Compiled by Aklilu G 39

Nanoparticles Synthesis
 The synthesis of nanomaterials of tailored properties
involve the control of Size, shape, structure,
composition and purity of their constituents.
 All the synthesis/deposition techniques are divided into
two categories or approaches based on the phase of
starting material for synthesis of nanomaterials and the
fabrication of nano structures.
I. Top-Down approach
► refers to slicing or successive cutting of a bulk material to get
nano sized particle.
II. Bottom-Up approach (or self-assembly approach)
► refers to the build up of a material from the bottom: atom by
atom, molecule by molecule
 Atom by atom deposition leads to formation of Self-
assembly of atoms/molecules and clusters
 These clusters come together to form self- assembled
monolayers on the surface of substrate
Compiled by Aklilu G
 Fig. 3.1.

 All the Bottom-up techniques, the starting

 Top-down techniques, the material is either gaseous state or liquid
state of matter
starting material is solid state
 Physical and chemical processing
methods:
 Physical processing methods:  Physical techniques-
 Mechanical methods :  Physical Vapor Deposition (PVD):
involves condensation of vapor phase
 - cutting , etching, grinding species
 - ball milling  Chemical techniques-
 CVD: Deposition of vapor phase
 Lithographic techniques: of reaction species
 - Photo Lithography  Self-assembled Monolayer :
 - Electron Beam Lithography
 Electrolytic deposition, Sol-
gel method, Hydrothermal,
pyrolysis.
Compiled by Aklilu G 41

 Advantages
 Large scale production:
 deposition over a large substrate is
possible
 Chemical purification is not
required
 Diadvantages
 Yields:
 broad size distribution (10-1000
nm)
 varied particle shapes or geometry
 Control over deposition parameters
is difficult to achieve
 Impurities: stresses, defects and
 imperfections get introduced
 Expensive technique
Compiled by Aklilu G
 Advantages
 Ultra-fine nanoparticles, nanoshells,
nanotubes can be prepared
 Deposition parameters can be
controlled
 Narrow size distribution is possible
(1-20 nm)
 Cheaper technique
 Diadvantages
 Large scale production is difficult
 Chemical purification of
nanoparticles is required
42
Mechanical grinding

 It involves the use of high-energy ball milling to create fine dispersed alloying particles in a grain-refined
matrix .
► it has been widely exploited for the synthesis of various nanomaterials, nanograins, nanocarbons,
nanoalloy, nanocomposites and nano -quasicrystalline materials.
 Mechanical alloying techniques are employed to produce amorphous and nanocrystalline alloys, as well as
metal/non-metal nanocomposites, by milling elemental or compound powders in an inert atmosphere .
► The mechanical milling process can also be combined with post-annealing or activation processes to
modify the synthesized nanomaterials .

Fig.3.2. A rock tumbler Fig. 3.3. High-energy ball milling process.

Ball mills Compiled by Aklilu G 43
Laser ablation

Fig. 3.4. Experimental setup of laser ablation for preparation of Bi

nanoparticles.
Compiled by Aklilu G
 nucleation growth

► is the first step in the formation of either a new thermodynamic phase or a

new structure via self-assembly or self-organisation.
► is the process whereby nuclei (seeds) act as templates for crystal growth.
Nucleation is very sensitive to impurities in the system.
 Reactant addition mode, stirring rate, container surface condition, temperature
uniformity, and many other factors can all affect the nucleation process.
There are two different categories of Nucleation:

 The nucleation of critical, nuclei forming at defects such as surface

imperfections, grain boundaries is called heterogeneous nucleation.
 Nucleation is much easier since stable “nucleating surface” is already
present;
► requires slight supercooling (0.1-10ºC)
Compiled by Aklilu G 45
 Homogenous nucleation – this happens
spontaneously!
►nuclei are formed in a completely uniform
environment
►nuclei form uniformly throughout the parent phase ;
requires considerable supercooling (typically 80-
300°C)
 Supercooling
 During the cooling of a liquid, solidification (nucleation) will
begin only after the temperature has been lowered below the
equilibrium solidification (or melting) temperature Tm. This
phenomenon is termed supercooling (or undercooling).
 The driving force to nucleate increases as ΔT increases
 Small supercooling → slow nucleation rate - few nuclei -
largecrystals
 Large supercooling → rapid nucleation rate - many nuclei
- small crystals

Compiled by Aklilu G
  determines if the obtained particles will be nano-sized or
micronsized and how wide the particle size distribution will be
 After stable nuclei are formed, nanoparticles can grow in three
ways:
A. homogeneous growth,
B. Ostwald ripening, and
C. aggregation.
A. Homogeneous growth
► nucleus size increases by molecular addition.
 solution supersaturation decreases with nucleus growth.
 three discrete steps
 diffusion of the growing species from the solution to the
nucleus surface, →diffusion-controlled growth
 adsorption of the growing species onto the nucleus, and
 the incorporation of the growing species into the nucleus.

Compiled by Aklilu G
B. Ostwald ripening
 phenomenon in solid solutions or liquid suspensions that, over time,
small particles dissolve and redeposit onto larger particles
► occurs when the solute concentration drops below supersaturation level
► Smaller particles dissolve because of their higher solubility and
precipitate on the surface of larger particles, where the solubility is lower.
 effective for narrowing the size distribution of semiconductor
nanoparticles, at the expense of increasing average particle size
C. Aggregation
 Because of the large surface area and high surface energy available,
nanoparticles can also grow through aggregation of small particles or
unstable nuclei.
 Aggregation occurs by engulfing smaller particles onto the surfaces of
large particle clusters; the growth rate is higher than that through
molecular addition, but the process is not as controllable.
► the barrier for aggregation increases with the particle size.
 aggregation is a more dominant phenomenon for nanoparticles
compared with their micron-sized counterparts
► To prevent aggregation of nanoparticles, stabilizing agents can be used

Compiled by Aklilu G
1.2.1 Sol–gel method

 is one of the most attractive and versatile methods to synthesize

nanomaterials at low temperature and low cost.
 During this process,
► metal alkoxide or ionic compound solutions have been commonly used as the
starting materials to form a heterogeneous mixture →Sol
► Due to its high molecular polarity, the water or alcohol–water mixture is
commonly used as the dispersing agent
 The liquid-phased sol can become a gel (xerogel under ambient conditions)
via constant Brownian motion upon hydrolysis and condensation during the
sol–gel transition
► The high surface tension of these dispersed nanoparticles allows them to
“glue” together when collisions occur
 The nanoparticles can either form bonding or agglomerate by electrostatic
forces.
 During these two steps, a continuous inorganic lattice containing the bonding of
or will be formed as a skeleton for the final products

49
 A “sol” is defined as a stable dispersion of colloidal particles or
polymers in a solvent, whereas colloid is defined as suspension of
dispersed solid particles (1–1000 nm).
 The gel consists of a 3-D continuous network, which encloses
liquid phase.
 Sol-gel processes can be categorized into alkoxides and
nonalkoxide processes according to volatility of the precursor
material.
 Metal alkoxides
 are widely used because metals are capable of forming the metal
alkoxides with general chemical formula M(RO)x,
► where M and R represent the metal and alkyl group and x is the
valence state of the metal.
 Sol-gel process involves hydrolysis and polycondensation
reactions using water as a medium.
► In some cases, catalysts are required to increase the reaction kinetics
that promotes the hydrolysis of the precursors.
► the hydrolysis (or polymerization) establishes metal–OH–metal or
metal–O–metal bridges between metallic atoms of the precursors.

Compiled by Aklilu G
FIG. A typical schematic diagram of hydrolysis and condensation reactions in the sol-gel
process.

Compiled by Aklilu G
 This gel has the ability to take the shape of the container or
mold in which it is prepared.
► Then, the gel structure is allowed to ripen in order to strengthen the
interparticle interactions prior to drying.
► The drying is usually done for several hours to several days. During
this (or aging) process, the gel continues to transform
► If the gel is dried by simple evaporation, a xerogel is formed
► If it is dried under supercritical conditions (eg. using CO2 ) the 3-D
network structure having high porosity forms, also called as aerogel.

Fig. 3.5a. Sol-gel synthesis Compiled by Aklilu G

Fig. 3.6b. Sol-gel synthesis
Compiled by Aklilu G
2.2.2. Chemical vapour deposition (CVD)
 CVD is a chemical process used to produce high-purity, high-
performance solid materials.
 In this method, vapors of the suitable precursors are put forward into a
preheated CVD apparatus where the vapors are adsorbed and thermally
decomposed or reacted with other vapors present in the reactor to
deposit the required material. Nucleation can either occur in the gaseous
phase or on the substrate.
 In the CVD process, at higher temperatures and below nonequilibrium
conditions, gas-phase reactions with the development of particles occur
 Generally, argon or nitrogen can be used as a carrier gas, which helps to
carry the volatilized precursors across a heated reaction compartment
 A tube-shaped furnace can be employed as a heat source with
temperatures up to 1500 K

Compiled by Aklilu G
  CVD is a chemical process used to produce high-purity, high-
performance solid materials.
 This technique is suitable for the manufacture of coatings, powders,
fibers and monolithic components.
 This technique is often used in many thin film applications.
 By varying the experimental conditions—substrate material, substrate
temperature, composition of the reaction gas mixture, total pressure gas
flows, etc.— materials with different properties can be grown.

Fig. 3.7. CVD

Compiled by Aklilu G
Hydrothermal/solvothermal

Compiled by Aklilu G
2.1.2. Hydrothermal and solvothermal methods
 Hydrothermal and solvothermal methods as solution-based chemical
reactions in a sealed vessel
 The temperature and pressures of the solvent are brought to their critical point
through heating
► Specifically, water is used as the solvent for a hydrothermal reaction, while
organic solvents are the solvents for a solvothermal process, such as alcohol, ether,
and other organic solvents
► Organic solvents allow the reactions to occur at relatively low temperatures and
pressures compared to water
► Like other solution-based synthetic methods, the nanomaterials are fabricated
through nucleation and growth stages.
 When the solute exceeds the solubility limit in the solvent, it precipitates out
into cluster
► concentrations of reactants, additives, temperature, reaction time, the filling ratio,
and solvents could all lead to fluctuations of solubility and ultimately shape the
growth of crystals
 The hydrothermal and solvothermal processes emphasize the properties of
solvent and heat
 One of the advantages of hydrothermal and solvothermal synthesis is the
largescale fabrication of nanomaterials.
► However, the thermal stability of organic chemicals constrains the temperature
range of those syntheses
Fig. 3.8. Hydrothermal synthesis method

Compiled by Aklilu G 58
Advantage of Hydrothermal Synthesis:
 Suitable for the nanomaterials which are not stable around
melting point.
 Nanomaterials with high vapor pressure can be synthesized via
this method with minimum loss of materials.
 Composition of nanomaterials to be produced can be well
controlled in this method.
 Simple to implement and scale up
 Particle size, morphology and physical properties of
nanomterials can be controlled.
 Rapid technique that can produce high product yields
 This method allows control over particle size and their properties.
 Various nanomaterials like nano rod, powder etc. can be
produced.

Compiled by Aklilu G
 Traditional synthesis methods usually affect the environment and human
health due to contaminant reagents and the generation of byproducts. NMs,
when manufactured using
 green synthesis methods, are especially desirable, being devoid of harsh
operating conditions (high temperature and pressure), pH, hazardous
chemicals, or external stabilizing or capping agents
 sol–gel-based green synthesis can be implemented as a primary synthetic
method assisted by other methods, particularly physical, like microwave,
ultrasound, and pulsed laser ablation

 The green synthesis of NMs using plant extract, microorganisms,

biomolecules, andwastes is cheap, environmentally friendly, sustainable, and
easy to operate
► Meanwhile, the relevant synthetic mechanisms need to be further elucidated.
The lack of understanding of the chemical components involved in the
synthesis and stabilization of NPs remains a great challenge for researchers

60
Read about the methods of nanomaterials synthesis by:

Compiled by Aklilu G 61