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UE 5501

• Nanoparticle
• Quantum Dots
– Quantum Dot
– Degrees of freedom
– Structure and Formation
– How Quantum dots work
– Quantum Dot features
• Solar Cells
– Working
– Construction
• Need for Quantum dots in Solar cells

• Quantum dots in Solar cells

– Infrared photovoltaic cells
– Multiple exciton generation solar cells
– Quantum dot dye sensitized solar cells
– Rainbow Solar cells
– Intermediate band solar cells
– Luminescent concentrator cells

• References

• In nanotechnology, a particle is
defined as a small object that
behaves as a whole unit in terms of
its transport and properties

• According to size:
– fine particles cover a range between 100
and 2500 nm
– ultrafine particles are sized between 1
and 100 nm
• Nanoparticles may or may not exhibit
size-related intensive properties

• Non-traditional semiconductor

• Crystals composed of periodic groups of

II-VI, III-V, or IV-VI materials

• Range from 2-10 nanometres

(10-50 atoms) in diameter

• An electromagnetic radiation emitter

with an easily tunable band gap

• 0 degrees of freedom
Quantum Dot
Quantum Dot Layer
Quantum Dot Layer
Bulk Crystal (3D)  Quantum Well (2D) 
3 Degrees of Freedom (x-, y-, and z-axis) 2 Degrees of Freedom (x-, and y-axis)

Quantum Dot (0D)  0 Degrees of Freedom

Quantum Wire (1D)  (electron is confined in all directions)
1 Degree of Freedom (x-axis)
Structure vs. Energy

Quantum Dots are sometimes called “artificial atoms”

Quantum Dots (Structure and Formation)

Self-Assembly (a.k.a Stranski-

Krastanow Method): Mismatched
lattice constants cause surface tension
which results in Qdot formation with
surprisingly uniform characteristics.

GaAs  5.6533 Å InAs  6.0584 Å


• Bands and band gaps

– Electrons and Holes
– Range of energies

• Quantum confinement
– Exciton Bohr Radius
– Discrete energy levels

• Tunable band gap

– the size of the band gap is controlled
simply by adjusting the size of the dot
• Emission frequency depends on the bandgap, therefore it is
possible to control the output wavelength of a dot with
extreme precision
• Small nanocrystals absorb shorter wavelengths or bluer light
• Larger nanocrystals absorb longer wavelengths or redder light

• The shape of the dot also changes the band gap energy level

• Tunable Absorption Pattern

– bulk semiconductors display a uniform absorption spectrum, whereas
absorption spectrum for quantum dots appears as a series of
overlapping peaks that get larger at shorter wavelengths

– the wavelength of the exciton peaks is a function of the composition

and size of the quantum dot. Smaller quantum dots result in a first
exciton peak at shorter wavelengths

• Tunable Emission Pattern

– the peak emission wavelength is bell-shaped (Gaussian)
– the Stoke's Shift
– the peak emission wavelength is independent of the wavelength of the
excitation light
– bandwidth of the emission spectra, denoted as the Full Width at Half
Maximum (FWHM) stems from :
• the temperature, natural spectral line width of the quantum dots,
and the size distribution of the population of quantum dots within a
solution or matrix material

• Molecular Coupling
– QDs can be attached to a variety of molecules via metal coordinating
functional groups. For eg: thiol, amine, nitrile, phosphine, phosphine
– by bonding appropriate molecules to the surface, the quantum dots
can be dispersed or dissolved in nearly any solvent or incorporated
into a variety of inorganic and organic films
– the surface chemistry can be used to effectively alter the properties of
the quantum dot, including brightness and electronic lifetime
• Quantum Yield
– The percentage of absorbed photons that result in an emitted photon
is called Quantum Yield (QY)
– controlled by the existence of nonradiative transition of electrons and
holes between energy levels
– greatly influenced by the surface chemistry

• Adding Shells to Quantum Dots

– Shell =several atomic layers of an inorganic wide band semiconductor
• it should be of a different semiconductor material with a wider
bandgap than the Core
– reduces nonradiative recombination and results in brighter emission
– also neutralizes the effects of many types of surface defects

• Photovoltaic cell is a device that

converts solar energy into electricity
by the photovoltaic effect

• Represents the entire electromagnetic

radiation (visible light, infrared,
ultraviolet, x-rays, and radio waves)

• Assemblies of cells are used to make

solar modules

• When a photon is absorbed, the

energy of the photon is transferred
to an electron in the crystal lattice
• This generates an electron-hole
• The flow of electrons is a DC
current (I) and electric field of the
cell is a voltage (V)
• Here power (P) is given by:
P = VI
• An inverter is used to convert DC
into AC

• Photovoltaic cells are made of two

thin sheets of silicon that are
separated from each other.
• An antireflective coating is applied to
the top of the cell to reduce reflection
• A glass cover plate then protects the
cell from weathering

• PV Construction Technologies:
– Single Crystalline
– Polycrystalline or Multicrystalline
– Amorphous or Thin-film

• Reduction in cost:
– of each kilowatt of electricity produced
– of raw materials
– of processes used to convert the raw materials into functional cells

• Inefficiencies in conventional single junction solar cells

– inability to absorb all of the solar energy
– inability to convert all of the photon energy that is absorbed to free
electrons and holes

• Traditional semiconductor materials are crystalline or rigid

Quantum dots are being used in following photovoltaic cells:

• Infrared photovoltaic cells

• Multiple exciton generation solar cells

• Quantum dot dye sensitized solar cells

• Rainbow Solar cells

• Intermediate band solar cells

• Luminescent concentrator cells


• Transform infrared light into electricity

• Nearly half of the approximately 1000 W/m3 of the intensity of
sunlight is within the invisible infrared region
• ‘Thermovoltaics’ - can even capture radiation from a fuel-fire
– co-generation of electricity and heat is quiet, reliable, clean and efficient
– A 1 cm2 silicon cell in direct sunlight generates about 0.01W, but an
efficient infrared photovoltaic cell of equal size can produce
theoretically 1W in a fuel-fired system
• Infrared PVs make use of light-sensitive conjugated polymers -
polymers with alternating single and double carbon-carbon

• Polymers are wrapped around lead sulphide quantum dots

tuned (by size) to respond to infrared
• The polymer poly(2-methoxy-5-(2’-ethylhexyloxy-p-
phenylenevinylene)] (MEH-PPV) on its own absorbs between
~400 and ~600 nm
• Quantum dots of lead sulphide (PbS) have absorption peaks
that can be tuned from ~800 to ~2000 nm
• Wrapping MEH-PPV around the quantum dots shifted the
polymer’s absorption into the infrared
• Multiple excitons per absorbed photon happens when the
energy of the photon absorbed is far greater than the
semiconductor band gap
• In bulk semiconductors the excess energy simply dissipates
away as heat
• In quantum dots, the rate of energy dissipation is significantly

• The charge carriers are confined within a minute volume,

thereby increasing their interactions and enhancing the
probability for multiple excitons to form

• Quantum yield of 300 percent for 2.9nm diameter PbSe (lead

selenide) quantum dots when the energy of the photon
absorbed is four times that of the band gap
Quantum dot dye sensitized solar cells

• Nanoparticles of titanium
dioxide are used in these cells
– Its band gap is too wide to
absorb much sunlight
• Working:
– TiO2 particles are coated with a
metal organic ruthenium-based
dye, the dye absorbs light,
becomes oxidized (loses
electrons), and injects these
electrons into the TiO2

– These diffuse to the electrode

while the holes pass to the LiI

– The electrons pass through an

external load, doing work, then
flow to the counter electrode

– Here the electrons are carried by

iodine ions to regenerate the dye
through reduction (gain of

• ‘Rainbow’ design involves arranging quantum dots according

to size, so that each one acts on a specific wavelength of the
electromagnetic spectrum, thus harvesting most of the power
light carries
• Size quantization effect - a quantum dot is able to absorb
and convert only a specific wavelength of the EM spectrum,
which is in direct relation to the size of the dot
• In conventional single p-n junction
solar cells a smaller bandgap would
result in a larger photo-generated
current, but the voltage delivered by
the solar cell is always smaller than
the bandgap
• In intermediate band solar cells the
photo-generated current increases
without reducing the bandgap and
thus the voltage
• Theoretical efficiency:
– No intermediate band: 40.7%
– 1 intermediate band: 63.2%
– 2 intermediate bands: 71.7%

• Ideal intermediate band solar cell:

1) Only radiative recombination
2) One electron-hole pair per photon
3) Absorption of all photons Eg>E
4) No high energy photons in low energy processes
5) Maximum concentration of solar radiation

• The quantum dots are simply placed in the pn-junction of the

conventional solar cell, to form a pin-junction.
Quantum dot

p n
• Spectrum of the incoming light is
converted such that it has a better
match with the absorption spectrum
of the solar cell 2
• Can reduce spectral losses, 2
especially in the case of a small
absorption band, such as for dye
sensitized solar cells and polymer QD
solar cells Solar Cell
Transparent Matrix

Schematic 3D view of a luminescent concentrator. AM Light is incident from the top. The light is absorbed by a
luminescent particle. The luminescence from the particle is randomly emitted. Part of the emission falls within
the escape cone (determined by the angel (a)) and is leaving the luminescent concentrator at the side (1). The
other part of the luminescence is guided to the Si cell by total internal reflection (2).
• The LC consists of a transparent matrix material, usually a flat
plate, with solar cells connected to one or more sides
• The transparent matrix contains luminescent particles such as,
e.g., organic dyes or quantum dots that absorb part of the
• Part of the light emitted by the luminescent particles is guided
towards the solar cells by total internal reflection
• Both direct and diffuse sunlight is collected, making solar tracking
• Ideally, the luminescence spectrum of the luminescent particles
matches the spectral response of the solar cell.This can be done by:
– combining two infrared photons to get one photon in the visible
(upconversion), or by splitting one ultraviolet photon into two visible photons
– using different dyes which cover different parts of the spectrum


• White Papers:
– Brad Gussin, John Romankiewicz
– Peter Green
– L.H. Slooff, R. Kinderman, A. R. Burgers, J.A.M. van Roosmalen
– UC-Davis Physics,CM Journal Club