Nanostructures

Module-2
 Nanostructures
The nanostructure materials can broadly be classified into four
general categories:
1. Zero dimensional nanostructures
2. One dimensional nanostructures
3. Two dimensional nanostructures
4. Three dimensional nanostructures
 Surface to Volume ratio
Nano materials have high surface to volume ratio.
𝟒
Volume of the sphere = 𝝅𝒓𝟑
𝟑
Surface Ares of the sphere = 4 𝝅𝒓𝟐 where r = radius of the sphere
Volume of cube = 𝒂𝟑 where 𝒂 = edge of the cube
Cube surface area = 6 𝒂𝟐
Volume of the cylinder = 𝝅𝒓𝟐 𝒍 where r = radius of the cylinder, l = length of the
cylinder

The surface area of the sphere will be 4πr2

The volume of the sphere = 4/3(πr3)

Surface area to the volume ratio will be 4πr2/{4/3(πr3)} = 3/r

Nanostructures
0D
1D
2D
2D
 Quantum dots
• Quantum dots (QDs) are often referred to very tiny
man-made semiconductor particles, whose size are
normally no more than 10 nanometers.
• Their extremely small size renders their optical and
electronic properties different from those of bulk
materials.
• A majority of QDs have the ability to emit light of
specific wavelengths if excited by light or electricity.
• According to existing literature, the electronic
characteristics of QDs are determined by their size
and shape, which means we can control their
emission wavelengths by tuning their size.
 Quantum dots
• Typically, smaller QDs (e.g., radius of 2~3 nm)
emit shorter wavelengths generating colors such
as violet, blue or green. While bigger QDs (e.g.,
radius of 5~6 nm) emit longer wavelengths
generating colors like yellow, orange or red.

• Their highly tunable optical properties based on

their size are fascinating, leading to a variety of
research and commercial applications including
bioimaging, solar cells, LEDs, diode lasers, and
transistors.
 Quantum dots

Fluorescence spectra of quantum dots with various sizes.

Optical Properties and Principles
• In semiconducting materials, they possess intrinsic
band gap, and the electrons are able to be excited
from the valence to the conduct band by absorbing
incident light, leaving behind a hole.
• The electron and the hole can bind to each other to
form an exciton. A photon with longer wavelength
will be emitted when this exciton recombines (i.e.
the excited electron returns to its ground state).
This phenomenon is known as Fluorescence.
• However, unlike bulk semiconducting materials,
QDs are too sparse to create the continuous
valence and conduct band. Generally, the smaller
the particle size the larger the band gap. As the
emission wavelength depends on the QDs’ size,
their fluorescence can be readily controlled by
changing their size during the synthesis process.
The electronic structure of quantum dots varies with the size of dots.
Quantum confinements affects the energy levels and electrical
conductivity

In bulk materials the electrons are not

Discrete
energy states confined. They are free to move in all
Directions to longer distance.

In quantum dots the electrons are

confined in all dimension.

Due to electron confinement

quantum dots have poor
electrical conductivity as compared to
bulk material
Bulk material Quantum dots (QD)
 Quantum dots (QD).
Quantum dots are semicrystaline
nanoparticles.

Example: Cadmium Sulphide (CdS) and

Cadmium Selenide (CdSe)

They show light absorbance and emission in

the visible region of the electromagnetic
spectrum.

The colour they absorb/emit depends on the

size of the nanoparticle.
 Relationship betwen the energy gap
and size of the QD

As shown in figure, bulk semiconductors have energy bands. Whereas quantum dots
have discrete quantized energy states. As size of the particle decreases the
gap energy increases.
18
 Bohr Exciton Radius
• Quantum Dot: A Zero Dimensional (0-D) Material

Size of the crystal is confined in all 3 dimensions

• Therefore, the motion of electrons and holes is also restricted in
all three spatial dimensions
• Thus, a quantum dot can be defined as a structure where all
dimensions are comparable to the Bohr exciton radius
 Bohr Exciton Radius

The energy states of the electrons and holes in quantum dots are
discrete and given by
3𝑛2 ℏ2
𝐸𝑛 =
2𝑚∗ 𝑎2
where n = 1, 2, 3,………
𝑚∗ − effective mass of electron
The excitonic Bohr radius is given by
𝑚𝑒
𝑎𝑒𝑥𝑐𝑖𝑡𝑜𝑛 = 𝑎0 ℇ ∗
𝜇𝑒𝑥𝑐𝑖𝑡𝑜𝑛
where ε is the dielectric constant of the semiconductor
a0 = Bohr radius
𝑎0 = 0.056 𝑛𝑚
∗ 1 1 1
𝜇𝑒𝑥𝑐𝑖𝑡𝑜𝑛 - effective exciton mass ∗ = 𝑚∗ + 𝑚∗
𝜇𝑒𝑥𝑐𝑖𝑡𝑜𝑛 𝑒 ℎ
𝑚𝑒= mass of the electron at rest
𝑚𝑒∗ = effective mass of electron
𝑚ℎ∗ = effective mass of hole
The excitonic Bohr radius is given by
𝑚𝑒
𝑎𝑒𝑥𝑐𝑖𝑡𝑜𝑛 = 𝑎0 ℇ ∗
𝜇𝑒𝑥𝑐𝑖𝑡𝑜𝑛
where ε is the dielectric constant of the semiconductor
a0 = Bohr radius
𝑎0 = 0.056 𝑛𝑚
∗ 1 1 1
𝜇𝑒𝑥𝑐𝑖𝑡𝑜𝑛 - effective exciton mass ∗ = + ∗
𝜇𝑒𝑥𝑐𝑖𝑡𝑜𝑛 𝑚𝑒∗ 𝑚ℎ
𝑚𝑒= mass of the electron at rest
𝑚𝑒∗ = effective mass of electron
𝑚ℎ∗ = effective mass of hole
 Quantum Dot Size & Band Gap
Size of Quantum Dot increases Effective Bandgap increases
 Quantum Dot Size & Band Gap
The energy of the bandgap of a nanoparticle differs from the bulk
by
𝐸𝑔, 𝑛𝑎𝑛𝑜𝑐𝑟𝑦𝑠𝑡𝑎𝑙 = 𝐸𝑔, 𝑏𝑢𝑙𝑘 + ∆𝐸𝑔
ℎ2 𝜋 2
𝐸𝑔, 𝑛𝑎𝑛𝑜𝑐𝑟𝑦𝑠𝑡𝑎𝑙 = 𝐸𝑔, 𝑏𝑢𝑙𝑘 + 2
2𝑚𝑟𝑛𝑎𝑛𝑜𝑐𝑟𝑦𝑠𝑡𝑎𝑙
As a particle becomes smaller, its bandgap increases.
Problem: If the radius of the first orbit is a0. Calculate the de-
Broglie wavelength of an electron in nth orbit.

We know that

𝑛ℎ ℎ 2𝜋𝑟
𝑚𝑣𝑟 = ⇒ =
2𝜋 𝑚𝑣 𝑛
From de-Broglie hypothesis

ℎ ℎ
𝜆= =
𝑝 𝑚𝑣

2𝜋𝑟𝑛 2𝜋𝑛2 𝑎0
𝜆𝑛 = = ∵ 𝑟𝑛 = 𝑛2 𝑎0
𝑛 𝑛
𝜆𝑛 = 𝟐𝝅𝒏𝒂𝟎
Problem: The bandgap of 4 nm quantum dots is 3 eV. If the
wavelength of the florescence spectra changes 600 nm to 500 nm
when the size of the quantum dot decreased from 4 nm to 2 nm.
Calculate the bandgap of the size of 2 nm quantum dots.
Solution:
Formula, E=hc/λ
One of the dimension of a nanomaterial is 4 nm and its dielectric
constant is 16. Determine the Bohr exitron radius. (Given that Bohr
radius = 0.056 nm, 𝑚𝑒∗ = 0.064𝑚e and 𝑚ℎ∗ = 0.42𝑚e where 𝑚e = mass
of electron)

Identify quantum confinement .

𝑚𝑒
𝑎𝑒𝑥𝑐𝑖𝑡𝑜𝑛 = 𝑎0 ℇ ∗
𝜇𝑒𝑥𝑐𝑖𝑡𝑜𝑛
 Applications of Matter wave

One of the major applications of wave nature of matter is electron microscopes.

Electron Microscope - a microscope that uses a beam of accelerated electrons instead of light as
a source for illuminating objects.
Electron Microscope

Optical Microscope

Why use electrons instead of light in a microscope?

Resolving Power
Human eye 0.2mm
Optical microscope 200 – 250 nm
Electron Microscope 1 – 10 nm
M. S. Ramaiah University of Applied Sciences
1. Electromagnetic 1. Electron beam
waves (light) (matter waves)

2. Glass lenses 2. Electromagnetic

lenses
3. 400 -700 nm
3. 0.0061 – 0.024nm
4. Low Resolution
4. High Resolution
 Comparison of Resolution and Depth of Field

Image of skeleton of a
small marine organism

OM SEM

Image of nanofibers
Applications of QDs
 Applications of QDs
1. Bioimaging
• Various kinds of organic dyes have been used in bioimaging for
decades. However, most of the organic dyes suffer from low
quantum yield and photostability. However, with the
advancement of nanotechnology, QDs have been considered to be
superior to traditional organic dyes in many respects. For example,
it has been found that QDs are 20 times brighter and 100 times
more stable more than traditional fluorescent reporters. With
well-established inorganic synthetic techniques now are available for
generating QDs with high brightness.
• For bioimaging applications, the fluorescent probes have to remain
well-dispersed and stable in the aqueous medium with a wide range
of pH and ionic strengths. Fortunately, numerous approaches have
been developed to make the QDs water-dispersible. Up until now,
great efforts have been devoted to employing QDs for in vitro and in
vivo imaging, which are expected to be important to the diagnoses of
many diseases, the understanding of embryogenesis, and
lymphocyte immunology.
 Applications of QDs
2. Light emitting devices
• QDs are promising for light emitting devices and may improve the
performance of light-emitting diode (LED), leading to the new design
of “Quantum Dot light Emitting Diode”. QDs are very useful for
display devices considering their unique optical properties. They are
capable of presenting visibly more accurate and outstanding
colors. A proof-of-concept QDs display has been successfully
achieved from technical perspective years ago, and shows a good
performance and bright emission in the region of visible and near
infrared spectrum.

3. Photovoltaic devices
• Because of the tunable of the absorption spectrum and high
extinction coefficient, QDs are desirable for light harvesting, is
beneficial for photovoltaic devices. QDs have the potential to boost
the efficiency of silicon photovoltaic cells and lead to reduced costs.
Applications of QDs
Applications of QDs
Applications of QDs
 Thin Film
• An ideal thin film can mathematically be defined as a
homogeneous solid material contained between two parallel planes
and extended infinitely in two directions (x, y) but restricted along
the third direction (z), perpendicular to the x- y plane. The
dimension along x-direction is known as the film thickness d. The
value of d may vary from a few nanometer to any arbitrary value
say to 10 micro meter or more.

• Modern life would not be possible without thin films and coatings.

• Thickness of thin film is very small. Due to this, thin films are
almost invisible to the naked eye or buried below other surface
layers.
 Characteristics features of
Thin Film
1. Thickness of thin film varies from nm to μm.

2. Properties like electrical (resistivity), optical (transmission),

mechanical (Young's modulus) and thermal (conductivity) depend
on thickness.

3. Structure of thin film may be amorphous, polycrystalline or

single crystal.

4. Structure of thin film depends on the method of deposition.

5. Structure of thin film changes with temperature.

6. Thin films suffer severe stresses (tensile or compressive).

 Applications of Thin Film
Advances in thin film deposition techniques during the 20th
century have enabled a wide range of technological
breakthroughs in areas
• magnetic recording media
• electronic semiconductor devices
• LEDs
• optical coatings (such as antireflective coatings)
• hard coatings on cutting tools.
• for energy generation (for examples thin film solar cells)
• storage (thin-film batteries).
• pharmaceuticals, via thin-film drug delivery.
 Quantum well
• A quantum well is a particular kind of
heterostructure in which one thin "well"
layer is surrounded by two "barrier" layers.
Both electrons and holes see lower energy in
the "well“ layer.

• In fact, the allowed states in this structure

correspond to standing waves in the
direction perpendicular to the layers.
Because only particular waves are standing
waves, the system is quantized, hence the
name "quantum well".

• If one dimension of the material is reduced to nano range while

the other two dimensions remain large, then the material or
structure is called quantum well. Quantum well is also called
nanolayers.
 Quantum well
• The quantum well in nanotechnology is formed by
sandwiching a material (for example GaAs) between
the two layers of another material having broader gap
(For example aluminium arsenide).

• In nanotechnology, a quantum well is like a potential

well in which the carrier particles are trapped and it
took place when the thickness of the well is
comparable to the de Broglie wavelength of the
carriers.
 Quantum well
• There are at least two techniques by which quantum well
structures can be grown, molecular beam epitaxy (MBE), and
metal-organic chemical vapor deposition (MOCVD).
• Both can achieve a layer thickness control close to about one
atomic layer.
• MBE is essentially a very high vacuum technique in which
beams of the constituent atoms or molecules emerge from ovens,
land on the surface of a heated substrate, and there grow layers
of material.
• MOCVD is a gas phase technique at low pressure (e.g., 25 torr).
• In this case the constituents are passed as gasses over a heated
substrate, with the resulting composition being controlled by the
relative amounts of the appropriate gasses.
• Hybrid techniques, using the gas sources of MOCVD in a high
vacuum molecular beam system, also exist, and are known
 Quantum well
• Discrete energy values.
 Application of Quantum well
Quantum Well lasers
• It is also known as semiconductor lasers or improved lasers. QWL
operate on the same basic principle as a laser diode.

• Heterostructures are the main components of this device.

• Quantum well devices can be made by combining heterostructure of

alternative nano thin layers with two semiconductors of different
band gap.

• This device feature provides novel and unique properties with

sharper junctions and size comparable to the de Broglie wavelength
of the electrons.

• Heterojunctions are used to sandwich a layer of material with

narrow band gap between the materials of wide band gap.

• The slight energy difference between the band gaps of the two
semiconductors set up a potential barrier that serves to confine the
charge carriers in the narrow region near the junction.
 Application of Quantum well

Quantum well laser

 Application of Quantum well
Quantum well laser
 Application of Quantum well
Quantum well detectors
➢ An avalanche photodiode (APD) is used to detect optical signal
from the visible to the far-infrared of the optical spectrum.
➢ This device is grown by epitaxial techniques MBE or MOCVD.
➢ It operates on the basis of a reverse biased P-N junction with a
relatively large voltage kept substantially below the avalanche
breakdown voltage.
➢ The large reverse bias voltage lowers the carrier transit time
through the depletion region of the semiconductor as well as its
capacitance.
➢ The APD is a homogeneous slab of semiconductor material with
separate absorbing and multiplication regions.
➢ A suitable bias voltage is applied across the contact to collect the
electron-hole pair that is generated.
 Application of Quantum well
Quantum well detectors
➢ When light is incident on the semiconductor material with
sufficient energy, photons are absorbed and electron-hole pair
are created.
➢ The electron-hole pair produced within the diffusion length of
the depletion region is accelerated to the multiplication region by
the bias.
➢ In the presence of the field the electron and hole will acquire
enough energy and ionizing collision with the lattice can occur.
➢ A necessary field to produce an ionizing collision is about (104-
105) V/cm depending on the type of material.
 Application of Quantum well
Quantum well detectors
➢ In this structure, the absorption and multiplication regions of APD is replaced
with either multi-quantum well (MQW) or superlattice structure having varying
sizes of wells and barriers.
➢ The multilayered superlattice structure is incorporated in the multiplication
region of the semiconductor materials.
➢ The electron acquires more energy than holes as they drop into GaAs well
because of the large band gap discontinuity in CB edge than VB edge.
➢ The superlattice (SL) is composed of AlGaAs thin layer.
➢ The purpose of the multilayered structure is to increase the ratio αe/αh, the
ionization coefficient of electron to holes.
➢ Furthermore, the difference between the conduction and valence band
discontinuities enhances the electron ionization rate relative to that of holes.
➢ Superlattice APD has large avalanche gain and reduces noise, thus very useful
in device application.
➢ Superlattice structure of InGaAs is used for APD. This structure improves the
speed and sensitivity of InGaAs APD.
 Application of Quantum well
Quantum well detectors