Apresentacao QD

Quantum Dots
Quantum Dots
Helena Marques - 67915, Joana Duarte - 67918
Nanotecnologias e Nanoelectrnica
Instituto Superior Tcnico
th , 2012
December 18
Quantum Dots
Introduction
Index
1
2
4
5
6
7
Introduction
What are Quantum Dots?
Structure of a Quantum Dot
Band-gap and quantum connement eects
Optical Properties of Quantum Dots
Size and photoluminescence
Shape of Emission and Absorbance Spectra
Quantum Yield
Fabrication of Quantum Dots
Colloidal Synthesis
Applications
Quantum Dots in Biology and Medicine
Quantum Dots in Photovoltaic devices
Quantum Dots in LEDs
Conclusion
References
Quantum Dots
Introduction
A Quantum Dot is a semiconductor nanocrystal whose excitons

(electron-hole pairs) are conned in all three spatial dimensions. As
a result, they have properties that are between those of bulk
semiconductors and those of discrete molecules.
Because of their really small sizes they are considered dimensionless.
Quantum Dots' characteristics are closely related to the size and
shape of the individual crystal.
The ability to tune the size of a QD allows to have very precise
control over the conductive properties of the material, making it
suitable for many applications such as transistors, solar cells, LEDs,
diode lasers and medical imaging.
Quantum Dots
Index
1
2
4
5
6
7
Introduction
Quantum Yield
Colloidal Synthesis
Applications
Conclusion
References
Quantum Dots
Index
1
2
4
5
6
7
Introduction
Quantum Yield
Colloidal Synthesis
Applications
Conclusion
References
Quantum Dots
Quantum dots are nanoparticles which range from 2 to 10

nanometers in diameter (about the width of 50 atoms).
Figura : The structure of the quantum dot can be separated in three

parts: core, shell and coating region.
Quantum Dots
The
core is a central nanocrystal that determines the optical
properties of the nal QD. It is the heart of the structure.
The crystalline inorganic
shell that surround the core increases
quantum yield and provides protection to the core atoms from

oxidation and other chemical reactions.
The most common
core/shell combinations are:
CdSe/ZnS, CdSe/CdS, and InAs/CdSe.
CdS/ZnS,
Quantum Dots
Figura : Sketch map of the QD.

The coating region is composed by functional ligands. This
functional group should be chosen depending on the functions we
need them for, such as polarization properties and connection with
molecules.
Quantum Dots
Index
1
2
4
5
6
7
Introduction
Quantum Yield
Colloidal Synthesis
Applications
Conclusion
References
Quantum Dots
The band-gap of a material is the energy required to create an

electron and a hole at rest (i.e., with zero kinetic energy) at a
distance far enough apart that their Coulombic attraction is
neglectable.
If one carrier approaches the other, they may form a bound
electron-hole pair, i.e., an exciton, whose energy is a few meV lower
than the band-gap.
Quantum Dots
Figura : Simplied representation of an exciton and the corresponding

energy levels.
Quantum Dots
The exciton behaves like a hydrogen atom, except that a hole, not
a proton, forms the nucleus. Obviously, the mass of a hole is much
smaller than that of a proton, which aects the solutions to the
Schrdinger wave equation.
The distance between the electron and hole is called the exciton
Bohr radius rb . The exciton Bohr radius for a bulk semiconductor
can be expressed by Equation 1:
rb =
~2
e2
me
mh
(1)
If the radius r of a QD approaches rb , r ' rb , or r < rb , the motion

of the electrons and holes is spatially conned to the dimensions of
the QD which causes an increase of the band-gap energy.
Quantum Dots
Figura : Relation between the exciton Bohr radius and the size of the QD
and its inuence to the band-gap.
Quantum Dots
The connement eect becomes important when r < rb .
Figura : Size-dependence on the energy levels of quantum dots due

to the quantum connement eect.
When a particle is conned to a volume in the space, two things
happen: it acquires kinetic energy (connement energy) and its
energy spectrum becomes discrete.
Since the allowed energy levels are discrete, we can represent the
density of states as delta functions.
Quantum Dots
Figura : Comparison of the quantization of density of states between

materials with dierent dimensions.
Quantum Dots
The energy levels of a QD can be adjusted with a proper

design according to the needs of the application.
The addition or subtraction of just a few atoms to the QD has

the eect of altering the boundaries of the bandgap.
Changing the geometry of the surface of the QD also changes

the bandgap energy, owing again to the small size of the dot,
and the eects of quantum connement.
Quantum Dots
Index
1
2
4
5
6
7
Introduction
Quantum Yield
Colloidal Synthesis
Applications
Conclusion
References
Quantum Dots
Index
1
2
4
5
6
7
Introduction
Quantum Yield
Colloidal Synthesis
Applications
Conclusion
References
Quantum Dots
An immediate feature of QDs is their coloration.
Quantum dots behave like very large atoms, emitting energy

as light when electrons return to its lower and stable state.
The energy source used to stimulate a quantum dot is
commonly
ultraviolet light.
The frequency or colour of light given o is not related to the

material used in the quantum dot, but by the size of the
quantum dot.
Large quantum dots produce light with a long wavelength and

small quantum dots produce light with small wavelengths.
Quantum Dots
Figura : Scheme of the band-gap and emitted waveleght of a QD

according to its size.
Quantum Dots
Figura : (1) Emission colors from small (blue) to large (red) CdSe
quantum dots excited by a near-ultraviolet lamp.(2) Photoluminescence
spectra of some CdSe QDs.
Quantum Dots
Index
1
2
4
5
6
7
Introduction
Quantum Yield
Colloidal Synthesis
Applications
Conclusion
References
Quantum Dots
According to the semiconductor knowledge for the band

energy, the probability of the absorption will increase as the
excitation energy increases -
spectrum.
broadband absorption
The emission energy consists of the energy gap between the

conductor and the valence band -
narrow emission spectrum.
Quantum Dots
Figura : The absorption and emission spectrum of QDs 605. We may

nd the broadband absorption spectrum as well as the narrow emission
spectrum.
Quantum Dots
The emission spectrum of a solution of quantum dots is the

sum of the spectra of many individual quantum dots that dier
slightly in size.
A sample that has a very uniform quantum dot size

distribution will have a
narrower emission spectrum than a
sample that is less uniform.
Quantum Dots
Quantum Yield
Index
1
2
4
5
6
7
Introduction
Quantum Yield
Colloidal Synthesis
Applications
Conclusion
References
Quantum Dots
Quantum Yield
Quantum yield is a measure of the brightness of a QD and is

dened as the ratio of light emitted to light absorbed by a
uorescent material.
Quantum dots retain their high quantum yield even after

conjugation to biological anity molecules.
Quantum Dots
Index
1
2
4
5
6
7
Introduction
Quantum Yield
Colloidal Synthesis
Applications
Conclusion
References
Quantum Dots
There are several ways to conne excitons in semiconductors,

resulting in dierent methods to produce Quantum Dots.
In general, QD are grown by advanced epitaxial techniques in

nanocrystals produced by chemical methods (colloidal
synthesis) or by ion implantation, or in nanodevices made by
lithographic techniques.
Quantum Dots
Colloidal Synthesis
Index
1
2
4
5
6
7
Introduction
Quantum Yield
Colloidal Synthesis
Applications
Conclusion
References
Quantum Dots
Colloidal Synthesis
The synthesis of colloidal quantum dots is based on a

three-component system composed of: precursors, organic
surfactants, and solvents.
The choice of precursors, surfactants and solvents depends on the
material and morphology desired.
Figura : A typical reaction setup and concept for colloidal synthesis

of nanoparticles.
Quantum Dots
Colloidal Synthesis
The simplest and often most used model for particle

nucleation and growth is the LaMer model in which particle
formation is separated into three stages: super-saturation,
nucleation and growth.
Figura : LaMer plot: Variation of the supersaturation as a function

of time .
Quantum Dots
Colloidal Synthesis
For a diusion controlled growth process, where the

precipitation onto a growing particle is limited by the diusion
of monomers to the particle's surface, two growth regimes
exist:
Focusing;
Defocusing.
Quantum Dots
Colloidal Synthesis
The growth rate of particles of size r can be expressed as
r
1
=k
t
r
r r

(2)
Figura : Growth model of Sugimoto: Change of the growth rate by the

particle size
Quantum Dots
Colloidal Synthesis
When the average particle size is less than twice the critical
particle size, defocusing occurs via an Ostwald's Ripening
process in which smaller particles dissolve while larger particles
grow more rapidly causing a broadening in the particle size
distribution.
Typical dots are made of binary alloys such as cadmium

selenide, cadmium sulde, indium arsenide, and indium
phosphide.
Quantum Dots
Colloidal Synthesis
Figura : Chemically synthesized colloidal suspensions of quantum dots in

inert solvents.
Quantum Dots
Applications
Index
1
2
4
5
6
7
Introduction
Quantum Yield
Colloidal Synthesis
Applications
Conclusion
References
Quantum Dots
Applications
Biology and Medicine : biosensors, organic dyes

Photovoltaic devices: solar cells
Light emitting diodes: LEDs
Quantum computation
Flat-panel displays
Memory elements
Photodetectors
Lasers
Quantum Dots
Applications
Index
1
2
4
5
6
7
Introduction
Quantum Yield
Colloidal Synthesis
Applications
Conclusion
References
Quantum Dots
Applications
Favourable absorbance characteristics

The absorbance band of a
uorescent dye is usually

(Fig.A), making ecient
spectrally close to the light emitted
collection of the emitted light more dicult owing to scatter,

autouorescence, and the need for precise optical lters.
Quantum dots absorb light at all wavelengths shorter than

the emission (Fig.B). This allows multiple colors of quantum
dots to be eectively excited by a single source of light (e.g.,
lamp, laser, LED) far from the emission of any color.
Quantum Dots
Applications
Figura : Comparison of absorbance and emission spectra (normalized) of

R 568 streptavidin conjugate and (B) Qdot
R 605 streptavidin
(A) Alexa
conjugate.(C) Comparison of emission spectra (nonnormalized). The
spectra were taken under conditions in which each uorophore absorbed
the same amount of excitation light.(D) Comparison of absorbance
spectra (nonnormalized).
Quantum Dots
Applications
Favourable emission spectrum

Most uorescent dyes display asymmetric emission spectra
that tail (sometimes dramatically) to the red
(Fig.C).
In contrast, QDs have narrow, symmetric emission spectra

that make possible detection of multiple colors of quantum
dots together (multiplexing) with low cross-talk between
detection channels.
Quantum Dots
Applications
Figura : Comparison of absorbance and emission spectra (normalized) of

R 568 streptavidin conjugate and (B) Qdot
R 605 streptavidin
(A) Alexa
conjugate.(C) Comparison of emission spectra (nonnormalized). The
spectra were taken under conditions in which each uorophore absorbed
the same amount of excitation light.(D) Comparison of absorbance
spectra (nonnormalized).
Quantum Dots
Applications
Quantum Yield
Some organic dyes have quantum yields approaching 100%,
but conjugates (from biological anity molecules) made from
these dyes generally have a signicantly lower quantum yield.
Quantum dots retain their high quantum yield even after

conjugation to biological anity molecules (Fig.C).
Quantum Dots
Applications
Photostability
Fluorescent dyes tend to be organic molecules that are steadily
bleached(degraded) by the light used to excite them,
progressively emitting less light over time.
Even under conditions of intense illumination, no degradation

is observed in QDs. This property makes quantum dots
enabling in applications requiring continuous observation of
the probe (cell tracking, some imaging applications, and so
on), and potentially more valuable as quantitative reagents.
Quantum Dots
Applications
R 605 and Alexa

Figura : Comparison of photostability between Qdot
R 488 streptavidin conjugates. Actin laments in two 3T3 mouse
Fluor
broblast cells were labeled with Qdot 605 streptavidin conjugate (red),
and the nuclei were stained with Alexa Fluor 488 streptavidin (green).
The specimens were continuously illuminated for 3 min with light from a
100-W mercury lamp.
Quantum Dots
Applications
Example 1: DNA nanosensors
Some studies have shown that QD-conjugated oligonucleotide

sequences (attached via surface carboxylic acid groups) may be
targeted to bind with DNA or mRNA.
Quantum Dots
Applications
Example 1: DNA nanosensors
Figura : Schematic of single-QD-based DNA nanosensors. (a)

Conceptual scheme showing the formation of a nanosensor assembly in
the presence of targets. (b) Fluorescence emission.
Quantum Dots
Applications
Example 2: Pathogen and toxin detection
QDs can be applied in the detection of pathogens and toxins.
Figura : Dual-color image of QD 605 - labeled Cryptosporidium parvum

(red) and QD 565 - labeled Giardia lamblia (green).
Quantum Dots
Applications
Index
1
2
4
5
6
7
Introduction
Quantum Yield
Colloidal Synthesis
Applications
Conclusion
References
Quantum Dots
Applications
Quantum dots may be able to increase the eciency and

reduce the cost of today's typical silicon photovoltaic cells.
The ability to tune the band-gap is what makes them desirable

for solar cell use. In particular, lead sulde (PbS) CQDs have
band-gaps that can be tuned into the far infrared, energy levels
that are normally unseen to traditional materials.
Quantum Dots
Applications
According to an experimental proof from 2006 (controversial

results), quantum dots of lead selenide can produce as many
as seven excitons from one high energy photon of sunlight (7.8
times the band-gap energy).
This compares favourably to today's photovoltaic cells which

can only manage one exciton per high-energy photon, with
high kinetic energy carriers losing their energy as heat.
Quantum Dots
Applications
Index
1
2
4
5
6
7
Introduction
Quantum Yield
Colloidal Synthesis
Applications
Conclusion
References
Quantum Dots
Applications
Quantum-dot-based LEDs are characterized by pure and

saturated emission colors with narrow bandwidth, and their
emission wavelength is easily tuned by changing the size of the
quantum dots.
The structure of QLED is similar to basic design of OLED.

The major dierence is that the light emitting centers are
cadmium selenide (CdSe) nanocrystals.
Quantum Dots
Applications
Some advantages of QLEDs are color range, low power

consumption, brightness, improved lifetime. The main
drawback is the diculty to manufacture blue quantum dots.
Commercialization of quantum dot display is yet to come, the
manufacturing cost of QLED is relatively high and
development of novel and more cost-ecient fabrication
process is desired in future.
Many expect that quantum dot display technology can replace
liquid crystal displays (LCDs) or originate light bulbs that can
provide greater energy eciency and longer lifetime.
Quantum Dots
Conclusion
Index
1
2
4
5
6
7
Introduction
Quantum Yield
Colloidal Synthesis
Applications
Conclusion
References
Quantum Dots
Conclusion
Among the various branches in nanotechnology, these zero

dimension nanostructures have paved the way for numerous
advances in both fundamental and applied sciences.
The ability of the QD to vary its band gap energy with size,
and the quantized energy states that result, are what give such
nanoscale device structures their potential.
Materials issues, fabrication control, and device design are all
issues in need of further investigation and understanding.
The quantum dot has already proved a unique and useful
structure for both the understanding of physics at the
nanoscale and for improving device design and performance.
As research continues, the ability to control the properties of
the quantum dot will allow advances in science and industry.
Quantum Dots
References
Index
1
2
4
5
6
7
Introduction
Quantum Yield
Colloidal Synthesis
Applications
Conclusion
References
Quantum Dots
References
[1 ] Khare, Ankur, Wills, Andrew W., Ammerman, Lauren M., Noris,

David J., and Aydil*, Eray S. (2011). "Size control and quantum
connement in Cu2ZnSnS4 nanocrystals". Chem. Commun.: 47.
[2 ] Ghosh, N. (2008), Methods in Molecular Biology, Vol. 374:
Quantum Dots: Applications in Biology. Edited by Marcel P.
Bruchez and Charles Z. Hotz. ChemBioChem, 9: 157.
[3 ] C.Y. Zhang, H.C. Yeh, M.T. Kuroki, T.H. Wang
Single-quantum-dot-based DNA nanosensor Nat Mater, 4 (2005),
pp. 826?831
[4 ] L. Zhu, S. Ang, W.T. Liu Quantum dots as a novel
immunouorescent detection system for Cryptosporidium parvum
and Giardia lamblia Appl Environ Microbiol, 70 (2004), pp. 597?598
[5 ] A. J. Nozik, Physica E (Amsterdam) 14, 115 (2002)
Quantum Dots
References
[6 ] Yiru Peng , Chunmei Qiu , Steen Jockusch , Amy M. Scott ,

Zengmin Li , Nicholas J. Turro and Jingyue Ju Photochem.
Photobiol. Sci., 2012,11, 881-884
[7 ] Tracie J. Bukowski, Joseph H. Simmons (2002): Quantum Dot
Research: Current State and Future Prospects, Critical Reviews in
Solid State and Materials Sciences, 27:3-4, 119-142
[8 ] Debasis Bera *, Lei Qian, Teng-Kuan Tseng and Paul H. Holloway
*Materials 2010, 3, 2260-2345
[9 ] Kwangjin An, Selim Alayoglu, Trevor Ewers, Gabor A. Somorjai,
Colloid chemistry of nanocatalysts: A molecular view, Journal of
Colloid and Interface Science, Volume 373, Issue 1, 1 May 2012,
Pages 1-13
[10 ] Richard D. Schaller, Milan Sykora, Jerey M. Pietryga, and Victor
I. Klimov Nano Lett., 2006,

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Quantum Dots

A Quantum Dot is a semiconductor nanocrystal whose excitons

Quantum dots are nanoparticles which range from 2 to 10

Figura : The structure of the quantum dot can be separated in three

core is a central nanocrystal that determines the optical

properties of the nal QD. It is the heart of the structure.

The crystalline inorganic

shell that surround the core increases

quantum yield and provides protection to the core atoms from

The most common

core/shell combinations are:

CdSe/ZnS, CdSe/CdS, and InAs/CdSe.

Figura : Sketch map of the QD.

The band-gap of a material is the energy required to create an

Figura : Simplied representation of an exciton and the corresponding

If the radius r of a QD approaches rb , r ' rb , or r < rb , the motion

The connement eect becomes important when r < rb .

Figura : Size-dependence on the energy levels of quantum dots due

Figura : Comparison of the quantization of density of states between

The energy levels of a QD can be adjusted with a proper

The addition or subtraction of just a few atoms to the QD has

Changing the geometry of the surface of the QD also changes

An immediate feature of QDs is their coloration.

Quantum dots behave like very large atoms, emitting energy

The frequency or colour of light given o is not related to the

Large quantum dots produce light with a long wavelength and

Figura : Scheme of the band-gap and emitted waveleght of a QD

According to the semiconductor knowledge for the band

The emission energy consists of the energy gap between the

narrow emission spectrum.

Figura : The absorption and emission spectrum of QDs 605. We may

The emission spectrum of a solution of quantum dots is the

A sample that has a very uniform quantum dot size

narrower emission spectrum than a

sample that is less uniform.

Quantum yield is a measure of the brightness of a QD and is

Quantum dots retain their high quantum yield even after

There are several ways to conne excitons in semiconductors,

In general, QD are grown by advanced epitaxial techniques in

The synthesis of colloidal quantum dots is based on a

Figura : A typical reaction setup and concept for colloidal synthesis

The simplest and often most used model for particle

Figura : LaMer plot: Variation of the supersaturation as a function

For a diusion controlled growth process, where the

Figura : Growth model of Sugimoto: Change of the growth rate by the

Typical dots are made of binary alloys such as cadmium

Figura : Chemically synthesized colloidal suspensions of quantum dots in

Biology and Medicine : biosensors, organic dyes

Favourable absorbance characteristics

uorescent dye is usually

spectrally close to the light emitted

collection of the emitted light more dicult owing to scatter,

Quantum dots absorb light at all wavelengths shorter than

Figura : Comparison of absorbance and emission spectra (normalized) of

Favourable emission spectrum

In contrast, QDs have narrow, symmetric emission spectra

Figura : Comparison of absorbance and emission spectra (normalized) of

Quantum dots retain their high quantum yield even after

Even under conditions of intense illumination, no degradation

R 605 and Alexa

Example 1: DNA nanosensors

Some studies have shown that QD-conjugated oligonucleotide

Example 1: DNA nanosensors

properties of the nal QD. It is the heart of the structure.

Figura : Simplied representation of an exciton and the corresponding

The connement eect becomes important when r < rb .

The frequency or colour of light given o is not related to the

Quantum yield is a measure of the brightness of a QD and is

There are several ways to conne excitons in semiconductors,

For a diusion controlled growth process, where the

uorescent dye is usually

collection of the emitted light more dicult owing to scatter,

Quantum dots may be able to increase the eciency and

[6 ] Yiru Peng , Chunmei Qiu , Steen Jockusch , Amy M. Scott ,