PARTICLE SCIENCE AND TECHNOLOGY
Unit V Synthesis of Nano particles
Colloidal Methods
Colloidal chemical methods are some of the most useful, easiest and
cheapest ways to create nanoparticles
Colloidal methods may utilize both organic and inorganic reactants
Typically a metal salt is reduced leaving nanoparticles evenly
dispersed in a liquid
Aggregation is prevented by electrostatic repulsion or the
introduction of stabilizing reagent that coats the particle surfaces
Particle sizes range from 1-200 nm and are controlled by the initial
concentrations of the reactants and the action of stabilizing reagent.
Unit V Synthesis of Nano particles
Colloidal Synthesis
A colloidal synthesis system consists of precursors, surfactants and solvents.
When the reaction medium is heated to a sufficiently high temperature, the
precursors transform into active atomic or molecular species (monomers) and
subsequently grow nanocrystals.
Thus, the formation of nanocrystals involves nucleation of an initial seed and
subsequent growth. In the nucleation step, precursors decompose or react at a
suitable temperature to form a supersaturation of monomers followed by a
burst of nucleation of nanocrystals.
These nuclei then grow further by consuming additional monomers. The
presence of surfactant molecules may help the subsequent growth of the
nanocrystals.
By varying the temperature and duration of heat treatment one can vary the
average size of the nanocrystals
Unit V Synthesis of Nano particles
The selection of suitable temperature for growth is important because the
degree of hotness controls the rearrangement of atoms and anneal during
growth.
There is a reduction in melting temperature for crystals of smaller size.
The reduction in melting temperature increases the range of inorganic colloidal
nanocrystals, which can be grown at temperatures (200-400ºC) where common
organic molecules are stable.
To stabilize a colloid in the small cluster size regime, it is necessary to use
some stabilizers that can attach to the cluster surface and thereby prevent the
uncontrolled growth into larger particles.
A more common approach is the use of a polymeric surfactant/stabilizer which
is added to a reaction designed to precipitate the crystal.
Unit V Synthesis of Nano particles
The polymer attaches to the surface of the growing clusters, and prevents their
further growth.
The most commonly used polymer surfactant is sodium polyphosphate.
Clusters of CdS, CdTe and ZnTe can be prepared with sodium polyphosphate
surfactant
Another common method for preparing colloidal gold nanoparticles involves
combining hydrogen tetrachloroaurate (HAuCl4) and sodium citrate
(Na3C6H5O7) in a dilute solution.
– Upon dissociation, the citrate ions (C6H5O73-) reduce Au3+ to yield 30-40 nm
gold particles.
Unit V Synthesis of Nano particles
Synthesis of Metal Nanoparticles by Colloidal Route
Colloidal metal nanoparticles are often synthesized by reduction of some metal
salt or acid.
For example highly stable gold particles can be obtained by reducing
chloroauric acid (HAuCl4) with tri sodium citrate (Na3C6H5O7).
The reaction takes place as follows
Unit V Synthesis of Nano particles
Unit V Synthesis of Nano particles
Unit V Synthesis of Nano particles
Metal gold nanoparticles exhibit intense red, magenta and other colours,
depending upon the particle size.
Gold nanoparticles discussed above are stabilized by repulsive interactions.
It is also possible to stabilize gold nanoparticles using thiol or some other
capping molecules.
Silver, palladium, copper and other metal nanoparticles can be synthesized
using appropriate precursors, temperature, pH, duration of synthesis etc.
Particle size, size distribution and shape strongly depend on the reaction
parameters and can be controlled to achieve desired results.
Unit V Synthesis of Nano particles
Unit V Synthesis of Nano particles
Unit V Synthesis of Nano particles
Unit V Synthesis of Nano particles
Synthesis of Semiconductor Nanoparticles by Colloidal
Route
Compound semiconductor nanoparticles can be synthesized by wet chemical
route using appropriate salts.
Sulphide semiconductors like CdS and ZnS can be synthesized as nano-
particles simply by co-precipitation.
For example, to obtain ZnS nanoparticles any zinc salt like zinc sulphate
(ZnSO4), zinc chloride (ZnCl2), zinc nitrate (ZnNO3) can be dissolved in
aqueous medium and Na2S is added to the solution or dissolve H2S gas in the
Zn salt solution).
Unit V Synthesis of Nano particles
Nanoparticles thus formed need to be surface passivated as they have a
tendency to coagulate.
Hindrance can be created by appropriately coating the particles to keep
them apart.
This is often known as ‘chemical capping’
Chemical capping can be carried out at high or low temperature
depending on the reactants.
Advantage of chemical capping method is mainly that nanoparticles are
chemically stable over a long time
Unit V Synthesis of Nano particles
A variety of molecules can be used to cap the nanoparticles. For
example capping of metal-sulphide nanoparticles by few organic and
inorganic molecules is illustrated below.
Unit V Synthesis of Nano particles
Gas phase synthesis
Gas phase nanoparticle preparation methods have attracted huge
interest over the years due to number of benefits that they can
deliver over other methods.
These techniques are typically characterized by the ability
to accurately control the process parameters to be able to tune
shape, size and chemical composition of the nanostructures.
Although, means and methods can differ, almost all gas phase
nanomaterial production methods follows following sequence
Suspending the precursor materials in a gas phase
Transforming the precursor material to small clusters
Enforcing the growth of these clusters to a nanoparticles
Method to collect prepared nanoparticles.
Unit V Synthesis of Nano particles
The growth of small nuclei clusters to nanoparticles is referred to as
condensation and it occurs only when the precursor vapor is
supersaturated.
Condensation process can be driven by both physical and chemical
methods
Unit V Synthesis of Nano particles
Inert gas condensation
This method is the most rudimentary of all the gas phase fabrication
techniques.
The method is simple as heating a material inside a furnace usually
under an inert gas such as Nitrogen or Helium.
This method however, is only appropriate for the materials that have
low vapor pressure.
Or in other words material is only vaporized at elevated temperatures
sometimes even 2000 degrees.
This method is quite useful in preparation of metallic nanoparticles,
as these materials show reasonable rates of evaporation at practical
temperatures.
Unit V Synthesis of Nano particles
Although the process is typically carried out at inert gas, reactive
gases can also introduced to the heated chamber to encourage
reactions.
This is particularly useful in making metal oxide and metal halide
nanoparticles.
Nanoparticle attributes such as shape, size and the distribution is
mainly controlled by the rate of evaporation (heating
rate/temperature), rate of condensation (cooling rate) and the gas
flow.
Unit V Synthesis of Nano particles
Chemical vapor synthesis
In Chemical Vapor Synthesis (CVS) chemical vapors of precursor
materials are brought to reaction in a reaction chamber.
The method is similar to chemical vapor deposition, however instead
of deposition of nanomaterial as a thin film, CVS process encourage
formation of nanoparticles.
Hence, the process parameters are adjusted appropriately during the
synthesis in order to suppress film formation and to encourage
nucleation of particles in the gas phase.
Typically, the resident time of the precursor in the reaction chamber
is the most critical parameter to determine whether the film or
parameter will be formed.
Unit V Synthesis of Nano particles
Chemical vapor synthesis
This method is well recognized for the flexibility it provides as a
nanomaterial synthesis process.
The precursors can be in solid, liquid or gas phase at the ambient
temperature but are delivered to the hot wall reactor at the vapor
phase.
The method has been adopted to fabricate wide range of
nanomaterials from variety of precursor materials.
CVS process has embraced much of the precursor chemistries
developed from CVD processes and has contributed significantly for
CVS process to stand as its own.
Unit V Synthesis of Nano particles
Chemical vapor synthesis
The main process parameters of the CVS process are the residence
time of precursors, gas flow rate, pressure different between inlet
and the main chamber and temperature of the hot wall.
In the simplest form of CVS, metal organic precursor is introduced to
the hot wall reactor at a controlled rate.
Unit V Synthesis of Nano particles
Unit V Synthesis of Nano particles
The reactor chamber can be filled with reactive gases to produce the
respective metal oxide, halide, nitride or carbide during the process.
In other technique, mixtures of nanoparticles of two phases can be
fabricated by supplying two or more precursors simultaneously.
The same strategy was used to make doped nanomaterials as well.
Some researchers have used CVS process to make coated or core
shell nanoparticles.
This is typically achieved by supplying the second precursor at a
later stage of the reactor.
CVS is also regarded as a high throughput process as the
production is continuous. Even a small scale reactor can produce
considerably high amount of nanomaterials compared to other
manufacturing techniques.
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