28-Apr-26

L-T-P-C
3-0-0-3

222EME017
Nanomaterials for Energy Applications
Module - V
Synthesis and preparation of Nano-materials

Prepared by:
Dr. Rejeesh C R, Professor,
Dept. of Mechanical Engineering
Federal Institute of Science and Technology
[Link]

Course Outcomes
After successful completion of this course, students will be able to

CO No: DESCRIPTION

CO 1 To understand the semiconductor physics behind the nanomaterials.

CO 2 To explain the application of nanomaterials for energy applications.

CO 3 To illustrate the use of nano-materials in fuel cell applications.

CO 4 To explain the Synthesis and preparation of nano-materials.

CO 5 To summarize the concepts of nano-materials for solar cells.

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Nanomaterials
➢ Nanomaterial - A single unit, sized between 1-100nm

➢ Eg: metal nanoparticles, quantum dots (QDs),

carbon nanotubes (CNTs), graphene, and their
composites.

➢ It possess unique physiochemical properties like

ultrasmall size, large surface area, and the ability to
target specific actions which arise from their
nanoscale dimensions.

➢ Nanomaterials can occur naturally, created as the

by-products of combustion reactions, or be produced
purposefully to perform a specialized function.

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Synthesis of Nanomaterials
➢ Nanomaterials/nanoparticles are prepared through diverse range of synthesis
approaches like lithographic techniques, ball milling, etching, and sputtering
➢ Synthesis/Fabrication of nanomaterials with tailored properties involve the
control of size, shape, structure, composition and purity of their constituents
➢ Hence the nanomaterial properties can be tuned as desired via precisely
controlling the size, shape, synthesis conditions, and appropriate
functionalization.

Approaches for the synthesis of nanomaterials

Fabrication of nanomaterials include nanostructured surface,
nanoparticles and nanoporous materials

Nanoparticles are typically synthesized from a

top-down or bottom-up approach

Top-down approach
Slicing of a bulk material to get nano sized particles

Bottom-up approach
Build up materials atom by atom
(in which nanoparticles are grown from simpler molecules)

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Synthesis of Nanomaterials
There are several processes to create nanomaterials. Two main approaches are used in nanotechnology.
Top-down approach
- Top-down approach refers to slicing or successive cutting of a bulk material to get nanosized particle.
- Processes:- Ball milling, Photolithography, Etching, Sputtering
- However, it’s synthesis is too expensive (and not industrially scalable) to arrange such small units into
their desired positions.
- The biggest problem with top-down approach is the imperfection of the surface structure.
- Conventional top-down techniques such as lithography can cause significant crystallographic damage to
the processed patterns and additional defects may be introduced even during the etching steps.
Bottom-up approach
- Bottom-up approach refers to the buildup of a material from the bottom: atom by atom, molecule by
molecule or cluster by cluster.
- Processes:- Chemical precipitation, Sol-gel, Solvothermal, Hydrothermal.
- Materials chemists are largely focused on “bottom-up” techniques that afford the self-assembly of
nanoscale species.

Synthesis of Nanomaterials

There are two approaches for

synthesis of nanomaterials and the
fabrication of nanostructures.
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Top-down approach
• Top down approach refers to slicing or successive cutting of a bulk material to get
nanosized particle.
• In Top-down techniques, the starting material is solid state.
Mechanical methods:-
➢ Cutting
➢ Etching
➢ Grinding
➢ Ball milling
Lithographic techniques:-
➢ Photo Lithography
➢ Electron Beam Lithography
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Solid state synthesis

➢ The solid-state process is the more common and widely used method for production of
micron-sized particles.

➢ In solid state synthesis of nanoparticles generally heat treatment followed by milling

is carried out to get an average particle size of 100nm or less.

➢ Mechanical milling is one of the most preferred and earliest techniques to produce
metallic microcrystalline powder. People claims to get a nanoparticle of very small
size of up to 30nm particle size by using media milling of very small size of 200 micro
meters.

➢ There are other commonly preferred milling methods used by different researchers
includes dry milling and ball milling techniques.

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Mechanical Milling

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Electrospinning

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Lithography
A useful tool for developing nanoarchitectures using a focused beam of light or electrons

Masked lithography
In masked nanolithography, nano- patterns are transferred over a large
surface area using a specific mask or template.
Includes photolithography, nano-imprint lithography & soft lithography

Mask less lithography

In mask less lithography, arbitrary nanopattern writing is
carried out without the involvement of a mask
3D freeform micro-nano- fabrication can be achieved via
ion implantation with a focused ion beam in combination
with wet chemical etching
Includes scanning probe lithography, focused ion beam
lithography, and electron beam lithography
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Bottom-up approach
• In this starting material is gaseous state or liquid state.
Physical techniques-
➢ Physical Vapor Deposition (PVD): involves condensation of vapor phase species
➢ Evaporation (Thermal , e-beam)
➢ Sputtering - Plasma Arcing
➢ Laser ablation
Chemical techniques-
➢ CVD: Deposition of vapor phase of reaction species -PECVD(RF-PECVD,MPECVD)
➢ Self-assembled Monolayer : Electrolytic deposition, Sol-gel method, Microemulsion
route, pyrolysis.

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Sputtering

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Laser Ablation
• Involves nanoparticle generation using a powerful laser beam that hits the target
material
• Source material or precursor vaporizes
due to the high energy of the laser
irradiation, resulting in nanoparticle
formation
• E.g., metal nanoparticles, carbon
nanomaterials, oxide composites, and
ceramics
• Utilizing laser ablation for the
generation of noble metal nanoparticles
can be considered as a green technique,
as there is no need for stabilizing agents
or other chemicals.
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Chemical techniques used for Nanoparticle Synthesis

➢ Nowadays, the attention of many scientists is focused on the development of new methods
for synthesis and stabilization of nanoparticles.

➢ Moreover, special attention is paid to monodispersed and stable particles formation.

Different metals, metal oxides, sulfides, polymers, core-shell and composite nanoparticles
can be prepared using a number of synthetic techniques, which are broadly classified into
two categories, namely, physical methods and chemical methods.

i. Chemical vapor deposition vapor-phase synthesis:

ii. Hydrothermal synthesis

Chemical Techniques
iii. Sol-gel technique

iv. Microemulsion technique

Chemical vapor deposition

➢ Chemical vapor decomposition is a chemical process used to produce high-purity,
high-performance solid materials.

➢ The process is often used in the semiconductor industry to produce thin films.

➢ In a typical CVD process, 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.

➢ Frequently, volatile by-products are also produced, which are removed by gas
flow through the reaction chamber

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Chemical vapor deposition

a Simplified scheme of a CVD

reactor for CNTs synthesys;
b base-growth model of CNT
growth mechanism;
c tip-growth model of CNT growth
mechanism

Schematic representation of chemical vapor deposition (CVD) process

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Steps involved in CVD

Chemical Vapor Deposition (CVD) is a process used to produce high-quality, high-performance solid
materials, usually thin films or coatings, by reacting gaseous precursors within a vacuum chamber.

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Steps involved in CVD

The core steps involve delivering precursors to the chamber, transporting them to the substrate, surface
reaction/decomposition, and removing byproducts. These steps occur under controlled conditions, often at
high temperatures within specialized equipment to ensure the formation of uniform and pure thin films. The
primary steps involved are:
➢ Precursor Gas Delivery and Transport:
Reactant gases (often diluted in carrier gases like argon or nitrogen) are transported into the reactor.
➢ Mass Transport to Substrate:
The reactants diffuse through a boundary layer to reach the heated surface of the substrate.
➢ Adsorption and Surface Reaction:
Gaseous reactants are adsorbed onto the heated substrate surface, where they undergo decomposition and
heterogeneous chemical reactions, forming a thin solid film.
➢ Desorption of Byproducts:
Byproducts from the chemical reaction are desorbed from the substrate surface.
➢ Removal of Waste Gases:
The gaseous byproducts and unreacted species are evacuated (exhausted) from the reactor chamber.
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Vapor-phase synthesis
➢ In vapor-phase synthesis of nanoparticles, the formation of nanoparticles takes
place in gas phase.

➢ In this synthesis technique the condensation of atoms and molecules is carried

out.

➢ The vapor phase synthesis is not new and many multinational companies have
been using flame reactors for decades for producing large quantities of
nanoparticles.

➢ The flame reactors were used for forming various nanoparticles such as carbon
black and titanium dioxide.

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Sol gel for synthesis of nanomaterials

The sol-gel method is a versatile chemical synthesis technique for producing nanoparticles, particularly
metal oxides and ceramics, through the transition of a colloidal suspension (sol) into an integrated solid
network (gel).
Basic Process:
Step 1: Sol Formation
• Metal alkoxide precursors or metal salts dissolved in solvent
• Form colloidal suspension of particles (1-100 nm)
• Common precursors: tetraethyl orthosilicate (TEOS) for silica, titanium isopropoxide for TiO₂
Step 2: Hydrolysis
Metal alkoxide reacts with water:
• M(OR)ₓ + H₂O → M(OR)ₓ₋₁(OH) + ROH
• Creates reactive hydroxyl groups
• Controlled by pH, water ratio, and temperature
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Sol gel for synthesis of nanomaterials

The sol colloidal solution

made of solid particles few
hundred nm in diameter,
suspended in a liquid
phase.

The gel solid

macromolecule immersed
in a solvent.

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Sol gel for synthesis of nanomaterials

Step 3: Condensation
➢ Hydroxylated species link together forming M-O-M bonds:
➢ Two pathways: water condensation or alcohol condensation
➢ Creates interconnected network
➢ Produces sol-to-gel transition
Step 4: Gelation
➢ Sol transforms into three-dimensional gel network
➢ Viscosity increases dramatically
➢ Solvent trapped in porous structure
Step 5: Aging & Drying
➢ Aging: Gel strengthens through continued condensation
➢ Drying: Removes solvent (critical step affecting final properties)
➢ Xerogels: Dried at ambient conditions (shrinkage, cracking)
➢ Aerogels: Supercritical drying (maintains porosity, very low density)
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Hydrothermal synthesis
➢ Hydrothermal synthesis can be defined as a method of synthesis of single crystals which
depends on the solubility of minerals in hot water under high pressure.

➢ The crystal growth is performed in an apparatus consisting of a steel pressure vessel called
autoclave, in which a nutrient is supplied along with water.

➢ A gradient of temperature is maintained at the opposite ends of the growth chamber so that the
hotter end dissolves the nutrient and the cooler end causes seeds to take additional growth.

➢ Possible advantages of the hydrothermal method over the 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 also be grown
by the hydrothermal method.

➢ The method is also particularly suitable for the growth of large good-quality crystals while
maintaining good control over their composition.

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Chemical Precipitation
➢ Certain soluble inorganic materials can be removed by the addition of suitable
reagents to convert the soluble impurities into insoluble precipitates.

➢ These precipitates can be flocculated and removed by sedimentation.

➢ The extent of removal depends on the solubility of the product and this is usually
controlled by factors such as pH and temperature.

➢ Chemicals precipitation can be used in industrial wastewater treatment

Micro emulsion Technique

➢ This is a new technique, which allows preparation of ultrafine metal particles within the
size range 5 nm<particle diameter <50 nm.
➢ The rate of particle nucleation is a function of the percolation degree of micro emulsion
droplets. Besides a short introduction into some aspects of the micro emulsion types and
formation, we mainly focus on the kinetics of metallic particle formation.
➢ Effects of stabilizer (emulsifier) type and concentration and the type of continuous phase,
reducing agent and additive on the particle formation are summarized and evaluated.
➢ The influence of several other parameters such as temperature, the incident light, the
nature of metal salts and reaction conditions are also reviewed.
➢ These results indicate that the nature of the stabilizer emulsifier, the surface activity of
additives and the colloidal stability of micro emulsion droplets play decisive role on the
particle size and distribution during the preparation of metal particles.

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