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4.

6 QUANTUM DOTS
Quantum dots, discovered in 1980, are tiny particles or nanocrystals of a
semiconductingmaterial with diameters in the range of 210 nm (1050 atoms).
Quantumdots display unique electronic properties, intermediate between those of
bulk semiconductorsand discrete molecules, which are partly the result of the
unusually highsurface-to-volume ratios for these particles [30]. The most apparent
result of this isfluorescence wherein the nanocrystals can produce distinctive colors
determined bythe size of the particles.Due to their small size, the electrons in
quantum dots are confine in a small space(quantum box), and when the radii of the
semiconductor nanocrystal is smaller thanthe exciton Bohr radius (exciton Bohr
radius is the average distance between theelectron in the conduction band and the
hole it leaves behind in the valence band),there is quantization of the energy levels
according to Paulis exclusion principle.The discrete, quantized energy levels of
quantum dots relate them more closely to amolecule rather than bulk materials and
have resulted in quantum dots being nicknamedartificia atoms [31]. Progress in
semiconductor technology has enabled thefabrication of structures so small that
they can contain just one mobile electron. Byvarying controllably the number of
electrons in these artificia atoms and measuringthe energy required to add
successive electrons, one can conduct atomic physicsexperiments in a regime that
is inaccessible to experiments on real atoms. Generally,as the size of the crystal
decreases, the difference in energy between the highestvalence band and the lowest
conduction band increases. More energy is then neededto excite the dot, and
concurrently, more energy is released when the crystal returnsto its ground state,
resulting in a color shift from red to blue in the emitted light. Asa result of this
phenomenon, quantum dots can emit any color of light from the samematerial
simply by changing the size of quantum dot. Additionally, it is possible tocontrol
over the band gap of the nanocrystals by changing the composition of
semiconductors;therefore, emission color of quantum dots can also be tuned by
changingdopant during synthesis [32] as shown in Figure 4.14b.Quantum dots can
be classifie as core, coreshell, and alloyed quantum dot
.Core-type quantum dots are single component materials with uniform
internalcompositions, such as chalcogenides (selenides or sulfides of metals such
ascadmium or zinc, for example, ZnS, CdS, or CdSe. The photoluminescence

andelectroluminescence properties of core-type nanocrystals can be fine-tune


bysimply changing the crystallite size.
Coreshell quantum dots (CSQDs) are nanomaterials with small regions of
onematerial embedded in another with a wider band gap, for example, CdSe in
thecore and ZnS as shell. Coating quantum dots with shells improves the
quantumyield by passivating nonradiative recombination sites and also makes
themmore robust to processing conditions for various applications. Further
coatingof coreshell QDs with hydrophilic polymers (Figure 4.15) makes them
watersoluble and biocompatible for various medical applications [33].
Alloyed quantum dots are formed by alloying together two semiconductors
withdifferent band gap energies and exhibit interesting properties distinct not
onlyfrom the properties of their bulk counterparts but also from those of their
parentsemiconductors. Thus, alloyed nanocrystals possess novel and
additionalcomposition-tunable properties aside from the properties that emerge due
toquantum confinemen effects.Several methods for the fabrication of quantum
dots, namely, molecular beam epitaxial(MBE), electron beam lithography and
MBE, metal-organic chemical vapordeposition (MOCVD), and colloidal synthesis
are in practice. Each method has itsown advantages. Semiconductor quantum dots
can be tuned and adjusted for manyapplications, including optics, medicine, and
quantum computation. Quantum dotsare used in biolabeling, anti-counterfeiting
applications to create special inks, dyesand paints, light displays, and chemical
sensing.
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