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Nanoscience and Nanotechnology:

An Introduction

Dr. M. Mary Sheeba


Department of Chemistry, NITT
What is Nano
What is Nanometer ?
A nanometer is one billionth of a meter
(1 nm = 109 m)
How Small is Nano?

Au NPs
13 nm & 50 nm

~ 2nm diameter
Nanoscience
The study of properties and manipulation of structures
having nanometer dimension (1-100 nanometers)

Nanoscience is concerned with materials and systems


whose structures and components exhibit novel and
significantly different physical, chemical and biological
properties, because of their small nanoscale size.
Nanotechnology
Design, fabrication and applications of nanostructures and
nanomaterials

Nanostructures and Nanomaterials


Have at least one dimension falling in nanometer scale
(1-100 nm)
Include nanoparticles, nanorods and nanowires, thin films, and
bulk materials made of nanoscale building blocks

Fundamental understanding of physical properties and phenomena


of nanomaterials and nanostructures

An interdisciplinary field which needs physics, chemistry,


engineering, biology etc.
History of Nanotechnology
The Lycurgus Cup
Made by the Romans around fourth century (AD)

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)

Unusual optical properties is due to the glass containing tiny amounts of


colloidal gold and silver
Medieval stained glass
6th-15th Centuries:
Trapped gold and silver nanoparticles in the glass matrix generate
the ruby red, orange and yellow colours in the windows of medieval
European churches
Damascus Sword
13th-18th Centuries:
- Damascus steel: Special type of steel used for
manufacturing sword blades in Western Asia
- Renowned and practically legendary for its mechanical
strength, flexibility and sharpness
- Contained carbon nanotubes and cementite nanowires

HRTEM images of remnants from dissolution of a


sample of genuine Damascus sword in hydrochloric acid
Michael Faraday's Recognition of Ruby Gold: The
Birth of Modern Nanotechnology

1857: Michael Faraday discovered colloidal ruby gold,


demonstrating that nanostructured gold under certain lighting
conditions produces different-colored solutions.
Vision of Nanotechnology in 1959: There's Plenty
of Room at the Bottom

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.

Nanostructured materials are classified as


zero-dimensional (0-D)
one-dimensional (1-D)
Two-dimensional (2-D)
Three-dimensional (3-D)

Classification is based on the number of dimensions, which are


not confined to the nanoscale range (<100 nm)
Zero-Dimensional Nanomaterials
Possess nano-dimensions in all the three directions
Includes nanoparticles and quantum dots
Many of these are spherical (diameter 1-50 nm range)

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

Iron Oxide nanoparticles with different particle size


One-Dimensional Nanomaterials
One dimension of nanostructure is
outside the nanoscale
Include nanotubes, nanorods, and
nanowires
Long (several m in length), but with
diameter of only a few nm
carbon nanotubes

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)

TEM image of Graphene HR-TEM image of Graphene


Three-Dimensional Nanomaterials
Three dimensions of the nanostructure are outside the nanometer
range.
These include bulk materials, where the sizes of the individual
blocks (or structural units) are in the nanoscale (1-100 nm)
Dispersions of nanoparticles, bundles of nanowires, and
nanotubes as well as multi-nanolayer
Special Nanomaterials or Carbon-based Nanomaterials
Composed mostly of carbon
Most commonly taking the form of a hollow spheres, tubes, or sheet

Graphene - Two dimensional (thickness of few nm)


Fullerenes - Spherical
Carbon nanotubes - Cylindrical (SWCNT & MWCNT)
Nanoscale Size Effect (cont.)
Size determines the properties
Bulk objects : Properties do not change much with size
Nano : Change in size affects properties enormously

50 nm and above: Properties similar


to those of the bulk
10-50 nm: Properties may vary
linearly with size
< 10 nm : Get unusual and new
properties
Whats interesting about the nanoscale?
Types of properties that often change
Optical (e.g. Colour)
Electrical (e.g. Conductivity)
Physical (e.g. Melting point)
Chemical (e.g. Reactivity)
Magnetic (e.g. Superparamagnetism)

Reasons for unique properties at nanoscale:


1. Very high surface area to volume ratio
2. Quantum size effect
Surface Area to Volume Ratio
Nanomaterials have very high surface area to volume ratio

Bulk Material Nanoparticles


High Surface Area to Volume Ratio (cont.)
Example of Gold Nano particle:

Sphere of radius 13 nm contains total approx. 480,000 atoms.


surface contains approx. 48,000 atoms.
So, approx. 10% atoms are on the surface.

Sphere of radius 5 nm contains total approx. 32,000 atoms.


surface contains approx. 8000 atoms.
So, approx. 25% atoms are on the surface.

Reactions are very quick - A greater amount of a substance comes in


contact with surrounding material
Can be used for catalysis - Surface atoms have unused electrons, so
very reactive
Quantum Confinement
Quantum confinement occurs when the particle size of the material
is too small to be comparable to the Bohr exciton radius (distance in
an electron-hole pair), thus confining the electron mobility

Confine the motion of randomly moving electrons to specific


energy levels Quantization of energy levels

The effect of confinement on the resulting energy states can be


calculated by quantum mechanics, as the particle in the box
problem.
Quantum Confinement
An electron is considered to exist inside of an infinitely deep
potential well, from which it cannot escape and is confined by
the dimensions of the nanostructure.
Quantum Confinement

Smaller the dimensions of the nanostructure (smaller L), the


wider is the separation between the energy levels, leading to a
spectrum of discrete energies.
1. Optical Properties Quantum Dots
Quantum dots
Tiny nanocrystals of a semiconducting material with diameters in
the range of 2-10 nanometers (10-50 atoms)
Quantum dots can emit any colour of light from the same material
simply by changing the dot size. (eg. CdSe, CdTe, ZnS)

e.g. Semiconductor CdSe


- Normally reddish in colour.
- Below 5 nm, dramatic change in its optical properties

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

In contact with 7 atoms

Melting point of bulk gold ~ 1064 0C


Nanoscale gold melts at ~ 300 0C
Understanding Melting Point: macro vs. nano
At the macro scale At the Nanoscale
The majority of almost all on the inside split between the inside
the atoms of the object and the surface of the
are object

Changing an has a very small effect has a big effect on the


objects size on the percentage of percentage of atoms on the
atoms on the surface surface

The melting doesnt depend on size is lower for smaller


point particles
3. Chemical Property: Reaction Rate
High surface area to volume ratio
A greater proportion of the material exposed for potential reaction
Very reactive
Example:
Which dissolves faster in water?

Granulated sugar Sugar cubes


4. Magnetic Properties: Superparamagnetism
Superparamagnetism - Appears in small ferromagnetic
materials
Ferromagnets
- Will tend to stay magnetized even after removal of external magnetic field
- Hysteresis: Tendency to "remember their magnetic history"
- Remanence: The fraction of the saturation magnetization retained when the
driving field is removed
4. Magnetic Properties: Superparamagnetism (cont.)
As particle size decreases, the number of magnetic domains per
particle decreases down to the limit where it is energetically
unfavorable for a domain wall to exist.
In superparamagnetism, each particle behaves like a single
magnetized domain, where the system is in a state of uniform
magnetization and behaves like a small permanent magnet.
Introduction: Synthesis of Nanomaterials
Two main approaches used for the synthesis and fabrications of
nanomaterials:

1. Bottom-up approach - Small structures to grow to large


particles
2. Top-down approach - Large structure to breakdown to
small structures
Bottom-up Approach
Construction of nanomaterial from the bottom, i.e. atom-by-
atom, molecule-by-molecule or cluster-by-cluster
Atoms or molecules are used as the building blocks to produce
nanoparticles, nanotubes, nanorods, thin films or layered
structures
Examples for Bottom-up approach:
Synthesis of large polymer molecule
Fabrication of integrated circuits
Crystal growth
Nanolithography
Top-down Approach
Starting from large pieces of material and producing the
intended structure by mechanical or chemical methods.
Cutting, grinding and etching are typical fabrication techniques
Sizes of the nanostructures produced are between 10 to 100 nm.

Examples for Top-down Approach:


Creating circuits on the surface of a silicon microchip by
etching
Attrition or milling in making nanoparticles

NOTE: Lithography A process in which a sample is patterned by


removing some part of it (i.e. etching) or by organising some material on a
suitable substrate
Considered as a hybrid approach, since the growth of thin films is
bottom-up whereas etching is top-down
Advantage & Disadvantages of
Bottom-up and Top-down Approaches
Bottom-up
Nanostructures with less defects, uniform morphology, more
homogeneous chemical compositions and better short/long
range ordering

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

2. Chemical methods:- Metal nanocrystals by reduction,


Solvothermal synthesis, Photochemical synthesis,
Electrochemical synthesis, Micelles and Microemulsions,
Chemical vapour deposition (CVD), Sol-gel process

3. Lithographic techniques: Photolithography, Electron beam


and Focused ion beam lithography
Ball Milling
Ball mill - Cylindrical device used for grinding (or mixing)
materials to as small as few nanometers.
How it works?
- A cylindrical capped container directly connected to motor for
rotation
- Container partially filled with the material to be ground (powder
or flakes) & the grinding medium (hard spherical balls, e.g.
Tungsten carbide balls, ceramic balls, flint pebbles, stainless steel
balls
- When the container is rotating about a
horizontal axis, the material is forced to
the walls and is pressed against the
walls. This internal cascading effect
reduces the material to a fine powder.
Ball Milling (cont.)
simplest ways of making nanoparticles of some metals and
alloys in the form of powder (Co, Cr, W, Ni- Ti, Al-Fe, Ag-Fe
etc.)
Size of container depends upon the quantity of interest
Larger balls used for milling, produce smaller grain size and
larger defects in the particles (2:1 mass ratio of balls to material
is advisable)
The grinding media should be denser than the material to be
ground
If the container is more than half filled, the efficiency of milling
is reduced
By controlling the speed of rotation of the container as well as
duration of milling, it is possible to ground the material to fine
powder (few nm to few tens of nm)
Ball Milling (cont.)
Advantages are:
Can be used dry or wet
Inexpensive and easy process
Can be intermittent or continuous operation
For explosive materials, the mill can be filled with inert gas
instead of air
High yield production

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

Arc plasma can be generated between two electrodes in chamber


when the electric current is high enough to initiate the electric
breakdown of the background gas

Arc discharge lead to the evaporation of source materials on the


electrodes
Arc discharge (cont.)
Note:
Electrical breakdown or dielectric breakdown is a long reduction
in the resistance of an electrical insulator when the voltage
applied across it exceeds the breakdown voltage

The breakdown voltage of an insulator is the minimum voltage


that causes a portion of an insulator to become electrically
conductive. This results in the insulator becoming electrically
conductive. The current through a normally nonconductive media
such as air produces a plasma

Plasma A mixture of free electrons, ions and photons.


Arc Discharge (cont.)
Simplest and useful method which leads to mass scale production
of fullerenes and carbon nanotubes
The positive electrode itself acts as the source of material
Gap between the electrodes is ~ 1 mm and high current ~ 50 to 100
amperes is passed from a low voltage power supply (12-15 volts)

Chamber is filled
with inert gas at low
pressure

When an arc is set up,


anode material
evaporates
Gas partial pressure, flow rate and temperature influence the particle size
Arc Discharge (cont.)
Synthesis of Carbon nanotubes
Two carbon rods placed end to end, separated by approximately 1mm,
in an enclosure that is usually filled with Ar gas at low pressure.
A direct current of 50 to 100 A, driven by a potential difference of
approximately 20 V, creates a high temperature discharge between the
two electrodes.
The discharge vaporizes the surface of one of the carbon electrodes,
and forms a small rod-shaped deposit on the other electrode.

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

In all these methods, discharge or plasma of some inert gas


atoms or reactive gases is being used

The deposition is carried out in a required gas pressurized


high vacuum or ultra high vacuum system equipped with
two electrodes (one is a sputter target and the other is a
substrate) and gas introduction facility etc.
DC Sputtering
Target and substrate serve as electrodes and face each other in a
typical sputtering chamber

Target is held at high negative voltage [i.e. acts as cathode:


conductive material, e.g. metal]
Substrate may be at positive voltage or ground [i.e. acts as
anode]
Substrates may be simultaneously heated or cooled depending
upon the requirement
DC Sputtering (cont.)
An inert gas (e.g. Ar) is introduced into the system at a pressure < 0.1
torr as the medium to initiate and maintain a discharge
When an electric field of several kilovolts per centimeter is applied
between the electrodes, a glow discharge is set up resulting a plasma
which is a mixture of free electrons, ions, neutrals and photons
released in various collisions
The positive ions (Ar+) produced in the discharge strike the cathode
(the source target) resulting in the ejection of neutral target atoms
through momentum transfer
Ejected atoms move towards the opposite electrode (anode: substrate)
and deposit there
RF and Magnetron Sputtering
RF sputtering
If the target to be sputtered is insulating, it is difficult to use DC
sputtering
We should use exceptionally high voltage (> 106 V) to sustain a
discharge between the electrodes
Such high voltage will harm the target source and produced film
Instead of applying a DC voltage to the cathode, apply a
oscillating at radio frequency (RF), typically around 13.5 MHz.
Magnetron Sputtering
RF or DC sputtering efficiency can be further increased by
using magnetic field
By adding a magnetic field in the system, the electron will move
in spiral path which will hugely increase the ionization density
of argon gas and opportunity of collision
Deposition rate will be increased
Laser Pyrolysis
Precursor in gaseous form is mixed with an inert gas and heated with
CO2 infrared laser, which initiates and sustains a chemical reaction.

Above a certain pressure and laser power, a critical concentration of


nuclei is reached in the reaction zone, which leads to homogeneous
nucleation of particles that are further transported to a filter by an
inert gas.

Small particle size


Narrow particle size distribution
Absence of aggregation
Si, SiC, Si3N4
Epitaxy
Greek words "epi" means "above" and "taxis means "in ordered
manner, epitaxy means "to arrange upon

Epitaxy is the method of depositing a thin film of single crystal material


on a mono-crystalline substrate
Epitaxial films can be grown from gaseous or liquid precursors, and
the substrate acts as a seed crystal
Orientation of the deposited film is identical to those of the substrate
If the film and substrate are same materials, then the process is
called homoepitaxy or simply isoepitaxy
If the film and substrate are different materials, then the process is
called heteroepitaxy
Widely used for the synthesis of nanostructured materials and
semiconductors (Si, Ge, GaN, GaAs etc.)
Different types: Vapour phase epitaxy, Molecular beam epitaxy, Liquid
phase epitaxy, Solid phase epitaxy and atomic layer epitaxy.
Molecular Beam Epitaxy
An effective epitaxy method for the fabrication of metal, insulator,
semiconductor thin-films

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)

The substrate is sufficiently heated and frequently rotated to improve


the growth homogeneity

By controlling the temperature as well as the sequence/timing of


opening and closing the shutters, one can deposit uniform films of
semiconductor materials
Molecular Beam Epitaxy (cont.)
Advantages
In-situ control of crystal growth at the atomic level
Precise control of surface composition and morphology
Deposition rate is slow (typically less than 3000 nm per hour) that
allows the films to grow epitaxially. Grow films with good crystal
structure
Absence of carrier gases as well as the ultra high vacuum
environment result in the highest achievable purity of the grown films
Low growth temperature (~ 550C for GaAs)

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.)

Reactor chamber: Chamber within which deposition takes place


Gas delivery system: For the supply of precursors to the reactor chamber
Energy source: Provide the energy/heat that is required to get the precursors
to react/decompose
Vacuum system: A system for removal of all other gaseous species other than
those required for the reaction/deposition
Exhaust system System for removal of volatile by-products from the reaction
chamber.
Chemical Vapour Deposition (cont.)
Steps involved in CVD
1. Transport of reactants by forced convection to the deposition
region
2. Transport of reactants by diffusion from the main gas stream
through the boundary layer to the wafer surface
3. Adsorption of reactants on the wafer surface
4. Surface processes, including chemical decomposition or
reaction, surface migration to attachment sites (such as atomic-
level ledges and kinks), site incorporation, and other surface
reactions
5. Desorption of by-products from the surface
6. Transport of by-products by diffusion through the boundary
layer and back to the main gas stream
7. Transport of by-products by forced convection away from the
deposition region
Chemical Vapour Deposition (cont.)

Steps involved in CVD


Chemical Vapour Deposition (cont.)
Note
Growth rate and film quality depend upon the gas pressure and
the substrate temperature

At high temperature, growth rate reduces due to desorption of


precursors from the substrate

Byproducts need to be volatile


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:

Precursors for CVD


processes must be volatile,
but at the same time stable
enough to be able to be
delivered to the reactor.

e.g. Silane (SiH4) is a


popular precursor to
deposit Silicon
Chemical Vapour Deposition (cont.)
CVD reaction types
Pyrolysis:
Thermal decomposition of gaseous species

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

Some of these precursors, especially the metal-organic precursors, can


also be quite costly

CVD precursors can also be highly toxic (Ni(CO)4 ), explosive (B2H6 ),


or corrosive (SiCl4)

Films are usually deposited at elevated temperatures. This puts some


restrictions on the kind of substrates that can be coated.

The byproducts of CVD reactions can also be hazardous (CO, HCl, HF


etc.)
Electrochemical Deposition
Process of using electrical current to reduce cations of a desired material
from a solution and coat that material as a thin film onto a conductive
substrate surface

Relevant to deposition of nanostructured materials (metals and metal


oxides)
Electrochemical Deposition (cont.)
Method
The material to be plated is the cathode of the circuit
Anode is made of the metal to be plated
Both components are immersed in an electrolyte containing one or
more dissolved metal salts as well as other ions that permit the flow
of electricity
A power supply supplies a direct current to the anode, oxidizing the
metal atoms that it comprises and allowing them to dissolve in the
solution.
The dissolved metal ions in the electrolyte solution are reduced at the
interface between the solution and the cathode and will get deposit
onto the cathode
The rate at which the anode is dissolved is equal to the rate at which
the cathode is plated (in relation to the current through the circuit)
Electrochemical Deposition (cont.)
Deposition of metal oxides
The deposition of metal oxides from aqueous solutions is mainly
performed in alkaline solutions containing metal complexes

The metal ion dissociates from the complex and precipitates on the
electrode as the oxide

What controls the ability to deposit an oxide is the stability of that


oxide under the experimental conditions
Examples
CuO from Cu(II)-tartrate or Cu(I) cyanide
Bi2O3 from Bi(III)-tartrate
AgO from Ag(II)-acetate
CeO2 from Ce(III)-acetate
NiOx and MnOx from Ni(II) and Mn(II) ammine complexes
Co3O4 from Co(II)-glycine in alkaline solutions
Electrochemical Deposition (cont.)
MnCo2O4 nanosheets

Electrodeposition of vertically aligned Ag nanoplates


Co3O4 nanosheets
Template-based growth of nanowires using
electrochemical deposition
Electrochemical synthesis of nanowires
Electrochemical deposition has been explored in the fabrication of
nanowires of metals, semiconductors and conductive polymers
Growth of nanowires of conductive materials is a self-propagating
process and it is difficult to control the growth

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

Experimental set-up for the template-based growth


of nanowires using electrochemical deposition

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

Self-assembly is a wet chemical


route to the synthesis of thin
films, mostly organic or
inorganic-organic hybrid films

Chemical bonds are formed


between the assembled
molecules and the substrate
surface, as well as between
molecules in the adjacent layer
Self-assembly (cont.)
Self-assembly (cont.)
A typical self-assembling surfactant molecule can be divided into three
parts:
1. Head group - Allows chemisorption on the substrate surface through
a chemical bond (such as covalent Si-O and S-Au bonds, and ionic -
CO2-Ag+ bond)
2. Alkyl chain
3. Terminal Functionality

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

Katherine Blodgett was able to transfer the monolayer onto a solid


support

The spontaneous formation of a monolayer was first reported by


Zisman, et al. in 1946. They observed the spontaneous monolayer
formation of alkyl amines on a platinum surface

The field observed a tremendous growth when in 1983 Nuzzo and


Allara found that ordered monolayer of thiols can be prepared on a
gold surface by the adsorption of di-n-alkyl disulfides from dilute
solutions
Self-assembled monolayers that chemisorb on the substrates
There are several types of self-assembly methods for the organic
monolayers and these include:
1. Alkanethiols on gold, silver and copper
2. Dialkyl sulfides on gold
3. Alcohols and amines on platinum
4. Carboxylic acids on aluminum oxide and silver
5. Organosilicon on hydroxylated surfaces

Another way to group the self-assembly methods could be based on the


types of chemical bonds formed between the head groups and substrates.
1. Covalent bond (e.g. Si-O) between organosilicon and hydroxylated metal
and oxide substrates
2. Polar covalent bond between alkanethiols or sulfides and noble metals
such as gold, silver, platinum and copper
3. Ionic bond between carboxylic acids, amines, alcohols on metal or ionic
compound substrates
Monolayers of organosilicon or alkylsilane derivatives
Typical formulas of alkylsilanes: RSiX3, R2SiX2 or R3SiX
- X is chloride or alkoxy group
- R is a carbon chain that can bear different functionalities like amine

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

After immersion, the substrate is rinsed with methanol, DI water and


then dried

Organic solvent is in general required for the self-assembly for the


alkylsilane derivatives, since silane groups undergo hydrolysis and
condensation reaction when in contact with water, resulting in
aggregation
Monolayers of organosilicon or alkylsilane derivatives

The fabrication of oxide-metal core-shell nanostructures is heavily relied


on the formation of an organic monolayer linking core and shell materials.
e.g. Fabrication of silica-gold core-shell nanostructures
Organosilicon with amine as a functional group is used to form a
monolayer on the surface of silica nanoparticles by self-assembly
The surface amine groups then attract gold nanoclusters in the solution,
which result in the formation of a gold shell
Monolayers of alkanethiols and sulfides
Monolayers of alkanethiols on gold surfaces are an extensively studied
SA system
When a fresh, clean, hydrophilic gold substrate is immersed into a dilute
solution (e.g.10-3M) of the organosulfur compound in an organic solvent,
a closely packed and oriented monolayer would form
Immersion times vary from a few minutes to a few hours for alkanethiols,
or as long as several days for sulfides and disulfides
Applications of self-assembled monolayers
SA monolayers have been exploited for applications such as surface
chemistry modification of substrates, introduction of functional
groups on the surface, construction of multilayer structures

SA monolayers have also been used to enhance the adhesion at the


interfaces

SAM has been explored to assemble nanostructured materials, such as


nanoparticles into an ordered macroscale structures, such as arrays or
thin films

SA monolayers have also be used in the synthesis and fabrication of


core-shell nanostructures with silane groups linking to oxides and
amines linking to metals
Synthesis of core-shell nanoparticles by self-assembly
Gold-silica core-shell structure
There are typically three steps involved:
1. Synthesis of gold cores with desired particle size and size
distribution sodium (e.g. citrate reduction method)
2. Modify the surface of gold particle by introducing an organic
monolayer
3. Deposition of oxide shell

Au (core)/silica shell nanoparticles


Synthesis of core-shell nanoparticles by self-assembly
Steps involved
Synthesis of gold cores with desired particle size and size distribution
sodium (e.g. citrate reduction method)
A freshly prepared aqueous solution of aminopropyl-trimethoxysilane
(APS) is added to gold colloidal solution under vigorous stirring
A complete coverage of one monolayer of APS is formed on the gold
particle surface.
During this process, the previously adsorbed, negatively charged citrate
groups are displaced by APS molecules, with the silane groups pointing
into solution.
The silane groups in APS molecules in aqueous solution undergo rapid
hydrolysis and convert to silanol groups, which may react with one
another through condensation reactions to form three-dimensional
network.
Synthesis of core-shell nanoparticles by self-assembly
Steps involved (cont.)
A layer of silica will be formed on the modified surface of the gold
nanoparticles by the addition of tetramethyl-orthosilicate solution to
the gold colloidal solution under vigorous stirring for at least 24 hours
In this step, slow condensation or polymerization reaction is
promoted by controlling the pH, so that the formation of a thin,
dense and relatively homogeneous silica layer around the gold
particle can be produced

Au-SiO2 core-shell nanoparticles with varying shell thickness


Synthesis of core-shell nanoparticles by self-assembly
Self-assembly of nanoparticles
Phenomenon of assembling nanoparticles into well-defined
configuration in space

Regular patterns formed during self-assembly of magnetic nanoparticles


Self-assembly of nanoparticles
Self-assembly of nanoparticles or nanowires can be done by:
1. Capillary force induced assembly
2. Dispersion interaction assisted assembly
3. Shear force assisted assembly
4. Assembly by electrostatic interactions
5. Electric-field assisted assembly
6. Magnetic-field assisted assembly
7. Gravitational field assisted assembly
8. Template assisted assembly
1. Capillary force induced assembly
One of the commonly used strategies for self-assembly of nanoparticles
into ordered 2D arrays is based on the lateral capillary interactions

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 magnitude of the capillary interaction between two colloidal


particles is directly proportional to the interfacial deformation created
by the particles
1. Capillary force induced assembly (cont.)
Solid particles will be spread onto the surface of the air-liquid interface
through a spreading agent

The presence of solid particles will deforms the liquid surface thereby
creating lateral capillary forces

Substrate

Lateral capillary interaction to minimize the surface free energy;


consequently, this will act as the driving force for the closely packed
two-dimensional self-assembly of particles
1. Capillary force induced assembly (cont.)
The arrays assembled on the surface of liquid are then transferred
onto solid substrates from the air-water interface
Substrate
Withdraw
substrate

Spherical colloids have been organized into hexagonal closely


packed 2D arrays either on solid substrates or in thin films of liquid
2. Dispersion interaction assisted assembly
According to Hamaker theory, the dispersion interaction force
between two finite-volume spheres is a function of separation
between the spheres
At large interparticle separations (D), the attractive potential (V) is
proportional to D-6, whereas at small interparticle separation
distances, V is inversely proportional to D.
For the self-assembly, V must be comparable to thermal energy (kT).
If V << kT, there is no driving force for assembly. On the other hand,
if V>> kT, the particles will aggregate
In order to form long-range ordered arrays, interparticle attractions
must be strong enough to drive nanoparticles to assemble into
ordered structure
Note: A narrow size distribution, the capping material, and the
nature of the nanoparticle, all play important roles
3. Shear force assisted assembly
Assembly assisted by a fluid flow
The suspensions of nanowires are passed through fluidic channel
structures formed between a polydimethysiloxane (PDMS) mold
and a flat substrate
A shear force is created by the motion of a fluid or substrate
The shear flow near the substrate surface aligns the nanowires in
the flow direction before they are immobilized on the substrate
All the nanowires are aligned along the flow direction over
hundreds of micrometers
Parallel and cross arrays of nanowires can be readily achieved
with single and sequential crossed flows, respectively,.
It was also found that the degree of alignment could be
controlled by the flow rates. Higher flow rates produce larger
shear forces and hence lead to better alignment
3. Shear force assisted assembly

SEM image shows assembly of


nanowires by shear force

Shear forces align nanowires with an


orientation parallel to the fluid flow
4. Assembly by electrostatic interactions
Assembly of nanowires can be driven by electrostatic interactions

These interactions rely on either the inherent polarizability of the


nanostructure or a surface modification of this material to adopt
a specific charge

E.g. Negative charge of silicon oxide at pH 7, that can attract


nanowires with a positive charge (e.g., nanowires coated with an
amine-terminated functionality)

Note: Some anisotropic nanostructures have an inherent charge due


to the formation of a dipole within the material or residual charge
from surface defects. E.g. V2O5 and ZnO nanowires
5. Electric field assisted assembly
Electric field has been explored to assist the assembly of rod-shaped
metallic nanoparticles, carbon nanotubes and metallic nanowire

An alternating electric field has been demonstrated to be able to


precisely align metallic nanowires from a colloidal between two
lithographically defined metal fingers

The metallic nanowires polarize readily in the alternating electric


field due to charge separation at the surface of the nanowires

Nanowires will then experience a dielectrophoretic force that


produces net movement in the direction of increasing field
strength
5. Electric field assisted assembly
As the nanowires approach the electrodes, the electric field
strength between the electrodes and nanowire tips increases
inversely proportional to the distance, and such a strong near
field strength connects the metallic nanowires with the
electrodes in addition to the alignment.

Apply electric field

SEM images ZnO nanowires


assembled between electrodes
5. Magnetic field assisted assembly
A magnetic field can direct the alignment of magnetic nanowires
suspended within a solution

Apply Magnetic field

Nanoparticles assembled onto the substrate will form chain-like structures

Magnetic field-induced self-assembly of Fe3O4 nanocubes into one-dimensional filaments


5. Magnetic field assisted assembly (cont.)
Without external magnetic field, the magnetic moments of
nanoparticles are oriented in random direction

With the increase in magnetic field, the moments of the nanoparticles


start to align themselves along the direction of the magnetic field

When the dipolar interaction energy becomes sufficiently strong, the


magnetic nanoparticles form a chain-like structures

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

The sedimentation process has to be slow enough so that the colloids


concentrated at the bottom of the container will undergo a hard-
sphere disorder-to-order phase transition to form a three-
dimensionally ordered structure
7. Gravitational field assisted assembly (cont.)

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

SEM images of highly ordered aggregates


built of silica particles
8. Template-assisted assembly (cont.)
Schematics of the evaporation-driven aggregation of nanoparticles:

(a) evaporation of a homogeneous droplet suspension, (b) formation


of surface aggregates on the shrinking interface, (c) formation of a
highly ordered surface layer, (d) dense packing of spherical aggregates
and (e) slow drying process of the final colloidal crystal.
8. Template-assisted assembly (contd.)
Colloidal particles are assemble at the interface of emulsion drops

Assembly of colloidal silica particles on the


interface of an emulsion droplet
8. Template-assisted assembly (cont.)
When an aqueous dispersion of colloidal particles was allowed to dewet
from a solid surface that had been patterned with appropriate structures,
the particles were trapped by the recessed regions and assembled into
aggregates whose structures were determined by the geometric
confinement provided by the templates

Arrays of colloidal aggregates that were assembled under


the confinement of templates
Importance of nanoparticle Self-assembly
Ensembles of nanoparticles can have collective properties that are
different to those displayed by individual nanoparticles and bulk
samples

Assembling nanocrystals into solids opens up the possibilities of


fabricating new solid-state materials and devices with novel or
enhanced physical and chemical properties, as interactions between
proximal nano-crystals give rise to new collective phenomena
.
The chemical properties of the monolayers can be used for sensing
applications. A variety of metal ion sensors can be made by
functionalizing the metal surface with a ligand with high specificity to a
particular ion.
E.g: Sensors selective to Cu2+ were made by functionalizing the gold
surface with 2,2-thiobisethyl acetoacetate.