Chemistry

CYL1010

Instructor: Dr. Suresh Sarkar

Email: [email protected]
Office: Chemistry Department, #319

1
Contents

2
 Contents

• Surface Chemistry[3 Lectures]: Surfaces and interfaces, surface modification, surface

energy, contact angle and surface tension.

• Solid State Chemistry [6 Lectures]: Lattice and Unit Cells, X-Ray Diffraction, Bands in solids,
semiconductors, Introduction to nanomaterials based on dimensionality and properties.

• Electrochemical Systems [5 Lectures]: Electrochemical cells and EMF, Applications of EMF

measurements: Steady state approximation, Chain reactions, photochemical kinetics, Fuel Cells
and Batteries, OER and HER reactions, Corrosion

3
Questions…

• What is nanostructures?
• What is a quantum dot? What is a nanowire? What is a nanotube?
• Why are they scientifically interesting?
• What are their unique properties and potential applications?
 Nanoscale
• At this scale physical and chemical properties of materials differ significantly
from those at a larger scale
 The science and technology which deals with the particles in size
between 1 to 100 nm is known as nano science and nano
technology.

1 nanometer (nm) = 10-9 m

– Nanoscience is the study of phenomena and manipulation of

materials at atomic, molecular and macromolecular scales,
where properties differ significantly from those at a larger
scale.
– Nanotechnologies are the design, characterisation, production
and application of structures, devices and systems by
controlling shape and size at nanometre scale.
Nanomaterials
“ any material that has unique or novel properties, due to the nanoscale ( nano meter- scale)
structuring, formed by incorporation or structuring of nanoparticles”
“materials which are characterized by an ultra fine grain size (< 100 nm) or by a
dimensionality limited to 100 nm”
 Types of nanomaterial

• Inorganic nanomaterials (NMs) are materials that can be made from a metal or non-metal
element, or as an oxide, hydroxide, chalcogenide, or phosphate compound.
• The organic-based nanomaterials are formed from organic materials excluding carbon
materials, for instance, dendrimers, cyclodextrin, liposome, and micelle.
• Bionanomaterials are promising materials produced from various biological elements, namely
plants, bacteria, fungi, peptides, nucleic acids, etc.

7
 Organic Vs inorganic nanomaterials
Nanomaterials are roughly separated into inorganic and organic materials. Inorganic nanomaterials include
examples of gold nanoparticles (AuNP), mesoporous silica nanoparticles (MSNP), quantum dots (QD),
carbon nanotubes (CNT). The organic-based nanomaterials are formed from organic materials excluding
carbon materials, for instance, dendrimers, cyclodextrin, liposome, and micelle. Organic nanomaterials are
non-toxic, biodegradable, and can be broken down naturally.

Selected examples of organic and inorganic nanoparticles.

(A) Organic materials used for nanoparticle construction
include lipids and polymers of natural or synthetic origin.
Nanoparticles within this class are commonly exploited as
drug delivery vehicles and may be functionalised with
ligands to enhance targeting to cell surface receptors, as
shown for polymeric nanoparticles. (B) Inorganic
materials used for nanoparticle construction include
carbon, silica and metals such as gold, silver and iron
oxide. Nanoparticles within this class are commonly
exploited for diagnostic and imaging purposes, although
they may also be deployed as therapeutics given their
capacity for drug loading and their unique
physicochemical properties that facilitate approaches such
as photothermal tumour ablation. As illustrated in (A),
targeting ligands may be similarly conjugated to inorganic
nanoparticles. Although selected examples are shown,
many other types of organic (e.g. polymersomes and solid
lipid nanoparticles) and inorganic (e.g. quantum dots and
lanthanidedoped upconversion nanoparticles) platforms
have been developed for wide-ranging biomedical 8
applications.
Introduction
Nanomaterials are increasingly
receiving recognition as practical
Classification of nanomaterials
structural and functional materials with
good prospects, and have been developed
extensively in recent years.
Because of the decrement in particle
size, some physical and mechanical
properties of the Nanomaterials will be
changed greatly.
Materials reduced to the nanoscale can
suddenly show very different properties
compared to what they exhibit on a
Examples:
macroscale, enabling unique Sphere-like particles
applications. Ag nanoparticles,
buckyballs
Rod-like particles
Si & Ni nanowires
Tube-like particles
Carbon nanotubes
TiO2 nanotubes
 Nanomaterial: refers to the matter whose length scale, in any
dimension is approximately 1 to 100 nanometers
 Advantages of nano-sized Regime
• Large surface area/volume ratio exhibited by
nanomaterials  very high surface reactivity
with the surrounding surface, Eg. catalysis or
sensor applications
• ability of varying their fundamental properties
(e.g., magnetization, optical properties (color),
melting point, hardness, etc.), relative to bulk
materials without a change in chemical
composition.
What happens on reducing the dimension of materials in nanoscale
from the bulk scale.

 Quantum confinement (size dependent optoelectrical properties)

 Contain very small number of atoms (molecules)

 Wave particle duality. The electrons exhibit wave behavior

Novel property

A piece of gold is golden in color

A colloid of golden nanoparticle is ruby red in color

 Volume to surface area ratio
2 cm cube has a
 As objects get smaller surface area of 24
they have a much greater cm2 and a
volume of 8 cm3
surface area to volume (ratio = 3:1)
ratio

10 cm cube has a
surface area of 600 cm2
and a volume of 1000
cm3 (ratio = 0.6:1)
Dimensionality

The Journal of Physical Chemistry Letters 4, 3292-3297

https://doi.org/10.1002/anie.201405148
 Colloidal quantum wells (CQWs), or nanoplatelets

Colloidal quantum wells (CQWs), also known as nanoplatelets (NPLs), are nanoscopic materials
that display quantum confinement in two dimensions. They are used in many photonic
applications, such as lasers and light-emitting diodes (LEDs).

18
Optical Properties, surface ligands, and electron microscopic images of flat semiconducting
nanoplatelet

a UV-vis absorbance (full line) and fluorescence (dotted line) spectra of 2 to 5 ML CdSe NPLs (from bottom to
top). b Schematic representation of the cross-section of a 3 ML CdSe NPL with oleic acid and acetate ligands
on its surface. Magenta corresponds to Cd, green to Se, red to O, brown to C, and white to H. c–g TEM images
of c 4 ML CdSe NPLs, d 5 ML CdSe NPLs, and e 4 ML CdSe NPLs with a monolayer of CdS. f 1.2 nm-thick
PbS nanosheets. g 2.2 nm-thick CdTe NPLs
 Quantum Dots (QDs)
• Spherical, semiconductor nanocrystals
• Size in nanometer scale Transmission electron
• Size dependent band gap & optical properties microscopic image
QDs

Band gap varies with size

Tunable emission of 2 nm
CdSe QDs with size

Surface modification
to tag drug, protein

QDs protein
Decreasing size

20

Smith AM et al., Nat. Biotech. (2009); Smith AM et al., Acc. Chem. Res. (2010)
 Artificial Atoms

Quantum Dots are more closely related to individual atoms rather than bulk materials because of their discrete
quantized energy levels instead of energy bands. Therefore they are also known as artificial atoms.
22
 Nanocluster
Nanoclusters are atomically precise, crystalline materials most often existing on the 0-2
nanometer scale. They are often considered kinetically stable intermediates that form
during the synthesis of comparatively larger materials such as semiconductor and metallic
nanocrystals.

(a) Absorption (blue line) and normalized fluorescence (red line) spectra of
Min-23@AuNCs (kex = 808 nm).
(b) Fluorescence decay curve of Min 23@AuNCs dispersed in water
(d) TEM image of AuNCs. Inset shows histogram of particle size distribution (core
size, d = 1.81 ± 0.26 nm; polydispersity
index, PDI = 0.02). Optimized structure of (e) the Au25(SCH2CHNH2COOH)18
cluster and (f) icosahedral Au13 core. Materials Today, Volume 51, December 2021
24
Applications
 QDs in various applications

Solar cell Television Bio-imaging

Energy harvesting Display device Contrasting agent

LEDs Photodetector Photocatalyst

catalyzing chemical
Lighting Photon sensing reaction
Source: Internet; Adv. Mater. 2017, 29, 1606576 30
https://www.powershow.com/view0/8ef3d2-ZThiZ/Application_of_Nanomaterials_powerpoint_ppt_presentation
38
 Classification of nanomaterials
based on quantum confinement
• zero-dimensional (0D),
• one-dimensional (1D),
• two-dimensional (2D)
• three-dimensional (3D) nanomaterials.

(i) Zero-dimensional nanomaterials: Here, all dimensions (x, y, z) are at nanoscale,

i.e., no dimensions are greater than 100 nm. It includes nanospheres and
nanoclusters.
(ii) One-dimensional nanomaterials: Here, two dimensions (x, y) are at nanoscale
and the other is outside the nanoscale. This leads to needle shaped nanomaterials. It
includes nanofibres, nanotubes, nanorods, and nanowires.
(iii) Two-dimensional nanomaterials: Here, one dimension (x) is at nanoscale
and the other two are outside the nanoscale. The 2D nanomaterials exhibit plate-
like shapes. It includes nanofilms, nanolayers and nanocoatings with nanometre
thickness.
(iv) Three-dimensional nanomaterials: These are the nanomaterials that are not
confined to the nanoscale in any dimension. These materials have three arbitrary
dimensions above 100 nm. The bulk (3D) nanomaterials are composed of a
multiple arrangement of nanosize crystals in different orientations. It includes
dispersions of nanoparticles, bundles of nanowires and nanotubes as well as multi-
nanolayers (polycrystals) in which the 0D, 1D and 2D structural elements are in
close contact with each other and form interfaces.
 Physical Properties of Nanomaterials

Nanoparticles or nanocrystals made of metals, semiconductors, or oxides are of interest for

their mechanical, electrical, magnetic, optical, chemical and other properties
Nanoparticles have been used as quantum dots and as chemical catalysts
Nanoparticles exhibit a number of special properties relative to bulk material
Nanoparticles have a very high surface area to volume ratio.
This provides a tremendous driving force for diffusion, especially at elevated temperatures.
Nanomaterials may have a significantly lower melting point or phase transition temperature
and appreciably reduced lattice constant due to a huge fraction of surface atoms in the total
amount of atoms.
Mechanical properties of the Nano materials are one or two order of magnitude higher than
that of single crystals in the bulk form, due to reduced probability of defects.
Electrical conductivity decreases with a reduced dimension due to increased surface
scattering.
Magnetic property of the nanostructured materials are distinctly different from that of bulk
materials. Ferromagnetism of bulk material disappears and transfers to super magnetism in
the nanometer scale due to huge surface energy.
Heat treatment of Nano materials increases the diffusion of impurities, intrinsic structural
defects and dislocations
 Unique Characteristics of Nanoparticles
• Large surface to volume ratio

• High percentage of atoms/molecules on the surface

• Surface forces are very important, while bulk forces are not as important.

• Metal nanoparticles have unique light scattering properties and exhibit plasmon resonance.

• Semiconductor nanoparticles may exhibit confined energy states in their electronic band

structure (e.g., quantum dots)

• Can have unique chemical and physical properties

• Same size scale as many biological structures

 Physical Properties of Nanoparticles
• Physical properties of nanoparticles are
dependent on:
– Size
– Shape (spheres, rods, platelets, etc.)
– Composition
– Crystal Structure (FCC, BCC, etc.)
– Surface ligands or capping agents
– The medium in which they are dispersed
 Advantages of nano-sized Regime
• Large surface area/volume ratio exhibited by
nanomaterials  very high surface reactivity
with the surrounding surface, Eg. catalysis or
sensor applications
• ability of varying their fundamental properties
(e.g., magnetization, optical properties (color),
melting point, hardness, etc.), relative to bulk
materials without a change in chemical
composition.
 Size
# of atoms
• Molecules, nanoparticles, 1
Molecules
and bulk materials can be 10

distinguished by the number

102
of atoms comprising each
type of material. 103

Nanoparticles
• Note: these are very 104
approximate numbers!
105

106

Bulk

Poole, C., Owens, F. Introduction to Nanotechnology. Wiley, New Jersey. 2003

 Surface Area : Volume Ratio
• This gives an approximate surface area to volume ratio of >107:1

which is significantly larger than a macro sized particle.

• As the surface area to volume ratio increases so does the percentage

of atoms at the surface and surface forces become more dominant.

• Generally accepted material properties are derived from the bulk,

where the percentage of atoms at the surface is miniscule. These

properties change at the nanoscale.

 Size
• Nanoparticles exhibit unique
properties due to their high
surface area to volume ratio.
• A spherical particle has a diameter
(D) of 100nm.
– Calculate the volume (V) and surface
area (SA)
4 3 πD3 SA = 4 πr 2 = πD2
V = πr =
3 6 SA = π(100 × 10 -9 )2
π(100 × 10 -9 )3 SA = 3.141× 10 -14 m2
V=
6
V = 5.24 x10 -22 m3
Poole, C., Owens, F. Introduction to Nanotechnology. Wiley, New Jersey. 2003
Size
Some example calculations for volume and surface area of nanoparticles.
These calculations use nm as unit of length.

Nanoparticle Nanoparticle Volume Surface Area SA:Vol Ratio

Diameter (nm) Diameter (um) (nm )
3
(nm )
2
(nm2/nm3)
1 0.001 0.524 3.14 6
10 0.01 524 314 0.6
100 0.1 523598 31416 0.06
1000 1 5.24E+08 3.14E+06 0.006
10000 10 5.24E+11 3.14E+08 0.0006
100000 100 5.24E+14 3.14E+10 0.00006
1000000 1000 5.24E+17 3.14E+12 0.000006

Why is Large Surface Area Important?

The large surface area to volume ratio of nanoparticles opens many possibilities for creating new materials and
facilitating chemical processes. In conventional materials, most of the atoms are not at a surface; they form the
bulk of the material. In nanomaterials, this bulk does not exist. Indeed, nanotechnology is often concerned with
single layers of atoms on surfaces. Materials with this property are unique. For example, they can serve as very
potent catalysts or be applied in thin films to serve as thermal barriers or to improve wear resistance of
materials.
Surface Area:Volume Ratio

In this graph:
SA = nm2
Vol = nm3

SA:Vol Ratio = nm2/nm3

The ratio increases

dramatically when the
nanoparticle diameter drops
below about 100 nm
 Size
Melting point as a function of particle size
• Nanoparticles have a lower melting point than their
bulk counterparts

Melting point of gold nanoparticles as a

function of size.

Source: Ph. Buffat and J-P. Borel, Phys. Rev. A 13,

2287–2298 (1976)
 mp versus Shape
• Particles: May sinter together at lower than
expected temperature.
• Rods: Can melt and form spherical droplets if
heated too high.
• Films: Thin films can form pin-holes.
Continued heating can lead to de-wetting
behavior and island formation.
GRAPHENE
GRAPHENE
What are Carbon nanotubes
Characterization Techniques

8. X-ray diffraction Crystal structure

 Properties of nanomaterials
• Optical properties
The optical emission and adsorption occurs when the transition of the electrons occur between
these two states.

• Magnetic properties

large surface area to volume ratio results in a substantial proportion of atoms having different
magnetic coupling with neighboring atoms leading to differing magnetic properties.

• Mechanical Properties
The ultra small size (<100 n m) of grains in these nanostructured materials can result in
dramatically improved of different properties from conventional grain size (>1µm) of same
chemical composition. These properties represent the subject of multidisciplinary research
efforts motivated by the wide range of their applications in high technologies.

• Electronic Properties
The changes which occur in electronic properties as the system length scale is reduced are
related mainly to the increasing influence of the wave-like property of the electrons (quantum
mechanical effects) and the scarcity of scattering centers.
Optical Properties
 Optical Properties

• The size dependence on the optical properties of nanoparticles is the

result of two distinct phenomena:

1. Surface plasmon resonance for metals

2. Increased energy level spacing due to the confinement of

delocalized energy state in semiconductors

Poole, C., Owens, F. Introduction to Nanotechnology. Wiley, New Jersey. 2003

 Optical Properties
• Surface Plasmons
– Recall that metals can be modeled as an arrangement of positive
ions surrounded by a sea of free electrons.
– The sea of electrons behaves like a fluid and will move under the
influence of an electric field
- - - -- -- - - - - - -- -- - - ---------------------------
- + - + - + - + - - - - - - - - -
- - - - - - - - - - - - - - - + - + -- + - + - -
- - - - - - - - - - - - - - - - - - - -
- + - + - + - + - - - - -
- - - - - - - - - - - - + + - + +
E-field
Surface Plasmons
– If the electric field is oscillating (like a photon), then the sea of electrons will oscillate
too. These oscillations are quantized and resonate at a specific frequency. Such
oscillations are called plasmons.
Resonance at a metal surface
Resonance in metal NP

Source: MRS Bulletin 2005, 30(5), 338.

 Optical Properties

• Surface Plasmons
– Formal definition: Plasmons are the coherent
excitation of free electrons in a metal.
– The plasmon resonance frequency (f) depends on
particle size, shape, and material type.
– Surface plasmons are confined to the surface of the
material.
– The optical properties of metal nanoparticles are
dominated by the interaction of surface plasmons
with incident photons.
 Optical Properties

Surface Plasmons
– Metal nanoparticles like gold and silver have
plasmon frequencies in the visible range.
– When white light impinges on metal nanoparticles
the wavelength corresponding to the plasmon
frequency is absorbed.
– The spectral locations, strengths, and number of
plasmon resonances for a given particle depend on
the particle’s shape and size.
 Optical Properties
The gold we know

• Absorption spectra of spherical Au nanoparticles

The gold we are discovering:

Material properties (such as optical

Absorption, shown here) change with the
Optical absorption spectrum of 20- and 80-nm gold nanoparticles embedded in glass.
[Adapted from F. Gonella et al., in Handbook of Nanostructured Material and Nanotechnology,
H. S. Nalwa, ed., Academic Press, San Diego, 2000, Vol. 4, Chapter 2, p.85.]
size of the gold nanoparticle.
 Optical Properties of semiconductor nanomaterials
Energy levels
In semiconductors and insulators, the valance band corresponds to the ground states of
the valance electrons.
In semiconductors and insulators, the conduction band corresponds to excited states
where electrons are a free to move about in the material and participate in conduction.
In order for conduction to take place in a semiconductor, electrons must be excited out of
the valance band, across the band gap into the conduction band. This process is called
carrier generation.
Conduction takes place due to the empty states in the valence band (holes) and electrons in
the conduction band.

Ec

band gap
Ev
Electron excited into conduction band
 Optical Properties of semiconductor nanomaterials

• Energy level spacing

– In semiconductors and insulators a photon with an energy equal to the band
gap energy is emitted when an electron in the conduction band recombines
with a hole in the valance band.
– The electronic band structure of a semiconductor dictates its optical properties.
– GaP, a material commonly used for green LEDs, has an intrinsic band gap of
2.26 eV. Carrier recombination across the gap results in the emission of 550 nm
light.

Eg = 2.26 eV
λ=550 nm
 Optical Properties of semiconductor nanomaterials

• Energy level spacing and quantum confinement

– 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 dimensions
of a nanoparticle approach the de Broglie wavelength of electrons
in the conduction band.
– As a result the spacing between energy bands of semiconductor or
insulator is increased (Similar to the particle in a box scenario, of
introductory quantum mechanics.)
Bulk Materials
Energy Nano Materials

Eg Increased
Eg
band gap
 What are 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.
 A crystal of semiconductor compound (eg. CdSe, PbS) with a diameter on the order
of the compound's Exciton Bohr Radius. Quantum dots are between 2 and 10
nanometers wide (10 and 50 atoms).
 An electromagnetic radiation emitter with an easily tunable bandgap.

Bohr exciton radius and quantum confinement

In an unconfined (bulk) semiconductor, an electron-hole pair is typically bound within a
characteristic length called the Bohr exciton radius. 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. The Quantum
dot is such an electronic structure which is based on the principle of Quantum confinement.

where the band gap of the material in the quantum-confined situation is described as a
modification of the bulk band gap, Eg,bulk. The increased kinetic energy from the localization of the
electron-hole pair inside a sphere with radius R is described in the second term and scales as R . The 65
third term is the Coulomb attraction in a screened environment and scales as R. The polarization
term, expressed as an average polarization, has the same scaling as the screened Coulomb
attraction.
 Quantum Confinement effect
Band gap tuning by tuning the size of quantum dots
Different fluorescent materials

QDs Compared with florescent dyes/proteins • Similar emission wavelength

• but different efficiency
•Brightness: 10-100 times higher
•High molar absorption coefficient
• Size-tunable: color
• Multiplexing capabilities
• narrow emission band, and wide excitation wavelength
ACS nano 14, 3227-3241;Curr. Opin.
• Photostability: 100-1000 time higher Biotechnol. 16, 63–72 (2005)
 Quantum Confinement effect

The highest energy level that an electron can occupy at the absolute zero temperature is
known as the Fermi Level.
What is fermi energy?
•Fermi energy is defined as the highest occupied energy level of a material at absolute zero
temperature (-273º C or 0K).
•In other words, all electrons in a body occupy energy states at or below that body's Fermi
energy at 0K.
•It is an energy difference of the kinetic energy of a system containing fermions.
•Fermi energy is constant for each solid.
Quantum Confinement effect
 Quantum Confinement

• Quantum confinement is observed when the size of the particle is too small to
be comparable to the wavelength of electron.
• Confinement: to confine the motion of randomly moving electron, to restrict its
motion in specific energy levels.
• Size of particle decreases till we reach a nano scale.
• The decrease in confining dimensions makes the energy level discrete and this
increases the band gap and band gap energy also increases.
• Changes in atomic structure – due to the influence of small length scale in
energy band structure
• Quantum confinement range for a semiconductor (1-25nm)
• Changes in particle size by adjusting the energy
Optical Properties of semiconductor nanomaterials
 Quantum Confinement
• Based on direction of confinement, three
categories:
• Quantum well(2D)
• Quantum wire(1D)
• Quantum Dot(0D)
 Quantum Confinement
• 3-D
– All carriers act as free carriers in all three
directions
• 2-D or Quantum Wells
– The carriers act as free carriers in a plane
– First observed in semiconductor systems
• 1-D or Quantum Wires
– The carriers are free to move down the
direction of the wire
• 0-D or Quantum Dots
– Systems in which carriers are confined in all
directions (no free carriers)
 Density of states
• Number of states available in a system
• Used for determining the carrier
concentrations and energy distribution of
carriers in a semiconductor
• Free motion of carrier is limited to 0D, 1D, 2D.
 Density of states

dN dN dk
DoS  
dE dk dE
k space vol
N (k ) 
vol per state
4 3 k 3

(2 ) 3 V

Structure Degree of dN
Confinement dE
Bulk Material 0D E
Quantum Well 1D 1
Quantum Wire 2D 1/ E
Quantum Dot 3D d(E)
 Density of states
• Density of states- quantum confinement
 Correlation between bohr radius and bandgap
When the dimensions are a lot greater than the electron’s wavelength in the sample the electron can be considered as free and
it is known from quantum mechanics that it will have a continuous spectrum. The decreasing of the dimensions will cause the
electron’s spectrum to become discrete and also an increase the material’s band gap will be observed. A rough way to justify
the previous statement is the equation for the energy states of the three dimensional particle in a box model:

 2 2  n  2  n y  2  n  2 
E  x       z   …………………1
2m  L   L   L  
From equation (1) it can be seen that a decrease in dimensions corresponds to an increase in the energy. Figure 1 shows the
transition from the bulk material to a quantum dot (see the next slide). In the same figure the blue shift in the optical
properties due to the increase of the energy can be observed.

Before moving forward, we will try to describe the quantum confinement effect in a semiconductor. In a semiconductor
it is known that with the increase of temperature an electron can acquire higher energy than the material’s band
gap and jump from the valence to the conduction band leaving a hole in the valence band. This electron-hole pair is
called an exciton and it can be simulated by a hydrogen atom. A way to test if we are in the quantum confinement
regime is to compare the radius of the material R with the exciton’s Bohr radius αB∗. We define the weak and the strong
confinement regime as follows:
When
R
1 , then we are in the weak confinement regime
 *
B

When
R

˂1
 *
B
, then we are in the strong confinement regime
The exciton’s Bhr radius is:

 me 
   r  *  B
*
B
Figure1: The decrease of

m 
dimensions results in the increase
of the band gap. The energy
difference results also the blue
shift in optical properties.
Figure taken from
http://www.sigmaaldrich.com.
Where ≈ 0.53Å is the Bohr radius, is the dielectric constant, me is the mass of the electron and m∗ =
(m∗e · m∗h)/(m∗e + m∗h) is the effective reduced mass of the electron-hole system, where m∗e, m∗h
are the effective masses of the electron and the hole respectively. Finally, the confinement energy for the
exciton is given by the formula:

B r

 1
2
1 
2
Econ  2 
 
2  me mh 
where α is the exciton’s radius and me and mh the masses of the electron and the hole respectively.

The exciton Bohr radius provides a very useful length scale to describe the spatial extension of excitons in
semiconductors, and ranges from ~2 to ~50 nm depending on the semiconductor . It is interesting to note
that the exciton Bohr radius and the band gap of the semiconductor are correlated, so that materials with
wider band gaps possess smaller (e.g., Eg and are, respectively, 0.26 eV and 46 nm for PbSe, 1.75 eV
and 4.9 nm for CdSe, and 3.7 eV and 1.5 nm for ZnS).
 Quantum Dots - A tunable range of energies
Because quantum dots' electron energy levels are discrete rather than continuous, the addition
or subtraction of just a few atoms to the quantum dot has the effect of altering the boundaries of
the bandgap.
Changing the geometry of the surface of the quantum dot also changes the bandgap energy,
owing again to the small size of the dot, and the effects of quantum confinement.

Size Dependent Control of Bandgap in Quantum Dots

 The bandgap in a quantum dot will always be energetically larger; therefore,

we refer to the radiation from quantum dots to be "blue shifted" reflecting the
fact that electrons must fall a greater distance in terms of energy and thus
produce radiation of a shorter, and therefore "bluer" wavelength.
 The quantum Dot allows us to control its band gap by adjusting its size hence
controlling the output wavelength with extreme precision

81
 Optical properties
The optical emission and adsorption occurs when the transition of the electrons occur between
these two states.

 Magnetic properties

large surface area to volume ratio results in a substantial proportion of atoms having different
magnetic coupling with neighboring atoms leading to differing magnetic properties.

• Mechanical Properties
The ultra small size (<100 n m) of grains in these nanostructured materials can result in
dramatically improved of different properties from conventional grain size (>1µm) of same
chemical composition. These properties represent the subject of multidisciplinary research
efforts motivated by the wide range of their applications in high technologies.

• Electrical Properties
The changes which occur in electronic properties as the system length scale is reduced are
related mainly to the increasing influence of the wave-like property of the electrons (quantum
mechanical effects) and the scarcity of scattering centers.
Magnetic properties

83
 Why to study the magnetic properties of nanomaterials

•It has been shown that magnets made of nanocrystalline yttrium–samarium–

cobalt grains possess unusual magnetic properties due to their extremely large
grain interface area (high coercivity can be obtained because magnetization
flips cannot easily propagate past the grain boundaries). This could lead to
applications in motors, analytical instruments like magnetic resonance imaging
(MRI), used widely in hospitals, and microsensors.

•Nanoscale-fabricated magnetic materials also have applications in data

storage.

•Devices such as computer hard disks storage capacity is increased with

Magnetic Nano materials
Why to study the magnetic properties of nanomaterials
• Drug Delivery

Magnetic Nanoparticles
– Drugs are bound to magnetic nanoparticles
– Carry drugs to malignant sites with
magnetic fields
– Release the drugs by enzymatic activity
 Superparamagnetic

Ferromagnetic

Figure 2. An external magnetic field induces an alignment of the magnetic moments of both
the domains of a ferromagnetic material and the single-domain of a superparamagnetic
nanoparticle. When no magnetic field is applied ferromagnetic materials maintain a net
magnetization while superparamagnetic nanoparticles present magnetization zero.

The unique properties of superparamagnetic nanoparticles have found numerous applications in the biomedical
field, such as tissue repair by local heating, detoxification of biological fluids, magnetically controlled delivery of
drugs or genes, or as contrast agents in magnetic resonance imaging (MRI).
 Single domain

Coercivity:
1.The smallest amount of magnetizing strength is necessary to return the component
to its former condition.
2.Coercivity, also called magnetic coercivity, coercive field, or coercive force is a
measure of the ability of a ferromagnetic material to withstand an external magnetic
field without becoming demagnetized.
3.Coercivity is usually measured in oersted or ampere/meter units and is denoted by

Nanoscale Research Letters 2012, 7:144

 Superparamagnetism

• Superparamagnetism (SPM) is a type of magnetism that occurs in

small ferromagnetic or ferrimagnetic nanoparticles. This implies sizes
around a few nanometers to a couple of tenth of nanometers, depending
on the material.

• Additionally, these nanoparticles are single-domain particles.

• In a simple approximation, the total magnetic moment of the

nanoparticle can be regarded as one giant magnetic moment,
composed of all the individual magnetic moments of the atoms which
form the nanoparticle.
 Super Paramagnetism
Superparamagnetism is a form of magnetism which appears in small ferromagnetic or ferrimagnetic
nanoparticles. In sufficiently small nanoparticles, magnetization can randomly flip direction under the
influence of temperature. The typical time between two flips is called the Néel relaxation time. In the
absence of an external magnetic field, when the time used to measure the magnetization of the
nanoparticles is much longer than the Néel relaxation time, their magnetization appears to be in average
zero; they are said to be in the superparamagnetic state. In this state, an external magnetic field is able
to magnetize the nanoparticles, similarly to a paramagnet. However, their magnetic susceptibility is
much larger than that of paramagnets.

Superparamagnetism is a form of magnetism exhibited by small ferromagnetic or ferrimagnetic

nanoparticles. At sizes of less than a hundred nanometers, the nanoparticles are single-domain particles,
allowing the magnetization of the nanoparticles to be approximated as one giant magnetic moment by
summing the individual magnetic moments of each constituent atom. This approximation is called the
“macro-spin approximation.” When the nanoparticles are small enough, the energy barriers for
magnetization reversal, which are proportional to grain volume, are relatively low compared to thermal
energy. With enough thermal energy, their magnetization can flip direction randomly over short periods of
time and the time between two flips in direction is called the Neel relaxation time. The superparamagnetic
state refers to how the average magnetization of the nanoparticles averages to zero when no external
magnetic field is applied and the measurement time for the magnetization of the nanoparticles is greater than
the Neel relaxation time. With an external magnetic field applied, the nanoparticles are magnetized like
paramagnets, but with much greater susceptibility.
While any ferromagnetic or ferromagnetic material can exhibit paramagnetic behavior, the difference is that
this usually occurs above the Curie temperature whereas in superparamagnets, this occurs below the Curie
temperature.
 Super Paramagnetism
Size Dependence

As mentioned in the introduction, superparamagnetivity occurs due to the small size of the
particles. In Figure 2 below, the magnetization of paramagnetic, ferromagnetic and
superparamagnetic materials in response to an external magnetic field.

Figure 2: The magnetization curves (plots of magnetization M vs. applied field H) for
paramagnetic, ferromagnetic, and superparamagnetic (when T > TB) materials.

As shown in the above figure, the ferromagnetic response has a hysteresis loop. When
ferromagnetic particles increase in size, the magnetic moment increases, which in turn increases
the magnetization and allows the magnetization to reach its saturation, or maximum, value
quicker. This translates to a thinner hysteresis loop. Conversely, decreasing the particle size will
widen the hysteresis loop until a certain nanoparticle size, called the critical size. Once this size is
reached, the hysteresis loop begins to narrow with decreasing size until the superparamagnetic
size threshold is reached. When the nanoparticles reach superparamagnetic sizes, response
curve retains the sigmoidal shape of a ferromagnetic response but loses the loop. Figure 3 below
shows this pattern in a plot of coercivity, or the intensity of the applied magnetic field to yield a
zero magnetization, against nanoparticle size.
• What are the implications of such superparamagnetic states?
Without external magnetic field, the net moment is zero. As soon as an
external field is applied, the nanoparticles react similar to a
paramagnet (hence the “paramagnetism” in the name) with the one
exception that their magnetic susceptibility is much larger (hence the
“super” in the name).
• A word of clarification: Normally, any ferromagnetic or ferrimagnetic
material can behave paramagnetically. This is from a certain
temperature on and upwards, the so called Curie temperature Tc
• However, superparamagnetic behaviour is observed below the Cure
temperature and thus has to be explained differently.
Diamagnetism
• Very weak; exists ONLY in presence of an external field, non-permanent. Cu, Ag, Si, Ag
and alumina are diamagnetic at room temperature. The induced magnetic moment is small, and
the magnetization (M) direction is opposite to the direction of applied field (H). The magnetic
susceptibility is negative, and is in order of -10-5

Paramagnetism
• Slightly stronger; when an external field is applied dipoles line-up with the field, resulting in a positive
magnetization. However, the dipoles do not interact. In the absence of an external field, the orientations of
atomic magnetic moments are random leading to no net magnetization. When an external field is applied
dipoles line-up with the field, resulting in a positive magnetization. Para-magnetism is produced in many
materials like aluminum, calcium, titanium, alloys of copper.

Both dia-and para-magnetic materials are considered as non-magnetic because they

exhibit magnetization only in presence of an external field.
Ferromagnetism
Certain materials possess permanent magnetic moments even in the absence of an external field. This is
result of permanent unpaired dipoles formed from unfilled energy levels.
These dipoles can easily line-up with the imposed magnetic field due to the exchange interaction or mutual
reinforcement of the dipoles Materials with ferro-magnetism (Examples: Fe, Co, Ni, Gd) possess magnetic susceptibilities
approaching 106.
Ferro Magnets are very strong; dipoles line-up permanently upon application of external field. Has two sub-classes:-
o Antiferromagnetism:
o Ferrimagnetism:
Anti-ferromagnetism
• Dipoles line-up, but in opposite directions, resulting in zero magnetization.
• Eg: Mn, Cr, MnO, NiO, CoO, MnCl2
• Exchange interaction which is responsible for parallel alignment of spins is extremely sensitive to inter-atomic spacing and
to the atomic positions. This sensitivity causes anti-parallel alignment of spins.
• When the strength of anti-parallel spin magnetic moments is equal, no net spin moment exists, and resulting
susceptibilities are quite small.
• One noticeable characteristic of anti-ferro-magnets is they attain maximum susceptibility at a critical temperature called
Neel temperature. At temperatures above this, anti-ferro-magnets become para-magnetic.

Ferrimagnetism
• Some ceramic materials exhibit net magnetization.
• Eg: Fe3O4, NiFe2O4, (Mn.Mg)Fe2O4, PbFe12O19, Ba Fe12O19, YIG – yttrium iron garnet Y3Fe5O12.
• In a magnetic field, the dipoles of a cation may line up with the field, while dipoles of other cation may not.
These ceramics are called ferrites, and the effect is known as ferri-magnetism.
• Ferrimagnetism is similar to anti-ferro-magnetism in that the spins of different atoms or ions line up anti-
parallel. However, the spins do not cancel each other out, and a net spin moment exists.
A ferrimagnetic material is defined as one in which the magnetic dipole of the atoms on different sublattices are
opposed as in antiferromagnetism but in ferrimagnetic materials, opposing moments are unequal and a
spontaneous net magnetization remains
• Below the Neel temperature, therefore, ferromagnetic materials behave very much like ferromagnetic
materials and are paramagnetic above the Neel temperature.
(a) Ferromagnetic (b) Antiferromagnetic
(c) Ferrimagnetic
The hysteresis loop shows the relationship between the magnetic flux density and the magnetizing field
strength. The loop is generated by measuring the magnetic flux coming out from the ferromagnetic substance
while changing the external magnetizing field.
•The magnetic flux density (B) is increased when the magnetic field strength
(H) is increased from 0 (zero).
•With an increase in the magnetic field, there is an increase in the value of
magnetism, and it finally reaches point A, which is called the saturation point
where B is constant.
•With a decrease in the value of the magnetic field, there is a decrease in the
value of the magnetism. But if B and H are equal to zero, when a substance
or material retains some amount of magnetism, it is called retentivity or
residual magnetism.
•When there is a decrease in the magnetic field towards the negative side,
magnetism also decreases. At point C, the substance is completely
demagnetized.
•The force required to remove the retentivity of the material is known as
Coercive force (C).
•In the opposite direction, the cycle is continued where the saturation point is
D, the retentivity point is E, and the coercive force is F.
•Due to the forward and opposite direction process, the cycle is complete,
and this cycle is called the hysteresis loop.
Magnetic Material Properties:
From the hysteresis loop, a number of primary magnetic properties of a material
can be determined.

Retentivity: A measure of the residual flux density corresponding to the saturation

induction of a magnetic material. In other words, it is a material's ability to retain a
certain amount of residual magnetic field when the magnetizing force is removed
after achieving saturation. (The value of B at point b on the hysteresis curve.)

Residual Magnetism or Residual Flux - the magnetic flux density that remains in
a material when the magnetizing force is zero. Note that residual magnetism and
retentivity are the same when the material has been magnetized to the saturation
point. However, the level of residual magnetism may be lower than the retentivity
value when the magnetizing force did not reach the saturation level.

Coercive Force : The amount of reverse magnetic field which must be applied to a
magnetic material to make the magnetic flux return to zero. (The value of H at
point c on the hysteresis curve.)

Permeability: A property of a material that describes the ease with which a

magnetic flux is established in the component.
Reluctance: Is the opposition that a ferromagnetic material shows to the
establishment of a magnetic field. Reluctance is analogous to the resistance in an
electrical circuit.
 Super Paramagnetism
It has been a long time since we have learned that “going nano” leads to new properties arising from matter. One of those size-
dependent properties that promises huge benefits due to its potential applications is magnetism. Magnetic materials are
classified according to their susceptibility to magnetic fields into diamagnetic, paramagnetic and ferromagnetic materials, the
first two categories behaving in a way that their magnetic properties don’t persist when the external magnetic field is removed.
On the contrary, in ferromagnetic materials their magnetic properties continue even when the external magnetic field is
removed. These materials are usually referred to as magnets. When magnets are subjected to the effect of a magnetic field
the individual magnetic moments of their atoms align with this field, and when the field is removed part of this alignment is
retained: the material has been magnetized.

Figure 1. Under the influence of a magnetic field paramagnetic materials are magnetized, but when the magnetic field is
removed this magnetization goes to zero. On the contrary, ferromagnetic materials present a remanent magnetization (MR) in
the absence of the magnetic field. Superparamagnetic materials share properties of ferromagnetism and paramagnetism.

https://mappingignorance.org/2014/03/05/superparamagnetic-nanoparticles-and-the-separation-problem/
 Properties of nanomaterials

 Optical properties
The optical emission and adsorption occurs when the transition of the electrons occur between
these two states.

 Magnetic properties

large surface area to volume ratio results in a substantial proportion of atoms having different
magnetic coupling with neighboring atoms leading to differing magnetic properties.

•Mechanical Properties
The ultra small size (<100 n m) of grains in these nanostructured materials can result in
dramatically improved of different properties from conventional grain size (>1µm) of same
chemical composition. These properties represent the subject of multidisciplinary research
efforts motivated by the wide range of their applications in high technologies.

• Electrical Properties
The changes which occur in electronic properties as the system length scale is reduced are
related mainly to the increasing influence of the wave-like property of the electrons (quantum
mechanical effects) and the scarcity of scattering centers.
Mechanical Properties

101
 Mechanical properties
• The mechanical properties of a material reflect the relationship between its response or
deformation to an applied load or force. Important mechanical properties are strength,
hardness, ductility and stiffness
• Nanoparticles have different mechanical properties compared to microparticles or bulk
materials. NMs provide a large surface area and are easy to modify, resulting in an increase
in mechanical properties such as hardness, adhesion, stress and strain, and the elastic
modulus.

• An enhancement of mechanical properties of nanomaterials can result due to this

modification, which are generally resultant from structural perfection of the materials.
The small size either renders them free of internal structural imperfections such as
dislocations, micro twins, and impurity precipitates or the few defects or impurities
present can not multiply sufficiently to cause mechanical failure. The imperfections
within the nano dimension are highly energetic and will migrate to the surface to relax
themselves under annealing, purifying the material and leaving perfect material
structures inside the nanomaterials. Moreover, the external surfaces of nanomaterials
also have less or free of defects compared to bulk materials, serving to enhance the
mechanical properties of nanomaterials
 • While there are numerous properties that may be dramatically changed when the microstructure is
nanoscale, the main aim of this paper is to give a brief overview on those which the recent work with
nanostructured materials has been most extensive that is the mechanical properties of nanostructured
materials such as elastic properties, ductility and toughness, hardness and strength, creep behavior, etc.

• The nano scale size of the nanomaterials tends to modify many of the mechanical properties of
nanostructured materials from the bulk materials. An enhancement of mechanical properties of nanomaterials
generally results from structural perfection of the materials

Mechanical properties like like strength, melting point etc. also shows drastic change at nano scale level.

Mechanical properties of nanomaterials: The unique mechanical properties of nanomaterials are due to the increased number of
surface atoms and interfaces, which in turn leads to increased density of defects like grain boundaries, dislocations, triple
junctions, etc. Nanomaterials exhibit the following mechanical properties as compared to bulk materials:

•Increased strength
•Increased toughness
•Increased hardness
•Increased ductility
•Decreased elasticity
As the Young's modulus of a material increases, so does its tensile
strength. This is because a material with a higher Young's modulus is
stiffer and more resistant to deformation, which means it can withstand
higher stresses before it breaks.
 Young’s modulus

Young’s modulus specifies the measure of the ability of a material to withstand length changes

under tensile or compressive forces. Young’s modulus is defined mathematically as the ratio of

the longitudinal stress to the strain within the elastic range of the material.

Young’s modulus is a fundamental mechanical property of a solid material that quantifies the

relationship between tensile (or compressive) stress and axial strain. It is denoted by the letter

“E” and mathematically expressed as E=Stress/Strain

E=σ/ϵ;
Here σ=Stress=Force (F)/Cross-Sectional Area
(A)=F/A
ϵ=Strain=Change in Length(δl)/Original Length
(l)=δl/l
So, E=(F/A)/(δl/l)=F*l/A*δl
Figure 1 for nanocrystalline Fe prepared by mechanical attrition and measured by a nano-indentation technique.

The intrinsic elastic modulus of a nanostructured

material is essentially the same as that of the bulk
material having micrometer-sized grains until the grain
size becomes very small, less than 5 nm.

Young’s modulus is the factor relating stress and strain.

It is the slope of the stress-strain curve in the linear
region.
The larger the value of Young’s modulus, the less
elastic the material. Figure is a plot of the ratio of
Young’s modulus E in nanograined iron, to its value in
conventional grain-sized iron Eo, as a function of grain
size. We see from the figure that below -20nm, Young’s
modulus begins to decrease from its value in
conventional grain-sized materials.

Figure 1: Plot of the ratio of Young‟s modulus E in nanograin iron to its value Eo in conventional granular iron as a
function of grain size.
 Properties of nanomaterials
 Optical properties
The optical emission and adsorption occurs when the transition of the electrons occur between
these two states.

 Magnetic properties

large surface area to volume ratio results in a substantial proportion of atoms having different
magnetic coupling with neighboring atoms leading to differing magnetic properties.

 Mechanical Properties
The ultra small size (<100 n m) of grains in these nanostructured materials can result in
dramatically improved of different properties from conventional grain size (>1µm) of same
chemical composition. These properties represent the subject of multidisciplinary research
efforts motivated by the wide range of their applications in high technologies.

• Electrical Properties
The changes which occur in electronic properties as the system length scale is reduced are
related mainly to the increasing influence of the wave-like property of the electrons (quantum
mechanical effects) and the scarcity of scattering centers.
Mechanisms for the effects of size on electrical conductivity of nanostructures and
nanomaterials can be generally grouped into four categories:

• Surface scattering
• Quantized conduction
• Coulomb charging and tunneling
• Widening and discrete of band gap.

Other factors:
- Change of microstructures
- Increased perfection
Surface scattering
Electrical conduction in metals or (Ohmic conduction) can be described by the various electron scattering, the total resistivity,
ρT, is a combination of individual and independent scattering, known as Matthiessen’s rule :

where, ρTh – the thermal resistivity, and ρD – the defect resistivity.

Thermal or phonon contribution, increases linearly with temperature.

The equation for this relationship is ρ = 1/σ,

where ρ is resistivity and σ is conductivity

Reduction in material’s dimensions would have two different effects on electrical resistivity:

- One is an increase in crystal perfection thus a reduction in resistivity. However, the defect scattering makes a minor
contribution, and thus has a very small influence on the electrical resistivity.

- The other is to create an additional contribution to the total resistivity due to surface scattering, which plays a very important
role.
- The electrons undergo either elastic or inelastic scattering. In elastic, also known as specular, scattering, the electron does not
lose its energy and its momentum or velocity along the direction parallel to the surface the electrical conductivity remains the
same.
- When scattering is totally inelastic, the scattered electron loses its velocity along the direction parallel to the surface or
the conduction direction, and the electrical conductivity decrease. There will be a size effect on electrical conduction.
Change of electronic structure
A reduction in characteristic dimension below a critical, i.e. the electron de Broglie wavelength, would result in a change of
electronic structure, leading to widening and discrete band gap (changing optical properties and a reduced electrical
conductivity). Some metal nanowires may undergo a transition to become semiconducting and semiconductor nanowires may
become insulators (quantum size effects). For example, single crystalline Bi nanowires undergo a metal-to-semiconductor
transition at a diameter of ≈ 52nm. Si nanowires of ≈ 15 nm became insulating.

Band gap varies with size

Decreasing size

The electrical conductivity of nanomaterials is generally lower than bulk materials. This is
because the band gap energy increases as the particle size of the nanomaterials decreases.
But, there are some exceptions
The properties such as conductivity or resistivity are considered under the category of electrical properties. Similar to optical or magnetic
properties, these properties are also observed to change at the nanoscale level.

The electrical properties of nanomaterials mainly concern the mobility of the charge carriers. When the dimensions of a material are
reduced to the nanometer range, the quantum-size effect and quantum confinement effect are bound to occur. Because of the
quantization of electron energy, some conductive metal nanoparticles can be turned into nonconductive under certain voltage. For
example, metals used as conductors such as copper can lose their conductivity if their size is reduced to a few nanometers, whereas
insulation materials such as silicon dioxide under size reduction will lose their insulating properties and become conductive
(exceptional case ).

Increased interfacial atoms or ions, sinking a large amount of

defects near the grain boundaries, grain size, and doping
impurities largely controls the dielectric properties, resistivity and
electrical transports of nanomaterials. The electrical conductivity
of nanomaterials is generally lower than the bulk materials due to
the increase of the band gap energy with a decrease in particle
size of the nanomaterials, especially for semiconductor
nanomaterials. For example, as the energy bands cease to overlap
at 2–3 nm range, in spite of being metallic, gold nanoparticles
cease to be conductive and turn into insulators.

https://sci-hub.se/downloads/2020-07-04/bc/[email protected]
7.pdf
With decreasing the size in discrete nanoclusters comprised very few atoms, the number of energy states decreases and
consequently the increasing spacing between adjacent energy levels result a shift in conductive properties of the
nanocluster, from metallic to semiconducting and insulating. The shifting of conductive properties from metallic to
semiconducting/insulating in discrete nanoclusters is shown in Fig. 15.10 (previous slide).

This fact is valid only for 0D nanomaterials, whereas for 1D or 2D nanomaterials, such as nanowire
or nanotube, the electrical conductivity may even increase relative to the aspect ratio and ordering in the structure of the
nanomaterials. Mechanical thinning or decreasing the diameter of nanowire at a constant applied voltage the number of
electron wave modes contributing to the electrical conductivity is becoming increasingly smaller by well-defined quantized
steps. When the diameter of the nanowires goes below the 20 nm, due to increased surface scattering for electrons and
phonons, increased surface areas, and very high density of electronic states, the conductivity of nanowires increases
abruptly compared to the bulk materials .

Carbon nanotubes also show a wide range of electrical behavior ranging from insulating, semiconducting, and metallic to
superconducting depending on their chemical composition, crystal structure, and size.

In a summary, reduction in material’s dimensions will increase crystal perfection or reduction of defects, which would result
in a reduction in defect scattering and, thus a reduction in resistivity and conductivity increases.
116
 Effect of nanostructure

Long range atomic periodicity leads higher device

performance