CY-416 Course Outline:: Nanotechnology, CY-416 BSIC Spring Semester VIII

Nanotechnology, CY-416; BSIC Spring, VIII Notes by Arsalan A.
Khan, BSIC-17043
Revised by Muzamil Jalil Ahmed, BSIC-17029
Paragraphs marked as are trivial and can thus be skipped
Nanotechnology, CY-416
BSIC Spring Semester VIII
CY-416 Course Outline:
1. Nanochemistry: Introduction, Definition, Length scales, Importance of nanoscale and its technology, Self-
assembly of materials & molecules, Porous Solids, Nanowires, Nano-machines and Quantum Dots.
2. (Metallic) Nanoparticles: Introduction, Types of nanoparticles, preparation, properties and uses of Gold,
Silicon, Silver, Zinc Oxide, Iron Oxide, Alumina and Titania Nanoparticles; (M2xOx).
3. Synthetic Techniques: Equipment and processes needed to fabricate nano devices and structures, top down
and bottom up approaches, common growth methods.
4. (Organic) Nanomaterials: Preparation, properties and applications of Carbon Nanotubes, Nanorods,
Nanofibres and Nanoclay.
5. Instrumental Techniques: Electron microscopes; basic principles only: Scanning Electron Microscopes
(SEM) – Transmission Electron Microscopes (TEM) – Scanning Probe Microscopy – Atomic Force
Microscopy (AFM) – Scanning Tunnelling Electron Microscope (STEM).
1
Table of Contents
Lecture 1 ....................................................................................................................................................................6
Week #1 Notes ...........................................................................................................................................................6
1.1. Introduction to Nanotechnology..................................................................................................................6
Nanotechnology ......................................................................................................................................................6
Nanodimension .......................................................................................................................................................6
Nanomaterials .........................................................................................................................................................7
Nanoparticles ..........................................................................................................................................................7
1.2. Differences from the Bulk:...........................................................................................................................7
Examples ................................................................................................................................................................8
Origin of Differences ..............................................................................................................................................8
1.3. Early Uses ......................................................................................................................................................9
1.4. Nanomaterial Classification.........................................................................................................................9
General Shapes .......................................................................................................................................................9
Nanocrystals .........................................................................................................................................................11
1.5. Synthetic Routes: ........................................................................................................................................11
Top-down approach ..............................................................................................................................................12
Bottom-up approach .............................................................................................................................................13
Summary ...........................................................................................................................................................14
1.6. Applications of Nanomaterials: .................................................................................................................14
General .................................................................................................................................................................15
Nanoconsumer Products .......................................................................................................................................15
1.7. Summary of Lecture Video 1.1: ................................................................................................................16
1.8. Molecular Self-Assembly ...........................................................................................................................17
Definition..............................................................................................................................................................17
What causes Molecular Self-Assembly? ..............................................................................................................17
Types on the basis of System State ......................................................................................................................17
Types on the basis of Supramolecular Chemistry ................................................................................................18
Scope of Self-assembly: .......................................................................................................................................19
Week #2 Notes .........................................................................................................................................................21
2.1. Porous Solids ...............................................................................................................................................21
Definition of Porosity ...........................................................................................................................................21
Classification of Porous Materials ........................................................................................................................21
Nanoporosity ........................................................................................................................................................21
Significance & Application of Nanoporous Material ...........................................................................................21
Example of Nanoporous Material.........................................................................................................................22
(a) Activated carbon (AC)..............................................................................................................................22
Precursor ...........................................................................................................................................................22
Manufacture ......................................................................................................................................................22
Porosity & Activity...........................................................................................................................................23
Forms: ...............................................................................................................................................................23
Market & Uses ..................................................................................................................................................23
(b) Metal Organic Frameworks (MOFs) ........................................................................................................23
Manufacture/Synthesis .....................................................................................................................................24
Porosity & Activity...........................................................................................................................................24
Market & Uses ..................................................................................................................................................24
2.2. Aspect (SV) Ratio .......................................................................................................................................24
Nanotechnology, CY-416; BSIC Spring, VIII Notes by Arsalan A. Khan, BSIC-17043
2.3. Nanomaterials .............................................................................................................................................24
2.3.1. Nanotubes .............................................................................................................................................24
Description .......................................................................................................................................................24
Synthesis ...........................................................................................................................................................25
Properties & Potential Uses .............................................................................................................................25
2.3.2. Nanorods...............................................................................................................................................25
Description .......................................................................................................................................................25
Synthesis ...........................................................................................................................................................25
Applications ......................................................................................................................................................26
2.3.3. Nanowires .............................................................................................................................................26
Description .......................................................................................................................................................26
Synthesis ...........................................................................................................................................................26
Nanowire Behaviour .........................................................................................................................................26
Applications ......................................................................................................................................................27
2.3.4. Quantum dots (QDs) .............................................................................................................................28
Description .......................................................................................................................................................28
Fabrication .......................................................................................................................................................28
Optoelectronic Property ...................................................................................................................................28
Size & Concentration........................................................................................................................................29
Applications ......................................................................................................................................................29
2.4. Nanomachines: ............................................................................................................................................30
Description ...........................................................................................................................................................30
Development.........................................................................................................................................................30
Nanorobots ...........................................................................................................................................................30
Potential ................................................................................................................................................................30
Contemporary Research .......................................................................................................................................30
2.5. Nanotechnology & Fiction .........................................................................................................................31
Nano-myth ............................................................................................................................................................31
Week #3 Notes .........................................................................................................................................................32
3.1. Nanofibres ...................................................................................................................................................32
Description ...........................................................................................................................................................32
Fabrication Methods .............................................................................................................................................32
(a) Electrospinning ...............................................................................................................................................32
(b) Other Techniques ............................................................................................................................................33
Properties ..............................................................................................................................................................34
Applications..........................................................................................................................................................34
Examples ..............................................................................................................................................................35
3.2. Nanoclay ......................................................................................................................................................36
Description ...........................................................................................................................................................36
Properties ..............................................................................................................................................................36
Nanoclay Fabrication............................................................................................................................................36
Classification ........................................................................................................................................................37
Applications..........................................................................................................................................................37
3
Lecture 2 ..................................................................................................................................................................39
Week #4 Notes .........................................................................................................................................................39
4.1. Recent Applications and Advancement of Nanotechnology: ..................................................................39
Everyday Materials & Processes ..........................................................................................................................39
4.2. Types of Nanomaterials (cont’d) ...............................................................................................................40
4.2.1. Carbon Nanotubes (CNTs) ...................................................................................................................40
Tubeforms – Configurations & Chirality .........................................................................................................40
Bonding ............................................................................................................................................................41
Fabrication ........................................................................................................................................................41
Summary of Lecture Video 4.1: .......................................................................................................................42
Applications of CNT ........................................................................................................................................43
Summary of Lecture Video 4.2: .......................................................................................................................44
4.2.2. Metallic Nanoparticles (MNPs) ............................................................................................................46
Purple of Cassius – An unrealised Medieval Nanotechnology .........................................................................46
Goals and Problems in Metallic Nanoparticles Synthesis ................................................................................47
4.2.3. Inorganic Nanowires.............................................................................................................................48
Description .......................................................................................................................................................48
Properties ..........................................................................................................................................................48
Applications ......................................................................................................................................................48
Benefits .............................................................................................................................................................48
Current Motivation for NW Synthesis..............................................................................................................48
4.2.4. Dendrimers ...........................................................................................................................................48
Description .......................................................................................................................................................48
Synthesis & Discovery .....................................................................................................................................49
Properties ..........................................................................................................................................................49
Applications ......................................................................................................................................................49
4.2.5. Nanocomposites & Nanohybrids ..........................................................................................................50
Description .......................................................................................................................................................50
Properties ..........................................................................................................................................................50
Effect of nano-reinforcement............................................................................................................................50
(a) Ceramic Matrix Nanocomposites (CMCs) ..................................................................................................51
(b) Metal Matrix Nanocomposites (MMCs) .....................................................................................................51
(c) Polymer Matrix Nanocomposites (PMCs)............................................................................................51
Manufacture ......................................................................................................................................................51
Applications ......................................................................................................................................................52
4.3. Nano-reinforced Composites -- Fine Particulate Technology: ................................................................52
Multifunctionality of Nanocomposites .................................................................................................................52
Possible nano-reinforcements targets ...................................................................................................................52
Role of Particle Size .............................................................................................................................................52
4.4. Getting down to the Nanoscale ..................................................................................................................52
Bottom-Up Approach ...........................................................................................................................................53
Description .......................................................................................................................................................53
Advantages .......................................................................................................................................................53
Disadvantages ...................................................................................................................................................53
Bottom-Up Processing......................................................................................................................................53
Top-Down Approach ............................................................................................................................................54
Description .......................................................................................................................................................54
Advantages .......................................................................................................................................................54
Disadvantages ...................................................................................................................................................54
4.5. Growth Kinetics – Nucleation & Growth Processes ................................................................................54
Nucleation.............................................................................................................................................................54
Crystal Growth .....................................................................................................................................................55
4.6. Summary of Lecture Video 4.3: ................................................................................................................56
Lectures 3-4 .............................................................................................................................................................57
Week #5 Notes .........................................................................................................................................................57
5.1. Bulk Synthetic Techniques ........................................................................................................................57
Issues with Nanoparticle Synthesis ......................................................................................................................57
Major Synthetic Techniques (on the basis of nature) ...........................................................................................57
5.1.1. Chemical Synthesis (Bottom-Up Approach) ....................................................................................58
5.1.2. Biological (Green) Synthesis (Bottom-Up Approach) .....................................................................69
5.1.3. Physical Synthesis (Top-Down Approach) ......................................................................................71
Lecture 5 ..................................................................................................................................................................85
Week #6 Notes .........................................................................................................................................................85
6.1. Nanoparticle Characterisation ..................................................................................................................85
6.2. X-Ray Diffraction Technique (XRD) ........................................................................................................85
What is Diffraction? .............................................................................................................................................86
Bragg’s Law .........................................................................................................................................................86
Scherrer Equation .................................................................................................................................................87
XRD of Haematite (α-Fe2O3) ...............................................................................................................................87
XRD Manufacturers & Vendors ...........................................................................................................................88
Summary of Lecture Video 6.1: ...........................................................................................................................89
Essentials of an XRD............................................................................................................................................94
Sample Preparation for XRD................................................................................................................................94
Diffraction Patterns ..............................................................................................................................................96
XRD Data Interpretation – What information can you get? .................................................................................96
XRD Applications ................................................................................................................................................96
XRD Advantages ..................................................................................................................................................97
XRD Disadvantages .............................................................................................................................................97
Full-Width Half-Maximum (FWHM) ..................................................................................................................97
X-Ray Powder Diffraction (XPRD) .....................................................................................................................97
6.3. XRD Numericals/Examples: ......................................................................................................................98
Q1. For the given XRD Pattern, calculate the crystalline mean size ‘’. Given that the λCu/Kα = 0.154 nm, k = 0.9
(assuming sphericity). Remainder of the data is available from the pattern.........................................................98
Q2. A sample shows diffraction peak at 2θ = 27o which has FWHM of 0.5o. Calculate the crystallite size, if
Cu/Kα X-ray radiation (0.154 nm) were used. .....................................................................................................98
Q3. Calculate the d-spacing using the Diffraction Data. ......................................................................................98
5
Lecture 1
Week #1 Notes
1.1. Introduction to Nanotechnology
Nanotechnology
The manipulation of matter on a near-atomic scale to produce new structures, materials, and devices—offers the
promise of unprecedented scientific advancement for many sectors, such as medicine, consumer products, energy,
materials, and manufacturing.
The concepts of 'nanotechnology’, was introduced by the physicist Richard Feynman in his talk "There's Plenty of
Room at the Bottom" at an American Physical Society meeting at Caltech on December 29, 1959. Feynman
described “a process by which individual atoms and molecules might be manipulate, using a set of precise tools to
build and operate another smaller scale set of tools, scaling down to the nano-scale”.
Nanodimension
A nanometer (nm) is one billionth, or 10−9, of a meter. By comparison, typical carbon-carbon bond lengths, or the
spacing between these atoms in a molecule, are in the range 0.12–0.15 nm, and a DNA double-helix has a
diameter around 2 nm. On the other hand the bacteria of the genus Mycoplasma, are around 200 nm in length.
To put that scale in another context, the comparative size of a nanometer to a meter is the same as that of a marble
to the size of the earth. By convention, nanotechnology is taken as the scale range 1-100 nm following the
definition used by the National Nanotechnology Initiative in the US
Nanomaterials
"Any material with any external dimension in the nanoscale or having internal structure or surface structure in
the nanoscale", with nanoscale defined as the "length range approximately from 1 nm to 100 nm".
(ISO/TS 80004)1
“A natural, incidental or manufactured material containing particles, in an unbound state or as an aggregate or
as an agglomerate and for 50% or more of the particles in the number size distribution2, one or more external
dimensions is in the size range 1 nm – 100 nm”.
(EU Commission, 18th Oct 2011)
Nanoparticles
Any particles3 of a size ranging from 1-100 nm (0.1-10 Å), with a definite shape, size, and exhibits as a whole unit
in their behaviour. These materials are invisible to the naked eye. The regime of nanoparticles falls between the
classic fields of: In the Bulk
Chemistry 0.5nm to 1-2 nm 1 to 100 atoms
Solid State Physics 10 nm 1×104 to 6×1023 atoms
1.2. Differences from the Bulk:
A drastic change in the properties of nanomaterials can be observed when they are breakdown to the nanoscale
level. As we go towards the nanoscale level from the molecular level, the electronic properties of materials get
modified due to the quantum size effect.
The bulk material should have constant physical properties regardless of its size, but at the nano-scale shape and
size-dependent properties are often observed. Au contraire, the nanoscale materials exhibit the following
variations in properties to the bulk material.
 Physical Properties i.e. the melting point, specific heats etc., can decrease with size
for nanomaterials.
 Electrical Properties i.e. band gaps4 can changed (lowered) for semiconductor-
based nanoparticles like Si.
 Chemical Properties such as the reactivity, solubility etc., can increase drastically
with higher surface area i.e. surfaces can be more reactive. For e.g. 1 kg of particles
of 1 mm3 has the same surface area as 1 mg of particles of 1 nm3
 Mechanical Properties i.e. the nanostructural metal specimens can have increased hardness by a factor ≥5.0.
Increased ductility of ceramics and plasticity.
 Optical Properties. i.e. the dispersity or light polarisation can be manipulated.
1
The ISO/TS 80004 series of standards, from the International Organisation for Standardisation, describe vocabulary for nanotechnology
and its applications.
2
The particle-size distribution (PSD) of a powder, or granular material, or particles dispersed in fluid, is a list of values or a mathematical
function that defines the relative amount, typically by mass, of particles present according to size. The PSD of a material can be important
in understanding its physical and chemical properties. It affects the strength and load-bearing properties of rocks and soils. It affects the
reactivity of solids participating in chemical reactions, and needs to be tightly controlled in many industrial products
3
Any particle that is defined as a small object that behaves as a whole unit with respect to its transport and properties.
4
A band gap is the distance between the valence band of electrons and the conduction band. Essentially, the band gap represents the
minimum energy that is required to excite an electron up to a state in the conduction band where it can participate in conduction.
7
 Magnetic Properties i.e. the coercive force5 in magnetic materials can be manipulated (increased for
nanomaterials).
Unexpected properties of nanoparticles are therefore largely due to the large surface area of the material, which
dominates the contributions made by the small bulk of the material.
It was observed that the quantum properties of the material can differ at the nanoscale. Material behaving as the
insulator at the molecular level can express the properties of the conductor when looked at its nanoscale level.
Michael Faraday provided the first description, in scientific terms, of the optical properties of nanometer-scale
metals, pointing out that: "It is well known that when thin leaves of gold or silver are mounted upon glass and
heated to a temperature that is well below a red heat (~500 °C), a remarkable change of properties takes place,
whereby the continuity of the metallic film is destroyed. The result is that white light is now freely transmitted,
reflection is correspondingly diminished, while the electrical resistivity is enormously increased."
Examples
 Nanoscale gold illustrates the unique properties that occur at the
nanoscale. Nanoscale gold particles are not the yellow colour with which
we are familiar; nanoscale gold can appear red-purple. At the nanoscale,
the motion of the gold’s electrons is confined. Because this movement is
restricted, gold nanoparticles interact (disperse) differently with light
compared to larger-scale gold particles.
 A material such as gold, which is chemically inert at normal scales, can
serve as a potent chemical catalyst at nanoscales.
 Stable materials can turn combustible (aluminium);
 Insoluble materials may become soluble (gold).
 Opaque substances can become transparent (copper nanoparticles).
Origin of Differences
Change in the mechanical, thermal and catalytic properties of the materials can
be seen with the increase in surface area to volume ratio at the nanoscale level.
At the nanoscale level, the interaction between particles is either due to the van
der Waal forces or strong polar or covalent bonds.
As shown in the Figure 1.1. In spherical nanoparticles, for example at a size of
3 nm, 50% of the atoms or ions are on the surface, allowing the possibility of
manipulation of bulk properties by surface effects and allowing near
stoichiometric reaction chemistry.
The changes observed can be attributed to:
1. An increase in the surface to volume ratio (aspect ratio)6, their surface
becomes more reactive on itself and other systems. The size of the
nanomaterials plays a significant role in their pharmacological behaviour.
2. Dominance of interfacial phenomena that occur at the interface or boundary surface between a suspended
particle and the continuous phase material in which it is suspended. For this reason, interfacial phenomena are
almost always associated with disperse systems.
5
A Coercivity, also called the magnetic coercivity, coercive field or coercive force, is a measure of the ability of a ferromagnetic material
to withstand an external magnetic field without becoming demagnetised. Ferromagnetic materials with high coercivity are called
magnetically hard, and are used to make permanent magnets. Materials with low coercivity are said to be magnetically soft. The latter are
used in transformer and inductor cores, recording heads, microwave devices, and magnetic shielding.
6
Aspect ratio is defined as the surface to volume ratio of nanoparticle. The nanoparticle shows a higher aspect ratio. This implies the
higher surface energy or higher activity of the nanoparticle.
3. Exhibition of Quantum behaviour or the Quantum Size Effect i.e. systems are not large enough for
classical laws of physics to apply. For the intermediate region of 2-10 nm, neither quantum chemistry nor
classic laws of physics hold.
When strong chemical bonding is present, delocalisation of valence electrons can be extensive, and this
delocalisation can vary with size; this in turn can lead to different chemical and physical properties. This effect
does not come into play by going from macro to micro dimensions.
1.3. Early Uses

The therapeutic use of gold can be traced back to Chinese medical history in 2500 BCE. Ayurvedic medicines
also involve colloidal gold and silver particles for antitoxin, immunomodulatory remedy, namely the Swarna
Bhasma (स्वर्ण भस्म; Golden Ash) & the Chandni Bhasma (च ां दी भस्म; Silver Ash).
Nanoparticles were used by artisans as far back as Rome in the fourth century in the famous Lycurgus cup7 made
of dichroic glass8 as well as the 9th century in Mesopotamia for creating a glittering effect on the surface of pots.
In modern times, pottery from the Middle Ages and Renaissance often retains a distinct gold- or copper-coloured
metallic glitter.
The dichroic effect is achieved by making the glass with tiny proportions of nanoparticles of gold
and silver dispersed in colloidal form throughout the glass material. The process used remains
unclear, and it is likely that it was not well understood or controlled by the makers, and was
probably discovered by accidental "contamination" with minutely ground gold and silver dust.
1.4. Nanomaterial Classification

General Shapes
Nanomaterials have extremely small size which having at least one dimension ≤100 nm. Nanomaterials can be
nanoscale in one dimension (e.g. surface films), two dimensions (e.g. strands or fibres), or three dimensions (e.g.
particles). Nanomaterials are materials which are characterised by an ultrafine grain size (< 50 nm).
They can exist in single, fused, aggregated or agglomerated forms with spherical, tubular, and irregular shapes.
Common types of nanomaterials include nanotubes, nanorods, dendrimers, quantum dots and fullerenes.
7
The Lycurgus Cup is a 4th century Roman glass cage cup made of a dichroic glass, which shows a different colour depending on whether
or not light is passing through it: red when lit from behind and green when lit from in front.
8
Dichroic glass is glass which displays one of two different colours depending on lighting conditions. One dichroic material is a modern
composite non-translucent glass that is produced by stacking layers of glass and micro-layers of metals or oxides which give the glass
shifting colours depending on the angle of view, causing an array of colours to be displayed as an example of thin-film optics.
9
VO2 Nanostars Au nanoparticle FePt nanosphere Ag nanocubes Ti nanoflower
(a) (b)
Transmission Electron Microscopy micrographs for Fe1.9V0.1O3.0 (5 mol%) showing well dispersed and spherical
nanoparticles at: (a) 5 nm and (b) 50 nm scales.
(a) (b)
Field Emission Scanning Electron Microscopy images of maghemite9 – MWCNTs nanohybrids (a) at 100,000 magnifications
(b) at 150,000 magnifications.
(a) (b)
Field Emission Scanning Electron Microscopy images of (a) ZnO prepared by sol gel method (b) ZnO prepared by solo
chemical method.
The shapes of nanoparticles may be determined by the intrinsic crystal habit10 of the material, or by the influence
of the environment around their creation, such as the inhibition of crystal growth on certain faces by coating
additives, the shape of emulsion droplets and micelles in the precursor preparation, or the shape of pores in a
surrounding solid matrix.
9
Maghemite or Maghaemite (Fe2O3, γ-Fe2O3) is a member of the family of iron oxides. It has the same spinel ferrite structure as
magnetite and is also ferrimagnetic. The name alludes to somewhat intermediate character between Magnetite and Hematite. It can appear
blue with a grey shade, white, or brown. Maghemite nanoparticles are also used in biomedicine, because they are biocompatible and non-
toxic to humans, while their magnetism allows remote manipulation with external fields.
10
Crystal habit is an external shape displayed by an individual crystal, but more often it is an external shape displayed by an aggregate of
crystals. Crystal habit names are often adjectives that help convey the shape of a crystal or a group of crystals.
Nanocrystals
A nanocrystal is a material particle having at least one dimension smaller than 100 nanometres, based on
quantum dots11 (a nanoparticle) and composed of atoms in either a single- or poly-crystalline arrangement.
Nanostructured materials are classified as basic motifs of nanocrystals, like:
 0D motifs such as spheres, cubes, and  2D motifs such as discs, prisms, and plate.
polyhedrons;  3D motifs are nanomaterials.
 1D motifs such as rods and wires;
The size of nanocrystals distinguishes them from larger crystals. For example, silicon nanocrystals can provide
efficient light emission while bulk silicon does not and may be used for memory components.
1.5. Synthetic Routes:

Top-down and bottom-up are two approaches for the manufacture of products. Schematic representation of ‘top-
down’ and 'bottom-up’ approaches for synthesis of nanoscale materials. (See Section 4.4)
11
Quantum dots (QDs) are semiconductor particles a few nanometres in size, having optical and electronic properties that differ from
larger particles due to quantum mechanics. Quantum dots are sometimes referred to as artificial atoms, emphasising their singularity,
having bound, discrete electronic states, like naturally occurring atoms or molecules. Quantum dots have properties intermediate between
bulk semiconductors and discrete atoms or molecules. Their optoelectronic properties change as a function of both size and shape.
If all three dimensions are of nanometer scale, the structure is referred to as a quantum dot. Hence a quantum dot has all three dimensions
in the nano-range and is the ultimate example of nanomaterials.
11
Top-down approach
Top-down approach involves the breaking down of the bulk material into nanosized structures or particles. These
are an extension of those that have been used for producing micron sized particles. Examples of such techniques
are:
(1) High-Energy Wet Ball Milling12 (2) Electron Beam Lithography13 (3) Atomic Force Manipulation14
(4) Gas-Phase Condensation15 (5) Aerosol Spray16
Characteristics: They are inherently simpler and depend either on removal or division of bulk material or on
miniaturisation of bulk fabrication processes to produce the desired structure with appropriate properties.
Problems: The biggest problem with the top-down approach is the imperfection of surface structure. For example,
nanowires made by lithography are not smooth and may contain a lot of impurities and structural defects on its
surface.
12
A ball mill is a type of grinder used to grind or blend materials. It works on the principle of impact and attrition: size reduction is done
by impact as the balls drop from near the top of the shell.
13
Electron-beam lithography (EBL) is the practice of scanning a focused beam of electrons to draw custom shapes on a surface covered
with an electron-sensitive film called a resist (exposing). The electron beam changes the solubility of the resist, enabling selective removal
of either the exposed or non-exposed regions of the resist by immersing it in a solvent (developing). The purpose, as with photolithography,
is to create very small structures in the resist that can subsequently be transferred to the substrate material, often by etching.
14
Atomic Force Microscopy is not only a nano-analytical instrument to perform imaging and spectroscopy on the atomic scale, but can
also be used as a tool to assemble atomic structures, manipulate and switch molecules, and induce chemical reactions including the
synthesis of individual molecules
15
Gas condensation was the first technique used to synthesize nanocrystalline metals and alloys. In this technique, a metallic or inorganic
material is vaporised using thermal evaporation sources such as a Joule heated refractory crucibles, electron beam evaporation devices
16
Aerosol Spray involves the nebulisation of precursors and then unwanted components are burnt in a flame to
get the required material
Bottom-up approach
Bottom-up approach refers to the build-up of a material from the bottom: atom-by-atom, molecule-by-molecule,
or cluster-by cluster. Some of the well-known bottom–up techniques reported for the preparation of luminescent
nanoparticles are:
(1) Organometallic Chemical Route17 (2) Reverse-Micelle Route
(3) Colloidal Precipitation (4) Hydrothermal Synthesis
(5) Sol-Gel Synthesis & (6) Template Assisted Sol-Gel (7) Electrodeposition
Characteristics: The alternative approach, which has the potential of creating less waste and hence the more
economical, is the ‘bottom- up’. Many of these techniques are still under development or are just beginning to be
used for commercial production of nanopowders.
17
The principle behind the process is that molecules such as stabilisers and emulsifiers; that can interact with the surface of a nanoparticle
influence nucleation and growth.
13
Summary
Top-Down Bottom-Up
The top-down approach often uses the traditional Bottom-up approaches, in contrast, use the chemical
workshop or microfabrication methods where properties of single molecules to cause single-
externally controlled tools are used to cut, mill, and molecule components to:
shape materials into the desired shape and order.
(a) Self-organise or self-assemble into some useful
Micropatterning techniques, such as conformation,
photolithography and inkjet printing belong to this (b) Rely on positional assembly.
category. Vapour treatment can be regarded as a new
These approaches utilise the concepts of molecular
top-down secondary approaches to engineer
self-assembly and/or molecular recognition.
nanostructures.
Such bottom-up approaches should, broadly
The top-down approach which is sourced from
speaking, be able to produce devices in parallel and
microelectronics has to do with a clear reduction or
much cheaper than top-down methods, but could
breaking down of systems in their current state by
potentially be overwhelmed as the size and
making existing technologies more efficient. This
complexity of the desired assembly increases.
results in a reduction in the size of the devices into
nanoscale aspects. The bottom-up approach further comprises of
creating nanomaterials and objects within the same
The biggest problem with top-down approach
nanosphere based on atoms, molecules, and
(physical methods) is the imperfection of the surface
aggregate grouping. This sort of grouping occurs in a
structure.
clear and manageable manner, which allows for an
increase in the functionality of the structure of such
materials.
“The bottom-up approach is more accepted in
synthesis of nanoparticles due to many merits It is found that the Gibbs free energy,
as fewer defects, more homogenous chemical thermodynamic equilibrium and kinetic methods are
composition and better ordering”. the main strategies of nanoparticles synthesis in
bottom-up approach
1.6. Applications of Nanomaterials:

Nanoparticles have been used as quantum dots and as chemical catalysts such as nanomaterial-based catalysts.
Recently, a range of nanoparticles are extensively investigated for biomedical applications including tissue
engineering, drug delivery, and biosensor. Nano materials are used in a variety of, manufacturing processes,
products and healthcare including paints, filters, insulation and lubricant additives.
General
Nanomaterials are used in components to control and optimise material properties and chemical reactivity. For
e.g.:
 Catalysis for fuel cells, bioprocessing, waste reduction and the chemical industry.
 Nanomaterials can also be used in three-way-catalyst (TWC) applications. TWC converters have the
advantage of controlling the emission of nitrogen oxides (NOx). In core-shell structure, nanomaterials
form shell as the catalyst support to protect the noble metals such as Pd-Rh
 Energy (Photovoltaics, Photonics, Hydrogen Storage). Manufacture of inexpensive photovoltaics and other
energy conversion devices.
 Electronics/Magnetics. Development of highly selective sensing materials and systems
 Environment (Geosciences, Waste Storage, Contaminant Transport, Atmospheric Chemistry). Design of
structures optimised for energy transport. High quality filters may be produced using nanostructures, these
filters are capable of removing particulate as small as a virus as seen in a water filter. Nanomaterials
membrane bioreactor (NMs-MBR), are recently proposed for the advanced treatment of wastewater
 Nanoscience/Nanotechnology (Oxide Nanostructures, Hard Soft interfaces).
 As a lubricant additive, nano materials have the ability to reduce friction in moving parts.
 Worn and corroded parts can also be repaired with self-assembling anisotropic nanoparticles called
TriboTEX.
 In paints nanomaterials are used to improve UV protection, UV aging, and improve ease of cleaning.
 Nanozymes are nanomaterials with enzyme-like characteristics. They are an emerging type of artificial
enzyme, which have been used for wide applications in such as biosensing, bioimaging, tumor diagnosis,
antibiofouling and more.
Nanomaterials Applications
Silicon Si Electronics, sensors
Germanium Ge Electronics, IR detectors
Iron Oxides Fe2Ox = 2, 3, 4 Magnetic separations, biomedical applications, Cancer Drug delivery,
sensors
Indium Oxide InO2 Chemical sensors, biosensors
Indium Tin Oxide In2O3:SnO2 Transparent conductive film in display electrodes, solar cells, organic light
emitting diodes
Zinc Oxide Zn2Ox = 2, 4 UV laser, field emission device, chemical sensor, desulfurisation
Copper Oxide Cu2O Field emission device
Wide Bandgap GaN High temperature electronics, UV detectors and lasers, automotive
Nitrides electronics and sensors
Tin Oxides Sn2Ox = 2, 3 Chemical sensors, solar cell
Indium Phosphide InP Electronics, optoelectronics
Zinc Selenide ZnSe Photonics (Q-switch, blue-green laser diode, blue-UV photodetector)
Copper-Tungsten CuW Electrical interconnects
Nanoconsumer Products
Examples (out of hundreds) of nanoconsumer products are as under:
Personal:
 First Response® Home Pregnancy Test by Carter-Wallace®
15
 Nano Cosmetics by SongSing Nano Technology Co., Ltd
 Zelens® Fullerene C-60 Eye Cream by Zelens®
Household Goods:
 Eagle One Nanowax® by Eagle One
 Antibacterial Kitchenware by Nano Care Technology, Ltd.
 Antibacterial Pet Products by Nano Care Technology, Ltd
Clothing:
 Dockers® Go Khaki® by Dockers®
 Eddie Bauer® Water Shorts by Eddie Bauer®
Sports/Recreation:
 AccuFlex® Evolution Golf Shaft by Accuflex®
 Stealth CNT® Baseball Bat by Easton® Sports, Inc
 Wilson® nCode® Tennis Rackets by Wilson®
 Atomic Snow® Izor Skis by Atomic Snow®
1.7. Summary of Lecture Video 1.1:

“What is Nanotechnology?” by Risk Bites
See the Video, https://www.youtube.com/watch?v=DAOFpgocfrg&t=35s
What’s the importance of atomic arrangement?
How the different atoms in something are arranged can affect things like, how strong or how weak it is. Or if it
conducts electricity. Or if you can see through it. Or even what it feels like. In fact, pretty much anything that the
stuff around you does, it does because of how all the different atoms it's made of are put together.
Can we alter atomic arrangements?
We could make totally new stuff by putting atoms together in ways that we've never done before but when you
start playing around with atoms, you can tap into some really weird quantum physics. Over the past few years,
scientists and engineers have become increasingly good at designing and engineering materials down at the level
of atoms, or small groups of atoms without much hindrance. This new technology involves doing stuff at such a
minute scale, it iss called nanotechnology. This is really powerful tech. It's helping us to do stuff we couldn't even
dream of just a few years ago.
What are the benefits? What are the risks?
 Using their news skills, nanotechnologists are  The last thing we want is to:
beginning to
 Make better solar cells that also destroy the
 Create materials that are really good at turning environment.
sunlight into energy.
 Design more efficient water filters that just
 Using nanoscopically small particles to deliver happen to cause more pollution.
anti-cancer drugs.
Because of this, scientists and others are working
 Even turning polluted water into drinkable
hard to make sure we develop and use
water.
nanotechnology responsibly.
 They're even finding new ways to make glass
that doesn't break when you drop it.
 Batteries that last longer.
 Even tee shirts that smell fresh after you've worn
them for a few days.
1.8. Molecular Self-Assembly

Definition
Self-assembly is a process in which a disordered system of pre-existing components forms an organised structure
or pattern as a consequence of specific, local interactions among the components themselves, without external
direction. When the constitutive components are molecules, the process is termed molecular self-assembly.
Common examples include the formation of colloids, biomolecular condensates, micelles, liquid crystal phases,
and monolayers by surfactant molecule.
AFM image of Napthalenetetracarboxylic Diimide (NTCDI) molecules on Ag interacting via H-bonding at 77 K. ("Hydrogen bonds" in the
top image are exaggerated by artifacts of the imaging technique)
Molecular self-assembly is the process by which molecules adopt a defined arrangement without guidance or
management from an outside source. Molecular self-assembly is the construction of systems without guidance or
management from an outside source (other than to provide a suitable environment).
What causes Molecular Self-Assembly?
Assembly of molecules is directed through non-covalent interactions (e.g., hydrogen bonding, metal coordination,
hydrophobic forces, van der Waals forces, pi-stacking interactions, and/or electrostatic) as well as
electromagnetic interactions.
Molecular self-assembly is an important aspect of bottom-up approaches to nanotechnology, in contrast to a 'top-
down' technique such as lithography where the desired final structure is carved from a larger block of matter.
Using molecular self-assembly the final (desired) structure is programmed in the shape and functional groups of
the molecules.
Types on the basis of System State
Self-assembly are classified mainly as static or dynamic self-assembly.
In static self-assembly, the ordered state forms as a In dynamic self-assembly, patterns of pre-existing
system approaches equilibrium, which will reduce its components organised by specific local interactions
free energy. are not commonly described as "self-assembled" by
scientists in the associated disciplines. These
structures are better described as "self-organised”.
Static Self Assembly of Gold Nanoparticles (AuNPs) under microscope forming chain
See the video: https://www.youtube.com/watch?v=MT9z73QnYDM by Argonne National Laboratories.
(1) (2) (3) (4)
17
Dynamic Self Assembly as explained by the analogue model of the self-organisation of magnetic dipoles.
See the video: https://www.youtube.com/watch?v=KPP-4-LEHXQ by manf124
Or, the video: https://www.youtube.com/watch?v=PeHWqr9dz3c by Stanford Complexity Group
(1) (2) (3) (4)
Types on the basis of Supramolecular Chemistry

The molecules are directed to assemble through non-covalent interactions. Self-assembly may be subdivided:
as temperature and pH also play a role in
1. Intermolecular self-assembly spontaneous self-assembly.
(form a supramolecular assembly).
2. Intramolecular self-assembly
 Nanoparticles can self-assemble as a result
(folding as demonstrated by foldamers
of intermolecular forces between them
because the nanoparticles system try to and polypeptides).
minimise the free energy to attain  Nanoparticles have the ability to assemble
equilibrium, self-assembly is one of the chemically through covalent or noncovalent
important option for the system to reach its interactions with their capping ligand.
lowest free energy thermodynamically.
 As the ligands tend to be complex and
 Nanoparticles can be programmed to self- sophisticated, self-assembly can provide a
assemble by changing the functionality of simpler pathway for nanoparticle
their side groups, taking advantage of weak organisation by synthesizing efficient
and specific intermolecular forces to functional groups.
spontaneously order the particles. NOTE:
 These direct inter-particle interactions can The terminal functional group(s) on the particle are known as
be typical intermolecular forces such as capping ligands (CLs). CLs intervene during nanocrystal
growth and have enabled chemists to synthesize nanoparticles
hydrogen bonding or Van der Waals forces, with exquisite control over shape and monodispersity. Ligand-
but can also be internal characteristics, such exchange reactions, enable the subsequent modification of the
as hydrophobicity or hydrophilicity. nanoparticle surface chemistry and the transfer from polar into
organic solvents and vice versa.
 For example, lipophilic nanoparticles have For instance, for PbS NPs: lead oleate (LO), formate (LF),
the tendency to self-assemble and form acetate (LA), nonanoate (LN) are used as CLs.
crystals as solvents are evaporated.
Capping Ligands vs Surfactants: The main distinction between
 While these aggregations are based on capping ligands and surfactants lies in the differences of the
strength of their binding to metal atoms at the nanocrystal
intermolecular forces, external factors such surface, which is greater in the case of capping ligands.
In the case of lipophilic nanoparticles, which are widely used in consumer products, there is evidence that particle
size and formulation influences skin permeability and that lipophilic particles <6 nm can embed in lipid bilayers18.
Commonly, the term molecular self-assembly refers to intermolecular self-assembly, while the
intramolecular analogue is more commonly called folding.
Scope of Self-assembly:
Organising Metallic & Nonmetallic molecules. Self-assembly provides a simple route to organise suitable
organic molecules on noble metal and selected nanocluster surfaces by using monolayers of long chain organic
molecules with various functionalities like -SH, -COOH, -NH2, -SiR3 etc. These surfaces can be effectively used
to build-up interesting nano level architectures.
Merits: Flexibility with respect to the terminal functionalities of the organic molecules allows the control of the
hydrophobicity or hydrophilicity of metal surface, while the selection of length scale can be used to tune the
distant-dependent electron transfer behavior.
Significance: Organo-inorganic materials tailored in this fashion are extremely important in nanotechnology to
construct nano-electronic devices, sensor arrays, supercapacitors, catalysts, rechargeable power sources etc. by
virtue of their size and shape-dependent electrical, optical or magnetic properties.
18
A lipid bilayer is a biological membrane consisting of two layers of lipid molecules. Each lipid molecule, or phospholipid, contains a
hydrophilic head and a hydrophobic tail. The tail regions, being repelled by water and slightly attracted to each other, congregate together.
19
Degradability: An advantage to constructing nanostructure using molecular self-assembly for biological materials
is that they will degrade back into individual molecules that can be broken down by the body.
The interesting applications of monolayers and monolayer-protected clusters in materials engineering are
discussed using recent examples of size and shape control of the properties of several metallic and
semiconducting nanoparticles.
Week #2 Notes
2.1. Porous Solids
Definition of Porosity
A porous solid or a porous material is a material containing pores (voids). The
skeletal portion of the material is often called the "matrix" or "frame". The property is
called ‘Porosity’. The pores are typically filled with a fluid (liquid or gas). The
skeletal material is usually a solid, but structures like foams are often also usefully
analysed using concept of porous media.
Many natural substances such as rocks and soil (e.g., aquifers, petroleum reservoirs),
zeolites, biological tissues (e.g. bones, wood, cork), and man-made materials such as
cements and ceramics can be considered as porous media. Many of their important
properties can only be rationalised by considering them to be porous media.
Classification of Porous Materials
Porous materials may be classified according to their
pore diameters, namely:
Pore Diameters
Microporess 50 nm
Mesopores 2-50 nm
Macropores >50 nm
The synthesis, development and application of
nanoporous materials are exclusively focused on the
micro- and mesoporous materials.
Nanoporosity
A nanoporous material consists of either an organic and/or inorganic framework, which maintains a porous
structure with a typically large surface area in excess of 400 m2 /g. Nanoporous materials are highly versatile and
can used in various industrial applications ranging from catalytic reactions, adsorption and environmental
processes due to the presence of voids of controllable dimension at the atomic, molecular and nanometer scales
Significance & Application of Nanoporous Material
An increasing environmental concerns worldwide, enhanced the employment of nanoporous materials in the
removal of polluting species from different media as well as the recovery of useful ones has become more
significant.
Nanoporotechnology: The synthesis and application of nanoporous materials is very exciting and is considered to
be the fastest developing field in materials science. The multidisciplinary nature of research into these materials
requires contributions from chemists, physicists and engineers in order to fully tap their potential for application
in various industrial processes.
Absorpability: The adsorptive ability contributed by macropores is practically negligible. Microporous materials
are generally used for gaseous applications while mesoporous materials are usually used in aqueous-based media,
21
since gaseous molecules (CO2, CH4 and H2) are smaller in size compared to aqueous-based species (heavy metals
and organics).
Example of Nanoporous Material
(a) Activated carbon (AC)
Activated carbon (AC) is a very established
nanoporous material, which is basically an
amorphous organic material with an extensive
network of micro- and mesopores.
Precursor
Activated carbon is carbon produced from carbonaceous source
materials such as bamboo, coconut husk, willow peat19, wood, coir20,
lignite21, coal, and petroleum pitch22. The conventional precursor of
AC is coal, although biomass sources such as wood and agricultural
wastes are being increasingly used as substitutes.
A typical porous texture of a biomass-based AC is shown.
When derived from coal it is referred to as activated coal. Activated
coke is derived from coke23.
Manufacture
It can be produced in two-steps or by one of the following processes:
1. Physical activation: 2. Chemical activation:
Simply, it is Charring to produce black carbon The carbon material is impregnated with certain
and subsequent physical (thermal). The source chemicals. The chemical is typically an acid,
material is developed into activated carbon using strong base, or a salt in formulations, such as:
hot gases. Air is then introduced to burn out the % w/v
gasses, creating a graded, screened and de- H3PO4 25
dusted form of activated carbon. This is KOH 5
generally done by using one or more of the NaOH 5
following processes: CaCl 2 25
ZnCl2 25
1.1. Carbonisation:
Material with carbon content is pyrolysed at The carbon is then subjected to lower
temperatures in the range 600–900 °C, temperatures (250–600 °C). It is believed that
usually in an inert atmosphere with gases the temperature activates the carbon at this stage
like Ar or N2. by forcing the material to open up and have
more microscopic pores.
1.2. Steam Activation/Oxidation:
Raw material or carbonised material is
exposed to oxidizing atmospheres (O2 or
steam) usually in the temperature range of
600–1200 °C.
Chemical activation is preferred to physical activation owing to the lower temperatures, better quality consistency,
and shorter time needed for activating the material.
19
Peat refers to Soil formed of dead but not fully decayed plants found in bog (decayed vegetation) areas, often burned as fuel.
20
Coir is the fibre obtained from the husk of a coconut.
21
Lignite is a low-grade, brownish-black coal.
22
Petroleum Pitch, Bitumen or Asphalt is a dark, extremely viscous material remaining in still after distilling crude oil and tar.
23
Coke is a grey, hard, and porous fuel with a high carbon content and few impurities, made by heating coal or oil in the absence of air—a
destructive distillation process.
Porosity & Activity

Due to its high degree of microporosity, 1g of activated carbon has a surface area in excess of 3,000 m2 (32,000
ft2) as determined by gas adsorption. An activation level sufficient for useful application may be
obtained solely from high surface area. Further chemical treatment often enhances adsorption
properties.
Forms:
Normally, activated carbons are made in particulate form as Powdered AC or fine Granular AC <1.0
mm in size with an average diameter between 0.15 and 0.25 mm. Thus they present a large surface to
volume ratio with a small diffusion distance.
Market & Uses
Activated carbon is used in methane and hydrogen storage, air purification, solvent recovery,
decaffeination, gold purification, metal extraction, water purification, medicine, sewage treatment, air
filters in respirators, filters in compressed air, teeth whitening, production of HCl and many other applications.
Medicinally, it is used to treat poisonings and overdoses following oral ingestion.
(b) Metal Organic Frameworks (MOFs)
Porous coordination polymers built from metal ions Whereas, MOFs consisting of light elements
connected by organic linkers referred to as Metal- (carbon, boron, hydrogen and oxygen) referred to as
Organic Frameworks (MOFs). Covalent Organic Frameworks (COFs); are more
recent additions to the ranks of ordered porous
materials.
MOFs are highly diversified materials composed of metal atoms (ions) linked together by multifunctional organic
ligands.
Zn4O(BDC)5 (1.85 nm pore dia)
MOFs are a class of compounds consisting of metal ions or clusters coordinated to organic ligands to form one-,
two-, or three-dimensional structures. They are often porous. The organic ligands included are sometimes referred
to as "struts" or "linkers", one example being 1,4-benzenedicarboxylic acid (BDC).
23
Manufacture/Synthesis
Except for the use of preformed ligands, MOFs and zeolites are produced almost exclusively by hydrothermal or
solvothermal techniques, where crystals are slowly grown from a hot solution. In contrast with zeolites, MOFs are
constructed from bridging organic ligands that remain intact throughout the synthesis.
See for more details: https://en.wikipedia.org/wiki/Covalent_organic_framework#Synthetic_Chemistry &
https://en.wikipedia.org/wiki/Metal%E2%80%93organic_framework#Synthesis
Porosity & Activity
MOFs have a huge surface area and pore volume makes them potentially useful for gas sequestration/storage. <
0.5g/cm3. The range of pore size which is covered extends from the region, 0.3 nm (ultra-micropore) to 300 nm
(macropore).
Market & Uses
MOFs are relatively novel nanoporous materials, though not readily available in the commercial market as yet,
may have huge market potential due to their proven high surface area and pore volume in addition to their highly
ordered and robust porous frameworks.
MOFs are of interest for the storage of gases such as H2 and CO2. Other possible applications of MOFs are in gas
purification, in gas separation, in catalysis, as conducting solids and as supercapacitors
2.2. Aspect (SV) Ratio

Aspect ratio is defined as the surface to volume ratio of nanoparticle. The nano-particle shows a higher aspect
ratio. This implies the higher surface energy or higher activity of the nano-particle. For various nanomaterials, the
aspect ratios are as follows:
Nanostructure Dimension Diametres/Width, Length Aspect Ratio
Nanowires (NWs) 1D 101 of nm, unconstrained L/D ≥ 1000.
Nanotubes (NTs) 1D 101 of nm, unconstrained L/D ≥ 1000 (higher than NW).
Nanorods (NRs) 1D 1–100 nm each L/W = 3-5.
Nanowires Nanorods Nanotubes
2.3. Nanomaterials
2.3.1. Nanotubes
Also refer to Section 4.2.1
Description
A Nanotube is a nanometer-scale tube-like structure, which are also like nanowires, in terms of aspect
ratio; but unlike wires, tubes are hollow! Nanotubes maybe single-walled or multi-walled.
Synthesis
Techniques have been developed to produce nanotubes in sizable quantities, including by batch processes
such as arc discharge, laser ablation, chemical vapour deposition (CVD) and by continuous process such
as high-pressure carbon monoxide disproportionation (HiPCO). Most of these processes take place in a
vacuum or with process gases. The CVD growth method is popular, as it yields high quantity and has a
degree of control over diameter, length and morphology. Using particulate catalysts, large quantities of
nanotubes can be synthesised by these methods.
See https://en.wikipedia.org/wiki/Carbon_nanotube#Synthesis
Properties & Potential Uses
Carbon nanotubes can exhibit remarkable electrical conductivity while others are semiconductors. They
also have exceptional tensile strength and thermal conductivity because of their nanostructure and
strength of the bonds between carbon atoms.
Carbon nanotube has a low density of 1.3-1.4 g/cm3, its specific strength24 of up to 48,000 kNm/kg is the
best of known materials, compared to high-carbon steel's 154 kNm/kg. The nanotube aspect ratio, or the
L/D ratio, can be as high as 132,000,000:1, which is unequalled by any other material. The highest tensile
strength of an individual MWCNT has been tested to be 63 GPa.
Metallic nanotubes can carry an electric current density of 4 × 109 A/cm2, which is more than 1,000 times
greater than those of metals such as copper. CNTs can carry current densities in excess of 1000 MA/cm2
without electromigration damage.
In addition, they can be chemically modified (functionalised). These properties are expected to be
valuable in many areas of technology, such as electronics, optics, composite materials (replacing or
complementing carbon fibers), nanotechnology, and other applications of materials science.
2.3.2. Nanorods
Description
Nanorods are one morphology of nanoscale objects. Their dimensionality has been discussed above in
Section 2.2.
Synthesis
Nanorods are produced by direct chemical synthesis from metals or semiconducting
materials. A combination of ligands act as shape control agents and bond to different
facets of the nanorod with different strengths. This allows different faces of the nanorod
to grow at different rates, producing an elongated object. Temperature and reaction time
both are important factors in determining the morphology and aspect ratios of nanorods.
One potential application of nanorods is in display technologies, because the reflectivity
of the rods can be changed by changing their orientation with an applied electric field.
Another application is for microelectromechanical systems (MEMS). Nanorods, along
with other noble metal nanoparticles, also function as theragnostic agents i.e. they
absorb in the near IR, and generate heat when excited with IR light. This property has
led to the use of nanorods as cancer therapeutics.
24
The specific strength or strength/weight ratio or strength-to-mass ratio is a material's strength (force per unit area at failure) divided by
its density. In textile applications, tenacity is the usual measure of specific strength. The SI unit for specific strength is Pa m3/kg, or
N·m/kg, which is dimensionally equivalent to m2/s2, though the latter form is rarely used.
25
Applications
 One of the most perspectives application of Au nanorods (AuNRs) is detecting target sequences of
infecting agents of many dangerous diseases, for example, a HIV-1. The method is based on
electrostatic interaction between GNRs and DNA molecules.
 In field emission TVs picture quality can be improved radically, by changing the orientation of the
nanorods with respect to an applied electric field, the reflectivity of the rods can be altered, which
resulted in a superior picture display.
 ZnO nanorod and nanowire films were fabricated on the Si substrates with comb type Pt electrodes
show high-humidity sensitivity, good long-term stability and fast response time.
 The gas sensor fabricated from ZnO nanorod arrays showed a high sensitivity to H2 from room
temperature to a maximum sensitivity at 250 °C and a detection limit of 20 ppm. In addition, the ZnO
gas sensor also exhibited excellent responses to NH3 and CO exposure.
2.3.3. Nanowires
Description
A Nanowires can be made from a variety of conducting and semiconducting materials like Cu, Ag, Au,
Fe, Si, ZnO and Ge. Many different types of nanowires exist, including:
 Superconducting (e.g. YBCO25)
 Metallic (e.g. Ni, Pt, Au, Ag),
 Semiconducting (e.g. silicon nanowires (SiNWs), InP, GaN)
 Insulating (e.g. SiO2, TiO2).
 Molecular nanowires are composed of repeating molecular units either organic (e.g. DNA) or
inorganic (e.g. Mo6S9−xIx, Li2Mo6Se6).
Synthesis
There are two basic approaches to synthesizing nanowires:
 A top-down approach reduces a large piece of material to small pieces, by various means such as
lithography, milling or thermal oxidation.
 A bottom-up approach synthesises the nanowire by combining constituent adatoms26. Most synthesis
techniques use a bottom-up approach.
Initial synthesis via either method may often be followed by a nanowire thermal treatment step, often
involving a form of self-limiting oxidation, to fine tune the size and aspect ratio of the structures.
Nanowire Behaviour
1. Quantum Effects: The minute size of nanowires means that quantum mechanical effects become
important. “Quantum Wires”27 exploit quantum mechanics to produce wires with a range of unique
electrical properties. The structure of a nanowire is so simple that there’s no room for defects, and
electrons pass through unimpeded (tunneling)28.
2. Nanowire Conductivity: Nanowires made from metals can have conductivity much lower than that
for the bulk material. Higher aspect ratio makes them very good as detectors, because all that surface
25
Yttrium barium copper oxide (YBCO) is a family of crystalline chemical compounds, famous for displaying high-temperature
superconductivity. It includes the first material ever discovered to become superconducting above the boiling point of liquid N2 (77 K) at
about 92 K. Many YBCO compounds have the general formula YBa2Cu3O7−x (also known as Y123)
26
An adatom is an atom that lies on a crystal surface, and can be thought of as the opposite of a surface vacancy. This term is used when
describing single atoms lying on surfaces and surface roughness. The word is a portmanteau of "adsorbed atom
27
In current application, a quantum dot such as a small sphere confines electrons in three dimensions, a quantum wire confines in two
dimensions, and a quantum well confines only in one dimension.
28
Tunneling is a wavelike quantum mechanical effect. A tunneling current occurs when electrons move through a barrier that they
classically shouldn't be able to move through.
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.
Nanowires are promising materials for many novel applications:
 Electrical and Optical properties in exceptionally small electronic circuits, Transistors, Memory
devices.
 Thermal and Mechanical properties in Biomolecular nano-sensors and Field Emitters.
Electrons in nanowires are quantum confined29 laterally and thus occupy energy levels that are different
from the traditional continuum of energy levels or bands found in bulk materials.
Applications
1. Electrical and Electronics:
 Nanowires can be used for transistors, used widely as fundamental element in electronic circuits.
In transistors without p-n junctions, NWs behave like a channel (enhancement mode devices) in
transistors. Due to the high aspect ratio, if the gate dielectric in transistor is wrapped around the
nanowire channel, we can get good control of channel ‘electrostatic potential’, in this manner we
can turn the transistor on and off efficiently.
 Due to the unique 1D structure with remarkable optical properties, the nanowire unwraps new
opportunities for realizing high efficiency photovoltaic devices.
 A solar cell using graphene coated with zinc oxide nanowires, has been developed, which is
believed to allow the production of low cost flexible solar cells with higher efficiency.
 By employing light absorbing Germanium nanowires embedded in a flexible polymer film is
another method being developed to produce low cost flexible solar panels.
 Researchers at Stanford University have grown silicon nanowires on a stainless steel substrate
and demonstrated that batteries using these anodes could have up to 10 times the power density
of conventional lithium ion batteries
2. Environmental:
 AgCl NWs are used as a photocatalyst to decompose organic molecules in polluted water.
 Different semiconductors (e.g. TiO2, ZnO, α-Fe2O3 and WO3) have been employed as
photocatalysts.
 TiO2 because of its high stability, low toxicity, chemical inertness and resistance to photo-
corrosion is widely studied for heterogeneous photocatalysis.
 Electrified filters composed of AgNWs, CNTs and cotton has been employed to kill bacteria in
water.
 KMnO2 NW mats are used to adsorb oil from a spillage, due to stability at high temperatures. Oil
within a loaded mat/membrane can be removed by heating above the boiling point of oil. The oil
evaporates, and can be condensed back into a liquid. The membrane--and oil--can be used again.
29
Quantum confinement can be observed once the diameter of a material is of the same magnitude as the de Broglie wavelength of the
electron wave. When materials are this small, their electronic and optical properties deviate substantially from those of bulk materials.
Quantum confinement is responsible for the increase of energy difference between energy states and band gap. As the size of the particles
decreases, the electrons and electron holes come closer, and the energy required to activate them increases.
27
2.3.4. Quantum dots (QDs)
Description
Quantum dots, which are also known as "artificial atoms”30; are groups of atoms
made from semiconductor materials that promise to revolutionize everything from
home lights and computer displays to solar cells and biological warfare detectors.
A quantum dot gets its name because it's a tiny speck of matter so small that it's
effectively concentrated into a single point (in other words, it's zero-dimensional).
As a result, the particles inside it that carry electricity (electrons and holes, which
are places that are missing electrons) are trapped ("confined") and have well-
defined energy levels according to the laws of quantum theory
Defined as “A semiconductor nanostructure that confines the motion of conduction band electrons,
valence band holes, or excitons (bound pairs of conduction band electrons and valence band holes) in all
three spatial directions’’.
Fabrication
There are colloidal methods to produce many different semiconductors. Typical dots are made of binary
compounds such as PbS, PbSe, CdSe, CdS, CdTe, InAs, and InP. Dots may also be made from ternary
compounds such as CdSeS.
Large batches of quantum dots may be synthesised via colloidal synthesis. Due to this scalability and the
convenience of benchtop conditions, colloidal synthetic methods are promising for commercial
applications. Heating the solution at high temperature, the precursors decompose forming monomers
which then nucleate and generate nanocrystals. Temperature is a critical factor in determining optimal
conditions for the nanocrystal growth.
Quantum dot manufacturing relies on a process called high temperature dual injection which has been
scaled by multiple companies for commercial applications. This reproducible production method can be
applied to a wide range of quantum dot sizes and compositions.
Optoelectronic Property
Quantum dots have properties intermediate between bulk semiconductors and discrete atoms or
molecules. Their optoelectronic properties change as a function of both size and shape. However, the
specific colours vary depending on the exact composition of the QD.
 Larger QDs of 5–6 nm diameter emit longer wavelengths, with colours such as orange or red.
 Smaller QDs (2–3 nm) emit shorter wavelengths, yielding colours like blue and green.
30
The quantum dot absorption features correspond to transitions between discrete, three-dimensional particle in a box states of the electron
and the hole, both confined to the same nanometer-size box. These discrete transitions are reminiscent of atomic spectra and have resulted
in quantum dots also being called artificial atoms.
Size & Concentration
Self-assembled quantum dots are typically between 10-50 nm in size. At 10 nm in diameter, nearly 3
million quantum dots could be lined up end to end and fit within the width of a human thumb. Quantum
dots are made from a semiconductor such as silicon (a material that's neither really a conductor nor an
insulator, but can be chemically treated, so it behaves like either). Although they're crystals, they behave
more like individual atoms. Some examples include QDs of CdSe and ZnS.
Applications
1. Biological and chemical applications:
 Quantum dots have potential cancer treatment applications. Dots can be designed so they
accumulate in particular parts of the body and then deliver anti-cancer drugs bound to them.
Their big advantage is that they can be targeted at single organs, such as the liver, much more
precisely than conventional drugs, so reducing the unpleasant side effects that are characteristic
of untargeted, traditional chemotherapy.
 Quantum dots are also being used in place of organic dyes in biological research; for example,
they can be used like nanoscopic light bulbs to light up and colour specific cells that need to be
studied under a microscope.
 They're also being tested as sensors for chemical and biological warfare agents such as
anthrax31.
 Unlike organic dyes, which operate over a limited range of colours and
degrade relatively quickly, quantum dyes are very bright, can be made
to produce any colour of visible light, and theoretically last indefinitely
(they are said to be photostable).
2. Optical applications:
Quantum dots are also finding their way into computer screens and displays, where they offer 3
important advantages:
 In a typical LCD (liquid crystal display screen), the image is made by tiny combinations of red,
blue, and green crystals (effectively colour filters that switch on and off under electronic control)
that are illuminated from behind by a very bright backlight. Quantum dots can be tuned to give
31
Anthrax is an infection caused by the bacterium Bacillus anthracis. It can occur in four forms: skin, lungs, intestinal, and injection. A 2-
month course of antibiotics such as ciprofloxacin, levofloxacin, and doxycycline after exposure can also prevent infection. Anthrax spores
have been used as a biological warfare weapon. Anthrax toxin allows the bacteria to evade the immune system, proliferate, and ultimately
kill the host.
29
off light of any colour, so the colours of a quantum dot display are likely to be much more
realistic.
 Quantum dots produce light themselves so they need no backlight, making them much more
energy efficient (an important consideration in portable devices such as cellphones where battery
life is very important).
 Quantum dots are much smaller than liquid crystals so they'd give a much higher-resolution
image. Quantum dots LEDs (QLEDs) are also brighter than a rival technology known as organic
LEDs (OLEDs) and could potentially make OLED displays obsolete.
2.4. Nanomachines:
Description
A nanomachine, also named a nanite, is a mechanical or electromechanical device
whose dimensions are measured in nanometres (10-6 mm, or 10-9 m). These tiny
devices provide diverse opportunities towards a wide range of important
applications, ranging from targeted delivery of drug payloads to environmental
remediation.
Development
Nanomachines are largely in the research-and-development phase, but some primitive devices have been tested.
The main challenge lies in the methods to manufacture. It has been suggested for future that some nanomachines
might be grown in a manner similar to the way plants evolve from seeds.
Nanorobots
Nanorobots may be made from almost any type of material, the manufacturing processes being researched are
varied as well. The two principle manufacturing conventions are top down or bottom up. The former process
involves the extreme miniaturisation of existing robotic devices while the latter describes a process of building
starting at the atomic level and constructing any object one atom at a time.
Specialised nanorobots known as assembler nanobots will be required to create more sophisticated units.
Theoretically, the assemblers would use the bottom up approach and stack atoms upon each other in layers to
form the desired nanomachine. However these assembler units have yet to be developed.
Potential
The advantage of nanomachines include usage of only a tiny amount of energy to operate for individual units.
Durability is another potential asset; nanites might last for centuries before breaking down.
Contemporary Research
See https://theconversation.com/meet-the-nanomachines-that-could-drive-a-medical-revolution-58107
1. Controllable nano-rockets are made from a polystyrene bead covered in Au and Cr. They are attached to
multiple “catalytic engine” molecules using strands of DNA. When placed in a solution of H2O2, the engine
molecules caused a chemical reaction that produced O2 bubbles, forcing the rocket to move in the opposite
direction. By shining a beam of UV light on one side of the rocket causes the DNA to break apart, detaching
the engines and changing the rocket’s direction of travel. The researchers hope to develop the rocket so it can
be used in any environment, for example to deliver drugs to a target area of the body.
See https://www.youtube.com/watch?v=xMu1Ae4hYO8&t=4s
2. Graphene Engine for Nanorobots: Researchers from Singapore have recently demonstrated a simple but
nano-sized engine made from a highly elastic piece of graphene. By inserting some chlorine and fluorine
molecules into the graphene lattice and firing a laser at it causes the sheet to expand. Rapidly turning the laser
on and off makes the graphene pump back and forth like the piston in an internal combustion engine.
3. Magnetic nano-vehicles for carrying drugs through the body with magnetic nanoparticles. Drugs are injected
into a magnetic shell structure that can expand in the presence of heat or light. Once inserted into the body,
they can be guided to the target area using magnets and then activated to expand and release their drug.
4. The technology is also being studied for medical imaging. Creating the nanoparticles to gather in certain
tissues and then scanning the body with a magnetic resonance imaging (MRI).
2.5. Nanotechnology & Fiction

Nano-myth
Grey goo is a hypothetical end of the world scenario involving molecular nanotechnology in which out-of-control
self-replicating robots consume all matter on Earth while building more of themselves, a scenario known as
ecophagy. ("eating the environment").
31
Week #3 Notes
3.1. Nanofibres
Description
A nanofiber is a fibre with a diameter of ≤100 nm. Nanofibers can be generated from different polymers and
displayed different physical properties and application potentials. The diameters of nanofibers depend on the type
of polymer used and the method of production.
Fabrication Methods
There exist many different methods to make nanofibers, including drawing, electrospinning, self-assembly,
template synthesis, and thermal-induced phase separation.
(a) Electrospinning
Description: Electrospinning is the most commonly used method to generate nanofibers because of the
straightforward setup, the ability to mass-produce continuous nanofibers from various
polymers, and the capability to generate ultrathin fibres with controllable diameters,
compositions, and orientations.
Instrumentation: The instruments necessary for electrospinning include:
1. A high voltage supplier (5-50 kV);
2. A capillary tube with a pipette or needle with a small diameter i.e.
a spinneret32 (typically a hypodermic syringe needle);
3. A polymer solution, sol-gel33, particulate suspension or melt is
loaded into the syringe and this liquid is extruded from the needle
tip at a constant rate by a syringe pump34
4. A metal collecting screen or rotating drum.
Technique: See, https://www.youtube.com/watch?v=apaq99suYfk

(1) One electrode is placed into the polymer solution and the other electrode is attached to
the collector.
32
A spinneret is a device used to extrude a polymer solution or polymer melt to form fibres. Streams of viscous polymer exit via the
spinneret into air or liquid leading to a phase inversion which allows the polymer to solidify. The individual polymer chains tend to align in
the fibre because of viscous flow.
33
A sol–gel process is a fabrication method for metal oxides, especially Si and Ti oxides. The process involves conversion of monomers
into a colloidal solution (sol) that acts as the precursor for an integrated network (or gel) of either discrete particles or network polymers.
34
A syringe driver or pump, is a small infusion pump, used to gradually administer or withdraw small amounts of fluid..
(2) An electric field is applied to the end of the capillary tube that contains the polymer
solution held by its surface tension and forms a charge on the surface of the liquid.
(3) As the intensity of the electric field increases, the hemispherical surface of the fluid at
the tip of the capillary tube elongates to form a conical shape known as the Taylor
cone35.
(4) A critical value is attained upon further increase in the electric field in which the
repulsive electrostatic force overcomes the surface tension and the charged jet of fluid
is ejected from the tip of the Taylor cone.
(5) The discharged polymer solution jet is unstable and elongates as a result, allowing the
jet to become very long and thin. Charged polymer fibres solidifies with solvent
evaporation.
(6) Randomly-oriented nanofibers are collected on the collector. Nanofibers can also be
collected in a highly aligned fashion by using specialised collectors such as the
rotating drum, metal frame, or a two-parallel plates system.
Considerations: Parameters involving jet stream movement and polymer concentration have to be
controlled to produce nanofibers with uniform diameters and morphologies.
Characteristics: This flexibility allows for controlling the shape and arrangement of the fibres so that
different structures (i.e. hollow, flat and ribbon shaped) can be fabricated depending on
intended application purposes.
The process does not require the use of coagulation chemistry or high temperatures to
produce solid threads from solution. This makes the process particularly suited to the
production of fibres using large and complex molecules.
Electrospinning from molten precursors is also practiced; this method ensures that no
solvent can be carried over into the final product.
(b) Other Techniques
Melt blowing is a conventional fabrication method of micro- and nanofibres where a polymer melt is extruded
through small nozzles surrounded by high speed blowing gas. The randomly deposited fibres form a nonwoven
sheet product applicable for filtration, sorbents, apparels and drug delivery systems.
35
Taylor cone refers to the cone observed in electrospinning, electrospraying and hydrodynamic spray processes from which a jet of
charged particles emanates above a threshold voltage. As this effect of the electric field begins to exert a similar magnitude of force on the
droplet as the surface tension does, a cone shape begins to form with convex sides and a rounded tip. This is called a cone-jet and is the
beginning of the electrospraying process in which ions may be transferred to the gas phase.
33
The substantial benefits of melt blowing are simplicity, high specific productivity and solvent-free operation.
Scientists and engineers at the University of Minnesota, have been able to make nanofibers as thin as only 36 nm
using this technique (see https://sci-hub.do/https://doi.org/10.1016/j.polymer.2018.04.051).
Properties
All polymer nanofibers are unique for their extremely high specific surface
area, high aspect ratio (large S/V ratio), high porosity, appreciable
mechanical strength, and flexibility in functionalisation compared to their
microfibre counterparts.
They are a class of nanomaterials with cross-sectional diameters ranging
from 10s to 100s of nm, nanofibres possess. They are capable of forming
networks of highly porous mesh with remarkable interconnectivity between
their pores, making them an attractive choice for a host of advanced
applications.
Applications
 Researchers are using nanofibers to capture individual
cancer cells circulating in the blood stream. They use
nanofibers coated with antibodies that bind to cancer cells,
trapping the cancer cell for analysis.
 Nanofibres can stimulate the production of cartilage in
damaged joints (since they imitate the structure of a bone
or collagen matrix) and to deliver therapeutic drugs by
employing carbon nanofibers, which can penetrate
diseased cells and deliver drugs.
 Researchers have developed an elastic material that is
embedded with needle like carbon nanofibers. The material is
intended to be used as balloons which are inserted next
diseased tissue, and then inflated. When the balloon is inflated
the carbon nanofibers penetrate diseased cells and deliver
therapeutic drugs.
 Researchers at MIT have used carbon nanofibers to make
lithium ion battery electrodes that show four times the storage
capacity of current lithium ion batteries.
 Nanofibrous systems have been strongly pursued as scaffolds for tissue engineering applications.
Examples
Natural Polymers Synthetic Polymers
 Collagen36  Poly(lactic acid) (PLA),
 Cellulose  Polycaprolactone (PCL),
 Silk fibroin37,  Polyurethane (PU),
 Poly(lactic-co-glycolic acid) (PLGA),

 Keratin38
 Gelatin39
 Polysaccharides such as chitosan40 and
alginate41.  Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)
(PHBV),
 Poly(ethylene-co-vinylacetate) (PEVA).
36
Collagen (Greek: κόλλαγέν kóllagen ‘glue-producing) is the main structural protein in the extracellular matrix found in the body's
various connective tissues. As the main component of connective tissue, it is the most abundant protein in mammals, making up from 25-
35% of the whole-body protein content.
37
Fibroin is an insoluble protein present in silk produced by numerous insects, such as the larvae of Bombyx mori, and other moth. Silk in
its raw state consists of two main proteins, sericin and fibroin. The high glycine (and, to a lesser extent, alanine) content allows for tight
packing of the sheets, which contributes to silk's rigid structure and tensile strength. A combination of stiffness and toughness make it a
material with applications in several areas, including biomedicine and textile manufacture.
38
Keratin is a fibrous structural protein. It is the key structural material making up scales, hair, nails, feathers, horns, claws, hooves,
calluses, and the outer layer of skin among vertebrates. Keratin also from damage or stress. Keratin is extremely insoluble in water and
organic solvents. Keratin monomers assemble into bundles to form intermediate filaments, which are tough.
39
Gelatin (Lat: gelatus "stiff" or "frozen") is a translucent, colourless, flavorless food ingredient, commonly derived from collagen taken
from animal body parts. It is brittle when dry and gummy when moist. It is commonly used as a gelling agent in food, beverages,
medications, drug and vitamin capsules, photographic films and papers, and cosmetics.
40
Chitosan is a linear polysaccharide composed of randomly distributed β-(1→4)-linked D-glucosamine (deacetylated unit) and N-acetyl-
D-glucosamine (acetylated unit). It is made by treating the chitin shells of shrimp and other crustaceans with an alkaline substance, such as
NaOH. Chitosan has a number of commercial and possible biomedical uses.
41
Alginic acid, also called algin, is a polysaccharide distributed widely in the cell walls of brown algae that is hydrophilic and forms a
viscous gum when hydrated. With metals such as sodium and calcium, its salts are known as alginates. Its colour ranges from white to
yellowish-brown
35
3.2. Nanoclay
Description
Nanoclays or Organoclays are minerals which have a high aspect
ratio and with at least one dimension of the particle in the nanometer
range.
Nanoclay Clay
RIGHT: Crystal lattice structure of montmorillonite nanoclay.
Properties
The purity and cations exchange capacity of the nano-clay are also critical characteristics.
 The purity is important in achieving maximum increases in mechanical properties and achieving optimum
clarity for use in polymer films.
 Impurities act as stress concentrators, resulting in poor impact and tensile properties.
 The cation exchange capacity provides the surface activity necessary for acceptance of modifiers or surface
treatments.
Nanoclay Fabrication
Nanoclays are synthesised by the wet-chemical sol-gel method (gelation) while EtOH and some acids are used as
organic solvents. Such methods are used primarily for the fabrication of materials starting from a chemical
solution which acts as the precursor for an integrated network (or gel) of either discrete particles or network clays.
CTAB is Cetyltrimethylammonium Bromide {(C16H33)N(CH3)3Br just like other

surfactants, forms micelles in aqueous solutions. The modification of Montmorrilionite
(MMT) surface by using cationic surface active substances, such as CTAB can change its
surface properties, such as surface charge, hydrophobicity and cation-exchange capacity.
Typical precursors are CH3COO, HNO3, HCl, HCHO and H2SO4 acids, which undergo various forms of reactions.
Clay may form a sol (quick clay) if it is washed sufficiently to remove the counter ions. Quick clay may be gelled
if enough counter ions are added, so that the colloidal particles aggregate.
Classification
Nanoclays are nanoparticles of layered mineral silicates. Depending on chemical composition and nanoparticle
morphology, Nanoclays are organised into several classes such as:
Kaolinite, Dickite, Al2Si2O5 (OH)4 Members are
Kaolinite
Nacrite polymorphs42
(composed of the
same formula and
different structure)
Montmorillonite (Ca,Na,H)(Al,Mg,Fe,Zn)2
Montmorilloni
te or Smectite
X indicates varying
level of water in
Pyrophyllite, Talc (Si,Al)4O10(OH)2-XH2O mineral type
Vermiculite, Sauconite,
Saponite, Nontronite
Illite (K,H)Al2 (Si,Al)4 O10(OH)2-XH2O X indicates varying
level of water in
Illite
mineral type
Amesite (Mg,Fe)4Al4Si2O10(OH)8 Each member of

mineral has separate
formula; this group
has relatively larger
Chlorite
Chamosite, (Fe,Mg)3 Fe3 AlSi3O10(OH)8 member minerals and

is sometimes
considered as a
separate group, not as
Cookeite, LiAl5 Si3O10 (OH) 8 part of clays
Nimite (Ni,Mg,Fe,Al)6AlSi3O10(OH)8
Applications
Organically-modified nanoclays (organoclays) are an attractive class of hybrid organic-inorganic nanomaterials
with potential uses in polymer nanocomposites, as rheological modifiers, gas absorbents and drug delivery
carriers.
 Ink formulation: It helps to adjust the consistency of printing inks to the desired value, avoiding pigment
sedimentation, providing good colour distribution, obtaining desired film thickness, etc. by incorporation of
small amount of organically modified layered silicate.
 High Temperature Greases: Thickening lubricating oils with nanoclays can produce especially high
temperature resistant lubricating greases.
 Cosmetic Industry: The performance of cosmetics is enhanced by the use of nanoclays and they allow good
colour retention and coverage for nail lacquers, lipsticks and eye shadows.
 Waste Water Treatment: The use of nanoclays in wastewater treatment has become common in industry
today. Nanoclays exhibit a synergistic effect with many commonly utilised water treatment unit processes
including granular-activated charcoal, reverse osmosis, and air strippers. Granular-activated carbon is
particularly effective at removing a large range of organic molecules from water, however, is very poor for
42
In materials science, polymorphism describes the existence of a solid material in more than one form or crystal structure. Polymorphism
is a form of isomerism. Any crystalline material can exhibit the phenomenon. Allotropy refers to polymorphism for chemical elements.
37
removing large molecules such as humic acid43 and wastewaters containing emulsified oil and grease.
Nanoclays have proven to be the technology of choice for treating oily wastewaters.
 Nanoclay as drug vehicle: nanoclays as drug vehicle for controlled release of drug is one of the born age area
in medicinal application, nanoclays have great potential as compared to polymer and carbon nanotubes for
drug delivery applications.
 Polymer Recycling: Nanoclays have also been utilised as strength-enhancers in the recycling of thermoplastic
polymers.
43
Humic acids (HAs) are macromolecules that comprise humic substances (HS), which are organic matter distributed in terrestrial soil,
natural water, and sediment. HAs are soluble in alkaline media, partially soluble in water, and insoluble in acidic media. Humic substances
are organic compounds that are important components of humus, the major organic fraction of soil, peat, and coal.
Lecture 2
Week #4 Notes
4.1. Recent Applications and Advancement of Nanotechnology:
By employing nanotechnology, materials can effectively be made stronger, lighter, more durable, more reactive,
more sieve-like, or better electrical conductors, among many other traits. Many everyday commercial products are
currently on the market and in daily use that rely on nanoscale materials and processes involving:
Everyday Materials & Processes
 Nanoscale additives to or surface treatments of fabrics can provide
lightweight ballistic energy deflection in personal body armour, or can help
them resist wrinkling, staining, and bacterial growth.
 Clear nanoscale films on eyeglasses, computer and camera displays,
windows, and other surfaces can make them water- and residue-repellent,
antireflective, self-cleaning, resistant to ultraviolet or infrared light, antifog,
antimicrobial, scratch-resistant, or electrically conductive.
 Nanoscale materials are beginning to enable washable, durable “smart
fabrics” equipped with flexible nanoscale sensors and electronics with
capabilities for health monitoring, solar energy capture, and energy harvesting
through movement.
 Light weight cars, trucks, airplanes, boats, and space craft could lead to
significant fuel savings. Nanoscale additives in polymer composite materials
are being used in baseball bats, tennis rackets, bicycles, motorcycle helmets,
automobile parts, luggage, and power tool housings, making them
lightweight, stiff, durable, and resilient.
 Carbon nanotube sheets are now being produced for use in next-generation
air vehicles. For example, the combination of light weight and conductivity
makes them ideal for applications such as electromagnetic shielding and
thermal management.
 Nano-bioengineering of enzymes (Nanozymes) is aiming to enable
conversion of cellulose from wood chips, corn stalks, unfertilised perennial
grasses, etc., into ethanol for fuel. Cellulosic nanomaterials have
demonstrated potential applications in a wide array of industrial sectors,
including electronics, construction, packaging, food, energy, health care,
automotive, and defense.
 Nano-engineered materials in automotive products include high-power
rechargeable battery systems; thermoelectric materials for temperature
control; tires with lower rolling resistance; high-efficiency/low-cost sensors
and electronics; thin-film smart solar panels; and fuel additives for cleaner
exhaust and extended range.
 Nanoparticles are used increasingly in catalysis to boost chemical reactions.
This reduces the quantity of catalytic materials necessary to produce desired
results, saving money and reducing pollutants. Two big applications are in
petroleum refining and in automotive catalytic converters.
39
 Nano-engineered materials make superior household products such as degreasers and stain removers;
environmental sensors, air purifiers, and filters; antibacterial cleansers; and specialised paints and sealing
products, such a self-cleaning house paints that resist dirt and marks.
 Nanoscale materials are also being incorporated into a variety of personal care products to improve
performance. Nanoscale titanium dioxide and zinc oxide have been used for years in sunscreen to provide
protection from the sun while appearing invisible on the skin.
 Nanotechnology-enabled lubricants and engine oils also significantly reduce wear and tear, which can
significantly extend the lifetimes of moving parts in everything from power tools to industrial machinery.
4.2. Types of Nanomaterials (cont’d)

Also refer to Section 2.3. for preliminary information.
As discussed prior, most current nanoparticles/nanomaterials
could be organised into 4 types: Carbon-based materials, Metal-
based materials, Dendrimers, and Composites/Nanohybrids.
4.2.1. Carbon Nanotubes (CNTs)
Carbon-based Nanotube (CNT) is a tubular form of carbon with
diameter ≤1 nm and an unconstrained length ranging from few nm
to m. CNT is configurationally equivalent (idealisation) to a
single or multiple 2D graphene sheet(s) rolled into a tube (single-
wall vs. multi-walled).
 Single-wall carbon nanotubes (SWCNTs) are one of the allotropes of carbon, intermediate between fullerene
cages and flat graphene. They possess no concentric tubes within their structures i.e. have only one wall.
 Multi-wall carbon nanotubes (MWCNTs) consisting of nested single-
wall carbon nanotubes weakly bound together by van der Waals
interactions in a tree ring-like structure. Based on the Matryoshka
(матрёшка; little beloved mother) Doll Model, or e.g., a (0,8) single-
walled nanotube (SWNT) within a larger (0,17) single-walled nanotube.
Tubeforms – Configurations & Chirality
Rolling up a hexagonal lattice along different directions to form different
infinitely long single-wall carbon nanotubes shows that all of these tubes not only
have helical but also translational symmetry along the tube axis.
The (n,m) Noation: The (n, m) notation as indicated on the figure to the right,
implies the classical x-y distance from a point zero; across units on the CNT
plane.
Chirality: A nanotube is chiral if it has type (n, m), with m > 0 and m ≠ n; then its
enantiomer (mirror image) has type (m,n), which is different from (n,m).
In the study of nanotubes, one defines:
 A Zigzag path (e.g. 8,0) on a graphene-like lattice as a path that turns 60°,
alternating left and right, after stepping through each bond.
 An Armchair path (e.g. 4,4) as one that makes two left turns of 60° followed
by 2 right turns every 4 steps. Armchair tubes are always metallic, others can
be semiconducting or metallic. When the diameter increases, tubes resemble
graphite, which can be metallic.
For CNTs, if the configuration is:
Configuration Nature Band-Gap* Chirality Index
Armchair metallic none m-n = 3
Zig-zag semiconducting tiny m-n ≠ 3
*between conduction and valence band
These electrical properties, however, do not depend on whether the
hexagonal lattice is rolled from its back to front or from its front to back
and hence, are the same for the tube (m, n) and its mirror image (n, m).
Also for SWCNTs:
CNT Nature Band-Gap* Chirality Index
SWCNT metallic none n-m = 3q
semiconducting tiny n-m ≠ 3q
*‘q’ is any integer (1,2,3,…).
Bonding
The chemical bonding of nanotubes involves entirely sp2 -hybrid carbon atoms.
In sp2-hybridisation, 3 of the valance shell atoms are involved in chemical bonding
and hence, there is one free electron, called the π-electron. These bonds, which
are similar to those of graphite and stronger than; alkanes and diamond (which
employ sp3 -hybrid carbon atoms), provide nanotubes with their unique strength.
Fabrication
Techniques have been developed to produce nanotubes in sizable quantities, including by batch processes such as
arc discharge, laser ablation, chemical vapour deposition (CVD) and by continuous process such as high-
pressure carbon monoxide disproportionation (HiPCO)44.
44
The HiPCO process advances in catalysis and continuous growth are making CNTs more commercially viable. The HiPCO process
helps in producing high purity SWCNTs in higher quantity. The HiPCO reactor operates at high temperature 900-1100°C and high pressure
~30-50 bar. It uses carbon monoxide as the carbon source and Fe(CO)5 or Ni(CO)4 as a catalyst. These catalyst acts as the nucleation site
for the nanotubes to grow. See Bronikowski, M. J., Willis, P. A., Colbert, D. T., Smith, K. A., & Smalley, R. E. (2001). Gas-phase
production of SWCNTs from CO via the HiPCO process: A parametric study. Journal of Vacuum Science & Technology A: Vacuum,
Surfaces, and Films, 19(4), 1800–1805. https://sci-hub.do/https://doi.org/10.1116/1.1380721
41
Most of these processes take place in a vacuum or with
process gases. The CVD growth method is popular, as
it yields high quantity and has a degree of control over
diameter, length and morphology. Using particulate
catalysts, large quantities of nanotubes can be
synthesised by these methods, but achieving the
repeatability becomes a major problem with CVD
growth.
Summary of Lecture Video 4.1:
“Explained: Chemical Vapour Deposition (CVD)?” by Massachusetts Institute of
Technology (MIT)
See the Video, https://www.youtube.com/watch?v=j80jsWFm8Lc
For a complete working required in manufacture nanomaterials using CVD,
See https://www.youtube.com/watch?v=OWChkgyp92g (for BN-NT)
And, https://www.youtube.com/watch?v=K309K-DFqpE&t=64s (for Graphene)
Chemical vapour deposition, or CVD is a basic tool of manufacturing. It is used in everything from sunglasses to
potato-chip bags and is fundamental to the production of much of today's electronics. The CVD process is
discussed herein:
The CVD process begins with tanks containing a dialkoxy initiator (red) and one or more vinyl (purple) or
divinylene (blue) monomers, which are the building blocks of the desired polymer coating. These materials are
vaporised, either by heating them or reducing the air pressure, and are then introduced into a vacuum chamber
containing the material to be coated.
The initiator helps to speed up the process in which the monomers link up in chains to form polymers on the
surface of the substrate material.
The hot gaseous material naturally forms a coating on the colder substrate, much as water vapour coats the outside
of the cold drinking glass on a hot day.
Applications of CNT
 High strength composites for Cables, tethers, beams
 Multifunctional materials. Functionalize and use as polymer back bone; plastics with enhanced properties like
“blow-molded steel”
 In Heat exchangers, radiators, thermal barriers, cryo-tanks45.
 For radiation shielding (with H2 or B storage).
 Filter membranes
 Catalyst supports.
 Body armour, space suits.
 As scaffolding for bone growth.
 Nano-tape or gecko-tape. A synthetic adhesive tape consisting of arrays of carbon nanotubes transferred onto
a backing material of flexible polymer tape. These arrays are called synthetic setae and mimic the
nanostructures found on the toes of a gecko;
 To create vantablack46 which may also increase the absorption of heat in materials used in
concentrated solar power technology, as well as military applications such as thermal
camouflage. Its emissivity and scalability support a wide range of application
 Hybtonite47 carbon nanoepoxy resins where carbon nanotubes have been chemically
activated to bond to epoxy, resulting in a composite material that is 20-30% stronger than
other composite materials. It has been used for wind turbines, marine paints and a variety of sports gear such
as skis, ice hockey sticks, baseball bats, hunting arrows, and surfboards.
 Single-walled nanotubes are likely candidates for miniaturizing electronics.
 CVD Operation
 During CVD, a substrate is prepared with a layer of metal catalyst particles, most commonly nickel,
cobalt, iron, or a combination (for CNTs) & MgO & Al2O3 for catalytic support.
 Control: The diameters of the nanotubes that are to be grown are related to the size of the metal particles.
This can be controlled by patterned (or masked) deposition of the metal.
 Feedstock: To initiate the growth of nanotubes, two gases are bled into the reactor: a process gas (such as
NH3, N2 or H2) and a carbon-containing gas (such as C2H2, C2H4, C2H5OH or CH4).
 Process: After purging with Ar, the substrate (usually a Silicon wafer) is heated to approximately 700 °C
(for CNT) at atmospheric pressures. Nanotubes grow at the sites of the metal catalyst; the carbon-
containing gas is broken apart at the surface of the catalyst particle, and the carbon is transported to the
edges of the particle, where it forms the nanotubes. The catalyst particles can stay at the tips of the
growing nanotube during growth, or remain at the nanotube base, depending on the adhesion between the
catalyst particle and the substrate.
45
A Cryotank or cryogenic tank is a tank that is used to store frozen biological material. The term “cryotank” refers to storage of super-
cold fuels, such as liquid oxygen and liquid hydrogen. Cryotanks and cryogenics can be seen in many sci-fi movies, but they are still
currently undeveloped.
46
Vantablack is a material developed by Surrey NanoSystems in the UK and is one of the darkest substances known (blackest black),
absorbing up to 99.965% of visible light (at 663 nm if the light is perpendicular to the material). The name is a portmanteau of the acronym
VANTA (vertically aligned nanotube arrays) and the color black. . When light strikes Vantablack, instead of bouncing off, it becomes
trapped and is continually deflected amongst the tubes, eventually becoming absorbed and dissipating into heat.
47
Hybtonite is trademark of Amroy Europe Oy for carbon nanoepoxy resins. It is a family of composite resins reinforced with carbon
nanotubes (CNTs). Ultrasound is used to disperse the nanotubes and to create radicals at the ends of CNT molecules. CNTs can then
chemically react with epoxy resin or other material forming strong covalent bonds. The manufacturing process allows controlling the
material properties such as electrical conductivity, thermal conductivity and viscosity. Different forms of hybtonite are available for
different purposes such as laminating (glass fiber, carbon fiber), epoxy paints and glues.
43
 Trace metals in the product: Unencapsulated catalyst metals may be readily removable by acid washing,
encapsulated ones require oxidative treatment for opening their carbon shell. During synthesis, catalysts
can convert carbon precursors into tubular carbon structures but can also form encapsulating carbon
overcoats.
“Carbon nanotubes and Their Future Applications” by Rawtim
See the Video, https://www.youtube.com/watch?v=qC6PTxV2QWU
What are Carbon Nanotubes (CNTs)? Tubeforms
Carbon nanotubes are allotropes of carbon with a Nanotubes are categorised as:
cylindrical nanostructure. The smallest have a  Single-walled nanotubes have only one layer of
diameter of close to 1 nm and that places them right graphene.
between the size of a molecule of water and glucose.
 Multi-walled nanotubes have two or more layers
of graphene. Multi-walled are therefore more
resistant to surface modifications.
Structure & Bonding

Individual nanotubes naturally align themselves into Like everything else in nature, nanotubes also have
"ropes" held together by van der Waals forces, more so called “freaks” or in other words unique forms.
Those are torus, nanobud, peapod, nitrogen-doped
specifically, -stacking.
and many other carbon nanotubes.
The chemical bonding of nanotubes is composed They all have different structures, which usually
entirely of sp2 bonds (-C=C-), similar to those of resolves in enhanced electrical conductivity.
graphite. These bonds, which are stronger than the
sp3 bonds found in diamond, provide nanotubes with
their unique strength.
Synthesis
Synthesis of carbon nanotubes is complicated, but there is more than one method on how to do it.
All of them depend on graphite, which is sublimated using lasers, plasma or arc-
discharge and then cooled down, so that nanotubes can form.
What characteristic gave them their name?
They got their name after long, hollow structure with the walls formed by one-atom-
thick sheets of carbon, called graphene. These sheets are rolled at specific and
discrete angles, and the combination of the rolling angle and radius decides the
nanotube’s conductive properties.
Applications
With carbon nanotubes even the sky isn’t the limit.
 Because they are so light, a space-elevator with a
ribbon-like cable anchored to the surface and extending
into space, is possible. On the end that is reaching in
outer space, there would be a counter weight, making
the elevator stable and allowing the climber to rise
safely. It would be very useful for space explorations
and maybe even tourism.
 Radar is a detection system, which sends out radio
waves. When the radio waves hit an object, they
bounce back and are detected by the detector. The
detector then determinates the location of the object.
However if an object would be covered with MWCNTs, it would be stealth to radar, because the carbon
nanotubes would absorb the incoming radio waves. Now that would be perfect for military operations.
 Imagine a world without cancer. Well nanotubes could be the
answer.
 Kanzius’ cancer therapy uses SWCNT, which are inserted
around cancerous cells and then excited with radio waves,
which causes them to heat up and kill the surrounding cells.
 Another way to remove the cancerous tissue would be by
building a nanochip out of nanotubes, programming it and then
inserting it into nanobots.
 Because of their strength and ability to stop smaller projectiles,
nanotubes could be used as a body armour for future soldiers.
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 The armour would also monitor soldier’s condition and increase his abilities. The
idea was already used in a video game called Crysis, which makes us one step
closer to the real thing.
 In the future people will be tempted whether to exchange the old, organic arm with the
bionic arm, made out of nanotube muscles, which can expand 4000x faster than the
human muscles do and can withstand extreme temperatures.
 The contraction of nanotube muscles is already possible by applying a voltage
across the width of the nanotube ribbon. This makes them repel one another, and the ribbon can expand
sideways by up to 3x its original width in an instant.
4.2.2. Metallic Nanoparticles (MNPs)
The term metal nanoparticle is used to describe nano-sized metals with dimensions (length, width or thickness)
within the size range 1‐100 nm.
Purple of Cassius – An unrealised Medieval Nanotechnology

In the late 17th century (1685), beautiful glass which came to be known as ruby-glass or cranberry glass48, from
its colour, was first made in Potsdam, Germany by Johann Kunckel, a glassmaker.
Synthesis of Cassius’ Purple
First Synthesis: Johann Rudolf Glauber prepared colloidal gold as Cassius’ purple by
reduction of gold salts by tin chloride. The recipe was costly, for it involved
dissolving fine gold powder in aqua regia, adding water, and then adding a piece of
pure tin (or pewter49, a tin alloy). After an hour or two, a brilliant purple precipitate
formed.
4HCl(aq) + 3HNO3(aq) + Au(s) → HAuCl4(aq) + 3NO2(g) + 2H2O
48
Cranberry glass or 'Gold Ruby' glass is a red glass made by adding gold salts or colloidal gold to molten glass. Tin, in the form of
SnCl2, is sometimes added in tiny amounts as a reducing agent. The glass is used primarily in expensive decorations.
49
Pewter is a malleable metal alloy consisting of tin (85–99%), antimony (approximately 5–10%), copper (2%), bismuth, and sometimes
silver. Copper and antimony (and in antiquity lead) act as hardeners but lead may be used in lower grades of pewter, imparting a bluish tint.
[AuCl4]-(aq) + Sn(s) + 2H2O → Au(ppt) (nanocolloidal) + Sn(OH)2(aq) + Cl2(g) + 2HCl(aq)
Modern Synthesis: Generally, the preparation of this material involves gold being dissolved in aqua regia50 (1:3
HNO3:HCl (aq) solution), then reacted with a solution of SnCl2. The SnCl2 reduces the HAuCl4 from the
dissolution of gold in aqua regia to a colloid of elemental gold supported on SnO2 to give a purple precipitate or
colouration.
[AuCl4]-(aq) + SnCl2(aq) + 2H2O → Au(ppt) (nanocolloidal) + SnO2(aq) + Cl2(g) + 4HCl(aq)
Use in Medieval Times
Purple of Cassius was used in some of the most world-famous porcelain from Meissen and Sèvres. The presence
of gold explains its extremely high cost, but it has immense colouring power and is still used today in very high
quality tableware.
The Nanochemistry behind Cassius’ Purple

Michael Faraday (1857): Several chemists suspected it to be a gold-tin compound, due
to its preparation. The existence of metallic nanoparticles in solution was first
recognised by Faraday in 185751, who stated that the colour was actually due to the
miniature size of the gold particle.
Gustav Mie (1908): A quantitative explanation of their colour was given by Gustav Mie
in 1908, who provided the theory for scattering and absorption by spherical particles.
Richard Zsigmondey (1925). Richard Zsigmondey, describes the phenomenon in 1925:
the gold is in nanocolloidal form, adsorbed on a base of Sn(OH)2. For his work on the
nature of colloids, Zsigmondey was awarded the Nobel Prize in 1925.
Modern Uses
It has been used to impart glass with a red colouration as well as to determine the presence of gold as a chemical
test. When used as a test, the intensity of the colour correlates with the concentration of gold present.
Goals and Problems in Metallic Nanoparticles Synthesis
Ideally, metallic nanoparticles should be prepared by a method, which:
1. Is reproducible;
2. Allows for control the shape of the particles;
3. Provides a good yield monodisperse metallic nanoparticles by using easy, cheap, and less toxic precursors;
4. In water or more environmentally benign solvents (e.g. Ethanol);
5. Use the least number of reagents
Pewter has a low melting point, around 170–230 °C (338–446 °F), depending on the exact mixture of metals. The word pewter is probably
a variation of the word spelter, a term for zinc alloys (originally a colloquial name for zinc).
50
Aqua regia (Lat. "regal water" or "royal water") is a mixture of nitric acid and hydrochloric acid, optimally in a molar ratio of 1:3. Aqua
regia is a yellow-orange (sometimes red) fuming liquid, so named by alchemists because it can dissolve the noble metals gold and
platinum, though not all metals. The relative concentrations of the two acids in water differ; values could be 65% w/v for nitric acid and
35% w/v for hydrochloric acid – that is, the actual HNO3:HCl mass ratio is less than 1:2.
51
He prepared the first pure sample of colloidal gold, which he called 'activated gold', in 1857. He used phosphorus in CS2 to reduce a
solution of gold chloride. The colloidal gold Faraday made 150 years ago is still optically active.
47
6. Use a reaction temperature close to room temperature;
7. Few synthetic steps as possible (one‐pot reaction); minimizing the quantities of generated by‐products and
waste
4.2.3. Inorganic Nanowires
Description Properties
Inorganic nanowires (INW) have been grown as 2D Metallic nanowires (NWs) have attracted great
thin films in the last 30 years although the current attention in the frontiers of nanomaterial science due
focus is shifted to grow 1D Nanowires. to their extraordinary properties, such as high
thermal and electrical conductivity, high aspect ratio,
They offer interesting electronic, optical and other
good mechanical flexibility, and excellent optical
properties, and may be used in the future to link tiny
transparency.
components into small scale circuits.
Applications
These films produced by nanowires have been
widely used in displays, touchscreens, and solar cells
to achieve next-generation electronics that can be
bent, stretched, compressed, twisted, and deformed
into complex, nonplanar shapes but maintain good
conductive performance, reliability, and integration.
Benefits
The NW technology not only improves the
functionalities of base materials (e.g., thermal
conductivity and flexibility) but also endows highly
valuable properties (e.g., hydrophobicity and self-
cleaning), enabling ground-breaking building
applications ranging from energy efficiency to
indoor environment quality.
Current Motivation for NW Synthesis
One-dimensional quantum confinement, band-gap
varies with wire diameter, single crystal with well-
defined surface structural properties, tunable
electronic properties by doping, and the true
possibility of bottom-up integration.
4.2.4. Dendrimers
Description
As per IUPAC;
“Part of a molecule with only one free valence, comprising exclusively
dendritic and terminal constitutional repeating units and in which each path
from the free valence to any end-group comprises the same number of
constitutional repeating units "
Dendrimers are highly ordered, branched polymeric molecules They
are tree-like polymers, branching out from a central core and
subdividing into hierarchical branching units. Their names come from
Greek δένδρον déndron i.e. “tree”.
Synthesis & Discovery
The first dendrimers were made by divergent synthesis approached by
Fritz Vögtle in 1978, then by R.G. Denkewalter at Allied Corporation in
1981. Synthetic processes can also precisely control the size and number
of branches on the dendrimer.
When metal ions are introduced to a dendrimer in aqueous solution they
form a complex with the tertiary amines of the dendrimer, these can be
reduced by NaBH4 to get Dendrite-encapsulated Nanoparticles (DENs).
Properties
Dendrimers can be considered to have three major portions: a core, an inner
shell, and an outer shell. Ideally, a dendrimer can be synthesised to have
different functionality in each of these portions to control properties such as
solubility, thermal stability, and attachment of compounds for particular
applications.
Dendrimers are symmetric about the core, and often adopt a spherical three-
dimensional morphology. Dendritic molecules are characterised by structural
perfection.
Dendrimers and dendrons are monodisperse and usually highly
symmetric, spherical compounds. They are ≤15 nm in size, possess
high molecular weight. These have very dense surface surrounding a
relatively hollow core (vs. the linear structure in traditional polymers).
Their surfaces can be functionalised so that it may consist of acids (-
COO-) or amines (-NH-), this helps in regulating their properties and
performance.
Applications
 Drug delivery. Dendrimer drug delivery has also shown major
promise as a potential solution for many traditionally difficult
drug delivery problems such as to the brain.
 Dendrimers can be used to increase the solubility and
stability of orally-administered drugs and increase drug
penetration through the intestinal membrane.
 Hydrophobic drugs have a very difficult time penetrating
the skin layer, as they partition heavily into skin oils.
Recently, PAMAM (Poly(amido)amine) dendrimers have
been used as delivery vehicles for NSAIDS to increase
hydrophilicity, allowing greater drug penetration.
49
 Administered drugs were more active and had increased bioavailability when delivered via dendrimers
than their free-drug counterparts.
 Dendrimers have the potential to completely change the pharmacokinetic and pharmacodynamic (PK/PD)
profiles of a drug.
 Gene therapy, to traffic genes into cells without damaging or deactivating the DNA
 Antimicrobial & Antiviral agents can also be delivered via dendrimers by passing the blood-brain barrier,
which couldn’t be crossed by other administrative attempts.
 Cancer therapy; Modifying nanoparticle dendrimers with peptides has also been successful for targeted
destruction of colorectal cancer. Dendrimers have been explored for the encapsulation of hydrophobic
compounds and for the delivery of anticancer drugs.
 Dendrimers have potential applications in sensors. Studied systems include H+ or pH sensors.
 As a catalyst due to their extremely high Aspect ratio.
 Improve the delivery of agrochemicals to enable healthier plant growth and to help fight plant diseases.
4.2.5. Nanocomposites & Nanohybrids
Description
Nanocomposite is a multiphase solid material where one of the phases has 1, 2 or 3D of <100 nm or structures
having nano-scale repeat distances between the different phases that make up the material. The idea is to create
new materials with unprecedented flexibility and improvement in their physical properties.
Properties
The mechanical, electrical, thermal, optical, electrochemical, catalytic properties of the nanocomposite will differ
markedly from that of the component materials. Size limits for these effects have been proposed:
For
<5 nm Catalytic activity
<20 nm ‘Softenining’ hard magnets
<50 nm Changes to refractive index
<100 nm Superparamagnetism52,
Mechanical strengthening
Restricting matrix dislocation movement
Difference with normal composites. In mechanical terms, nanocomposites differ from conventional composite
materials due to the exceptionally high surface to volume ratio of the reinforcing phase and/or its exceptionally
high aspect ratio.
Effect of nano-reinforcement
 In general, the nano reinforcement is dispersed into the matrix during processing. A relatively small amount
of nanoscale reinforcement can have an observable effect on the macroscale properties of the composite. For
e.g., adding carbon nanotubes improves the electrical and thermal conductivity.
 The addition of these nanoparticles in the polymer matrix at low concentrations (~0.2 weight %) cause
significant improvements in the compressive and flexural mechanical properties of polymeric nanocomposites
 Other kinds of nanoparticulates may result in enhanced optical properties, dielectric properties, heat resistance
or mechanical properties such as stiffness, strength and resistance to wear and damage.
52
A form of magnetism which appears in small ferromagnetic or ferrimagnetic nanoparticles (those with unequal moments and
spontaneous magnetism). In sufficiently small nanoparticles, magnetisation can randomly flip direction under the influence of temperature
(a) Ceramic Matrix Nanocomposites (CMCs)
Ceramic matrix composites (CMCs) consist of ceramic fibres embedded in
a ceramic matrix. The matrix and fibres can consist of any ceramic material,
including carbon and carbon fibres. The ceramic occupying most of the
volume is often from the group of oxides, such as nitrides, borides,
silicides, whereas the second component is often a metal. Ideally both
components are finely dispersed in each other in order to elicit particular
optical, electrical and magnetic properties as well as tribological, corrosion-
resistance and other protective properties.
(b) Metal Matrix Nanocomposites (MMCs) (c) Polymer Matrix Nanocomposites (PMCs)
Metal matrix nanocomposites can also be defined as In the simplest case, appropriately adding
reinforced metal matrix composites. This type of nanoparticulates to a polymer matrix can enhance its
composites can be classified as continuous and non- performance, often dramatically, by simply
continuous reinforced materials.One of the more capitalizing on the nature and properties of the
important nanocomposites is Carbon Nanotube nanoscale filler (nanofilled polymer composites).
Metal Matrix Composites (CNT-MMC), which is an
This strategy is particularly effective in yielding high
emerging new material that is being developed to
performance composites, when uniform dispersion
take advantage of the high tensile strength and
of the filler is achieved and the properties of the
electrical conductivity of carbon nanotube materials.
nanoscale filler are substantially different or better
Critical to the realisation of CNT-MMC possessing than those of the matrix.
optimal properties in these areas are the development
of synthetic techniques that are (a) economically
producible, (b) provide for a homogeneous
dispersion of nanotubes in the metallic matrix, and
(c) lead to strong interfacial adhesion between the
metallic matrix and the carbon nanotubes.
The SEM images of the surfaces of Pristine Polyurethane

(PU), PUs - C30B (nanoclay) nanocomposites with 3wt%
and PUs - MWCNTs nanocomposites with 0.3wt%.
Nanoparticles such as graphene, CNT, MoS2 and
WS2 are being used as reinforcing agents to fabricate
mechanically strong biodegradable polymeric
FESEM images of maghemite–MWCNT nanohybrids: (a) nanocomposites for bone tissue engineering
Lower magnification (b) Higher magnification.
applications.
In addition to CNT-MMC, boron nitride (BN-
MMCs) and carbon nitride (CN-MMCs) reinforced
metal matrix composites are the new research areas
on metal matrix nanocomposites
Manufacture
Non-covalent hybrid assemblies of functionalised nanoparticles such as nano-clays with metallic or polymeric
system; done so via electrostatic adhesion/adsorption techniques such as Gas flow sputtering53 (Physical Vapour
Deposition) & Hollow Cathode. The reinforcing material can be made up of particles (e.g. minerals), sheets (e.g.
exfoliated clay stacks) or fibres (e.g. carbon nanotubes or electrospun fibres).
53
The process operates as a vacuum-based deposition technique and is associated with high deposition rates up to some µm/s and the
growth of nanoparticles in the gas phase
51
Applications
It has impressive advanced applications; including biomedical and industrial separation processes. Nanoscale
organo-clays have been used to control flow of polymer solutions (e.g. as paint viscosifiers) or the constitution of
gels (e.g. as a thickening substance in cosmetics, keeping the preparations in homogeneous form). A range of
polymeric nanocomposites are used for biomedical applications such as tissue engineering, drug delivery, cellular
therapies.
4.3. Nano-reinforced Composites -- Fine Particulate Technology:

Nano-reinforcement aids in replacing existing materials where properties can be superior and is for applications
where traditionally composites were not a candidate Nanotechnology provides new opportunities for radical
changes in composite functionality. Functionalities can be added when we control the orientation of the nanoscale
reinforcement.
Multifunctionality of Nanocomposites Role of Particle Size
Multifunctionality in nanocomposites always implies Adding certain inorganic clays to rubber
“structure + …” since in most cases the major dramatically improves the lifetime and wear-
function of a structure is to carry load or provide characteristics of tires. The nanoscale clay particles
shape. Additional functions can be bind to the ends of the polymer molecules - which
 Control of position, shape or load; you can think of as molecular strings - and prevent
them from unraveling. For most applications, there is
 Increments or hindrance to electrical and thermal
an optimum particle size:
conductance.
 Health monitor, control  Taste of peanut butter is affected by particle size.
 Stealth-managing electromagnetic or visible  Extremely fine amorphous silica is added to
signature (heat or radiowaves by aircraft) by control the ketchup flow.
inhibitive absorptive powers (used in stealth  Medical tablets dissolve in our system at a rate
aircraft and ships). controlled by particle size.
 Self-healing repair localised damage  Pigment size controls the saturation and
 Sensing physical, chemical variables for brilliance of paints.
biosensing or physiosensing applications.  Effectiveness of odour removers is controlled by
Possible nano-reinforcements targets the surface area of adsorbents.
Common powders encountered in our daily use

includes Cement, fertiliser, face powder, table salt,
sugar, detergents, coffee creamer, and baking soda.
Some products in which powder incorporation is not
obvious - Paint, tooth-paste, lipstick, mascara,
chewing gum, magnetic recording media, slick
magazine covers, floor coverings, automobile tires.
4.4. Getting down to the Nanoscale

Refer to Section 1.5.
The key to make nanoparticles is how to control and stop the reaction to make nano-size products because the
properties of nanoparticles depend on their size and morphology. There are 2 general approaches to the synthesis
of nanomaterials and the fabrication of nanostructures.
Bottom-Up Approach
Description
Bottom-up refers to methods where devices 'create themselves' by self-assembly by chemical synthesis. These
approaches include the miniaturisation of materials components (up to atomic level) with further self-assembly of
nanostructures. During self-assembly the physical forces operating at nanoscale are used to combine basic units
into larger stable structures.
Start with bulk wafer Alter area of wafer Grow or assemble the
where structure is to structure on the area
polymer or seed determined by the seed
crystals or other crystals or polymer.
techniques. (self-assembly)
Bottom-up methods start with atoms or molecules and build up to nanostructures. Typical examples are quantum
dot formation during epitaxial54 growth and formation of nanoparticles from colloidal dispersion.
Advantages Disadvantages
 Fabrication is much less expensive.  Large scale production is difficult.
 Ultra-fine nanoparticles, nanoshells, nanotubes  Chemical purification of nanoparticles is
can be prepared. required.
 Deposition parameters can be controlled.
Narrow size distribution is possible (1-20 nm).
 Cheaper technique.
Bottom-Up Processing
A bottom up synthesis method implies that the nanostructures are synthesised onto the substrate by stacking atoms
onto each other, which gives rise to crystal planes, crystal planes further stack onto each other, resulting in the
synthesis of the nanostructures. A bottom-up approach can thus be viewed as a synthesis approach where the
building blocks are added onto the substrate to form the nanostructure. There are two approaches:
1. Physical Processing i.e. the thermodynamic equilibrium approach. It involves the following stages:
generation of supersaturation, nucleation, and subsequent growth.
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Epitaxy (Greek: ἐπίτάξις epitaxis “above the ordered manner ”) refers to a type of crystal growth or material deposition in which
new crystalline layers are formed with one or more well-defined orientations with respect to the crystalline substrate. The deposited
crystalline film is called an epitaxial film or epitaxial layer. The relative orientation(s) of the epitaxial layer to the crystalline substrate is
defined in terms of the orientation of the crystal lattice of each material.
53
2. Chemical Processing i.e. the kinetic approach. It involves the limiting of the amount of precursors for the
growth and confining the growth system in a limited space.
Top-Down Approach
Description
Top-down refers to the traditional workshop or microfabrication method where tools are used to cut, mill and
shape materials into the desired shape and order. These approaches use larger of nanostructures, which can be
externally-controlled in the processing of nanostructures.
Start with bulk wafer Apply layer of Expose wafer with Etched wafer with
photoresist UV light through desired pattern
mask and etch wafer
Top-down methods begin with a pattern generated on a larger scale, then reduced to nanoscale. Typical examples
are etching through the mask, ball milling, and application of severe plastic deformation.
A top down synthesis method implies that the nanostructures are synthesised by etching out crystals planes
(removing crystal planes) which are already present on the substrate. A top-down approach can thus be viewed as
an approach where the building blocks are removed from the substrate to form the nanostructure.
Advantages Disadvantages
 Large scale production as deposition over a large  By nature, aren’t cheap and quick to
substrate is possible. manufacture.
 Chemical purification is not required  Slow and not suitable for large scale production.
 Yields broad size distribution (10-1000 nm) and
particles of varied shapes or geometry.
 Control over deposition parameters is difficult to
achieve due to impurities that lead to the
introduction of stresses, defects and
imperfections.
4.5. Growth Kinetics – Nucleation & Growth Processes

Synthesis of nanoparticles is a combination of two stage process, nucleation and growth. Most phase
transformations begin with the formation of numerous small particles (clusters) of the new phase that increase in
size until the transformation is complete.
Nucleation
Nucleation is the process whereby nuclei (seeds) act as templates for crystal growth. It is the initial process that
occurs in the formation of a crystal from supersaturated aqueous solutions, a liquid, or a vapor, in which a small
number of ions, atoms, or molecules become arranged in a pattern characteristic of a crystalline solid, forms a site
upon which additional particles are deposited as the crystal grows.
Nuclei formation is favoured by high initial concentration or supersaturation, low viscosity and a low critical
energy barrier. To obtain a uniform nanoparticle size, it must be ensured that there is a same time formation
(constant nucleation rate), an abruptly high supersaturation that quickly brings below the minimum nucleation
concentration.
It is the first step in the formation of a new structure via self-assembly and occurs at higher temperatures. It is
often found to be very sensitive to impurities in the system. During the supercooling of a liquid, solidification
(nucleation) will begin only after the temperature has been lowered below the melting temperature Tm.
The change in volume free energy, surface free energy and a

total free energy, as function of nucleus radius is illustrated
by the Free Energy and the Phase change is illustrated by the
Le-Mer Concentration Diagram.
Crystal Growth
Crystal growth is the process where a pre-existing crystal
becomes larger as more molecules or ions add in their
positions in the crystal lattice. A crystal is defined as being
atoms, molecules, or ions arranged in an orderly repeating
pattern, a crystal lattice, extending in all three spatial
dimensions.
Crystal growth differs from growth of a liquid droplet in that during growth the molecules or ions must fall into
the correct lattice positions in order for a well-ordered crystal to grow.
55
The steps involved are: growth species generation,
Diffusion from bulk to the growth surface,
Adsorption – surface growth – Diffusion-limited
growth – Low/controlled supply growth species
concentration, Increase in the solution viscosity
and Introduction of a diffusion barrier.
When the molecules or ions fall into the positions
different from those in a perfect crystal lattice,
crystal defects are formed.
Typically, the molecules or ions in a crystal lattice
are trapped in the sense that they cannot move
from their positions, and so crystal growth is often
irreversible, as once the molecules or ions have
fallen into place in the growing lattice, they are
fixed in place.
4.6. Summary of Lecture Video 4.3:

“Behaviour of Magnetic (Maghemite) Nanoparticles?” by A.G Azar
Magnetic nanoparticles are a class of nanoparticle that can be manipulated using magnetic fields. Such particles
commonly consist of two components, a magnetic material, often iron, nickel and cobalt, and a chemical
component that has functionality. Magnetic nanoparticle clusters that are composed of a number of individual
magnetic nanoparticles are known as magnetic nanobeads with a diameter of 50–200 nm.
The magnetic nanoparticles have been the focus of much research recently because they possess attractive
properties which could see potential use in catalysis including nanomaterial-based catalysts, biomedicine and
tissue specific targeting, microfluidics, magnetic resonance imaging, data storage, environmental remediation,
nanofluids, optical filter, magnetic cooling and sensors.
Lectures 3-4
Week #5 Notes
5.1. Bulk Synthetic Techniques
Issues with Nanoparticle Synthesis

Several key issues of nanoparticle synthesis are: uniformity
of particle size, size control, crystal structure, shape,
control and alignment for various device applications.
The synthesis of discrete nanoparticles with sizes ranging
from 2-20 nm is of significant importance, because of their
specialised applications including multi-terabit55 magnetic
storage devices. In magnetic nanoparticles, the unique
magnetic behaviours of the nanoparticles arises largely due
to the reduced sizes of isolated nanoparticles; where the
contributions from inter particle interactions are negligible.
Major Synthetic Techniques (on the basis of nature)
There are 3 major methods of synthesis, involving: Chemical, Physical & Biological methods.
Magnetic nanoparticles prepared in solution by: (a) Coprecipitation (maghemite). (b) Polyol process (Fe-based
alloy). (c) Microemulsions (maghemite)
55
1 terabit = 1012 bits = 1,000 gigabits.
57
5.1.1. Chemical Synthesis (Bottom-Up Approach)
Nanomaterials are a subclass of colloids56, in which the dimensions of colloids is in the nanometre range. These
colloids may appear in different shapes including spherical particles, plates, fibres and many more depending
upon synthesis parameters. Nanoparticles synthesised by chemical methods form “colloids in liquid (sols) or
vapour (gels)”. Two or more phases (solid, liquid or gas) of same or different materials formed, can co-exist with
the dimensions of at least one of the phases <1 m (<1-1000 nm).
Advantages
Chemical synthesis offers simplicity, inexpensivity, ease of instrumentation, low temperature (<350ºC) synthesis,
doping of foreign atoms (ions) is possible during synthesis and larger yields of variety of sizes and shapes. Self-
assembly or patterning is possible.
Typical Methods
Chemical (Bottom-Up) methods are further classified as:
Gas (Vapor) Phase Fabrication such as Pyrolysis Liquid Phase Fabrication such as Solvothermal
and Inert Gas Condensation reaction, Sol-gel, and Microemulsion. The liquid
phase fabrication entails a wet chemistry route.
The advantages of vapour phase pyrolysis include it

being a simple process, cost effective, a continuous Effectiveness of Solvothermal Methods and Sol-gel
operation with high yield. methods demands a simple process, low cost,
continuous operation and high yield.
(a) Pyrolysis.
A vaporous precursor (liquid or gas) is forced through a hole or opening at high pressure and burned. The
resulting solid is air classified to recover oxide particles from by-product gases.
Pyrolysis often results in aggregates and agglomerates rather than singleton primary particles. Instead of gas,
thermal plasma can also deliver the energy necessary to cause evaporation of small micrometer size particles. The
56
A colloid (Greek κόλλοειδής kólloeidḗs, “glue-like form”) is a mixture in which one substance of microscopically dispersed insoluble
particles are suspended throughout another substance. A colloid has a dispersed phase (the suspended particles) and a continuous phase (the
medium of suspension). The dispersed phase particles have a diameter of approximately 1-1000 nm.
thermal plasma temperatures are in the order of 10,000 K, so that solid powder easily evaporates. Nanoparticles
are formed upon cooling while exiting the plasma region.
(b) Sol-gel method
The sol-gel process is a wet-chemical technique (chemical solution deposition), widely used recently in the fields
of materials science and ceramic engineering. Sol-gel process exhibits the chemical transformation of a liquid (the
sol) into a gel state and with subsequent post-treatment to form a network and transition into solid oxide or
ceramic material. Liquid is dried to obtained powders, thin films or even monolithic57 solids.
Precursors: The Sol-Gel process allows to synthesize ceramic materials of high purity and homogeneity by
means of preparation techniques different from the traditional process of fusion of oxides. Precursors must have a
tendency to form gels. The precursors for synthesising these colloids consist of metal alkoxides and metal
chlorides. They readily react with water. The pH value of the solution is adjusted with an acid or a base which, as
a catalyst, also triggers the transformation of the alkoxide.
For e.g: Tetramethyl orthosilcate (TMOS) and Tetraethyl orthosilcate (TEOS) is used for nano-SiO2 sol-gel.
For e.g., Zirconium (IV) Propoxide and Titanium (IV) Butoxide. for ceramics of ZrO2 and TiO2 nano-coatings resp
Advantages: The main benefits of sol–gel processing are the high
purity and uniform, well-controlled nanostructure achievable at
low temperatures. Less energy consumption and less pollution,
economical route, provided precursors are not expensive. It is
possible to synthesise nanoparticles and nanorods etc. Very thin of
metals oxide can be obtained. Better alternative approach to
conventional production of glasses. The liquid phase enables
highly porous materials to be produced; this would normally not
be possible in gas phase reactors due to the high temperatures.
Disadvantages: The desired crystalline shapes often cannot be
configured and that the thermal stability of the product powder is
lower. This requires thermal post-treatment with repeated reduction of the particle surface.
Major Steps in a Sol-Gel Process: This process occurs in liquid solution of organometallic precursors by means
of hydrolysis and condensation reactions, lead to the formation of a new phase (sol). Three reactions are generally
used to describe the sol-gel process:
Hydrolysis → Condensation → Polycondensation.
57
Monolithic (Greek μονόλιθος monólithos, “made from a single block of stone”) means something consisting of a single chunk of hard
material rather than an assembly of discrete parts.
59
1. Hydroxylation is a chemical process that introduces a hydroxyl group (-OH) into
an organic compound.
2. Condensation reaction is the combination of two molecules to form a single
molecule, usually with the loss of a small molecule such as water (dehydration).
The opposite of a condensation reaction that releases a water molecule is called a
hydrolysis reaction.
3. By polycondensation or alcohol condensation process sols are nucleated and sol-
gel is formed, at constant temperature. These are concerned with the covalent
connection of monomer molecules, leading to high molecular weight polymers
with the release of a small molecule like water, or a low carbon number alcohol.
This is also called Isothermal treatment.
Products: Sol gel material can be obtained as bulks, thin films, and (nano) powders;
with enhanced Opto-mechanical characteristics. Fe2Ox–SiO2 gel composites are 2-3x
more reactive than conventional Fe2Ox. Complex oxides, Organic-Inorganic hybrids, biomaterials can be
synthesised.
For coatings, the alkoxide initial solution of the sol-gel process can be applied on surfaces of any geometry. After
the wetting, the build-up of the porous network takes place through gel formation, yielding thicknesses of 50-500
nm.
Characteristics of Products: Sol-gel allows one to obtain pure, size-

controlled stable and mono-dispersed nanoparticles ranges 20-200
nm, due to temporal nucleation followed by diffusion-controlled
growth; and, colloid stabilisation by electrostatic double layer
(rather than a polymer steric barrier58).
Contamination from by-products expected, product needs to be post
treated.
58
Steric stabilisation arises as a consequence of polymer adsorption onto the surface of particles that prevents agglomeration. The
dispersant tail must be soluble in, or at least compatible with, the polymer. Layers of large molecules, such as long chain polymers, are
adsorbed onto a particle surface.
(c) Microemulsion (two-phase) method

Microemulsions are defined as clear or slightly turbid systems of
lipophilic and hydrophilic phases, including surfactants and in most
cases high amounts of co-surfactants59. Due to their unique
properties, namely, ultralow interfacial tension, large interfacial area,
thermodynamic stability and the ability to solubilize otherwise
immiscible liquids.
Micro-emulsions, for e.g., consist of two liquids that cannot be mixed
with one another in the concentrations used, usually water and oil
along with at least one surfactant. In certain solvents this gives rise to
small reactors in which nucleation and controlled particle growth take
place. Particle size is determined by the size of the nanoreactors and,
at the same time, particle agglomeration is prevented.
Characteristics of Products: The microemulsion technique promises
to be one of the versatile preparation method which enables to control
the particle properties such as mechanisms of particle size control, geometry, morphology, homogeneity and
surface area. 4-15 nm size with narrow size distribution is obtained.
Nature of microemulsions: Microemulsions are isotropic, macroscopically
homogeneous, and thermodynamically stable solutions containing at least three
components, namely a polar phase (usually water), a nonpolar phase (usually oil) and a
surfactant. On a microscopic level the surfactant molecules form an interfacial film
separating the polar and the non-polar domains. This interfacial layer forms different
monodisperse microstructures ranging from:
 Oil droplets dispersed in a continuous water phase (O/W-microemulsion)
 Water droplets dispersed in a continuous oil phase (W/O-microemulsion). This can
be used as nanoreactors for the synthesis of nanoparticles with a low polydispersity60
(monodispersity).
59
Co-surfactants are usually alcohols or amines like CTAB ranging from C4-C10 and helps in the formation and stabilisation of
micelles/microemulsions.
60
The dispersity is a measure of the heterogeneity of sizes of molecules or particles in a mixture. A collection of objects is called uniform
(monodisperse) if the objects have the same size, shape, or mass. A sample of objects that have an inconsistent size, shape and mass
distribution is called non-uniform (polydisperse).
61
.
Applications: The uses and applications of microemulsions are numerous in chemical and biological fields. The
nanoparticles not only are of basic scientific interest, but also have resulted in important technological
applications, such as catalysts, high-performance ceramic materials, microelectronic devices, high-density
magnetic recording and drug delivery.
Problems: Surfactants are not easy to handle and a low product yield is obtained.
(d) Colloidal Co-precipitation
The technique usually involves the reduction of some metal salt or acid by a base. For e.g. highly stable gold
nanoparticles can be obtained by reducing chloroauric acid (HAuCl₄) with trisodium citrate (Na₃C₆H₅O₇).
HAuCl4+ Na3C3H4(OH)(COOH)3 → Au(ppt) + C3H4(OH)(COO-)3 + CO2 + HCl + 3NaCl
Metal gold nanoparticles exhibit intense red-magenta etc., colours depending upon the
particle size. Gold nanoparticles can be stabilised by adding thiol (-SH) or some other
capping molecules.
In a similar manner, silver, palladium, copper and few other metal nanoparticles can be
synthesised.
Characteristics: Capping agents such as ionic surfactants or protein coatings
are used to avoid aggregation. Nanoparticles obtained have broad size
distribution. By controlling pH and concentration of precursors, mean size of
nanoparticles can be controlled from 2 -15 nm.
In precipitation processes, particle size and size distribution, crystallinity and
morphology (shape) are determined by reaction kinetics (reaction speed). The
influencing factors include, beyond the concentration of the source material,
the temperature, pH value of the solution, the sequence in which the source
materials are added, and mixing processes.
To obtain Zns nanoparticles, any Zn salt is dissolved in aqueous (or
nonaqueous) medium and H₂S is added.
ZnCl₂+ H₂S → ZnS + 2HCl
Chemical capping can be done at high or low temperature depending on the
reactants. For high temp reactions, cold organometallic reactants are injected in
solvent like trioctylphosphine oxide (C18H37)3P=O (TOPO)61 held at > 300ºC.
Although it is a very good method of synthesis, most organometallic
compounds are expensive.
(e) Polyols method.
A polyol is an alcohol containing multiple hydroxyl groups.
Polyol process is the synthesis of metal-containing compounds using
poly(ethylene glycol)s as the reaction medium, that plays a role of solvent,
reducing agent and complexing agent at the same time, with dissolved
stabilizing/protecting agents; thereby controlling the growth of particles and
also preventing the aggregation of particles.
Method: In this method, precursor compounds such as hydroxides, oxides,
nitrates, sulphates, and acetates are either dissolved or suspended in a polyol,
and the reaction mixture is then heated to reflux (the boiling point of polyol).
During the reaction, the soluble metal precursor in polyol forms an
intermediate compound and reduced to metal nuclei which will nucleate to
metal nanoparticles.
61
In the research laboratory, both TOP and TOPO are frequently useful as a capping ligand for the production of CdSe quantum dots. It
serves as solvent for the synthesis and solubilises the growing nanoparticles. These quantum dots are also used in biological applications as
part of the protective barrier to prevent degradation as it travels through the harsh climate of the body
63
As the temperature is increased, the reduction potential of the ethylene glycol increases, which leads to nucleation.
Polyvinylpyrrolide (PVP) is also used as a stabiliser and shape-controlling reagent for the polyol synthesis
methods.
Characteristics: Nucleation and growth process are completely separated, uniform nanoparticles are obtained
with size ranges 10-90 nm. The particle size can be controlled by adding foreign nuclei for heterogeneous
nucleation and increasing temperature for thermal degradation of the polyol. Types of polyols used, salts and their
concentration, hydroxyl ion and reaction temperature are some important factors to control.
Applications: Very promising technique for well-defined shapes and size-controlled nanoparticles for biomedical
applications.
This chemical process was used to synthesize a wide range of metal based NPs (Ag, Pt, Pd, Pr, Cu), metal oxide
NPs (ZnO, indium-tin-oxide (ITO), Gd2O3, Cu2O), magnetic NPs and metal hybrid NPs. Synthesis of spherical Ag
NPs with controlled size and high monodispersity was established using the polyol process.
(f) Solvothermal reaction
Also known as Hydrothermal Reaction. Hydrothermal synthesis can be defined as a method of synthesis of single
crystals that depends on the solubility of minerals in hot water under high pressure (>2000 psi; >13.8 MPa) and
relatively high temperature (>200 oC).
Hydrothermal synthesis is considered as a promising method because it not only offers an effective control over
the size and shape of the particles at short reaction times, but also provides well-crystallised nanostructures with
high degree of homogeneity and definite composition
Method: The crystal growth is performed in an apparatus consisting of a steel pressure vessel called an autoclave,
in which a nutrient is supplied along with water. A temperature gradient is maintained between the opposite ends
of the growth chamber. At the hotter end the nutrient solute dissolves, while at the cooler end it is deposited on a
seed crystal, growing the desired crystal.
Advantages: The hydrothermal method over other types

of crystal growth include the ability to create crystalline
phases which are not stable at the melting point. Also,
materials which have a high vapour pressure near their
melting points can be grown by the hydrothermal
method.
The method is also particularly suitable for the growth of
large good-quality crystals while maintaining control
over their composition. Monodispersed particles are
produced at short residence time in aqueous media,
obtained in a size ranges 10-50 nm.
Easy to scale up method, additional post-processing steps
are required to achieve the engineered particle surfaces.
Disadvantages: The method include the need of expensive autoclaves, and the impossibility of observing the
crystal as it grows if a steel tube is used
.
(g) Sonolysis
Sonication is the act of applying sound energy to agitate particles in a sample, for various
purposes. Ultrasonic irradiation causes cavitations in an aqueous medium i.e. the formation,
growth, and implosive collapse of bubbles irradiated with sound. Ultrasonic frequencies of
(>20 kHz) are usually used, leading to the process also being known as ultra-sonication.
These properties are often responsible for shape and size selective nanoparticles synthesis
such as nanoemulsions and nanocrystals.
What is Sonochemistry? Sonochemistry62 arises from acoustic cavitation which involves the
formation, growth, and implosive adiabetic (massive energy build-up without loss) collapse
of bubbles in a microscopic region of the sonicated liquid which creates high pressure and
temperature that result in chemical excitation, followed by high rate of cooling.
How to perform sonocavitation? Sonochemistry can be performed by using a bath (usually used for ultrasonic
cleaning) or with a high power probe, called an ultrasonic horn63, which concentrates energy at one (typically
small) point.
The sonolysis or sonochemical technique is consistent with the production of iron oxide nanoparticles by using
the physical impacts of ultrasound that are being produced by acoustic cavitation. Instead of using high pressure,
temperature, and lengthy reactions, sonolysis provides an alternative way for iron oxide nanoparticle production.
Advantages: In many cases thermally induced processes provide crystalline nanoparticles. In contrast, ultrasonic-
driven reactions yield amorphous materials that are produced in collapsing cavitations bubble as enormous
heating-cooling rates (1010 K/s) prevent their crystallisation during quenching, thus calling for heat-treatment after
synthesis. These bubbles have temperatures around 5000 K and pressures of roughly 1000 atm (101 MPa).
Characteristics: Limits the growth by forming cavitation in an aqueous media. Nanoparticles obtained from sizes
range 20-40 nm.
Disadvantages: Cavitation can generate temperature around 5000oC, and pressure of >1.8 MPa. Expensive
equipment and very high energy is required to run the equipment.
(h) Microwave irradiation
Microwave irradiation provides rapid decomposition of metal precursors and can be extended for synthesis of a
wide range of metal oxide nanoparticles with various compositions, sizes and shapes. Microwave Irradiation
(MWI) methods provide simple and fast routes to the synthesis of nanomaterials since no high temperature or
62
Sonochemistry is concerned with understanding the effect of ultrasound in forming acoustic cavitation in liquids, resulting in the
initiation or enhancement of the chemical activity in the solution.
63
An ultrasonic horn (also known as acoustic horn, sonotrode, ultrasonic probe) is a tapering metal bar commonly used for augmenting
the oscillation displacement amplitude provided by an ultrasonic transducer operating at the low end of the ultrasonic frequency spectrum
(commonly between 15-100 kHz). The device is necessary because the amplitudes provided by the transducers themselves are insufficient
for most practical applications of power ultrasound.
65
high pressure is needed. Furthermore, MWI is particularly useful for a controlled large-scale synthesis that
minimizes the thermal gradient effects.
Effects: The heating of a substance by microwave irradiation depends on the
ability of the material (solvent or reagent) to absorb microwave radiation and
convert it into heat. Large microwave absorption cross-sections relative to the
solvent can lead to very high effective reaction temperatures.
The Microwave: A conventional

microwave oven (2.45 GHz) operating
at 600–1,000 W was used. In most
cases, the reaction mixture was
microwaved in 30 s cycles (on for 10 s,
off and stirring for 20 s) for reaction
times that varied from 10 s to several
minutes.
Characteristics: Uniform heating of precursors, leads to homogenous nucleation and a shorter growing time, may
be adopted for large scale production.
The long-time processing at high temperature could result in substantial coarsening and grain growth. It could be
a unique approach to achieve densification of nano-phase materials. Anisotropy arrangement64 is low resulting in
spherical shaped nanoparticles, size ranges from 10-30 nm.
Advantages: Microwave irradiation is that it can heat a substance uniformly through a glass or plastic reaction
container, leading to a more homogeneous nucleation and a shorter crystallisation time compared with those for
conventional heating.
64
Anisotropy (Greek: ἄνισοτροπία ánisotropía, “unequal turning”).) is the property of a material which allows it to change or assume
different properties in different directions as opposed to isotropy. It can be defined as a difference, when measured along different axes, in a
material's physical or mechanical properties (absorbance, refractive index, conductivity, tensile strength, etc.) An example of anisotropy is
light coming through a polarizer. Another is wood, which is easier to split along its grain than across it.

“Colloidal Synthesis of Gold Nanoparticles” by techNyouVids Education
See the Video: https://www.youtube.com/watch?v=JLrn6AsKfuk
Nanoparticles? What are they?
A nanoparticle has a diameter of 10-100 nm and is made up of a cluster of atoms. Nanoparticles often exhibit
different characteristics from the bulk form of the element because of their size and greater surface area to volume
ratio. Colour changes at the nanoscale directly relate to the size of the nanoparticle. A characteristic that is
particularly evident in the synthesis of gold nanoparticles.
This experiment aims first to make gold nanoparticles in solution. We call this 'colloidal gold'. Then to
demonstrate how a laser beam is used to test for their presence and finally to demonstrate how increasing the size
of the nanoparticle changes its colour.
(1) Making (nano)colloidal Gold
Reagents & Apparatus: The solutions and equipment are:
20mL of hydrochloroauric solution HAuCl4, 2mL of sodium
citrate Na3C3H4(OH)(COOH)3 solution, 1mL of NaCl solution,
distilled water, a magnetic stirrer and hot plate combination.
Procedure: Now let's make some nanoparticles.
1. We'll start by adding 20mL of the gold solution to the
conical flask.
2. We'll heat this solution until it boils which usually takes four to five minutes.
3. We will just keep it stirring to ensure it heats evenly.
4. Please note the watch glass on top of the conical flask. It's there to prevent the solution evaporating as it heats.
67
5. Once it boils, we'll remove the watch glass and add the citrate solution.
6. Leave the stirrer on and add 2mL of sodium citrate which facilitates a chemical reaction and produces
uniformly sized particles.
7. Now we turn off the heat. You can see the colour change. It's gone from light gold through a blue colour
phase.
8. As we continue stirring you can see the color change again too bright red.
The red colour indicates that we have produced nano-sized gold particles of around 10-20 nm
in diameter, or colloidal gold, that is gold nanoparticles suspended in solution.
Reaction: This is the chemical equation for the redox reaction.
HAuCl4+ Na3C3H4(OH)(COOH)3 → Au(ppt) + C3H4(OH)(COO-)3 + CO2 + HCl + 3NaCl
The citrate ions C3H4(OH)(COO-)3 act as a reductant and reduce the AuIV to the AuIII atoms.
They also act as shielding (capping) agents, wrapping around the cluster of atoms which
constitute the nanoparticles. This creates an electrostatic sheath around each nanoparticle,
which prevents agglomeration and stabilises the particles in solution.
How do we know the nanoparticles are present?
Let's look at the prepared nano-gold solution. Remember gold nanoparticles are a colloid. We can't see them, but
we can usually detect them by the way they react to light.
1. Remove the red solution from the stirrer, allow it to cool and then transfer some of the solution into a test
tube.
2. Pour distilled water and gold chloride AuCl2 solution into two other test tubes.
3. We now shine the red laser beam through each of the test tubes to find out which, if any, contains gold
nanoparticles.
3.1. If we shine this beam through the, test tube with distilled water you'll see its entry and exit points, that's
all. There is no visible passage of light.
3.2. If we shine it through the original gold chloride solution, we get the same result. No passage of light. It's
just a bright spot on either side.
3.3. Now we'll shine our red laser through the test tube that we hope has the gold nanoparticles. What you see
now is the passage of light as a red beam from one side of the test tube to the other. The suspended
nanoparticles are reflecting and scattering the light as it passes through the solution. A response known as
'The Tyndall Effect'.
The effect of size change

We have indeed produced gold nanoparticles and have just confirmed their presence. We will now increase the
size of the nanoparticles and observe how that impacts on their colour. Here in the test tube holder are two
samples of the particles we've just produced.
1. We will add to one of the test tubes a few drops of NaCl solution. Shake it and observe the results.
2. What we now see is a darker solution in the left hand test tube.
By adding NaCl to the original gold nanoparticles we've caused the particles to increase in size which affects the
way they reflect light and therefore changes their observed colour. Adding sodium chloride disturbs the
electrostatic sheath around each nanoparticle resulting in positive attraction between nanoparticles, agglomeration
and therefore particles > 20 nm.
So we've not only created gold nanoparticles, we have created nanoparticles of different sizes and observed how
their size determines their colour. That concludes our experiment. We have shown how to produce gold
nanoparticles, how to confirm their presence and how to exploit some of their behaviours.
5.1.2. Biological (Green) Synthesis (Bottom-Up Approach)
Three major types are involved in Green synthesis:
69
(a) Synthesis using microorganisms
Nanoparticles are biosynthesised when the microorganisms grab target ions from their environment and then turn
the metal ions into the element metal through enzymes generated by the cell activities.
Such as fungi, yeasts (eukaryotes65) or bacteria such as actinomycetes66 (prokaryotes67). Microorganisms are
capable of interacting with metals coming in contact with them through their cells and form nanoparticles. The
cell-metal interactions are quite complex. Certain microorganisms are capable of separating metal ions.
Semiconductor nanoparticles like CdS, ZnS, PbS etc., can be produced using different microbial routes.
 Pseudomonas stutzeri Ag259 bacteria are commonly found in silver mines.
Capable of accumulating silver inside or outside their cell walls. Numerous
types of AgNPs of different shapes can be produced having size <200nm
intracellularly.
 Low concentrations of metal ions (Au⁺, Ag⁺ etc.) can be converted to metal
nanoparticles by Lactobacillus strain present in butter milk.
 Fusarium oxysporum challenged with gold or silver salt produces gold or
silver nanoparticles extracellularly, in 3 days.
 Extremophilic68 actinomycete Thermomonosporaceae sp. produces gold
nanoparticles, extracellularly.
 Sulphate reducing bateria of the family Desulfobacteriaceae can form 2-5nm
ZnS nanoparticle.
 Klebsiella pneumoniae can be used to synthesize CdS nanoparticles. when
[Cd(NO₃)₂] salt is mixed in a solution containing bacteria and solution is
shaken for about1 day at ~38ºC, CdS nanoparticle in the size range ~5-200 nm
can be formed.
(b) Synthesis using plant extracts or enzymes;
Leaves of geranium plant (Pelargonium graveolens; ‫ )شمعدانی عطری‬have been used to synthesize gold
nanoparticles. Plant associated fungus produce compounds such as taxol69 and gibberellins70.
Exchange of intergenic genetics between fungus and plant allows nanoparticles to be produced by fungus and
leaves have different shapes and sizes.
Finely crushed leaves → Boiled in water → Cooled, Decanted → Added to HAuCl4(aq) → AuNPs
(Erlenmeyer flask) (1 min) (<1 min)
65
An eukaryote (Greek: εὖκάρυοωτός eukaryotos, “having well-formed kernel”) is an organism consisting of a cell or cells in which the
genetic material is DNA in the form of chromosomes contained within a distinct nucleus
66
Actinomycetes (Greek: ἀκτίμύκης aktímúkēs, “ray-like fungus”) are any of various filamentous or rod-shaped bacteria, of the order
Actinomycetales that resemble fungi. Some actinomycetes are pathogens and some are sources of antibiotics.
67
A prokaryote (Greek: πρόκάρυοωτός prokaryotos, “being before kernel”) is a microscopic single-celled organism which has neither a
distinct nucleus with a membrane nor other specialised organelles, including the bacteria and cyanobacteria.
68
An extremophile (from Latin extremus meaning "extreme" and Greek philiā (φιλία) meaning "love") is an organism with optimal growth
in environmental conditions considered extreme in that it is challenging for a carbon-based life form, such as all known life on Earth, to
survive.
69
Paclitaxel (PTX), sold under the brand name Taxol among others, is a chemotherapy medication used to treat a number of types of
cancer
70
Gibberellins (GAs) are plant hormones that regulate various developmental processes, including stem elongation, germination,
dormancy, flowering, flower development, and leaf and fruit senescence (maturation). All known gibberellins are diterpenoid acids.
Nanoparticles obtained using Colletotrichum sp., fungus is mostly spherical while those obtained
from geranium leaves are rod and disk shaped.
(c) Synthesis using templates:
Such as DNA, membranes, viruses and many diatoms71 (single-celled algae). CdS or other sulfide
nanoparticles can be synthesised using DNA. DNA can bind to the surface of growing
nanoparticles. DNA bonds through its negatively charged PO4 group to positively charged (Cd⁺)
nanoparticle surface. The ds Salmon sperm DNA can be sheared to an average size of 500bp (base-pair)72.
1. (CH3COO)2Cd is added to a desired medium like water, ethanol,
propanol etc.
2. Reaction is carried out in a glass flask- facility to purge the solution
and flow with an inert gas like N2.
3. Addition of DNA should be made and then Na₂S can be added dropwise.
4. Depending on the concentrations of cadmium acetate, sodium chloride and DNA, nanoparticles of CdS with
sizes <10 nm can be obtained.
5.1.3. Physical Synthesis (Top-Down Approach)
Top down fabrication or physical methods synthesis can be compared to sculpting from a block of stone, where a
piece of the base material is gradually eroded until the desired shape is achieved. By nature, these methods aren’t
cheap and quick to manufacture, and are slow and unsuitable for large scale production. Top-down methods begin
with a pattern generated on a larger scale, then reduced to nanoscale. Two major physical methods are involved in
nanomaterials synthesis:
(a) Mechanical methods:
i. Nanolithography
Description: Nanolithography (Greek: νᾶνολίθογράφειν nanolíthográphein “tiny writing on the stone”) is
a growing field of techniques within nanotechnology dealing with the engineering (etching, writing,
printing) of nanoscale (1-100 nm) structures. It is essentially the most top-down approach to fabricate
nanostructures.
Basic Process: In the process, required material is protected by a mask73 and the exposed material (of the
wafer) is etched away. Depending upon the level of resolution required for features in the final product,
71
A Diatom (Greek: διάτομος diátomos, “cut in half”) is any of a group of minute unicellular algae having a siliceous covering of great
delicacy.
72
A base pair (bp) is a fundamental unit of double-stranded nucleic acids consisting of two nucleobases bound to each other by hydrogen
bonds. They form the building blocks of the DNA double helix and contribute to the folded structure of both DNA and RNA. Base-pairing
between DNA and incoming nucleotides provides the mechanism through which DNA polymerase replicates DNA and RNA polymerase
transcribes DNA into RNA.
73
A photomask is an opaque plate with holes or transparencies that allow light to shine through in a defined pattern. They are commonly
used in photolithography and the production of integrated circuits (ICs or "chips") in particular.
71
etching of the base material can be done chemically using acids or mechanically using UV light, X-rays
or Electron beams.
Etching: Etching is used in Etchants for common microfabrication materials

microfabrication to chemically Material to Wet etchants Plasma (Dry)
remove layers from the surface be etched etchants
of a wafer76 during At 35–45 °C: Cl2, CCl4, SiCl,
manufacturing. H3PO4: 80% BCl3
Some etches undercut the Al CH3COOH: 5%
masking layer and form cavities HNO3: 5%
with sloping sidewalls. The H2O: 10%
distance of undercutting is At 40°C (as 1:0.1:1):
called bias. ITO HCl: 47.62% ---
(In2O3:SnO2) HNO3: 4.76%
H2O: 47.62%
GaAs 1:1 Citric Acid (dil), Cl2, CCl4, SiCl4
H2O2, H2O , BCl3, CCl2F2
Aqua regia (1:3
Isotropic Anisotropic
Au HNO3:HCl), Iodine ---
Modern processes greatly prefer solution I2(aq)
anisotropic etches, because they HNO3, HF, KOH CF4, SF6, NF3
produce sharp, well-controlled Si EDP/EDW74 Cl2, CCl2F2
features. N(CH3)4+OH-
Etching is a critically important SiO2 HF, BOE75 CF4, SF6, NF3
process module, and every NH4F:HF
wafer undergoes many etching At 180 °C (requires CF4, SF6,
steps before it is complete. Si3N4 SiO2 etch mask): NF3, CHF3
H3PO4: 85%
Significance of
Nanolithography: This is applied to the manufacture of
computer chips and Microelectromechanical Systems
(MEMs), i.e. the integration of mechanical elements,
sensors, actuators, and electronics on a common silicon
substrate through microfabrication technology.
Types of Nanolithography: All nanolithographic
techniques depending upon the nature of process being
used for etching of the substrate surface, can be separated
into two categories:
 Those that etch away molecules leaving behind the
desired structure,
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Ethylenediamine pyrocatechol (EDP), also known as ethylenediamine-pyrocatechol-water (EPW), is an anisotropic etchant solution for
silicon. A typical formulation consists of ethylenediamine, pyrocatechol, pyrazine and water. It is carcinogenic and very corrosive. It is
mainly used in research labs, and is not used in mainstream semiconductor fabrication processes.
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A Buffered oxide etch (BOE), also known as buffered HF or BHF, is a wet etchant used in microfabrication for more controllable
etching.. Its primary use is in etching thin films of SiO2 or Si3N4. It is a mixture of a buffering agent, such as NH4F and HF. Concentrated
HF (typically 49% HF in water) etches SiO2 too quickly for good process control and also peels photoresist used in lithographic patterning.
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In electronics, a wafer (also called a slice or substrate) is a thin slice of semiconductor, such as a crystalline silicon (c-Si), used for the
fabrication of integrated circuits and, in photovoltaics, to manufacture solar cells. The wafer serves as the substrate for microelectronic
devices built in and upon the wafer. It undergoes many microfabrication processes, such as doping, ion implantation, etching, thin-film
deposition of various materials, and photolithographic patterning.
 Those that directly write the desired structure to a surface (similar to the way a 3D
printer creates a structure).
Some of the commonly employed techniques involve:
1. Photolithography, aka Optical or UV lithography
Photolithography, also termed optical lithography or UV lithography, is a process used in
microfabrication or nanofabrication to pattern parts of a thin film or the bulk of a
substrate.
Process: It uses light to transfer a geometric pattern from a photomask to a light-sensitive
chemical "photoresist", or simply "resist," on the substrate. A photoresist is a light-
sensitive material used to form a patterned coating on a surface. A series of chemical
treatments then either engraves the exposure pattern into, or enables deposition of a new
material in the desired pattern upon the material underneath the photo resist.
Major steps in Photolithography are:

1. Water cleaning. If organic or inorganic
contaminations are present on the wafer surface, they
are usually removed by H2O2, CH3OH, (CH3)2CO and
C2CHCl3 solution.
2. Barrier layer formation. The wafer is initially heated
to a 150 °C for 10 mins to drive off any moisture that
may be present on the wafer surface and an adhesion
promoter (to the photoresist) hexamethyldisilazane
(HDMS) is applied. This reacts with SiO2 to form a
highly hydrophobic trimethylated SiO2 barrier layer.
In order to ensure the development of the image, it is
best covered and placed over a hot plate and let it dry
while stabilizing the temperature at 120 °C.
3. Photoresist application. The wafer is covered with
photoresist by spin coating. Thus, the top layer of
resist is quickly ejected from the wafer's edge while
the bottom layer still creeps slowly radially along the
wafer. In this way, any 'bump' or 'ridge' of resist is
removed, leaving a very flat layer.
4. Pre baking. The photoresist-coated wafer is then prebaked to drive off excess photoresist solvent,
typically at 90-100 °C for 30 to 60 seconds on a hotplate.
5. Exposure & Development. The photomask is aligned with the treated wafer and then the photoresist is
exposed to a pattern of intense light. The exposure to light causes a chemical change that allows some
of the photoresist to be removed by a special solution, called "developer" such as N(CH)4OH. Positive
photoresist, the most common type, becomes soluble in the developer when exposed; with negative
photoresist, unexposed regions are soluble in the developer.
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6. Hard-baking. The resulting wafer is then "hard-baked" if a non-chemically amplified resist was used,
typically at 120-180 °C for 20-30 minutes. The hard bake solidifies the remaining photoresist, to
make a more durable protecting layer in future ion implantation, wet chemical etching, or plasma
etching.
7. Etching. In etching, a liquid ("wet") or plasma ("dry") chemical agent removes the uppermost layer of
the substrate in the areas that are not protected by photoresist.
8. Photoresist Removal. After a photoresist is no longer needed, it must be removed from
the substrate. This usually requires a liquid "resist stripper", which chemically alters
the resist so that it no longer adheres to the substrate, such as by a plasma containing
O2, which oxidises it. This process is called ashing. The use of 1-Methyl-2-pyrrolidone
(NMP) solvent for photoresist is another method used to remove an image. When the
resist has been dissolved, the solvent can be removed by heating to 80 °C without leaving any residue.
In complex integrated circuits, a modern CMOS (Complementary Metal–Oxide–Semiconductor)77 wafer
will go through the photolithographic cycle up to 50 times.
Merits: This method can create extremely small patterns, down to a few 101 nm in size. It provides
precise control of the shape and size of the objects it creates and can create patterns over an entire surface
cost-effectively.
Drawbacks: Its main disadvantages are that it requires a flat substrate to start with, it is not very effective
at creating shapes that are not flat, and it can require extremely clean operating conditions.
Spin-coating: Spin coating is a procedure used to deposit uniform thin films onto flat substrates. There
are four basic parameters that are involved in spin coating: solution viscosity, solid content (density),
angular speed, and spin time. A range of thicknesses can be achieved by spin coating. Most commonly
thicknesses range from 1-200 µm. The main properties that affect the thickness of the film are viscosity
and spin speed. The more viscous the solvent the thicker the film will be and the faster the wafer is spun
the thinner the film will be.
Usually a small amount of coating material is applied on the centre of the substrate, which is either spinning at low speed or not
spinning at all. The substrate is then rotated at speed up to 10,000 rpm to spread the coating material by centrifugal force.
Photoresist: Photoresist compounds are used create a mask on the surface of a silicon wafer. The mask
allows for precise control over the doping and etching processes used to form devices on silicon wafers. It
is important for the mask to hold up to chemical attack during the etching process. Photoresists have three
major components, a solvent, resin, and sensitiser (or photoactive compound).
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A complementary-symmetry metal–oxide–semiconductor (COS-MOS), is a type of metal–oxide–semiconductor field-effect transistor
(MOSFET) fabrication process that uses complementary and symmetrical pairs of p-type and n-type MOSFETs for logic functions. CMOS
technology is used for constructing integrated circuit (IC) chips, including microprocessors, microcontrollers, memory chips (including
CMOS-BIOS), and other digital logic circuits
Dizaonaphthoquinone DNQ-Novalac Positive Photoresist SU-878 Negative Photoresist
Triphenylsulphonium as positive photoresist Biazide as negative photoresist
Hexamethyldisilazane (HMDS): A common method to increase adhesion of photoresist on the silicon

wafer surface is to treat the wafer with Hexamethyldisilazane (HMDS) aka Bis(trimethylsilyl)amine. A
new silicon wafer has a polar surface and has some adsorbed water on the surface. The wafer can undergo
a dehydration bake to remove adsorbed water, and followed by the HMDS treatment also known as the
priming stage.
Treating a silicon wafer with HMDS, to make the silicon wafer hydrophobic (shown):
Photolithographic Chemistry: Optical lithography uses very short light wavelengths in order to change
the solubility of certain molecules, causing them to wash away in solution, leaving behind a desired
structure.
 In photolithography process selected portions of thin films are removed to get fabrications at nano or
micro scale, typically on the surface of silicon wafers for the production of microelectromechanical
systems (MEMS).
 Photolithography makes this process possible through the combined use of
hexamethyldisilazane (HMDS) aka Bis(trimethylsilyl)amine, photoresist (positive or
negative)79, a spin or spray coater, photomask, an exposure system and other various
chemicals.
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SU-8 derives its name from the presence of 8 epoxy groups. SU-8 is a commonly used epoxy-based negative photoresist.
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A positive photoresist is a type of photoresist in which the portion of the photoresist that is exposed to light becomes soluble to the
photoresist developer. The unexposed portion of the photoresist remains insoluble to the photoresist developer. A negative photoresist is a
type of photoresist in which the portion of the photoresist that is exposed to light becomes insoluble to the photoresist developer. The
unexposed portion of the photoresist is dissolved by the photoresist developer.
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Characteristic Positive Photoresist Negative Photoresist
Adhesion to silicon Fair Excellent
Relative cost More expensive Less expensive
Developer base Aqueous Organic
Solubility in the developer Exposed region is soluble Exposed region is
insoluble
Minimum feature 0.5 µm 2 µm
Step coverage Better Lower
Wet chemical resistance Fair Excellent
 It is possible to create nearly any geometry microstructure on the surface of a silicon wafer. The
chemical interaction between all the different components and the surface of the silicon wafer makes
photolithography an interesting chemistry problem. Current science has been able to create features
on the surface of silicon wafers between 1-100 µm.
2. Electron beam nanolithography
Electron beam lithography (EBL) or electron-beam direct-write lithography (EBDW) scans a focused
beam of electrons on a surface covered with an electron-sensitive film or resist e.g. poly(methyl
methylacrylate) (PMMA) or hydrogensilsesquioxane [HSiO3/2]n (HSQ), to draw custom shapes.
By changing the solubility of the resist and subsequent selective removal of material by immersion in a
solvent, sub-10 nm resolutions have been achieved. This form of direct-write, maskless lithography has
high resolution and low throughput, limiting single-column e-beams to photomask fabrication, low-
volume production of semiconductor devices, and R&D. EBL can be utilised for selective protein
nanopatterning on a solid substrate, aimed for ultrasensitive sensing.
3. X-ray nanolithography
X-ray lithography, is a process used in electronic industry to selectively remove
parts of a thin film. It uses X-rays (short wavelengths, <1 nm) to transfer a
geometric pattern from a mask to a light-sensitive chemical photoresist, or simply
"resist," on the substrate. The mask consists of an X-ray absorber, typically of Au
or compounds of Ta or W, on a membrane that is transparent to X-rays, typically
of SiC or diamond.
A series of chemical treatments then engraves the produced pattern into the material underneath the
photoresist. Sample fabricated by X-ray nanolithography is shown:
4. Nano-imprint lithography
Nanoimprint lithography (NIL), and its variants are promising nanopattern replication technologies where
patterns are created by mechanical deformation of imprint resists, typically monomer or polymer
formations that are cured by heat or UV light during imprinting. This technique can be combined with
contact printing and cold welding. Nanoimprint lithography is capable of producing patterns at sub-10 nm
levels.
5. Dip pen nanolithography
Dip pen nanolithography (DPN) is a scanning probe lithography technique
where an atomic force microscope (AFM) tip is used to create patterns directly on
a range of substances with a variety of inks. This technique allows surface
patterning on scales of <100 nm. Sample fabricated by dip-pen nanolithography
process is shown:
DPN is the nanotechnology analogue of the dip pen (also called the quill pen), where the tip of an atomic
force microscope cantilever acts as a "pen," which is coated with a chemical compound or mixture acting
as an "ink," and put in contact with a substrate, the "paper."
How are Silicon Wafers made?

A wafer, also called a slice or substrate, is a thin slice of
semiconductor material, such as a crystalline silicon, used in
electronics for the fabrication of integrated circuits and in
photovoltaics for conventional, wafer-based solar cells.
The Czochralski (choke-rawl-skee) process is a method of
crystal growth used to obtain single crystals of
semiconductors (e.g. silicon, germanium and gallium
arsenide), metals (e.g. palladium, platinum, silver, gold), salts
and synthetic gemstones.
Discovery: Jan Czochralski made this discovery by accident: instead of dipping his pen into his
inkwell, he dipped it in molten tin, and drew a tin filament, which later proved to be a single
crystal
Process: Silicon wafers are cut from a solid ingot80 of nearly-pure (99.9999999%) silicon. This
is done through the process of Czochralski growth, and produces a single intact diamond cubic
silicon crystal.
1. High-purity, semiconductor-grade silicon (only a few ppm of impurities) is melted in a
crucible at 1,425 °C (2,597 °F; 1,698 K), us ually made of quartz.
2. Dopant impurity atoms such as boron or phosphorus can be added to the molten silicon in
precise amounts to dope the silicon, thus changing it into p-type or n-type silicon, with
different electronic properties.
3. A precisely oriented rod-mounted seed crystal is dipped into the molten silicon. The seed
crystal's rod is slowly pulled upwards and rotated simultaneously.
4. By precisely controlling the temperature gradients, rate of pulling and speed of rotation, it
is possible to extract a large, single-crystal, cylindrical ingot from the melt.
5. This process is normally performed in an inert atmosphere, such as argon, in an inert
chamber, such as quartz.
Characteristics: The Si wafers produced are can be up to 2 metres in length, weighing several
hundred kilogram, 200-300 mm dia and 0.2–0.75 mm thick. Due to its structure, monocrystalline silicon is
anisotropic, which gives it different structural and electrical properties in different plane directions.
Significance: Monocrystalline silicon (mono-Si) grown by the Czochralski method is often referred to as
monocrystalline Czochralski silicon (Cz-Si). It is the basic material in the production of integrated circuits used in
computers, TVs, mobile phones and all types of electronic equipment and semiconductor devices.
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An ingot is a piece of relatively pure material, usually metal, that is cast into a shape suitable for further processing
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ii. High energy ball milling
High-energy ball milling is a ball milling process in which a powder mixture placed in a ball mill is
subjected to high-energy collisions from the balls. High-energy ball milling, also called mechanical
alloying, can successfully produce fine, monodisperse or (uniform dispersions of) nanoparticles. The
simplest mechanical method of making nanoparticle in the form of powder.
Various types of mills are available such as Planetary, Vibratory, Rod and Tumbler mills
A planetary ball mill consists of at least
one grinding jar which is arranged
eccentrically on a so-called sun wheel.
The grinding balls in the grinding jars are
subjected to superimposed rotational
movements. The interplay between the
frictional and impact forces produces the
high and very effective degree of size
reduction of the planetary ball mill.
“Ball-milling Method” by LearnEngg
See the Video, https://www.youtube.com/watch?v=MikiTYpg2aQ
Description: One machine that is heavily used for crushing
and grinding tasks is the ball-mill. This machine is described
as a grinding device capable to crush and transform large
hard materials into fine powder. A ball mill is a cylindrical
machine generally used for mashing and crushing paints,
ceramic materials, ores and other hard materials.
Working: By rotating on a horizontal axis the ball mill
effectively turns hard materials into fine powder. The
grinding materials are actually small balls which crush and
grind the material that is inside the ball mill usually stainless
steel or ceramic balls are used as grinding materials. When
the ball mill rotates the balls crush and grind the material
inside creating in this way loose powder the end result is
crushed material that can be used for other purposes.
iii. Melt mixing
Melt intercalation81 is a promising method extensively used in the industry. This method involves mixing
the nanofillers (organo-clays, see Section 3.2) into the polymer matrix at molten temperature. In this
method, mixture of polymer and nanofibres are annealed either statically or under shear. Typically, the
polymer is melted and combined with the desired amount of the intercalated clay using an extruder.
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Intercalation means to insert (something) between layers in a crystal lattice, geological formation, or other structure.
Melt blending is carried out in the presence of an inert gas, such as argon, nitrogen, or neon.
Alternatively, the polymer may be dry mixed with the intercalant, then heated in a mixer and subject to
shear sufficient to form the desired clay polymer nanocomposites. Melt blending is environmentally
benign due to the absence of organic solvents. Melt blending is compatible with current industrial
processes, such as extrusion and injection moulding.
“Extruder Operation and Control” by Paulson Training
See the Video, https://www.youtube.com/watch?v=MikiTYpg2aQ
1. The plastic raw material in the hopper travels by gravity to the feed throat and drops on to the rotating
screw.
2. The rotation of the screw conveys the plastic forward through the heated barrel.
3. As the plastic has conveyed forward along the screw the channel depth decreases forcing the plastic
through a smaller area.
4. The combination of compression and screw rotation causes friction which generates heat this is called
shear-heating. This heat along with the heat from the barrel heating system melts the plastic.
5. By the time the plastic is conveyed to the end of the screw it should be well-mixed and at a proper
temperature and pressure needed by the die. The plastic is called a melt at this stage.
6. There can be a screen pack beyond the screw, i.e. a set of wire mesh
filters that the plastic must flow through the screens are typically from
20-100 mesh (0.84-0.15 mm) which indicates the wires per inch. The
screen pack filters contaminants from the melt.
7. The screen pack is supported by a breaker-plate which is a sturdy metal
plate with many holes for the plastic to pass through.
The screen pack must be set in place with a coarsest screen next to the
breaker plate so each screen can support a finer one otherwise the pressure
difference may break the fine wires, contaminating the product and possibly
doing permanent damage to the die.
(b) Vapour based methods:
Only PVD has been discussed in detail as per the scope of the course, the rest are trivial.
i. Physical Vapour Deposition (PVD)
Description: PVD describes a variety of vacuum deposition methods which can be used to produce thin
films and coatings. PVD is characterised by a process in which the material goes from a condensed phase
to a vapour phase and then back to a thin film condensed phase. The most common PVD processes are
sputtering and evaporation.
Procedure: The procedure for physical vapour deposition is as follows:
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1. Sputtering/evaporation of different components to produce a vapour phase;
 Evaporative Deposition a common method of thin-film deposition. The source material is heated
to a high vapour pressure by electrical resistance heating in "high" vacuum. The vacuum allows
vapour particles to travel directly to the target object (substrate), where they condense back to a
solid state.
 Sputtering is another common method of thin film deposition by sputtering. This involves
ejecting material from a "target" that is a source onto a "substrate" such as a silicon wafer. A
sputtering gas such as Ar, Ne, Kr or Xe is analogous to the function of a carrier gas. A glow
plasma discharge (usually localised around the "target" by a magnet) bombards the material
sputtering some away as a vapour for subsequent deposition.
2. Supersaturation of the vapour phase in an inert atmosphere to promote the condensation of metal
nanoparticles;
3. Consolidation of the nanocomposite by thermal treatment under inert atmosphere.
All processes are carried out in a vacuum chamber so that the desired purity of end product can be
obtained. When evaporation is performed in poor vacuum or close to atmospheric pressure, the resulting
deposition is generally non-uniform and tends not to be a continuous or smooth film
Merits: Demerits:
 Materials can be deposited with  It is a line of sight technique meaning
improved properties compared to the that it is extremely difficult to coat
substrate material; undercuts and deep bores features;
 Almost any type of inorganic material  Some processes operate at high vacuums
can be used as well as some kinds of and temperatures requiring skilled
organic materials as well; operators;
 The process is more environmentally  High capital cost;
friendly than processes such as  Processes requiring large amounts of
electroplating. heat require and appropriate cooling
systems
 The source material is unavoidably also
deposited on most other surfaces interior
to the vacuum chamber, including the
fixturing used to hold the parts.
Applications:
 PVD is used in the manufacture of items which require thin films for
mechanical, optical, chemical or electronic functions.
 PVD coatings are generally used to improve hardness, wear resistance
and oxidation resistance. There are many uses for coatings prepared by
PVD; applications include aluminum tracks and ceramic resistors for electronic
circuitry; anti-reflective ceramic coatings for optics; decorative coatings on
plastics; corrosion resistant coatings on gas turbine blades; and wear prevention
coatings for machine and press tools.
 Examples include semiconductor devices such as thin film solar panels,
aluminised PET film for food packaging and titanium nitride coated
cutting tools for metalworking.
 Besides PVD tools for fabrication, special smaller tools (mainly for
scientific purposes) have been developed. Common industrial coatings
applied by PVD are TiN, ZrN, CrN and TiAlN.
 By varying the gases and duration of process, a range of colours are
produced by PVD on stainless steel. The resulting coloured stainless steel
product can appear as brass, bronze and other metals or alloys. This PVD
coloured stainless steel can be used as exterior cladding for buildings and
structures, such as the Vessel sculpture in New York City and The Bund
(Wàitān; outer beach) in Shanghai.
 It is also used for interior hardware, panelling and fixtures, and is even
used on some consumer electronics, like the Space Gray and Gold
finishes of the iPhone X, XS, and 11 Pro.
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ii. Sputter Deposition
Description: Sputter deposition is a method of depositing thin films by
sputtering that involves eroding material from a "target" source onto a
"substrate" e.g. a silicon wafer, solar cell, optical component, or many other
possibilities. Resputtering, in contrast, involves re-emission of the deposited
material, e.g. SiO2 during the deposition also by ion bombardment
Process: This involves ejecting material from a "target" that is a source onto a
"substrate" such as a silicon wafer. The sputtered ions (typically only a small
fraction of the ejected particles are ionised — on the order of 1%) can
ballistically fly from the target in straight lines and impact energetically on the
substrates or vacuum chamber (causing resputtering). Alternatively, at higher
gas pressures, the ions collide with the gas atoms that act as a moderator and
move diffusively, reaching the substrates or vacuum chamber wall and
condensing.
The sputtering gas is often an inert gas such as Ar. For efficient momentum transfer, the atomic weight of
the sputtering gas should be close to the atomic weight of the target, so for sputtering light elements Ne is
preferable, while for heavy elements Kr or Xe are used.
Applications: Coatings and thin-film depositions
iii. Electric Arc Deposition
Cathodic arc deposition or Arc-PVD is a physical vapour deposition technique in which an electric arc is
used to vaporize material from a cathode target. The vaporised material then condenses on a substrate,
forming a thin film.
Applications: The technique can be used to deposit metallic, ceramic, and composite films. A high-power
electric arc discharged at the target (source) material blasts away some into highly ionised vapour to be
deposited onto the workpiece.
Process: The arc evaporation process begins with

the striking of a high current, low voltage arc on the
surface of a cathode (known as the target) that gives
rise to a small (usually a few micrometres wide),
highly energetic emitting area known as a cathode
spot. The cathode spot is only active for a short
period of time, then it self-extinguishes and re-
ignites in a new area close to the previous crater.
This behaviour causes the apparent motion of the
arc. Cathodes can also be rotated during deposition.
By not allowing the cathode spot to remain in one
position too long aluminium targets can be used and
the number of droplets is reduced
Problems: One downside of the arc evaporation process is that if the cathode spot stays at an evaporative
point for too long it can eject a large amount of macro-particles or droplets, leading to non-uniform layers.
iv. Laser Ablation
Description: Laser ablation or photoablation is the process of removing material from a solid (or
occasionally liquid) surface by irradiating it with a laser beam. Usually, laser ablation refers to removing
material with a pulsed laser (wavelength of 200 nm), but it is possible to ablate material with a continuous
wave laser beam if the laser intensity is high enough. Several workers have employed laser ablation and
gas condensation to produce nano particles of metal, metal oxides and metal carbides.
Process: The use of a laser to ablate a block of pure graphite, and later graphite mixed with catalytic
metal (Co, Ni, Nb, or Pt) was. The graphite powder paste & catalytic paste is placed in a cylindrical
mould and baked for several hours. After solidification, the graphite block is placed inside an oven with a
laser pointed at it, and Ar gas is pumped along the direction of the laser point. The oven temperature is
approximately 1200 °C. As the laser ablates the target, carbon nanotubes form and are carried by the gas
flow onto a cool copper collector. Single-walled nanotubes are formed from the block of graphite and
metal catalyst particles, whereas multi-walled nanotubes form from the pure graphite starting material.
v. Ion Implantation
Description: Ion implantation is a low-temperature process by which ions of one element are accelerated
into a solid target, thereby changing the physical, chemical, or electrical properties of the target.
Composite materials based on dielectrics such as sapphire that contain dispersed metal nanoparticles are
promising materials for optoelectronics and nonlinear optics.
Problems: Because ion implantation causes damage to the crystal structure of the target which is often
unwanted, ion implantation processing is often followed by a thermal annealing. This can be referred to as
damage recovery. Crystal defects are a major issue and annealing is required.
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Setup: Ion implantation equipment typically consists of an ion source, where ions of the desired element
are produced, an accelerator, where the ions are electrostatically accelerated to a high energy, and a target
chamber, where the ions impinge on a target, which is the material to be implanted.
Nanoparticle Manufacture: Ion implantation may be used to induce nano-dimensional particles in oxides
such as sapphire and silica. Typical ion beam energies used to produce nanoparticles range from 50-150
keV, with ion fluences that range from 1016-1018 ions/cm2. The particles may be formed as a result of:
 The precipitation of the ion-implant.
 The production of a mixed oxide species that contains both the ion-implant and the substrate.
 The reduction of the substrate.
A wide variety of nanoparticles can be formed, with size ranges from 1-20 nm and with compositions that
can contain the implanted species, combinations of the implanted ion and substrate, or that are comprised
solely from the cation associated with the substrate.
Produces Metal Implanted Substrate Ion Beam Fluence Annealing Result
Nanoparticles Species Energy (ions/cm2)
from (keV)
Oxides Zn α-Al2O3 48 1×1017 In O2 atmosphere ZnO nanoparticles form
at 600 °C
Ag α-Al2O3 1500, 2×1016 600-1100 °C in Ag nanoparticles in Al2O3 matrix
Implanted 2000 8×1016 Ar or N2
Species Fe α-Al2O3 160 1×1016 1 hr from 700- Fe nanocomposites
2×1017 1500 °C in N2
Substrate Ca Al2O3 150 5×1016 --- Al nanoparticles in amorphous
matrix containing Al2O3 and CaO
Lecture 5
Week #6 Notes
6.1. Nanoparticle Characterisation
There are many techniques devised so as to characterise nanoparticles in terms of their morphological, crystalline,
electromagnetic, physical, chemical and other distinct properties. Some of which are as follows, which shall be
discussed in detail in the precedent weeks:
1. X-ray diffraction 3. Microscopy techniques 4. Thermal analysis
technique 3.1. Scanning Electron 4.1. Thermogravimetric
Microscope (SEM) Analysis (TGA)
2. Spectroscopy techniques
3.2. Transmission electron 4.2. Differential thermal
2.1. X- ray photoelectron
microscope (TEM) analysis (DTA)
Spectroscopy (XPS)
3.3. Field emission scanning 4.3. Differential scanning
2.2. Vibrational (Fourier
electron microscope calorimetry (DSC)
transform infrared)
spectroscopy (FTIR) (FESEM)
5. Brunauer-Emmet-Teller
2.3. Energy Dispersive X-ray (BET) surface area
spectroscopy (EDX) technique
6. Vibrating sample
magnetometer (VSM)
6.2. X-Ray Diffraction Technique (XRD)

Description: X-ray crystallography (XRC) or X-ray Diffraction (XRD) is the experimental
science determining the atomic and molecular structure of a crystal, in which the crystalline
structure causes a beam of incident X-rays to diffract into many specific directions.
Significance: By measuring the angles and intensities of these diffracted beams, a
crystallographer can produce a three-dimensional picture of the density of electrons within the
crystal. From this electron density, the mean positions of the atoms in the crystal can be
determined, as well as their chemical bonds, their crystallographic disorder, and various other
information.
Principles: The physical principles of characteristic X-ray generation are schematically
illustrated in schematic figure:
Data Interpretation: An XRD provides information about phase identification, crystal size and crystal perfection,
structural parameters (unit cell, edge, lengths) and degree of substitution of ions by other ions.
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What is Diffraction?
Diffraction is the slight bending of light as it passes around the edge of an object.
Diffraction is the bending of waves around the corners of an obstacle or through an
aperture into the region of geometrical shadow of the obstacle/aperture.
The diffracting object or aperture effectively becomes a secondary source of the
propagating wave.
Extent of Diffraction & Dependence: The amount of bending depends on the
relative size of the wavelength of light to the size of the opening. If the opening is
much larger than the light's wavelength, the bending will be almost unnoticeable.
The change in direction of a wave, such as a light or sound wave, away from a
boundary the wave encounters. Reflected waves remain in their original medium rather than entering the medium
they encounter.
Bragg’s Law
Bragg diffraction is a consequence of interference between waves reflecting from different
crystal planes. When x-rays are scattered from a crystal lattice, peaks of scattered intensity are
observed which correspond to the following conditions: θ ∝ λ and n ∝ d; i.e. the condition of
constructive interference is given by Bragg's law:
Where:
nλ = 2dsin(θ)
o ‘λ’ is the wavelength;
o ‘d’ is the distance between crystal planes;
o ‘θ’ is the angle of the diffracted wave.
o ‘n’ is an integer known as the order of the diffracted beam.
Radiation Source: Bragg diffraction may be carried out using either electromagnetic radiation of very short
wavelength like X-rays whose wavelength is on the order of (or much smaller than) the atomic spacing. The
pattern produced gives information of the separations of crystallographic planes d, allowing one to deduce the
crystal structure.
XRD Pattern: The X-ray diffraction pattern of a powdered sample is a plot of the
observed diffracted intensity of the X-rays against the Bragg angle, i.e. the angle at
which the X-rays strike the crystal and for which the maximum interference is
observed. The X-ray pattern is preferably recorded stepwise using a Goniometer
equipped with a proportional or scintillation82 counter and a registration unit.
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Scintillation is a flash of light produced in a transparent material by the passage of a particle (an electron, an alpha particle, an ion, or a
high-energy photon). See scintillator and scintillation counter for practical applications. For photons such as gamma rays, thallium
activated NaI crystals (NaI(Tl)) are often used. For a faster response (but only 5% of the output) CsF crystals can be used.
 A Goniometer is an instrument for the precise measurement of angles, especially one used to measure the
angles between the faces of crystals. In a single-crystal X-ray diffraction measurement, a crystal is mounted
on a goniometer that positions the crystal at selected orientations.
 A Scintillation counter is an instrument for detecting and measuring ionizing radiation by using the excitation
effect of incident radiation on a scintillating material, and detecting the resultant light pulses. It generates
photons in response to incident radiation, a sensitive photodetector (usually a photomultiplier tube (PMT), or
a photodiode), which converts the light to an electrical signal and electronics to process this signal.
Scherrer Equation
Scherrer equation in X-ray diffraction and crystallography, is a formula that relates the size of sub-μm particles, or
crystallites83, in a solid to the broadening of a peak in a diffraction pattern. It is used in the determination of size
of particles of crystals in the form of powder. An XRD pattern of a crystalline phase, therefore, consists of a
number of reflections (peaks) of different intensities which provide a fingerprint of the atomic structure.
It is calculated as:
Where:
τ = kλ⁄Bcos⁡(θ)
o ‘’ is the mean size of the ordered (crystalline) domains, which
may be ≤ grain size, (itself ≤ particle size);
NOTE: no = (𝑛𝜋⁄180)⁡𝑟𝑎𝑑
o ‘k’ is a dimensionless shape factor ≤1.0. The shape factor has a
typical value of about 0.9 (for spherical particles), but varies
with the actual shape of the crystallite;
o ‘’ is the X-ray wavelength; typically for Cu/Kα = 0.154 nm.
o ‘’ or ‘B’ is the line broadening at half the maximum intensity
(FWHM)84, after subtracting the instrumental line broadening, in
radians. This quantity is also called the Warren factor (B),
calculated as: B2 = BM2 – BS2 for ‘M’ matrix and ‘S’ Sample
solid.
o ‘θ’ is the Bragg angle, given as 𝜃𝐵 = 2𝜃⁄2.
d-spacing as a fingerprint for crystals: From these patterns the mineral-specific distances between the atomic
layers (d-values: where d is the distance between crystal planes), can be calculated using the Bragg equation and
from the set of d-values the mineral(s) can be identified.
XRD of Haematite (α-Fe2O3)
Hematite, also spelled as haematite (Greek: αἱματίτης λίθος haimatitēs
lithos, "blood-red stone"), is a common iron oxide compound and an iron
ore. Hematite crystals belong to the hexagonal lattice system which is
designated the polymorph of Fe2O3.
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A crystallite is a small or even microscopic crystal which forms, for example, during the cooling of many materials. Crystallites are also
referred to as grains. Different degrees of ordered structures: a monocrystalline crystal, polycrystalline structure, and amorphous or non-
crystalline solid
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In a distribution, full width at half maximum (FWHM) is the difference between the two values of the independent variable at which the
dependent variable is equal to half of its maximum value. In other words, it is the width of a spectrum curve measured between those points
on the y-axis which are half the maximum amplitude. The FWHM is 2.355σ (st. deviation) of the Normal/Gaussian peak.
87
Characteristics: Hematite (α-Fe2O3) is one of the most important, stable, non-toxic, nature-friendly and corrosion-
resistant metal oxides. Hematite naturally occurs in black to steel or silver-gray, brown to reddish-brown, or red
colours.
Nanoscale Properties: It is electrically conductive. The magnetic properties of bulk hematite differ from their
nanoscale counterparts. For example, the Morin transition temperature85 of hematite decreases with a decrease in
the particle size i.e. becomes more antiferromagnetic86. The suppression of this transition has been observed in
hematite nanoparticles and is attributed to the presence of impurities, water molecules and defects in the crystals
lattice
Phase Formula Space ICDD
2θ (o) d (Å) Height Int. I(cps FWHM(o) Size Phase
name group
(cps) v deg) name
Hematite Fe2O3 167 : R -3c, 11053
24.29(2) 3.661(3) 78(9) 37.3(12) 0.369(18) 230(11) Hematite,
Hexagonal (ICDD)
(0,1,2)
Crystal System: 33.319(9) 2.6869(7) 287(17) 149.9(18) 0.422(7) 205(3) Hematite,
Hexagonal (trigonal) (1,0,4)
(a = b,  =  35.782(9) 2.5074(6) 278(17) 108.5(15) 0.314(7) 277(6) Hematite,
(1,1,0)
Lattice Parameters 41.012(19) 2.1989(10) 89(9) 39.2(9) 0.344(15) 258(12) Hematite,
a = 5.03 Å 90o (1,1,3)
b = 5.03 Å 90o 49.67(2) 1.8341(7) 147(12) 70.8(14) 0.375(19) 244(12) Hematite,
c = 13.74 Å  (0,2,4)
54.231(15) 1.6900(4) 168(13) 87.2(14) 0.426(11) 219(6) Hematite,
(1,1,6)
57.81(4) 1.5936(10) 36(6) 19.5(9) 0.46(4) 207(19) Hematite,
(1,2,2)
62.60(2) 1.4826(4) 125(11) 60.0(13) 0.394(15) 246(9) Hematite,
(2,1,4)
64.191(17) 1.4497(3) 146(12) 61.8(11) 0.327(14) 299(13) Hematite,
(3,0,0)
69.75(8) 1.3471(13) 11(3) 6.1(5) 0.52(5) 194(20) Hematite,
(2,0,8)
72.04(3) 1.3099(5) 35(6) 22.8(9) 0.60(3) 170(7) Hematite,
(1,0,10)
75.62(4) 1.2564(6) 30(5) 14.7(7) 0.45(3) 234(15) Hematite,
(2,1,7)
For the .cif (Crystallographic Information File) here(Fe2O3, 

Haematite.zip).
XRD Manufacturers & Vendors

1. Angstrom Advanced (EU)
2. Bruker AXS GmbH (Germany)
3. Liaodong Radioactive Instrument (China, People’s Republic of)
4. Malvern Panalytical (USA)
5. Olympus (USA)
6. Rigaku (Japan)
7. Sky Ray Instrument (UK)
8. ThermoScientific (USA)
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The Morin transition (also known as a spin-flop transition) is a magnetic phase transition in α-Fe2O3 hematite where the
antiferromagnetic ordering is reorganised from being aligned perpendicular to parallel. A change in magnetic properties takes place at the
Morin transition temperature.
86
In the special case where the opposing moments balance completely, the alignment is known as antiferromagnetism. Therefore
antiferromagnets do not have a spontaneous magnetisation (doesn’t spontaneously behave like a magnet).

“X-Ray Diffraction” by Materials & Devices for Information Technology Research
(MDITR); Mat Sci Dept, University of Washington, USA.
See the Video, https://www.youtube.com/watch?v=DAOFpgocfrg&t=35s
X-ray diffraction (XRD) is a tool for characterizing arrangement of atoms in crystals and distances between
crystal faces. This can be used to identify atoms and the crystalline form. The Bruker D8 Focus X-Ray
Spectrometer is used to measure the crystal structure of powders or thin film materials.
How are the X-Ray Produced?
The X-rays are produced in an evacuated tube similar to a cathode ray tube. An applied current heats up a
tungsten filament which liberates electrons. The liberated electrons are accelerated by a high voltage and hit a
copper target where copper x-rays are generated. The X-rays exit the tube and are incident on the sample from
which they are diffracted into a scintillating type detector
Through what the X-Ray passes?

The beam that passes through a slit which determines the angular width of the
beam. Wider slits gives more energy but have wider peaks, smaller slits give less
energy but better resolution. The beam also passes through a nickel filter. The
nickel filter removes the K energy87 before the diffracted beam enters the
detector.
X-rays at angle ‘‘are reflected from internal crystal planes separated by

distance,‘d’. Bragg diffraction results from constructive wave interference when
the quantity n = 2dsin(), is an integral number of wavelengths.
Fine Powder XRD (XRPD)
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Kβ emissions, similar to Kα emissions, result when an electron transitions to the innermost "K" shell (principal quantum number 1) from
a 3p orbital of the third or "M" shell (with principal quantum number 3). The characteristic lines in X-ray emission spectra correspond to
atomic electronic transitions where an electron jumps down to a vacancy in one of the inner shells of an atom.
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A fine powder material contains many crystals located at random angles. Certain crystals happen to be oriented
so that the x-ray beam, crystal and detector satisfy Bragg’s equation. This causes a signal spike at specific detector
angles.
It is important to have a sufficient number of crystals to have an even distribution at all possible crystal
orientations. During a scan the detector is rotated over a range of angles to detect bands of diffracted x-rays
produced by the correctly aligned crystals within the sample.
Sample Preparation & Loading:
 Recommended Particle Size: For X-Ray Powder Diffraction it is important to have a
well-defined polycrystalline88 material and the individual particle size of your material
should <45m (<0.45 nm).
 Quantity: You need enough to fill one of these wells and it should be packed in. What
is important is to have enough of each individual crystalline plane so that when the
beam hits it at a particular angle Braggs’ equation is satisfied and you get a peak. This
is a statistics issue so you want to make sure to have plenty of sample so that all those
planes are represented.
 Well Size: There are two sizes of sample holders here. This is preferred, this large
well here because as I said the more particles you have represented on the surface in
all the various crystal planes the better your data is going to be. But often most people
don’t have this much material and this will work. If your material has been prepared
correctly it’s just really important to make sure you have a very fine powder.
 Packing: Press your sample in the well and just estimate how much you are going to
need. You are going be pressing it down and you want to make sure it’s filling the
well but is still flat with the surface of the sample holder and just gently scrape off
whatever comes out of the well.
 Flattening (Tight-packing): You want to keep it cleaned up because keep in mind
that you going to put this in and there is going to three pins on three places on the
sample holder and if there is a lot of material underneath there that is going alter the
angle that it is sitting at and your positions will be off. Flatten it down and that’s ready
to go.
 Packing loose powders: Even though it’s loose powder if you have prepared it properly it will actually hold
together on its own. To verify that you have that just kind of tip it up at a 45o and make sure that it’s holding.
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Polycrystalline materials, or polycrystals, are solids that are composed of many crystallites of varying size and orientation. Most
materials are polycrystalline, made of a large number crystallites held together by thin layers of amorphous solid. Most inorganic solids are
polycrystalline, including all common metals, many ceramics, rocks, and ice.
 Position: The sample stage is held in place with a pressure plate. The position of the beam is fixed and
therefore the position in the z-axis must be very accurate. The plane of the sample must be the same as the
plane of the sample holder that is defined by three pins.
XPRD Run:
Closing the Door: Once your sample is loaded you can close the doors. The doors are
leaded-glass89 and are part of the safety circuit in the instrument. So we are generating X-
rays and those are radiation and could be dangerous. Radiation doesn’t travel very far and
doesn’t travel through thick objects and it doesn’t travel through lead, so these are leaded
glass.
XPRD Safety: And they have little pins in the handles that will engage mechanical
switches right in here in the door and there are also electronic switches in the door in the
bottom and top. What this does is that it ensures that when you close the door all the
switches are engaged correctly and that the door is correctly closed. If the door is not
closed correctly it will cause the safety circuit to trip and it will shut everything down.
XPRD Control: There is a control panel here and the exact same set of control panels over
there. And there are LED lights; ready, on, alarm and busy, they’re all important to note
what state they are in. These buttons up here you must never touch. The only button that
you ever want to push on this panel is this big green square button and that’s the door
open button. To check to make sure you have done it correctly just check down here and verify that the alarm
LED has gone off.
Tungsten Filament Care: Two of the mechanical things that are really important to watch for is how you open
and close the door because that can trigger the safety circuit and also how you load and unload your sample. The
reason that we are concerned about the safety circuit is that inside our evacuated tube is our tungsten filament and
this filament has a really high power across it. And just like with a regular lightbulb over time that filament will
become brittle and break and we want to extend that amount of time as much as possible. And so when we bring
the current and voltage down and when we bring the current and voltage up we are doing it slowly so that this
filament has a chance to soak and to slowly get up to power and this will help to extend its lifetime.
Computer Control & Power Modes: Now that we have looked at the physical part of
the instrument we are now going to go the computer and this is where we do the
controlling and we control the ramp and where we control the power to the tube.
This is XRD commander, this application should always be on. One of the reasons is
that the XRD commander is what is controlling the X-Ray Diffractometer and it’s also
controlling the power. This is where the power is changed by the user:
Mode Volt Current Colour Code
Set 40 kV 40 mA Black
Current As per setting As per setting Blue
Standby 20 kV 5 mA Green
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Lead Glass is a variety of glass in which lead replaces the calcium content of a typical potash glass. Lead glass contains typically 18–
40% (by weight) lead(II) oxide (PbO), while modern lead crystal, historically also known as flint glass due to the original silica source,
contains a minimum of 24% PbO. The presence of lead is used in glasses absorbing gamma radiation and X-rays, used in radiation
shielding as a form of lead shielding (e.g. in cathode ray tubes, where lowering the exposure of the viewer to soft X-rays is of concern).
91
Standby Control: If XRD commander is not open it will not go into this standby status and the tube will be at
maximum power for too long. And we want to extend the life of the tube as much as possible so we want it to be
able to allow it to go into standby mode. It will do this automatically after 30 minutes of non-use. But if no one is
using it for the rest of the day we do want it to go into standby mode. So we just leave this open and leave it like it
is.
When you do want to begin you want to ramp your power up to 40 mA and 40 kV. It’s important to not just hit set
right here, you want to ramp it up slowly so what you want to do is input the values first. So we’re going to ramp
up by: Ramp No. Voltage Current Time gap
First 10 kV 0 mA 30 sec to 1 min (to allow soaking)
Second 30 kV 5 mA 30 sec to 1 min (to allow soaking); press SET
Third 40 kV 5 mA 30 sec to 1 min (to allow soaking)
Fourth 40 kV 20 mA 30 sec to 1 min (to allow soaking)
Fifth 40 kV 30 mA End of regime
Running a Scan:. We just put in the start value and the x axis here refers to
position of the detector and we call it 2. To set the scanning regime,
consider:
Setting 2 Scan rate: 2 secs/step
Start 25.0o 1 secs/step (standard)
10.0o (standard)
Stop 85.0o
90.0o (standard)
Increment 0.03o
0.02o (standard)
Shutter & X-Ray Placement: Now the other thing to note is the Shutter and X-Ray. The shutter is closed and it’s
green which indicates that you can open and close the door and the power to the x-ray is on. There are other
buttons here open, close, (on and off) that you do not want to select. If you select these manually it there can be
problems with the timing in the computer, it is set up to do this automatically.
Detector Position: Up here we have another place where you can actually change the positions of the detector and
the sample. The setting regime for the goniometer follows the same colour coding as that of power.
Mode Start 2 Stop 2 Colour Code
Set 30o 60o Black
Current 42o 85o Blue
There is a little icon up heat that says “move drives”, just press
that and the drives will move to that position. This is not
necessary to do to run your scan. When you hit the start button
it’s just going to go to whatever value you have in here but it is
convenient to move the detector and sample exchanger if it is at
a weird angle to start with.
Saving a Scan: So if I run a scan from this window I can get a
perfectly good scan, I can run the standard or do a quick scan or
whatever I want, however, this data will not automatically be saved.
In order to automatically save data I need to set up a parameters file
and then call that parameters file in the Jobs tab. If you come down
here at the bottom you see a number of tabs, in the Jobs tab you this
is where we create our job.
Running a scan from this window and from your parameters and
hitting start here ensures that your data will be saved automatically.
The way to set up a parameters file is in a separate application and
the link to it is on the toolbar down here and it’s called the XRD
wizard. The only thing you really care about here is to putting your name in here, and determining your scan
definition and verifying your generator voltage and current.
Taking a Scan: Your scan type is locked coupled and continuous this the standard way to do it. What this means
is that your detector will be following at 2 from your sample.
1. You put in your start value and stop value in 2. Your step size is also in 2, it calculates the number of steps.
2. You put in your time and it will calculate the total scan time and this is important because it will calculate
your total scan time and this important because you want to know how long your scan is going to take and this
is an important to know when you are reserving your time for the instrument.
3. Also see that generator voltage and current the default is 40 kV and 40 mA which is the maximum and if you
want to change that you can do that here.
4. Most analysis software need a number of points for a peak to even recognize that the peak exists. So the
maximum step size recommended is 0.1 but 0.02 is preferred.
5. Once you have filled this all this in you can just save it as your name and it will automatically put the .dql
extension it and save it in the scan parameters file.
6. I want to always make sure that the blue, which is the status, matches whatever is in the parameters file
before I hit the start button because the values that are in the parameters file takes precedence. So if I’m at
20 and 5 here and I hit start for a parameter file that is at 40 and 40 it will automatically ramp the power up to
40 kV and 40 mA without going through the steps and this is not healthy for the tube.
7. Now it’s actually up to maximum power and I can go ahead and run my sample. I recommend that you wait 5
minutes or so while it’s at maximum power.
8. The sample ID is now changed to “demonstration”, it has automatically loaded my start and stop and
increment values and its running a scan.
9. It has moved the stage and detector automatically so everything is
being done automatically.
10. You can see a number of peaks already. This is alumina which is a
NIST90 standard. Right now it is just drawing lines, if I right click in
here you and select dots I can actually see the data-points and
hopefully you can see right away that this would not be something
that would be recognised in analysis software there is only one data
point here and you want to have a minimum of at least three on its
way up and on its way down.
11. That click indicates that it is finished. The shutter is now closed
which means you can open the door and the power is still on and it’s still at 40 kV
and 40 mA. It is not necessary to ramp the power down when you are finished.
12. Get your data out of your scans. Make sure you remember to fill in the log. And you
may remove your sample and you’ve finished your scan.
13. Your scan file is automatically saved to a scan folder and we have a shortcut to it on
the desktop.
14. To open the door there is a big green square open door button here it’s the only button
you ever want push.
15. Press it, the alarm light starts to flash, pull the handles out towards you and away.
90
The National Institute of Standards and Technology (NIST) is a physical sciences laboratory and a non-regulatory agency of the United
States Department of Commerce. NIST's activities are organised into laboratory programs that include nanoscale science and technology,
engineering, information technology, neutron research, material measurement, and physical measurement.
93
16. When you are removing your sample you want to make sure first that you have hold of your sample. There is
a little switch under here, put your thumb outside of there and then flip the switch towards you.
17. Resist the temptation to squeeze the switch and the pressure unit together. This pressure unit is hollow
aluminum and if you squeeze it like that you will bend it.
18. Hang on to your sample, flip the switch and remove your sample. When your sample has been removed you
can close the doors, no need to slam them. Verify that the doors are closed by checking the alarm light and
you’re finished.
Essentials of an XRD
1. X-ray Tube is the source of X rays, typically a Cu-anode in a vacuum tube as a
source of emission; wavelength, Cu/Kα = 0.154 nm. The various X-Ray tube types
and their strengths are shown under:
Element Kα2 Kα1 Kβ
Cr 0.2293663 0.2289760 0.2084920
Co 0.1792900 0.1789010 0.1620830
Cu 0.1544426 0.1540598 0.1392250
Mo 0.0713609 0.0709319 0.0632305
2. Incident-beam optics sets the condition of the X-ray beam before it hits the sample;
3. Goniometer is the platform that holds and moves the sample, and detector;
4. The sample & its holder;
5. Receiving-side optics sets the condition of the X-Ray beam after it has encountered the sample;
6. (Scintillation) Detector counts the number of X rays scattered by the sample
The schematic diagram of an X-Ray Diffractometer, where,

o ‘T’ is the X-Ray Source, o ‘C’ is the detector,
o ‘S’ is the specimen, o ‘O’ is the axis around which the specimen and
detector rotate
Sample Preparation for XRD
An ideal powder sample should have many crystallites in random
orientations. If the crystallites in a sample are very large, there will
not be a smooth distribution of crystal orientations.
Crystallites should be <10 mm in size to get good
powder statistics. Large crystallite sizes and non-
random crystallite orientations both lead to peak
intensity variation.

“Powder X-Ray Diffraction Familiarisation” by Southampton Diffraction Centre
(SDC); Mat Sci Dept, University of Southampton, UK.
See the Video, https://www.youtube.com/watch?v=ZYzKd2qMn1o
What is a Powder (XRPD) Pattern?
A powder pattern is a non-destructive (the sample doesn’t undergo physiochemical changes) technique used for
analysis of the bulk material. The XRPD experiment uses a Rigaku MiniFlex 600 System.
XRPD Setup
The powder x-ray diffractometer contains three main components: an
X-Ray Generator, the Sample Holder and an X-Ray Detector.
 The X-Rays Detector is similar to a typical digital camera except
that it detects X-Rays instead of visible wavelengths.
 Inside the X-Ray Generator electrons are accelerated across a
potential difference towards a metal target.
X-Ray Generation
As the electrons hit the target some will
collide with and eject the core shell electron
from the metal leaving a vacant site an
electron from a higher energy orbital we relax
into the vacant orbital and an X-Rays photon
will be emitted.
Most of the x-rays produced pass straight
through the sample though a small proportion
are diffracted by the sample and measured by
the detector.
XPRD Experiment
1. Ensuring your sample is dry, start by grinding it in a pestle and mortar to a fine powder of evenly sized
particles.
2. Then spread it uniformly across the frosted well on the glass plate.
3. Take care while spreading the sample to ensure that the delicate glass plate is not damaged.
4. To unlock the door press the door lock button, an alarm will sound until the door is locked again.
95
5. Once your sample is prepared, open the door and slide the sample into clips to hold it in place.
6. Lock the door once the sample is in place and the beeping will stop.
7. Open the Mini-Flex software ensuring a diffractometer is on
so that to can connect to collect a pattern.
7.1. Click the yellow general measurement button this will
bring up a new window in which you can choose a name
and directory for your data to be saved.
7.2. After choosing name and directory select the STOP THE
X-RAY option and press SET MEASUREMENT
CONDITIONS.
7.3. Ensure the settings are as described in your lab script
and click OK.
7.4. Press RUN and then OK to start the experiment.
Diffraction Patterns
A monocrystalline sample will produce only one A polycrystalline sample contain thousands of
family of peaks in the diffraction pattern, as it crystallites, therefore all possible diffraction peaks
consists purely of crystalline phase. will be observed, as the sample consists of both
amorphous and crystalline phases.
XRD Data Interpretation – What information can you get?

Qualitative analysis The kinds of materials that compose a solid.
Quantitative analysis The quantity of materials that compose the solid.
Crystallinity The quantity of materials that are crystallised.
Residual Stress The amount of stress present in the solid.
Crystallite size The size of crystallites that compose the solid.
Texture Average orientation of crystallites that compose the solids.
XRD Applications
1. Structure of crystals (phase and orientations) 4. State of anneal in metals (atomic arrangements)
2. Particle size determination 5. Applications of diffraction methods to
complexes.
a. Spot counting method
a. Determination of cis-trans isomerism.
b. Broadening of diffraction lines
b. Determination of linkage isomerism
c. Low-angle scattering
3. Polymer characterisation
X-ray crystallography has been fundamental in the development of many scientific fields. In its first decades of
use, this method determined the size of atoms, the lengths and types of chemical bonds, and the atomic-scale
differences among various materials, especially minerals and alloys. The method also revealed the structure and
function of many biological molecules, including vitamins, drugs, proteins and nucleic acids such as DNA.
X-ray crystallography is still the primary method for characterising the atomic structure of new materials and in
discerning materials that appear similar by other experiments so as to shed light on chemical interactions and
processes, or serve as the basis for designing pharmaceuticals against diseases.
XRD Advantages XRD Disadvantages
 XRD is the least expensive, the most convenient  XRD has size limitations. It is much more
& the most widely used method to determine accurate for measuring large crystalline
crystal structures. structures rather than small ones. Small
 XRD Techniques give information about the structures that are present only in trace amounts
structure of solids, the arrangement of the atoms will often go undetected by XRD readings,
that compose the solid. which can result in skewed results.
 XRD permits non-destructive structure analyses.  X-Rays do not interact very strongly with lighter
elements.
 It is relatively low in sensitivity.
Full-Width Half-Maximum (FWHM)
In a distribution, full width at half maximum (FWHM) is the
difference between the two values of the independent variable
at which the dependent variable is equal to half of its maximum
value. In other words, it is the width of a spectrum curve
measured between those points on the y-axis which are half the
maximum amplitude.
The FWHM is 2.355σ (st. deviation) of the Normal/Gaussian
peak.
X-Ray Powder Diffraction (XPRD)
X-Ray Powder Diffraction (XRPD) uses information about the
position, intensity, width, and shape of diffraction peaks in a
pattern from a polycrystalline sample. The x-axis (2θ),
corresponds to the angular position of the detector that rotates around the sample.
Consider an XRPD pattern of the Titania (TiO2) polymorphs:
Anatase Rutile Brookite.
97
6.3. XRD Numericals/Examples:
Q1. For the given XRD Pattern, calculate the Q2. A sample shows diffraction peak at 2θ =
crystalline mean size ‘’. Given that the λCu/Kα 27o which has FWHM of 0.5o. Calculate the
= 0.154 nm, k = 0.9 (assuming sphericity). crystallite size, if Cu/Kα X-ray radiation
Remainder of the data is available from the (0.154 nm) were used.
pattern. DATA::
λCu/Kα = 0.154 nm 2θB = 27.0o B = 0.5°
SOLUTION:
Bragg’s Angle, θB = 2θB/2 = 27.0o/2 = 13.5o.
B = 0.5o = 0.5(π/180) = 0.00873 rad
kλCu,Ka (0.9)(0.154)
𝛕 = Bcos(θ )
= (0.00873)(0.972)
𝐵
𝛕 = 𝟏𝟔. 𝟑⁡𝒏𝒎 
Q3. Calculate the d-spacing using the
Diffraction Data.
DATA:
λCu/Kα = 0.154 nm, 2θB = 25.3o
SOLUTION:
BM = 0.86o = 0.86(π/180) = 0.015 rad
BS = 0.10o = 0.10(π/180) = 0.0017 rad.
B2 = BM2 – BS2 = (0.015)2 – (0.0017)2 rad2
= 2.2211 × 10-4 rad2
B = 0.0194 rad.
kλCu,Ka (0.9)(0.154)
𝛕 = Bcos(θ )
= (0.0194)(0.975)
𝐵
𝛕 = 𝟗. 𝟓⁡𝒏𝒎 
To find the unit cell size (inter-planar distances, unit
 cell dimension), we use Bragg’s Law.
 DATA (same as Q1):
 λCu/Kα = 0.154 nm, 2θB = 25.3o
 SOLUTION:
nλ (1)(0.154)
nλ = 2dsin(θB ) ⇒ ⁡d = 2sin(θ =
B) 2(0.219)
𝒅 = 𝟑. 𝟓𝟏𝟕⁡𝒏𝒎
BSIC Spring Semester VIII
Week #6 (Cont’d), 7-14 Notes
Table of Contents
Week #6-7 Notes (Cont’d) ........................................................................................................................................2
Nanoparticle Characterisation ................................................................................................................................2
6.1.3. XRD Numericals/Examples (Cont’d): ..........................................................................................................2
The diffraction pattern of copper metal was measured with x-ray radiation of wavelength of 1.315Å. The first
order Braggs’ diffraction peak was found at an angle 2θ of 50.5°. Calculate the spacing between the diffracting
planes in the copper metal? ....................................................................................................................................2
6.1.4. XRD Examples: ..............................................................................................................................................2
(a) Maghemite, γ-Fe2O3 ..........................................................................................................................................2
(b) Hematite, α-Fe2O3 .............................................................................................................................................2
(c) Carbon Nanotubes (CNTs)................................................................................................................................2
(d) Maghemite-decorated CNTs .............................................................................................................................2
(e) Hematite-doped ZnO .........................................................................................................................................3
(f) Vanadium-doped Maghemite: ...........................................................................................................................3
6.2. Microscopic Techniques ...............................................................................................................................4
6.2.1. Types of Electron Microscopies ...................................................................................................................4
Week #8-14 Notes .....................................................................................................................................................5
6.2.1. Types of Electron Microscopies (Cont’d) .....................................................................................................5
6.2.1(a). Scanning Electron Microscopy, SEM ..................................................................................................5
6.2.1(b). Transmission Electron Microscopy, TEM ..........................................................................................6
6.3. Spectroscopic Techniques ............................................................................................................................7
6.3.1. Energy Dispersive X-ray (EDX) spectroscopy.......................................................................................7
6.3.2. X-ray photoelectron spectroscopy (XPS) ...............................................................................................8
6.3.2. Fourier Transform Infrared spectroscopy (FTIR) ...................................................................................9
7. Lithium Ion Batteries .....................................................................................................................................10
8. Nanocolloids .......................................................................................................................................................11
8.1. Zeta Potential, ZP or ζ: .................................................................................................................................12
9. Nanocrystalline Diamonds (NCDs) ..................................................................................................................12
10. Nanofluids (NFs) ...............................................................................................................................................13
11. Nanoemulsions (NEs) .......................................................................................................................................15
Summary of Lecture Video 11.1: .........................................................................................................................16
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Lecture 5
Week #6-7 Notes (Cont’d)
Nanoparticle Characterisation
There are many techniques devised so as to characterise nanoparticles in terms of their morphological, crystalline,
electromagnetic, physical, chemical and other distinct properties. Some of which are as follows, which shall be
discussed in detail in the precedent weeks:
1. X-Ray Diffraction technique 3. Spectroscopy techniques (EDX, XPS, FTIR)
2. Microscopy techniques (SEM, TEM, FESEM) 4. Thermal analysis (TGA)
6.1.3. XRD Numericals/Examples (Cont’d):

The diffraction pattern of copper metal was measured with x-ray radiation of wavelength of 1.315Å. The
first order Braggs’ diffraction peak was found at an angle 2θ of 50.5°. Calculate the spacing between the
diffracting planes in the copper metal?
DATA: SOLUTION:
λCu/Kα = 1.315Å ⇒ 0.135 nm (1Å = 1/10 nm); The Braggs’ equation for the unknown d-spacing:
n = 1.0; nλ
nλ = 2𝑑sin(θ) ⇒ 𝑑 =
2 sin(θ)
Bragg’s Angle, θB = 2θB/2 = 50.5o/2 = 25.25o. (1.0)(0.1315)
⇒ = 𝟎. 𝟏𝟓𝟒𝟏 𝒏𝒎
2(0.4266)
6.1.4. XRD Examples:

(a) Maghemite, γ-Fe2O3 (b) Hematite, α-Fe2O3
(c) Carbon Nanotubes (CNTs) (d) Maghemite-decorated CNTs

FE-SEM Image:
γ-Fe2O3/CNT
(e) Hematite-doped ZnO (f) Vanadium-doped Maghemite:
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FE-SEM Image: FE-SEM Image:
α-Fe2O3/ZnO V/ γ-Fe2O3
6.2. Microscopic Techniques

Microscopy techniques enable crystal or particle size, morphology and domain character to be observed directly.
Higher magnification and resolution makes electron microscopies extremely useful for revealing ultrafine details
of nanostructure material up to the order of 0.1 nm.
Why not use simple light microscopy (LM)? It is not suitable for morphological studies of nanoparticles, and
limited to 500x or 1000x magnification and resolution of 0.2 μm. The scientific need to see the fine details of
cellular structures required >10,000x magnification, impossible using light microscopes.
History: The foundations for electron microscopy were laid by the discovery of of electrons (J. Thompson, 1897)
and wave-like electron nature i.e. ≈ hν (de Broglie, 1924). Knoll & Ruska built the 1st electron microscope (1926),
however, the first practical EM was built by Siemens (1938). Later developments lead to improved EMs with 2.4
nm resolution (1940), and subsequently 1.0 nm resolution (1945).
Comparison of Eye and Electron Microscopies:
6.2.1. Types of Electron Microscopies

Transmission Electron Provides 2D images of crystals ranging in size from a few nm to 1-2 pm across. Extreme
Microscopy (TEM) vacuum upto 1x10-20 Pa (ca. 3 times more than FESEM/SEM), based on transmitted
Use: electrons. Atomic scale imaging i.e. high resolution than SEM, on fluorescent screens.
imaging of dislocations, tiny TEM provides the details about internal composition such as morphology, crystallization,
precipitates, grain boundaries, stress or even magnetic domains. TEM samples must be cut thinner, unlike SEM. The
and other defect structures transmitted sample electron produce a 2D image in TEM. Lesser sample amount analyzed
per time.
Field-Emission or simple Provides 3D images of particle at moderate magnification. High vacuum of upto 1x10-7
Scanning Electron Pa, based on scattered electrons. Non-atomic scale imaging i.e. lower resolution than
Microscopy (FESEM/SEM) TEM, on monitors. SEM focuses on the sample’s morphology and its composition.
Use: Sample ejected BSEs, secondary electrons, and characteristic X-rays produce 3D image.
Solid surfaces, powders, Larger sample amount analyzed per time.
Polished/etched microstructures,
IC chips.
Lecture 6-7, 12-13
Week #8-14 Notes
6.2.1. Types of Electron Microscopies (Cont’d)
6.2.1(a). Scanning Electron Microscopy, SEM
A type of electron microscope that images a sample by scanning it with a high energy beam of
electrons in a raster scan pattern. A standard SEM uses secondary electrons & back scattered
electrons (BSE). Whereas, other types can also use X-rays and light rays.
Image Formation: The electrons interact with the atoms that make up the sample producing signals
that contain information about the sample's surface topography, composition, and other properties.
Accelerated electrons significant amounts of kinetic energy dissipating as a variety of signals,
produced when the incident electrons are decelerated in the solid sample. These signals include
secondary electrons that produce SEM images.
Viewable Characteristics:
Topography The surface features of an object or "how it looks", its texture; direct
relation between these features and materials properties.
Morphology The shape and size of the particles making up the object; direct relation
between these structures and materials properties.
Composition The elements and compounds that the object is composed of and the
relative amounts of them; direct relationship between composition and
materials properties.
Crystallographic How atoms are arranged; direct relation between arrangements and
Information material properties.
SEM Sample Preparation: The operation will only work if the sample is properly
prepared. Metals require no preparation, as they already conduct electricity and will
respond favorably when bombarded with electrons. However, non-metals need to be
prepared with a material known as a sputter coater, covering sample with a thin
conductive coating (gold). In addition, preparation traditionally includes the removal of
all water. Water molecules will vaporize in a vacuum, creating obstacles for the electron
beams and obscuring the clarity of the image.
Fig (right). Field Emission Scanning Electron Microscope (FE-SEM) Schematic.
If, X-ray spectrometer is included. It comprises with four basic components: excitation source (electron beam or
x-ray beam), X-ray detector, pulse processor, and analyser.
SEM Types:
Conventional High- Most common type. Requires a dry, high-vacuum stable sample with ca. 10nm thick conductive
vacuum SEM (SEM) layer (by sputter coating with Pt, Au, Ag, and Cr).
Low-vacuum SEM Similar to conventional SEM, but allows more precise qualitative and quantitative evaluation of
(LVSEM) interfaces at lower variable vacuum pressures (18-40 Pa). Compared to SEM, the specimen
evaluated can still be subjected to LM and TEM, reducing costs and minimizes quantity of
biomedical samples needed. LVSEM can be employed to analyze non-conductive samples, as is.
Cryo-SEM: Similar to conventional SEM, but allows samples to be viewed in frozen state, cooled by liquid N2.
The equipment is particularly useful to view directly the hydrated (wet) samples, biological
samples, hydrogels, pharmaceutical suspensions, fats and waxes, and nanoparticles etc.
Environmental SEM A radical breakthrough from the vacuum-based conventional SEM, allows for the collection of
(ESEM) electron micrographs of wet, uncoated specimens, or both by using an inert gaseous environment
in the specimen chamber, at temperature from <0o to >1000 °C. Biological specimens can be
maintained fresh and live.
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SEM Advantages: SEM Disadvantages:
Gives detailed 3D and topographical imaging and Expensive and large. Special training is required to
the versatile information garnered from different operate. Sample preparation can result in artifacts
detectors. This instrument works very fast. Modern (damaged structures). Limited to solid samples.
SEMs allow for the generation of data in digital Carry a small risk of radiation exposure associated
form, very fast and require minimal preparation with the electrons that scatter from beneath the
actions. sample surface.
SEM Applications: One of the most versatile technique, SEM can be used to-
1. Image morphology of samples.
2. Image compositional and some bonding differences.
3. Examine wet and dry samples while viewing them (ESEM), frozen material (cryo-SEM).
4. Generate X-rays from samples for microanalysis (EDS).
5. View grain orientation/crystallographic orientation and heterogeneity.
6. Forensics use SEM to examine and compare evidence, including: metal fragments, paints, inks, hair and
fibers, to match (or otherwise) the samples from the crime scene to prove its scenario.
7. Can also be employed for electron mapping and point analysis.
6.2.1(b). Transmission Electron Microscopy, TEM
TEM is a very powerful tool for material science. A high energy beam of electrons is shone
through a very thin sample, and the interactions between the electrons and the atoms can be
used to observe features such as the crystal structure and features in the structure like
dislocations and grain boundaries. TEM can be used to study the growth of layers, their
composition and defects in semiconductors.
High Resolution Transmission Electron Microscope (HRTEM) can be used to analyze the
quality, shape, size and density of quantum wells, wires and dots.
Fig (right). Transmission Electron Microscope (TEM) Schematic.
Viewable Characteristics:
Thickness The transmission of unscattered electrons is inversely proportional to the
specimen thickness.
Orientation, Phases, Given by incident electrons via elastic scattering of specimen atoms.
Arrangements These electrons follow Bragg's Law:
nλ = 2dSinθ.
These scattered electrons can be collated using magnetic lenses to form;
a pattern of spots each spot corresponding to a specific atomic
spacing.
Composition Determined by analyzing the energy with the electron microscope +
Atomic bonding spectroscope (Electron Energy Loss Spectroscopy). By selecting
state electrons with a specific loss energy, element distribution in specimen
can be visualized.
Image Formation: Operates on the same principles as the LM but uses electrons. When
an electron beam passes through a thin-section specimen of a material, electrons are
scattered. A sophisticated system of electromagnetic lenses focuses the scattered
electrons into an image or a diffraction pattern, or a spectrum. This transmitted portion
is focused by the objective lens into an image on phosphor screen or charge coupled
device (CCD) camera. The image then passed down the column through the
intermediate and projector lenses, is enlarged all the way.
Fig. Staphylococcus aureus platinum replica image shot on a TEM at 50,000x
magnification (left). A TEM image of a cluster of polio virus (30 nm dia) (second to
left).
Lenses:
Condenser Lenses Control beam focus onto specimen and intensity (condensation). At low magnification, they
(2 qt.) spread beam to illuminate a large area. At high magnification, they strongly
condense beam onto a single point.
Objective Lens Focuses image (image formation) and contribute most to the magnification and resolution .
Magnifier Lens Determine the magnification. As the magnification is changed, the currents through lenses change.
System (4 qt.) .
TEM Sample Preparation: The TEM preparation technique depends on the type of
sample and also on the property of interest. The specimen holder has one or two wells at
the end. The sample is loaded into this via a flange or a ring that screws into the well to
hold it securely in place. It is imperative that the grid is secured so that it does not fall out
of the specimen holder. The holder is then inserted into the column. During the process
the sample airlock is evacuated which can take a few minutes, then ready to analyze.
The sample should be electron transparent. If not the whole sample at least very thin. Typical thickness values for
metallic samples should be 30 - 50 nm. Usually, 100 nm is a upper limit for the sample thickness.
TEM Applications:
TEM has wide biomedical applications, in analysis for various diseases or the human body organs including:
Renal, muscle and skin diseases etc; tumor classifications,
TEM Advantages: TEM Disadvantages:
High resolution, detailed image and magnification, Expensive, large instrument requiring extreme
gives elemental or compositional information. vacuum. Gives monochromatic (black and white)
images. Sample preparation is difficult and are
limited to electron transparent materials.
6.3. Spectroscopic Techniques

6.3.1. Energy Dispersive X-ray (EDX) spectroscopy
Energy Dispersive X-ray spectroscopy (EDX) is a non-destructive, qualitative
and quantitative technique employed for elemental analysis and chemical
characterization of a sample, based on fundamental X-ray excitation of
electrons in atomic structure producing characteristic peaks for each element.
The EDX specimens can be examined in situ with little or no sample
preparation.
The data generated by EDX analysis consist of spectra showing peaks corresponding to
the elements making up the true composition of the sample being analyzed. Elemental
mapping of a sample and image analysis to provide spatial distribution are also possible.
Operation: A detector is used to convert X-ray energy into
voltage signals; this information is sent to a pulse processor,
which measures the signals and passes them onto an analyzer for
data display and analysis. X-ray intensities are calculated by
counting the photons emitted and the precision accessible is
limited by statistical error. Incoming X-ray emits an inner shell
electron, leaving a vacancy which is filled by an outer shell electron by releasing a
photon.
Limitation: The technique is limited to elements above atomic number 4 (Be) to 92 (U)
can be detected in principle.
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Accuracy: In general, systematic accuracy is commonly nearer ± 2%, owing to variability in standard
compositions and correction errors. The bombarding electrons can generate characteristic X-Ray lines, that
dampen smaller peaks, resulting in a background. The nature of the sample and the likelihood of an X-ray
escaping the specimen depends on the X-ray energy, the material amount and density.
EDX Applications: In a multi-technique approach EDX becomes very powerful, particularly in contamination
analysis and industrial forensic science investigations.
Quality Control & Assurance: Product de-formulation and competitor analysis. Disputed claims and failure
investigations. Catalyst quality. Product imperfections and defect analysis. Contamination detection, isolations
and identification. Quality control, raw material and end product. Assessment of plant particulate emissions.
Process Control & Optimization: Improved quality control; Rapid identification of contaminant and source; Full
control of environmental factors, emissions etc. Greater on-site confidence, higher production yield & identifying
the source of the problem in process chain. Construction and maintenance monitoring (asbestos control).
6.3.2. X-ray photoelectron spectroscopy (XPS)
XPS, aka Electron Spectroscopy for Chemical Analysis (ESCA), is a surface-sensitive quantitative
spectroscopic technique based on Einstein’s photoelectric effect (1905), can identify the elements
within a material (elemental composition) or on its surface, as well as the chemical state, the
overall electronic structure and density. Material properties are inferred from the measurement of
the kinetic energy and the number of the ejected electrons.
The Philips 560 XPS/AES/SIMS-UHV System & Schematics

Background: XPS belongs to the family of photoemission spectroscopies in which electron population spectra
are obtained by irradiating a material with a beam of X-rays. Photoemission as an analytical tool demonstrated by
Kai Siegbahn (1961) Nobel Prize.
Operation: An XPS equipment comprises a source of X-rays, anultra high vacuum pump (UHV), electron energy
analyzer, magnetic field shielding, electron detector system, and a set of stage manipulators. A monoenergetic X-
ray beam emits photoelectrons from the surface of the sample by penetration of about few nanometer of the
sample surface. Cylindrical Mirror Analyzer (CMA) measures the KE of emitted e-s. The spectrum plotted by the
computer from the analyzer signal. The binding energies can be determined from the peak positions and the
elements present in the sample identified. The XPS spectrum contains information of the top of the sample surface
in 10–100 Ǻ.
Why is an Ultrahigh Vacuum (UHV) required? XPS requires high vacuum (residual gas pressure P = 10−6 Pa)
or ultra-high vacuum (P <10−7 Pa), removing atmospheric O2 and increase the photoelectronic mean free path, to
avoid contamination of surface because of surface sensitivity. Contaminates can produce an XPS signal and lead
to incorrect composition or surface analysis. Ambient-pressure XPS is also available, operating pressures of a few
tens of mbar. Other than the UHV, to remove contamination, the sample surface is bombarded (purged) with
Argon ions (Ar+ = 3 KeV). Heat and O2 can be used to remove hydrocarbons.
XPS Sample Preparation: Out of a few universally accepted methods, the favored method is to press the powder
into clean, high purity indium foil. Alternatively, the powder may be dissolved in a suitable solvent and then drop
cast onto the surface of a clean silicon wafer. Finally, powders that cannot be prepared by either of the above
methods can be either sprinkled onto the surface of sticky carbon tape or pressed into a tablet for analysis.
Calculations: Because the energy of an X-ray with particular wavelength is known, the electron binding energy
of each of the emitted electrons can be determined by using an equation that is based on the work of Ernest
Rutherford (1914):
E = hv – BE – φ.
Where, BE is the binding energy of the electron,
hv is the energy of the X-ray photons being used,
KE is the kinetic energy of the electron as measured,
φ is the work function (minimum energy needed for photoelectric effect)
of the spectrometer.
XPS Applications: XPS is routinely used to analyze inorganic compounds, metal alloys, semiconductors,
polymers, elements, catalysts, glasses, ceramics, paints, papers, inks, woods, plant parts, make-up, teeth, bones,
medical implants, bio-materials, coatings, viscous oil and glues etc. Organic chemicals are not routinely analyzed
because of degradation by the X-rays or the heat from non-monochromatic X-ray sources.
For qualitative or quantitative elemental analysis; present within 1-10 nm top surface of the sample. It can detect
all elements with an atomic number Z>3 (73Li). H and He are undetectable due extremely small diameter,
reducing the X-ray collision probability to almost zero.
For Chemical State analysis of polymer surfaces, the presence or absence of the C states is revealed, namely:
carbide (C2-), alcohol (OH), ketone (COR), ester (COOR), carbonates (CO3), and tri fluorocarbon (CF3).
XPS Advantages XPS Disadvantages
Non-destructive technique, surface sensitive (10- Very expensive due to high vacuum is required.
100Å), quantitative measurements are obtained. Slow processing (0.5-8 hrs/sample). Large area
Provides information about chemical bonding and analysis is required. H and He can not be identified.
elemental mapping. Data collection is slow 5 to 10 min.
6.3.2. Fourier Transform Infrared spectroscopy (FTIR)
A technique used to obtain infrared spectrum of absorption or transmittance of a
solid, liquid or gas. To identify the presence of certain functional groups in a
molecule, and to confirm the identity of a pure compound or to detect the presence
of specific impurities. FTIR spectrometers are mostly used for measurements in the
mid and near IR regions. For the mid-IR region, 2−25 μm (5000–400 cm−1).
FTIR Spectrophotometer (Nicolet 5DX FT-IR, Thomas Scientific, USA).
Fourier transform spectrum is a single beam spectrum converted
from an interferogram, which includes both spectra from the
sample and background. The background spectrum contains only
the information from the instrument and the atmosphere, not from
the sample being examined.
Operation: The instrument contributions to background spectrum
are from the detector, beam-splitter, mirror and the IR source. The
atmospheric contributions are mainly from water vapor and CO2.
IR from a source enters the Michelson interferometer, composed
of one beam-splitter and two mirrors. The former transmits half of
the IR and reflects the other half, each strike a fixed and a moving
mirror. The function of the moving mirror is to change the optical
path lengths to generate light interference between the two. After
reflecting, the two split beams combine at the beam-splitter again
to irradiate the sample before being received by a detector.
FTIR Sample Preparation: Homogeneous mixture of sample and KBr will give the best results, an excessive
grinding of the potassium bromide is not required. The finely powdered KBr will absorb more humidity
(hygroscopic) from the air and therefore lead to an increased background in certain ranges.
9/16
Test if the anvil with the long pin can freely move through the collar before you start loading the die set. If not,
check for obstructions on the inside of the collar. Place the anvil with the shorter pin on the bench (left side).
Place the collar on top of it. Add a small amount of the KBr/sample-mixture, which covers the bottom pin in the
collar. Place the die with the longer pin (middle) on the top and turn the piece by 360o to spread the sample out
evenly. Remove the top anvil and check if the entire bottom pin is covered evenly. This is necessary to ensure that
the pellet sticks to the walls of the collar afterwards
What is the importance of Fourier Transform in FTIR? Fourier transformation is necessary to convert an
interferogram into an infrared spectrum, which is a plot of the light intensity versus wavenumber. A computer
equipped with FTIR constructs the infrared spectrum using a fast Fourier transform (FFT) algorithm which
substantially reduces the computation time.
FTIR Applications: Identification, structure determination, tautomerization/isomerism and kinetic studies of an
organic compound and organometals. Detection of impurities and conformational analysis.
FTIR Advantages: FT-IR Disadvantages:
FTIR instruments have distinct advantage over Cannot detect atoms or monoatomic ions (no
dispersive spectrometers, owing to its simple, chemical bonds), symmetrical identical molecules
inexpensive, sensitive, rapid, universal, powerful (N2 or O2), aqueous solutions are very difficult to
operation and mechanical design. Elimination of analyze as water is a strong IR absorber. Complex
stray light and emission contributions. Majority of mixtures give rise to complex spectra.
molecules (i.e. chemical bonded) absorb mid-IR
light, making it a highly useful tool.
7. Lithium Ion Batteries

Rechargeable lithium ion cells are the key components of the today's information-rich mobile
society. Li ion battery has highest volumetric and gravimetric energy density (smaller and
lighter) compared to other battery technologies.
Lithium (Li) is the lightest of metals with excellent electrochemical properties and it is also a
highly reactive material. Li can achieve very high energy storage capacity: 370–300 Wh/cm3).
Lithium batteries are primary batteries in which lithium metal (or compound) acts as an anode.
A lithium cell can produce voltage from ca. 1.5-4.0 V based on the types of materials used.
Types of Lithium-based Batteries: There are two types of lithium-based batteries available.
1. Lithium batteries (Primary) Pure metallic lithium anode. Not rechargeable.
2. Lithium-ion batteries (Secondary) Lithium-liberating compounds (LiCoO2, LiMn2O4, LiNiO2)
are used as cathode whereas the anode comprises Lithium
ions adsorped onto a carbon-based substrate. These batteries
are known as re-chargeable batteries. Lithium-ion batteries are common in home
electronics with a high energy density, tiny memory effect, low self-discharge.
Structure of a Lithium Ion Battery: Li-ion cell has a four-layer structure. A positive electrode (anode) made
with Lithium Metal Oxide has a current collector made of thin aluminum foil–cathode. A negative electrode
(cathode) made with specialty carbon (graphite) has a current collector of thin copper foil–anode. A separator is a
fine porous polymer film. An electrolyte made with lithium salt in an organic solvent. The electrolytes are
selected in such a way that there should be an effective transport of Li-ion to the cathode during discharge. The
type of conductivity of electrolyte is ionic in nature rather than electronic.
Working of a Lithium Ion Battery: During the charge
and discharge processes, lithium ions are inserted or
extracted from interstitial space between atomic layers
within the active material of the battery.
Simply, the Li-ion is transfers between anode and cathode
through lithium Electrolyte. Since neither the anode nor
the cathode materials essentially change, the operation is
safer than that of a Lithium metal battery.

“Charge-Discharge of a Lithium Ion Battery?” by TUM EES.
See the Video, https://www.youtube.com/watch?v=p8ecZ5oK7Fc
Discharging: During the first stage of discharge Li Charging: If an external voltage with the same
atoms oxidize by forming Li+ ions and e-, whereas polarity is applied between the current collectors, the
Li+ ions move to the positive electrode (anode) charge process will start. The Li atoms leave the
diffusing through the electrolyte and the separator. metal oxide structure and ionize into Li+ ions under
The electrons flow from the negative electrode to the the release of an electron of each one. In analogy
positive on the external circuitry, where the resulting with the discharge process Li+ ions diffuse to the
current flow can be used for an application. At the negative electrode. At the surface of the graphite
positive electrode the electrons recombine with the particles the Li+ ions and electrons recombine with
Li+ ions and are stored in the molecular structure of each other forming neutral Li atoms and are
the active material. reintercalated into the molecular structure of the
graphite particles.
Advantages: They have high energy density than other rechargeable batteries, possess less weight, produce high
voltage out about 4 V as compared with other batteries, have improved safety, i.e. more resistance to overcharge
No liquid electrolyte means they are immune from leaking, fast charge and discharge rate.
Disadvantages: They are expensive, are not available in standard cell types.
Future: Tesla Motors, Inc. is an American automotive and energy storage company that designs, manufactures,
and sells electric cars, electric vehicle powertrain components, and battery products.
8. Nanocolloids
A colloid (Greek: κολλα kolla ‘glue’) is a heterogenous mixture of
dispersed particles dispersed throughout another substance. These particles
pass through a filter paper but not through a semipermeable membrane.
Colloids can be made settle or separated by the process of centrifugation.
The colloids are large enough to scatter beam of light passing through it
and making its path visible.
Colloid prior and post-mixing.

The colloidal system consist of two phases: a dispersed (discontinuous)
phase and a dispersion (continuous) phase.
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The dispersed-phase particles have a diameter of between approximately 1–100nm. Such particles are normally
invisible in an optical microscope, though their presence can be confirmed with the use of an electron microscope.
Interaction of colloid particles:
Van der Waals force: Sum of attractive or repulsive forces between molecules other than forces due to
covalent, H- bonds, or the electrostatic interactions
Electrostatic interactions: Colloidal particles often carry an electrical charge and therefore attract or repel each
other. The charges of both phases, as well as the mobility are factors affecting the
interactions.
Steric forces: Steric effects arise from the fact that each atom within a molecule occupies a certain
amount of space. If atoms are brought too close together, there is an associated cost in
energy due to overlapping electron clouds (Pauli or Born repulsion), and this may affect
the molecule's preferred shape (conformation) and reactivity.
8.1. Zeta Potential, ZP or ζ:

In the colloidal chemistry, Zeta Potential is the electrokinetic potential in colloidal dispersions, measured as
are volts (V) or millivolts (mV). Zeta potential is a measure of the magnitude of the electrostatic or charge
repulsion/attraction between particles and is one of the fundamental parameters known to affect stability.
Theoretically, the ZP is the electric potential in the
interfacial double layer (DL), or the potential difference between
the dispersion medium and the stationary layer of fluid attached to
the dispersed particle.
Stability behaviour of a colloid depending on zeta potential

Zeta potential (mV) Stability behavior
0 to ±5 Rapid coagulation or flocculation
±10 to ±30 Incipient instability
±30 to ±40 Moderate stability
±40 to ±60 Good stability
>61 Excellent stability
Consideration: The sign and magnitude of ζ affects process control, quality control and product specification. A
large positive or negative value of zeta potential of nanocrystals indicate good physical stability of
nanosuspensions due to electrostatic repulsion of individual particles. High ZP implies highly charged particles,
which prevents aggregation of the particles due to electric repulsion. If the ZP is low, attraction overcomes
repulsion, and it is likely that the mixture forms coagulates.
Optimum ZP for nanodispersions: A ZP value other than ±30 mV (moderate nanodispersion stabilization) is
generally considered to have sufficient repulsive force to attain better physical colloidal stability. A small zeta
potential value can result in particle aggregation and flocculation due to the van der Waals attractive forces act
upon them showing physical instability of a system.
Other Factors: Certain other factors such as material properties, presence of surfactants, and solution chemistry
other than zeta potential also affect the physical stability of obtained nanosuspensions.
Advantages: Zeta potential (ζ) measurement is a very useful technique, which provides information about the
material surface-solution interface, to predict and control stability of suspensions/emulsions, often key to
understanding dispersion and aggregation processes. The presence/or absence of surface charged moieties on
materials (revealed by their ζ) directly affect their performance and processing characteristics in suspension.
ZP measurements to improve formulation stability and shelf life and reduce formulation time and cost.
9. Nanocrystalline Diamonds (NCDs)
Definition: Nano-structured diamond has rekindled much of this interest, offering many bulk diamond properties
in a thin film package or small particle form. The term nanocrystalline diamond usually refers to a solid film of
diamond typically grown on a substrate such as silicon in a chemical vapor deposition (CVD) reactor. The films
are comprised of nano sized diamonds held together in a matrix of amorphous carbon.
Chemical Vapor Deposition (CVD): In typical CVD, the wafer (substrate) is exposed to one or more volatile
precursors, which react and/or decompose on the substrate surface to produce the desired deposit. CVD is
a vacuum deposition method used to produce high quality, high-performance, solid materials including diamonds.
CVD allows the deposition of NCDs on many other substrates such as metals, quartz and other transparent
glasses, piezoelectrics1.
The lack of suitable dopants (a substance used to produce a desired electrical characteristic in a semiconductor)
for electronic applications, led to a marked reduction of interest in CVD diamond research from the end of the
20th century.
Differences in property from Bulk diamonds: Small grain sizes increase the grain
boundary, volume fraction and the amount of nondiamond carbon, thus will tend to
make the film properties which deviate from bulk diamond properties. The amorphous
carbon can be more or less graphitic depending on growth conditions which means that
nanocrystalline films can be electrically insulating or electrically conducting. They are
very tough and have been used as wear resistant coatings.
NCDs has most of the extreme properties of diamond but at a substantially reduced
cost, larger area and more practical format.
Fig. NCD films grown on silicon. The color comes from interference between the reflected light from the silicon wafer and
NCD film. The blue wafer is 70 nm thick and the gold 140 nm.
Applications: Nano-diamond particles have been used as abrasive materials for some time and have recently
found more sophisticated applications such as single photon sources and bio-markers (a characteristic behavior to
measure and evaluate as an indicator of normal biological processes, pathogenic processes or pharmacological
responses to a therapeutic intervention).
Seeding: They are also of critical importance as seeds for the deposition of nano-diamond films.
Drug-Delivery: Nano diamonds based innovative system for drug delivery due to its natural biocompatibility,
non-toxic nature, and increase water solubility. Among the many Nano carbon materials that have been
investigated for use as drug carriers, ND, is the most promising due to its many favorable properties, including,
chemical inertness, biocompatibility, and easy availability compared to other Nano carbon materials.
Chemotherapeutics: Delivery of therapeutic agents across the blood brain barrier, drug-induced toxicities and
pharmacokinetic limitations commonly result in poor compliance and disease-related complications. Each ND’s
surface may be comprised of functional groups that allow a wide spectrum of compounds for multiple
applications specifically for chemotherapy treatments.
Proposed Methodology prior Applications:
 Cell culture and reagents procurement and synthesis,  Pharmaco-dynamic and kinetic studies (HPLC-
 Nano-drug Characterization (XRD, Raman, TEM), MS/MS) and dissolution study.
 Reactive Oxygen Species (ROS) or cellular toxicity  Human synaptic plasticity RT2 profile PCR array,
assay of Nano drug.  Drug delivery through BBB,
 Therapeutic efficacy, and statistical analysis
Problems and Shortcomings: One of the critical problems with such materials is the tendency of the core
particles to aggregate into larger agglomerates which are difficult to disperse. This is a particular problem with
material grown where particles are tightly bound by sp2 bonding. Therefore, the purification of nano-diamond
particles is an active and complex research area which will determine the applications of such particles.
10. Nanofluids (NFs)
Definition: Nanofluids are colloidal nano-sized particles suspended in various base fluids which alter the fluid
flow and heat transfer characteristics of the base fluids. These particles are generally stable metals or metal oxide
1
Piezoelectricity (Greek: πιέζωἤλεκτρον piézōḗlektron, “to squeeze (out) amber i.e. electrons”) is the electric charge that accumulates in
certain solid materials (such as crystals, certain ceramics, and biological matter in response to applied mechanical stress
13/16
(Al2O3, ZrO2, SiO2, Fe3O4, Cu, Au,), carbon-based materials (diamond, C60) and polymers (Teflon) etc. Several
liquids including water, ethylene glycol, and oils have been used as base fluids.
Comparison of properties to conventional cooling fluids: Recent development of nanotechnology brings out a
new heat transfer coolant called Nanofluids (NFs). The much larger relative surface area of nanoparticles
compared to conventional particles, not only significantly improves heat transfer capabilities, but also increases
the stability of the suspension.
NF Preparation: Nanoparticles can be produced from several
processes such as gas condensation, mechanical attrition or
‘wet’ chemical precipitation techniques. Gas condensation
processing has an advantage over other techniques. Although
stabilization can be a challenge, on-going research indicates that
it is possible. Nanomaterials used include metallic, ceramic and
oxide particles, as well as carbon nanotubes, graphene
nanoflakes.
Two major routes of synthesis can be adopted for NF synthesis:
1. One-Step: Simultaneously synthesizing and uniformly, stably dispersing the nanoparticles in the
□ Direct evaporation (sputtering), base fluid, which ultimately reduces agglomeration. Drying, storage, transportation
□ Chemical reduction, are avoided, so the agglomerates are minimized, and the stability of fluids is increased
□ Laser ablation, Some disadvantages, such as the residual reactants in the nanofluids, making it difficult to
□ Microwave irradiation2, elucidate the nanoparticle effects without eliminating this impurity
□ Phase-transfer (sol-gel).
2. Two-Step: Widely used, economic, large-scale method. First dry nanoparticle powders are produced
□ Wet synthesis by chemical or physical methods, then dispersed into a fluid by intensive magnetic force
□ Attrition or ultrasonic agitation; high-shear mixing; homogenizing and ball milling.
□ Vapour deposition Disadvantages due to the high surface area and surface activity, nanoparticles have the
□ Agitation tendency to aggregate. To enhance the stability of nanoparticles in fluids is the use of
surfactants. However the functionality of the surfactants under high temperature is also a
big concern, especially for high temperature applications.
NF Characterization: SEM, TEM, XRD, FT-IR, DLS, TGA and ZP analysis. Dynamic Light Scattering (DLS)
estimates the average disperse size of nanoparticles in the base liquid media and Thermogravimetric analysis
(TGA) studies the influence of heating and melting on the thermal stabilities of nanoparticles. ZP is related to the
stability of nanoparticle dispersion in base fluid.
NF Advantages: NF Disadvantages:
High specific surface area, more heat transfer High cost, complexity and difficulty in production
surface between particles and fluids. High dispersion which hinders commercialization. Lower specific
stability with predominant Brownian motion of heat than base fluid e.g. CuO/EG-NFs nanofluids,
particles. SiO2/EG-NFs and Al2O3/EG-NFs exhibit lower
Reduced pumping power as compared to pure liquid specific heat compared to base fluids.
to achieve equivalent heat transfer intensity. Agglomeration limits the benefits of the high surface
Reduced particle clogging as compared to area, mitigatable using dispersants/surfactants that,
conventional slurries, thus promoting system however, can change the particle surface properties
miniaturization. and increase impurities to unacceptable levels.
Adjustable properties, including thermal Most studies to date have been limited to sample
conductivity and surface wet ability, by varying sizes <100 mL NFs, hindering assessment of their
particle concentrations to suit different applications. potential uses.
NF Applications: It has applications in microelectronics, fuel cells, pharmaceutical processes, and hybrid-
powered engines, engine cooling/vehicle thermal management, industrial and nuclear cooling applications, space
and defense industry, domestic refrigerator, chiller, heat exchanger, in grinding, machining and in boiler flue gas
temperature reduction.
2
Irradiation is the process by which an object is exposed to radiation. Most frequently the term refers to ionizing radiation i.e. Gamma
rays, X-rays, higher ultraviolet radiations and alpha particles, beta particles and neutrons that have sufficient energy to ionize species.
11. Nanoemulsions (NEs)

Definition: Nanoemulsions (NE) are transparent or slightly opalescent, oil-in-water (o/w) emulsions with mean
droplet diameters ranging from 50-1000 nm and average droplet size is between 20-100 nm. Usually, NEs contain
(10-20% oil stabilized with 0.5-2.0% egg or soya lecithin). A typical formulation is given as under:
Internal structures of NEs depend on relative component concentrations and other characteristics.
NE Properties: Due to their small droplet size, NEs possess stability against sedimentation or creaming with
Ostwald ripening3 forming the main mechanism of NE breakdown.
NE Preparation:
High-pressure The technique makes use of high-pressure homogenizer to produce NEs of extremely low particle
Homogenization size (up to 1nm).
Microfluidization: A high-pressure positive displacement pump (0.35-138 MPa) forces the product through the
interaction chamber. The product flows through the small microchannels on to an impingement
area resulting in very fine particles of submicron range. The two solutions (aqueous and oily
phase) are combined together and processed to obtain stable NEs.
Ultrasonication Produces ultrasonic frequency of (20 kHz) sound to reduce particle size. NE is formulated to a
fixed composition and then ultrasonically agitated, causing the droplet to break into nano-sized
droplets. The emulsion is recirculated through region of high shear to produce uniform droplet size
distribution. A water jacket can be used to control and maintain the temperature.
High-pressure Homogenization Microfluidization Ultrasonication

NE Applications: NEs are useful in developing liquid formulation of poorly water soluble drugs for oral or
injectable administration. NE show great promise for the future of cosmetics; diagnostics; drug therapies and
antimicrobials, prophylactic (prevents adverse effects), as a mucosal vaccines, as non-toxic disinfectant cleaner
Medicines: O/W NEs can also be used to stabilize/encapsulate hydrophilic and lipophilic
systemic drugs which undergoes hydrolytic and oxidative degradation. O/W NEs are
administered by oral, topical, parenteral, transdermal and intranasal routes. NEs can increase the
oral bioavailability of hydrophobic drugs like the chemotherapeutic Paclitaxel using O/W NE of
100-120 nm droplet size, moderate to excellent stablility (ZP = 34-245 mV), made from pine nut
oil, water and egg lecithin.
Cosmetics: NEs support the skin penetration of active ingredients. High surface area (nano-sized droplet)
allowing effective transport through the skin. NEs can show their own bioactive effects, may reduce the
3
Ostwald ripening is the dissolution of small crystals or sol particles and the re-deposition of the dissolved species on the surfaces of larger
crystals or sol particles in solid solutions or liquid sols.
15/16
transepidermal water loss (skin dryness). NEs are acceptable in cosmetics because there are no inherent creaming,
sedimentation, flocculation, or coalescence that are observed with macroemulsions.
Fig (right). % Consumption of NEs by major cosmetic manufacturers.
Antimicrobial: NE has broad-spectrum activity against bacteria (e.g.
E. coli, Salmonella, S. aureus), enveloped viruses (e.g. HIV, Herpes
simplex), fungi (e.g. Candida, Dermatophytes), and spores (e.g.
anthrax).
Prophylaxis: NE prophylactics as creams, foams, aerosols and
liquids, are a human protective treatment and decontaminant to
prevent exposure to Anthrax (US Army, RestOps; 1999 & 2001) and
Ebola. Tested against gangrene4 and C. botulism spores, and on
contaminated wounds to salvage limbs.
Disinfectant cleaner: Healthcare, travelling, food processing, and military biocompatible, non-
hazardous, NE disinfectant applications has been developed by the EnviroSystems, Inc., a 100 nm
PCMX (p-chloro, m-xylenol) nanosphere O/W NE that inhibits/kills diseases like tuberculosis and
viruses, fungi, bacteria in 5-10 min. Common disinfectants have a large doses of various active
ingredients to which attack pathogen cellular walls to kill them.
NE Advantages: NEs are nontoxic, non-irritant, human- and veterinary-compatible, thermodynamically and
kinetically stable (flocculation, aggregation and creaming do not occur). 20-200 nm droplet size allow for higher
surface area, increasing the absorption rate and enhance drug bioavailability. NEs also enhance drug skin
permeation. NE particles are thermodynamically driven to fuse with lipid-membranes of organisms; increased by
the electrostatic affinity within the NEs’ charges and formulation.

“Emulsions?” by FuseSchool - Global Education.
See the Video, https://www.youtube.com/watch?v=bC_czAL24zY
Unlike solutions, some substances simply do not want to associate with one another. As an example, when oil and
water are added together, they form two distinct layers. Even if you shake these two liquids vigorously, they will
still remain immiscible. There are tiny oil droplets interspersed throughout the water. We have just created an
emulsion. If we let this emulsion stand for 5 to 10 minutes, the oil droplets will re-form the original layer.
All emulsifiers have two components: - a hydrophilic (water-loving) head, and a hydrophobic (water-fearing) tail.
If we added lecithin to our original oil and water emulsion, its hydrophilic head will prefer to associate with
water, and the hydrophobic tail with the oil droplets. This prevents separation, and thus, stabilizes the emulsion.
Common everyday emulsions include milk, mayonnaise, ice cream, and paint. These emulsions are mostly oil
droplets in water. Emulsions can also exist as water droplets in oil. Real life examples include margarine, lotions,
and facial creams. The world’s most popular emulsion is, without a doubt, ice cream. The main ingredients are
milk or cream, and sugar along with flavouring and colouring components.
So what prevents an emulsion such as ice cream from separating? Substances known as emulsifiers are added to
stabilize emulsions. When making ice cream, egg yolk is commonly added. The active emulsifier in egg yolk is
called lecithin. Too little lecithin will cause the ice cream to separate, and too much will ruin its texture and
flavour.
LECTURE NOTES FOR WEEK 6-14 HEREBY CONCLUDE THE COURSE CONTENT FOR CY-416
NANOTECHNOLOGY
4
Gangrene (Greek gangraina (γάγγραινα), "tissue putrefaction") is tissue death caused by a lack of blood supply. Symptoms may include a
change in skin color to red or black, numbness, swelling, pain, skin breakdown. The feet and hands are most commonly affected.

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Nanotechnology, CY-416; BSIC Spring, VIII Notes by Arsalan A.

1.3. Early Uses

1.4. Nanomaterial Classification

1.5. Synthetic Routes:

(4) Gas-Phase Condensation15 (5) Aerosol Spray16

(1) Organometallic Chemical Route17 (2) Reverse-Micelle Route

(3) Colloidal Precipitation (4) Hydrothermal Synthesis

1.6. Applications of Nanomaterials:

1.7. Summary of Lecture Video 1.1:

1.8. Molecular Self-Assembly

(1) (2) (3) (4)

Or, the video: https://www.youtube.com/watch?v=PeHWqr9dz3c by Stanford Complexity Group

(1) (2) (3) (4)

Types on the basis of Supramolecular Chemistry

Porosity & Activity

Zn4O(BDC)5 (1.85 nm pore dia)

2.2. Aspect (SV) Ratio

Nanowires Nanorods Nanotubes

2.5. Nanotechnology & Fiction

Technique: See, https://www.youtube.com/watch?v=apaq99suYfk

 Collagen36  Poly(lactic acid) (PLA),

 Cellulose  Polycaprolactone (PCL),

 Silk fibroin37,  Polyurethane (PU),

 Poly(lactic-co-glycolic acid) (PLGA),

CTAB is Cetyltrimethylammonium Bromide {(C16H33)N(CH3)3Br just like other

Amesite (Mg,Fe)4Al4Si2O10(OH)8 Each member of

Chamosite, (Fe,Mg)3 Fe3 AlSi3O10(OH)8 member minerals and

4.2. Types of Nanomaterials (cont’d)

Structure & Bonding

Purple of Cassius – An unrealised Medieval Nanotechnology

The Nanochemistry behind Cassius’ Purple

The SEM images of the surfaces of Pristine Polyurethane

4.3. Nano-reinforced Composites -- Fine Particulate Technology:

Common powders encountered in our daily use

4.4. Getting down to the Nanoscale

4.5. Growth Kinetics – Nucleation & Growth Processes

The change in volume free energy, surface free energy and a

4.6. Summary of Lecture Video 4.3:

Issues with Nanoparticle Synthesis

The advantages of vapour phase pyrolysis include it

Hydrolysis → Condensation → Polycondensation.

Characteristics of Products: Sol-gel allows one to obtain pure, size-

(c) Microemulsion (two-phase) method

Advantages: The hydrothermal method over other types

The Microwave: A conventional

Summary of Lecture Video 5.1:

The effect of size change

Etching: Etching is used in Etchants for common microfabrication materials

Major steps in Photolithography are:

Dizaonaphthoquinone DNQ-Novalac Positive Photoresist SU-878 Negative Photoresist

Triphenylsulphonium as positive photoresist Biazide as negative photoresist

Hexamethyldisilazane (HMDS): A common method to increase adhesion of photoresist on the silicon

How are Silicon Wafers made?

Process: The arc evaporation process begins with

6.2. X-Ray Diffraction Technique (XRD)

For the .cif (Crystallographic Information File) here(Fe2O3, 

XRD Manufacturers & Vendors

Summary of Lecture Video 6.1:

Through what the X-Ray passes?