Dr. G.

Murugesan
 NANOMATERIALS SYNTHESIS & FABRICATION
Nanomaterials are synthesized by two major approaches
• Top down approach
• Bottom up approach

TOP DOWN APPROACH

In this process, bulk materials are broken into nano-
sized particles. In this approach there is no control
over the size and the morphology of particles. There
are many methods in top-down approach to get nano-
sized particles from bulk materials, some of the
common methods are

 Mechanical milling/Ball milling

 Lithographic techniques – Photolithographic & Electron beam lithography

BOTTOM UP APPROACH

This refers to the building of materials from the

bottom, i.e., atom by atom, molecule by molecule or
cluster by cluster. Some methods of bottom up
process are
 Sol-Gel method
 Chemical/Physical Vapour deposition
 Spray pyrolysis
Nanomaterials are fabricated by various process like

 Mechanical milling/Ball milling

 Chemical/Physical vapour deposition

 Photolithography

 Electron beam lithography

 Molecular beam epitaxy

 Solvothermal synthesis

 Photochemical synthesis

 Green synthesis

 Spray pyrolysis etc…

1
 NANOMATERIALS SYNTHESIS & FABRICATION

MECHANICAL MILLING

It’s a typical top-down method for nanoparticle preparation. The basic working principle of ball
milling method is making use of small hard balls to rotate inside a container and then it is made to
fall on a solid with high force to crush the solid into nanoparticles.

CONSTRUCTION

 Ball mill consists of hollow cylinder.

 The length of cylinder is greater than its diameter.
 The hollow cylinder rotates on its longitudinal axis fixed on the metallic frame.
 The cylinder consists of different sized spherical balls depending on the capacity
of the cylinder.

WORKING

• Hardened steel or tungsten balls are put in a container along with the powder of
desired material.

• The container is closed with tight lids.

• The container is rotated around the central axis.

•
• The material is forced to press against the spherical balls and wall of the container.

• The milling ball imparts energy on collision and produce smaller grain size of
nanoparticles.
2
 NANOMATERIALS SYNTHESIS & FABRICATION
TYPES OF BALLS USED

• Chrome steel
• Stainless steel
• Zirconia
• Tungsten carbide
• Ceramic
• Rubber
The main advantage of this method is few milligrams to several kilograms of
nanoparticles can be prepared in a short period of time. This technique is operated in
large scales.

APPLICATIONS

Some important applications of Ball milling technique is,

• It is used for elemental preparation of metal oxide nanocrystals like cobalt,
chromium, iron, aluminium ferrites etc.
• A variety of intermetallic compounds of nickel and aluminium can be formed.
• This method is useful to produce new types of building materials, fire proof
materials, glass ceramics etc.

CHEMICAL VAPOUR DEPOSITION

It is a vacuum deposition technique used to produce high quality, nanoparticles

which is often used in semiconductor industry to produce thin films.
APPARATUS
A CVD apparatus will consist of several basic components:

• Gas delivery system – For the supply of precursors to the reactor chamber.
• Reactor chamber – Chamber within which deposition takes place.
• Substrate loading mechanism – A system for introducing and removing substrates.
• Heat source – To heat substrate that is required to get the precursors to react/decompose.
• Vacuum system – A system for removal of all other gaseous species other than
those required for the reaction/deposition.
• Exhaust system – System for removal of volatile by-products from the reaction
chamber.
• Process control equipment – Gauges, controls etc to monitor process parameters
such as pressure, temperature and time. 3
 NANOMATERIALS SYNTHESIS & FABRICATION

WORKING

The substrate is exposed to one or more volatile precursors, which react or decompose
on the surface of the substrate to produce the desired coating. The sequential steps are
followed inorder to deposit the desired material on the surface of the substrate,

 The substrate to be coated is placed inside the vacuum chamber with the help of
substrate loading mechanism.
 The precursors are taken in gaseous form and sent inside the vacuum chamber
through gas delivery system.
 Adsorption and diffusion of precursors takes place on the surface of the substrate.
 Precursors react on the surface of substrate and gets deposited.
 Desorption of by-products takes place.
 The by-products are removed from the vacuum chamber using exhaust system.

APPLICATIONS
CVD is extremely useful in depositing extremely thin layers of material.

Coatings for a variety of applications like

 Corrosion resistance  Optoelectronic devices

 High temperature protection  Passive layers

 Integrated circuits

 Sensors

4
 NANOMATERIALS SYNTHESIS & FABRICATION
LITHOGRAPHIC TECHNIQUES
The term “LITHOGRAPHY” originated from the Greek word LITHOS
meaning stone and GRAPHEIN meaning to write, is a method of printing a desired
pattern on the surface of stone or smooth metallic surface.

The two major lithographic techniques which are used for printing a pattern on the
surface of substrate is,

 Photolithography
 Electron beam lithography

PHOTOLITHOGRAPHY

It is also called as optical lithography or UV lithography which uses light to transfer a

geometric pattern from a photomask (optical mask) to the surface of the substrate.

COMPONENTS

The key components of photolithography are,

 Light source
UV light is used as source

 Photomask
It is a transparent plate (made of glass or quartz) that
has a thin metal pattern. The mask is transparent to
light everywhere except the metal part of the mask.
This metal blocks the light on the substrate resulting
in the formation of pattern on the surface of the
substrate. Photomask size depends on the size of the
substrate.
 Optical lens
is used to converge the light

 Substrate coated with photoresist

Photoresist polymer is coated on the surface of the
substrate

Positive photoresist – Exposed area is more soluble

Negative photoresist – Exposed area is less soluble

5
 NANOMATERIALS SYNTHESIS & FABRICATION
PROCESS

The following process is involved in photolithographic process,

 Initially a thin layer of photoresist polymer layer is coated on the surface of

substrate by spin coating technique.

 Spin coating is done by dropping few ml of liquid polymer on the surface of the
substrate and substrate is rotated at high speed to spread the polymer solution
evenly.

 Wafer and photoresist polymer is heated around 100 to 200 oC.

 Depending on the desired process, the thickness of photoresist is varied from 10-20
micrometre, substrate thickness is around 200-600 micrometre.

 UV light is illuminated on the photomask which transmit the light in the transparent
region and the metal region blocks the light.

 The metal pattern cast shadow on the surface of the substrate.

 At developer stage, the exposed substrate is dissolved in the developer solution.

 The exposed region is more soluble for positive photoresist and unexposed resist
remains on the surface of the substrate.

 The unexposed region is more soluble for negative photoresist and exposed resist
remains on the surface of the substrate.

APPLICATIONS

 IC patterning process
 Fabrication of microcircuits
 Manufacturing computer chips
 MEMS and sensor devices
PHOTOLITHOGRAPHY PROCESS

6
 NANOMATERIALS SYNTHESIS & FABRICATION

ELECTRON BEAM LITHOGRAPHY

This technique uses electrons to make a pattern on the surface of a substrate.

COMPONENTS
1
The key components for Electron beam lithography are,
1. Electron source 2
Electron beam (negatively charged particles is 3
generated in an electron beam gun. Electron beam
gun provides high velocity electrons over a very
small spot size.
4
2. Magnetic lens system
Magnetic lens are used to converge the electron CATHODE
beams. GRID

3. Beam deflectors
Magnetic deflection coil is used to make electron ANODE
beam circular and focus electron beam at a point.

4. Substrate (coated with electron resist) MAGNETIC

LENS
Substrate is coated with a thin layer of electron
resist using spin coating technique.
DEFLECTION
COILS
PROCESS
VACUUM
The following process is involved in electron beam CHAMBER
lithography ELECTRON
RESIST
LAYER
 Electron beam is generated in an electron beam
gun. SUBSTRATE

 The electrons are accelerated while passing

through the anode by applying high voltage at
anode.

 Magnetic deflection coils are used to make electron beam circular and focus the
electron beam at a particular point.

 The high energy electrons are focussed on the surface of the substrate.

7
 NANOMATERIALS SYNTHESIS & FABRICATION

 Electron resist is coated on the surface of the substrate by spin coating.

 Highly focussed electron beam is focussed on the sample to write out a pattern
designed with suitable Computer – Aided Design (CAD) tools.

 The electron beam induces a change in the molecular structure and solubility of the
resist film.

 Following the exposure to the electron beam, the resist is developed in a suitable
solvent to selectively dissolve either the exposed or unexposed areas of the resist.

APPLICATIONS

 It is used in cyro-electric device fabrication.

 Opto-electronic device fabrication.

 Quantum structures.

 Optical devices fabrication.

ADVANTAGES
 High resolution

 Print complex patterns directly on wafers (no mask required).

 Flexible technique
ELECTRON BEAM LITHOGRAPHY

8
 NANOMATERIALS SYNTHESIS & FABRICATION
MOLECULAR BEAM EPITAXY
Molecular beam epitaxy is an epitaxy method for thin film deposition of single
crystals. It is an evaporation process performed in an ultra-high vacuum for the
deposition of compounds of extreme regularity of layer thickness and composition from
well controlled deposition rates.
Molecular beam epitaxy (MBE) is an atomic layer by atomic layer crystal growth
technique based on reaction of molecular or atomic beams with a heated crystalline
substrate performed in an ultra high vacuum environment. The term “molecular beam”
described the unidirectional kinematic flow of atoms or molecules with no collisions
among them. The term “epitaxy” is composed of the Greek words “epi” meaning
“upon” and “taxis” meaning arrangement or order. Expitaxy refers to ordered growth of
one crystalline layer on another crystalline layer with same crystal arrangement.

COMPONENTS
 Substrate with heater
Substrate is placed on heater and heated at high temperature.

 Effusion cells
The precursor to be deposited on the surface of the substrate is taken and
vapourised by the heater coils. The required material is released in controlled
manner to be deposited on the substrate.

 Vacuum chamber
The whole process is carried out in high vacuum environment inorder to
protect the substrate from impurity interactions.

 RHEED gun
Reflection high energy electron diffraction (RHEED) is used to characterize
the surface of crystalline surfaces. It gathers information from the surface
of the substrate.

9
 NANOMATERIALS SYNTHESIS & FABRICATION
PROCESS

 Initially substrate (semiconductor material like silicon, germanium or gallium

arsenide) is heated at higher temperatures around 500-600oC.

 For example, if we want to form a Gallium arsenide coating, gallium and arsenic
are taken in ultra pure form and heated in separate effusion cell until they begin to
slowly sublime (a solid substance change directly into vapour when heated,
typically forming a solid deposit again on cooling).

 The gaseous elements then condense on the wafer, where they may react with each
other. In this example of gallium and arsenic, gallium arsenide single crystals are
formed.

 Controlling the temperature of the source will control the rate of material impinging
(striking) on the substrate surface and the temperature of the substrate will affect the
rate of hoping or desorption.

 The term “beam” means that evaporated atoms do not interact with each other or
vacuum chamber gases until they reach the wafer, due to the long mean free paths of
the atoms.

APPLICATIONS

It is used for fabrication of

 Diodes

 MOSFETs (Transistors)

 Lasers to read Optical discs such as CDs and DVDs

 Microwave devices
Growth direction

Crystalline layer
Substrate atoms
10
 NANOMATERIALS SYNTHESIS & FABRICATION
SPRAY PYROLYSIS

In spray pyrolysis, precursor solution is atomized through a nozzle. The

nozzle converts the solution into small droplets, known as aerosols. These aerosols
are allowed to incident onto the preheated substrates. The pyrolytic decomposition of
the aerosols depends on substrate temperature. The formation of thin films with
desired properties are possible only at optimum substrate temperature.

COMPONENTS

 Atomizer nozzle
 Spray solution unit
 Atomizer control mechanism
 Substrate placed on a heater
 Temperature controller

PROCESS

1) In the first step, an aqueous precursor solution is converted into aerosols by spray
nozzle.

2) Solvent evaporation takes place in the second step.

11
 NANOMATERIALS SYNTHESIS & FABRICATION

3) In this step, vaporization of the solvent leads to precipitate formation as the

droplets / aerosol approaches the substrate.

4) Pyrolysis of the precipitate occurs in succession before the precipitate reaches the
substrate.

5) In step 5, when the precipitate reaches the substrate, nucleation and growth of
metal oxide thin films on the substrate surface takes place.

6) Finally, growth of the nuclei leads to the formation of continuous thin layer of
metal oxide.

APPLICATIONS
It is used for fabrication of

 Solar cells

 Sensors

 Solid oxide fuel cells

12
 NANOMATERIALS SYNTHESIS & FABRICATION
SOLVOTHERMAL SYNTHESIS

Solvothermal synthesis is a method for preparing a variety of materials such as

metals, semiconductors, ceramics, and polymers. The process involves the use of a
solvent under moderate to high pressure (typically between 1 atm and 10,000 atm) and
temperature (typically between 100 °C and 1000 °C) that facilitates the interaction of
precursors during synthesis. If water is used as the solvent, the method is called
“hydrothermal synthesis.” The synthesis under hydrothermal conditions is usually
performed below the supercritical temperature of water (374 °C). The process can be
used to prepare many geometries including thin films, bulk powders, single crystals, and
nanocrystals. In addition, the morphology (sphere (3D), rod (2D), or wire (1D)) of the
crystals formed is controlled by manipulating the solvent supersaturation, chemical of
interest concentration, and kinetic control.

COMPONENTS

1. Autoclave

2. Precursor solution

3. Teflon liner

4. Stainless steel lid

5. Spring

13
 NANOMATERIALS SYNTHESIS & FABRICATION

PROCESS

 The reactants are taken in a closed vessel called Autoclave.

 An autoclave is usually constructed from thick stainless steel to withstand high

pressure and is fitted with a safety wall. It has a liner with Teflon material (inert
material).

 Autoclave is heated which results in increase of pressure inside the vessel which
ignites the reaction.

APPLICATIONS
 This method can be used to prepare thermodynamically stable and metastable
states including novel materials that cannot be easily formed from other synthetic
routes.

 The desired morphology of the product (spheres, plates, cubes or rods) are
controlled by adjusting various parameters like reaction temperature, reaction
time, solvent type, precursor type etc.

14
 NANOMATERIALS SYNTHESIS & FABRICATION
GREEN SYNTHESIS
Green synthesis- an emerging field of nanoparticle synthesis which provides
economic and environmental benefits as an alternative to chemical and physical
methods. Green synthesis is a eco-friendly process which adapt mild reaction
conditions and nontoxic precursors in the development of nanoparticles.

SYNTHESIS PROCESS

Just a example synthesis process for silver nitrate nanoparticles is given below,

 Leaves of desired plant is taken, washed and cut into small pieces.

 The small pieces of leaves are stirred in deionized water using magnetic stirrer.

 Temperature in the magnetic stirrer is kept around 80-90oC.

 The green extract in Burette is filtered and used as reducing and capping agent for
the reaction.

 10mg of silver nitrate is mixed with deionized water at a temperature around 60-
70oC.

 The leaf extract is added dropwise until the desired product is obtained.

15
 NANOMATERIALS SYNTHESIS & FABRICATION
PHOTOCHEMICAL SYNTHESIS
Photochemical reactions takes place by absorption of the visible and UV
radiations. The branch of chemistry which deals with the study of photochemical
reactions is called photochemistry. The presence of light is the primary requirement
for reactions to take place. Photochemical activation is highly selective, the absorbed
photon excites a particular atom or group of atoms which become site for the reaction.

SYNTHESIS PROCESS

 The precursor solution is taken in a test

tube.

 Photoinitiator solution is added to ignite the

reaction when exposed to UV light.

 UV light is exposed on the tube, the

reactions starts when the light is being
absorbed by the photoinitiators.

 Photochemical reactions occurs which results in the formation of nanoparticles.

Photochemical synthesis of Cadmium sulphate

16