Module 4: Engineering Materials

⚫Properties of materials: conductor,

semiconductor & insulator
⚫carbon nanorods/nanotubes/nanosheets,
fullerenes
⚫photoconductors, organic solar cells
⚫Thermionic and photoelectric effect
⚫Nanomaterials - distinction between
molecules, nanoparticles and bulk
materials
⚫Size dependent properties
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Conductors
Conductors are generally substances which have the property
to pass different types of energy.

When the temperature is raised,

greater random motion of the atoms
hinders electron movement, which
decreases the conductivity of
a metal.

Metals
Salts
3
Insulators
Insulators possess no free charge carriers and thus
are non-conductive.

A perfect insulator does not exist,

because even insulators contain
small numbers of mobile charges
(charge carriers) which can carry
current.

Insulators are used in electrical

equipment to support and separate
electrical conductors without
allowing current through themselves. 4
Semiconductor
sSemiconductors are solids whose conductivity lies
between the conductivity of conductors and insulators.
Unlike metals, the conductivity increases with increasing
temperature.

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Unit 2 - Engineering Materials
Electrical conductivity
 Conductors
 Semiconductors
 Insulators

Optical properties
 Semiconductors

 Band Diagram
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Bulk vs. Nano - materials

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Molecular Orbital Theory
 Formation of Molecular Orbitals

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 Energy and Shape of H2 Molecular
Orbitals

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MO of Li2

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Formation of Bands in Solid

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Band diagram of Conductor,
Semiconductor and Insulator

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Conductors (metals): The valence and conduction bands of a
conductor have no gap between them, so electrons flow
when even a tiny electrical potential difference is applied.

At higher temperatures, the metal cations undergo increased

vibrational motion about their lattice sites and vibration of
the cations disrupts the flow of electrons through the
crystal.

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Semiconductors (metalloids): In a semiconductor, a
relatively small energy gap exists between the valence
and conduction bands.

Thermally excited electrons can cross the gap, allowing a

small current to flow. Thus, in contrast to a conductor, the
conductivity of a semiconductor increases when it is heated.

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Insulators (nonmetals): In an insulator, the gap between the
bands is too large for electrons to jump even when the
substance is heated, so no current is observed.

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Figure (a) Classification of a material according to energy bands and interatomic spacing. (b)
The semiconductor band gap energy model
How to increase
conductivity of a
semiconductor?
 Increase
temperatures

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Doping: n-type semiconductor
 When Si is doped with
phosphorus [or another Group
5A(15) element], P atoms occupy
some of the lattice sites.

 Since P has one more valence

electron than Si, this
additional electron must enter
an empty orbital in the
conduction band, thus
bridging the energy gap and
increasing conductivity.
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Doping: p-type semiconductor
 When Si is doped with
gallium [or another
Group 3A(13) element],
Ga atoms occupy some
sites.

 Since Ga has one fewer

valence electron than Si, some
of the orbitals in the valence
band are empty, which creates
a positive site.

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p-n Junction

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21
Semiconductor Devices
1.Diodes that convert alternating
current to direct current
2.Light-emitting diodes (LEDs)
that serve as light sources in traffic
signals, vehicle brake lights,
digital clocks, and hospital pulse
oximeters that monitor the oxygen
saturation of hemoglobin in blood

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Semiconductor Devices
3.Diode lasers that produce the
bright, red light of laser pointers
and supermarket bar-code scanners
4.Photovoltaic (solar) cells that
convert sunlight into electricity
5.Transistors that control and
amplify electrical signals in the
integrated circuits of computers,
cell phones, and many other
consumer electronic products

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Optical Properties
We would like to explore the consequences of interactions
between electromagnetic radiation and solids.
Our focus will be on the origins of phenomena that relates to
the design of useful devices, such as lasers and light -
emitting diodes.

What happens when a solid absorbs

light?

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Optical Properties: LEDs and Solid
state lasers

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 Example of various
 LEDs
Gallium Arsenide (GaAs) – infra-red
 Gallium Arsenide Phosphide (GaAsP) –
red to infra-red, orange
 Aluminium Gallium Arsenide Phosphide
(AlGaAsP) – high-brightness red, orange-
red, orange, and yellow
 Gallium Phosphide (GaP) – red, yellow
and green
 Aluminium Gallium Phosphide (AlGaP)
–
green
 Gallium Nitride (GaN) – green,
emerald green
 Gallium Indium Nitride (GaInN) – near
ultraviolet, bluish-green and blue
 Silicon Carbide (SiC) – blue as a
substrate
 Zinc Selenide (ZnSe) – blue 25
What is the origin of different
colors in LEDs?

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Band gap and emission color
E = hν = hc/λ;

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Problem:

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Problem:

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If Ge crystals has been doped with arsenic, it
will behave as n-or p-type semiconductor?
Demonstrate the change with band theory.

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Nanotechnology: Designing
Materials Atom by Atom
Nanotechnology is the science and engineering of
nanoscale systems, whose sizes range from 1 to 100 nm.

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Classification of Nanomaterials

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Examples of Nanomaterials

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 Applications of Nanoparticles
 Silver nanoparticles have good antibacterial properties, and are
used in surgical instruments, refrigerators, air-conditioners,
water purifiers etc.
 Gold nanoparticles are used in catalytic synthesis of silicon
nano wires, sensors carrying the drugs and in the detection
of tumors.
 ZnO nanoparticles are used in electronics, ultraviolet (UV) light
emitters, piezoelectric devices and chemical sensors.
 TiO2 nanoparticles are used as photocatalyst and
sunscreen cosmetics (UV blocking pigment).
 Antimony-Tin-Oxide (ATO), Indium-Tin-Oxide (ITO)
nanoparticles are used in car windows, liquid crystal
and in solar cell preparations.
displays 34
Size Dependent Properties of
Nanomaterials
The various properties, which get tremendously
altered due to the size reduction in at least one
dimension are:
a) Chemical properties: Reactivity; Catalysis.
b) Thermal property: Melting point temperature.
c) Electronic properties: Electrical conduction.
d) Optical properties: Absorption and scattering of light.
e) Magnetic properties: Magnetization.

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Size Dependent Optical Properties

Nanocrystals are also called Quantum Dots 36

Size Bandgap Emission
increases decreases wavelength
increases
Size Bandgap Emission wavelength
decreases increases decreases
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Match the following nanocrystals of
different sizes with their emission color
Size of Emission
Nanocrystal Color
s
1.5 nm Green
3.25 nm Violet
5.3 nm Red
8.1 nm Orange

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 Electronic Properties
 In bulk materials, conduction of electrons is delocalized, that is,
electrons can move freely in all directions.
 When the scale is reduced to nanoscale, the quantum effect
dominates. For zero dimensional nanomaterials, all the
dimensions are at the nanoscale and hence the electrons
are confined in 3-D space. Therefore no electron
delocalization (freedom to move) occurs.
 For one dimensional nanomaterials, electrons confinement
occurs in 2-D space and hence electron delocalization takes place
along the axis of nanotubes/nanorods/nanowires.
 Due to electron confinement, the energy bands are
replaced by discrete energy states which make the
conducting materials to behave like either semiconductors
or insulators 39
Chemical Properties
Based on the surface area to volume effect,
nanoscale materials have:
a) Increased total surface area.
b) Increased number of atoms accessible on the surface.
c)Increased catalytic activity of those large number surface
atoms.
d)Different/tunable surface catalytic properties by the change
in shape, size and composition.
Hence, nanoscale catalysts can increase the rate,
selectivity and efficiency of various chemical
reactions.
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 Carbon Materials
Forms of carbon:
a) Graphite 3D
b) Diamond 3D
c) Buckminsterfullerene
“Buckyballs” 0D
d) Carbon nanotube 1D
e) Graphene 2D

2010 Nobel Prize in Physics

http://www.nobelprize.org/nobel_prizes/
Andre Geim physics/laureates/2010/ Konstantein Novoselov41
 Properties of graphene

Thinnest material possible (~0.345 nm thick)

Strongest material ever measured
 200 times more stronger than steel

Electrical conductivity is best known

so far for any material
 10,00,000 times more conductive
than copper

Flexible and stretchable

Transparent (~97.7% white light can pass
through a single layer of graphene)

Angew. Chem. Int. Ed. 2011, 50, 6967

 Potential applications of graphene
Optoelectronics
LEDs, Touch screens,
Flexible displays etc.

Energy
generation
and storage
Photovoltaics,
Supercapacitor etc.

Drug
delivery
Sensors
Anticancer
drug: Doxorubicin
DNA sensor
Chem. Eur. J. 2012, 18, 4208

Angew. Chem. Int. Ed. 2010, 49, 6549