NANO TECHNOLOGY

ENMT807951
 # Lecture 6

0-D NANOSTRUCTURES SYNTHESES

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SIZE DOES MATTER !!

nanometer regime
atom molecules clusters aggregates bulk
Classification of nanomaterials according to their dimensions:
• Zero dimension (0D)
• One dimension (1D)
• Two dimension (2D)
while 3D nanomaterials may not be included in the category of nanostructures
unless their internal structure is nanostructured.
• A zero-dimensional (0D) structure is the simplest block
for the design of nanomaterials.
• The dimensions are in the nanometer regime and have
a diameter less than 100 nm.
• They can be in the form of :
• Nanoparticles
• Nanocrystals
• Nanoclusters
 NANOPARTICLES
• Nanoparticles are particles between 1 and
100 nanometres (nm) in size with a surrounding
interfacial layer.
• The interfacial layer is an integral part
of nanoscale matter, fundamentally affecting all of
its properties.
• The interfacial layer typically consists of ions,
inorganic and organic molecules. Organic molecules
coating inorganic nanoparticles are known as
stabilizers, capping and surface ligands, or
passivating agents. In nanotechnology, a particle is
defined as a small object that behaves as a whole
unit with respect to its transport and properties.

(Source: https://en.wikipedia.org/wiki/Nanoparticle)
 NANOPARTICLES
• Usually used to define in
general all the 0-D
nanostructures, or those that
are amorphous and have an
irregular shape.
• They can be of : natural origin,
semiconductor, metal, oxides,
fullerenes or quantum dots.

• During synthesis or fabrication,

the nanoparticles that make up TEM images Iron Oxide (Fe2O3)
the nanomaterials can be of Nanoparticles
different sizes, which can vary
by more than 15%.
NANOCLUSTERS
• Nanoclusters consist of a small number of
atoms, at most in the tens. These nanoclusters
can be composed either of a single or of
multiple elements, and typically measure less
than 2 nm. Such nanoclusters exhibit attractive
electronic, and chemical properties compared
to their larger counterpart
• Nanoclusters can be considered as aggregates
of small nanoparticles that are formed due to
attractive interactions between individual
nanoparticles
NANOCRYSTAL
A nanocrystal is a material particle having at least one dimension smaller than 100 nm.
based on quantum dots (a nanoparticle) and composed of atoms in either a single- or
poly-crystalline arrangement.

Oriented attachment of
TiO2 nanocrystals in
aqueous phase

Silicon Nanocrystals for

Superefficient Solar Cells
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0
  BOTTOM-UP APPROACHES
 Homogeneous Nucleation
 Sol-gel processing
 Forced hydrolysis

• TOP-DOWN APPROACHES  Vapor phase reaction

• Attrition/milling  Solid state phase segregation

• Repeated quenching  Heterogeneous Nucleation
• Lithography  Confined chemical reaction
 Microemulsion

 Aerosol synthesis

 Growth termination

 Spray pyrolysis

 Epitaxial Core-Shell 11
TOP-DOWN vs BOTTOM-UP APPROACHES
TOP-DOWN vs BOTTOM-UP APPROACHES
TOP DOWN APPROACHES
• Attrition/Milling
• Ranging from couple tens
to several hundreds nano
in diameter
• Broad size distribution and
varied particle size and
distribution
• Used for nanocomposite
and nanograined bulk
materials
• Deffect may be annealed
during sintering
 TOP DOWN APPROACHES
• Repeated thermal cycling/quenching
• Break bulk materials into small
pieces
• Difficult to design and control
• Limited to materials with very poor
thermal conductivity

Grain morphologies (×500) of pre-treated

specimen and cyclically heat treated specimens for
Route 1: (a) pre-treated (0-cycle); (b)1-cycle; (c) 2-
cycle; (d) 3-cycle; (e) 4-cycle; (f) 7-cycle.

Effects of Two Different Cyclic Heat Treatments on Microstructure and Mechanical Properties of Ti-V Microalloyed Steel, Mat. Res. vol.18 no.2 São Carlos Mar./Apr. 2015,
http://dx.doi.org/10.1590/1516-1439.302414
BOTTOM-UP APPROACHES

•Thermodynamic equilibrium approach

• Generation of supersaturation
• Nucleation
• Subsequent growth
•Kinetic approach
• Limiting the amount of precursors for the growth
• Confining in a limited space
HOMOGENEOUS NUCLEATION

• Liquid, vapor or solid by Supersaturation technique:

• Temperature reduction
• Metal quantum dots in glass matrix by annealing
• In situ chemical reactions (converting highly soluble chemicals into
less soluble chemicals)
HOMOGENEOUS NUCLEATION
Thermodynamic parameter : Gibbs free energy, G
A function of the internal energy of the system (enthalpy, H), and the randomness
or disorder of the atoms or molecules (entropy, S).

Liquid
Liquid

G1 Solid nuclei G2
An important thermodynamic parameter in the phase transformations is
the change in free energy DG; a transformation will occur
spontaneously only when DG has a negative value.
HOMOGENEOUS NUCLEATION
For the sake of simplicity, it is assumed that each nucleus is spherical in
geometry and has a radius r.
 HOMOGENEOUS NUCLEATION
There are two contributions to the total free energy change that accompany a
solidification transformation:

• The free energy difference between the solid and liquid phases, or the
volume free energy, ∆GV.
Its value will be negative if the temperature is below the equilibrium
solidification temperature, and the magnitude of its contribution is the
product of DGV and the volume of the spherical nucleus (4/3πr3).

• The formation of the solid–liquid phase boundary during the

solidification transformation.
Associated with this boundary is a surface free energy, γ ,which is positive;
The magnitude of this contribution is the product of and the surface area of
the nucleus (4πr2).
HOMOGENEOUS NUCLEATION

∆G = – 4/3πr3∆GV + 4πr2γSL

First term Second term

HOMOGENEOUS NUCLEATION
The curve associated
with the sum of both terms first
increases, passes through a
maximum, and finally decreases.

What does it mean?

In a physical sense, this means that as a solid particle begins to form as
atoms in the liquid cluster together, its free energy first increases. If this
cluster reaches a size corresponding to the critical radius r*, then growth will
continue with the accompaniment of a decrease in free energy.
 HOMOGENEOUS NUCLEATION

On the other hand, a cluster of radius less than the critical

will shrink and redissolve.
This subcritical particle is an embryo, whereas the particle of radius greater than
r* is termed a nucleus.
HOMOGENEOUS NUCLEATION

Since and ∆G and r* appear at the

maximum on the free energy-versus-
radius curve, the differentiation the
previous equation with respect to r and
set the resulting expression equal to zero,
then:
HOMOGENEOUS NUCLEATION

This volume free energy change ∆GV is the driving force for the
solidification transformation, and its magnitude is a function of
temperature.
 HOMOGENEOUS NUCLEATION

 In the synthesis and preparation of nanoparticles or quantum

dots by nucleation from supersaturated solution or vapor, this
critical size represents the limit on how small nanoparticles can
be synthesized
 To reduce the critical size and free energy, one needs to:
• increase the change of Gibbs free energy, ∆Gv, and
• reduce the surface energy of the new phase, γ.
 NUCLEI FORMATION
• Favorable formation :
• High initial concentration or supersaturation
• Low viscosity
• Low critical energy barrier ∆G*
• Uniform nanoparticle size:
• Same time formation
• Abruptly high supersaturation
• quickly brought below the minimum nucleation
concentration
NUCLEI GROWTH

 Steps upon nuclei growth:

 Generation of growth species
 Diffusion from bulk to the growth surface
 Adsorption
 Surface growth
 Size distribution
 A diffusion-limited growth vs A growth-limited processes
DIFFUSION-LIMITED GROWTH

• Monosized nanoparticles
• How?
• Low/controlled supply growth
species concentration
• Increase the solution viscosity
• Introduction a diffusion barrier
SYNTHESIS OF METALLIC NANOPARTICLES

• General method in the synthesis of metal colloidal dispersion is by

reduction of metal complexes in dilute solutions.
• In the synthesis of metallic nanoparticles, various type of
precursor, reduction reagents, other chemicals, and methods can
be used to control the reduction reactions.
• Precursors include elemental metals, inorganic salts, and metal
complexes such as Ni, Co, HAuCl4, H2PtCl6, RhCl3 and PdCl2.
• Reduction reagents include sodium citrate, hydrogen peroxide,
hydroxylamine hydrochloride, citric acid, and hydrogen.
• Polymeric stabilizer include polyvinyl alcohol (PVA) and sodium
polyacrylate.
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SYNTHESIS OF METALLIC NANOPARTICLES

• Reduction of metal complexes in dilute solution

• Diffusion-limited process maintaining
• Example: nano-gold particles
• Chlorauric acid (2.5 x 10-4 M) 20 ml boiling solution+
sodium citrate (0.5%) 1 ml
• 100°C till color change + water to maintain volume
• uniform and stable 20 nm particles

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SYNTHESIS OF METALLIC NANOPARTICLES

SEM micrographs of gold nanoparticles prepared with

(a) sodium citrate, and
(b) citric acid
as reduction reagents under otherwise similar synthesis condition
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SYNTHESIS OF METALLIC NANOPARTICLES

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SYNTHESIS OF METALLIC NANOPARTICLES

Atomic-structure image of a single

GOLD nanoparticle. This object is only
10 nm in diameter!
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SYNTHESIS OF METALLIC NANOPARTICLES

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 SYNTHESIS OF SEMICONDUCTOR
NANOPARTICLES

• Pyrolysis of organometallic precursor(s) dissolved in

anhydrate solvents at elevated temperatures in an airless
environment in the presence of polymer stabilizer (i.e.,
capping material)
• Coordinating solvent
• Solvent + capping material
• Phosphine + phosphine oxide (good candidate)
• Controlling growth process, stabilizing the colloidal
dispersion, electronically passivating the surface

DEPARTMENT OF METALLURGICAL AND MATERIALS ENGINEERING ENMT 804927-NANOTECHNOLOGY

SYNTHESIS OF SEMICONDUCTOR
NANOPARTICLES

PROCESS
• Discrete nucleation by rapid increase in the reagent
concentration  Ostwald ripening during aging at
increased temperature (large particle grow) size
selective precipitation
• Ostwald ripening
• A dissolution-growth processes
• Large particles grow at the expense of small particles
• Produce highly monodispersed colloidal dispersions
SYNTHESIS OF SEMICONDUCTOR
NANOCRYSTALLITES

• C.B. Murray (CdE, E=S, Se, Te), 1993

• Dimethylcadmium (Me2Cd) + bis(trimethylsilyl) sulfide ((TMS)2S)
or trioctylphosphine selenide (TOPSe) or Trioctylphosphine
telluride (TOPTe) + solvent (Tri-n-octylphosphine, TOP) +
capping material (tri-n-octylphosphine oxide, TOPO)
• Before aging (440 ~ 460nm), after aging at 230-260°C
(1.5~11.5 nm)
• Size-selective precipitation
 SYNTHESIS OF OXIDE
NANOCRYSTALLITES

• Several methods
• Principles: burst of homogeneous nucleation + diffusion
controlled growth
• Most commonly: sol-gel processing
• Most studied: silica colloids

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40

VAPOR PHASE REACTIONS

• In this method, reaction and synthesis are carried out at

elevated temperature and under a vacuum.
• Vacuum is needed to ensure a low concentration of growth
species so as to promote diffusion-controlled subsequent
growth.
• Growth nanoparticles are normally collected on a non-sticking
substrate down stream at relatively low temperature.
 VAPOR PHASE REACTIONS

• Same mechanism as liquid phase reaction

• Elevated temperatures + vacuum (low concentration of growth)
• Collection on a down stream non-sticking substrate @ low
temperature
• Example: 2~3 nm silver particles
• May migrate and agglomerate

DEPARTMENT OF METALLURGICAL AND MATERIALS ENGINEERING ENMT 804927-NANOTECHNOLOGY

VAPOR PHASE REACTIONS
• Agglomerates:
• Large size spherical particles
• Needle-like particle
• Au on (100) NaCl and (111) CaF substrate
• Ag on (100) NaCl substrate
• Change in temperature and precursor concentration did not affect
the morphology
• Size affections
• Reaction and nucleation temperature
SOLID STATE PHASE SEGREGATION

• Applications
• Metals and semiconductor particles in glass matrix
• Homogeneous nucleation in solids state
• Metal or semiconductor precursors introduced to and
homogeneously distributed in the liquid glass melt at high
temperature
• Glass quenching to room temperature
• Glass annealing above the Tg
• Solid-state diffusion and nanoparticles formed
SOLID STATE PHASE SEGREGATION

• Glass matrix (or via sol-gel, polymerization):

• Metallic ions
• Reheating (or UV, X-ray, gamma-ray):
• Metallic atoms
• Nuclei growth by solid-state diffusion (slow!)
HETEROGENEOUS NUCLEATION

• A new phase forms on a surface of another material

• Thermal oxidation, sputtering and thermal oxidation, Argon
plasma and hidden thermal oxidation
• Associate with surface defects (or edges)

• The activation energy (i.e.,

energy barrier) ∆G* for
nucleation is lowered when
nuclei form on preexisting
surfaces or interfaces, since the
surface free energy, g is It is easier for nucleation to occur at
reduced. surfaces and interfaces than at other sites.
HETEROGENEOUS NUCLEATION
Consider the nucleation, on a flat surface, of a solid particle from a liquid
phase. It is assumed that both the liquid and solid phases “wet” this flat
surface, that is, both of these phases spread out
and cover the surface.

There are three interfacial energies (represented as vectors) that

exist at two-phase boundaries- the solid–interface γSI , solid–liquid γSL, and
interface–surface γLI- as well as the wetting angle θ (the angle between the γSI
and γSL vectors)
HETEROGENEOUS NUCLEATION
Remember for the homogeneous nucleation:

Using the same approach, then the entities for the heterogeneous nucleation:

The term S(θ) of this last equation is a function only of θ (i.e., the shape of the nucleus),
which will have a numerical value between zero and unity (0 – 1)
For example, for angles of 30o and 90o values of S(θ) are approximately 0.01 and
0.5,respectively.
 HETEROGENEOUS NUCLEATION

γSL
Liquid (L)
Solid (S) θ γML
γSM
Mould (M)

Thus:

DEPARTMENT OF METALLURGICAL AND MATERIALS ENGINEERING ENMT 804927-NANOTECHNOLOGY

 HETEROGENEOUS NUCLEATION
It is evident that the activation
energy barrier for heterogeneous
nucleation is smaller than the
homogeneous barrier by an amount
corresponding to the value of this
S(θ) function:

This lower ∆G* for heterogeneous means

that only a smaller energy must be
overcome during the nucleation process
(than for homogeneous),
and, therefore, heterogeneous nucleation
occurs more readily
KINETICALLY CONFINED SYNTHESIS

• Spatially confine the growth

• Limited amount of source materials or available space is
filled up
• Groups
• Liquid droplets in gas phase (aerosol & spray)
• Liquid droplets in liquid (micelle & micro-emulsion)
• Template-based
• Self-terminating
 MICELLES OR MICROEMULSION

• Micelles
• Surfactants or block polymers
• Two parts: one hydrophilic and one
hydrophobic
• Self-assemble at air/aqueous solution
or hydrocarbon/aqueous solution
interfaces
• Micro-emulsion
• Dispersion of fine organic liquid
droplets in an aqueous solution
MICELLES OR MICROEMULSION

• CdSe nanoparticles by Steigerwald et al.

• Surfactant bis(2-ethylhexyl) sulfosuccinate, AOT (33.3 g) + heptane
(1300 ml)+ water (4.3 ml)
• Stirred  microemulsion
• 1.0M Cd2+ (1.12 ml) + microemulsion
• Solution of bis(trimethylsily) selenium, Se (TMS)2 (210μl) + heptane
(50ml) + microemulsion (via syringe)
• Formation of CdSe crystallites
POLYMER NANOPARTICLES

• Water-soluble initiator + surfactant + water +

monomer
• Monomer (large droplets, 0.5 ~ 10μm )
• Initiator
• Polymerization
• Nanoparticles (50 ~ 200nm)
 AEROSOL SYNTHESIS

• Characteristics
• Regarded as top-down (maybe?)
• Can be polycrystalline
• Needs collection and re-dispersion
• Process
• Liquid precursor  mistify  liquid aerosol  evaporation or
reaction  nanoparticles
• Polymer particle 1~20 μm (from monomer droplets)
AEROSOL SYNTHESIS
 AEROSOL SYNTHESIS

DEPARTMENT OF METALLURGICAL AND MATERIALS ENGINEERING ENMT 804927-NANOTECHNOLOGY

 SPRAY PYROLYSIS
• Solution process
• Metals (Cu, Ni …) and metal
oxide powders
• Converting microsized liquid
droplets of precursor or precursor
mixture into solid particles through
heating
• Droplets  evaporation  solute
condensation  decomposition &
reaction  sintering
• e.g. silver particle: Ag2CO3, Ag2O
and AgNO3 with NH4HCO3 @
400°C

DEPARTMENT OF METALLURGICAL AND MATERIALS ENGINEERING ENMT 804927-NANOTECHNOLOGY

 TEMPLATE-BASED SYNTHESIS

• Templates
• Cation exchange resins with
micropores
• Zeolites
• Silicate glasses
• Ion exchange
• Gas deposition on shadow
mask (template)
 CORE-SHELL NANOPARTICLES

• The growth condition control

• No homogeneous nucleation occur
and only grow on the surface
• Concentration control: not high
enough for nucleation but high
enough for growth
• Drop wise addition
• Temperature control

Ag-Ag2Se Core Shell Nanoparticles

DEPARTMENT OF METALLURGICAL AND MATERIALS ENGINEERING ENMT 804927-NANOTECHNOLOGY
DEPARTMENT OF METALLURGICAL AND MATERIALS ENGINEERING ENMT807951-NANO TECHNOLOGY