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Quantum Dots

Introduction

• What are they?


• How are they made?

Image courtesy of Dr. D. Talapin, University of Hamburg


Introduction

What is a quantum dot?


• A semiconductor nanocrystal.
• Easily tunable by changing the size and composition of the
nanocrystal
• Exhibit energy band gap that determines required
wavelength of radiation absorption and emission spectra.
• The energy band gap increases with a decrease in size of
the quantum dot.
• Quantum dots range from 1-10 nanometers (10-50 atoms)
in diameter.
• have electronic properties intermediate between those of
bulk semiconductors and those of discrete molecules.
Properties
Properties of QDs Compared to Organic Fluorphores?
High quantum yield; often 20 times brighter
 Narrower and more symmetric emission spectra
 100-1000 times more stable to photobleaching
 High resistance to photo-/chemical degradation
Tunable wave length range 400-4000 nm

CdSe CdTe

J. Am. Chem. Soc. 2001, 123, 183-184

http://www.sussex.ac.uk/Users/kaf18/QDSpectra.jpg
Introduction

What are they?


• They are made of many of the
same materials as ordinary
semiconductors (mainly
combinations of transition metals
and/or metalloids).

• Unlike ordinary bulk


semiconductors, which are
generally macroscopic objects,
quantum dots are extremely small, CdSe Quantum dots:
on the order of a few nanometers. 5 nm dots: red
They are very nearly zero- 1.5 nm dots: violet
dimensional.
Introduction

A Brief History of QDs


 Research into semiconductor colloids began in
the early 1960s.
 Quantum dot research has been steadily
increasing since then, as evidenced by the
growing number of peer-reviewed papers.
 In the late ‘90s, companies began selling
quantum dot based products, such as
Quantum Dot Corporation.
 2004 - A research group at the Los Alamos
Laboratory found that QDs produce 3 electrons
per high energy photon (from sunlight).
 2005 - Researchers at Vanderbilt University
found that CdSe quantum dots emit white light
when excited by UV light. A blue LED coated in
a mixture of quantum dots and varnish
functioned like a traditional light bulb.
Semiconductor
Semiconductor

Semiconductor Synthesis: Semiconductor Nanoparticles


Typically occurs by the rapid reduction II-VI: CdS, CdSe, PbS, ZnS
of organmetallic precusors in hot III-V: InP, InAs
organics with surfactants MO: TiO2, ZnO, Fe2O3, PbO, Y2O3
Excitation

Figure 9.12. A valence electron jumping across the energy gap in pure
silicon resulting in the generation of a free electron and hole in the crystal:
(a) energy band model, (b) bond model.
Excitation

Exciton Bohr Diameter


Excitation
Bandgaps are the forbidden zone for electrons they are the space in-between energy
levels. Above the bandgap is the conduction band and bellow is the valence bond.
With light, electricity, or heat can give the electron enough energy to jump up a
energy level. When the electron falls back down it releases the acquired energy in the
form of light in a certain wavelength range depending on the size of the QD and
surface chemistry. The smaller the QD the farther the electron must fall back “in term
of energy” after being exited, thus producing a shorter wavelength towards the blue
end of the spectrum. “The percentage of the absorbed photons that resull in an
emitted photon is called Quantum Yields (QY)”. Dots coated with several atomic layers
of an inorganic wide band semiconductor give a significant increase in the quantum
yield because of changes to the surface chemistry .
Excitation

Fig. 4. The energy band gap associated with semi-conducting materials. In


order to produce electric current electrons must exist in the conduction band.
Excitation
Excitation in a Semiconductor
The excitation of an electron from the valance band to the
conduction band creates an electron hole pair
E

ECB h=E g

h  e (CB) h (VB)
Creation of an electron hole pair
where h is the photon energy EVB



semiconductor Band Gap


optical
detector (energy barrier)
E=h

exciton: bound electron and hole pair usually


associated with an electron trapped
in a localized state in the band gap
Release
Recombination of Electron Hole Pairs
Recombination can happen two ways: radiative and
non-radiative
E

ECB
recombination processes

E EVB

ECB
E=h band-to-band recombination
atinterband trap s tates
recombination
(e.g. dopants, impurities)

EVB radiative recombination  photon


non-radiative recombination  phonon (lattice
vibrations)
radiative non-radiative
recombination recombination e (CB) h (VB)  h
Model
Effective Mass Model
 Developed in 1985 By Louis Brus
 Relates the band gap to particle size of a spherical quantum
dot
1
* bulk   1
2 2
1  1.8e 0.124e 3  1 1 
E  Eg  
2 m m
 
 4 r  
2 m m
 

2er  e 0 m m
h 0  0
2
4 0   e 0 m h m0 

Egbulk - bulk band gap (eV), h - Plank’s constant (h=6.626x10-34 J·s)


r - particle radius e - charge on the electron (1.602x10-19 C)
me - electron effective mass  - relative permittivity
mh - hole effective mass 0 - permittivity of free space (8.854 x10-14 F cm-1)
m0 - free electron mass (9.110x10-31 kg)

Brus, L. E. J. Phys. Chem. 1986, 90, 2555


Formation

How to Make Quantum Dots


• There are three main ways to confine excitons in
semiconductors:
– Lithography
– Epitaxy
– Colloidal synthesis

20
Formation
Lithographically defined quantum dots
• Quantum wells are covered with a polymer mask and exposed
to an electron or ion beam.
• The surface is covered with a thin layer of metal, then cleaned
and only the exposed areas keep the metal layer.
• Pillars are etched into the entire surface.

• Multiple layers are applied this


way to build up the properties
and size wanted.
• Disadvantages: slow,
contamination, low density,
defect formation.

Resulting quantum dot etched in GaAs/AlGaAs superlattice.


L. Jacak, P. Hawrylak, A. Wojs. Quantum dots fig. 2.2.
Formation

Epitaxially self-assembled quantum dots


• Molecular beam epitaxy (MBE) is the deposition of
one or more pure materials onto a single crystal
wafer one layer of atoms at a time in order to form a
perfect crystal
– This is done by evaporating each of the elements to
combine, then condensing them on top of the wafer.
– The word “beam” means that the evaporated atoms only
meet each other on the wafer
Formation

Colloidal quantum dots


• Immersion of semiconductor microcrystals in glass dielectric
matrices.
• Heating for several hours at high temperature.
 Formation of microcrystals of nearly equal size.

• Typically group II-VI materials (e.g. CdS, CdSe)


• Size variations (“size dispersion”).
Applications
Applications of Quantum Dots
• Photovoltaic devices: solar cells
• Biology : biosensors, imaging
• Light emitting diodes: LEDs
• Quantum computation
• Flat-panel displays
• Memory elements
• Photodetectors
• Lasers
Applications

Solar Cells
• Photovoltaic effect:
– p-n junction.
– Sunlight excites electrons and
creates electron-hole pairs.
– Electrons concentrate on one
side of the cell and holes on
the other side.
– Connecting the 2 sides
creates electricity.
Applications

Different Generations of Solar Cells


• First generation:
– Single crystal silicon wafer.
– Advantages: high carrier mobility.
– Disadvantages: most of photon energy
is wasted as heat, expensive.
• Second generation:
– Thin-film technology.
– Advantages: less expensive.
– Disadvantages: efficiency lower
compared with silicon solar cells.
• Third generation:
– Nanocrystal solar cells.
– Enhance electrical performances of the
second generation while maintaining
low production costs.
Applications
How Can Quantum Dots Improve the
Efficiency?
• The quantum dot band gap is tunable and can be used to
create intermediate bandgaps. The maximum theoretical
efficiency of the solar cell is as high as 63.2% with this
method.
Applications
Quantum Dot Imaging
 QDs with antibodies to human prostate-specific membrane
antigen indicate murine tumors developed from human
prostate cells
 15 nm CdSe/ZnS TOPO/Polymer/PEG/target

Gao et al., “In vivo cancer targeting and imaging with semiconductor quantum dots,” Nat. Biotechnol. 22, 969 (2004).
Applications
Composite with A Novel Structure for Active Sensing in Living cells

① Cobalt core : active manipulation


diameter : ~10 nm
superparamagnetic NPs
Co
→ manipulated or positioned by an external
CdSe field without aggregation in the absence of
ZnS
an external field
Silica ② CdSe shell : imaging with fluorescence
thickness : 3-5 nm
visible fluorescence (~450 – 700 nm)
ability to tune the band gap
④ Silica shell : bio-compatibility &
→ by controlling the thickness, able to tune the
functionalization with specific targeting group emission wavelength, i.e., emission color
thickness : ~10 nmbio-compatible, & non- ③ ZnS shell : electrical passivation
toxic to live cell functions thickness : 1-2 nm
stable in aqueous environment
having wider band gap (3.83 eV) than CdSe
ability to functionalize its surface with (1.91 eV)
specific
enhancement of QY → CdSe (5-10%) 
targeting group CdSe/ZnS (~50%)

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