NANOMATERIALS

6TH Semester B. Tech 2014-15

Developed by:
Neha Gupta, PhD
Good Things Come In Small Packages

A Right Proverb For Nanomaterials

 Course: Nanomaterials
Lectures: Wed 9:40 – 11:20 am, Thurs 11:20 -12:10 pm, Room No: 207/seminar
room

Faculty: Dr. Neha Gupta, Assistant Professor

Email: nehagupta181183@gmail.com
Department of Metallurgical and Material Engineering
Room: Process Metallurgy Lab

Recommended Books-
1. Nano structure and nano-materials by Guozhong (AO.(Imperial College Press),
London), 2004.
2. Introduction to Nano technology by Charles P. Poole, Jr and Frauk J. Owens.
(Wiley Interscience , New Jersey, 2003.
3. Nano-structured materials: Processing , properties and Potential Applications
by Carl. C. Koch. (Noyes Publication and William Andrew Publishing) New York.
2002.
 Course Outline: Module 1 (3.5 weeks)

Introduction: Emergence and challenges of

nanotechnology, types of nanomaterials.
Synthesis and characterization: Bottom-up
and top-down approaches, solid, liquid, gas
phase synthesis, Hybrid phase synthesis.
Course Outline: Module 2 (3.5 weeks)
Structural characterization by XRD, SAXS, SEM,
TEM, SPM, gas adsorption.
Chemical characterization by spectroscopic
techniques.
Course Outline: Module 3 (3.5 weeks)
Properties and applications of nanomaterials:
stability of nanomaterials, mechanical
properties, optical, electrical and magnetic
properties, diffusion.
Application of nanomaterials: electronics and
optoelectronics applications, nanobots,
biological applications, catalytic applications,
quantum devices, application of CNTS,
nanofluids.
 Assessment
Total: 100 marks
 Assignment and tutorials: 2.5+2.5 marks
 Attendance + class test: 2.5+2.5 marks
 Exam:
– Internal Mid-Term 1: 10 marks
– Internal Mid-Term 2: 10 marks
– Final: 70 marks
 Thought

No one was ever really taught by another.

Each of us has to teach himself. The external
teacher offers only the suggestion which
rouses the internal teacher to work to
understand things.
- Swami Vivekananda
LECTURE 1
Engineering ??
 Engineering
 Engineering: The branch of science and technology
concerned with the design, building and use of engines,
machines and structures.

Science and technology???????

Science: Intellectual and practical activity
encompassing the systematic study of the
structure and behaviour of the physical and
natural world through observation and
experiment.
Technology: Application of scientific knowledge
for practical purposes.
Deptt. Of Metallurgical and Material
Engineering

Metallurgy and Material ????

 Metallurgy
 Metallurgy: The branch of science and technology concerned
with the properties of metals and their production and
purification.
 Material
 Material: The matter from which a thing is or can be
made.
Introduction to Nanomaterials
 Nanomaterials/Nanostructures
 Nanomaterials are generally the
materials/structures in nanometer (nm) scale
 Nanometer (nm) scales typically range from
subnanometers to several hundred nanometers.
1 nm = = 10-9 m (bulk) = 10-3 μm (micro properties)
Typically 1 nm length = 10 hydrogen or 5 Si atoms
aligned in a line.
 Materials in μm scale, mostly exhibit properties
same as of bulk form.
 Materials in nm scale, may exhibit distinct physical
properties than bulk - increased surface area to
volume ratios - so the small features permit more
functionality in a given space.
Examples: Property Difference in Bulk and nm
 nm crystals exhibit low MP (difference as large as
1000˚C) and reduced lattice constants.
This means that the crystal structure which is stable at
elevated temperatures are now stable at much lower
temperature.
 Bulk semiconductors become insulators when the
characteristic dimension becomes sufficiently small.
 Bulk gold doesn’t exhibit catalytic properties,
nanocrystal gold demonstrates excellent low
temperature catalyst.
 Bulk ferroelectrics and ferromagnets may lose their
ferroelectricity and ferromagnetism, when in
nanodimensions.
Nanomaterials can be natural or manmade.
For example:
1. Nanoparticles are produced naturally by
plants, algae and volcanic activity. They are also
present as proteins in the body.
2. They have also been created for thousands of
years as products of cooking and burning, and
more recently from vehicle exhausts.
 Nanotechnology
 Nanotechnology is design, fabrication and application
of nanostructures or nanomaterials, and the
fundamental understanding of the relationships
between physical properties/phenomena and material
dimensions.
 Why Nanotechnology ?
 On nanometer scale, materials or structures may possess new
physical properties or exhibit new physical phenomena.
For example, band gaps of semiconductors can be tuned by
varying material dimension.
 Miniaturization of current and new instruments, sensors and
machines.
Examples: nanorobots that can repair internal damage and
remove chemical toxins in human bodies.
 High Aspect ratio Quantum Effect

Specific Surface Area of Nanoparticles

1000

800
Surface / km2/m3

600

400

200

0
0 100 200 300 400 500 600 700 800 900 1000
Radius /nm
 Application Perspective
 Nanotechnology has an extremely broad range of
potential applications from nanoscale electronics and
optics, to nanobiological systems and nanomedicine,
to new materials.
 Examples:
1. Nanobots have the potential to serve as vehicles for
delivery of therapeutic agents, detectors or guardians
against early disease and perhaps repair of metabolic
or genetic defects.
2. Au nanoparticles can function as carrier vehicles to
accommodate multiple functionalities through
attaching various functional organic molecules or bio-
components.
3. Small whisker-like particles are used to coat the
surface fibers of the fabric, creating a stain-
repelling surface.
4. Healthcare: antimicrobial bandages coated with
silver nanocrystals.
5. Silver nanoparticles on the surfaces of many new
refrigerators, air conditioners and laundry
machines act as antibacterial and antifungal
agents.
Applications of Nanotechnology

VDI
Applications of Nanotechnology

VDI
 Physical Properties of Nanomaterials
- Reduced Melting Point: Nanomaterials may have a significantly
lower melting point or phase transition temperature and
appreciably reduced lattice constants (spacing between atoms is
reduced), due to a huge fraction of surface atoms in the total
amount of atoms.
- Mechanical properties of the Nano materials are one or two order
of magnitude higher than that of single crystals in the bulk form,
due to reduced probability of defects.
- Optical properties of nanomaterials can be significantly different
from bulk crystals.
1. Semiconductor Blue Shift in adsorption and emission due to an
increased band gap.
2. Metallic Nanoparticles Color Changes in spectra due to Surface
Plasmons Resonances
- Electrical conductivity decreases with a reduced dimension due
to increased surface scattering.
- Magnetic property of the nanostructured materials are distinctly
different from that of bulk materials. Ferromagnetism of bulk
material disappears and transfers to super magnetism in the
nanometer scale due to huge surface energy.
- Self-purification is an intrinsic thermodynamic property of
nanostructures and nanomaterials due to enhanced diffusion of
impurities/defects/dislocations to the nearby surface.
- Increased perfection enhances chemical stability
- and so on…………..

Most are tunable with size!

 Properties of Nanomaterials

Optical properties – color changes with size

The size dependence can be generally classified into two groups:

-One is due to the increased energy level spacing as the system becomes more confined,
- Surface plasmon resonance.
LECTURE 2
 Emergence of Nanotechnology

 Nanotechnology is new, but research on nanometer scale

is not new at all.
 The study of biological systems and the engineering of
many materials such as:
- colloidal dispersions,
- metallic quantum dots,
- catalysts etc.
have been in the nanometer regime for centuries.
For example:
1. Chinese used Au nanoparticles as an inorganic dye to
introduce red color into their ceramic porcelains more
than thousand years ago.
2. Colloidal gold was, and is still, used for treatment of
arthritis.
3. A number of diseases were diagnosed by the interaction
of colloidal gold with spinal fluids obtained from the
patient.
 What has changed ?
 Our ability to image, engineer and manipulate
systems in the nanometer scale.
 We are now able to reduce the size of a
semiconductor device –miniaturization is possible.
 Also, there is availability of characterization and
manipulation techniques at the nanometer level:
- Scanning tunneling microscopy (STM)
- Scanning probe microscopy (SPM)
- Atomic force microscopy (AFM)
- TEM
A molecular person consisting of 14 carbon
monoxide (CO) molecules arranged on a
metal surface fabricated and imaged by
scanning tunneling microscopy.

P. Zeppenfeld & D.M. Eigler, New Scientist 129,20 (23 February 1991)
 BUT !!

The continued size shrinkage of such devices (as

transistors) will sooner or later meet with the limitations
of the materials’ fundamentals.

For example:
Bandgap widening of semiconductors occurs when the
size of the material reaches de Broglie’s wavelength.
 Approaches of Nanotechnology
(growth methods ):
 Two approaches to the synthesis of nanomaterials and
the fabrication of nanostructures:
a. Top-down
b. Bottom-up

Note: Different synthesis and processing approaches

often result in appreciable differences in chemical
composition, crystallinity, and microstructure of the
material due to kinetic reasons. Consequently, the
material exhibits different physical properties.
Bottom-up or top-down?
 Top-Down Approach
 Seek to create nanoscale devices by using larger, externally controlled ones to
direct their assembly.
 The top-down approach often uses the traditional workshop or
microfabrication methods where externally controlled tools are used to cut,
mill, and shape materials into the desired shape and order.
Example: Attrition or milling to make nanoparticles, etching
 The biggest problem with top-down approach is the imperfection of the
surface structure.
 Top-down techniques such as lithography can cause significant
crystallographic damage to the processed patterns. Moreover, additional
defects may be introduced even during the etching steps.
 Such imperfections would have a significant impact on physical properties and
surface chemistry of nanostructures and nanomaterials - since the surface
over volume ratio in nanostructures and nanomaterials is very large.
Example: The surface imperfection would result in a reduced conductivity due
to inelastic surface scattering, which in turn would lead to the generation of
excessive heat and thus impose extra challenges to the device design and
fabrication.
Overall top-down approach is most likely to
introduce:
1. Internal stress
2. Surface defects
3. Contaminants
 Bottom-Up Approach
 Bottom-up approach refers to the build-up of a material from the
bottom: atom-by-atom, molecule-by-molecule, or cluster-by-
cluster.
Example: colloidal dispersion, nanolithography
 Bottom-up approaches, use the chemical properties of single
molecules to cause single-molecule components to:
(a) self-organize or self-assemble into some useful conformation,
or
(b) rely on positional assembly.
Bottom-up is nothing new in materials synthesis.
Typical material synthesis is to build atom by
atom on a very large scale, and has been in
industrial use for over a century.
Example: growth of single crystals and
deposition of films in electronic industry
Polymers are synthesized by connecting
individual monomers together.
In crystal growth, growth species, such as atoms,
ions and molecules, after impinging onto the
growth surface, assemble into crystal structure
one after another.
Overall, the bottom-up approach promises a
better chance to obtain nanostructures with:
1. Less defects,
2. More homogeneous chemical composition,
3. Better short and long range ordering.

This is because: the bottom-up approach is driven

mainly by the reduction of Gibbs free energy, so
that nanostructures and nanomaterials such
produced are in a state closer to a thermodynamic
equilibrium state.
 Challenges in Nanotechnology

Integration of nanostructures and nanomaterials

into or with macroscopic systems that can
interface with people.
 Building and demonstration of novel tools to
study at nm level, what is being manifested at the
macro level.
Remember: The ability to monitor and manipulate
the material processing in the atomic level is
crucial.
 For the fabrication and processing of nanomaterials
and nanostructures, the following challenges must be
met:
(1) Overcome the huge surface energy, a result of
enormous surface area or large surface to volume
ratio.
(2) Ensure all nanomaterials with desired size, uniform
size distribution, morphology, crystallinity, chemical
composition, and microstructure, that altogether
result in desired physical properties.
(3) Prevent nanomaterials and nanostructures from
coarsening through Ostwald ripening or
agglomeration as time evolutes.
 Category of Example
Nanostructures
Zero-dimensional are known as nanoparticles and
nanostructures include precipitates, colloids and
quantum dots (tiny particles of
semiconductor materials)
One-dimensional Nanowires and nanorods
nanostructures
Two-dimensional Thin Films
nanostructures
Nanostructure Size Example Material or
Application

Clusters, nanocrystals, Radius: Insulators, semiconductors, metals,

quantum dots 1-10 nm magnetic materials

Other nanoparticles Radius: Ceramic oxides, Buckyballs

1-100 nm

Nanowires Diameter: 1- Metals, semiconductors, oxides,

100 nm sulfides, nitrides

Nanotubes Diameter: 1- Carbon, including fullerenes, layered

100 nm chalcogenides

Adapted from J.Jortner and C.N.R.Rao, Pure Appl Chem 74(9), 1491-1506, 2002
LECTURE 3
SOLID SURFACES
 Thermodynamics:

tells us that a material/system is stable only when it is in a

state with lowest Gibb’s free energy.
Surface:
a continuous set of points that has length and breadth but
no thickness.

Solid:
have three dimensions (length, breadth and thickness), as a
geometrical body or figure. And is
firm, hard, or compact in substance.
 Nanomaterials and nanostructures possess a large fraction
of surface atoms per unit volume
Example: Fe cube of 1nm3 has every atom surrounded by
surface atoms

Note:
 As number of surface atoms increases the influence of
surface and hence surface energy becomes significant.
 The specific surface area, and thus the surface energy for
large cubes is negligible, however becomes significant for very
small particles.
 Surface Energy
 Surface energy/surface tension: is the extra energy
possessed by the surface atoms
Or
It is the energy required to create a unit area of a new
surface

Here,
G = Gibbs free energy
A= surface area
 As the surface area is very large, so all the
nanomaterials/nanostructures possess a huge surface
energy
- thus are thermodynamically unstable/metastable.
 Therefore, one of major challenges in fabrication and
processing of nanomaterials is:
- to overcome this large surface energy
- to prevent nanostructures/nanomaterials from size
growth (driven by the reduction of the overall surface
energy)
 Hence, in order to produce and stabilize
nanostructures/nanomaterials – it is essential to have a
good understanding of the:
- surface energy
- surface physical chemistry of solid surfaces
 The atoms/molecules on a solid surface posses fewer
nearest neighbours (coordination number). Thus, they have
dangling/unsatisfied bonds, exposed to surface.
 Due to these dangling bonds on the surface:
-The surface atoms/molecules are under an inwardly directed
force.
- The bond distance between the surface atoms/molecules and
sub-surface atoms/molecules – is smaller than that between
the interior atoms/molecules
- For small solid particles, this decrease in bond length becomes
significant and the lattice constants of the entire solid particle
reduces.
- Therefore, the properties of the surface atoms/molecules are
different from interior atoms/molecules – due to fewer bonds
linking to nearest neighbour atoms/molecules, as compared to
their interior.
 Consider separating a
rectangular solid material into
two halves
Newly created surfaces

Singular surface

 On these newly created surfaces: each atom is located in an

asymmetric environment - hence will move towards the interior (due to
surface bond breakage)
 Therefore, an extra force is required to pull the surface atoms back
to its original position (singular surface) – surface energy
Reduction in Surface Energy for a Fixed Surface Area

 For a given surface, having fixed surface area,

the surface energy can be reduced through:

1. Surface relaxation
2. Surface restructuring
3. Surface adsorption
4. Composition segregation/impurity enrichment
 Surface Relaxation

The surface atoms/ions shift inwardly or exhibit

lateral shift
This occur more readily in liquid phase (less
rigid) compared to solid phase
 Such surface relaxation, can result in a
noticeable reduction of bond length in
nanoparticles
 Inward Shift Lateral Shift
Surface atoms are linked with one atom directly beneath Surface atoms may also shift
and other surrounding surface atoms laterally relative to the
subsurface atomic layer.
Considering each chemical force acting as attractive
force, all the surface atoms are under the influence of
net force pointing inwardly and perpendicular to the
surface
Under such a force, distance between the surface atomic
layer would be smaller than inside bulk

Also, distance between atomic layers under surface

would be reduced
 Surface Restructuring
 If a surface atom has more than one broken bonds,
surface restructuring is a possible mechanism to
reduce the surface energy.
 Surface restructuring happens through combining
the surface dangling bonds into strained new
chemical bonds.
 Surface Adsorption
 SA occurs through chemical/physical adsorption of
terminal chemical species onto the surface by forming
chemical bonds/weak attraction forces such as
electrostatic or van der Waals forces
 Example:
1. Diamond surface is terminated with H2
2. Si surface is covered by OH- groups, before restructuring
Composition segregation/impurity enrichment
Composition segregation/impurity enrichment,
through solid state diffusion.
CS, as enrichment of surfactants on the surface
of a liquid, is an effective way to reduce the
surface energy.
In bulk solids, CS is not significant, since the
activation energy required for solid state diffusion
is high and the diffusion distance is large.
In nanomaterials, CS becomes significant in
reducing the surface energy (short diffusion
distance)
Lecture 4,5
 SE Reduction at Nanostructure Level

At individual nanostructure level, the reduction in

total surface energy can happen by two
approaches:

a. Reduction of the overall surface area, assuming

the material is entirely isotropic.
b. Agglomeration of individual nanostructures
without altering the individual nanostructures.
a. Reduction of the overall surface area, assuming the material is
entirely isotropic:
Individual nanostructures can be combined together to form large structures so
as to reduce the overall surface area.
(i) Liquid and amorphous solids: have isotropic microstructure and thus isotropic
surface energy. For such materials the reduction in overall surface energy can
occur by reducing the overall surface area.
example:
Water on a hydrophobic surface always balls up forming a spherical droplet, to
minimize the overall surface area.
Heating glass piece above its Tg, causes sharp corners to round up.
(ii) Crystalline solid: have different crystal facets and hence possess different
surface energy.
- Crystalline particle normally form facets, instead of having a spherical shape and
the thermodynamic equilibrium shape of a given crystal can be determined by
considering the surface energies of all facets.
Generally, crystal surfaces with low miller indices, have a lower surface energy
than that with high miller indices i.e. crystal is often surrounded by low index
surfaces
Wulff plot is often used to represent the ideal situation i.e. the crystal reaches
the minimum surface energy level, thermodynamically.
- However, not all crystals form facets.
Often the equilibrium crystal facets are not smooth and the difference in the
surface energy of various crystal facets may disappear. This transition is known as
surface roughening or roughening transition.
Below the roughening temperature, crystal is faceted, while above this
temperature the crystal does not form facets (as thermal motion predominates).

Note: Most nanoparticles grown by solution methods at elevated temperature are

spherical in shape and do not form any facets.
Mechanisms to combine individual nanostructures into large structures:
A. Sintering
B. Ostwald Ripening (OR)

Macroscopically, reduction in total surface energy is the driving force for

both sintering and OR. Microscopically, the differential surface energy of
surfaces with different surface curvature is the true driving force for mass
transport.
Sintering:
- The individual structures are merged together.
- It is generally negligible at low and room temperature and only becomes significant
when the materials are heated to elevated temperatures (typically 70% MP of
material).
- It is process to replace solid-vapor surface by solid-solid interface through
reshaping the nano-structures such that the individual nanostructures are packed
that there is no gap among solid nanostructures.
- Product obtained is a polycrystalline material.
- Generally, sintering process must be prevented in the fabrication and processing of
nanomaterials.

Ostwald Ripening:
-Relatively large structures grow at the expense of smaller ones.
- Occurs at a wide range of temperatures and proceeds at relatively low temperature
when nanostructures are dispersed and have an appreciable solubility in a solvent.
- The two individual nanostructures become a single one. Large one grows at the
expense of smaller one till the latter disappears completely.
- Occurs in form of solid-solid diffusion and evaporation-condensation.
- Results in a single uniform structure.
 Chemical Potential as a function of
surface curvature
The chemical potential is dependant on the radius of
curvature of a surface (convex/concave).
Convex Concave
The curvature is positive, so the The curvature is negative, so the
chemical potential of an atom on such a chemical potential of an atom on such a
surface is higher than that on a flat surface is lower than that on a flat
surface. surface.

Mass transfer from a flat surface to a When mass is transferred from a flat
convex surface results in an increase in surface to a concave surface, the
surface chemical potential. chemical potential decreases.

Thermodynamically, an atom on a An atom on a concave surface has the

convex surface possess the highest lowest chemical potential.
chemical potential
Note: Smaller particle has larger solubility
Ostwald Ripening (OR) Process:

- Smaller particle has a larger solubility or vapor pressure due to its large
curvature, whereas the larger particle possesses a smaller solubility/vapor
pressure.
- To maintain the local concentration equilibrium:
1. Smaller particle would dissolve into the surrounding medium.
2. Solute at the proximity of smaller particle diffuses away.
3. Solute at proximity of larger particle would deposit.
4. The process will continue till the disappearance of the smaller particle.

- Example:
When two particles of different radii, R1>> R2 are put into a solvent, then each
particle will develop an equilibrium with the surrounding solvent.
According to the dependence of solubility on surface curvature:

where Sc is the solubility of a curved solid surface,

S is the solubility of a flat surface.
This equation is also known as the Gibbs-Thompson
relation

Hence, the solubility of smaller particle will be larger than that of larger particle
-The above equation shows that the solubility of smaller particle will be larger than
that of the larger particle.

- In the process, consequently, there would be a net solute diffusion from the
proximity of small particle to the proximity of larger particle.

- So, to maintain the equilibrium, solute will deposit onto the surface of large
particle. However, the smaller particles has to continue dissolving so as to
compensate for the amount of solute diffused away. As a result, the small particle
gets smaller, whereas the large particle gets larger.

- As dissolution of a nanoparticle proceeds, the nanoparticle becomes smaller and

has higher solubility. Once a nanoparticle starts dissolving into the solvent, the
dissolution process stops only when the nanoparticle is dissolved completely. And
the growth (larger particle)process would continue and would stop when the
concentration of solid in the solvent equals the equilibrium solubility of these
relatively large nanoparticles.
-Depending on the process and applications, Ostwald ripening can have either
positive or negative influence on the resulting materials ie. Often OR is not
desirable.

Example : In sintering of polycrystalline materials, Ostwald ripening results in

abnormal grain growth, leading to inhomogeneous microstructure and hence
inferior mechanical properties of the products (as typically one or a few large grains
grow at the expense of surrounding small grains, resulting in inhomogeneous
Microstructure).

The result id the elimination of smaller particles, thus the size distribution of
nanoparticles becomes narrower.
b. Agglomeration of individual nanostructures without altering the individual
nanostructures:
- In agglomerates, many nanostructures are associated with one another
through chemical bonds and physical attraction forces at interfaces.
- Once formed, agglomerates are very difficult to destroy.
- Stronger they are associated with one another, more are they difficult to
separate.
- For practical applications of nanomaterials, the formation of agglomerates
should be prevented. When small nanostructures form agglomerates,
dispersion becomes difficult.
-When small nanostructures form agglomerates, it is very difficult to disperse
them.
- In nanostructure fabrication and processing, it is very important to overcome
the huge total surface energy to create the desired nanostructures.
-As the dimension of nanostructured materials reduces, van der Waals
attraction force between nanostructured materials becomes increasingly
important. Without appropriate stabilization mechanisms applied, the
nanostructured materials are most likely and readily to form agglomerates.
- It is important to prevent the nanostructures from agglomeration.
There are two major stabilization mechanisms widely used:
i. Electrostatic stabilization (kinetically stable) and
ii. Steric stabilization (thermodynamically stable)

i. Electrostatic stabilization :
When a solid emerges in a polar solvent or an electrolyte solution, a surface charge
will be developed through one or more of the following mechanisms:
(1) Preferential adsorption of ions
(2) Dissociation of surface charged species
(3) Isomorphic substitution of ions
(4) Accumulation or depletion of electrons at the surface
(5) Physical adsorption of charged species onto the surface

-The surface potential of a solid varies with the concentration of the ions in the
surrounding solution, and can be either positive or negative.
- The attraction force between two particles decay much slowly and extends over
distances of nanometers. As a result, a barrier potential must be developed to
prevent agglomeration. Two methods are widely applied to prevent agglomeration
of particles: electrostatic repulsion and steric exclusion.
- The total interaction between two particles, which are electrostatic stabilized, is
the combination of van der Waals attraction and electrostatic repulsion:

-The surface potential of a solid varies with ion concentration in the surrounding
solution and can be positive or negative.
- Ions adsorbed on the solid surface determine the surface charge and thus are
referred to as charge determining ions/cations.
- As the concentration of charge determining ions vary, the surface charge density
changes from positive to negative and vice versa.
- The distributions of both ions are mainly controlled by a combination of the
following forces:
(1) Coulombic force or electrostatic force,
(2) Entropic force or dispersion,
(3) Brownian motion.

Note: The electric potential at the proximity of solid surfaces decreases with
increased concentration and valence state of counter ions.
Limitations of Electrostatic stabilization

(1) Electrostatic stabilization is a kinetic stabilization method.

(2) It is only applicable to dilute systems.
(3) It is not applicable to electrolyte sensitive systems.
(4) It is almost not possible to redisperse the agglomerated particles.
(5) It is difficult to apply to multiple phase systems, since in a given condition,
different solids develop different surface charge and electric potential.
ii. Steric stabilization
- Steric stabilization/polymeric stabilization is a method widely
used in stabilization of colloidal dispersions.
- Polymeric stabilization does offer several advantages over electrostatic
stabilization:
(1) It is a thermodynamic stabilization method, so that the particles are always
redispersible.
(2) A very high concentration can be accommodated, and the dispersion medium
can be completely depleted.
(3) It is not electrolyte sensitive.
(4) It is suitable to multiple phase systems.
- Polymer layer adsorbed on the surface of nanoparticles serves as a diffusion
barrier in the subsequent growth of nuclei.
-Diffusion-limited growth would reduce the size distribution of the initial nuclei,
leading to monosized nanoparticles.
- The adsorption can be either by forming chemical bonds between surface
ions/atoms on the solid and polymer molecules or by weak physical adsorption.
Lecture 6
 Thought

Material should be:

that is useful for human preservance and is
healthy for mother earth.
 Category of Example
Nanostructures
Zero-dimensional are known as nanoparticles and
nanostructures include precipitates, colloids and
quantum dots (tiny particles of
semiconductor materials)
One-dimensional Nanowires and nanorods
nanostructures
Two-dimensional Thin Films
nanostructures
Classification of Nanomaterials
0-D Nanostructures
 0D Nanomaterials

O-D structure is the simplest building block used

for nanomaterials design.
 These have diameters < 100nm
 Can be classified as:
- Nanoparticles
- Nanoclusters
- Nanocrystals
 0D Nanomaterials
 Nanoparticles:
Amorphous/semicrystalline O-D nanostructures with
dimensions larger than 10 nm and relatively large (≥15 %)
size distribution.
 Nanoclusters:
Amorphous/semicrystalline O-D nanostructures with smaller
dimensions (1-10 nm) and relatively narrow size distribution.
 Nanocrystals:
These are crystalline (presence of an orderly lattice array of
constituent subunits) nanomaterials and are mostly single
crystals.
 Quantum Dots:
Are a special case of nanocrystal that is comprised of a
semiconductor. The typical dimensions are in range of 1-
30nm.
0D nanostructure nomenclature
 Nanocrystals
Amorphous Nanoclusters
Absence of pattern

TEM images
Comparison of 0D Nanoarchitectures
with Traditional Colloids
The influence of size and shape on the light-scattering,
and resultant colors, of silver nanoparticles.
 Approaches to obtain 0-D
Nanoparticles
A. Top Down
B. Bottom Up
 A. Top Down Approach
 Top down approaches include:
1. Milling/attrition
2. Repeated quenching
3. Lithography
1. Milling/attrition:
- Obtain nanoparticles in couple of tens to
several hundred nanometers in diameter.
- Gives broad size distribution due to:
- varied particle size/geometry
- significant amount of impurities from
milling medium
- significant defects resulting from milling
2. Repeated quenching/repeated thermal cycling:
- This process can break the bulk material into
smaller pieces, if the material has very small
thermal conductivity but a large volume change
as a function of temperature.
- The process produces finer particles.
- Limitations:
a. The process is difficult to design and control so
as to produce the desired particle size and
shape.
b. The process is limited to materials with poor
thermal conductivity but large volume change.
3. Lithography:
- Lithography is also often referred to as photoengraving, and is the
process of transferring a pattern into a reactive polymer film, termed as
resist, which will subsequently be used to replicate that pattern into an
underlying
thin film or substrate.
- Various lithographic techniques
(a) Photolithography
(b) Phase shifting optical lithography
(c) Electron beam lithography
(d) X-ray lithography
(e) Focused ion beam lithography
(f) Neutral atomic beam lithography
- Amongst these, the most common technique is Photolithography.
Photolithography
 B. Bottom Up Approach
 Various methods used to obtain 0-D
nanomaterials are:
1. Nanoparticles are synthesized by homogeneous
nucleation from liquid or vapor, or by
heterogeneous nucleation on substrates.
2. Nanoparticles/quantum dots prepared by phase
segregation through annealing (at appropriate
elevated temperatures).
3. By confining chemical reactions, nucleation and
growth processes in a small space (eg. Micelles).
Various synthesis methods or techniques can be grouped
into two categories:
I. Thermodynamic equilibrium approach
- In the thermodynamic approach, synthesis process
consists of
(i) generation of supersaturation,
(ii) nucleation, and
(iii) subsequent growth.
II. Kinetic approach
- In the kinetic approach, formation of nanoparticles is
achieved by either:
i. limiting the amount of precursors available for the growth
such as used in molecular beam epitaxy, or
ii. confining the process in a limited space such as aerosol
synthesis or micelle synthesis.
Note: In order for nanomaterials to be used for
“bottom up” design, their synthesis and
resultant properties must be reproducible. This
can be easily accomplished through using
stabilizing agents with well defined structure
that do not react with the entrained
nanostructures.
 Fabrication of Nanoparticles
 Possible morphologies of nanoparticles: spheres, cubes
and platelets
 For the fabrication of nanoparticles, a small size is not
the only requirement. For any practical application, the
processing conditions need to be controlled in such a
way that resulting nanoparticles have the following
characteristics:
(i) Identical size of all particles (also called monosized or
with uniform size distribution),
(ii) Identical shape or morphology,
(iii) Identical chemical composition and crystal structure
(iv) No agglomeration.
Lecture 7,8: Bottom Up Approach
 I. Nanoparticles through Homogeneous
Nucleation
For the formation of nanoparticles by homogeneous nucleation, a
supersaturation of growth species must be created by:
1. A reduction in temperature of an equilibrium mixture, such as a
saturated solution would lead to supersaturation.
Example: Formation of metal quantum dots in glass matrix by
annealing at moderate temperatures.
2. Through in situ chemical reactions by converting highly soluble
chemicals into less soluble chemicals.
Example: semiconductor nanoparticles produced by pyrolysis of
organometallic precursors.
- Through homogeneous nucleation, the nanoparticles can be
synthesized in 3 mediums: solid, liquid, gas.
 Fundamentals of Homogeneous
Nucleation
- When the concentration of a solute in a solvent
exceeds its equilibrium solubility or temperature
decreases below the phase transformation point, a
new phase appears.
Example: consider the case of homogeneous
nucleation of a solid phase from a supersaturated
solution.
A solution with solute exceeding the solubility or
supersaturation possesses a high Gibbs free
energy.
This overall energy of the system would be
reduced by segregating solute (forming a solid
phase) from the solution, while maintaining the
equilibrium concentration in the solution.
This reduction in Gibb’s free energy is the driving
force for both nucleation and growth.
- The change of Gibbs free energy per unit volume
of the solid phase, ΔGv, is dependent on the solute
concentration (C):

- Without supersaturation (i.e. σ = 0), ΔGv is zero, and no

nucleation would occur.
- When C> Co, ΔGv = negative and nucleation occurs
spontaneously.
  Assuming a spherical nucleus with a radius r,
the change of Gibbs free energy or volume energy, can be
described by:

 But this energy reduction is counter balanced by the introduction

of surface energy (accompanied with the formation of a new phase).
This results in an increase in the surface energy of the system:

where ϒ is the surface energy per unit area.

 The total change of chemical potential for the formation of the
nucleus ΔG, is given by:
 From this figure, one can easily observe that the newly formed
nucleus is stable only when its radius exceeds a critical size, r*.
 A nucleus smaller than r* will dissolve into the solution to reduce
the overall free energy.
 A nucleus larger than r* is stable and continues to grow bigger.
 At the critical size r = r*, dΔG/dr = 0 and the critical size, r*, and
critical energy, ΔG*, are defined by:

ΔG* is the energy barrier that a nucleation process must overcome

and r* represents the minimum size of a stable spherical nucleus.
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.
Now, to reduce the critical size and free energy, one needs to
increase the change of Gibbs free energy, ΔGv, and reduce the
surface energy of the new phase, ϒ.
1. Equation below indicates that ΔGv can be significantly increased
by increasing the supersaturation, σ, for a given system.

2. Temperature also influences surface energy. Surface energy

of the solid nucleus can change more significantly near the
roughening temperature.
3. Other possibilities include: (i) use of different solvent, (ii) additives
in solution, and (iii) incorporation of impurities into solid phase, when
other requirements are not compromised.
- Formation of large number of nuclei is dependant on the rate of
nucleation.
- The rate of nucleation per unit volume and per unit time, RN, is
proportional to
(i) the probability, P, that a thermodynamic fluctuation of critical
free energy, ΔG*, given by:

(ii) the number of growth species per unit volume, n, which can be used
as nucleation centers (in homogeneous nucleation, n = Co).
(iii) the successful jump frequency of growth species, ζ, from one site to
another, which is given by:

where λ is the diameter of the growth species and ƞ is the viscosity of

the solution.
So the rate of nucleation RN can be described by:
Above equation indicates that:
1. High initial concentration or supersaturation (a large number of
nucleation sites),
2. Low viscosity and
3. Low critical energy barrier
favour the formation of a large number of nuclei.
Note: For a given concentration of solute, a larger number of nuclei
mean smaller sized (λ) nuclei.
 The nucleation occurs only when the supersaturation reaches a certain value
above the solubility (which corresponds to the energy barrier for the formation of
nuclei).
 After the initial nucleation, the concentration or supersaturation of the growth
species decreases and the change of Gibbs free energy reduces.
 When the concentration decreases below this specific concentration, which
corresponds to the critical energy, no more nuclei would form, whereas the growth
will proceed until the concentration of growth species has attained the equilibrium
concentration or solubility.
- For the synthesis of nanoparticles with uniform size distribution, it
is
best if all nuclei are formed at the same time.
1. In this case, all the nuclei are likely to have the same or similar
size, since they are formed under the same conditions.
2. In addition, all the nuclei will have the same subsequent growth.
Consequently, monosized nanoparticles can be obtained.
So it is highly desirable to have nucleation occur in a very short
period of time.
-In practice, to achieve a sharp nucleation,
1. The concentration of the growth species is increased abruptly to a
very high supersaturation and then quickly brought below the
minimum concentration for nucleation.
Below this concentration, no more new nucleus forms, whereas
the existing nuclei continue to grow until the concentration of the
growth species reduces to the equilibrium concentration.
2. The size distribution of nanoparticles can be further altered in the
subsequent growth process.
The size distribution of initial nuclei may increase or decrease
depending on the kinetics of the subsequent growth process. The
formation of uniformly sized nanoparticles can be achieved if the
growth process is appropriately controlled.
 Subsequent Growth of Nuclei
 The size distribution of nanoparticles is dependent on the
subsequent growth process of the nuclei.
 The growth process of the nuclei involves multi-steps, those
can be further grouped into two processes:
a. Diffusion Limited Process: Supplying the growth species to
the growth surface is termed as diffusion. It includes the
generation, diffusion and adsorption of growth species onto
the growth surface.
b. Growth Limited Process: Incorporation of growth species
adsorbed on the growth surface into solid structure.
Note : A diffusion-limited growth would result in a different
size distribution of nanoparticles as compared with that by
growth-limited process.
 A. Growth controlled by diffusion
If the growth process is controlled by the diffusion
of growth species from the bulk solution to the
particle surface, the growth rate is given by:

Where r is the radius of spherical nucleus,

D is the diffusion coefficient of the growth species,
C is the bulk concentration,
Cs is the concentration on the surface of solid particles, and
Vm is the molar volume of the nuclei
Solving above differential equation and assuming the initial size of
nucleus, ro, and the change of bulk concentration negligible, we
have:

For two particles with initial radius difference, δro, the radius
difference, δr, decreases as time increases or particles grow bigger,
according to:

{[2D(C-Cs)Vm t + ro2].t + ro2}1/2

This implies radius difference decreases with increase of nuclear
radius and prolonged growth time.
Note: The diffusion controlled growth promotes the formation of
uniformly sized particles.
B. Growth Controlled by Surface Process
 When the diffusion of growth species from the bulk to the growth
surface is sufficiently rapid, i.e. the concentration on the surface is
the same as that in the bulk, the growth rate is controlled by the
surface process.

There are two mechanisms for the surface processes:

i. mononuclear growth and
ii. poly-nuclear growth.
Mononuclear Growth Polynuclear Growth
Growth proceeds layer by layer. The Occurs when the surface
growth species are incorporated concentration is very high. The
into one layer and proceeds to surface process is so fast that the
another layer only after the growth second layer proceeds before the
of previous layer is complete. growth of first layer is complete.
Sufficient growth time for species to Particle growth rate is independent
diffuse on the surface. of the particle size or time i.e
growth rate is constant. So, particles
grow linearly with time.
The radius difference increases with Relative radius difference remains
prolonged growth time. constant regardless of the growth
time and absolute particle size.

This growth mechanism does not As the particles get bigger, the
favor the synthesis of monosized radius difference becomes smaller.
particles. This favours the synthesis of
monosized particles.
From these plots, we can say
that diffusion controlled growth
mechanism is required for the
synthesis of monosized particles
by homogeneous nucleation.
Lecture 9, 10
- Using bottom-up approach of homogeneous
nucleation, O-D nanomaterials can be
synthesized by various methods:
1. Solution based process
2. Vapor phase reactions
3. Solid state phase segregation
 I. Synthesis of Nanoparticles through
solution process
- Formation of nanoparticles dispersed in a solvent is the most
common approach and offers several advantages:

(1) stabilization of nanoparticles from agglomeration,

(2) extraction of nanoparticles from solvent,
(3) surface modification and application,
(4) processing control,
(5) mass production.
 A. Synthesis of Metallic Nanoparticles
- Can be synthesized by:
1. Reduction of metal complexes in dilute solutions.
2. Formation of monosized metallic nanoparticles by a
combination of a low concentration of solute and
polymeric monolayer adhered onto the growth
surfaces.
3. Electrochemical deposition method.
- Various types of precursors, reduction reagents,
other chemicals, and methods are used to promote
or control the reduction reactions, the initial
nucleation and the subsequent growth of initial
nuclei.
- The precursors include:
elemental metals, inorganic salts and metal complexes,
such as, Ni, Co, HAuC14, H,PtCl6, RhCl3, and PdCI2.
- Reduction reagents includes:
sodium citrate, hydrogen peroxide, hydroxylamine
hydrochloride, citric acid, carbon monoxide, phosphorus,
hydrogen, formaldehyde, aqueous methanol, sodium
carbonate and sodium hydroxide.
- Examples of polymeric stabilizers include:
polyvinyl alcohol (PVA) and sodium polyacrylate

Note: Go through various examples given in section 3.2.3

 a. Influence of Reduction Reagent
 The size and size distribution of metallic colloids vary
significantly with the type of reduction reagents used in
the synthesis.
 Generally a stronger reduction reaction promotes a faster
reaction rate and favours the formation of smaller
nanoparticles.
 A weak reduction reagent induces a slow reaction rate
and favours relatively larger particles. The slow reaction
may either lead to:
i. Wider size distribution: If slow reaction leads to
continuous formation of new/secondary nuclei.
ii. Narrow size distribution: If no if no further
nucleation/secondary nucleation occurs, a slow reduction
reaction would lead to diffusion-limited growth.
Consequently, a narrow size distribution would be
obtained.
 Using same reduction reagent, nanoparticle size
can be varied by changing the synthesis conditions.
 Reduction reagents also influences particle
morphology.

Spherical Faceted

SEM micrographs of gold nanoparticles prepared with sodium

citrate (a) and
citric acid (b) as reduction reagents, respectively,
under otherwise similar synthesis conditions.
 Concentration of the reduction reagents and pH value of the
reagents have noticeable influences on the morphology of the grown
gold nanoparticles.

For example, lowering the pH value caused the { 1 1 1 } facets to

develop at the expense of the {100} facets in colloidal gold
nanoparticles.
 b. Influences by other factors
 Increasing the amount of polymer in the reaction mixture
increase the sphericity of the particles; as the increased
amount of polymer produces steric resistance for the
diffusion. Consequently resulting in a diffusion controlled
growth, which favours the formation of spherical particles.

 A decreased reduction rate can be achieved using a low

concentration of reactant.

 Many time addition of certain ions in the reaction mixture

promotes monodispersion, spherical particle shape, favours
smooth and rounder surfaces under similar conditions.
 c. lnfluences of polymer stabilizer
 Polymer stabilizers are introduced primarily to form a monolayer on the surface
of nanoparticles so as to prevent agglomeration of nanoparticles.
 The presence of such polymer stabilizers during the formation of nanoparticles
can have various influences on the growth process of nanoparticles:
- Interaction between the surface of a solid particle and polymer stabilizer may vary
significantly depending on the surface chemistry of solid, the polymer, solvent and
temperature.
 A strong adsorption of polymer stabilizers would occupy the growth sites and
thus reduce the growth rate of nanoparticles.
 A full coverage of polymer stabilizer would also hinder the diffusion of growth
species from the surrounding solution to the surface of growing particle.
 Polymer stabilizers may also interact with solute, catalyst, or solvent, and thus
directly contribute to reaction.
 Polymer stabilizers can have catalytic effect on reduction reactions.
 Polymer stabilizers can change the pH of the solution.
 Under same experimental conditions, changing the concentration of Polymer
stabilizers , the shape and morphology of particles can be changed.
 B. Synthesis of non-oxide
semiconductor nanoparticles
CdTe, CdSe, CdS……
Nonoxide semiconductor nanoparticles are
commonly synthesized by pyrolysis of
organometallic precursor(s) dissolved in
anhydrate solvents at elevated temperatures in
an airless environment in the presence of
capping (polymer stabilizer).
Capping materials are linked to the surface of
nanocrystallites via either covalent bonds or
other bonds such as dative bonds.
- The formation of monodispersed semiconductor nanocrystallites is
generally achieved by the following approaches.
i. Temporally discrete nucleation is attained by a rapid increase in
the reagent concentrations resulting in an abrupt
supersaturation.
ii. Ostwald ripening during aging at increased temperatures
promotes the growth of large particles at the expense of small
ones, narrowing the size distribution.
iii. Size selective precipitation is applied to further enhance the size
uniformity.
iv. Thermal decomposition of complex precursor in a high boiling
point solvent to obtain nanoparticles with a narrow size
distribution.

Note: Study examples given in sec 3.2.4

 C. Synthesis of oxide nanoparticles
- Reaction and growth to form oxide nanoparticles are difficult to
manipulate, since oxides are generally more stable thermally and
chemically than most semiconductors and metals.
For example, Ostwald ripening is applied in the synthesis of oxide
nanoparticles to reduce size distribution.

-Oxide nanoparticles can be synthesized using various methods:

1. Sol-gel process
2. Forced hydrolysis
3. Controlled release of ions
 1. Sol-Gel Process
- Sol-gel processing is a wet chemical route for the synthesis of
colloidal dispersions of inorganic and organic-inorganic hybrid
materials, particularly oxides and oxide-based hybrids.
- From such colloidal dispersions: powders, fibers, thin films and
monoliths can be readily prepared.
-Advantages:
a. Low processing temperature and
b. Molecular level homogeneity

-Typical sol-gel processing consists of hydrolysis and condensation of

precursors (either metal alkoxides or inorganic and organic salts).
- Organic or aqueous solvents may be used to dissolve precursors.
- Catalysts are often added to promote hydrolysis and condensation
reactions.
-Condensation results in the formation of nanoscale clusters of
metal oxides or hydroxides, often with organic groups embedded
or attached to them.
- The size of the nanoscale clusters, along with the morphology and
microstructure of the final product, can be tailored by controlling
the hydrolysis and condensation reactions.
-By a careful control of sol preparation and processing,
monodispersed nanoparticles of various oxides, including complex
oxides, organic-inorganic hybrids, and biomaterials, can be
synthesized.
- The particle size can be varied by changing the concentration and
aging time.
- In a typical sol, nanoclusters formed by hydrolysis and
condensation reactions commonly have a size ranging from 1 to
100nm.
- Diffusion controlled growth is achieved through controlled
release and a low concentration of growth species in the sol.
 2. Forced Hydrolysis
Simplest method for the generation of uniformly
sized colloidal metal oxides is based on forced
hydrolysis of metal salt solutions.
 To produce such metal oxide colloids, one just
needs to age hydrolyzed metal solutions at
elevated temperatures.
Hydrolysis reaction should proceed rapidly and
produce an abrupt supersaturation to ensure a
burst of nucleation, resulting in the formation of
a large number of small nuclei, eventually
leading to the formation of small particles.
 3. Controlled Release of ions
 Controlled release of constituent anions and/or cations has a significant
influence on the kinetics of nucleation and subsequent growth of oxide
nanoparticles, and is achieved by the spontaneous release of anions from
organic molecules.
 For example, solutions of urea, CO(NH2)2, when heated liberate hydroxide ions,
can cause precipitation of metal oxide or hydroxide.
 Generally, certain types of anions are commonly introduced into the system as
a catalyst.
 In addition to the catalytic effect, anions commonly exert other influences on
the processing and the morphology of the nanoparticles.
 Presence of anions may result in a change of the surface properties and
interface energy of nanoparticles, and subsequently influence the growth
behavior of the particle.
 Anions may be incorporated into the structure of nanoparticles, or adsorbed
onto the surface of nanoparticles.
 Anions significantly influences the stability of the colloidal dispersion, when
nanoparticles are stabilized by electrostatic stabilization mechanism.
II. Synthesis through vapor phase reactions
 In general, reaction and synthesis are carried out at elevated
temperatures and under a vacuum.
 Vacuum is needed to ensure a low concentration of growth species so
as to promote diffusion-controlled subsequent growth.
 Grown nanoparticles are normally collected on a non-sticking substrate
placed down stream at a relatively low temperature.
 An increase in reaction and nucleation temperature; increased
concentration of precursors; results in an increased particle size.
 However, change in temperature and precursor concentrations have
negligible influence on the morphology of nanoparticles.

- Limitations:
1. Only a small fraction of nanoparticles do settle on the substrate
surface and may not represent the true particle size distribution.
2. It is also difficult to introduce stabilization mechanism during
synthesis to prevent the formation of agglomerates.
 III. Solid-state phase segregation
A. Nanoparticles of metals and semiconductors in glass matrix are
commonly formed by homogeneous nucleation in solid state.
• First the desired metal or semiconductor precursors are
introduced to and homogeneously distributed in the liquid glass
melt at high temperatures during glass making, before quenching
to room temperature.
• Then the glass is annealed by heating to a temperature about the
glass transition point and held for a pre-designed period of time.
During the annealing, metal or semiconductor precursors were
converted to metals and semiconductors.
• As a result, supersaturated metals or semiconductors formed
nanoparticles through nucleation and subsequent growth via
solid-state diffusion.
B. Homogeneous glasses are made by dissolving metals, in the form
of ions, in the glass melts and then rapidly cooled to room
temperature.
 In such glasses metals remain as ions.
 Upon reheating to an intermediate temperature region, metallic
ions are reduced to metallic atoms by certain reduction agents (as
antimony oxide).
 Although metallic ions may be highly soluble in the glass melts or
glasses, metallic atoms are not soluble in glasses.
 When heated to elevated temperatures, metallic atoms acquire
needed diffusivity to migrate through the glasses and subsequently
form nuclei.
 These nuclei would grow further to form nanoparticles of various
sizes (diffusion controlled growth to form monosized particles).
C. Nanoparticles dispersed in glass matrix can be synthesized
through sol-gel processing.
-There are two approaches:
(i) mixing presynthesized colloidal dispersion with matrix sol
before gelation, and
(ii) making a homogeneous sol containing desired ions for the
formation of nanoparticles first and annealing the solid product at
elevated temperatures.
D. Nanoparticles of metals in polymer matrix can be synthesized
through the reduction of metal ions by growing polymer chain
radicals.
- The metal ions are reduced to metal atoms by the growing polymer
chain radicals, and consequently metal atoms nucleated to form
nanoparticles.
-The post heating at higher temperatures is considered to promote
further growth of already formed metallic nuclei.
- The type and concentration of polymerization initiators were found
to have significant effects on size and size distribution of the grown
metallic nanoparticles.
- An increased concentration of polymer initiators result in an
increased amount of polymer chain radicals, which promotes the
reduction of metal ions and thus produce more metal atoms for
nucleation (supersaturation).
- A higher supersaturation permits a smaller size but generates a larger
number of nuclei.
- A high concentration of metal atoms favor the surface process
limited growth, leading to a wide size distribution
E. Metallic nanoparticles are also prepared
through precipitation or crystallization by
annealing amorphous metal alloys at elevated
temperatures.
Lecture 11
Nanoparticles through Heterogeneous
Nucleation

Homogenous Nucleation Heterogeneous Nucleation

Nucleation occur without Nucleation occurs at

preferential nucleation sites preferential nucleation sites (as
phase boundaries, surfaces,
impurities)

Occurs spontaneously and Faster than homogenous

randomly, but requires nucleation and occurs more
superheating/supercooling of often than homogenous
the medium nucleation.
 Surfaces promote nucleation because of wetting
(contact angle >0) between phases.

θ is the contact angle or wetting angle

For Heterogeneous nucleation,

Here, wetting factor,

f (θ) = {(2-3cos θ+cos3 θ)/4}
0 ≤f (θ) ≤1
We know for homogeneous nucleation:

This implies:

ΔG*het = ΔG*hom x f (θ)

 In heterogeneous nucleation, wetting angle determines
the ease of nucleation by reducing the energy required.
 For θ =180˚, f (θ)=1, ΔG*het = ΔG*hom
i.e. no wetting of the surface happens and only
homogeneous nucleation occurs.
 For θ =0˚, f (θ)=0, ΔG*het = 0, i.e. There exist no energy
barrier for nucleation at surface. So, full wetting occurs.
 For θ <180˚, ΔG*het < ΔG*hom
i.e. heterogeneous nucleation becomes easier than
homogeneous nucleation.

Barrier energy for heterogeneous

nucleation becomes less
 Nanoparticle synthesis by heterogeneous
nucleation requires preferential sites which can be
created by:
- Generation of homogeneous surface defects to act
as nucleation centres using: thermal oxidation,
sputtering and thermal oxidation, argon plasma
and ulterior thermal oxidation.
Example: evaporated silver tend to form small
particles on highly oriented pyrolytic graphite
substrate.
- Other defects as surface edges, pit holes etc.
 Nanoparticles can also be synthesized by vapor
phase reactions, where the growth species impinge
onto and form nuclei on the substrate surface.
 Kinetically Confined Synthesis of
Nanoparticles
 Kinetically controlled growth is to spatially confine the growth
so that the growth stops when the limited amount of source
materials is consumed or the available space is filled up.
 Various spatial confinements for the synthesis of
nanoparticles can be divided into several groups:
(i) liquid droplets in gas phase (including aerosol synthesis and
spray pyrolysis),
(ii) liquid droplets in liquid (such as micelle and micro emulsion
synthesis),
(iii) template-based synthesis, and
(iv) self-terminating synthesis.
A. Synthesis inside micelles or using microemulsions

1. In micelle synthesis, reactions proceed among the reactants that

are available only inside the micelle and the particle stops
growing when the reactants are consumed.
-When surfactants or block polymers (consisting of hydrophilic and
another hydrophobic part) are dissolved into a solvent. At critical
concentration, they preferentially self-assemble to form micelles at
the interfaces of air/aqueous solution or hydrocarbon/aqueous
solution.
- Inside micelle, reaction occur and nuclei forms

Scheme of a micelle formed

2. A microemulsion is a dispersion of fine liquid droplets of an
organic solution in an aqueous solution and can be used for the
synthesis of nanoparticles.
- The chemical reactions can take place either at the interfaces
between the organic droplets and aqueous solution, when
reactants are introduced separately into two non-mixable
solutions, or inside the organic droplets when all the reactants
are dissolved into the organic droplets.

 Various monodispersed polymer particles can be prepared using

carefully controlled emulsion polymerizations.
Typically a water-soluble polymerization initiator and a surfactant
are added into a mixture of water and monomer. The hydrophobic
monomer molecules form large droplets, typically 0.5 to 10 pm in
diameter, which are stabilized by the surfactant molecules whose
hydrophilic ends point outward and whose hydrophobic ends point
inward toward the monomer droplet.
 B. Aerosol Synthesis
 Top-down approach
1. Nanoparticles prepared can be polycrystalline (compared with either
single crystalline or amorphous structures prepared by other ethods).
- Here, nanoparticles prepared need to be collected are redispersed for
many applications.
- Process:
a. First, liquid precursor (mixture solution of the desired constituent
elements or colloidal dispersion) is prepared.
b. Liquid precursor is then mistified to make liquid aerosol (uniform
dispersion of liquid droplets in gas).
c. The aerosol may simply solidify through evaporation of solvent or
further react with chemicals (present in gas).
d. Resulting in spherical particles.
- The size of the particles can be determined by the size of the initial
liquid droplets and solid concentration.
- Example: Ti02 particles can be produced from TiC14 aerosols.
2. Aerosol technique can also be used to
prepare polymer colloids.
- Droplets of organic monomers can be either
polymerized in contact with an initiator in
gaseous state, or copolymerized with another
organic reactant.
- Polymer particles formed using aerosol
synthesis are large particles (diameter ~ 1-20
micron)
 C. Growth Termination
 The nanoparticle size can be controlled by growth termination.
 When organic components or alien ions are attached to the
growth surface strongly, so that all the available growth sites are
occupied, growth process stops.
 Example: Synthesis of colloidal particles of CdS is based on the
competitive growth and termination of CdS species in the
presence of thiophenol surface capping agents

The final size of grown

nanoparticles can be controlled
by the concentration of organic
ligands introduced to the system.
  Is a solution process
4. Spray Pyrolysis
 Widely used in the preparation of metal and metal oxide powders.
 The process involves - converting microsized liquid droplets of
precursor or precursor mixture into solid particles through heating.
 Steps involved:
(i) generating microsized droplets of liquid precursor or precursor
solution,
(ii) evaporation of solvent,
(iii) condensation of solute,
(iv) decomposition and reaction of solute, and
(v) sintering of solid particles.

Example: Production of silver particles using

precursor solutions of Ag2C03, Ag20 and
AgN03 with NH4HC03 at temperatures
of 400°C or less.
 5. Template Based Synthesis
 Template possess a well confined void, which is in the form of channels,
pores or connected hollow spaces.
 The connectivity of the pores/channels stringly influences the structure of
the resulting solid product.
 Solid product forms inside the isolated pores, replicating the shape of the
void space in templates. As a result, aligned nano structures are obtained
after removing the template scaffold.
 Example: Fe3O4 nanoparticles dispersed in solid polymer matrix can be
obtained by infiltration of iron chloride solution.
 6. Epitaxial Core–Shell Nanoparticles
 The core/shell type nanoparticles can be broadly defined as comprising a core
(inner material) and a shell (outer layer material).
 Core/shell nanoparticles are highly functional materials with modified properties.
 The purpose of the coating on the core particle are many fold, such as surface
modification, the ability to increase the functionality, stability, and dispersibility,
controlled release of the core, reduction in consumption of precious materials, and
so on.
Nano- and microsized hollow particles are used for different purposes such as
microvessels, catalytic supports, adsorbents, lightweight structural materials and
thermal and electric insulators.

In addition, the shell provides protection

against environmental changes, photo-
oxidative degradation, and provides
another route for modularity
 Classes of Core/Shell
Nanoparticles
 These can consist of a wide range of different combinations
in close interaction, including
inorganic/inorganic,
inorganic/organic,
organic/inorganic, and
organic/organic materials.
 The choice of shell material of the core/shell nanoparticle is
generally strongly dependent on the end application and
use.
 Multiple core core/shell particles are formed when a single
shell material is coated onto many small core particles
together
 CORE/SHELL NANOPARTICLE SYNTHESIS
 In general, core/shell nanoparticles are synthesized using a two-step process,
first synthesis of core and second the synthesis of the shell.
 The synthesis techniques of core/shell nanoparticles can be classified into two
types depending on the availability of core particles:
 (i) the core particles are synthesized and separately incorporated into the
system with proper surface modification for coating the shell material;
 (ii) the core particles are synthesized in situ, and this is followed by coating
of the shell material.
 The basic advantage of external core synthesis is the fact that core particles are
available in pure form and hence there is less possibility of impurities on the
core surface.
 Whereas, in in situ synthesis, the main problem is that some impurity from the
reaction media may be trapped between the core and shell layer.
 The most important step during synthesis of core/shell particles is to maintain
uniform coating and to control the shell thickness.
 Some of the various synthetic methods for core/ shell particles used by
different research groups are precipitation, polymerization, microemulsion, sol-
gel condensation, layer by layer adsorption techniques etc.
 Figure: Schematic diagram for Cu/Cu2O core/shell nanoparticle synthesis using the
thermal decomposition of a metal organic complex

Generally core/shell nanoparticles are well-known for better stability, for

being able to protect the core material from the surrounding environment,
for improved physical and chemical properties, for improved semiconductor
properties, for easy biofunctionalization, etc.

• The main difficulties are

(i) agglomeration of core particles in the reaction media,
(ii) preferential formation of separate particles of shell material
rather than coating the core,
(iii) incomplete coverage of the core surface, and
(iv) control of the reaction rate.
 Example Application

Biomedical Applications- Controlled Drug

Delivery and Specific Targeting, Bioimaging,
Sensors, Replacement, Support, and Tissues
 Lecture 12

1D Nanomaterials
 Various 1D nanostructures:
- whiskers
- nanorods
- nanowires
- Fibers/fibrils
- Nanotubules
- Nanocables
 Whiskers and nanorods are shorter than fibers and
nanowires
 Whiskers and fibers – diameters range from several nm
to several 100 nm
 Nanowires and nanorods – diameters upto few 100 nm
 Nanowires have high aspect ration than nanorods
 Synthesis Methods
Bottom up:

Top Down
(4) Lithography
Spontaneous growth commonly results in formation of single crystal nanowires/nanorods
along a preferential crystal growth direction.
Template based synthesis, mostly produces polycrystalline or amorphous products.
 1. Spontaneous Growth
 Growth is driven by reduction of Gibbs free
energy or chemical potential, by phase
transformation or chemical reaction or stress
release.
 For formation of 1D nanostructures - Growth
along a certain orientation faster than other
direction – anisotropic growth.
 Uniformly sized nanowires (same diameter along
longitudinal direction of nanowire) can be
obtained- when crystal growth proceeds along
one direction, but no growth along other
directions.
1a. Evaporation (Dissolution) – Condensation
Growth
 Evaporation-condensation process is also referred to as a vapor-solid
(VS) process.
 Chemical reactions among various precursors may be involved to produce
desired materials.
 Nanowires and nanorods grown by evaporation-condensation methods
are commonly single crystals with fewer imperfections and their formation
is due to is due
to the anisotropic growth.
 Several mechanisms are known to result in anisotropic growth:
a. Different crystal facets have different growth rate.
For example, in silicon with a diamond structure, the growth rate of { 11 1}
facets is
smaller than that of { 110}.
b. Presence of imperfections in specific crystal directions ( such as screw
dislocation).
c. Preferential accumulation of or poisoning by impurities on specific
facets.
Crystal growth is generally considered as a heterogeneous reaction, and proceeds by
following the sequences:
(1) Diffusion of growth species from the bulk (such as vapor or liquid phase) to the
growing surface.
This diffusion is generally considered to proceed rapid enough and, thus, not at a rate
limiting process.
(2) Adsorption and desorption of growth species onto and from the growing surface.
This process can be rate limiting, if the supersaturation or concentration of growth
species is low.
(3) Surface diffusion of adsorbed growth species.
During surface diffusion, an adsorbed species may either be incorporated into a
growth site, which contributes to crystal growth, or escape from the surface.
(4) Surface growth by irreversibly incorporating the adsorbed growth species into the
crystal structure.
When a sufficient supersaturation or a high concentration of growth species is present,
this step will be the rate-limiting process and determines the growth rate.
(5) If by-product chemicals were generated on the surface during the growth, by-
products would desorb from the growth surface, so that growth species can adsorb
onto the surface and the process can continue.
(6) By-product chemicals diffuse away from the surface so as to vacate the growth sites
for continuing growth.
 Rate Limiting Steps
For most crystal growth, rate-limiting step is either adsorption-desorption of
growth species on the growth surface (step 2) or surface growth (step 4).
 When step 2 is rate limiting, the growth rate is determined by condensation
rate (which is dependent on the number of growth species adsorbed onto the
growth surface, which is directly proportional to the vapor pressure or
concentration, of the growth species in the vapor).
Step 2 can be rate limiting if the supersaturation or concentration of growth
species is low.
For a given system, the growth rate increases linearly with the increase in the
concentration of growth species.
 Further increase in the concentration of growth species would result in change
from an adsorption limited process to surface growth limited process (Step 4).
A high concentration or vapor pressure of growth species in the vapor phase
would:
- increase the probability of defect formation, such as impurity inclusion and
stack faults.
- may result in a secondary nucleation on the growth surface or even
homogeneous nucleation, which would effectively terminate the epitaxial or
single crystal growth.
 At low concentration, growth is diffusion limited and thus increases linearly with
increasing reactant concentration.
 At high concentration, surface reaction is the limiting step and the growth rate
becomes independent of reactant concentration.
When step 2 proceeds sufficiently rapid,
surface growth, i.e. step 4, becomes a rate-
limiting process
 In earlier discussion we have discussed that different facets have
different surface energy. (Different facets in a given crystal have
different atomic density and atoms on different facets have a different
number of unsatisfied bonds (also referred to as broken or dangling
bonds), leading to different surface energy).
 Such a difference in surface energy or the number of broken
chemical bonds leads to different growth mechanisms and varied
growth rates.
Periodic Bond Chain (PBC) theory developed by Hartman and
Perdok: According to it all crystal facets can be categorized into three
groups based on the number of broken periodic bond chains on a
given facet: flat surface, stepped surface and kinked surface.
 A. KSV Theory/Surface nucleation model
 Explains the growth mechanisms on a flat surface.
 KSV theory is a step growth theory developed by Kossel, Stranski and
Volmer.
 This theory presumes that crystal growth is a discontinuos process, taking
place bby adsorption of matter layer by layer on the crystal surface.
 It was recognized that the crystal surface, on the atomic scale, is not
smooth, flat or continuous, and such discontinuities (steps, kinks) are
responsible for the crystal growth.
 Example:
Consider a { 100) surface of a simple cubic crystal as an example and each
atom as a cube with a coordination number of six (six chemical bonds).
According to this theory, the growth units/atoms arriving on a crystal
surface do not incorporate immediately into the lattice, but gets adsorbed
and migrate over the surface and thus diffuses randomly on the surface.
When it diffuses to an energetically favourable site, it will be irreversibly
incorporated into the crystal structure, resulting in crystal growth.
However, it may escape back to the vapor from surface.
 On a flat surface, an adsorbed atom may find different sites with
different energy level:
a. An atom adsorbed on a terrace would form one chemical bond between
atom and surface (such atom is adatom). This is a thermodynamically
unstable site.
b. If an adatom diffuses to a ledge site, it would form 2 chemical bonds and
become stable.
c. If an atom is incorporated to a ledge-kink site, 3 chemical bonds are
formed.
d. Atom incorporated to a kink site would form four chemical bonds.
 Ledge, ledge-kink and kink sites are considered as growth sites. The
incorporation of atoms into these sites is irreversible and results in
growth of surface.
 Thus, the maximum binding energy between the adatom and crystal
surface occurs for the incorporation at a kink site.-Hence adatoms over
the crystal surface migrate towards a step and moves along it to a kink
site and get incorporated.
 Under ideal conditions, this step-wise stacking will continue until the
whole layer is completed.
 So, the growth of a flat surface is due to the advancement
of steps/ledges.
 For a given crystal facets and given growth condition, the
growth rate will depend on the step density – an increased
step density will favour irreversible incorporation of
adatoms (by reducing the surface diffusion distance
between the impinging site and growth site, before adatoms
escape back to vapor phase). This increased step density will
consequently lead to high growth rate
 This implies that a step advances by incorporating more
and more adtoms at kink sites. This mode of advancement
of a step is analyzed by Burton, Cabrera and Frank
 Limitation: Regeneration of growth sites, when all available
steps are consumed.
Step Growth or KSV Theory
4. Kink site (4 CB),
5. ledge-kink site (3 CB),
7. adatom (1 CB, unstable
8. ledge site (2 CB)
 B. BCF Theory/Screw dislocation
theory
 Burton, Cabrera and Frank proposed that screw dislocation serves
as a continuous source to generate growth sites so that the stepped
growth would continue (this eliminates the need for surface
nucleation).
 The presence of screw dislocation will ensure the continuing
advancement of the
growth surface and enhance the growth rate.
 It is known that different facets have a significantly different ability
to accommodate dislocations. The presence of dislocations on a
certain facet can result in anisotropic growth, leading to the formation
of nanowires or nanorods.
 By controlling the experimetal condition for the growth of a given
crystal facet, one can increase the density of screw dislocations
parallel to the growth direction and hence control the growth rate of
that facet.
 A screw dislocation emerging at a point on a crystal surface
provides a step on the surface with a height of b (burger vector).
 The step provided by a screw dislocation is anchored at the
emergence point of dislocation.
 The inner parts of the step move radially at a faster rate than outer
parts. Therefore the growth takes place by step rotation around the
dislocation point.
 Under a given condition of super saturation, these steps wind
themselves up into a spiral, centred on the dislocation.
 Note: in this theory the growth rate does not depend on the
concentration of screw dislocations.
BCF Theory
 BCF Theory – presence of screw dislocation
ensures continuous growth and enhances the
growth rate
 PBC Theory
 According to PBC theory, there are:
- F-faces (flat surfaces)
- S-faces (stepped surfaces)
- K-faces (kinked surfaces)
 Generally S-faces and K-faces have higher growth rates than F-faces.
 For both S-faces and K-faces, the growth process is always
adsorption limited, as all the impinging atoms are captured and
incorporated into the growth surface.
 For F-faces there can be both: no growth at all and the growth can
also be adsorption limited depending on the availability of king and
ledge sites.
PBC Theory
(100), F-face, unstable

(110), S-face

(111), K-face
 The above theories enable us to understand why some facets in a
given crystal grow much faster than others.
 We know, that in a thermodynamic equilibrium crystal only those
surfaces with the lowest surface energy will survive (as determined by
Wulff plot) – so, facets with fast growth rate tend to disappear (i.e.
surfaces with high surface energy will disappear)- Therefore, the
formation of high aspect ratio nanorods or nanowires entirely based
on the different growth rates of various facets is limited to materials
with special crystal structures.
 Therefore, other growth mechanisms as defect induced growth and
impurity inhibits growth are required for continued growth along the
axis of nanowires/nanorods.
 Note:
1. A low supersaturation is required for anisotropic growth
2. Medium supersation is required for bulk crystal growth
3. High supersaturation results in secondary or homogeneous
nucleation leading to formation of polycrystalline or powders.
Lecture 13
1a. Evaporation-Condensation Growth
 Growth of Single Crystal Nanobelts of
Semiconducting or metal oxides

 Evaporating the metal oxides (ZnO, SnO2, In2O3, CdO)

at high temperatures under a vacuum of 300 torr and
condensing on an alumina substrate, placed inside the
same alumina tube furnace, at relatively low
temperature.
 Or heating the metal oxide or metal nanoparticles at
T=780 - 820oC in air, Nanorods can be obtained
depending upon annealing T and time.
 Nanowires such as ZnO, Ga2O3, MgO, CuO or Si3N4 and
SiC can be made by this method.
By controlling growth kinetics,
a consequence of minimizing
the total energy attributed by
spontaneous polarization and
elasticity, left-handed helical
nanostructures and nano-
rings can be formed by rolling
up single crystal nanobelts.
Nanorods/Nanowires by converting nanoparticles at elevated
temperatures.
 Dissolution-Condensation growth
 Dissolution-condensation process differs from evaporation-
condensation in growth media.
 In dissolution-condensation process, the growth species first
dissolve into a solvent or a solution, and then diffuse through the
solvent or solution and deposit onto the surface resulting in the
growth of nanorods or nanowires.
Growth of Ag Nanowire Using Pt
Nanoparticles as Growth Seeds
 Nanowires synthesized by decomposing
organometallic compounds in the presence of
coordinating organics
Nanowire grown by EC most likely have faceted
morphology and are generally short in length
with relatively small aspect ratios, particular
when grown in liquid medium.
However, anisotropic growth induced by axial
imperfections, such as screw dislocation,
microtwins and stacking faults, or by impurity
poisoning, can result in the growth of
nanowires with large aspect ratios.
1b. Vapor (or solution)-liquid-solid
(VLS or SLS) growth
VLS theory is developed to explain the growth of 1D
nanostructures that could not be explained by EC theory. As
when the growth occurs:

(1) There are no screw dislocations or other imperfections along

the growth direction.
(2) The growth direction <1 1 1> is the slowest as compared with
other low index directions as <110> in Si.
(3) Impurities are always required and
(4) A liquid-like globule is always found in the tip of nanowires.
 VLS is a growth mechanism for growth of 1D nanostructures by
CVD. Generally the crystal growth through direct adsorption of
gas phase is slow, therefore a catalyst is used.

 In the VLS growth, a second phase material (either impurity or

catalyst), is purposely introduced to direct and confine the crystal
growth on to a specific orientation and within a confined area.

 A catalyst forms a liquid droplet:

- by itself or
- by alloying with growth material
during the growth, which acts as a trap of growth species.

 Enriched growth species in the catalyst droplets subsequently

precipitates at the growth surface resulting in the one-directional
growth.
 Requirements for VLS growth
(1) The catalyst or impurity must form a liquid solution with the crystalline material to be
grown at the deposition temperature.
(2) The distribution coefficient of the catalyst or impurity must be less than unity at the
deposition temperature.
(3) The equilibrium vapor pressure of the catalyst or impurity over the liquid droplet
must be very small- Although the evaporation of the catalyst does not change the
composition of the saturated liquid composition, it does reduce the total volume of the
liquid droplet. Unless more catalyst is supplied, the volume of the liquid droplet reduces.
Consequently, the diameter of the nanowire will reduce and the growth will eventually
stop, when all the catalyst is evaporated.
(4) The catalyst or impurity must be inert chemically- It must not react with the chemical
species such as by-products present in the growth chamber.
(5) The interfacial energy plays a very important role. The wetting characteristics
influence the diameter of the grown nanowire. For a given volume of liquid droplet, a
small wetting angle results in a large growth area, leading to a large diameter of
nanowires.
(6) For a compound nanowire growth, one of the constituents can serve as the catalyst.
(7) For controlled unidirectional growth, the solid-liquid interface must be well defined
crystallographically (One of the simplest methods is to choose a single crystal substrate
with desired crystal orientation).
 Process of VLS Growth
1. The growth species is evaporated.
2. The growth species diffuses and dissolves into a liquid droplet
(liquid surface is a preferred site for deposition).
3. Saturated growth species in the liquid droplet will diffuse to and
precipitate at the interface between the substrate and the liquid.
4. The precipitation first follows nucleation and then crystal
growth.
5. Continued precipitation/growth will separate the substrate and
the liquid droplet, resulting in the growth of nanowires.
 Example: Growth of Si nanowires with
gold as catalyst
1. A thin layer of gold is sputtered on a silicon substrate and annealed
at an elevated temperature (same as the growth temperature).
2. During annealing, silicon and gold react to form a liquid mixture,
which forms a droplet on the silicon substrate surface.
3. When silicon species is evaporated from the source and
preferentially condensed at the surface of the liquid droplet - the
liquid droplet will become supersaturated with silicon (Once the
growth species is adsorbed onto the liquid surface, it will dissolve
into the liquid. The material transport in the liquid is diffusion-
controlled).
4. Subsequently, the supersaturated silicon will diffuse from the liquid-
vapor interface and precipitate at the solid-liquid interface resulting
in the growth of silicon.
5. The growth will proceed unidirectionally perpendicular to the solid-
liquid interface.
 Schematic illustration of Si whisker growth
from the reaction of SiCl4 and H2 vapor
phases.
This reaction is catalyzed by gold-silicon
droplet deposited on the wafer surface prior
to whisker growth.

CVD Growth of Si nanowires using Au particle

catalysts
Schematic illustration of metal-alloy catalyzed whisker growth depicting the
pathway of source materials through the droplet to the growing interface.

1. Preparation of a liquid alloy droplet

upon the substrate from which a wire
is to be grown

2. Introduction of the substance to be

grown as a vapor, which adsorbs on
to the liquid surface, and diffuses into
the droplet

3. Super saturation and nucleation at

the liquid/solid interface leading to
axial crystal growth
Schematic illustration of metal-alloy catalyzed
whisker growth depicting the catalyst droplet
formation during the early stages of whisker
growth.
Advantages:

1. Greatly lowered reaction energy compared to normal

vapor-solid growth.
2. Wires grow only in the areas activated by the metal
catalysts and the size and position of the wires are
determined by that of the metal catalysts.
3. This growth mechanism can also produce highly
anisotropic nanowire arrays from a variety of material.
 Crystalline defects (as screw dislocations), if present at interface,
may promote the growth and will lower the required
supersaturation.
 The nanowires obtained can be:
- Single crystal
- Polycrystalline
- Amorphous
depending on the substrates and growth conditions.
 The growth surface is the interface between the liquid droplet and
solid surface.
 Condensation surface is the interface between the liquid droplet
and vapor phase.
 Depending upon contact angle, the liquid surface area can be
several times the growth surface.
 Also, if condensation surface area of growth species is larger than
the surface area of crystal growth – enhanced growth rate could
be achieved.
 VLS growth mechanism can be chosen by
identifying metals in which the nanowire
component elements are soluble in liquid phase
but do not form stable solid compounds other
than the desired nanowire phase.
i.e. ideal metal catayst should be physically active
by chemically stable/inert.
 Nanowires/nanorods grown by VLS method
generally have a cylindrical morphology (i.e.
without facets on side surface and having a
uniform diameter).
However, facets ay develop if there is VS
deposition on the side surface.
 Control of Nanowire Size
 The size of nanowires grown by VLS method is determined by the size of the liquid
catalyst droplets.
 To grow thinner nanowires, one can simply reduce the size of the liquid droplets.

 Typical methods used to form small liquid catalyst droplets:

A. Coat a thin layer of catalyst on the growth substrate and to anneal at elevated
temperature ie. The size of the liquid catalyst droplets can be controlled by the thickness of
the catalyst film on the substrate.
In general, a thinner film forms smaller droplets, giving smaller diameters of nanowires
subsequently grown.
For example, 10 nm Au film yields single crystal germanium nanowires of 150 nm in
diameter, while 5 nm Au film results in the growth of 80nm sized germanium nanowires.

B. By dispersing monosized catalyst colloids on the substrate surface

Example: GaP nanowires are grown by laser catalytic growth using gold colloids.
 Barriers of Size Reduction
We know that thin nanowires can be grown using small liquid droplets, but:
A. As the droplet size decreases, its solubility increases (as a convex surface
with very small radius have very high solubility).
As a result of increased solubility, a high supersaturation in vapor phase has
to be generated.
a. But this high supersaturation in vapor phase may promote the lateral
growth on the side surfaces of nanowires (vapor-solid mechanism).
Therefore, a conicl structure may be developed instead of uniformly sized
nanowires.
b. High supersaturation may also initiate homogeneous nucleation in gas
phase or secondary nucleation at the nanowire surface.
B. An equilibrium solubility and supersaturation of growth species in larger
liquid catalyst droplets can be obtained easily than that in smaller
droplets.
But, nanowire growth will proceed only when the concentration of growth
species is above equilibrium solubility.
When the concentration/supersaturation in vapor phase is appropriately
controlled (to obtain small droplets), the vapor pressure can be kept below
the equilibrium solubility and thus the growth of thinnnest nanowire would
terminate. This can be a barrier for synthesis of thin nanowires, which may
require high deposition temperatures.
 Precursors and Catalysts

 Gaseous precursors (as SiCl4 for Si nanowires)

 Evaporations of solids by heating to elevated
temperatures
 Laser ablation of solid targets to generate
vapor precursors
 In-situ introduction of catalyst
 Solution-liquid-solid (SLS) Growth
 In VLS growth generally high temperature and vacuum are required.
 SLS growth method allows growth of nanowires at relatively low temperatures.
 This method is similar to VLS growth theory, however here solution is used to
supply growth species.
 Nanowires obtained can be polycrystalline or near single-crystal with diameter
of 10-150 nm and length upto several micro meters.
 1c. Stress induced Recrystallization

 Application of pressure (stress) on solids at elevated

temperatures can result in the growth of whiskers/nanowires with
diameters as small as 50 nm.
 The growth rate of such 1D nanostructures can be increased
proportionally with the applied pressure.
Lecture 14, 15
2. Template Based Synthesis
 Used to fabricate 1D nanostructures of polymers, metals,
semiconductors and oxides.
 Templates contain very small cylindrical pores/voids
within the host material, and the empty spaces are filled
with the chosen material, which adopts the pore
morphology to form nanowires.
 Parameters affecting template assisted synthesis:
- Template pore: size, morphology, size distribution and density.
- Template materials should be:
a. Chemically and thermally inert during synthesis.
b. Depositing materials or solution must wet the internal pore
walls.
c. Template materials must be compatible with the processing
conditions. For example: template must be an electical
insulator in electro-chemical deposition.
d. Deposition must start from the bottom or one end of the
template channels (i.e. pore blockage must not happen)
 Various Type of Templates
 Anodized alumina membrane
 Radiation track-etched polymer membrane
 Nano channel array glass
 Radiation track-etched mica
 Mesoporous materials
 Porous silicon by electrochemical etching of Silicon wafer, zeolites,
CNTs
2a. Electrochemical Deposition or Electro deposition
 Electrolysis result in the deposition of solid material on an
electrode.
 The deposition is confined inside the pores of template
membranes to obtain nanocomposites (nanoporous membrane
covers the cathode during process).
 This method is only applicable to electrically conductive
materials as metals, alloys, semi-conductors, electrical conductive
polymers.
 The length of nanowires/nanorods can be controlled by
deposition time- Increased deposition time can lead to thick
nanotube wall, finally leading to formation of solid nanorods.
Process:

1. Template is attached onto the cathode, which is subsequently

brought in contact with the deposition solution ( metal film can
be vapour deposited on one side of membrane as cathode).
2. Anode is placed in the deposition solution parallel to cathode.
3. When an electric field is applied, cations diffuse toward and
reduce at the cathode, resulting in nanowire growth inside the
pores of template.
Scheme of the electrodeposition of nanowires in a nanoporous template. The
potential is controlled by a potentiostat through a reference electrode, not shown.
The resistance in the membrane is monitored by a potentiometer.
 Electrophoretic Deposition
 Colloidal particles suspended in liquid medium migrate under the influence of
electric field and are deposited onto electrode.
 Electrophoretic deposition differs from electrochemical deposition in several
aspects:
1. The deposit by electrophoretic deposition need not be electrically conductive.
2. Nanosized particles in colloidal dispersions are typically stabilized by
electrostatic mechanisms.
 Upon application of external electric field to the colloidal system or sol, the
constituent charged particles are set in motion in response to the electric field and
deposit onto electrode.
 2b. Template Filling
 Direct filling a template with a liquid mixture precursor is
the most straightforward and versatile method for
preparing nanowire or nanorod arrays.
 Both nanorods and nanotubles can be obtained
depending on the interfacial adhesion and solidification
modes:
1. If adhesion between pore walls and filling material is
weak or if solidification starts at center, solid nanorods
are likely to form.
2. If adhesion is strong or if solidification starts at
interfaces and proceeds inwardly, hollow nanotubules
are likely to form.
 Drawback: It is difficult to ensure complete filling of the
template pores.
 Concerns during template filling:
1. Wetability of the pore wall should be good
enough to permit the penetration and complete
filling of the liquid precursor or precursor mixture.
2. Template materials should be chemically inert.
3. Control of shrinkage during solidification is
required.
 Template filling can be obtained using various
methods:
a. Colloidal dispersion filling
b. Melt and solution filling
c. CVD
d. Deposition by centrifugation
 Colloidal Dispersion Filling
 Formation of various oxide nanorods and nanotubules by filling the
templates with colloidal dispersions (prepared using appropriate sol-gel
processing).
1. Template is placed in stable sol for various time periods.
2. The capillary force drive the sol into the pores if the sol has good
wetability for template (diffusion through membrane and enrichment of
solid inside the pores is a rapid process).
3. After the pores are filled with sol, the template is withdrawn from sol
and dried prior to firing at elevated temperatures.
Firing at elevated temperature allow:
a. Removal of template so that free standing nanorods can be obtained.
b. Densification of sol-gel derived green nanorods.
4. Upon drying and subsequent firing processes, a significant amount of
shrinkage is expected.
 Commonly used for polycrystalline and amorphous materials.
 Drawback: Difficult to ensure complete pore filling.
 Melt or Solution Filling
 Filling template with molten metals.
Example: preparation of bismuth nanowires by
pressure injection of molten bismuth into the
nanochannels of an anodic alumina template.
Polymeric fibrils can be made by filling a
monomer solution (containing desired
monomer and polymerization reagent) into
template pores and then polymerizing the
monomer solution.
 Chemical Vapor Deposition (CVD)
 Substrate is exposed to one or more volatile precursors,
which react and/or decompose on the substrate surface to
produce the desired product.
Example: Ge nanowires can be grown by diffusing Ge2H6
gas into nanoporous silica and heating. The precursors
react with the surface of hydroxyl groups in template
forming Ge and H2.
 Deposition by Centrifugation
 Template filling is assisted with
centrifugation force
 Example: Lead zirconate titanate (PZT)
nanorod arrays can be grown in
polycarbonate membrane from PZT sol by
centrifugation at 1550 rpm for 60 min.
 Advantages: Applicable to any colloidal
dispersion system.
 2c. Conversion Through Chemical Reactions
 Nanorods or nanowires can be synthesized using consumable
templates, although the resultant nanowires and nanorods are
generally not ordered to form aligned arrays.
 Process:
1. Nanowires or nanorods of one constituent element are prepared.
2. These nanowires are then reacted with the chemicals containing
other element, desired in order to form final products.
Example: ZnO nanowires are prepared by oxidizing metallic zinc
nanowires.
a. First, polycrystalline zinc nanowires without preferential crystal
orientation are prepared by electrodeposition using anodic alumina
membrane as a template.
b. Grown zinc nanowires are oxidized at 300°C for up to 35 hr in air,
yielding polycrystalline ZnO nanowires .
c. Although ZnO nanowires are embedded in the anodic alumina
membranes, free standing nanowires may be obtained by selectively
dissolving alumina templates.
Converting Through Chemical Reactions
 3. Electrospinning/Electrostatic fiber
processing technique
 Generally used to obtain ultrathin polymer fibers or organic-
inorganic hybrid fibers.
Here, a polymer droplet is elongated by a strong electric field.
1. The electrical forces at the surface of polymer solution or melt
overcomes surface tension and cause an electrically charged jet to
be ejected.
2. When the jet dries/solidifies, an electrically charged fiber
remains.
3. This charged fiber can be directed/accelerated by electrical forces
and then collected in sheets or other useful geometric forms.
 Fiber morphology depends on process parameters as:
a. solution concentration
b. applied electric field strength
c. feeding rate of precursor solution
Example: porous anatase titania nanofibers are made by ejecting an ethanol
solution containing both poly(viny1 pyrrolidone) (PVP) and titanium
tetraisopropoxide through a needle under a strong electric field, resulting in the
formation of amorphous Ti02/PVP composite nanofibers.
Upon pyrolysis of PVP at 500°C in air, porous Ti02 fibers with diameter ranging
from 20 to 200nm, depending on the processing parameters are obtained.
 4. Lithography
 Top-down approach
 Nanowires with diameters less than 10 nm and aspect ratio of 100
can be readily prepared.
 Lithography uses simple chemical processes to create an image by
transferring a pattern from a mater plate/mask to another medium.
 The nanoscale features are defined in the thin film of photoresist
by exposing it to a UV light source and the pattern are transferred
into the underlying substrate using etching.
 Various lithography techniques are used to obtaingg nanowires:
1. Electron beam lithography
2. Ion beam lithography
3. STM lithography
4. X-Ray lithography
5. Proaxial probe lithography
6. Near field photolithography
 Lecture 16

2D Nanomaterials: Thin Films

 Film deposition predominantly involves:
a. Heterogeneous processes (chemical reactions, evaporation, adsorption and
desorption on growth surfaces),
b. Heterogeneous nucleation and
c. Surface growth.

 Most film deposition and characterization processes are conducted under a

vacuum.

 Film growth methods can be generally divided into two groups:

A. Vapor-phase deposition [evaporation, molecular beam epitaxy (MBE),
sputtering, chemical vapor deposition (CVD), and atomic layer deposition
(ALD)]
B. Liquid-based growth [electrochemical deposition, chemical solution
deposition (CSD), Langmuir-Blodgett films and self-assembled monolayers
(SAMs)]
Nucleation:

- The nucleation process plays a very important role in determining the crystallinity,
microstructure and thickness of the resultant films.
-Nucleation in film formation is generally a heterogeneous nucleation.
- The size and the shape of the initial nuclei are assumed to be solely dependent on
the change of volume of Gibbs free energy (due to supersaturation, and the
combined effect of surface and interface energies).
- Interaction between film and substrate plays an important role in determining
the initial nucleation and the film growth.
- Generally there are three basic nucleation modes:
(1) Island or Volmer-Weber growth,
(2) Layer or Frank-van der Merwe growth, and
(3) Island-layer or Stranski-Krastonov growth
1. Island growth occurs when the growth species are more strongly bonded to
each other than to the substrate. (Many systems of metals on insulator
substrates, alkali halides, graphite and mica substrates display this type of
nucleation during the initial film deposition.)
- Subsequent growth results in the islands to coalesce to form a continuous film.
-Here, contact angle θ >0

2. The layer growth is the opposite of the island growth as the growth species are
equally bound more strongly to the substrate than to each other.
- Here, first the complete monolayer is formed, before the deposition of second
layer occurs.
- Example: epitaxial growth of single crystal films.
- Here, the deposit wets the substrate completely i.e. θ = 0
3. Island-Layer Growth: is an intermediate combination of layer growth and island
growth.
- But, this growth mode typically involves the stress, which is developed during the
formation of the nuclei or films.
- Due to the difference in chemical composition of substrate and film, the lattice
constants of the deposit are most likely different from those of the substrate. Such
a difference commonly leads to the development of stress in the deposit; stress is
one of the common reasons for the island-layer growth.

Note:
The aforementioned nucleation models and mechanisms are applicable to the
formation of single crystal, polycrystalline and amorphous deposit, and of
inorganic, organic and hybrid deposit.
Whether the deposit is single crystalline, polycrystalline or amorphous, depends on
the growth conditions and the substrate.
(note: this discussion is only applicable to single element films).
1. Growth of single crystal films is the most difficult and requires:
(i) a single crystal substrate with a close lattice match,
(ii) a clean substrate surface so as to avoid possible secondary nucleation,
(iii) a high growth temperature so as to ensure sufficient mobility of the growth
species and
(iv) low impinging rate of growth species so as to ensure sufficient time for surface
diffusion and incorporation of growth species into the crystal structure and for
structural relaxation before the arrival of next growth species.
2. Deposition of amorphous films typically occurs :
(i) when a low growth temperature is applied, there is insufficient surface mobility
of growth species and/or
(ii) when the influx of growth species onto the growth surface is very high, growth
species does not have enough time to find the growth sites with the lowest
energy.
3. The conditions for the growth of polycrystalline crystalline films fall between the
conditions of single crystal growth and amorphous film deposition.
In general, the deposition temperature is moderate ensuring a reasonable surface
mobility of growth species and the impinging flux of growth species is moderately
high.
 EPITAXY
Epitaxy refers to the formation/growth of single crystal on top of a
single crystal substrate or seed.
-Epitaxial growth can be divided into homoepitaxy and heteroepitaxy.
A. Homoepitaxy is to grow film on the substrate, in which both are
the same material.
- Depositing film has the same crystal structure and chemical
composition as that of substrate.
- This is a simple extension of the substrate and thus there is no
interface between the substrate and depositing film and no
nucleation process.
- There is no lattice mismatch between films and substrates by
homoepitaxial growth.
B. Heteroepitaxy refers to the case that films and substrates are different materials.
-Depositing film has a close matching structure as that of substrate.
- The film and substrate are different materials.
- There will be a lattice mismatch between films and substrates in heteroepitaxial
growth. The lattice mismatch is also called misfit, given by:

where
as is the unstrained lattice constant of the substrate and
af is the unstrained lattice constant of the film.

If,
f > 0, the film is strained in tension,
whereas f< 0, the film is trained in compression.
 Vacuum
 Most film deposition and processing are carried out in a vacuum.
 In addition, almost all the characterization of films is performed under vacuum.
a. Mean free path
- In a gas phase, gas molecules are constantly in motion and colliding among
themselves as well as with the container walls.
-Pressure of a gas is the result of momentum transfer from the gas molecules to
the walls, and hence is a variable in vacuum technology.
- Mean free path is the mean distance traveled by molecules between successive
collisions and is an important property of the gas that depends on the pressure,
given by:

- When the P < 10-3 torr, the gas molecules in typical film deposition and
characterization systems virtually collide only with the walls of the vacuum chamber,
i.e. there is no collision among gas molecules.
2. It is only because for film deposition, only molecules impinging onto the growth
surface will be able to contribute to the growth process.
- The gas impingement flux in the film deposition is a measure of the frequency
with which gas molecules impinge on or collide with a surface, and is the most
important parameter.
- The number of gas molecules that strike a surface per unit time and area is
defined as the gas impingement flux, ø:
3. Gas flow is defined as a net directed movement of gas in a system and occurs
when there is a pressure drop.
-Depending on
-the geometry of the system involved
-the pressure, temperature and type of gas in question
gas flow can be divided into three regimes: molecular flow, intermediate flow
and viscous flow.
a. Free molecular flow occurs at low gas densities or high vacuum, when the
mean free path between intermolecular collisions is larger than the
dimensions of the system and the molecules collide with the walls of the
system only.
b. Viscous flow: At high pressure, intermolecular collisions become predominant
since the mean free path is reduced and the gas flow is referred to as in the
viscous flow regime.
Flow behaviour can be defined by the so-called Reynolds number, Re, which is
given below of gas flow inside a pipe:

where D is the diameter of the pipe, v the velocity, ρ the density, and ƞ, the
viscosity of the gas.
Viscous flow can be further divided into laminar flow (Re <2100), turbulent flow
(Re>4000) and transition flow (2100<Re<4000).
Laminar Flow:
At a low gas flow velocity, the flow is laminar where layered, parallel flow lines
may be visualized, no perpendicular velocity is present, and mixing inside the gas
is by diffusion only. In this flow, the velocity is zero at the gas-wall interface and
gradually increases as moving away from the interface, reaching a maximum at
the center when flowing inside a pipe.
Note: There is always a laminar flow near to the solid surface in both turbulent
and transition flows, since the friction viscous forces a deceleration of the gas at
the surface.

c. Between free molecular flow and viscous flow, there is a transition regime:
intermediate flow.
This gas flow can be defined by the magnitude of the Knudsen number:

where D is the characteristic dimension of the system, e.g. the diameter of

a pipe, and λmfp is the gas mean free path.
 Lecture 17
I. Vapor Phase Growth
 1. Physical Vapor Deposition (PVD)
 PVD is a process of transferring growth species from a source or target and
deposit them on a substrate to form a film.
 The process proceeds atomistically.
 PVD involves a variety of vacuum deposition methods used to deposit thin films
by condensation of a vaporized form of the desired film material onto substrates.
 PVD mostly involves no chemical reactions and involves purely physical
processes such as high temperature vacuum evaporation with subsequent
condensation or plasma sputter bombardment.
 The processes of depositing materials directly from vapor phase comprise of
following methods:
a. Evaporation: The growth species are removed from the source by thermal
means (types: thermal evaporation and E-beam evaporation)
b. Sputtering: In sputtering, atoms or molecules are dislodged from solid target
through impact of gaseous ions (plasma) [types: DC sputtering, DC magnetron
sputtering and RF Sputtering].
Electron based PVD
 Advantages of PVD
 Multitude of substrate materials can be coated: metals, alloys, ceramics, glass,
polymers etc.
 Unlimited choice of coating materials: metals, alloys, semiconductors, metal
oxides, carbides, nitrides, cermets, sulfides, selenides, tellurides etc.
 Excellent coating adhesion
 Easy tuning of microstructure by choice of the coating parameters.
 Disadvantages of PVD
 Relatively low deposition rates and film thickness.
 Technologically demanding processes ( vacuum based)
 Coating of geometrically complex parts is difficult.
 A. Evaporation
 Is the simplest deposition method for the deposition of elemental films.
The evaporation system consists of:
a. an evaporation source that vaporizes the desired material by introduction of
energy to a suitable temperature (by resistance heating, laser ablation, electron
beam evaporation, arc evaporation etc) and a substrate is located at an appropriate
distance facing the evaporation source.
The thermally released atoms/molecules leave the surface of the evaporated
material and form a coating on the substrate/surrounding walls.
b. Both the source and the substrate are located in a vacuum chamber.
As the process is conducted under high vacuum (~10-3 Pa), the coating particles
basically move from the source to the substrates on straight trajectories (i.e. without
the collisions with residual gas atoms).
c. The substrate can be heated or electrically biased or rotated during deposition.
d. The desired vapor pressure of source material can be generated by simply heating
the source to elevated temperatures, and
the concentration of the growth species in the gas phase can be easily controlled by
varying the source temperature and the flux of the carrier gas. The equilibrium
vapor pressure of an element can be estimated as:
where ΔHe is the molar heat of evaporation, Rg gas constant,
T temperature, and C constant
 Evaporation System
Evaporation is based on the concept that there exists a finite “vapor pressure”
above any material. The material either sublimes (direct solid to vapor
transition) or evaporates (liquid to vapor transition).
-Deposition of thin films by evaporation is carried out in a low pressure (10-3 – 10-10
torr); so that the atoms and molecules in vapor phase do not collide with one
another prior to the arrival at growth surface (since the mean free path is very large
as compared to the source – to – substrate distance).
 The rate of evaporation is dependent on the material:

It is difficult to deposit complex/compound films using evaporation method:

As the composition of source would change as the evaporation proceeds, since one
element may evaporate much faster than another, resulting in the depletion of the
first element. As a result, the composition in vapor phase will change.
Thus, for a multi-component system, the chemical composition of evaporated film
becomes different from that of the source and varies with thickness.
 Evaporation Sources
Evaporation sources can be categorized by the method of energy supply.
One has also to consider that not each material can be evaporated from each
source.
Chemical reactions between crucible and evaporation material are possible which
can lead to impurities in the film and/or to the destruction of the evaporation
source.
In addition the power density in different source types may vary strongly.
1. Direct Resistive Heating: Some (electrically conductive) elements which exhibit a
vapor pressure >10-2 mbar (1Pa) below their melting point can be evaporated by
sublimation.
The evaporation material has the shape of wires or rods and is directly heated by a
high electrical current. This method is not frequently employed since it is limited to
only few materials (e. g. C, Cr, Fe, Mo, Ni, Pd, Rh, Ti, Al).
2. Indirect Resistive Heating: The principle of this frequently employed method is to
put the evaporation material on or into a container (called "boat"), spiral wire,
ribbon or crucible made from W (or Mo, Ta, C, Pt, BN, TiB2) which is heated by a
high electrical current and to evaporate it from there.
3. Inductive Heating: In this case the evaporated material is heated by high or low
frequency induction. The evaporated material has to be conductive.
4. Electron Beam Evaporator: Apart from a high power density which can be
achieved there is also practically no reaction between the evaporation material
and the crucible in these devices. The reason for this is that the evaporated
material is kept in a water cooled crucible. Therefore highly reactive materials (Ta,
Ti, Zr) and refractory metals (W, Mo, Pt, Rh) can be evaporated. Also dielectric
substances can be deposited at high rates and high purity. Because of these
properties electron beam evaporation has established itself as a universal method
for the deposition of high quality coatings in large quantities.
5. Arc Discharges: Arc discharges (Hollow Cathode Arc, Low Voltage Arc,
Thermionic Arc) are extremely important for ion plating processes.
6. Laser Evaporator or Laser Ablation: The continuous interaction of laser
radiation with matter can lead to thermal evaporation. Pulsed laser beams, on
the other hand, may release particles from the solid by alternative mechanisms
because of their low pulse duration and high power density. Local plasmas and
explosive evaporation play an important role. The use of pulsed lasers, is
termed "laser ablation“.
Evaporation:

Advantages: Highest purity (Good for Schottky contacts) due to low

pressures.

Disadvantages:
1. Poor step coverage (due to shadowing),
2. Forming alloys can be difficult,
3. Lower throughput due to low vacuum.
The transport of atoms/molecules from source to the growth surface
is straightforward along the line of sight and therefore the conformal
coverage is relatively poor and a uniform film over a large area is
difficult to obtain.
Therefore, some special arrangements are required to be developed
to overcome such issue:
1. Using multiple sources instead of single point source.
2. Rotating the substrate
3. Loading both source and substrate on surface of a sphere
4. Combination of all the above
 B. Molecular Beam Epitaxy (MBE)
MBE is a technique for epitaxial growth via the interaction of one/several
molecular/atomic beams that occurs on a surface of a heated crystalline
substrate.
This is a special case of evaporation for single crystal film growth.
Process:
1. The solid source materials are placed
in evaporation cell to provide an
angular distribution of
atoms/molecules in a beam.
2. Atoms/molecules are produced by
heating the source.
3. The substrate is heated to the
necessary temperature and when
needed, continuously rotated to
improve the growth homogeneity.
4. The atoms/molecules migrate in UHV
environment and impinge on the hot
substrate, where they diffuse and
eventually results in the formation of
the desired epitaxial film.
 UHV is an essential environment for MBE. Therefore, the rate of gas evolution
from the materials in the chamber has to be low.
 The effusion cells used, act as molecular flux source in vacuum
 The evaporated atoms do not interact with each other or vacuum chamber gases,
until they reach the wafer, due to the long mean free paths of the atoms.
 Precise fabrication of nanostructures/nanomaterials at a single atomic layer is
enabled by:
a. Extremely clean environment: UHV ensures absence of
impurity/contamination, thus producing pure film.
b. Slow growth rate: ensures sufficient surface diffusion and relaxation so that
formation of any crystal defects is kept minimal.
c. Independent control of evaporation of individual sources: permits the precise
control of chemical composition of deposit at any given time.
Various realtime structural and chemical characterization capabilities and analytical
instruments can be attached to deposition chamber or to a separate analytic
chamber (from which the grown films can be transferred to and from the growth
chamber without exposing to the ambient):

1. Reflection high energy electron diffraction (RHEED),

2. X-ray photoelectric spectroscopy (XPS),
3. Auger electron spectroscopy (AES).

Note: During operation, RHEED is often used for monitoring the growth of crystal
layer.
Computer control shutters in front of each furnace, allow precise control of the
thickness of each layer, down to a single layer of atoms.
Intricate layer structures of different materials may be fabricated this way.
Such control allows development of structures where the electrons can be
confined space (quantum wells/dots).
 C. SPUTTERING
 Sputtering is a process whereby atoms are ejected from a solid target material
due to bombardment of target by energetic particles. It only happens when the
K..E. of incoming particles is much higher than the conventional thermal energies
(>>1eV).
 Plasma generation:
1. Gases are usually electrically insulating
2. At sufficient low pressures and high applied voltage, the gas breaks down and
conducts electricity.
3. The resulting ionized gas is called “plasma”.
 Process:
1. A plasma at higher pressure is used to ‘knock’ metal atoms out of a target.
2. These energetic atoms deposit on a wafer located near the target.
 Higher pressure produces better step coverage due to more random angled
delivery.
 Excess energy of ions, aids in increasing the surface mobility.

 Advantages:
1. Better step coverage.
2. Less radiation damage than evaporation
3. Easier to deposit alloy.
4. Since, the coating material is transferred into the gas phase by impulse transfer
and not by thermal excitation, any substance can be sputtered.
5. Sputtering a mixture of elements/compounds will not result in a change of
composition in the target and thus the composition of the vapor phase will be
same as that of target and remain the same during deposition

 Disadvantage: some plasma damage can happen

Sputter Targets:
 Based on the kind of sputtering geometry a large choice of materials; pure
elements, alloys and compounds can be used.
 Targets can be manufactured by:
- common melting and casting
- vacuum melting
- powder metallurgical processes
- coating (ex. Thermal spraying)

Types of sputtering:
i. DC sputtering
ii. RF Sputtering
iii. Magnetron sputtering
iv. Reactive Sputtering
i. DC Sputtering:
1. Target and substrate (as electrodes) face each other in the sputtering chamber.
2. An inert gas (Ar) with pressure ranging from few to 100m torr is introduced into
the system.
This gas act as a medium to initiate and maintain a discharge
3. DC voltage is applied to electrodes
4. A glow discharge (PLASMA) is
initiated and maintained between the
electrodes.
5. Free electrons are accelerated by
electric field which then gain
sufficient energy to ionize argon
atoms.
6. The resulting positive ions (Ar+) in
the discharge strike target (cathode),
resulting in ejection of neutral target
atoms through momentum transfer.
7. These atoms pass through the
discharge and deposit on the
opposite electrode (substrate)
Disadvantages of DC Sputtering:
1. Low deposition rates.
2. High thermal load of substrate due to energetic electrons
3. Sputtering of insulators is impossible due to charging of target
4. Incorporation of working gas atoms into the film.
5. Scattering of deposition particles at working gas atoms lead to energy loss of the
film forming atoms, which can lead to low quality coatings

These disadvantages can be counteracted by the development of

new process types.
ii. RF (radio frequency) Sputtering:
For deposition of insulating films, an ac (alternating) electric field is applied to
generate plasma between two electrodes.
Typical RF frequencies employed range from 5-30 MHz
 To prevent simultaneous sputtering on the substrate, the sputter target must be
an insulator and should be capacitively coupled to the RF generator.
 Advantages:
a. Possible to sputter semiconductors and insulators
b. Possible to sustain gas discharge at much lower pressures (0.5-2 Pa) with a high
frequency ac voltage (13.56 Hz) than with a dc voltage.
iii. Magnetron sputtering:
 Magnetic field has been introduced into sputtering processes to increase the
resistance time of growth species in vapor phase.
 The additional magnetic field causes electrons to move in a helical pathway,
concentrated near the cathode to improve yield of sputtered atoms.
 Magnetic field helps to confine electrons near the target to sustain plasma.

Advantage: Allow achievement of high deposition rates at low working gas

pressure and at low substrate heating.

iv. Reactive Sputtering:

 Reactive gases are introduced into the deposition chamber to form compound
films.
A reactive gas is mixed with Ar to produce a plasma in which the target atoms
are sputtered but additionally react with the reactive gaseous component to
produce compound films (Al2O3, TiC, TaN, SiO2).
 Evaporation
Uses low deposition pressures (10-3-10-
10 torr)
Atoms/molecules in evaporation
chamber do not collide with each other
Evaporation can be described by
thermodynamic equilibrium
Growth surface is not activated
Evaporated films consist of large grains
Fractionization of multi-component
systems is difficult.
Sputtering
Requires relatively high pressure (~ 100
torr)
Atoms/molecules in sputtering do
collide with each other prior to the
arrival at growth surface
Sputtering can not be described by
thermodynamic equilibrium
Growth surface is constantly under
electron bombardment and thus is
highly energetic
Sputtered films consist of smaller grains
with better adhesion to substrates
Composition of the target and film can
be same.
Lecture 18
 2. Chemical Vapor Deposition (CVD):

 CVD is a process whereby a solid material is deposited from a vapor by a

chemical reaction occurring on or in the vicinity of a normally heated substrate
surface.

The principle of CVD

CVD process involves:
1. Introduce reactive gases to chamber: Flowing a precursor gas/gases into a
chamber containing one/more heated objects to be coated.
2. Activate gases (decomposition) by heat/plasma.
3. Gas adsorption by substrate surface: Chemical reactions occur on and near the
hot surfaces, resulting in film deposition.

Gaseous reactants = solid material + gaseous products

4. This is accompanied by production of chemical by products that are exhausted

out of the chamber alongwith unreacted precursor gases.

 By varying the experimental conditions:

1. Substrate material
2. Substrate temperature
3. Composition of reaction gas mixture
4. Total pressure of gas flows
materials with different properties can be grown.
Disadvantages:
1. CVD precursors can be highly toxic, explosive or corrosive.
2. By products of reactions can be hazardous.
3. Some of the precursors can be costly.
4. Films are usually deposited at elevated temperature:
- This puts restrictions on the kind of substrates that can be coated.
- It leads to stresses in films deposited on materials with different thermal
expansion coefficients, which can cause mechanical instabilities in the deposited
film.

Advantages:
1. Production of coatings of uniform thickness and properties with a low porosity
(even on substrates having complicated shapes) – i.e. CVD produces films that
are quite conformal. In contrast PVD, generally works on line-of-sight principle.
2. Localized/selective deposition on patterned substrates is possible.
3. Wide variety of materials can be deposited and that too with very high purity.
4. High deposition rates
5. CVD often does not require as high vacuum as PVD processes.
Variety of chemical reactions can occur depending on the precursors used and
the deposition conditions applied:

a. Pyrolysis or thermal decomposition:

Gaseous compound AX is thermally dissociated into A and X.

AX (g) A (s) + X (g)

b. Reduction:

Here generally hydrogen acts as a reducing agent.

2 AX (g) + H2 (g) 2A(s) + 2HX(g)

Such reactions are exclusively used in the CVD of elements

c. Oxidation

d. Compound formation

e. Disproportionation:
Rarely used in CVD.
Disproportionation means a reaction where oxidation number of an element both
increases and decreases through the formation of two new species.

2AX(g) A (s) + AX2 (g)

3AX(g) 2A (s) + AX3 (g)
4AX(g) 3 A (s) + AX4 (g)

f. Exchange Reactions:
Element E replaces another element.
AX (g) + E (g) AE (s) + X (g)
Zn (g) + H2S (g) ZnS (s) + H2 (g)
There exist 5 reaction zones that are developed during the CVD process and the
properties of CVD materials are affected by the interacting processes occurring in
these reaction zones.
a. Zone 1:
- A stagnant boundary layer occurs in the vapor adjacent to the substrate/coating.
- During deposition process, the gaseous reactants and reaction products are
transported across this boundary layer.
- In this zone and in main gas stream, homogeneous reactions in the vapor may
occur.
- These reactions may lead to undesirable homogeneous nucleation resulting in a
flaky and a non-adherent coating.
b. Zone 2:
- Heterogenous reactions occur in the phase boundary vapor/coating.
- These reactions determine the deposition rate and properties of the coating.

c. Zones 3-5:
-Various solid state reactions (phase transformations, precipitation, recrystallization,
grain growth etc) occur during the process in zones 3-5.

d. Zone 4:
- Is a diffusion zone.
- Here, various intermediate phases may be formed.
- Reaction in this zone are important for adhesion of the coating to the substrate.
CVD is a non-equilibrium process controlled by chemical kinetics and transport
phenomena.

A. Reaction Kinetics:
The chemical reaction and phase equilibrium determines the feasibility of a
particular process and the final state attainable.

B. Transport Phenomenon (TP):

 Govern the access of film precursors to the substrate, by influencing the
degree of desirable and unwanted gas phase reactions taking place before
deposition.
 The complex reactor geometries and large thermal gradient characteristics of
CVD chambers lead to a wide variety of flow structures that affect film
thickness, compositional uniformity and impurity level.

Example: CVD reactors operating at a low pressure, where the mean free path of
gas molecules is 10 times larger than the characteristic length of the reactor, there
is no collision between gas molecules and thus the transport of gas is in the free
molecular flow regime.
 CVD Reactor Types
The choice of reactor is determined by:
a. Application
b. Requirements for substrate material, coating
c. Film thickness and uniformity
d. Availability of precursors and cost
A. Hot – Wall CVD Reactor:
 Chamber containing the parts is surrounded by a furnace that heats the system.
 Parts are loaded into the system, it is heated to desired temperature and then
the reactive gases are introduced.
 These systems often run at very high temperatures.
 The substrates and reactor wall have the same temperature.
 Film growth occurs on the substrates as well inside the reactor walls.
 With thicker films on the reactor walls there is a risk that particles will break
loose from reactor walls and fall down on the surface of growing film and thus
introduce pinholes in it.
 Many substrates can be deposited simultaneously.
B. Cold-wall CVD reactors:
 Substrates are heated but walls are cooled.
These reactors often run at relatively high pressures and usually have reactive
precursors diluted in a carrier gas.
 Walls of reactor are cold and usually no deposition occurs on the walls,
eliminating the risk of particles breaking loose from the walls.

 Advantages:
1. Reduced material deposition
on the walls (so less cleaning).
2. Lower energy consumption
3. Avoidance of vacuum
equipment
4. High deposition rates.
5. Thickness uniformity

 Disadvantages:
1. Large temperature uniformities on the substrate, which may lead to non-
uniformities in film thickness and smaller batch sizes.
2. Possible thermal stresses on the substrates if the heating/cooling is too rapid.
 CVD Methods
 For deposition of large area films, depletion of growth species above the
growth surface can result in non-uniform film deposition.
To overcome such non-uniformity in deposited films, various reactor designs are
developed to improve the gas-mass transport through the boundary layer.

 Variety of CVD reactors and methods have been developed depending upon:
a. Type of precursor used.
b. Deposition conditions applied.
c. Forms of energy introduced to the system to activate the chemical reactions
desired for deposition of solid films on substrates

1. Metal organic CVD (MOCVD): metalorganic compounds are used as precursors.

2. Plasma enhanced CVD (PECVD): Plasma is used to promote chemical reactions.
Introduction of plasma results in much enhanced deposition rates, thus permits
film growth at relatively low substrate temperatures.
3. Low pressure CVD (LPCVD)
4. Laser enhanced CVD (LECVD)
5. Aerosol assisted CVD (AACVD)
3. Atomic Layer Deposition (ALD):
 ALD is also called:
- atomic layer epitaxy (ALE),
- atomic layer growth (ALG),
- atomic layer CVD (ALCVD), and
- molecular layer epitaxy (MLE)
 Has a self-limiting growth nature, such that each time only one atomic or
molecular layer can grow (i.e. one layer at a time).
Therefore, ALD offers the best possibility of controlling the film thickness and
surface smoothness in truly nanometer/sub-nanometer range.
 ALD is a special modification of CVD where typically:
1. The surface is first activated by chemical reaction.
2. When precursor molecules are introduced into the deposition chamber, they
react with the active surface species and form chemical bonds with the substrate.
Since the precursor molecules do not react with each other, no more than one
molecular layer could be deposited at this stage.
3. The monolayer of precursor molecules that are chemically bonded to the
substrate is activated again through surface reaction. (Either the same or different
precursor molecules are subsequently introduced to the deposition chamber and
react with the activated monolayer).
4. As the steps repeat, more molecular or atomic layers are deposited one layer at
a time.
 1. The substrate is hydroxylated first, prior to the
Example: Growth of Titania film
introduction of precursor (TiCl4)
2. TiCl4 will react with the surface hydroxyl groups
through a surface condensation reaction

where Me represents metal or metal oxide

substrates.
The reaction will stop when all the surface
hydroxyl groups reacted with titanium
tetrachloride.
3. The gaseous by-product (HCl), and excess
precursor molecules are purged, and water
vapor is subsequently introduced to the
system.
TiCl3 chemically bonded onto the substrate
surface undergo hydrolysis reaction

4. Neighboring hydrolyzed Ti precursors

subsequently condensate to form Ti-0-Ti
linkage:
5. One layer of TiO2 is thus grown by completion of one cycle of these chemical
reactions.
6. The surface hydroxyl groups are ready to react with titanium precursor
molecules again in the next cycle.
7. By repeating the above steps, many more TiO2 layers can be deposited in a
very precisely controlled way.
Compared to other vapor phase deposition methods, ALD offer following
Advantages:

(i) Precise control of film thickness : Precise control of film thickness is due to
the nature of self-limiting process, and the thickness of a film can be set
digitally by counting the number of reaction cycles.
(ii) Conformal coverage : Can only be achieved when the precursor doses and
pulse time are sufficient for reaching the saturated state at each step at all
surfaces and no extensive precursor decomposition takes place.

Disadvantage:
Low deposition rate, typically <0.2 nm (less than half a monolayer) per cycle
 Lecture 19
II. Liquid Based Growth
A.Self – Assembly:

 Is a wet-chemical route to the synthesis of thin films, mostly organic/inorganic-

organic hybrid film.
 A process that ordered arrangement of molecules and small components such
as small particles occur spontaneously under the influence of certain forces
(such as chemical reactions, electrostatic attraction and capillary forces).

 This method is often used for surface modification by formation of a single layer
of molecules referred to as self assembled monolayers (SAMs).
 SAMs are molecular assemblies that are formed spontaneously by the
immersion of an appropriate substrate into a solution of an active surfactant in
an organic solvent.
Typical self- assembling surfactant molecule can be divided into three
parts:
1. Head group: provides the most exothermic process, i.e. chemisorption on the
substrate surface. The very strong molecular-substrate interactions result in an
apparent pinning of the head group to a specific site on the surface through a
chemical bond.
2. Alkyl chain and the exothermic energies associated with its interchain van der Waals
interactions.
3. Terminal functionality: these surface functional groups in SA monolayers are
thermally disordered at room temperature.

As a result of the exothermic

head group-substrate
interactions, molecules try to
occupy every available
binding site on the surface
and adsorbed molecules may
diffuse along the surface.
 The driving force for the self-assembly includes:
1. electrostatic force,
2. hydrophobicity and hydrophilicity,
3. capillary force, and
4. chemisorption

 All spontaneous growth processes of formation of materials as single crystal

growth/ thin film deposition, can be considered as self-assembly process;
as in these processes, the growth species self-assemble at low energy sites.
Typical procedure:
Example: Formation of monolayers by reacting alkyl silane derivatives with
hydroxylated surfaces (ex. SiO2)
1. Hydroxylated surface is introduced into a solution of alkyltrichlorosilane in an
organic solvent for a few minutes ( A longer immersion time is required for
surfactants with long alkyl chains.)
2. 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
3. After immersion, the substrate is rinsed with methanol, DI water and then dried.
Note:
Organic solvents are generally
required for self-assembly for the
alkyl silane derivatives, since silane
groups undergo hydrolysis and
condensation reaction when
contact with water, resulting in
aggregation.
B. Langmuir-Blodgett Films (LB Films):

 Langmuir and Blodgett discovered that when a solid surface is inserted into an
aqueous solution containing monolayers of organics then the monolayer will
deposit homogeneously over the surface. This process created Langmuir–Blodgett
films.
 A Langmuir–Blodgett film contains one or more monolayers of an organic
material, deposited from the surface of a liquid onto a solid by immersing the solid
substrate into (or from) the liquid.
 A monolayer is adsorbed homogeneously with each immersion step, thus films
with very accurate thickness can be formed.
This thickness is accurate because the thickness of each monolayer is known and can
therefore be added to find the total thickness of a Langmuir–Blodgett film.
The monolayers are assembled vertically and are usually composed of amphiphilic
molecules with a hydrophilic head and a hydrophobic tail (example: fatty acids).
 LB films are formed when amphiphilic molecules like surfactants interact with air
at an air–water interface. Surfactants (or surface acting agents) are molecules with
hydrophobic 'tails' and hydrophilic 'heads'.
When surfactant concentration is less than critical micellar concentration (CMC), the
surfactant molecules arrange themselves as shown in Figure 1 below.
 Since the tails are hydrophobic, their exposure to air is favoured over that to
water. Similarly, since the heads are hydrophilic, the head–water interaction is more
favourable than air– water interaction. The overall effect is reduction in the surface
energy (or equivalently, surface tension of water).
Note:
The solubility of an amphiphilic molecule in water depends on the balance
between the alkyl chain length and the strength of its hydrophilic head.

Certain strength of the hydrophilic head is required to form LB films.

If the hydrophilicity is too weak, no LB film can be formed.
However, if the strength of the hydrophilic head is too strong, the amphiphilic
molecule is too soluble in water to allow the formation of a monolayer.
 LB technique is unique, as the monolayers can be transferred to many different
substrates.
 Film structure can be controlled at molecular level.
 An alternative technique of creating single monolayers on surfaces is that of self
assembled monolayers.
Process: Formation of LB Films (molecular films at water-air interface)
1. A drop of a dilute solution of an amphiphilic molecule in a volatile solvent (ex.
CHCl3), is spread on the water-air interface of a trough.
2. As the solvent evaporates, the amphiphilic molecules are dispersed on the
interface.
3. The barrier moves and compresses the molecules on the water-air interface; the
intermolecular distance decreases and the surface pressure increases.
4. A phase transition may occur, from the “gas” to the “liquid” state. In the liquid
state, the monolayer is coherent, except the molecules occupy a larger area than in
the condensed phase.
5. When the barrier compresses the film further, a second phase transition can be
observed from the “liquid” to the “solid” state. In this condensed phase, the
molecules are closely packed and uniformly oriented.
2 methods are used to transfer monolayers from the water-air interface onto a
solid surface
1. Vertical Deposition:
a. Substrate is moved through the monolayer at the water-air interface,
b. The monolayer is transferred during emersion (retraction or upstroke) or
immersion (dipping or down stroke).
[A monolayer usually will be transferred during retraction when the substrate
surface is hydrophilic, and the hydrophilic head groups interact with the surface.]
c. Multiple layer films can be synthesized just by repeating the process
2. Horizontal lifting or Schaefer’s method.

 Useful for the deposition of very rigid

films.
a. a compressed monolayer is first
formed at the water and air interface, a
flat substrate is placed horizontally on
the monolayer film.
b. When the substrate is lifted and
separated from the water surface, the
monolayer is transferred onto the
substrate.
C. Electro-chemical deposition

D. Sol-gel films
 Superlattice

 Are thin film structures composed of periodically alternating single crystal film
layers.
 Such structures can be fabricated by MBE, CVD, ALD.
 Organic superlattices can be fabricated using LB technique or by self-assembly.
Note:
1. Self-assembly and LB technique offer the possibility of design and the
construction of stable organic superlattices.
2. Both MBE and ALD offer the most precise control of the deposition at the
single atomic level and the best quality of grown film.