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Introduction to Nanomaterials
Zero Dimensional Nanostructures

Approaches for Synthesis of

Nanostructures

Top Down Approaches: Milling, repeated thermal cycling,

lithography etc.

Bottom Up Approaches: Homogeneous and heterogeneous

nucleation, Aerosol synthesis, molecular beam epitaxy

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Desired Characteristics of Synthesized

Nanoparticles

• Uniform size distribution

• Identical shape and morphology

• Identical chemical composition and crystal

structure

• Individually dispersed..no agglomeration

Nanoparticles through Homogeneous

Nucleation

• Supersaturation by exceeding solubility

• Lowering the Temperature below phase

transformation point

• Supersaturation by in-situ chemical reaction – into

less soluble species

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Fundamentals of Homogeneous
Nucleation

kT kT
 GV   ln( C o / C e )   ln( 1   )
 
K – Botzmann Constant,  - atomic volume,  - super-saturation = (C0-Ce)/Ce,
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Ce– equilibrium concentration or solubility, C0 – concentration of the solute

Fundamentals of Homogeneous Nucleation

Surface Free Energy - destabilizes
the nuclei (it takes energy to make
an interface)
GS  4r 2 
 = surface tension

GT = Total Free Energy

= GS + GV

Volume (Bulk) Free Energy –

stabilizes the nuclei (releases energy)
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GV  r 3 G
3
volume free energy
G 
unit volume
r* = critical nucleus: for r < r* nuclei shrink; for r >r* nuclei grow (to reduce energy)
Adapted from Fig.10.2(b), Callister & Rethwisch 8e. 6

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Controlling Nanocrystal Size

• By lowering – r*
• Can be achieved by increasing Gv or reducing 

TE > T1 > T2 > T3

Nucleation Rate

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Nucleation vs. Growth

Controlling Size by Nucleation

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Growth of Nuclei

• Generation/availability of growth species

• Diffusion of growth species from bulk to particle

surface

• Adsorption of growth species onto the surface

• Surface growth through irreversible incorporation

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By Diffusion and Growth Control

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Controlling Size by Diffusion

• Keeping concentration of Growth Species low –

diffusion distance is large

• Increasing viscosity of solution

• Introducing diffusion barrier

• Controlled supply of growth species

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Nanoparticles through solution

Process
Advantages

• Stabilization of nanoparticles from agglomeration

• Extraction of nanoparticles from solvent

• Surface modification

• Mass production

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Synthesis of Metallic Nanoparticles:

Colloidal Dispersion

• By initiating and controlling reduction reactions

• Low concentration solute is used – diffusion control

• Polymeric monolayer on surface – hinder growth by

- strong adsorption on growth site
- full coverage of surface – restrict diffusion

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Colloidal Dispersion
1. Metal Compound
• Positively charged metal salt, or
• Metal centres of complexes
2. Solvents (depends on the nature of the salt)
• Water
• Polar organic solvents
• Non-polar organic solvents
3. Reducing Agent (determined by the nature of the metal
compound)
• Gaseous hydrogen
• Hydridic compounds
• Reducing organics, e.g. alcohols
• Alkali metals, e.g. K ((AlCl3+ 3 K Al + 3KCl in dry xylene)
• Many others (e.g. CO) 16

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Colloidal Dispersion

4. Stabilizers
Stabilizing agents/ligands/capping agents/passivating agents
• prevent uncontrollable growth of particles
• prevent particle aggregation
• control growth rate
• controls particle size
• allows particle solubility in various solvents

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Stabilizers

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Schematic of Synthesis

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Synthesis of Gold Nanoparticles

Procedure
 Bring to boil 50 mL of 2.5×10-4 M chlorauric acid solution
 Add 0.16 to 1.0 mL of 34 mM sodium citrate solution to the
boiling solution while stirring
 After a minute will be faint blue and then darkening over 5 min
to a brilliant red
 The size of the gold nanoparticles can be controlled by varying
the amount of sodium citrate solution. The above procedure
can grow controlled sizes from 147 nm (0.16 ml) down to 16 nm
(1.0 ml).

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Reduction reagents
• Affect the size and size distribution
– weak reduction reaction
• larger particles
• wider or narrower distribution (depends on “diffusion
limited”)
• Affect the morphology
– type, concentration, pH value

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Influence of Reducing Agents

 Particle size and morphology changes with type of reducing
agent
Gold particles prepared with

Sodium Citrate - Citric Acid - faceted

Sphere

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Influence of Reducing Agents

Particle size of Pd-colloids as a function of peak potentials Ep(Ox) of

the carboxylates
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Influence of Stabilizer

Pt nanoparticle with sodium-polyacrylate

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Influence of Stabilizer

27 C 30 C 35 C

Ag Nanoparticles – likely stabilized by electrostatic stabilization

mechanism
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Non-Oxide Semiconducting
Nanoparticles

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Size of Semiconductor Nanoparticles

Size of quantum dots can be used to tune color and emission
wavelength

Emission from Colloidal CdSe Quantum

Dots Dispersed in Hexane

Size: ~2 nm to 8 nm

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Controlling Size

 Injecting reagents together in hot reaction vessel – short burst

of homogeneous nucleation

 Depletion of reagent stops further nucleation and growth

 Gentle reheating causes slow and uniform growth

 To make larger uniform size …reheating causes small nuclei to

dissolve and further deposit on large ones – Ostwald ripening

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Oxide Nanoparticles
• Several methods
– Principles: burst of homogeneous nucleation +
diffusion controlled growth

– Controlling size is more difficult by Ostwald

ripening – as oxides are chemically and thermally
more stable

– most common technique – Sol gel method

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Sol Gel Processing

Precursors
* Metal alkoxides, M(OR)Z, in organic Gel formation
solvent
where M = Si, Ti, Zr, Al, Sn, Ce
OR = an alkoxy group
Z = the valence or the oxidation state of the
metal
* Metal salts (chloride, oxychloride,
nitrate..) in aqueous solution
-much cheaper and easier to handle

Basic mechanism
* Hydrolysis M-OR+ H2O = M-OH + ROH
* Polycondensation
M-OH + RO-M = M-O-M + ROH
M-OH + HO-M = M-O-M + H2O
- Occurs sequentially and in parallel 30

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Traditional Sol-Gel Methodology

Hydrolysis

Condensation

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Characteristics of Sol Gel Processing

 Low processing temperature

 Molecular-level homogeneity

 Useful in making complex metal oxides, temperature-

sensitive organic-inorganic

 hybrid materials and thermodynamically unfavorable

or metastable materials

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Sol-Gel Processing

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Oxide Nanoparticles

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Sol-Gel Products

• Monodispersed nanoparticles
– temporal nucleation followed by diffusion-
controlled growth
– colloid stabilization: by electrostatic double layer
– size = f(concentration, aging time)

• Complex oxides, organic-inorganic hybrids,

biomaterials

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Vapor Phase Reactions

• Same mechanism as liquid phase reaction
• Elevated temperatures + vacuum (low
concentration of growth species)
• Collection on a down stream non-sticking
substrate at low temperature
• example: 2~3 nm silver particles
• may migrate and agglomerate – difficult to
prevent agglomeration

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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 - no effect on morphology

• Size increases with

– reaction and nucleation temperature
– Concentration of growth species
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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 (mostly as ions)
– glass quenching to room temperature
– glass anneal above the Tg
– solid-state diffusion and nanoparticles formed

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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!)

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Heterogeneous Nucleation

 Wetting angle represents S-L-A interaction

Young’s Equation:
SA = SL + LA Cos

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Heterogeneous Nucleation
A new phase forms on a surface of another material
– associate with surface defects (or edges)

– thermal oxidation, sputtering and thermal oxidation, Ar

plasma – used to create surface defects

– Growth species impinge onto and form nuclei on

substrate

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Heterogeneous Nucleation

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Kinetically Confined Synthesis

• Spatially Confine the Growth

limited amount of source materials

– liquid droplets in liquid (micelle & microemulsion)

– liquid droplets in gas phase (aerosol & spray)

or
available space is filled up

– template-based
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Emulsion & Microemulsion

A dispersion of droplets of one liquid in another,

immiscible liquid
• Macroemulsions (d > 1000 nm)

• Miniemulsions (100 nm < d < 1000 nm)

• Microemulsions ( 10 nm < d < 100 nm)

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Micelles
surfactants or block polymers

two parts: one hydrophilic and one hydrophobic

self-assemble at air/aqueous solution or

hydrocarbon/aqueous solution interfaces

- Decrease of surface tension

- Droplet stabilization

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Polyelectrolyte-Modified Microemulsions

 Oppositely charged PEL

can be incorporated

 PEL increase the

stability of the surfactant
film

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Nanoparticle Synthesis by Microemulsions

Microemulsion I Microemulsion II

containing
e.g. 1mM BaCl2

Precipitation

containing
e.g. 1mM Na2SO4

BaSO4 nanoparticle
formation!
Mix Microemulsion I and II

Collision and
coalescence of droplets

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Aerosol Synthesis

• Process
– liquid precursor -> mistify -> liquid aerosol ->
evaporation or reaction -> nanoparticles
– polymer particle 1~20 μm (from monomer
droplets)

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Aerosol Synthesis
Droplet-to-Particle Conversion

• Process
– liquid precursor -> mistify ->
liquid aerosol ->
evaporation or reaction ->
nanoparticles

– Polymer Particles of 1~20

μm (from monomer droplets)

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S.E. Pratsinis, Tutorial session at the 14th Annual Meeting of the AAAR, Pittsburgh, Pa, 9 October 1995.

Spray Pyrolysis

• Solution process
– metal (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 at 400°C

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Spray Pyrolysis

Messing et al, J. Am. Ceram. Soc., 1993

evaporation – evaporation of solvent from the surface, diffusion of solvent vapor away
from droplet, change in droplet temperature, diffusion of solute toward the center of the
droplet, change in droplet size

precipitation/drying – involves volume precipitation or surface precipitation of the solute,

followed by the evaporation of the solvent through the nanoporous crust

thermal decomposition or pyrolysis – forms a nanoporous structure

sintering – involves the adhesion/solidification of the crystallites

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Spray Pyrolysis
Messing et al, J. Am. Ceram. Soc., 1993

Che et al, J. Aer. Sci., 1998

precipitation behavior can be controlled by the solubilities of the

starting materials or by introducing a precipitation reaction into the
droplet 52

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Template-Based Synthesis
• Templates
– cation exchange resins with micropores
– zeolites
– silicate glasses
• Ion exchange
• Nanoparticles form in the pores of templates

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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

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