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UNIT - I

1 Introduction

Syllabus

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Nanoscale Science and Technology - Implications for Physics, Chemistry, Biology and
Engineering - Classifications of nanostructured materials - nano particles - quantum
dots, nanowires - ultra - thin films - multilayered materials. Length Scales involved and
effect on properties : Mechanical, Electronic, Optical, Magnetic and Thermal properties.
Introduction to properties and motivation for study (qualitative only).

Contents
1.1 Nanoscale Science and Technology
1.2 Implications for Physics, Chemistry, Biology and Engineering

1.3 Classifications of Nanostructured Materials

1.4 Nano Particles


1.5 Quantum Dots, Nanowires

1.6 Nanowire

1.7 Ultra-thin Films

1.8 Multilayered Materials


1.9 Length Scales Involved and Effect on Properties : Mechanical, Electronic,
Optical, Magnetic and Thermal Properties
1.10 Introduction to Properties and Motivation for Study
1.11 Part A : Short Answered Questions [2 Marks Each]

1.12 Part B : Long Answered Questions

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Fundamentals of Nanoscience (1 - 2) Introduction

➠ 1.1 Nanoscale Science and Technology


 Nanoscale science involves understanding the fundamental interactions of physical systems
confined to nanoscale dimensions and when matter is controlled at the nanoscale,
fundamental properties of things like temperature, electricity, magnetism and chemical
reactions can change completely. The laws of classical physics describe our cosmic
universe : The motions of the planets, the trajectory of a baseball and the behavior of things
we experience everyday. However, the laws of quantum mechanics apply in the nano-
world. The operation of computer chips in present-day computers can be explained by the

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laws of classical electron flow; but when electrons are confined to nanoscale dimensions,
they behave according to the laws of quantum mechanics. Consequently, future chips made
with nanoscale dimensions (called q-bits) will process information differently and lead to
computers with new logic and functionality. Similarly, materials formed from nanoscale
grains can exhibit dramatic property improvements and drugs at the nanoscale can become
more effective with fewer side effects. Nanoscale science strives to understand these
changes.

Fig. 1.1.1
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Fundamentals of Nanoscience (1 - 3) Introduction

 Nanoscale science and technology refers to the understanding and controlled manipulation
of structures and phenomena that have nanoscale dimensions. Scientists have adopted the
Greek word nano as a prefix to mean one billionth of a unit of measure. So a nanosecond is
one billionth of a second, a nanometer (nm) is one billionth of a meter (m), etc. Over time,
man has developed telescopes and microscopes that aid us in “seeing” the world around us.
To put the nano or micro universe in perspective with our more familiar world, the spacing
–1
of atoms in matter is about 1/10 (10 ) of a nm; a strand of DNA is 2 nm wide; 100,000
5
(10 ) nm is about the diameter of a human hair which is about as small as the human eye


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can resolve; and a six foot person is about 2,000,000,000 (2  10 ) nm tall.

1.2 Implications for Physics, Chemistry, Biology and Engineering


 There is a long tradition of physicists and physics-based techniques making important
contributions to biology and medicine. Here the director of the National Institutes of
Health, one of the world’s foremost biomedical research centres, argues that this tradition
must go on.

 The aim of most biomedical research is to uncover new knowledge that will lead to better
health. At the National Institutes of Health (NIH) in the US we do this by supporting
research on the prevention, detection, diagnosis and treatment of disease and disability,
from the rarest genetic disorder to the common cold, as well as research on the basic
principles of biology.
❒ Physics and biology
 The effects of physics on the medical sciences from three perspectives. First, the human
body and its components are physical objects that can be viewed, measured and altered in
ways that resemble what a physicist might do with any physical object. Second, an
enormously important phase in the history of biology in which physicists transformed the
study of living things by helping to discover the principles of heredity. Third, some
contemporary problems in the biomedical sciences that I believe present challenges to
physicists, young and old. I will also explain the ways in which the NIH is attempting to
ease the path from a formal training in physics to an active, investigative role in biomedical
science.

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Fundamentals of Nanoscience (1 - 4) Introduction

❒ Correlations between physics and medicine


Physics Medicine
Statics (Mechanics) Orthopaedics
Dynamics (Mechanics) Heart motion
Elasticity and strength of materials Orthopaedics
Fluid statics Blood pressure
Fluid dynamics Blood flow in vascular system
Surface tension Capillary action

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Sound and acoustics
Electricity
Stethoscope, ultrasound, acoustic microscope
All life processes, ion transfer at membranes
Magnetism Nuclear magnetic resonance imaging
Light and optics Light microscopy, laser therapy, fibre optics
Heat and thermodynamics Heat balance
Kinetic theory and statistical Brownian motion, osmosis, diffusion of gases
mechanics
Atomic physics and spectroscopy “Chemical shift” in NMR imaging, lasers in
medicine
Molecular physics Genetics, antibodies, protein structure, electron
microscope
Ultraviolet and infrared energy Skin treatment and imaging
X-rays Radiology, CT imaging
Quantum mechanics Electron diffraction microscope
Relativity Synchrotron radiation imaging
Crystallography Structure of proteins
Solid-state physics and Computers in medicine, scintigraphy
semiconductors
Nuclear physics Radioisotope labelling, nuclear medicine, radiation
therapy
Radioactivity Positron Emission Tomography (PET)
Elementary particle physics Pion therapy
Accelerators, cyclotrons, etc Tumour therapy, Hodgkin’s disease
Astronomy and astrophysics Discovery of helium, trewatwmwe .nEt aosyf
Eansgthinmeaer(inOgb.nseotlete)
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Fundamentals of Nanoscience (1 - 5) Introduction

❒ Physicists, heredity and the rise of molecular biology


 Exactly 50 years ago, in a speech entitled “A physicist looks at biology”, Max Delbruck, a
leading physicist who had made a conversion to biology some years earlier, attempted to
th
describe the transition. In the speech, delivered to the 1000 meeting of the Connecticut
Academy of Arts and Sciences, Delbruck said: “A mature physicist, acquainting himself for
the first time with the problems of biology, is puzzled by the circumstance that there are no
‘absolute phenomena’….The animal or plant or micro-organism he is working with is but a
link in an evolutionary chain of changing forms, none of which has any permanent validity.

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Even the molecular species and the chemical reactions which he encounters are the fashions
of today to be replaced by others as evolution goes on. The organism he is working with is
not a particular expression of an ideal organism, but one thread in the infinite web of all
living forms, all interrelated and all interdependent. The physicist has been reared in a
different atmosphere. The materials and phenomena he works with are the same here and
now as they were at all times and as they are on the most distant star.”
 Delbruck had been a student of Niels Bohr and then a powerful proselytizer for biology.
With the assistance of Bohr’s book Light and Life and more importantly, Schrödinger’s
book What is Life?, he attracted many other physicists to biology. The effects of his
missionary zeal were powerful - Not just because some very smart people started to do
biology, but because they brought to biological problems a quantitative, analytic approach -
An approach that created the atmosphere in which principles of molecular biology were
discovered by seeking the physical basis of heredity. The leading physicist Leo Szilard was
among the converts and claimed that what physicists brought to biology was “not any skills
acquired in physics, but rather an attitude : The conviction which few biologists had at that
time, that mysteries can be solved” (see Fleming in further reading).

➠ 1.3 Classifications of Nanostructured Materials


❒ Top-down and bottom-up
 Nanomaterials can be constructed by top down techniques, producing very small structures
from larger pieces of material, for example by etching to create circuits on the surface of a
silicon microchip.
 They may also be constructed by bottom up techniques, atom by atom or molecule by
molecule. One way of doing this is self-assembly, in which the atoms or molecules arrange
themselves into a structure due to their natural properties. Crystals grown for the
semiconductor industry provide an example of self assembly, as does chemical synthesis of
large molecules. www.EasyEngineering.net
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Fundamentals of Nanoscience (1 - 6) Introduction

 A second way is to use tools to move each atom or molecule individually. Although this
‘positional assembly’ offers greater control over construction, it is currently very laborious
and not suitable for industrial applications.
❒ The importance of scanning probe techniques
 It has been 25 years since the Scanning Tunneling Microscope (STM) was invented,
followed four years later by the atomic force microscope and that's when nanoscience and
nanotechnology really started to take off. Various forms of scanning probe microscopes
based on these discoveries are essential for many areas of today's research. Scanning probe

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techniques have become the workhorse of nanoscience and nanotechnology research.
 Here is a Scanning Electron Microscope (SEM) image of a gold tip for Near-field Scanning
Optical Microscopy (SNOM) obtained by Focussed Ion Beam (FIB) milling. The small tip
at the center of the structure measures some tens of nanometers.
❒ Applications
 Current applications of nanoscale materials include very thin coatings used, for example, in
electronics and active surfaces (for example, self-cleaning windows).
 In most applications the nanoscale components will be fixed or embedded but in some,
such as those used in cosmetics and in some pilot environmental remediation applications,
free nanoparticles are used.
 The ability to machine materials to very high precision and accuracy (better than 100 nm) is
leading to considerable benefits in a wide range of industrial sectors, for example in the
production of components for the information and communication technology, automotive
and aerospace industries.
❒ Defining Nanomaterials
 If 50 % or more of the constituent particles of a material in the number size distribution
have one or more external dimensions in the size range 1 nm to 100 nm, then the material is
a nanomaterial. It should be noted that a fraction of 50 % with one or more external
dimensions between 1 nm and 100 nm in a number size distribution is always less than
50 % in any other commonly-used size distribution metric, such as surface area, volume,
mass or scattered light intensity. In fact it can be a tiny fraction of the total mass of the
material.
 Even if a product contains nanomaterials, or when it releases nanomaterials during use or
ageing, the product itself is not a nanomaterial, unless it is a particulate material itself that
meets the criteria of particle size and fraction. www.EasyEngineering.net
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Fundamentals of Nanoscience (1 - 7) Introduction

❒ Dimensions of nanomaterials
 This classification is based on the number of dimensions of a material, which are outside
the nanoscale (<100 nm) range.
 Accordingly, in zero-dimensional (0-D) nanomaterials all the dimensions are measured
within the nanoscale (no dimensions are larger than 100 nm). Most commonly, 0-D
nanomaterials are nanoparticles.
 In one-dimensional nanomaterials (1-D), one dimension is outside the nanoscale. This class
includes nanotubes, nanorods and nanowires.

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 In two-dimensional nanomaterials (2-D), two dimensions are outside the nanoscale. This
class exhibits plate-like shapes and includes graphene, nanofilms, nanolayers and
nanocoatings.
 Three-dimensional nanomaterials (3-D) are materials that are not confined to the nanoscale
in any dimension. This class can contain bulk powders, dispersions of nanoparticles,
bundles of nanowires and nanotubes as well as multi-nanolayers.

Fig. 1.3.1

❒ Classification of nanoscale dimensions


 Some of these materials have been available for some time; others are genuinely new. The
aim of this chapter is to give an overview of the properties and the significant foreseeable
applications of some key nanomaterials.

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Fundamentals of Nanoscience (1 - 8) Introduction

❒ The key differences between nanomaterials and bulk materials


 Two principal factors cause the properties of nanomaterials to differ significantly from
other materials : Increased relative surface area and quantum effects. These factors can
change or enhance properties such as reactivity, strength and electrical characteristics.
 As a particle decreases in size, a greater proportion of atoms are found at the surface
compared to those inside. For example, a particle of size 30 nm has 5 % of its atoms on its
surface, at 10 nm 20 % of its atoms and at 3 nm 50 % of its atoms.
 Thus nanoparticles have a much greater surface area per unit mass compared with larger

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particles. As growth and catalytic chemical reactions occur at surfaces, this means that a
given mass of material in nanoparticulate form will be much more reactive than the same
mass of material made up of larger particles.
 To understand the effect of particle size on surface area, consider an American Silver Eagle
coin. This silver dollar contains 31 grams of coin silver and has a total surface area of
approximately 3000 square millimeters. If the same amount of coin silver were divided into
tiny particles - say 10 nanometer in diameter - the total surface area of those particles would
be 7000 square meters (which is equal to the size of a soccer field - or larger than the floor
space of the White House, which is 5100 square meters). In other words : When the amount
of coin silver contained in a silver dollar is rendered into 10 nm particles, the surface area
of those particles is over 2 million times greater than the surface area of the silver dollar!
❒ Properties of nanomaterials
 In tandem with surface-area effects, quantum effects can begin to dominate the properties
of matter as size is reduced to the nanoscale. These can affect the optical, electrical and
magnetic behavior of materials, particularly as the structure or particle size approaches the
smaller end of the nanoscale. Materials that exploit these effects include quantum dots and
quantum well lasers for optoelectronics.
 For other materials such as crystalline solids, as the size of their structural components
decreases, there is much greater interface area within the material; this can greatly affect
both mechanical and electrical properties.
 For example, most metals are made up of small crystalline grains; the boundaries between
the grain slow down or arrest the propagation of defects when the material is stressed, thus
giving it strength. If these grains can be made very small, or even nanoscale in size, the
interface area within the material greatly increases, which enhances its strength. For
example, nanocrystalline nickel is as strong as hardened steel.
 Understanding surfaces and interfaces is a key challenge for those working on
nanomaterials and one where new imaging and analysis
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Fundamentals of Nanoscience (1 - 9) Introduction

➠ 1.4 Nano Particles


 A nanoparticle or ultrafine particle is usually defined as a particle of matter that is between
1 and 100 nanometres (nm) in diameter. The term is sometimes used for larger particles, up
to 500 nm, [citation needed] or fibers and tubes that are less than 100 nm in only two
directions. At the lowest range, metal particles smaller than 1 nm are usually called atom
clusters instead.
 Nanoparticles are usually distinguished from microparticles (1-1000 m), "fine particles"
(sized between 100 and 2500 nm) and "coarse particles" (ranging from 2500 to

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10,000 nm), because their smaller size drives very different physical or chemical properties,
like colloidal properties and optical or electric properties.
 Being more subject to the brownian motion, they usually do not sediment, like colloidal
particles that conversely are usually understood to range from 1 to 1000 nm.
 Being much smaller than the wavelengths of visible light (400-700 nm), nanoparticles
cannot be seen with ordinary optical microscopes, requiring the use of electron
microscopes. For the same reason, dispersions of nanoparticles in transparent media can be
transparent, whereas suspensions of larger particles usually scatter some or all visible light
incident on them. Nanoparticles also easily pass through common filters, such as common
ceramic candles,so that separation from liquids requires special nanofiltration techniques.
 The properties of nanoparticles often differ markedly from those of larger particles of the
same substance. Since the typical diameter of an atom is between 0.15 and 0.6 nm, a large
fraction of the nanoparticle's material lies within a few atomic diameters from its surface.
Therefore, the properties of that surface layer may dominate over those of the bulk material.
This effect is particularly strong for nanoparticles dispersed in a medium of different
composition since the interactions between the two materials at their interface also becomes
significant.
 Nanoparticles occur widely in nature and are objects of study in many sciences such as
chemistry, physics, geology and biology. Being at the transition between bulk materials and
atomic or molecular structures, they often exhibit phenomena that are not observed at either
scale. They are an important component of atmospheric pollution and key ingredients in
many industrialized products such as paints, plastics, metals, ceramics and magnetic
articles. The production of nanoparticles with specific properties is an important branch of
nanotechnology.

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Fundamentals of Nanoscience (1 - 10) Introduction

 In general, the small size of nanoparticles leads to a lower concentration of point defects
compared to their bulk counterparts, but they do support a variety of dislocations that can
be visualized using high-resolution electron microscopes. However, nanoparticles exhibit
different dislocation mechanics, which, together with their unique surface structures, results
in mechanical properties that are different from the bulk material.
 Anisotropy in a nanoparticle leads to a lot of changes in the properties of the nanoparticles.
Non-spherical nanoparticles of gold, silver and platinum due to their fascinating optical
properties are finding diverse applications and are of great interest in the field of research.
Non-spherical geometries of nanoprisms give rise to high effective cross-sections and
deeper colors of the colloidal solutions. The possibility of shifting the resonance

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wavelengths by tuning the particle geometry is very interesting for using these
nanoparticles in the fields of molecular labeling, for biomolecular assays, trace metal
detection and nanotechnical applications. Anisotropic nanoparticles display a specific
absorption behavior and stochastic particle orientation under unpolarized light, showing a
distinct resonance mode for each excitable axis. This property can be explained based on
the fact that on a daily basis there are new developments being made in the field of
synthesis of these nanoparticles for preparing them in high yield.

➠ 1.5 Quantum Dots, Nanowires


 Quantum Dots (QDs) are man-made nanoscale crystals that can transport electrons. When
UV light hits these semiconducting nanoparticles, they can emit light of various colors.
These artificial semiconductor nanoparticles that have found applications in composites,
solar cells and fluorescent biological labels.
 Nanoparticles of semiconductors - quantum dots - were theorized in the 1970s and initially
created in the early 1980s. If semiconductor particles are made small enough, quantum
effects come into play, which limit the energies at which electrons and holes (The absence
of an electron) can exist in the particles. As energy is related to wavelength (or color), this
means that the optical properties of the particle can be finely tuned depending on its size.
Thus, particles can be made to emit or absorb specific wavelengths (colors) of light, merely
by controlling their size.

Fig. 1.5.1 : Quantum dots are nanoscale man-made crystals that have the ability to
convert a spectrum of light into different colors. Each dot emits a different color
depending on its size www.EasyEngineering.net
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Fundamentals of Nanoscience (1 - 11) Introduction

 Quantum dots are artificial nanostructures that can possess many varied properties,
depending on their material and shape. For instance, due to their particular electronic
properties they can be used as active materials in single-electron transistors.
 The properties of a quantum dot are not only determined by its size but also by its shape,
composition and structure, for instance if it's solid or hollow. A reliable manufacturing
technology that makes use of quantum dots' properties - For a wide-ranging number of
applications in such areas as catalysis, electronics, photonics, information storage, imaging,
medicine, or sensing - Needs to be capable of churning out large quantities of nanocrystals

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where each batch is produced according to the exactly same parameters.
 Because certain biological molecules are capable of molecular recognition and self-
assembly, nanocrystals could also become an important building block for self-assembled
functional nanodevices.
 The atom-like energy states of QDs furthermore contribute to special optical properties,
such as a particle-size dependent wavelength of fluorescence; an effect which is used in
fabricating optical probes for biological and medical imaging.
 So far, the use in bioanalytics and biolabeling has found the widest range of applications for
colloidal QDs. Though the first generation of quantum dots already pointed out their
potential, it took a lot of effort to improve basic properties, in particular colloidal stability
in salt-containing solution. Initially, quantum dots have been used in very artificial
environments and these particles would have simply precipitated in 'real' samples, such as
blood. These problems have been solved and QDs have found numerous use in real
applications.

Fig. 1.5.2 : Vials of quantum dots producing vivid colors. For instance, a cadmium-
based quantum dot showing pure, highly specific
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Fundamentals of Nanoscience (1 - 12) Introduction
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Fundamentals of Nanoscience (1 - 13) Introduction

 Quantum dots have found applications in composites, solar cells (Grätzel cells) and
fluorescent biological labels (For example to trace a biological molecule) which use both
the small particle size and tuneable energy levels.
 Advances in chemistry have resulted in the preparation of monolayer-protected, high-
quality, monodispersed, crystalline quantum dots as small as 2 nm in diameter, which can
be conveniently treated and processed as a typical chemical reagent.
❒ Quantum dots in medicine
 Quantum dots enable researchers to study cell processes at the level of a single molecule

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and may significantly improve the diagnosis and treatment of diseases such as cancers. QDs
are either used as active sensor elements in high-resolution cellular imaging, where the
fluorescence properties of the quantum dots are changed upon reaction with the analyte, or
in passive label probes where selective receptor molecules such as antibodies have been
conjugated to the surface of the dots.
 Quantum dots could revolutionize medicine. Unfortunately, most of them are toxic.
Ironically, the existence of heavy metals in QDs such as cadmium, a well-established
human toxicant and carcinogen, poses potential dangers especially for future medical
application, where q dots are deliberately injected into the body.
 As the use of nanomaterials for biomedical applications is increasing, environmental
pollution and toxicity have to be addressed and the development of a non-toxic and
biocompatible nanomaterial is becoming an important issue.
❒ Quantum dots in photovoltaics
 The attractiveness of using quantum dots for making solar cells lies in several advantages
over other approaches : They can be manufactured in an energy-saving room-temperature
process; they can be made from abundant, inexpensive materials that do not require
extensive purification, as silicon does; and they can be applied to a variety of inexpensive
and even flexible substrate materials, such as light weight plastics.
 Although using quantum dots as the basis for solar cells is not a new idea, attempts to make
photovoltaic devices have not yet achieved sufficiently high efficiency in converting
sunlight to power.
 A promising route for quantum dot solar cells is a semiconductor ink with the goal of
enabling the coating of large areas of solar cell substrates in a single deposition step and
thereby eliminating tens of deposition steps necessary with the previous layer-by-layer
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Fundamentals of Nanoscience (1 - 14) Introduction

❒ Graphene quantum dots


 Graphene, which basically is an unrolled, planar form of a carbon nanotube therefore has
become an extremely interesting candidate material for nanoscale electronics. Researchers
have shown that it is possible to carve out nanoscale transistors from a single graphene
crystal (i.e. graphene quantum dots). Unlike all other known materials, graphene remains
highly stable and conductive even when it is cut into devices one nanometer wide.

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Fig. 1.5.3 : Quantum dot carved from a graphene sheet

 Graphene Quantum Dots (GQDs) also show great potential in the fields of
photoelectronics, photovoltaics, biosensing and bioimaging owing to their unique
photoluminescence (PL) properties, including excellent biocompatibility, low toxicity and
high stability against photobleaching and photoblinking.
 Scientists still are working on finding efficient and universal methods for the synthesis of
GQDs with high stability, controllable surface properties and tunable PL emission
wavelength.
❒ Perovskite quantum dots
 Luminescent Quantum Dots (LQDs), which possess high photoluminescence quantum
yields, flexible emission color controlling and solution is processability are promising for
applications in lighting systems (warm white light without UV and infrared irradiation) and
high quality displays.
 However, the commercialization of LQDs has been held back by the prohibitively high cost
of their production. Currently, LQDs are prepared by the HI method, requiring at high
temperature and tedious surface treating in order to improve both optical properties and
stability.
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Fundamentals of Nanoscience (1 - 15) Introduction

 Although developed only recently, inorganic halide perovskite quantum dot systems have
exhibited comparable and even better performances than traditional QDs in many fields.
 By preparing highly emissive Inorganic Perovskite Quantum Dots (IPQDs) at room
temperature, IPQDs' superior optical merits could lead to promising applications in lighting
and displays.
❒ Quantum dot TVs and displays
 The most commonly known use of quantum dots nowadays may be TV screens. Samsung
and LG launched their QLED TVs in 2015 and a few other companies followed not long

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after.
 Quantum dots, because they are both photo-active (photoluminescent) and electro-active
(electroluminescent) and have unique physical properties, will be at the core of next-
generation displays. Compared to organic luminescent materials used in Organic Light
Emitting Diodes (OLEDs), QD-based materials have purer colors, longer lifetime, lower
manufacturing cost and lower power consumption. Another key advantage is that, because
QDs can be deposited on virtually any substrate, you can expect printable and flexible –
even rollable - quantum dot displays of all sizes.

➠ 1.6 Nanowire
− 9
 A nanowire is a nanostructure, with the diameter of the order of a nanometre (10
meters). It can also be defined as the ratio of the length to width being greater than 1000.
Alternatively, nanowires can be defined as structures that have a thickness or diameter
constrained to tens of nanometers or less and an unconstrained length. At these scales,
quantum mechanical effects are important which coined the term "quantum wires". Many
different types of nanowires exist, including superconducting (e.g. YBCO), metallic
(e.g. Ni, Pt, Au, Ag), semiconducting (e.g. silicon nanowires (SiNWs), InP, GaN) and
insulating (e.g. SiO2, TiO2). Molecular nanowires are composed of repeating molecular
units either organic (e.g. DNA) or inorganic (e.g. MO6 S9 – x Ix).

 The initial discovery of carbon nanotubes - Tiny tubes of pure carbon, essentially
sheets of graphene rolled up, to a cylinder is generally credited to a paper published in
1991 by the Japanese physicist SumioIjima (Although some forms of carbon nanotubes
had been observed earlier).
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Fundamentals of Nanoscience (1 - 16) Introduction

 Due to their extreme slenderness, both nanotubes and nanowires are essentially one-
dimensional. “They are quasi-one-dimensional materials,” says MIT associate professor of
materials science and engineering SilvijaGradečak: “Two of their dimensions are on the
nanometer scale.” This one-dimensionality confers distinctive electrical and optical
properties.
 For one thing, it means that the electrons and photons within these nanowires experience
“quantum confinement effects,” Gradečak says. And yet, unlike other materials that
produce such quantum effects, such as quantum dots, nanowires’ length makes it possible

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for them to connect with other macroscopic devices and the outside world.
 The structure of a nanowire is so simple that there’s no room for defects and electrons pass
through unimpeded, Gradečak explains. This sidesteps a major problem with typical
crystalline semiconductors, such as those made from a wafer of silicon : There are always
defects in those structures and those defects interfere with the passage of electrons.
 Made of a variety of materials, nanowires can be “grown” on many different substrates
through a vapor deposition process. Tiny beads of molten gold or other metals are
deposited on a surface; the nanowire material, in vapor, is then absorbed by the molten
gold, ultimately growing from the bottom of that bead as a skinny column of the material.
By selecting the size of the metal bead, it is possible to precisely control the size of the
resulting nanowire.
 In addition, materials that don’t ordinarily mix easily can be grown together in nanowire
form. For example, layers of silicon and germanium, two widely used semiconductors, “are
very difficult to grow together in thin films,” Gradečak says. “But in nanowires, they can be
grown without any problems.” Moreover, the equipment needed for this kind of vapor
deposition is widely used in the semiconductor industry and can easily be adapted for the
production of nanowires.
 While nanowires’ and nanotubes’ diameters are negligible, their length can extend for
hundreds of micrometers, even reaching lengths visible to the unaided eye. No other known
material can produce such extreme length-to-diameter ratios: millions of times longer than
they are wide.
 Because of this, the wires have an extremely high ratio of surface area to volume. That
makes them very good as detectors, because all that surface area can be treated to bind with
specific chemical or biological molecules. The electrical signal generated by that binding
can then easily be transmitted along the wire.
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Fundamentals of Nanoscience (1 - 17) Introduction

 Similarly, nanowires’ shape can be used to produce narrow-beam lasers or light-emitting


diodes (LEDs), Gradečak says. These tiny light sources might someday find applications
within photonic chips, for example - Chips in which information is carried by light, instead
of the electric charges that relay information in today’s electronics.
 Compared to solid nanowires, nanotubes have a more complex structure : Essentially one-
atom-thick sheets of pure carbon, with the atoms arranged in a pattern that resembles
chicken wire. They behave in many ways as one-dimensional materials, but are actually
hollow tubes, like a long, nanometer-scale drinking straw.

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 The properties of carbon nanotubes can vary greatly depending on how they are rolled up, a
property called chirality. (It’s similar to the difference between forming a paper tube by
rolling a sheet of paper lengthwise versus on the diagonal : The different alignments of
fibers in the paper produce different strength in the resulting tubes.) In the case of carbon
nanotubes, chirality can determine whether the tubes behave as metals or as
semiconductors.
 But unlike the precise manufacturing control that is possible with nanowires, so far
methods for making nanotubes produce a random mix of types, which must be sorted to
make use of one particular kind. Besides single-walled nanotubes, they also exist in double-
walled and multi-walled forms.
 In addition to their useful electronic and optical properties, carbon nanotubes are
exceptionally strong and are used as reinforcing fibers in advanced composite materials. “In
any application where one-dimensionality is important, both carbon nanotubes and
nanowires would provide benefits,” Gradečak says.

➠ 1.7 Ultra-thin Films


 Ultra-thin films are used in a variety of technologically advanced applications. Most
ultra-thin films are grown using complex chemical and physical deposition techniques
using gas-precursors phase precursors and plasma processes.
 Bruker is the industry leader in nanomechanical and nanotribological property
characterization of ultra-thin films. Continued development of nanoindentation
technologies and techniques has enabled the force sensitivity, displacement sensitivity and
control algorithms necessary for quantitative ultra-thin film measurements. Patented models
remove substrate effects from the nanoindentation data to obtain intrinsic thin film modulus
values.
 Bruker’s nanoscratch testing technologies enables quantitative tribological and interfacial
adhesion characterization of ultra- thin films. Patented
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Fundamentals of Nanoscience (1 - 18) Introduction

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Fundamentals of Nanoscience (1 - 19) Introduction

with 2 dimensional actuation capabilities enable highly sensitive measurements of forces


acting on the scratch probe during normal loading and lateral actuation, providing highly
sensitive nanoscale tribological and interfacial adhesion characterization capabilities.

➠ 1.8 Multilayered Materials


 By combining different materials, it is possible to create “customised” protective packaging
with the least possible material consumption, above all for foodstuffs. The most common
combination is paper, plastic and aluminium foil. These materials are all good on their own,

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but the combination is even better. The composite materials are lighter and less resource-
consuming than one single material with the same properties. Thus, the amount of waste is
reduced. This is of course even more valid for flexible plastic packaging.
 In general, many different properties are demanded from a package. The classical
description of the main demands on a package says that it shall contain, protect and
preserve, facilitate handling and use, inform and sell.
 In practice, it is exceptional to find one single packaging material whose properties meet all
these demands. This is the reason why much of our present-day packaging consists of
multi-layer materials in the form of laminates, e.g. materials that are composed and
combined in different ways.
 By combining two or more materials, it is possible to build several properties into the
package and to have the composite material fulfil many functions. Each separate material
layer can represent one or more properties. The combination of many thin layers of
different materials gives a package that provides the product the best possible protection,
using the least amount of material. Compare with the “multi-layer principle” recommended
when dressing for bad weather. You should have one windbreaking layer, one for warmth,
one against moisture, etc.
❒ The foundation for modern distribution
 It is a fact that composite packaging materials have been of vital importance to our modern
way of distributing goods. Cardboard and paper were used originally without being
combined with other materials, e.g. wrapping paper, shoe boxes, cake cartons, flour bags
and sweet papers, for purposes with simple functional demands.
 The development of composite materials began when we learnt how to coat paper or
cardboard with plastic. Now quick and reliable heat sealing (welding) could be substituted
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Fundamentals of Nanoscience (1 - 20) Introduction

for paste and glue. The technique suddenly made it possible to pack liquids in paper! It
became possible to develop different cardboard and paper based packaging solutions for
new products, e.g. deep-frozen food. This also created new opportunities for rational
production and distribution of food.
 The self-service system and an increasing variety of products created a demand for
packaging with even better protection for the products. This meant fast development
towards more and more “customised” multi-layer packaging. Not only were different types
of materials combined (e.g. paper, aluminium and plastic), but different plastics were also

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combined into materials with very advanced properties.
❒ Recovery - a challenge
 As can be understood, the use of multi-layer materials is highly motivated. But new
demands for material recovery from household packaging waste cause an undeniable
problem. Therefore, the development of new techniques for the manufacture of multi-layer
materials suitable for material recovery has now become high-priority for the packaging
industry. Some problems are well on the way to being solved. For example, there exists a
functioning method for the separation of the polyethylene, aluminium and paper in milk
and juice cartons.
 It is also highly likely that it will be possible to material-recover plastic laminates. This will
be enabled by the development of super-thin layers of newly developed barrier materials
(Barrier materials = Materials that are impervious to gases, aromas and light). One such
material is silicon oxide (In principle = Glass) which is used as coating on plastic film in
such thin layers that they can be disregarded when the packaging material is recovered.
 If the recovery of multi-layer materials is aimed instead at energy recovery by incineration
of the material in ovens where the generated heat is recovered, the multi-layer materials are
an interesting resource, as they generally make splendid fuels with high energy content.

➠ 1.9 Length Scales Involved and Effect on Properties : Mechanical,


Electronic, Optical, Magnetic and Thermal Properties
 The mechanical behaviour of nanoparticles is due to the nature of interfaces in them.
Mechanical properties such as hardness, toughness, elastic modulus, scratch resistance,
fatigue strength and crack initiation and propagation are significantly different for
nanostructures than bulk material. For example in metals and alloys, the hardness and
toughness increases by reducing the size of nanoparticles. In ceramics, ductility and super
plasticity are increased on reducing the particle size. Fe and Ni continue to harden with
decreasing grain size. By decreasing the size of
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Fundamentals of Nanoscience (1 - 21) Introduction
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Fundamentals of Nanoscience (1 - 22) Introduction

and the hardness increases by 2 to 7 times. As the grain size is reduced below 10 nm the
hardness reduces in some nanomaterials. At higher temperatures, some nanoparticles
possess superplastic property. When the material is superplastic, it can undergo large tensile
deformation without getting cracks.
 The energy band structure and charge carrier density in the materials can be modified quite
differently from the bulk material and in turn that will modify the electronic properties of
the materials. Nanoparticles made of semiconducting materials like Germanium, Silicon
and Cadmium are not semiconductors. Further, nanoclusters of different sizes will have
different electronic structures and different energy level separations. So they show diverse

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electronic properties which depend on its size.
 The optical emission and adsorption occurs when the transition of the electrons occur
between these two states. Semiconductors and many metals show drastic changes in
optical properties such as color, as a function of particle size. Colloidal suspensions of
gold nanoparticles have a deep red color, which becomes progressively more yellow as
the particle suspensions size increases.
 Thermal expansion arises from the addition of heat energy in the atoms and their
subsequent movement away from their equilibrium positions as the temperature rises in
solid. This expansion or contraction resulting from increase or decrease in temperature is
three dimensional but in practice linear thermal expansion is used for simplicity instead of
volume expansion.
 The increase in length per unit length per degree rise in temperature is called coefficient of
linear expansion. Thermal expansion does not necessarily vary uniformly with
temperature but it is sufficiently linear over narrow ranges of temperature.
 If the bonds between the atoms are strong and highly directional as in ionic and covalent
solids, the thermal expansion will be relatively small. If on the other hand the atoms are
more loosely bound as in metals, a greater degree of expansion is there. In molecular solid,
where bonding least resists the movement of the molecules, the thermal expansion will be
the greatest.
 The thermal expansion of solid is related to other thermal properties such as specific heat
and melting point as all these properties have their origin in lattice vibrations which
increase with the temperature. The atoms or molecules as earlier explained oscillate
(vibrate) with a certain amplitude about their equilibrium positions.

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Fundamentals of Nanoscience (1 - 23) Introduction

 The amplitude of this vibration increases as the temperature rises resulting in moving
further away of atoms and molecules from their equilibrium position causing an increase in
volume (or linear expansion) of solid. In this way magnitude of the coefficient of thermal
expansion of solids will depend on their interatomic and intermolecular forms and also on
their structural arrangement.
 It has been observed that between absolute zero temperature and the melting point, total
volume range of elements is approximately constant. This can be interpreted that materials
with lower softening (melting) points will have higher expansion coefficients. This also
means that thermal expansion will approach zero at the absolute zero temperature.

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 Organic polymers such as plastics and rubber have many times higher expansion
coefficients than metals because of their relatively lower softening point. This may be
reduced by addition of filler materials (such as glass fibre, asbestos, alumina etc.)
possessing lower thermal expansion coefficients. Alloying of metals have a minor effect on
this property.

➠ 1.10 Introduction to Properties and Motivation for Study


 Nanoscience is all about the ultra-small, but it has the potential to have an enormous impact
on our lives. We are already using and enjoying many products enhanced with
nanotechnology, but it is the potential to revolutionise fields such as medicine, or to help
solve some of the world’s difficult environmental problems, that makes the future of
nanoscience and nanotechnology most exciting.
 However, nanotechnology - as with all new emerging technologies - is bringing up just as
many problems as solutions. How can regulation and testing keep up with technology and
what impact might these new nanomaterials have on human health or the wider
environment ? These are issues that still need to be addressed. As greater investments
continue to be made in nanotechnology and ever more nanoparticles find their way into our
environment, products and even bodies, it is vitally important that the potential benefits of
this technology are carefully weighed and considered against the unknown risks.

➠ 1.11 Part A : Short Answered Questions [2 Marks Each]


Q.1 Define nanoscale science and technology.
🞕 Ans. : Nanoscale science involves understanding the fundamental interactions of
physical systems confined to nanoscale dimensions, and when matter is controlled at the
nanoscale, fundamental properties of things like temperature, electricity, magnetism, and
chemical reactions can change completely.
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Fundamentals of Nanoscience (1 - 24) Introduction

Q.2 Define correlations between physics and medicine.

🞕 Ans. :
Physics Medicine
Statics (Mechanics) Orthopaedics
Dynamics (Mechanics) Heart motion
Elasticity and strength of materials Orthopaedics
Fluid statics Blood pressure
Fluid dynamics Blood flow in vascular system

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Surface tension
Sound and acoustics
Capillary action
Stethoscope, ultrasound, acoustic microscope
Electricity All life processes, ion transfer at membranes
Magnetism Nuclear magnetic resonance imaging
Q.3 List the classifications of nanostructured materials.
🞕 Ans. :
1. Top-down
2. Bottom-up
Q.4 Define nanomaterials.

🞕 Ans. : If 50 % or more of the constituent particles of a material in the number size


distribution have one or more external dimensions in the size range 1 nm to 100 nm, then the
material is a nanomaterial. It should be noted that a fraction of 50 % with one or more
external dimensions between 1 nm and 100 nm in a number size distribution is always less
than 50 % in any other commonly-used size distribution metric, such as surface area,
volume, mass or scattered light intensity.
Q.5 Explain the classification of nanoscale dimensions.

🞕 Ans. : Some of these materials have been available for some time; others are genuinely
new. The aim of this chapter is to give an overview of the properties, and the significant
foreseeable applications of some key nanomaterials.
Q.6 List properties of nanomaterials.

🞕 Ans. : In tandem with surface-area effects, quantum effects can begin to dominate the
properties of matter as size is reduced to the nanoscale. These can affect the optical,
electrical and magnetic behavior of materials, particularly as the structure or particle size
approaches the smaller end of the nanoscale. www.EasyEngineering.net
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Fundamentals of Nanoscience (1 - 25) Introduction

Q.7 Define nano particles.


🞕 Ans. : A nanoparticle or ultrafine particle is usually defined as a particle of matter that is
between 1 and 100 nanometres (nm) in diameter. The term is sometimes used for larger
particles, up to 500 nm, or fibers and tubes that are less than 100 nm in only two directions.
At the lowest range, metal particles smaller than 1 nm are usually called atom clusters
instead.
Q.8 Define quantum dots.
🞕 Ans. : Quantum Dots (QDs) are man-made nanoscale crystals that can transport

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electrons. When UV light hits these semiconducting nanoparticles, they can emit light of
various colors.
Q.9 Define nanowires.

🞕 Ans. : A nanowire is a nanostructure, with the diameter of the order of a nanometre


−9
(10 meters). It can also be defined as the ratio of the length to width being greater than
1000.
Q.10 Define quantum dots in medicine.
🞕 Ans. : Quantum dots enable researchers to study cell processes at the level of a single
molecule and may significantly improve the diagnosis and treatment of diseases such as
cancers.

➠ 1.12 Part B : Long Answered Questions


Q.1 Explain in detail about nano scale science and technology.. (Refer section 1.1)

Q.2 Describe the Implications for Physics, Chemistry, Biology and Engineering.
(Refer section 1.2)
Q.3 Explain the classifications of nanostructured materials. (Refer section 1.3)

Q.4 Explain Quantum dots, nanowires-ultra-thin films-multilayered materials.


(Refer section 1.5)

Q.5 Describe the Length scales involved and effect on properties. (Refer section 1.6)



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