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An Introduction
Au NPs
13 nm & 50 nm
~ 2nm diameter
Nanoscience
The study of properties and manipulation of structures
having nanometer dimension (1-100 nanometers)
The cup appears red in transmitted light (if a light source is kept within
the cup) and appears green in reflected light (if the light source is outside)
Richard Feynman
Classification of Nanomaterials
Nanomaterials are materials with at least one dimension falling
in nanometer scale (1-100 nm) or where the sizes of the
individual blocks are less than 100 nm.
Amorphous or crystalline
Single crystalline or polycrystalline
Composed of single or multi-
chemical elements
Exhibit various shapes and forms
Exist individually or incorporated 50 nm
in a matrix
Metallic, ceramic, or polymeric
Nanoparticles: Types
Metals: Au, Ag, Cu, Fe
Oxide ceramics: Al2O3, CuO, Fe3O4, ZnO, CeO2
Nitride/carbide ceramics: AlN, SiC
Semiconductors: TiO2, SiO2, SnO2
Metal alloys: Al2Cu, Ag2Al
Nanowire and nanotubes of metals, oxides and other materials have been made
Two-Dimensional Nanomaterials
Two of the dimensions are not confined to the nanoscale
Include nanofilms, nanolayers, nanosheets and nanocoatings
The area of the nano films can be large (several m), but their
thickness is very small (only few nm)
CdTe CdSe
1. Optical Properties Quantum Dots
Bulk semiconductor solids - Energy levels are closely spaced and form
quasi-continuous bands
Quantum dots - Energy level separation increases and discrete energy
levels are observed due to quantum confinement
The quantized energy levels in quantum dots lead to electronic structures that
are intermediate between single molecules (which have a single HOMO-
LUMO gap) and bulk semiconductors which have continuous energy levels
within bands
1. Optical Properties Quantum Dots (cont.)
Semiconductor band gap increases with decrease in size of the
nanocrystal
More energy is
needed to excite the
dot and thus more
energy is released
when the crystal
returns to its ground
state resulting in a
color shift from red to
blue in the emitted
light
1. Optical Properties: Colour of Gold
Bulk gold
appears yellow in colour.
Nano-sized gold
The colour of gold can range from purple to red depending on
the size of the atom clusters.
Different sizes of particles reflect and absorb light differently
1. Optical Properties: Colour of Gold (cont.)
Bulk gold reflects light - Shiny appearance
At the nanoscale, the electron cloud at the surface of a gold
nanoparticle resonates with different wavelengths of light
Depending on the size of the nanoparticle, the electron cloud will
be in resonance with a particular wavelength of light and absorb
that wavelength.
e.g.
- 90 nm size Absorb colours on the red-yellow end Blue-
green appearance
- 30 nm size Absorbs blues and greens Red appearance
2. Physical Property: Melting Point of a Substance
Melting Point
Temperature at which the atoms, ions, or molecules in a substance
have enough energy to overcome the intermolecular forces that hold
the them in a fixed position in a solid
Surface atoms require less energy to move because they are in contact
with fewer atoms of the substance.
Melting point decreases with size
In contact with 3 atoms
Top-down
Introduces internal stress, in addition to surface defects and
contaminations
Imperfection of the surface structure - Defects in the surface
structure can have a significant impact on physical properties
and surface chemistry of the nanostructure
Synthesis of Nanomaterials
There are physical as well as chemical methods to prepare
nanomaterials
1. Physical methods: - Ball milling, Inert gas condensation,
Arc discharge, Ion sputtering, Laser ablation, Spray
pyrolysis, Flame pyrolysis, Thermal evaporation, Pulsed
laser deposition, Molecular beam epitaxy
Disadvantages:
Shape of the nanomaterial will be irregular
There may be contaminants inserted from ball and milling
additives
Produces crystal defects
Inert Gas Condensation
Most known and simplest technique for production of
nanoparticles (e.g. metal nano-powders)
Evaporate the material (e.g.: metal) in a chamber using resistive
heating
Previously evacuated to
about 107 torr and backfilled
with inert gas (e.g. helium
gas) to a low-pressure.
Inert Gas Condensation (cont.)
The metal vapour cools through collisions with the inert
gas atoms and losses their kinetic energy,
Cooled metal vapour becomes supersaturated and then
nucleates homogeneously
The particle size is usually in the range 1100 nm
The particles are collected in a particle collector
Particle size can be controlled by varying the inert gas
pressure
Arc discharge
Involves the evaporation of the source materials or precursors
through arc discharging between two electrodes
Chamber is filled
with inert gas at low
pressure
TEM
Other e.g.
Fe3C, Fe3N
Laser Ablation
Laser ablation is the process of removing material from a solid
surface (or occasionally liquid) by irradiating it with a laser beam
Consists of a high vacuum or ultra high vacuum system filled with inert
gas or reactive gas, laser beam, solid target and cooled substrate
Laser Ablation (cont.)
Atoms from solid surface of the target are evaporated by making
powerful laser beam to fall on the surface of the target.
Evaporated atoms collide with inert gas atoms (or reactive
gases) forming clusters
Clusters condense on the cooled substrate
Note:
Gas pressure in system is very critical in determining the
particle size and distribution
Simultaneous evaporation of another material and mixing the
two evaporated materials in inert gas leads to the formation of
alloys or compounds.
This method can produce some novel phases of the materials,
which are not normally formed by other techniques (e.g. SWNT)
Ion Sputtering
Sputtering is a process in which atoms are ejected from a solid
target material due to bombardment of the target by energetic
particles (commonly utilized for thinfilm deposition)
Ion Sputtering (cont.)
Sputter deposition can be carried out using Direct Current
(DC) sputtering, Radio Frequency (RF) sputtering or
magnetron sputtering
Consists of an ultra-
high vacuum chamber
[UHV: ~ 1011 mbar]
into which a substrate
is loaded onto a
heated sample holder
Precursors (i.e. source materials) of desired elements (e.g.: Ga, As, Al, P, In,
etc.) are then loaded into heated crucibles or furnaces called Knudsen cells or
effusion cells, outfitted with computer controlled shutters on their exits.
Molecular Beam Epitaxy (cont.)
Method:
The precursors are heated such that, when the shutters are opened,
one obtains a beam of atoms directed towards the substrate
Under such low pressures, the atomic species have very long mean
free paths allowing them to reach the substrate without collisions
with other gas phase species in the chamber (i.e. geometrical size of
the chamber is less than the mean free path of the particle)
Disadvantages
Slow and laborious method (crystal growth rate is typically a few
microns per hour)
More suited for scientific research laboratories than high-volume
production
Equipment involved is complex and very expensive
Chemical Vapour Deposition
Formation of a non-volatile solid film on a substrate by the reaction of
vapour phase chemicals (reactants) that contain the required constituents.
Many materials may be deposited using CVD (e.g. Metals, oxides, sulfides,
nitrides, phosphides, arsenides, carbides, borides, silicides etc.)
Chemical Vapour Deposition (cont.)
CVD reactor
Chemical Vapour Deposition (cont.)
Energy Sources
There are several suitable sources of heat for CVD processes
These include:
Resistive Heating e.g. tube furnaces
Radiant Heating e.g. halogen lamps
Radio Frequency Heating e.g. induction heating
Lasers
Chemical Vapour Deposition (cont.)
Precursors
CVD precursor materials fall into a number of categories such as:
Reduction:
Use hydrogen gas to reduce halides, carbonyl halides and Oxyhalides
Oxidation:
Using oxygen gas to produce oxides
Compound Formation:
A variety of carbide, nitride and boride films can be formed.
Chemical Vapour Deposition (cont.)
Materials That Can be Produced by CVD Processes
CVD is an extremely versatile process that can be used to process almost
any metallic or ceramic compound
Elements
Metals and alloys
Carbides
Nitrides
Borides
Oxides
Intermetallic compounds
Chemical Vapour Deposition (cont.)
Examples for CVD
Chemical Vapour Deposition (cont.)
Advantages of CVD
Can be used for a wide range of metals and ceramics
Has controllable thickness and morphology
Can simultaneously coat multiple components
High growth rates possible
Forms alloys
Good reproducibility
Films deposited will be of very high purity
Can deposit materials which are hard to evaporate
Chemical Vapour Deposition (cont.)
Disadvantages
The precursors need to be volatile at near-room temperature
The metal ion dissociates from the complex and precipitates on the
electrode as the oxide
Templates with desired channels are used for the growth of nanowires in
electrochemical deposition
Template is attached onto the cathode, which is subsequently brought
into contact with the deposition solution
The anode is placed in the deposition solution parallel to the cathode
When an electric field is applied, cations diffuse toward and reduce at
the cathode, resulting in the growth of nanowires inside the pores of
template
Template-based growth of nanowires using electrochemical deposition
When an electric field is
applied, cations diffuse
toward and reduce at the
cathode, resulting in the
growth of nanowires inside
the pores of template
Ag Ni Pt
Advantages of Electrochemical Deposition
The thickness and morphology of the nanostructure can be precisely
controlled by adjusting the electrochemical parameters (by varying
the current density, the time for which the current flows etc.)
Relatively uniform and compact deposits can be synthesized in
template-based structures
Higher deposition rates are obtained
The process is relatively cheap, fast and allows complex shapes
The equipment is inexpensive due to the non-requirements of either a
high vacuum or a high reaction temperature
The final films can range in thickness from a few nanometers to tens
of microns and can be deposited onto large specimen areas of
complex shape, making the process highly suitable for industrial use
As a water-based process, it is often more environmentally friendly
than deposition methods that require hazardous solvents and reactive
precursor chemicals (eg. organometallic compounds, metal carbonyls
etc.)
Self-assembly
An ordered arrangement of molecules or small components such as
small particles occurred spontaneously under the influence of certain
forces such as chemical reactions, electrostatic attraction or capillary
forces
A typical self-assembling
surfactant molecule
consisting of three parts:
surface group, alkyl and
surface-active headgroup.
Self-assembled monolayers (SAM)
Self-assembly is often used for the surface modification by
formation of a single layer of molecules, which is commonly
referred to as self-assembled monolayer
Self-assembled monolayers are ordered and closely packed
molecular assemblies that have a two-dimensional crystalline-like
structure, though there exist a lot of defects.
Mostly formed by the immersion of an appropriate substrate into a
solution of an active surfactant in an organic solvent
A longer immersion time is required for surfactants with long alkyl
chains
A reduction in surfactant concentration in solution takes longer time
to form a complete monolayer
The ability to form a complete monolayer is obviously dependent on
the substrate, or the interactions between the monolayer molecules
and the substrate surface etc.
Self-assembled monolayers (cont.)
The concept of monolayers was first introduced by Irving Langmuir in
1917, during his study of amphiphiles in water
Method:
A hydroxylated surface is introduced into a solution (e.g. ~ 5 X 10-3M) of
alkyltrichlorosilane in an organic solvent for a few minutes
The origin of the lateral capillary forces is the deformation of the liquid
surface, which is supposed to be flat in the absence of particles
Substrate
The presence of solid particles will deforms the liquid surface thereby
creating lateral capillary forces
Substrate
Limitation:
The materials requirement that the nanoparticles being assembled must
respond to a magnetic field
7. Gravitational field assisted assembly
Sedimentation in a gravitational field is used in self-assembly of
nanoparticles and used in the growth of colloidal crystal
Size and density of the particles and the rate of sedimentation are
few parameters that have to be carefully chosen to grow highly
ordered colloidal crystals
Assembly by sedimentation
Disadvantages
The major disadvantage of the sedimentation method is that it has
very little control over the morphology of the top surface and the
number of layers.
It also takes relatively long time to complete the sedimentation.
8. Template-assisted assembly
Templates made of microstructures can be used to assist the self-
assembly; in which active sites embedded on the substrate can selectively
induce nanoparticle deposition.
Surface confinement
provided by liquid droplets
has been used to
assemble colloidal
particles into spherical
objects