Physics of Nanomaterials
Module I
Nanotechnology
Learning objectives
Introduction to nanocrystalline materials, Brief history of research in nanomaterials,
Significance of nanotechnology,Finite size effects and properties, Classification of nanostructure
materials, Challenges and future prospects
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The size of nanoscale objects and phenomena compared with the size of small everyday objects.
Courtesy of Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy.
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1.What are nanomaterials? Compare nanoscale with bulk observable things.
Nanomaterials:
1. The materials which are created from blocks of nanoparticles or they are defined as a set of
substances where at least one dimension is less than approximately 100 nanometers.
2. Nanoscience is a new discipline concerned with the unique properties associated with
nanomaterials, which are assemblies of atoms or molecules on a nano scale. „Nano’ refers a
scale of size in the metric system.
3. It is used in scientific units to denote one-billionth of the base unit - approximately 100,000
times smaller than the diameter of a human hair. ‘Scale’ refers an order of magnitude - of size or
length- reference to objects that are sized on a scale that is relevant to nanometer.
4. A nanometer is 10-9meter (1nm = 10-9meter), a dimension in the world of atoms and molecules
(the size of H atom is 0.24 nm and for instance, 10 hydrogen atoms lined up measure about 1
nm).
5. For comparison, a red blood cell is approximately 7,000 nm wide and a water molecule is
almost 0.3nm across.
6. People are interested in the nanoscale (which we define to be from 100nm down to the size of
atoms (approximately 0.2nm)) because it is at this scale that the properties of materials can be
very different from those at a larger scale.
7. Nanomaterials are of interest because at this scale unique optical, magnetic, electrical, and
other properties emerge. These emergent properties have the potential for great impacts in
electronics, medicine, and other fields.
8. Nano carbons such as fullerenes and carbon nanotubes are excellent examples of
nanomaterials.
2. How nanomaterials are more interest than bulk materials? Give significance of
Nanotechnology.
1. The bulk properties of materials often change dramatically with nano ingredients. Composites
made from particles of nano-size ceramics or metals smaller than 100 nanometers can suddenly
become much stronger than predicted by existing materials-science models.
2. For example, metals with a so-called grain size of around 10 nanometers are as much as seven
times harder and tougher than their ordinary counterparts with grain sizes in the hundreds of
nanometers.
3. The properties of materials can be different at the nanoscale for two main reasons:
First, nanomaterials have a relatively larger surface area when compared to the same
mass of material produced in a larger form. This can make materials more chemically reactive,
and affect their strength or electrical properties.
Second, quantum effects can begin to dominate the behaviour of matter at the nanoscale -
particularly at the lower end - affecting the optical, electrical and magnetic behaviour of
materials. Materials can be produced that are nanoscale in one dimension (for example, very thin
surface coatings), in two dimensions (for example, nanowires and nanotubes) or in all three
dimensions (for example, nanoparticles)
4. Properties like color, melting point, electrical, magnetic properties etc. for bulk materials
doesn‟t depend on size, but after a certain size limit which is less than 100 nm the properties
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changes. For example, bulk gold is yellowish in color but at nanoscale it is ruby red. Therefore,
the properties of materials change when we approach nanoscale. Thus, it is possible to arrange
molecules in a manner/way that is different from their natural or normal occurrence and hence
bring about a change in the properties of materials. Nanotechnology, thus possesses the ability to
create better materials, and devices.
Significance
Nanomaterials in Automobile industry: The Auto mobile parts prepared from Nano materials
are flexible, light weight and exhibiting high strength compared to the bulk. We can use these
nanomaterials in cars, aero planes etc.
Example nanomaterials: Carbon nanosheets, Graphene sheets.
Nanomaterials in Electronics: Many electronic products such as computers, mobile phones,
photographic cameras and memory cards/hard disk drives etc., were already reduced in their size
and also improvement in their performance. This is mainly due to the transistor size reduction by
Nanotechnology/nanomaterials.
Example nanomaterials: Carbon nanotubes, semiconductor nanowires, nanorods.
Nanomaterials in Energy: Solar cells prepared from Nanomaterials are able to produce much
power/efficiency compared to the bulk. This high efficiency is attributed to the large surface area
and light trapping capability of the nano material. We are also able to produce high storage Li-
ion batteries using nanomaterials. These Li-ion batteries are very useful in cell phones,
automobiles etc.
Example nanomaterials: Silicon nanowires, Zinc oxide, Titanium oxide nanowires.
Nanomaterials in water purification: Due to large surface area of Nanomaterials, water
purification by these nanomaterials are efficient, clean and also cost effective (cheap) compared
to bulk.
Example nanomaterials: Nano TiO2, Carbon nanotubes,
Nanomaterials in medicine: Nanomaterials are very helpful in the drug delivery with precise
control over the delivery location. Nanomaterials are reacting only with the infected cells without
damaging the healthy cells in thehuman body.
Example nanomaterials: Au, Ag nanoparticles.
Super hydrophobicity: Nanomaterial coating on any surface act as a super hydrophobic surface
like as a lotus leaf. This behavior is due the air trapped between the nano materials,which pushes
the water drop up. We can coat water repellent (super hydrophobic) coating on any surface such
as clothes, metals, shoes, car windshield, window glasses and tissue papers etc. The above said
surfaces act as a super hydrophobic surfaces like shown in below.
Example nanomaterials: Silicon nanowires,
Nanotech and Nature
Nanotechnology is a new word but not a new process and field. Nature, is filled with
objects that function on micro to nano scale. The bacterial flagella rotates at over 10,000 rpm
(revolutions per minute) giving us a classic example of biological molecular machine. Another
example would be the Lotus effect, which refers to high water repellence exhibited by leaves of
lotus plant. Dirt particles are taken up and removed by water droplets due to complex
architecture at the surface of leaves of lotus plant involving manipulation at micro-nanoscopic
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scale! This principle has been used to develop treatments, coatings, paints, fabrics on other
surfaces that can stay dry and clean themselves in a similar way.
Nanotechnology and Biology
Nanotechnology and Biology are strongly interlinked; there are many biological systems with
nanoscale dimensions.For example, diameter of DNA molecule is around 2 nm and size range of
many enzymes is few nanometers. Applications of Nanotechnology in Biology ranges from
detection of pathogens and biomolecules, Drug and Gene delivery, Diagnostic and Treatment of
cancer, Tissue Engineering and Creation of nanostructures mimicking biomolecules.
Nanobiotechnology or Bionanotechnology
Nano-biotechnology is defined as a field that uses nanoscale principles and techniques to
understand and transform biosystems. The field of nanobiotechnology is best described as
helping modern medicine in overcoming barriers in effective treatment and diagnostic of disease.
Small magnetic nanoparticles have opened a new window of diagnostic and treatment of cancer,
these small magnetic nanoparticles can be used as contrast agent for Magnetic Resonance
Imaging(MRI) and for hyperthermia (heating of tumor cells in temperature range of 42-45˚C )
treatment of cancer. Non-Cancerous cells are less susceptible to high temperature so
hyperthermia treatment do not affect non-cancerous cells.
Bio-nanotechnology is defined as a field that uses biological systems to develop
nanoscale systems, like DNA nanotechnology which utilizes properties of nucleic acids (DNA)
to create useful materials. It is best described as development of new nanostructures, devices and
materials taking inspiration from nature.
The primary objective of this field of nanobiology (Nanobiotechnology and
Bionanotechnology) is to apply nanotools in biological systems to overcome the current
problems in medical/biological world and also developing better nanotools by mimicking
processes happening in biology.
3. What is Size effect? Explain surface to volume ratio and Quantum confinement? Or
Why the properties of nanoparticles are different?
The properties of nanomaterials are very much different from those at a larger scale.
Two principal factors cause the properties of Nano Materials to differ significantly from other
materials (1) Increased relative surface area and (2) Quantum confinement effect. These factors
can charge or enhance properties such as reactivity, strength and electrical characteristics.
Why properties of nanomaterials are different? The following two factors make the
nanomaterials to have considerably different properties that its bulk one. 1. Increase in relative
surface area 2. Quantum confinement effect
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Increase in surface area to volume
Nanomaterials have a relatively greater surface area when compared to the same volume or mass
3
of the same material in bulk form. For example, consider cube of 1m volume (Fig.), it has
2
surface area of 6m . If this cube of same volume is divided into eight small cubes, then the total
2
surface area increases to 12m . Further dividing cube leads to increase in surface area. This is
illustrated in the following figure. Also if the size of nanomaterials decreases, a greater
proportion of atoms are found at the surface compared to those inside. This makes materials
more chemically reactive.
Large surface to Volume ratio: Nanomaterials have a relatively
large surface to Volume ratio when compared to the same
volume of the material in bulk form. For example consider a
sphere of radius “r”
Surface area = 4πr2
Volume=4πr3/3
Surface/ Volume = 3/r
As “r” decreases Surface/Volume ratio increases
Quantum Confinement: In nanocrystals, 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
If one length of three dimensional nanostructures is at nano-dimension, then it is called a
Quantum Well. If two sides of three dimensional nanostructures are at nano-dimension, then it is
called a Quantum Wire. If all three dimensional nanostructures is at nano-dimension (Nano
Crystals), are referred as Quantum Dots (QDs).
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4. Define nanoscale materials and give classification of nanomaterials. OR
Give classification of nanomaterials based on dimension? OR
What are low dimensional nanoparticles? Give classification of nanomaterials.
Nanoscale materials: The materials which are created from blocks of nanoparticles or they are
defined as a set of substances where at least one dimension is less than approximately 100
nanometers
A Nanocrystallite is generally understood to possess crystalline order in addition to nanoscale
size. They can exist in single, fused, aggregated or agglomerated forms with spherical, tubular,
and irregular shapes.
Classification of nanomaterials:
Nano-structured materials are classified as
1.Zero Dimensional(0 D),2.One Dimensional (1D),3.Two Dimensional (2 D),4.Three
Dimensional(3 D)
1. Zero Dimensional (0 D): If all the three dimension of the nanostructure is at nano scale, then
it is called Zero Dimensional(0 D) materials
a. Nanocrystallites are also called quantum dot.
b. e.g., precipitates, colloids
2. One Dimensional (1D): If two dimension of the three dimensional nanostructure is at nano
scale, then it is called One Dimensional (1D) materials
a. Nanocrystallites are also called quantum wire.
b. e.g., nano fibers, nano rods
3.Two Dimensional (2 D): If one dimension of the three dimensional nanostructure is at nano
scale, then it is called Two Dimensional (2 D) materials
a. Nanocrystallites are also called quantum well.
b. e.g. surface films,
4.Three Dimensional(3 D): If all dimensions of the three dimensional nanostructure is at bulk
scale, then it is called Three Dimensional (3 D) materials
a. e,g.Grains and grain boundaries
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5. Almost every element in the periodic table, together with various alloys and compounds, can
form nanoparticles. They can be metallic, semiconducting, or insulating and typically their
properties are very different to those of the corresponding bulk material.
6. An important idea that underpins much of nanotechnology is that by controlling composition,
size, and structure at the nanoscale one can engineer almost any desired properties.
7. For an object of the macroscopic size, the surface atoms comprise a negligible proportion of
the total number of atoms and will therefore play a negligible role in the bulk properties of the
material. When the size of the object is reduced to the nanometric range the proportion of surface
atoms no longer negligible. So a large fraction of the atoms are located at the surface of the
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object in the nanomaterials, it will modify its properties. The properties of nanomaterials become
totally different from what is observed in the bulk solid system
5. Give different properties of nanomaterials? Explain variation of properties with nano
size
Properties of Nanomaterials: Nanomaterials have properties that are different from those of
bulk materials. Most nanostructure materials are crystalline in nature and they have unique
properties. Filling polymers with nanoparticles or nanorods and nanotubes, respectively, leads to
significant improvements in their mechanical properties.
Physical Properties: Crystal structure of nanoparticles 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 nanoparticles
decreases with size.
Optical Properties: Nanocrystalline systems have novel optical properties. Depending on the
particle size different colors are seen. Gold nanospheres of 100 nm appear orange in colour while
50 nm appear green in colour. If semiconductor particles are made enough small, quantum
effects come into play, which limit the energies at which hole and electrons exist inside the
particles. The particle are made to emit or absorb specific wavelengths (colours) of light,merely
by controlling their size.
Chemical Properties: A large fraction of the atoms are located at the surface of the
nanomaterial which increase its reactivity and catalytic activity. The large surface area to volume
ratio, the variations in geometry and the electronic structure of nano particles have a strong effect
on catalytic properties.
Electrical properties: The energy band structure and charge carrier density in the materials can
be modified quite differently from their bulk and in turn will modify the electronic properties of
the materials. Nanoparticles made of semiconducting materials like Germanium, Silicon and
Cadmium are not semiconductor. Nanoclusters of different sizes will have different electronic
structures and different energy level separations. So they show diverse electronic properties
which depend on its size.
Magnetic Properties: The magnetic moment of nano particles is found to be very less when
compared them with its bulk size. Actually, it should be possible that non-ferromagnetic bulk
exhibit ferromagnetic-like behavior when prepared in nano range. Bulk Gold and Pt are non-
magnetic, but at the nano size they are magnetic.
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Reduction of lattice parameter
Laplace tension PL for nanoparticle is so big that can cause a bulk
compression that in turn reduces a lattice parameter on the a value
shown in fig. It may be estimated from the rule of proportionality:
The value is small but it is able to cause phase transitions under
some conditions. For example, the inclusions of Y2O3 in oxide
ZrO2 change its structure from monoclinic into triclinic.
For some alloys the reversible effect is arisen, e.g. the increasing of lattice parameter in
nanoparticles. That means that sign of the effect depends not only Laplace pressure but on a
change of interatomic potential and forces under transition from a bulk to surface.
Decrease in melting point
Fig. illustrates the general experimental dependence of a melting
point Тm on the nanoparticle size d showing a decrease in Tm with
d reduction. Its physical origin is the increase of surface energy,
the increase of amplitude of atomic vibrations, and the additional
surface growth of thermal vibration energy in the result.
Increasing of plastic yield strength and
hardness of polycrystal
In physics of strength the Hall-Petch relation is well known of
which accordance a hardness and yield strength are increased under
the reduction of the grain size d of polycrystal:
where deformation strength of monocrystal is, is a strength of
polycrystal, К1 is a coefficient of fracture ductility. The
dependence is shown in fig. and successfully used in the industry.
However in extreme case this relation do not works. The
critical size d =d * exists when approaches its maximal value and then drops again. The
reason is disappearance of dislocation, the carriers of plastic deformation, due to nanoparticle
size becomes to be smaller than a dislocation length, d<ldislocation, because of which all
dislocations come to a surface.
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Blue shift – the increasing of band gap and
luminescence frequency
Fig. Shows the transformation of a luminescence spectrum of
ZnO under conversion to nanostructured state. A blue shift of
luminescence spectrum under a reduction of the particle
(grain) size is seen
Dependence of dielectric permittivity of barium-titanate ceramics BaTiO3 on size of
nanoparticles
Under decreasing of size of polycrystal the size of single
domain is constant or weakly changes, so the number of
domains is decreased at first stage of the size decreasing, that
result in decrease of total magnetic moment. At d=d* (~100
nm), the total moment of polycrystal decreases to a moment of
single domain. Further decreasing of domain size, when a
nanoparticle size becomes smaller than a spin wave length
, causes a decrease of the number of atomic magnetic
moments, their correlation energy is decreased and at some critical value (d*~10 nm) it becomes
to be smaller than induced magnetic moment of single atom. From this size all magnetic
properties of nanoparticle with depends on the induced magnetic moment of single
atom, meaning a phase transition in a paramagnetic state.
Broadening of energetic bands
Electronic spectra of atoms are known to be the discrete
spectrum of energy levels En.
In accordance with Pauli principle two or more electrons
cannot occupy the same place or take the same energy.
Therefore the energy levels are splitten to some small
value n, forming an energetic band, a width of which is
proportional to a number of the levels or atoms N,
. It means that the band gap increases
simultaneously when reducing the size of particle, hence
. From fig. is seen that the luminescence
frequency is proportional to g E due to . Hence for nanoparticles the luminescence
frequency is increased , that in physical sense is just the blue shift.
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6. Write a short note on challenges and future prospects of nanaomaterials?
Nanotechnology Challenges
1. Providing Renewable Clean Energy
2. Supplying Clean Water Globally
3. Improving Health and Longevity
4. Healing and Preserving the Environment
5. Making Information Technology Available To All
6. Enabling Space Development
Challenge -1
Synthesis/Preparation: The challenge is to design, to synthesize, and to characterize new
functional nanomaterials with controllable sizes, shapes, composition, and/or structures.
Ex: Preparing a p-n junction in the form of a nanowire.
Challenge -2
Nanomanipulation: Handling nanomaterials/manufacturing nanodevices using nanomaterials is
an another challenge due to nanoscale features.
Ex: Preparing single nanowire transistor.
Challenge -3
Risk with the Nanotechnology:
(a)Human health risks
Inhaled nanoparticles can reach the blood and may reach other target sites such as the liver, heart
or blood cells. The challenge is to study the interaction of nanoparticles and biological systems
(human body).
(b) Environmental health risks
All the electronics waste (Computer,Phone IC chips, Batteries contains nanomaterials) recycling
is a major challenge. Improper recycling leads to polluting the environment with nano materials
specially nanoparticles. Similarly, nanowaste (super hydrophobic nano film coated shoes, cloths,
car wind shield, nano water filter filters,damaged solar panels etc) recycling is a major challenge.
Challenge -4
Providing Renewable Clean Energy
Balancing humankind‟s need for energy to our planet is a major challenge infront of the
nanomaterials. Nanomaterials based solar cells already under production but the challenge is
preparing solar cells with more conversion efficiency, long period usage, less expensive and easy
recycling.
Challenge -5
Supplying Clean Water Globally
Nanomaterial based water filters already producing clean water but the challenge is preparing
water filters with more purification, long period usage, less expensive and easy recycling.
Challenge -6
Making Information Technology Available To All
The use of nanotechnology/nanomaterials will drastically reduce the cost and increase the
performance of memory, displays, and processors. Making technology available for remote
places is a challenge.
Challenge -7
Health and safety (Medicine)
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New methods of drug delivery, faster development of new drugs, repairing DNA and cellular
damage are the major challenges in medical field
Applications of Nanomaterials:
(1) Chemical Industry: Fillers for point systems. Coating systems based on nano composites,
Magnetic fluids
(2) Automotive Industry: Light weight construction, Painting, Catalysts, Sensors
(3) Medicine: Drug delivery systems, Active agents, Medical rapid tests, Antimicrobial agents
and coatings, Agents in cancer therapy
(4) Electronic Industry: Data memory, Displays, Laser diodes, Glass fibers, Filters,
Conductive,antistatic coatings
(5) Energy Sources: Fuel cells, Solar cells, Batteries, Ultracapacitors
(6) Cosmetics: Sun protection creams, Tooth paste
Applications of Nanomaterials in Medicine: Medical application of nanomaterials include
(a) Fluorescent biological labels
(b) Drug and gene delivery
(c) Bio-detection of pathogens
(d) Detection of proteins
(e) Probing of DNA structure
(f) Tissue engineering
(g) Tumour destruction
(h) Separation and purification of biological molecules and cells.
Future application of Nanomedicine is as follows:
(1) The elimination of bacterial infections in a patient within minutes
(2) The ability to perform surgery at the cellular level, removing individual diseased cells and
even repairing defective portions of individual cells
(3) Qdots: that identify the location of cancer cells in the body, here nanomaterials that deliver
chemotherapy drugs directly to cancer cells to minimize damage to healthy cells
(4) Nanocells: that concentrate the heat from infrared light to destroy the cancer cells with
minimal damage to surrounding health cells.
• The cell membranes, and several other functional organelles within the biological cell of living
beings are in fact of nanometric size.
• It is envisaged that nanotechnology will lead to tiny robotic devices, utilizing nanoelectronics,
sensors and MEMS for invivo monitoring and diagnosis of deficiencies and malfunctions of
human systems.
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Module II
MICROSTRUCTURE AND DEFECTS IN NANOCRYSTALLINE MATERIALS
In order to understand the novel properties of nanostructured materials, we need to understand
the structure and its interrelationship with properties. The microstructural features of importance
in nanomaterials include:
• Grain size, distribution and morphology
• The nature of grain boundaries and interphase interfaces
• Nature of intragrain defects
• Composition profiles across grains and interfaces
• Residual impurities from processing
Crystal lattice imperfections, such as point, linear, planar and volume defects, lead to the
structure-sensitive properties of materials.
Crystals: Crystals are three-dimensional, periodic arrangements of atoms/molecules in space
Defect: Any imperfection leading to disruption of periodicity is referred to as a „crystalline
defect
These defects are usually classified based on their dimensionality, namely,
1. point defects (0D),
2. line defects (1D),
3. surface defects (2D) and
4. volume defects (3D).
Point defects: Vacancies and substitutional and interstitial solutes are the common point defects
observed in metals and alloys. In case of ionic solids, Schottky (anion–cation vacancy pairs) and
Frenkel (vacancy-interstitial pairs of the same ions) defects may also be observed.
Line defects: Dislocations are the most commonly observed line defects and refer to a missing
plane of atoms. Among the surface defects, grain boundaries, twins, stacking faults and free
surfaces are the most common.
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Volume defects: Inclusions, voids and micro cracks constitute the volume defects.
Dislocations
Missing rows of atoms in a crystal are regions of high energy and stress due to disruption of the
atomic bonds in the plane. This provides a driving force for dislocations to be annihilated at
surfaces or grain boundaries to minimize the strain energy of the crystal.
Types of Dislocations
1. Edge dislocation
2. Screw dislocation
Voids: Voids in nanocrystallites may be situated at either triple junctions or as large porosities
due to insufficient compaction and sintering of nanocrystallites synthesized from the powder
route.
Stacking faults: crystallographic defects arising due to wrong stacking sequence of planar
arrangement of atoms
Twins: are generally observed in crystals subjected to deformation under high strain rate or at
low temperatures.
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