Selected topics in materials
science
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Course Contents
• Physics of low dimensional systems
• Thin Films
• Current advances in III-V semiconductors
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Physical Properties of Nanomaterials
1. 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.
2. Ultra Hard -- Mechanical properties of nanomaterials may reach the theoretical strength,
which are one or two orders of magnitude higher than that of single crystals in the bulk
form. The enhancement in mechanical strength is simply due to the reduced probability
of defects.
3. Optical properties of nanomaterials can be significantly different from bulk crystals.
--- Semiconductor Blue Shift in adsorption and emission due to an increased band
gap.
Quantum Size Effects, Particle in a
box.
--- Metallic Nanoparticles Color Changes in spectra due to Surface Plasmons
Resonances
Lorentz Oscillator Model.
Physical Properties of
Nanomaterials
1. Electrical conductivity decreases with a reduced dimension due to increased
surface scattering.
Electrical conductivity increases due to the better ordering and ballistic
transport.
2. Magnetic properties of nanostructured materials are distinctly different from
that of bulk materials. Ferromagnetism disappears and transfers to
superparamagnetism in the nanometer scale due to the huge surface
energy.
3. Self-purification is an intrinsic thermodynamic property of nanostructures and
nanomaterials due to enhanced diffusion of impurities/defects/dislocations
to the nearby surface.
4. Increased perfection enhances chemical stability . 5
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SIZE
A meter is about the distance from the tip of your
nose to the end of your hand (1 meter = 3.28 feet).
Millimeter- One thousandth of meter.(10-3m)
Micron: a micron is a millionth of a meter (or) one
thousandth of millimeter (10-6m)
Nanometer:
A nanometer is one thousandth of a micron (10–9m)
(or) a billionth of a meter. ie.,one billion nanometers
in a meter.
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• Composites made from particles of nano-size ceramics or metals
smaller than 100 nanometers can suddenly become much stronger
than predicted by existing materials-science models.
• For example, metals with a so-called grain size of around 10
nanometers are as much as seven times harder and tougher than
their ordinary counterparts with grain sizes in the micro meter
range.
• The Nano particles affects many properties such as
Melting point
Boiling point
Band gap
Optical properties
Electrical properties
Magnetic properties 9
• .Even the structure of materials changes with respect to Size
The properties of materials can be different at the Nanoscale for two
main reasons:
First, Nanomaterials have a relatively larger surface area when
compared to the same mass of material produced in a larger form.
Nano particles can make materials more chemically reactive and affect
their strength or electrical properties.
Second, quantum effects can begin to dominate the behaviour of matter
at the Nanoscale
Nanoscale materials are divided into three category,
1. Zero dimension – length , breadth and heights are confined at single
point. (for example, Nano dots)
2. One dimension – It has only one parameter either length (or) breadth
(or) height ( example:very thin surface coatings)
3. Two dimensions- it has only length and breadth (for example,
nanowires and nanotubes)
4. Three dimensions -it has all parameter of length, breadth and height.
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(for example, Nano Particles).
What do you mean by Nano Particles ?
Nano Particles are the particles of size between 1 nm to 100 nm
• 1 nm is only three to five atoms wide.
• ~40,000 times smaller than the width of an average human hair
Nanometer - One billionth (10-9) of a meter
• The size of Hydrogen atom 0.04 nm
• The size of Proteins ~ 1-20 nm
• Feature size of computer chips 180 nm
• Diameter of human hair ~ 10 µm
At the nanoscale, the physical, chemical, and biological properties
of materials differ in fundamental and valuable ways from the
properties of individual atoms and molecules or bulk matter 11
Why Nano Particles ?
Noparticles are of interest because of the new properties (such as
chemical reactivity and optical behaviour) that they exhibit compared
with larger particles of the same materials.
For example, titanium dioxide and zinc oxide become transparent at
the nanoscale and have found application in sunscreens.
Nanoparticles have a range of potential applications:
In the short-term application such as in cosmetics, textiles and
paints.
In the longer term applications such as drug delivery where they
could be to used deliver drugs to a specific site in the body.
Nanoparticles can also be arranged into layers on surfaces, providing
a large surface area and hence enhanced activity, relevant12 to a
range of potential applications such as catalysts.
• Examples
- Carbon Nanotubes
- Proteins, DNA
- Single electron transistors
Carbon Nanotubes
AFM Image of DNA
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Nanotechnology deals with the creation of USEFUL
materials, devices and systems using the particles of
nanometer length scale and exploitation of NOVEL
properties (physical, chemical, biological) at that length
scale
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Based on the size and shape, the Nano materials are classified as
follows
• Nanoparticles • Nanotubes
• Nanocapsules • Nanosprings
• Nanofibers • Nanobelts
• Nanowires • Quantum dots
• Fullerenes (carbon 60) • Nanofluidies
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Quantum well
• It is a two dimensional system
• The electron can move in two directions and restricted in one
direction.
Quantum Wire
• It is a one-dimensional system
• The electron can move in one direction and restricted in two
directions.
Quantum dot
• It is a zero dimensional system
• The electron movement was restricted in entire three
dimensions
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Why called Quantum ?
• Because, the electronic property is quantized
• The spatial distance is very very small
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Semiconductor substrate
growth (single
layer) 18
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Quantum wire
Quantum wires are ultra fine wires or linear arrays of Nano
dots, formed by self-assembly
They can be made from a wide range of materials such as
Semiconductor Nanowires made of silicon, gallium nitride and
indium phosphide.
Nanowires have potential applications in
1. In high-density data storage, either as magnetic read heads or as
patterned storage media
2. In electronic and opto-electronic Nanodevices, for metallic
interconnects of quantum devices and Nanodevices.
Nanowires can be prepared by growth techniques such as
1. Chemical Vapour deposition (CVD)
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2. Electroplating
Quantum wire cont…
In quantum wire, Two dimensions are reduced and one
dimension remains large
Therefore, the electrical resistivity of quantum wire can be
calculated using conventional formula as follows,
We need two dimension to calculate area of conducting material,
but not present in quantum wire
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General properties of Nanowire
Diameter – 10s of nanometers
Single crystal formation -- common crystallographic
orientation along the nanowire axis
Minimal defects within wire
Minimal irregularities within nanowire arrays
Some example of Nanowire
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Magnetic nanowires
Example: Cobalt, gold, copper and cobalt-copper
nanowire arrays
Important for storage device applications
Electrochemical deposition is the fabrication
technique
<20 nm diameter nanowire arrays can be fabricated
by electrochemical deposition
Cobalt nanowires on Si substrate
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(UMass Amherst, 2000)
In quantum dot all the three dimensions are reduced to zero
Quantum dot
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Dimension Variation
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Properties of Nano Materials
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Melting Point
The melting point decreases dramatically as the particle size
gets below 5 nm
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Source: Nanoscale Materials in Chemistry, Wiley, 2001
Melting points and lattice constants
Nanoparticles of metals, if < 100 nm have a
semiconductors and
molecular crystals
a lower melting point (the difference can be as large as 1000 deg C)
and reduced lattice constant.
Reason:
surface energy to volume energy ratio changes dramatically.
what is easier to get off? surface atom or volume atom.
If you keep cutting you increase the
overall surface free energy and Gibbs
Free Energy by increasing the number
of free bonds (H internal energy)
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Band gap
The band gap is increases with reducing the size of the
particles
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Surface Area
The total surface area (or) the number of surface atom increases
with reducing size of the particles
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• For semiconductors such as ZnO, CdS, and Si, the bandgap
changes with size
- Bandgap is the energy needed to promote an electron
from the valence band to the conduction band
- When the bandgaps lie in the visible spectrum, changing
bandgap with size means a change in color
• For magnetic materials such as Fe, Co, Ni, Fe3O4, etc., magnetic
properties are size dependent
- The ‘coercive force’ (or magnetic memory) needed to
reverse an internal magnetic field within the particle is
size dependent
- The strength of a particle’s internal magnetic field can33be
size dependent
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Applications of Nano Materials
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1. Nanotechnology Applications in Medicine
• Because of their small size, nanoscale devices can readily
interact with biomolecules on both the surface of cells and
inside of cells.
• By gaining access to so many areas of the body, they have the
potential to detect disease and the deliver treatment.
• Nanoparticles can can deliver drugs directly to
diseased cells in your body.
• Nanomedicine is the medical use of molecular-
sized particles to deliver drugs, heat, light or
other substances to specific cells in the human
body.
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• Quantum dot- that identify the location of cancer
cells in the body.
• Nano Particles - that deliver chemotherapy drugs
directly to cancer cells to minimize damage to healthy
cells.
• Nanoshells - that concentrate the heat from infrared
light to destroy cancer cells with minimal damage to
surrounding healthy cells.
• Nanotubes- used in broken bones to provide a
structure for new bone material to grow.
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Nano shells as Cancer Therapy
Nano shells are injected into cancer area and they recognize
cancer cells. Then by applying near-infrared light, the heat
generated by the light-absorbing Nano shells has successfully
killed tumor cells while leaving neighboring cells intact.
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Nanowires – used as medical sensor
• In this diagram (next page), Nano sized sensing wires are laid
down across a micro fluidic channel. As particles flow through the
micro fluidic channel, the Nanowire sensors pick up the molecular
identifications of these particles and can immediately relay this
information through a connection of electrodes to the outside
world.
• These Nanodevices are man-made constructs made with carbon,
silicon Nanowire.
• They can detect the presence of altered genes associated with
cancer and may help researchers pinpoint the exact location of
those changes
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2. Nano Computing Technology
Past
Shared computing thousands of
people sharing a mainframe computer
Present
Personal computing
Future
Ubiquitous computing thousands of computers sharing each
and everyone of us; computers embedded in walls, chairs, clothing,
light switches, cars….; characterized by the connection of things43in
the world with computation.
3. Sunscreens and Cosmetics
• Nanosized titanium dioxide and zinc oxide are currently used in
some sunscreens, as they absorb and reflect ultraviolet (UV) rays.
• Nanosized iron oxide is present in some lipsticks as a pigment.
4. Fuel Cells
The potential use of nano-engineered membranes to intensify
catalytic processes could enable higher-efficiency, small-scale fuel
cells.
5. Displays
• Nanocrystalline zinc selenide, zinc sulphide, cadmium sulphide and
lead telluride are candidates for the next generation of light-emitting
phosphors.
• CNTs are being investigated for low voltage field-emission displays;
their strength, sharpness, conductivity and inertness make them
potentially very efficient and long-lasting emitters. 44
6. Batteries
• With the growth in portable electronic equipment (mobile phones,
navigation devices, laptop computers, remote sensors), there is great
demand for lightweight, high-energy density batteries.
• Nanocrystalline materials are candidates for separator plates in
batteries because of their foam-like (aerogel) structure, which can
hold considerably more energy than conventional ones.
• Nickel–metal hydride batteries made of nanocrystalline nickel and
metal hydrides are envisioned to require less frequent recharging and
to last longer because of their large grain boundary (surface) area.
7. Catalysts
In general, nanoparticles have a high surface area, and hence provide
higher catalytic activity.
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8. Magnetic Nano Materials applications
• It has been shown that magnets made of nanocrystalline yttrium–
samarium–cobalt grains possess unusual magnetic properties due
to their extremely large grain interface area (high coercivity can be
obtained because magnetization flips cannot easily propagate past
the grain boundaries).
• This could lead to applications in motors, analytical instruments
like magnetic resonance imaging (MRI), used widely in hospitals,
and microsensors.
• Nanoscale-fabricated magnetic materials also have applications in
data storage.
• Devices such as computer hard disks storage capacity is increased
with Magnetic Nano materials
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9. Medical Implantation
• Unfortunately, in some cases, the biomedical metal alloys may wear
out within the lifetime of the patient. But Nano materials increases
the life time of the implant materials.
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• Nanocrystalline zirconium oxide (zirconia) is hard, wear resistant,
bio-corrosion resistant and bio-compatible.
• It therefore presents an attractive alternative material for implants.
• Nanocrystalline silicon carbide is a candidate material for artificial
heart valves primarily because of its low weight, high strength and
inertness.
10. Water purification
•Nano-engineered membranes could potentially lead to more energy-
efficient water purification processes, notably in desalination process.
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11. Military Battle Suits
• Enhanced nanomaterials form the basis of a state-of- the-art
‘battle suit’ that is being developed.
• A short-term development is likely to be energy-absorbing
materials that will withstand blast waves;
• longer-term are those that incorporate sensors to detect or
respond to chemical and biological weapons (for example,
responsive nanopores that ‘close’ upon detection of a
biological agent).
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Physisorption vs Chemisorption
PHYSISORPTION CHEMISORPTION
WEAK, LONG RANGE BONDING STRONG, SHORT RANGE BONDING
Van der Waals interactions Chemical bonding involved.
NOT SURFACE SPECIFIC SURFACE SPECIFIC
Physisorption takes place between all E.g. Chemisorption of hydrogen takes place on
molecules on any surface providing the transition metals but not on gold or mercury.
temperature is low enough.
ΔHads = 5 ….. 50 kJ mol-1 ΔHads = 50 ….. 500 kJ mol-1
Non activated with equilibrium achieved Can be activated, in which case equilibrium can
relatively quickly. Increasing temperature be slow and increasing temperature can favour
always reduces surface coverage. adsorption.
No surface reactions. Surface reactions may take place:- Dissociation,
reconstruction, catalysis.
MULTILAYER ADSORPTION MONOLAYER ADSORPTION
BET Isotherm used to model adsorption Langmuir Isotherm is used to model adsorption
equilibrium. equilibrium.
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