu

Meyers et al. Progress in Materials Science 51 (2006) 427–556

 Ordered Structures of Carbon

3-D Quasi 2-D 1-D 0-D

Interlayer: 3.35 nm
bond-length : 1.42nm
• Diamond: sp3 Bonding; hard and insulating
• Graphite: sp2 Bonding; Soft between graphene layers
• C60 “bucky-ball”: sp2 + sp3 Bonding, hollow sphere ~1.4 x10-9 m
(nm) in diameter
 Mechanical properties
Materials Young's Tensile Elongation Density
modulus Strength at break % (g/cm3)
(GPa) (GPa)
SWNT 1054 150 23
MWNT 1200 150 2.6

Steel 208 0.4 15 – 50 7.8

Kevlar ~150 ~3.5 ~2

Epoxy 3.5 0.005 1.25

Wood 16 0.008 0.6
Ferroelectric Nanostructures
(a) (b)
Ferroelectric Nanostructures shows unusual &
different properties compared to their bulk
counterparts resulting from the larger surface
area.
(d)
Nanowires of BaTiO3 (10 nm diameter) shows
ferroelectricity & may be used in nonvolatile
memory applications
[Yun et al, Nanoletters 2, 447(2006)]

The Curie temperature (Tc) of PbTiO3 nanotube

arrays is observed at 620 °C.
(for Bulk PT, Tc = 490oC).
[Appl. Phys. Lett, 92, 122907 (2008)]

Cp -T curve of PbTiO3 nanotube arrays

 Why properties of Nanomaterials are different?
Three principal factors cause the properties of
Nanomaterials to differ significantly from other
materials.

1. Increased relative surface area.

2. Gravitational forces become negligible and

electromagnetic forces dominate.

3. Quantum confinement effect.

These factors can charge properties such as reactivity,

strength and electrical characteristics.
 Increase in a Surface Area to Volume ratio
Nanomaterials have a relatively
larger Surface area when compared
to the same volume or mass of the
material produced in a larger form.
r
Let us consider a Sphere of radius “r”.
Its Surface Area =4πr2.
Its volume= (4/3)πr3
Surface Area to Volume Ratio= 3/r.

Thus when the radius of the Sphere decreases , its Surface

to Volume ratio increases.
Now, consider one Cubic Volume

1m

surface area  6 1m  6m

2 2
When it is divided into eight pieces

1
m
2

1 2
Its surface area  6  ( m)  8  12m2
2

When the same volume is divided into 27 pieces.

Its Surface Area becomes 18m2.
 Thus we find that when the 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.

• 30 nm 5%
• 10 nm 20%
• 3 nm 50%

Different properties such as reactivity, strength, electrical..

 Dominance of Electromagnetic Forces

 Gravitational force
is a function of mass and distance and is
weak between (low-mass) Nano sized
particles.

 Electromagnetic force
is a function of charge and distance is
not affected by mass, so it can be very
strong even when we have Nano sized
particles.
Quantum Confinement Effect
h
de Broglie wavelength 
mv

The quantum confinement effect is observed when one or more dimensions of the
system is too small to be comparable (or less than) to the de Broglie wavelength of
the electron.

 Confinement means to confine the motion of randomly moving electron to restrict

its motion in specific energy levels( discreteness)

Propagation in those directions is not possible and the density of states of the
system is modified accordingly.
Particle-in-a-box@ Quantum Mechanics:

En = n2h2/8mL2 ,
For n = 1, E1 = h2/8mL2
Now if L =L/2 , E1(L/2) = 4h2/8mL2 =4 E1
The spacings between the energy levels
increase as the length of the box decreases.
 Quantum Confinement Effect
• Quantum Confinement is the spatial confinement of electron-hole pairs
(excitons) in one or more dimensions within a material.

– 1D confinement: Quantum Wells

– 2D confinement: Quantum Wire

– 3D confinement: Quantum Dot

• Quantum confinement is more prominent in semiconductors because they

have an energy gap in their electronic band structure.

• Metals do not have a bandgap, so quantum size effects are less prevalent.
Quantum confinement is only observed at dimensions below 2 nm.
 Quantum Confinement Effect
• Recall that when atoms are brought together in a bulk material the number of
energy states increases substantially to form nearly continuous bands of states.

Energy
Energy Energy

N Eg Eg

• The reduction in the number of atoms in a material results in the confinement

of normally delocalized energy states.
• Electron-hole pairs become spatially confined when the diameter of a particle
approaches the de Broglie wavelength of electrons in the conduction band.
• As a result the energy difference between energy bands is increased with
decreasing particle size.
 Quantum Confinement Effect
The spacings between the energy levels increase as the length of the box
decreases.
In semiconductors this simply means that the band gap, starting from the
bulk value, increases as the size of the nanocrystal decreases.
Going to the nano-regime the energy level separation increases and
discrete energy levels are observed.

The band gap energy increases with

decreasing QD size.
 Density of states : 2D, 1D, 0D systems
3
1  2m  2

g3D ( E )  2  2 
E
2   

2D:Quantum Well 1D:Wire 0D:Dot

2D: confines electrons 1D: electrons travel 0D: no freely

within a thin layer only along the wire moving ones
Enm
“Enlm“
g2D(E) E1 g1D(E) g0D(E)
E0 E00
E3D

E E E
m 2m 1
g2D (E)  g1D ( E )  g 0 D ( E )  discrete
 2 2 E