Topic: Chemistry of Smart Materials (Module 2)

Course: Chemistry

1
2A. Introduction to conductor, semi-
conductor, insulator, band structure of
solids and the role of doping on band
structures.

2B. Chemistry of Nanostructures,

Nanocomposites, graphene and other 2D
materials.
Introduction to conductor, semi-
conductor, insulator, band
structure of solids and the role of
doping on band structures.
Insulators

Semiconductors

Metals
 Valence Band?
The valence band is simply the electron present
in the outermost orbital of an atom of any
specific material.
Conduction Band?
The conduction band is the band of electron
orbitals that electrons can jump up into from
the valence band when excited. These electrons
have tendency to move freely and are
responsible for electrical conductivity.
Band gap energy?
Band gap energy
 Band gap energy of Materials

Copper, Steel,
Glass, Mica, Silicon and Gold, Al, Silver,
Wood, Quartz Germanium Brass, Mercury
 Doping of Semiconductor:

Pure Si and Ge can be made semiconducting of

n-type or p-type in a controlled way by adding
dopants which act as charge carriers.
 n-type semiconductor:

As or P (pentavalent atom) is added deliberately added

to the Si or Ge-crystal. The 5th electron is localized on
the As or P atom. Since the current is carried by excess
electrons, it is n-type semiconductor.
 p-type semiconductor

In or B (trivalent atom) is added deliberately to the Si or

Ge -crystal. Here, B is doped, one electron is missing in
Si-crystal. Missing electron is called positive hole. Here
current is carried by the positive hole, it is p-type
semiconductor.
 Chemistry of
Nanostructures
 Introduction
Nano means 10-9. ( Nanometer is one thousand
Millionth of a Meter)

To understand how small one nmis let us seefew

comparisons
1. A Red blood cell is approximately 7000 nm wide.
2. Water Molecule is almost 0.3 nm across.
3. Human hair which is about 80,000 nm wide.
 Nanomaterials
Nano Materials could be defined as the materials
with at least one of its dimensions in the range of a 1
to 100 Nano meter.

Electron behavior:
Quantum well – 1D confined and changed to
nano range.
Quantum wire –2D confined and changed to
nano range.
Quantum dot – all 3D confined changed to nano
range
 Nanoscienc
e
Nanoscience can be defined as the study of
phenomena and manipulation of materials
at Atomic, Molecular and Macromolecular
scales where properties differ significantly
from those at a larger scale.

Nano Science is the study and

understanding of properties of Nano size of
Particles.
 Properties of Nano size differ significantly
from those at a larger scale
Au is inert (not reactive) in macro scale, in
nano scale Au is very reactive and can be used as
Catalyst.
In Macro scale Auis not soluble but in nano

scale Au particle is soluble.

Opaque (Non transparent) copper become transparent

in case of Cu nano particle.

In Technology
Why properties of Nanomaterials are different?

The properties of Nanomaterials are very much

different from those at a larger scale.

1) Increased relative surface area.

2) Quantum confinement effect. (Restrict the
movement of within a small space, as the
nano materials are small in size)

These factors can change or enhance properties such as

reactivity , strength and electrical characteristics.
 Properties of Nanomaterials
1. The surface area to volume ratio of the
nanomaterials is relatively larger than that of bulk
materials of the same mass. This increases the
chemical reactivity and affects strength and
electrical properties of the material.
2. The quantum confinement is observed at nanometer
sizes that changes the optical, electronic and
magnetic properties of the material. The band gap
increases as the size of the material is reduced to
nanometer range.
 1
m

surface area = 6×1m2 ⇒ 6m2

1
m
2

1
surface area = 6×( m)2 ×8 =
12m2
2
Increase in a Surface Area to Volume ratio

Nano Materials have a relatively larger Surface area

when compared to the same volume or mass of the
material produced in a larger form.
Let us consider a Sphere of radius
“r”. Its Surface Area =4πr2.
Its volume= 4/3πr3
Surface Area to Volume Ratio= 3/r.
Thus when the radius of the Sphere decreases , its
Surface to Volume ratio increases.
 Size-Dependent Properties
Particle-Size vs. Surface Area
If a macroscopic object is divided into smaller parts, the
ratio of surface atoms to interior atoms becomes a
significant number of the total fraction of atoms.

Surface Chemistry of Materials

Due to increased surface area, nanomaterials possess
greater surface energy. The atoms or molecules that
exist on the surface or the interface are somewhat
different from atoms/molecules in the bulk/interior of
the material. These have higher surface energy and are
relatively unstable / more reactive.
 Quantum Confinement
In Nano Crystals, the Electronic energy levels are
not continuous as in the bulk but are discrete (finite
density of states), because of the confinement of the
electronic Wave function to the physical dimensions
of the particles. This phenomenon is called
Quantum confinement and therefore Nano Crystals
are also referred to as quantum dots (QDs).
 Electronic Properties
Various physical properties such as thermal, optical and
magnetic properties are dependent on the electronic state of
the material. Some characteristics of electronic structure of
solids are:
1. In an isolated solid, the electrons move in
quantified energy levels. When the distance
between atoms is less, electron orbitals interact
with each other, which leads to broadening of
energy levels to form energy bands.
2. Optical properties of nanomaterials can be
significantly different from bulk crystals. ( Band
gap increase with decrease in size)
 Energy Bands

▪ Number of molecular orbitals (energy band) formed is same is number of

atomic orbitals which makes the molecular orbital.
As for nano materials, the number of atomic orbital participating in
molecular orbital formation is very few so the number of MO formed is
also very few, so the discrete energy level is formed.
Size Effect vs Energy Levels
 Electronic Properties
❑As the nano particle is close to size of atom/ molecule
Quantum mechanical laws are used to describe their
behavior.

❑According to particle in a box concept –E = n2h2/ 8mL2

❑With decrease in size of nanoparticle (L), The band gap
increases.
❑Addition and subtraction of every single atom changes the
electronic property of the nano particle.
❑ With decrease in size of nano particle, the band gap
increases.
 Quantum dot
A quantum dot is a crystal semiconductor material
whose diameter is on the order of several nanometers a
size results in its free charge carriers experiencing
“quantum confinement” in all three spatial dimensions.

The electronic properties of quantum dots are

intermediate between these of bulk semiconductors
and of discrete molecules and closely related to their
size and shape.

This allows properties such as;

The bandgap, emission colour and absorption
Spectrum: Highly tunable band gap energy
during fabrication

Applications of quantum dots are:

o Transistor
o Solar cells
oLeDs
o Diode laser
 Synthesis of Nanomaterials

• High energy Ball Milling •Chemical vapor

• deposition
• Laser abalation
technique
•Chemical synthesis
 Nanocomposites

Nanocomposites are materials that incorporate

nanoparticles into a matrix of material. The result
of the addition of nanoparticles is a drastic
improvement in properties that can include
mechanical strength, toughness and electrical or
thermal conductivity.
The effectiveness of the nanoparticles is such that
the amount of material added is around ≤ 20 % by
weight.
 Properties of Nanocomposites

Nanocomposites can dramatically improve properties

like:
❑ Mechanical properties (strength, modulus and
dimensional stability)
❑ Electrical conductivity
❑ Thermal conductivity
❑ Chemical resistance
❑ Thermal stability
❑ Optical Property
 Applications of Nanocomposites
Nanocomposites are currently being used in a number
of fields and new applications are being continuously
developed.
• Thin-film capacitors for computer chips
• Solid polymer electrolyes for batteries.
• Supercapacitors
• Automotive engine parts and fuel tanks
• Impellers and blades
• Oxygen and gas barriers
• Food packaging
• Bio-medical applications
Graphene & other 2-D Materials
Two-dimensional materials are substances with a
thickness of a few nanometres or less. Electrons in
these materials are free to move in the
two-dimensional plane, but their restricted motion in
the third direction is governed by quantum
mechanics. Prominent examples include quantum
wells and graphene
These materials have found use in applications such as photovoltaics,
semiconductors, electrodes and water purification.
 Properties of Graphene
Graphene is an allotrope of carbon in the form of a single layer
of atoms in a two-Dimensional honeycomb structure in which
one atom occupies each vertex.

Highest flexible elastic

Electrical conductivity ~2000 S cm-1
Sp. SA 1500 m2/g
Thermal conductivity ~5300 Wm-1K-1
Semi metal & zero-gap semiconductor
Stronger than steel, harder than
diamond, yet stretchy like rubber,
‘wonder material’ graphene
promises to transform future
technologies.
• Graphene is more than 100 times stronger
than the strongest steel!

• Weigh ~1/40 of aluminum

 Electronic

Biomedical Fuel cell

Graphene

Super-capacit Photovoltaic
or Cell

Mechanical
 Graphene
Properties: Applications:
❖High electrical conductivity (2×102 S/m) ✔Supercapacitors

❖ Thermal conductivity ✔ Solar energy conversion

❖ Breaking strength (40 Nm-1) ✔ Secondary batteries

❖ Young modulus ( ten times greater than steel) ✔ Fuel cells

✔ Bio-medical diagnosis & Therapy
 Other 2-D Materials
❑2D boron nitride is an sp2-conjugated compound
that forms a honeycomb structure of
alternating boron and nitrogen atoms with a
lattice spacing of 1.45Å.
❑It adopts the hexagonal (h-BN) allotrope of the
three possible crystalline forms of boron nitride
because it is the most ubiquitous and stable
structure.
❑Due to several similar structural similarities
with graphene, boron nitride nanosheets are
considered graphene analogs, often called “white
graphene".
 Applications
Boron nitride nanosheets have a wide bandgap that
ranges from 5 to 6 eV. Due to this large bandgap and
tunability as well as its surface flatness, boron nitride
nanosheets are considered to be an excellent electric
insulators and are often used as dielectrics in electrical
devices.[
2D boron nitride structures are excellent thermal
conductors,[with a thermal conductivity range of 100–270
W/mK.
The thermal stability of boron nitride nanosheets is very high
. As single layer and few-layer boron nitride nanosheets
begin to oxidize and lose their electrical properties at 800 °C.