In the name of ALLAH, the most Gracious, the Most Merciful

MSE – 856
Nano Materials & Processing
Course Instructor: Dr. Amna Safdar
 Synthesis Methods—bottom up

1. Thermodynamic Equilibrium Approach:

a. generation of supersaturation,
b. nucleation,
c. subsequent growth.
2. Kinetic approach:
a. microemulsion, aerosol pyrolysis, template based
deposition

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1. Thermodynamic Equilibrium Approach:
a. Generation of supersaturation,
b. Nucleation,
c. Subsequent growth.

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Case of homogeneous nucleation of a solid phase from a supersaturated
solution

Schematic showing the reduction of the overall Gibbs free energy of a supersaturated
solution by forming a solid phase and maintaining an equilibrium concentration in the
solution.
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This reduction of Gibbs free energy is the driving force for both
nucleation and growth.

When the concentration of a solute in a solvent exceeds its equilibrium solubility or temperature
decreases below the phase transformation point, a new phase appears. Let us consider the case
homogeneous nucleation of a solid phase from a supersaturated solution as an example. A solution with
solute exceeding the solubility or supersaturated possesses a high Gibbs free energy; the overall energy of
the system would be reduced by segregating solute from the solution.

• Supersaturation
• Supercooling

A schematic showing the reduction of the overall Gibbs free

energy of a supersaturated solution by forming a solid phase
and maintaining an equilibrium concentration in the
solution.

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 kT kT
GV = − ln(C / Co ) = − ln(1 +  )
 
Supersaturation

(C − Co )
=
Co
Case 1: Without supersaturation: 𝜟𝑮𝑽=0

Case 2: C>Co= 𝜟𝑮𝑽=negative

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 “
The limit how small nanoparticles can be synthesized.

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 At the critical size r = r*, d(∆G)/dr = 0 and the critical size,
r*, and critical energy, ∆G*, are defined by:

r* = -2γ/∆Gv
The above discussion was based on a supersaturated
∆G*for=a16πγ/3(∆Gv)2
solution; however, all the concepts can be generalized
supersaturated vapor and a supercooled vapor or liquid.

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 Compares the critical sizes and critical free energy of three spherical nuclei with different values of
supersaturation, which increases with a decreasing temperature.

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 Nucleus spherical in shape
Lower Higher

r* = -2γ/∆Gv

∆G* = 16πγ/(3∆Gv)2

4 3
G = V +  S =  r Gv + 4 r 2
𝜎
3
𝛥𝐺𝑣 𝑇
𝐶 − 𝐶𝑜 kT
𝛾 𝜎= GV = − ln(1 +  )
𝐶𝑜 
Lecture#7&8 27/02/2024 11
 4 3
G = V +  S =  r Gv + 4 r 2
3

The surface energy γ can be changed by

1) use of different solvent,
2) additives in solution, and
3) incorporation of impurities into solid phase.

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 The rate of nucleation per unit volume and per unit time, RN

RN = n P Γ = {Co k T/(3πλ3η)}exp(-∆G*/kT)

(1) the probability, P, that a thermodynamic fluctuation of critical free energy, ∆G*,
(2) the number of growth species per unit volume, n, which can be used as nucleation centres (in
homogeneous nucleation, it equals to the initial concentration, Co,
(3) the successful jump frequency of growth species, Γ, from one site to another, which is given
by:

Favourable conditions for the formation of a large number of nuclei.

• High initial concentration or supersaturation (so a large number of nucleation sites),
• low viscosity, and
• low critical energy barrier

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 The supersaturated state of the solution is a
prerequisite but not a sufficient cause for a
system to begin to crystallize. A free energy
barrier must be overcome for the generation of
a new crystalline phase from the solution. A
newly-formed nucleus is stable only when its
radius exceeds a critical value. A small nucleus
dissolves in the solution to reduce the overall
free energy.

Equilibrium solubility

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 Dissolution of nuclei
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 Synthesis of Monosized Nanoparticles

For the synthesis of nanoparticles with uniform size distribution, it will be the best if
• all nuclei form at the same time with the same size.
• In addition, all the nuclei will have the same subsequent growth.

Consequently, monosized nanoparticles can be obtained. But how?

Subsequent Growth of Nuclei

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 But how?

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 Subsequent Growth of Nuclei
Multi-steps and the major steps are
(1)generation of growth species,
(2) diffusion of the growth species from bulk to the growth surface,
(3) adsorption of the growth species onto the growth surface, and
(4) surface growth through irreversible incorporation of growth species onto
the solid surface.

Two processes:

• Supplying the growth species to the growth surface

• Incorporation of growth species adsorbed on the growth surface into solid
structure is denoted as growth.

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 Nuclei

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 Nuclei Growth

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 Requirements of Nanoparticles-Need for Bottom up Approach

1. identical size of all particles (monosized or with uniform

size distribution),
2. identical shape or morphology,
3. identical chemical composition and crystal structure
among different particles and within individual particles,
such as core and surface composition much be the same,
4. individually dispersed

If the nanoparticles are single crystalline, they are often referred to as

nanocrystals. When the characteristic dimension of the nanoparticles is
sufficiently small and quantum effects are observed, quantum dots are the
common term used to describe such nanoparticles.

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 Synthesis Methods—bottom up

1. Thermodynamic Equilibrium Approach:

a. generation of supersaturation,
b. nucleation,
c. subsequent growth.
2. Kinetic approach:
a. microemulsion, aerosol pyrolysis, template based
deposition

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 But how?

Lecture#7&8 27/02/2024 23
 Subsequent Growth of Nuclei

Two processes:

• Supplying the growth species to the growth surface

• Incorporation of growth species adsorbed on the growth surface into solid
structure is denoted as growth.

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 Nuclei Growth

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 Subsequent Growth of Nuclei

1. Growth controlled by diffusion 2. Growth controlled by surface process

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 Subsequent Growth of Nuclei
1. Growth controlled by diffusion
• Below the minimum concentration for nucleation, nucleation stops, whereas the
growth continues

• Diffusion of growth species from the bulk solution to the particle surface

dr Vm
= D(Cl − CS )
dt r

• Cl is the bulk concentration, CS is the concentration on the surface of solid particles

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 1. Growth controlled by diffusion

Concentration profile of an impurity distribution across the solid/liquid interface, showing the
formation of a depletion boundary layer in the liquid phase

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 1. Growth controlled by diffusion
Diffusion- controlled growth promotes the formation of uniformly sized particles

dr Vm
= D(Cl − CS ) r 2 = 2 D(Cl − CS )Vmt + ro2
dt r
𝑘𝐷

For two particles with initial radius difference,δro ,the ro ro

radius difference, δr, decreases as time increases or r =
particles grow bigger: r
ro ro
r =
k D t + ro2

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