Nanoscience and Nanotechnology
Dr. M. Midhun Kumar
Assistant Professor
School of Chemical Engineering (SCHEME)
Vellore Institute of Technology, Vellore
Email ID: midhunkumar.m@[Link]
Course Assessment Configurations
Assessment Title Marks Exam Dates
Quiz 10 Jan, 19-23
Critical Review of
20 Apr, 6-10
Research Paper
CAT- Continuous
15 As per the Institute
Assessment Test ‐ I
CAT- Continuous As per the Institute
15
Assessment Test ‐ II
FAT ‐ Final Assessment As per the Institute
40
Test
About the course
Inside the course
Module-1
Introduction
What and
Why?
Nanoscience and Nanotechnology
• Distinguish between Science, Engineering and Technology
Fundamentals
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Definitions
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.
Nanotechnology is the design, characterisation, production and application of structures,
devices and systems by controlling shape and size at nanometer scale:~ (0.2–100) nm
(where unique phenomena enable novel applications)
Encompassing nanoscience, engineering and technology, nanotechnology
involves imaging, measuring, modeling and manipulating matter at this length scale.
(The Royal Society 2004)
Why do nanoparticles show different properties?
Very high surface area to volume ratio
•More atoms are on the surface than in the bulk.
•Surface atoms are more reactive.
•This changes catalytic, thermal, and mechanical properties.
Quantum confinement effects
•When particle size is close to the electron wavelength, quantum effects appear.
•This changes optical, electrical, and magnetic behaviour.
These two effects are strongest in the nano range, which is why this size is considered
special.
Size range Do properties change? Reason
Bulk (>100 μm) Mostly normal Classical behavior
Micro (1–1000 μm) Slight changes Surface effects
Nano (1–100 nm) Major changes Surface + quantum
Atomic/molecular scale
Pico (<1 nm) Very different
quantum
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Module_1
#Lecture-2
Introduction
• Matter is composed of atoms and molecules
• But, get converted into one another depending upon their stability at different
pressures, temperatures or variations of both
• At the triple point, solid, liquid and gas co-exist.
• Beyond the critical point, there is no distinction between the gas and liquid phases
• The density of gas is usually very low, whereas that of solids and liquids is high
• In solids and liquids, the distances between atoms or molecules are typically 0.2–0.4
nm, while in gases, they are 3-4 nm.
Note: One can see that the density and distances between the atoms or molecules for both liquids and solids are
comparable
Introduction
• Liquid does not have a particular shape and takes the shape of its container
• Why not for gases and solids?
• Atoms or molecules in a liquid, as in a gas, are under a state of continuous,
random motion known as Brownian motion
• In solids, the atoms and molecules are also in a state of motion, but the
motion is about their fixed positions.
• Atoms and molecules vibrate about their fixed positions with some
characteristic frequencies.
Contd…
• Let us now consider a solid like Al2O3. It can appear as a transparent,
opaque or translucent even without change of its chemical formula or
presence of impurities.
• Why is it so? What is the origin of such a change, one may wonder!
• Crystalline vs. Amorphous
• Single crystal, polycrystalline and
Introduction
• In a ‘single crystal’, there is an almost infinitely long arrangement of atoms or
molecules with certain symmetry characteristics of the material.
• When we say infinite distance, it means a length many times larger than the
distance between two atoms.
• In a polycrystalline solid, there are some ‘grain boundaries’.
• A grain boundary is the interface between two crystals (grains) in a polycrystalline
solid where the atomic arrangement is misaligned
• Many small nuclei begin to grow as crystals.
• Each grows in a different direction.
• When they meet, their misoriented crystal lattices cannot
perfectly match → grain boundary forms.
• The size of the grain can depend upon the processing and typically can be
few microns.
• Each grain itself is a ‘single crystal’ but the orientations of these different
crystals are different or random.
• Each grain also has a kind of ‘grain wall’ in which atoms may be more or
less randomly distributed.
• The thickness of such walls is often very crucial in determining the various
properties of materials such as mechanical, optical or electrical.
• At the grain boundary, the long-range periodicity of the solid is broken.
• If each grain in the material becomes too small, comparable to the
distance between the atoms or molecules, we get what is known as an
‘amorphous’ solid.
• In amorphous solids, the grain boundaries disappear.
• Thus, transparent, precious form of Al2O3 known as ‘sapphire’, a gemstone,
is a single crystal; its translucent form is a polycrystalline, and the opaque
form is an amorphous solid.
• Although the distances and even the arrangement between nearest or even
next nearest atoms may look similar for most of the atoms, they lack long-
range order as in a poly or single crystal.
• Consider, for example, diamond and graphite, two well-known crystalline forms of
carbon.
• Diamond is transparent, colourless and very hard.
• Graphite with the same chemical constituent viz. carbon is soft, black and opaque.
• Diamond is electrically insulating, but graphite is conducting.
• Why do two materials made of the same constituents differ so much?
• For this, one should try to understand how the atoms in two materials are
arranged, how the arrangement of atoms affects the bonding of atoms and
ultimately the properties.
• The differences in the properties are usually correlated to the
arrangement of atoms or structure and bonding.
• By studying a large number of solids, scientists have been able to
understand how atoms are arranged in different crystal structures.
• This has led them to make a classification and develop some useful
techniques by which one can identify atomic arrangements in some
unknown sample.
• We shall start with some definitions to understand all this.
Arrangements of atoms
Lattice: It is an arrangement of points repeated in one, two or three directions, making
it a one-dimensional, two-dimensional or three-dimensional lattice.
• A lattice point is an imaginary point in space that represents a position where
the environment is identical throughout the crystal.
• A lattice point is NOT an atom, but a location where an atom can be placed.
Crystal: When an atom or a group of atoms are attached to each lattice point,
it forms a crystal
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Unit Cell: Crystal structures can be understood in terms of unit cell, which
when translated in any direction, can fill the complete space without leaving
any space in between or without overlapping.
Unit cell is a conventional cell and can be of any volume, size, orientation
or shape.
However it is often taken in such a way that it has atoms at some corners or
centre.
Primitive Cell: Unit cell with smallest volume is known as ‘primitive cell’.
• It is also necessary to consider the unit cell vectors, which define the
boundaries or edges of the unit cell.
• It can be seen that in direction of a, if we translate the cell by ‘a unit, the cell
is repeated. The same is true for b. Thus, a and b are translation vectors.
A Wigner–Seitz cell is a special
type of primitive cell used to
describe the arrangement of
atoms in a crystal lattice.
• Translation vectors of primitive or smallest unit cell are known as
‘primitive vectors’.
• It is not always necessary to consider primitive vectors but one can have
‘unit vectors’ of any convenient length.
• As is clear from above figure, the choice of unit cell, unit vector, primitive
cell or primitive vector is not unique.
• In order to classify the crystals further, it is necessary to understand
certain symmetry operations around a point (also known as point
operation, which helps to classify the crystals).
Symmetry: Symmetry transformation about a point is the one which
leaves the system invariant or without any change even after some
operation.
• Rotational Symmetry: Circle is a perfectly symmetric object which
can be rotated about an axis through its centre by any angle without
it appearing as if it were rotated.
• Thus by rotating through any angle we make an invariant
transformation for a circle or a sphere
• Three-dimensional solids are divided into seven crystal systems and
fourteen Bravais lattices
• Any three-dimensional crystalline solid (except quasicrystals to be discussed
later in this chapter) would be one or the other type of the fourteen Bravais
lattices.
Module_1
#Lecture-2
Quasi Crystal
• Quasicrystals are solids exhibiting long-range atomic order without
periodic repetition, characterised by aperiodic tiling and sharp diffraction
patterns with symmetries forbidden in classical crystallography.
• They are poor heat and electricity conductors.
• They also do not rust easily. Ex: metallic alloys like AlMn, AlPdMn
Liquid Crystals
• Liquid crystals are materials that exhibit an intermediate phase between liquid
and solid, where molecules flow like a liquid but maintain some orientational
or positional order like a crystal.
• They are widely used in the display screens of televisions, computers,
watches and many other applications.
Bonding in Solids
• When two atoms approach each other, they start interacting.
• The type and the amount of interaction depend upon the distance between the
two atoms and the type (element or electronic configuration) of the atom.
• Consider two atoms
• The attractive force and the repulsive force between the two atoms due to mutual
electrostatic interaction
• This arises due to the positive charges of nuclei and the negative charges of
electron clouds
• All other forces are neglected
• At a certain distance between the two atoms, the
attractive interaction dominates as compared to
the repulsive interaction.
• At this distance, say ro, the two atoms can form
what is known as ‘bond’ with ‘bond energy’ Eo
• The equilibrium distance at which the energy is Eo
is the ‘bond length’ of the molecule.
• The phenomenon leads to different types of bonds
• As the atoms come closer or have a distance
smaller than ro between them, their electron
charge clouds start overlapping.
• Due to similar charges, they start repelling each
other.
Covalent Bond
• When two atoms form a molecule by sharing some of their valence electrons, a
covalent bond is established.
• Sometimes atoms may use all the valence electrons for sharing.
• Stable electronic configuration is required
• When two hydrogen atoms come very close to each other so that their 1s shells
overlap, then both have as if two electrons.
• Therefore, they form a molecule attaining a state of lower energy together than
both were independent.
• Other molecules like CH4, O2 or N2 which are covalent in nature
• In solids we have covalent bonds in many crystals like
diamond, silicon, germanium etc.
• Electronic configuration of carbon
• This enables each carbon atom to have four bonds (known as
sp3 bonds), which are then shared with four neighbouring
carbon atoms.
• This also gives rise to a tetrahedral arrangement of carbon
atoms so that the angle between C-C-C atoms is equal.
Ionic Bond
• A chemical bond is formed when atoms are in the vicinity and electrons (s) from
one atom is transferred to another.
• The one able to transfer the electron or electrons is termed as electropositive
and the one that tends to accept electron or electrons is known as
electronegative.
• The ions thus formed are called cations and anions, respectively
• NaCl, KCl and CaCl2 are good and simple examples of ionic bond formation.
• The energy required to remove an electron from a metal atom, like a sodium
atom, is known as the energy of ionisation.
• Ionic crystals are easily soluble in polar liquids like water, high melting point
• In general, electrically and thermally nonconducting.
Metallic Bond
• Atoms like Na, K, Cu, Au, Ag, Fe, Co and Ca in which there are one or more electrons
which can be easily removed (valence electrons) from them form metals and the bond
that holds the crystal together is known as metallic bond.
• The loose electrons can move quite easily from one atom to another and cannot be
localised to a particular atom or the other.
• Such electrons form what is known as an electron gas (of free electrons) and are
responsible for the metallic bond, which is an electrostatic interaction between the
positive ions of atoms that have lost the electrons and are unable to move themselves
(however, ions vibrate about their mean positions) in the crystal.
• The free electrons in metals respond to electric or magnetic field quite easily making
them electrically or thermally good conducting materials.
Miller indices