Introduction to Nanoscience

and Engineering

Dr. Ranjana Das

Chemical Engineering Department
Jadavpur University

“Nanotechnology is already all around us if you know where to look, Nature is the
master nanotechnologist
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 Course content

• Synthesis

• Characterisation

• Unique implications of nanoscale

• Scientific basis for the implications

• Specific applications

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Course Syllabus
Introduction to Top Down and Bottom up approach
Concept of Homogeneous Nucleation

Synthesis methodologies pertaining to Top-down approach

Lithographic process and its limitations, Ball milling

Synthesis methodologies pertaining to Bottom up approach

Plasma Arc Discharge, Sputtering and its advantage, Chemical Vapour Deposition and its types, Molecular
Beam Epitaxy, Sol-Gel Technique: Chemistry and Examples, Template-based growth of Nanomaterials,
Vapour-Liquid-Solid (VLS) method

Characterization tools of Nanomaterials

Concept of Atomic Forced Micrograph (AFM), Details of Electronic Microscopy, Spectroscopic insights
(Raman Spectroscopy, X-Ray photo electron Spectroscopy)

Introduction to Nanostructured materials

Introduction to Carbon nanotubes and Fullerenes, Graphene: Synthesis, applications, Quantum Dots,
Nanocomposites, Metal and Metal Oxide Nanowires, Intelligence engraved in Silicon

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Learning Objectives

1. Define nanomaterial

2. Explain why nano materials are of interest

3. Indicate different types of nano materials

4. Describe the different options available for synthesis of nano materials

5. Mention challenges associated with work in the area of nano materials

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Understanding of Nanomaterial
Crystallographic planes, atoms are Within a grain atoms
orderly arranged are perfectly ordered.
Distinct change of
order

Single crystal Polycrystalline material, large

crystal size

Polycrystalline Polycrystalline material, very small

material, Small crystal size
crystal size
08-09-2022 While the crystal size in in nano scale then the material is Nano Crystalline material
5
Definition of Nanomaterial

Materials having one or more dimensions less than 100nm (broad idea)

“Nano effect” confirms the Nano scale (drastic/significant changes in certain properties of materials based on size )

‘Nanoscale’ is considered to cover the range from 1-100nm

Nanotechnology Technology at the nanoscale

 The nanotechnology is the ability to work at the molecular level, atom-by atom, to create large structures with
fundamentally new molecular organisation.

 Nanotechnology is concerned with materials and systems whose structures and components exhibit novel and
significantly improved physical, chemical, and biological properties, phenomena and process due to their
“nanoscale size”.

 The aim of nanotechnology application is the design, synthesis, characterisation and application of materials,
devices and systems that have a functional organisation in at least one dimension on the nanometre scale.

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Why Nanomaterials
• Materials reduced to the nanoscale can suddenly show very different properties (opaque substances become
transparent (copper); inert materials become catalysts (platinum); stable materials turn combustible
(aluminum); solids turn into liquids at room temperature (gold); insulators become conductors (silicon).

• Various macroscopically measured properties (electrical conductivity, magnetic properties, mechanical

strength) are based on phenomena that occur at an altogether different size range.

• Manipulating materials at or near this characteristic size range often results in new control on material
properties

• Interesting nanomaterial with unique properties

Natural nanomaterials

Types of
Nanomaterials
Incidental nanomaterial
(based on source)
Engineered nanomaterial
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Dimensions of nanomaterials
This nanomaterial classification is based on the number of dimensions of a material, which are outside the
nanoscale (<100 nm) range.

• In zero-dimensional (0D) nanomaterials all the

dimensions are measured within the nanoscale (no
dimensions are larger than 100 nm). Most commonly,
0D nanomaterials are nanoparticles
• In one-dimensional nanomaterials (1D), one dimension
is outside the nanoscale. This class includes
nanotubes, nanorods, and nanowires.

• In two-dimensional nanomaterials (2D), two dimensions

are outside the nanoscale. This class exhibits plate-like
shapes and includes graphene, nanofilms, nanolayers,
and nanocoatings.

• In Three-dimensional nanomaterials (3D) are materials

that are not confined to the nanoscale in any
dimension. This class can contain bulk powders,
dispersions of nanoparticles, bundles of nanowires,
and nanotubes as well as multi-nanolayers.
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 *Quantum size effect
The key differences between describes the physics of
nanomaterials and bulk materials electron properties in
solids with great
reductions in particle
size, Bohr exciton
Two principal factors cause the radius
properties of nanomaterials to differ
significantly from other materials:
increased relative surface area, and
quantum effects. These factors can
change or enhance properties such as
reactivity, strength and electrical
characteristics.

Thus nanoparticles have a much

greater surface area per unit mass
compared with larger particles. As Nanotube
growth and catalytic chemical reactions Nanowire Hollow nano
occur at surfaces, this means that a Electrically fiber
given mass of material in nano- conducting
particulate form will be much more nanofiber
reactive than the same mass of Nanorod rigid
material made up of larger particles. nanofiber
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• Nanostructured Materials (NsM) are materials with a microstructure the characteristic length scale of
which is on the order of a few (typically 1–10) nanometers.

• NsM is produced using bottom to bottom technology (mechanosynthesis). The mechanochemical synthesis
(Mechanosynthesis) of nanophase materials can be realized by direct synthesis of compounds from the
elemental powders or by several exchange in an eutectic environment.
An eutectic is a minimum-melting
composition of 2 or more
components, each of which melts
and freeze congruently forming a
mixture of the component
crystals during crystallization

• Mechanochemical synthesis is a processing technique of solids in which mechanical and chemical

phenomena are coupled on a molecular scale.

• Nano object embedded in a matrix, sometimes also called nanocomposites

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• Nanostructured Materials (NsM) are materials with a microstructure the characteristic length scale of
which is on the order of a few (typically 1–10) nanometers.

• NsM is produced using ‘bottom to bottom’ technology (mechanosynthesis). The mechanochemical synthesis
(Mechanosynthesis) of nanophase materials can be realized by direct synthesis of compounds from the
elemental powders or by several exchange in an eutectic environment.
An eutectic is a minimum-melting
composition of 2 or more
components, each of which melts
and freeze congruently forming a
mixture of the component
crystals during crystallization

• Mechanochemical synthesis is a processing technique of solids in which mechanical and chemical

phenomena are coupled on a molecular scale.

• Nano object embedded in a matrix, sometimes also called nanocomposites

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Distinguishing in terms of attractive energy

• If the attractive energy between objects is insignificant compared with thermal energy (Powder)

• If objects attract each other weakly (agglomerate). External surface area is just sum of individual surface area

• If objects are strongly bonded (aggregate). External surface area is smaller than sum of surface area.

The ontology of Nano dispersion

Matrix Solid Liquid Gaseous

solid Nanocomposite* - Nanofoam**
liquid Nanosuspension Nanoemulsion Nanofoam
gaseous Aerosol Aerosol

*Nano alloy, metal matrix composite

**nanoporous, nanofluid
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Key issues of Nanomaterial Synthesis

Followings are the key issues or challenges in the fabrication of nanostructured

materials

using any process or technique:

• Control the particle size.

• Control the shape of nanoparticles.

• Control the structure either crystalline or amorphous?

• Particle size distribution (monodespersive: all particles are of same size).

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 Synthesis of Nanomaterials
Top-Down and Bottoms Up Approach

https://ro.uow.edu.au/cgi/viewcontent
.cgi?article=5553&context=eispapers
Synthesis of Nanomaterials

• Nanomaterials can be constructed by top down techniques, producing very small structures from larger pieces of
material, for example by etching to create circuits on the surface of a silicon microchip.

• They may also be constructed by bottom up techniques, atom by atom or molecule by molecule. One way of doing this is
self-assembly, in which the atoms or molecules arrange themselves into a structure due to their natural properties.
Crystals grown for the semiconductor industry provide an example of self assembly, as does chemical synthesis of large
molecules.

Top Down Bottom up

Suitable for bulk industrial Nature uses this technique

production
Chemical precipitation
Mechanical grinding
Useful for nanostructure
Crystal imperfection and More homogeneous chemical
surface imperfections are composition
introduced

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Top-down approach:
• Top-down approach involves the breaking down of the bulk material into nanosized structures or
particles.

• Top-down approaches are inherently simpler and subtractive in nature division of bulk material or on
miniaturization of bulk fabrication processes to produce the desired structure with appropriate
properties.

• Top down approach begins with pattern generated on a larger scale which is reduced to nanoscale
after a sequence of operation.

• The problem with the top-down approach are being Expensive, not suitable for soft samples
imperfection of surface structure.

• Top-down making nanoscale structures by lithography and etching techniques, ball milling, plasma
arc discharge, thin film deposition or sputtering (PVD) (Physical methods), Chemical Vapor
deposition (CVD).

• Some other techniques, machining, coating, atomisation, electron beam lithography, atomic force
manipulation, gas-phase condensation, aerosol spray.
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Bottom-up approach
• The alternative approach, which has the potential of creating less waste and hence the more economical,
is the ‘bottom- up’.

• It’s principle is molecular recognition or self assembly.

• Its cheaper but becomes completed with increase in sizes.

• It starts with atoms or molecules, and build nanostructure by direct manipulation of atoms and
molecules.

• This approach involves atom by atom, molecule by molecule, cluster by cluster manipulation for synthesis
of nanostructure.
• Bottom up methods provide improved nanostructure with less of defect free, homogeneous and short
orders.

• Oraganometallic chemical route, revere-micelle route, sol-gel synthesis, colloidal precipitation,

hydrothermal synthesis, template assisted sol-gel, electrodeposition etc, are some of the well- known
bottom–up techniques reported for the preparation of luminescent nanoparticles.
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 Nano fabrication

Bottom-up Top- down

Lithography Cutting, Etching,

Chemical Self Positional Grinding
Synthesis assembly assembly

Electronic Precision
Particle Crystals Experimental devices chip engineered
Molecules Films, atomic or masks surfaces
Tubes molecular
devices
Cosmetics, Displays Quantum well High quality
Fuel
laser computer optical mirrors
additives
chips MEMS

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Ball Milling
• Ball mill works on the principle of impact and attrition

• Grinding media are balls made of ceramic, flint pebbles, stainless steel

• Materials to be ground is fed from the left

through a 600 cone, resulting material is
discharged at 300 cone from right.
• Grinding works on the principle of critical
speed, after which the steel ball starts rotating
along the direction of rotating device, causing no
effective grinding

Key properties of grinding media Parameters to control during milling process

 Size: smaller media size smaller product size. Size should be larger
than the largest size of feed material.
 Density: Density should be higher than feed material
 Hardness: hard enough than feed material
 Composition: depend on product quality. Flammable substance avoid
steel ball
Types of ball mill
The Ball Mill is designed to grind materials by turning
the cylindrical shell with grinding medium
As per discharge characteristics ball mill are of –
Overflow/ over fall Type: The overflow type of Ball Mill is designed to overflow and discharge materials
from the trunnion on the outlet side
Grate-discharge Type:The grate-discharge type of Ball Mill
has a grate at the outlet of the shell and causes less excessive
grinding, compared to the overflow type.
Compartment type:The compartment type of Ball Mill has a
longer shell, inside of which is comparted into 2 to 3
chambers with grates

As per impact pattern

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Working of Ball mill

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Problem 1: Calculate the operating
speed of a ball mill with Dia of the ball
mill,800mm, dia of ball 60mm and
critical speed 40% less than the
operating speed
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The power required to grind a material from a given feed size to a given product size can be estimated by using
the following equation:

where:
W = power consumption expressed in kWh/short ton (HPhr/short ton = 1.34 kWh/short ton)
Wi = work index, which is a factor relative to the kwh/short ton required to reduce a given material from
theoretically infinite size to 80% passing 100 microns
P = size in microns of the screen opening which 80% of the product will pass
F = size in microns of the screen opening which 80% of the feed will pass
When the above equation is used, the following points should be borne in mind:
•The values of P and F must be based on materials having a natural particle size distribution.
•The power consumption per short ton will only be correct for the specified size reduction when grinding wet in
closed circuit. If the method of grinding is changed, power consumption also changes as follows:

1. Closed Circuit = W
2. Open Circuit, Product Top-size not limited = W
3. Open Circuit, Product Top-size limited = W to 1.25W

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Ball Mill Power Calculation Example #1
A wet grinding ball mill in closed circuit is to be fed 100 TPH of a material with a work index of 15 and a
size distribution of 80% passing ¼ inch (6350 microns). The required product size distribution is to be
80% passing 100 mesh (149 microns). In order to determine the power requirement, the steps are as
follows:

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Advantage and Disadvantages of ball mill

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Lithography
The process for imprinting, writing or etching patterns in a microscopic level in order to create
incredibly small structures.

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The patterns of integrated circuits are created on wafers by lithography
Films of specialized materials pattern on base is created called
resists. Resists typically do not adhere properly to untreated
surfaces of base (wafer)

Resists typically comprise organic polymers applied from a

solution, dispensed on wafer, spun about its axis to flange off
excess, solvent evaporates.

A bake is used to densify the resist film

and drive off residual solvent

Patterns are generated

Exposed to source for pattern development.
To drive additional chemical involved
Removal of resist

An optional final bake is often used to drive out volatile

organic materials and water
The steps in the lithography process
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 Lithography

A schematic of the lithography process for making nanostructures (a) a layer of resist is spin-coated on the substrate,
(b) the resist is exposed to either UV radiation in case of photolithography or an electron beam in case of electron-
beam lithography through a mask which has the required pattern cut out from it, (c) the substrate with the resist is
soaked in a developer which removes the parts of the resist that were exposed to radiation earlier (in case of positive
resist) or parts that were not exposed to radiation earlier (in case of negative resist), (d) material is evaporated onto
the substrate with the resist acting as a mask, (e) the substrate is soaked in a solvent that dissolves the remaining
resist and also the layer of evaporated material on the resist. This ‘lift-off’ process only leaves behind the material
evaporated directly on the substrate in step (d)
Types of Lithography The performance of a lithographic exposure is
determined by three parameters: resolution,
• Optical Lithography/ registration, and throughput.
Photolithography
• Resolution is defined to be the minimum feature
• X-Ray Lithography dimension that can be transferred with high fidelity
to a resist film on a wafer.
• Electron Lithography
• Registration is a measure of how accurately
• Ion Lithography patterns on successive masks can be aligned or
overlaid with respect to previously defined
patterns on the same wafer.

• Throughput is the number of wafers that can be

exposed per hour for a given mask level and is thus
a measure of the efficiency of the lithographic
process

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 (a) Optical lithography.

(b) Electron lithography.

(c) X-ray lithography.

(d) Ion lithography

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Optical equipment using ultraviolet light (λ = 0.2 μm to 0.4 μm). There are basically two optical exposure
methods: shadow printing and proximity printing.

In shadow printing, the mask and wafer may be in direct contact. very high resolution but defect due to
particle interference.

Photoresists are materials that undergo photochemical reactions

when exposed to light. There are two types of photoresists––
positive and negative.
• Positive resists insoluble in the chemicals referred to as resist
developers, but soluble by exposure to light. Negative resists :
Soluble in developer and rendered insoluble by exposure. The
pattern can be created in the resist film by selective exposure in
optical lithography by the imaging of a mask.
• Photomasks are sheets of glass, partially covered by an opaque
material, usually chromium, that has been removed according to
the pattern of the circuit. Optical Lithography
• By shining light onto the mask, and then projecting the
transmitted image onto the resist film, the pattern of one layer of
the circuit is transferred to the resist film on the wafer.
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Electron lithography

Electron lithography offers high resolution because of the small wavelength of electrons (< 0.1 nm for
10-50 keV electrons).
The resolution of an electron lithographic system is not limited by diffraction, but rather by electron
scattering in the resist and by the various aberrations of the electron optics.

The advantages of electron lithography are:

• Generation of micron and submicron resist

geometries
• Highly automated and precisely controlled
operation
• Greater depth of focus
• Direct patterning without a mask
• The biggest disadvantage of electron lithography is
its low throughput (approximately 5 wafers / hour
at less than 0.1 μm resolution).

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X-ray lithography

X-ray lithography employs a shadow printing method similar to optical proximity printing. The x-ray
wavelength (0.4 to 5 nm) is much shorter than that of UV light (200 to 400 nm). Hence, diffraction effects
are reduced and higher resolution can be attained.

Ion lithography

Ion lithography can achieve higher resolution than optical, x-ray, or electron beam lithographic
techniques because ions undergo no diffraction and scatter much less than electrons. In addition,
resists are more sensitive to ions than to electrons.

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Limitations

1) It is not applicable for curved surfaces

2) Scaling up is cumbersome
3) Photosensitive polymers are necessary
4) The mask is expensive
5) Processing conditions are very harsh, so it cannot be used in biological samples.

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Problem 1: The killing defect density is responsible for yield loss and depends on the design rule or size of the
device on a chip. This is because when the design rule becomes smaller, a smaller particle can contribute to yield
loss. For a 16M DRAM chip, the design rule is 0.5 µm, chip size is 1.4 cm2 , and killing defect size is 0.18 µm. Due
to contamination that occurs in a cleanroom, the wafer defect density measured at size 0.3 µm increases fivefold
from 0.2 D/cm2 to 1.0 D/cm2 . Using the relationship Y = 𝑒𝑒 −𝐷𝐷𝐷𝐷 where D is the defect density and A is the chip
area, calculate the yield loss of a 16M DRAM wafer due to the increase in the aforementioned defect density
assuming that the defect density is roughly inversely proportional to the defect size to the second power.

The defect density is inversely proportional to the defect size.

That is, the killing defect density D = 0.2 x (0.3/0.18)2 = 0.2 x 2.78 = 0.56.

The yield before contamination is 45.7%

Due to contamination, D = 1 x (0.3/0.18)2 = 2.78

The yield after contamination is 2%.

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An arc discharge, is an electrical breakdown of a gas that produces a prolonged electrical
discharge. The current through a normally nonconductive medium such as air produces a plasma;
the plasma may produce visible light.

Plasma is fourth fundamental states of matter. It contains a significant portion of charged particles –
ions and/or electrons. The presence of these charged particles is what primarily sets plasma apart
from the other fundamental states of matter.

An arc discharge is characterized by a lower voltage than a glow discharge and relies on thermionic
emission of electrons from the electrodes supporting the arc. An archaic term is voltaic arc, as used
in the phrase "voltaic arc lamp
In this method plasma, which is an ionised gas, is used a potential difference
between two electrodes is applied and the gas between ionises. The
electrode (anode) vaporises as electrons are taken from it, for instance, a
carbon electrode is used to produce the carbon nanotubes.

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In the arc-discharge set-up, two graphite rods of 7 and 20 mm in diameters are used as anode and
cathode electrodes, respectively.

The main parameters are the intensity of the arc and the voltage between the electrodes. The voltage
depends on the distance between electrodes, so the distance between the torch and the part is one of the
most relevant parameters. If the distance between the torch and the part increases, it is necessary to
increase the voltage. If the distance is too large, the arc becomes unstable and the energy input drops, so
it is necessary to control the arc distance.

Fullerenes and CNTs are formed by plasma arcing of carbonaceous materials, particularly graphite.
The fullerenes appear in the soot that is formed, while the CNTs are deposited on the opposing electrode,
the cathode.

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Brief into Plasma Arc Discharge Plasma Arc Discharge
• An arc passes from one electrode to the other.
• The electrons are emitted from the first electrode
(anode) due to potential differences.
• Positively charged ions pass to the other
electrode(cathode) and gets deposited to form
nano particle.
• The depth of deposited surface must by only few
layers
• Each particle must be nanosized and
independent.
 Plasma Arc Discharge-Mechanism

A direct current of 50 to 100 A driven by

approximately 20 V creates a high-
temperature discharge between the two
electrodes 2000-3000 °C.

The discharge vaporizes one of the carbon

rods and forms a small
rod-shaped deposit on the other rod.

Producing nanotubes in high yield depends

on the uniformity of the plasma arc and the
temperature of the deposit form on the
carbon electrode
• The carbon arc discharge method, initially used for producing C60 fullerenes, is the most
common and perhaps easiest way to produce carbon nanotubes as it is rather simple to
undertake.
• However, it is a technique that produces a mixture of components and requires separating
nanotubes from the soot and the catalytic metals present in the crude product.
• This method creates nanotubes through arc-vaporization of two carbon rods placed end to
end, separated by approximately 1mm, in an enclosure that is usually filled with inert gas
(helium, argon) at low pressure (between 50 and 700 mbar).
• Recent investigations have shown that it is also possible to create nanotubes with the arc
method in liquid nitrogen.

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Bottom-up approach

The bottom-up approach utilizes physical and chemical processes that function at the nanoscale to integrate main
components into bigger structures.

Sol-gel techniques

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.

The sol-gel method focuses on the growth of chemical compounds in the solution. The sol is changed into some
sort of three- dimensional network in the solvent. The process is then frozen and the sol-gels are transformed to
deformed solid material by the removal of liquid from the air-gel or by evaporation.

One benefit of the process is the ability to manage the size and oneness of the material spread-out.

One main disadvantage of the technique is that the precursors are too pricy with very low gain; low weigh
products and very dangerous to human health.

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 Application of
Sol-Gel
Technique

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• When the liquid from the gel is evaporated at room temperature, the solid gels left are called xerogels. Xerogel is
a solid formed from a gel by drying with unhindered shrinkage. Xerogels usually retain high porosity (15–50%)
and enormous surface area (150–900 m2/g), and very small pore size (1–10 nm).

• When solvent removal occurs under supercritical conditions, the network does not shrink and a highly porous,
low-density material An Aerogel is produced.

• When the liquid from the gel is extracted at supercritical state of liquid, these materials are called Aerogels.
Aerogels are generally monolithic and have low density than xerogels. Xerogels on the other hand are generally
cracked, shrinken or sometimes powdered.

• Cryogels term is used for those materials in which liquid from the gel is extracted at much lower temperature
using vaccum (sublimation phase of solvent).

• Hydrogel: is a network of polymer chains that are water-insoluble, sometimes found as a colloidal gel in which
water is the dispersion medium. Hydrogels are superabsorbent (they can contain over 99% water) natural or
synthetic polymers. Hydrogels also possess a degree of flexibility very similar to natural tissue, due to their
significant water content.

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• The sol-gel process is a chemical method (wet chemical method) for the synthesis of various nanostructures,
especially metal oxide nanoparticles. In this method, the molecular precursor (usually metal alkoxide) is
dissolved in water or alcohol and converted to gel by heating and stirring by hydrolysis/alcoholysis.

• The basis of the sol-gel method is the production of a homogeneous sol from the precursors and its conversion into a
gel. The solvent in the gel is then removed from the gel structure and the remaining gel is dried.

• Since the gel obtained from the hydrolysis/alcoholysis process is wet or damp, it should be dried using appropriate
methods depending on the desired properties and application of the gel.

• After the drying stage, the produced gels are powdered and then calcined. The sol-gel method is a cost-effective
method and due to the low reaction temperature there is good control over the chemical composition of the
products.

• The properties of the dried gel depend significantly on the drying method. In other words, the “removing solvent
method” is selected according to the application in which the gel will be used. By grinding the gel by special mills, it
is possible to achieve nanoparticles.

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Principle of Sol-Gel Method:
(Coating)

Metal alkoxide is dissolved in organic solvent

to form homogeneous solution with the
addition of chelating agents.

Inorganic thin films are prepared by coating

on the substrate, followed by drying, thermal
decomposition, and annealing.

The preparation of thin film via the sol–gel

process has unique properties:
(i) The reaction takes place in solution and
chemical uniformity can be maintained at
the molecular level with their
multidimensional utility.
(ii) heat treatment (annealing) is lower than
the traditional methods.

(iii) Stoichiometric ratio is retained while

modifying the functional properties.
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 (iv) Optimization depends on the concentration of dopant .
The size and morphological properties can be fine-tuned by varying 1. concentration ratio of capping agent 2.
suitable reducing agent and 3. reaction conditions
(v)Generation of an appropriate precursor solution
(vi) Deposition of the solution onto a substrate
(vii) Thermal treatment for their precursor and its conversion into the oxide nanopowder with desired functional
properties with highest purity.

The liquid-phase synthesis can be carried out in two different ways -

1. Aqueous sol–gel chemistry

Inorganic polymerisation reaction

Molecular precursor Metal oxide network

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Reaction Mechanism involved

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(A) Acid catalyzed and (B) based catalyzed hydrolysis of silicon alkoxide.

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 2. Nonaqueous sol–gel chemistry

No water
Molecular precursor +Organic solvent Metal oxide network

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The formation of inorganic networks depends on many critical parameters such as pH, temperature, reaction time,
concentration of reagents, nature of catalyst, aging, and drying.

The preparation of nanocrystalline materials takes place from a solution-based chemical approach: (1) chemical
homogeneity with a high phase purity, (2) narrow particle size distributions, (3) microstructural uniformity, and (4)
finally with their low crystallization and sintering temperature.

The concept of sol–gel process depends in the conversion of the precursors into nanomaterial by removing
unnecessary products before gelation, leading to the formation of an architectural nano-unit gel with a controlled
pore size and with structural properties.

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08-09-2022 51
The key advantages :
• It uses relatively low temperatures (200C).
• It can create very fine powders.
• Uniform particle size distribution
• Good homogeneity
• Concentration of metal in coating can be controlled with ease.
• It produces compositions not possible by solid-state fusion

Drawbacks
• High cost
• Long processing times
.

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 Template-based growth of Nanomaterials
Template synthesis is a versatile method to fabricate aligned nanostructures with desired size, especially the
diameter.

Template synthesis is a method for preparing nanofibers within the pores of a microporous membrane or
other solid. The microporous membrane, or template, is preconfigured to obtain the desired nanofiber morphology.

Template method is not sensitive regarding the preparation conditions, easy to operate and implement, which
controls the structure, morphology, and particle size of nanomaterials through the template material (template).

The template method has three steps: (i) the template is prepared. (ii) some common synthetic approach such as
hydrothermal method, precipitation, and sol-gel method is used to synthesize the target production under the
function of template (iii)template removal.

The choice of template for nanomaterial preparation is critical. Templates usually can be grouped in two major
categories: natural substances (biological molecules, cells and tissues) and synthetic materials (surface active
agents, porous materials and nanoparticles).

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Template-based growth of Nanomaterials
 Template Method Types and Examples

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Templates have two groups (hard template and soft template) based on the difference in the template structure.

Hard template: A rigid material, whose stable structure directly determines the size and morphology of sample
particle.

Choices are polymer microspheres, porous membrane, plastic foam, ion exchange resin, carbon fiber, and porous
anodic aluminum oxide (AAO) . Because of their special structures and effect on particle size restriction, they play an
important role in many fields.

Soft template: The soft template does not have a fixed rigid structure. In the synthesis of nanoparticles, an aggregate
with some certain structural features is formed by means of the intermolecular or intramolecular interaction force
(hydrogen bonding, chemical bonding, and static electricity).

Soft template can be a surfactant, polymer and biopolymer

Inorganic species are deposited on the surface or the interior of these templates by means of electrochemical method,
precipitation, and other synthetic methods, forming particles with certain shape and size.

The soft template has broad prospects for development in the synthesis of nanomaterials because of its advantages
such as its good repeatability, simplicity of the process, and no requirement for the removal of template.

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Colloidal-Templating Method
• By coupling inorganic templates with polymers, the advantages from soft-templating and hard-templating methods
can be said to emerge as the “colloidal-templating” method.
• Colloidal templates are composed of an inorganic NP core tethered with flexible polymer tails. In view of the
topology of colloidal templates, they are extremely like polymer micelles, which have been used in the soft-
templating method to grow mesoporous materials.
• Polymers as soft templates are responsible for coordinating inorganic metal ions to self-assemble into
nanostructures, similar to that of the soft-templating method.
• The inorganic NPs, on the other hand, serve as hard templates to offer thermal stability and nanoconfinement to
crystallize the framework under high-temperature annealing. Colloidal templates similar to the surfactants/block
copolymers can form periodically ordered nanostructures in the course of sol-gel to fabricate mesoporous
materials.

Mesoporous graphene using oleic acid (OA)-capped Fe3O4 nanocrystals

i. The self-assembled OA-capped Fe3O4 first formed the ordered 3D Fe3O4 nanocrystal super lattices.
ii. The super lattices were further calcined at 1,000°C under argon.
iii. As inorganic components, Fe3O4 nanocrystals are thermally very stable with respect to annealing, while OA can
be carbonized to form continuous carbon frameworks.
iv. The removal of Fe3O4 nanocrystals using HCl, the ordered mesoporous carbon was derived and then transformed
into highly ordered mesoporous graphene with fcc symmetric mesoporosity.
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Template Method Types and Examples
 Thin film deposition
Thin film deposition is the process of creating and
depositing thin film coatings onto a substrate
material. These coatings can be made of many different
materials, from metals to oxides to compounds.

Thin film coatings also have many different

characteristics to alter or improve some element of the
substrate performance e.g some are transparent; some
are very durable and scratch-resistant; and some increase
or decrease the conductivity of electricity or transmission
of signals.

Thin film deposition is an important manufacturing step in the

production of many opto-electronic, solid state and medical
devices and products, including consumer electronics,
semiconductor lasers, fiber lasers, LED displays, optical filters,
compound semiconductors, precision optics, microscopy &
microanalysis sample slides, and medical implants.
 WHAT IS PHYSICAL VAPOR DEPOSITION (PVD)?
Physical vapor deposition (PVD) describes a group of thin film deposition
techniques that involve physical changes only, i.e. vaporizing a solid material in a
vacuum, then depositing that material onto a substrate.

Film created in this manner are highly durable, and resistant to scratching and
corrosion. PVD is useful in the production of devices ranging from solar cells to
eyeglasses to semiconductors.

The process involved four steps:

1.Evaporation
2. Transportation
3.Reaction
4.Deposition

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 µm
µm

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Sputtering
A special case of physical vapour deposition

In PVD thermal excitation is required but when the thermal excitation may damage the material then a
special case is used called sputtering.

• Here the material to deposit is scooped

from the surface literally by atoms by
atoms by shooting some tiny projectiles.
3
• The scooped out atoms will find their way
to get deposited on colder surface.
• Very fast process. PVD about 1hr, while its
5
takes few seconds.
• Cathodic black zone and Anodic black 6 2
zone thickness are the deciding factor for 7
4
process efficiency.
1

10-6 mbar
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Mechanism of Sputtering
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 Radio Frequency

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Types of PVD (Evaporation and Magnetron)
EVAPORATION

There are multiple types of evaporative deposition:

E-beam evaporation (electron beam): In this process, a highly-charged electron beam evaporates the target material.
The evaporated material is then deposited onto the substrate, and the atoms formed create the thin film. This process is often
used for optical thin films such as solar panels, glasses and architectural glass.

Ion assisted deposition (IAD): This process produces films with less scatter than typical evaporation.

Thermal evaporation: In this simpler form of PVD, a resistive heat source heats the target material until vapor
pressure is produced. The evaporated material then coats the substrate, forming the thin film. It is used to deposit metals
such as silver and aluminum for solar cells and thin film transistors.

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MAGNETRON SPUTTERING

Magnetron sputtering is a versatile, plasma-based coating technique. In this process, magnetically confined
plasma is created near the surface of the target material.

Ions from that plasma collide with the target material, and the atoms ejected from those collisions are what
are “sputtered”, or deposited onto the substrate to create the thin film.

It is often used for metallic or insulating coatings for optical and electrical purposes.

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ION BEAM SPUTTERING

• Ion beam sputtering (IBS) is also called ion beam deposition (IBD).

• This process uses an ion source to sputter the target material—either metallic or dielectric—onto the
substrate, forming the thin film.

• Thin films created through ion beam sputtering are of a high quality, and have very precise thickness due to
the monoenergetic ion beam used. This process is often used to create coatings for precision optics and
semiconductors, where the utmost precision is required.

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PULSED LASER DEPOSITION (PLD)

• Pulsed laser deposition is a type of evaporation process that uses laser pulses to evaporate the target material.

• This produces a plume of plasma that then deposits onto the substrate, forming the thin film.

• While optimizing this process can require more time and effort than other methods, due to the many variables at play,
its benefits include high deposition rates and a streamlined process, as well as no filaments for easier maintenance.

• The benefits of PVD are numerous, and include the creation of a hard coating that is resistant to corrosion
and scratching.

• PVD also creates thin films that can tolerate high temperatures.

• Potential drawbacks of PVD include cost, as these methods may require a larger investment than other thin
film deposition processes.

• The cost can also vary among PVD methods themselves. For example, evaporation is a lower-cost type of
PVD, while ion beam sputtering is a rather costly option. Magnetron sputtering is more expensive than
other methods, but has better scalability.
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• The benefits of PVD are numerous, and include the creation of a hard coating that is
resistant to corrosion and scratching.
• PVD also creates thin films that can tolerate high temperatures.
• Potential drawbacks of PVD include cost, as these methods may require a larger
investment than other thin film deposition processes.
• The cost can also vary among PVD methods themselves. For example, evaporation is a
lower-cost type of PVD, while ion beam sputtering is a rather costly option. Magnetron
sputtering is more expensive than other methods.

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CVD: Chemical Vapour Deposition
Chemical vapor deposition (CVD) describes a group of thin film deposition techniques in which a
substrate is placed into a vacuum chamber, two chemical precursors are heated, which causes them to
vaporize. When they meet on the substrate surface, a chemical reaction occurs to form a high-
performance thin film coating.

The film has different composition than the precursor

CVD is useful in creating coatings for a wide variety of applications including medical devices,
automotive components and silicon wafers

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Films are formed by two steps of reaction

1. Homogeneous reaction (reaction in gas phase)

1. Heterogeneous reaction (reaction on surface of substrate)

Homogeneous reaction

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The main steps that occur in a typical CVD process can be summarized as –

(1) transport of reacting gaseous species to the surface of a substrate,

(2) Gas phase reaction
(3) Mass transfer of growth precursor to growth surface
(4) Adsorption of the species on that surface,
(5) Heterogeneous surface reaction catalyzed by the surface of the substrate,
(6) Surface diffusion (migration) of the species to growth sites,
(7) Nucleation and growth of the film on the substrate,
(8) Desorption of gaseous reaction products and transport of reaction products away from the
surface.

The main CVD process parameters—such as temperature, pressure, reactant gas concentration,
and total gas flow—require accurate control and monitoring.

The chemical reactions include pyrolysis, oxidation, reduction, hydrolysis, polymerization,

halide disproportionation or a combination of these. The actual chemical reactions determine
the operating temperature range.

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Benefits of CVD methods include the ability to use these processes on a wide variety of substrates, as well as the
ability to coat intricate or complex topographies. Thin films created through CVD also typically maintain their
bonds well in high-stress environments.

Some drawbacks may include limitations in size, which is dependent on the size of the vacuum chamber, as well as
that most methods typically require a higher temperature to drive the chemical reactions. It can also be difficult to
mask the surface of the coating.

There are a variety of CVD methods.

ATMOSPHERIC PRESSURE CVD
In this process, which takes place at normal, or atmospheric, pressure and a lower temperature than other methods,
the substrate is exposed to at least one volatile precursor. The precursor(s) react on the surface of the substrate to
deposit the thin film. It can be used to deposit doped and undoped oxides, and the deposition is fairly quick. Thin
films produced by this method are low-density and have moderate coverage.

LOW-PRESSURE CVD
In low-pressure CVD, heat is used to break down a precursor gas inside the chamber where the reaction will take
place. This causes the reactive gas to react with the substrate when it is injected into the chamber, and this reaction
creates the thin film coating. Low-pressure CVD is commonly used for the deposition of materials including
polysilicon and silicon nitride, and can be useful for batch processes. Coatings created with this process are more
uniform and feature fewer defects, but the process requires a higher temperature which can limit the materials
available to use.
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ULTRAHIGH VACUUM CVD
In ultrahigh vacuum CVD, the substrate is exposed to precursor gases in an ultrahigh vacuum (<10^{-6} Pa).
These precursors then react and deposit onto the substrate, forming the thin film.

ATOMIC LAYER DEPOSITION

While atomic layer deposition falls under the CVD umbrella, it differs in that precursor materials are kept
separate during the reaction. In this process, the reaction occurs due to sequential pulsing of precursor
vapors—one atomic layer is formed during each pulse. Pulses are repeated until the thin film reaches its
desired thickness. Benefits of atomic layer deposition include high quality defect-free coating, as well as
improved thickness uniformity.

PLASMA-ENHANCED CVD
Plasma-enhanced CVD is a lower-temperature alternative to standard CVD, and is often used in the production of
electronic devices. One common application for PE-CVD coatings is to protect these devices from corrosion. It can create,
for example, high-quality silicon dioxide (SiO2) film at 300°C to 350°C as opposed to the temperature range of 650°C to
850°C required by standard CVD to create similar films. In plasma-enhanced CVD, a pair of reactive gases are excited to
create a plasma. This causes a chemical reaction that results in the thin film being deposited onto the substrate.

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Epitaxy refers to the deposition of an overlayer on a crystalline substrate, where the overlayer is in registry
with the substrate.
96
• The principle underlying MBE growth is relatively simple: it consists essentially of atoms or clusters of
atoms, which are produced by heating up a solid source. They then migrate in an UHV environment and
impinge on a hot substrate surface, where they can diffuse and eventually incorporate into the growing film.
• Molecular beam epitaxy (MBE) is a process in which a thin single crystal layer is deposited on a single
crystal substrate using atomic or molecular beams generated in Knudsen cells contained in an ultra-high
vacuum chamber. MBE growth takes place in ultra-high vacuum (UHV) environment (10-8 to 10-10 Torr).

• Typical MBE experimental setup consists of two or more Knudsen

effusion cells (K-cells), located at the bottom of a UHV chamber and
aligned towards the center of the chamber where a sample holder with a
substrate is located.

• Each individual K-cell contains a different element in ultra pure solid

form (i.e. elemental 99.999% Selinum, Bismuth, etc.) which can be used
in the thin film synthesis. Each individual K-cell contains a different
element in ultra pure solid form (i.e. elemental 99.999% Selinum,
Bismuth, etc.) which can be used in the thin film synthesis.
• The process of MBE growth starts by heating the K-cells to appropriate
temperatures until the elements in each cell reach a sublimation point.
Then, the shutters are opened and physical vapor from each K-cell
diffuses though the chamber until it reaches the substrate where it gets
deposited, and the thin film gets formed. 97
The final composition and stoichiometry of the film will depend on the temperature and surface atomic
structure of the substrate, as well as the flux ratios of individual components reaching the substrate

To characterize the samples in-situ during growth, we use reflection high-energy electron diffraction
(RHEED). Electrons emitted from the RHEED gun (Figure 1) incident at a very low angle with respect to
the sample surface are diffracted, and the resulting diffraction pattern is observed on the screen. This
pattern can reveal: (1) quality of the film surface, and (2) film thickness down to a single monolayer.

Molecular Beam Epitaxy (MBE) MBE can be considered as a precise form of PVD.

Molecular beam epitaxy provides several important capabilities favorable for the growth of high-
purity, epitaxial thin-film metals. The UHV environment ensures high purity and RHEED capability,
which allows in situ preparation of atomically clean substrates with specific surface reconstruction

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 Epitaxial growth: Due to interaction of molecular or
atomic beams on a surface of a heated crystalline
substrate.
 The solid source material sublimes.
 It provides an angular distribution of atoms or
molecules in a beam.
 The substrate is heated to necessary
temperature
 The gaseous element then condense on the
wafer where they may react with each other.

 Atoms on a clean surface are free to move until

finding correct position in the crystal lattice to
bond.

 Growth occurs at the step edges formed: More

binding force at an edge.

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Advantages of Molecular Beam Epitaxy Over CVD Process:
• MBE is low temperature process which is advantageous for VLSI technology.

• While preparing thin layers using MBE process, autodoping and autodiffusion both are minimized.

• The MBE process can be used for generating complicated doping profiles as it regulates the amount of dopant.

• As MBE process is based on the evaporation of silicon and the dopants, hence no chemical reactions are
involved in it.

• For MBE process safety precautions are not required extensively as compared to those required in CVD
process.

Disadvantages of MBE Process:

• For overall perfect and pure film, it is necessary to maintain a very low pressure of the order of 10-
10 T which is slightly difficult.
orr

• This process is very expensive as compared to CVD process.

• The growth rate in MBE process is 0.01 – 0.3 μm/min which is very small compared to the growth rate of
1 µm/min in CVD process.

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