Dimensions of nanoparticles

Nanomaterials are classified into four types based on their size dimensions:
1. Zero-dimensional nanomaterials: all dimensions (x, y, z) are at nanoscale, i.e.,
no dimensions are greater than 100 nm. It includes nanospires and nanoclusters.
2. One-dimensional nanomaterials: two dimensions (x, y) are at nanoscale and
the other is outside the nanoscale. This leads to needle-shaped nanomaterials. It
includes nanofibres, nanotubes, nanorods, and nanowires.
3. Two-dimensional nanomaterials: one dimension (x) is at nanoscale and the
other two are outside the nano scale. The 2D materials exhibit plate like shapes.
It includes nanofilms, nanolayers, and nanocoating with nanometre thickness.
4. Three-dimensional nanomaterials: these are the nano materials that are not
confined to the nanoscale in any dimension. These materials have three arbitrary
dimensions above 100 nm. The bulk (3-D) materials are composed of a multiple
arrangement of nanosize crystals in different orientation. It includes dispersion
of nanoparticles, bundles of nanofibres, and nanotubes, as well as multi
nanolayers (polycrystals) in which the 0D, 1D, and 2D, structural elements are
in close contact with each other and form interfaces.
Nanoparticles are classified as 0-, 1-, 2- and 3-dimensional
Synthesis of Nanomaterials
 Synthesis methods are broadly classified into three classes:
• Physical methods: Nanoparticles can be synthesised using number of physical
methods. These methods are mainly of two types, mechanical type and vapour
deposition type.
• Chemical methods: These are simple and inexpensive methods to synthesise
nano particles. Large quantities of materials can be produced with different sizes
and shapes.
• Biological methods: biological methods are based on the use of micro organisms
like fungi, yeast, bacteria et cetera or plant extracts or enzymes or use of templates
such as DNA, viruses, and membranes et cetera. This type of synthesis is
environment friendly and least toxic and therefore called green synthesis.
Factors affecting synthesis of nano particles
• Temperature: This is an important parameter that affects synthesis of nano
particles using physical, chemical, or biological methods. In physical methods, the
highest working temperatures are required which is usually about 350°C; chemical
methods require a temperature less than 350°C; however, in biological methods,
synthesis of nano particles requires either ambient temperature or a temperature
less than 100°C. Temperature of the reaction medium determines the nature of the
nano particle formed.

• Pressure: Pressure is another important parameter for the synthesis of

nanoparticles. Pressure applied to the reaction medium affects the shape and size
of the nano particles being synthesised.

• Time: The quality and type of nano particle being synthesised depends upon the
• Particle size and shape: Particle size is a key factor in determining the properties
of nanoparticles. For example, the melting point of nanoparticles decreases with
decrease in size of particles. The colour of emitted light also changes with
nanoparticle size. The shape of the nanoparticles influence the chemical
properties.

• Cost of preparation: The cost of synthesis is a key issue that decides the
potential applications of nanoparticles. The cost of synthesis needs to be regulated
and controlled. Method of synthesis should be cost effective so as to be useful for
mass production. Chemical methods do have a high yield and cheaper than
physical methods and not very cost-effective. However, biological synthesis
method involves least cost and is there useful for large-scale production of nano
particles.
• Pore size: The quality and application of nano particles is very much influenced
by the porosity parameter of nano particles. This parameter is important when
nano particles are used in drug delivery system.

• pH value: It has been observed that pH of the solution medium affects the size
and texture of the synthesised nanoparticles. So the size of nano particles can be
controlled by varying the pH of the solution being used for synthesis.

• Environment: during biological synthesis, the nano particles form a coating that
makes them sticker and larger size. The environment influences the physical
structure and chemistry of the synthesise nano particle.
Depending on the approach of assembling atoms, ions, or molecules, splitting up
bulk materials, generation of the raw materials, and protocol of nanoparticle
synthesis, there are various kinds of nanoparticle synthesis approaches.

Broadly, nanoparticle synthesis can be classified into two categories:

• Bottom up approach

• Top down approach

Top down approach
• Size reduction techniques such as top-down or physical procedures are used to
produce nanostructured material from big bulk material.
• It consists of ultra fine micro machining of materials using lithography, epitaxy,
nd etching.
• The ability to synthesize huge quantities of materials is one benefit of the top
down approach.
• However, this method makes it difficult to control shape and size.
• This method is also time consuming and relatively costly.
• Instead of producing nanoparticles, this approach is typically useful in the
synthesis of nanostructured bulk materials.
Bottom up approach
• In this approach, nanostructures are assembled from the smaller starting materials
such as atoms, molecules, or clusters.
• Short-range forces like van der Waals forces, electrostatic forces, and different
interatomic or intermolecular forces cause these atoms or molecules to coalesce
into nanometer-sized particles.
• The bottom up technique is mostly used in the chemical synthesis of
nanoparticles.
• The key advantages of bottom up approach are the generation of a wide range of
nanoparticles with very small to large scale nano-sizes, and a more homogenous
particle size distribution.
• Generally, bottom-up methods are most attractive for both laboratory and
industrial-scale nanomaterial synthesis due to the controllability in size and
properties of materials via proper control of the reaction conditions.
Some of the bottom up approaches for the synthesis of nanomaterials are:
• Sol-gel method
• Physical vapour deposition
• Chemical vapour deposition
• Molecular beam epitaxy
• Spray conversion processing
• Wet chemical synthesis
• Self assembly
 Ball milling
• Ball milling also known as mechanical grinding is a simple and popular ancient
method.
• Here the materials are ground into extremely fine powders. It is one of the most
important and common processes used in industries to synthesize nanomaterials.
• This method has many advantages such as compact design, energy efficient,
minimum maintenance, inexpensive, and scalable.
• It works on the principle of impact. The size reduction is achieved through the
impact caused when the balls drop from the top of the chamber in which the
source material is placed.
• Nano particles formed in a mechanical device generally referred to as a mill in
which energy is imparted to a coarse grained material to cause a reduction in
particle size.
1. As the name suggests, the ball milling method consists of balls and a mill
chamber. Therefore over all a ball mill contains a stainless steel container and many
small iron, hardened steel, silicon carbide, or tungsten carbide balls are made to
rotate inside a mill (drum).
2. The powder of a material is taken inside the steel container. This powder will be
made into nanosize using the ball milling technique. A magnet is placed outside the
container to provide the pulling force to the material and this magnetic force
increases the milling energy when milling container or chamber rotates the metal
balls.
3. These silicon carbide balls provide very large amount of energy to the material
powder and the powder then get crushed. This process of ball milling is done
approximately 100 to 150 hrs to get uniform fine powder.
4. Ball milling is a mechanical process and thus all the structural and chemical
changes are produced by mechanical energy.
• The fundamental principle of size reduction in mechanical attrition devices lies in
the energy imparted to the sample during impacts between the milling media.
• This model represents the moment of collision, during which particles are trapped
between two colliding balls within a space, occupied by mass of powder particles.
During the high-energy ball milling process, the powder particles are subjected to
high energetic impact. Microstructurally, the mechanical alloying process can be
divided into four stages: (a) initial stage, (b) intermediate stage, (c) final stage, and
(d) completion stage.

(a) At the initial stage of ball milling, the powder particles are flattened by the
compressive forces due to the collision of the balls. Micro-forging leads to changes
in the shapes of individual particles, or cluster of particles being impacted
repeatedly by the milling balls with high kinetic energy. However, such deformation
of the powders shows no net change in mass.
(b) At the intermediate stage of the mechanical alloying process, significant changes
occur in comparison with those in the initial stage. Cold welding is now significant.
The intimate mixture of the powder constituents decreases the diffusion distance to
the micrometer range. Fracturing and cold welding are the dominant milling
processes at this stage. Although some dissolution may take place, the chemical
composition of the alloyed powder is still not homogeneous.
(c) At the final stage of the mechanical alloying process, considerable refinement
and reduction in particle size is evident. The microstructure of the particle also
appears to be more homogenous in microscopic scale than those at the initial and
intermediate stages. True alloys may have already been formed.
(d) At the completion stage of the mechanical alloying process, the powder particles
possess an extremely deformed metastable structure. At this stage, the lamellae are
no longer resolvable by optical microscopy. Further mechanical alloying beyond
this stage cannot physically improve the dispersoid distribution. Real alloy with
composition similar to the starting constituents is thus formed.
Advantages of ball milling process:
1. Nanopowders of 2 to 20 nm in size can be produced. The size of nanopowder
also depends upon the speed of the rotation of the balls.
2. It is an inexpensive and easy process.

Disadvantages:
1. As the process is not so sophisticated, therefore the shape of the nanomaterial is
irregular.
2. There may be contaminants inserted from ball and milling additives.
3. This method produces crystal defects.
Steps in ball milling method:
1. As the name suggests, the ball milling method consists of balls and a mill
chamber. The mill contains a stainless steel container and many small iron,
hardened steel, silicon carbide, or tungsten carbide balls are made to rotate inside a
mill (drum).
2. The powder of a material is taken inside the steel container. This powder will be
made into nano size using the ball milling technique. A magnet is placed outside the
container to provide the pulling force to the material and this magnetic force
increases the milling energy when milling container or chamber rotates the metal
balls.
3. These silicon carbide balls provide very large amount of energy to the material
powder and the powder then gets crushed. This process of ball milling is done
approximately 100 to 150 hrs to get uniform fine powder.
4. Ball milling is a mechanical process and thus all the structural and chemical
changes are produced by mechanical energy.
Advantages of ball milling process:
1. Nanopowders of 2-20 nm in size can be produced. The size of nanopowder also
depends upon the speed of the rotation of the balls.
2. It is an inexpensive and easy process.

Disadvantages:
1. As the process is not so sophisticated, therefore the shape of the nanomaterial is
irregular.
2. There may be contaminants inserted from ball and milling additives.
3. This method produces crystal defects.
 Laser Ablation
• Nanoparticles by laser ablation, involves the generation of NPs by laser ablating a
solid target that lies in a gaseous or a liquid environment and collection of the NPs
in the form of nanopowder or a colloidal solution.
• It is an easy, fast, and straightforward method for generation of NPs as compared
to other methods. It does not require long reaction times or multistep chemical
synthetic procedures.
• It does not require the use of toxic/hazardous chemical precursors for
nanomaterial synthesis and thus is an environmentally friendly “green” and
laboratory safe method.
• In the event that generation occurs in water, the resulting nano particles, colloidal
solutions are ultra pure, (i.e., they do not contain any counterions or reaction by-
products), and this facilitates the use of these NPs in biological or biochemical in
vivo applications.
• The produced nano particles can easily be functionalised with ligand of choice,
through the subsequent addition of the ligand into the Nanoparticles colloidal
solution after its synthesis or by performing the ablation in a suitable solvent.

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 Synthesis of NPs by laser ablation method
• To synthesise Ag (Cu) nanoparticles
by LA, a high purity silver (copper)
slice is placed on the bottom of glass
vessel containing 20 ml of distilled
water.
• It is then irradiated with focused
output of 1064 nm of pulsed laser
operating at fixed energy for 30
minutes.
• This results in a yellow colour in Ag
(light green in copper) colloidal
solution.
 Experimental configurations and equipment
• Generation in liquids:
• Synthesis of NPs by laser ablation in liquids the simplest experimental
configuration commonly used by many groups around the world.
• The target is placed at the bottom of a beaker or petri dish, which is filled with the
liquid and fixed into an XYZ translational stage. The laser beam irradiates the
target vertically.
Physical Vapour Deposition (PVD)

• Vacuum evaporation is one of the common physical vapor

deposition methods.
• The source material to be deposited is evaporated in a high
vacuum by heating it, using one of the following heating
sources: direct resistance, eddy current, electron beam,
laser beam, or an arc discharge.
• The vacuum allows vapor particles to travel directly to the
substrate, where they condense to form a thin solid film.
PVD Resistive method
• During the process of resistive thermal evaporation, a material in a high-vacuum
environment is heated to its evaporation point using electrical energy.
• The vaporized molecules then travel from the source to the substrate where they
nucleate together, forming a thin-film coating.
• High levels of vacuum are needed for resistive evaporation deposition for two
reasons:
i. The first is that when gas is evacuated from a chamber, vapor molecules inside
it can travel longer distances before they collide with a gas molecule. Collisions
with gas molecules are undesirable during evaporation because they change the
direction of travel of material vapor and thus can adversely affect the coverage
on the substrate.
ii. The second reason why high vacuum is important is film purity. Gases that are
present in air can be deleterious to film properties if they become incorporated
into the deposition.
PROS:
• Can be used with metals or nonmetals, including aluminum, chrome, gold,
indium, and is well-suited for applications using electrical contacts
• Good for materials with low melting points, such as alloys containing mercury or
gallium
• Excellent uniformity if you are using planetary substrate fixturing and uniformity
masks (but poor without)
• High deposition rate of <50 Angstroms per second (Å/s)
• Good directionality
• Very low cost relative to other PVD methods
• Least complex PVD process
• Compatible with ion-assist source
CONS
• Poor uniformity
• Highest impurity levels of any PVD method
• Film quality is low density, but can be improved with ion-assist
• Moderate film stress
• Limited scalability

USES
• Thin-film devices (OLEDs, solar cells, thin-film transistors) that require the
deposition of metallic contact layers
• Wafer bonding (when indium bump deposition is needed)
• Enables the co-deposition of several components by controlling the temperature of
separate crucibles
PVD Sputerring method
• Sputtering is a plasma-based coating method where positively charged energetic ions from a
magnetically confined plasma collide with a negatively charged target material, ejecting (or
“sputtering”) atoms from the target that are then deposited onto a substrate.
• This process occurs in a closed magnetic field to trap electrons and boost efficiency—
creating plasma at lower pressures which reduce gas incorporation in the film and energy
losses in the sputtered atom.
• This method produces good film quality and the highest scalability of any PVD type.

PROS
• Good for metals and dielectrics
• Uniformity is good for better yield, although uniformity improvement can be difficult and
costly
• Low level of impurity
• Film density is very good with moderate to high stress
• High deposition rate of <100 Å/s for metals, good for high throughput applications
• Highest rate of scalability (with automation available)
CONS
• Poor deposition rate for dielectrics (1-10 Å/s)
• Low directionality, but can be improved with system geometry
• High system cost and complexity
• Energetic target material can cause substrate heating

USES
• Very dense films that require strong adhesion
• Depositing metallic or insulating coatings for specific optical and electrical
properties
• Applications requiring high levels of automation
 Chemical Vapour Deposition (CVD)

• The material precursor is heated and evaporated. The atoms and molecules are in
gaseous phase. The atoms or molecules react homogenously or heterogeneously
and deposits on a solid surface. By CVD we can produce defect free and high
purity nano materials.
• CVD involves formation of non-volatile thin solid film by reaction of ion/species
in the vapor state and subsequent deposition.
• Reactant gases decompose and react on heated surface to form thin film.
• CVD involves exposing the heated substrate to one or more volatile precursors
which react on the substrate surface to produce the film.
• CVD is a very versatile process to produce coatings, powders, fibres, and
monolithic parts.
• CVD can produce almost any metallic or nonmetallic elements like C and Si, and
compounds like carbides, nitrides, borides, oxides, etc.
• CVD is widely used in the semiconductor industry, as part of semiconductor
device fabrication process, to deposit various films.
• CVG can also produce synthetic diamond, diamond like coating, cubic-BN et
cetera
• https://youtu.be/j80jsWFm8Lc?si=jqUSoZ_rAoLFxPBD
 Nanolithography
• Lithography is the transfer of a required pattern from a master slide/plate/mask to
another medium.
• Nanolithography is one of widely used top down techniques for the preparation of
nanostructured materials and patterns.
• Nanolithography techniques are based on depositing, masking, etching or writing
the desired patterns with dimensions of the order of nanometers on a solid
material surface.
• Using this technique, a pattern or design can be transferred at once on the surface
of a device by exposure with a radiation.
• Depending on the exposure radiation sources, like photons, X-rays, electrons and
ions, the technique is classified as photolithography, X-ray lithography, electron-
beam lithography and ion beam lithography, respectively.
Principle
Mechanism
Mask aligner system
 Sol-Gel Synthesis

• Sol-gel is one of the simple wet chemical techniques suitable for the preparation
of nanoparticles (mostly oxides) and nanocrytalline thin films.
• It is a superior method to all available methods since this method is employed for
large scale production at low cost.
• This method is based on inorganic polymerization reaction including hydrolysis,
polycondensation, gelation, aging, drying and calcinations or sintering.
It’s the formation of inorganic networks through the formation of a colloidal
suspension (sol) and gelation of the sol to form a network in a continuous liquid
phase (gel)
• Sol-gel method is a tedious but simple method.
• It starts with a complex solution (sol) and achieves a colloidal 3D network (gel).
• In the sol-gel chemical procedure, the 'sol' (or solution) evolves into a gel-like
semicrystalline system containing both liquid and solid phases with morphologies
ranging from discrete particles to continuous polymer networks.
• sol-gel technology is favourable owing to its less chemical use, low cost, more
effective, functionality, and durability with low environmental impact and
toxicity.
• Sol-gel is a purely wet processing, chemical-based process that entails the
formation of inorganic networks by establishing a colloidal suspension (sol) and
gelating it to form a network in a continuous liquid phase (gel).
 Mechanism

1. Sol formation
2. Gel formation
3. Drying
4. Xerogel
5. Calcination
6. Heat treatment
Mechanism
• The process begins with the formation of a “sol” which is a stable dispersion of
colloidal particles (amorphous or crystalline) or polymers in a solvent.
• A “gel is formed by a three-dimensional continuous network, which contains a
liquid phase, or by the joint of polymer chains. In a colloidal gel, the network is
built from aggolomerates of colloidal gel.
• While in a polymer gel, the particles have a polymeric substructure composed of
aggregates of sub colloidal particles. Generally, van der Waals forces or hydrogen
bonds dominate the interactions between the sol’s particles.
Advantages of sol-gel
Disadvantages of sol-gel