Quantum Wells, Wires, and

Dots

Quantified semiconductors
Quantum confined semiconductors
include:
quantum wells, which confine electrons or
holes in one dimension and allow free
propagation in two dimensions.
quantum wires, which confine electrons or
holes in two spatial dimensions and allow free
propagation in the third.
quantum dots, which confine electrons in all
three spatial dimensions

Semiconductors

Figure 9.2. Evolution of integrated circuit technology.

Figure 9.3. Moore's law (data points are for INTELs microprocessors; the
projections are based on the 2002 Technology Roadmap ITRS02) 2.

Figure 9.4. Trend of the minimum feature size (2002 Technology

Roadmap ITRS02)2.

Figure 9.5. Average selling price per bit of DRAM memory since 1980 5.

Figure 9.7. Clock speed of microprocessors since 1980 5.

Figure 9.8. Part of the periodic table showing the III, IV, and V columns.
The elemental semiconductors Si and Ge belong to column IV.

Figure 9.9. Schematic representation of the orbital model of a single

silicon atom, with its 14 electrons of which the 4 valence electrons reside
in the outermost shell. The energy levels are shown to the right (not to
scale).

Figure 9.10. (a) Tetrahedral bonding of silicon in the diamond structure

showing the four nearest neighbors connected through covalent bonds; (b)
2-D bond model illustrating the sharing of the valence electrons between
nearest-neighbor silicon atoms. Each line between the silicon core
represents one valence electron.

Figure 9.11. (a) Energy levels in an isolated silicon atom and (b) in a
silicon crystal of N atoms, illustrating the formation of energy bands. The
valence band contains 4N states and can accommodate all 4N valence
electrons.

Figure 7.1. Schematic plot of the single particle energy spectrum in a bulk
semiconductor for both the electron and hole states on the left side of the
panel with appropriate electron (e) and hole (h) discrete quantum states
shown on the right. The upper parabolic band is the conduction band, the
lower the valence.

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.

Figure 9.1. Use of silicon oxide as a masking layer during diffusion of

dopants.

Figure 9.13. Extrinsic n-type silicon doped with P donor atoms. (a)
Energy band diagram and (b) Bond model.

Figure 9.14. Extrinsic p-type silicon doped with B acceptor atoms. (a)
Energy band diagram and (b) Bond model.

Figure 9.15. (a) Schematic cross-sectional view of a MOS capacitor; (b)

Energy band diagram (not to scale) of the MOS capacitor under flat band
conditions along the cross section AA'.

Figure 9.18. Current flow in a NMOS transistor, illustrating the three

operating regions (linear, triode and saturation).

Figure 9.23. Schematic illustration of the effect of Ge atoms, implanted in

a Si crystal, on the strain of Silicon. (From Ref. 25 by permission of the
Institute of Electrical and Electronics Engineers. 2003IEEE)

Figure 9.24. Scaling of the physical gate dielectric thickness and effective
oxide thickness (EOT), based on data from the ITRS2002. (From Ref. 4
by permission of the Institute of Electrical and Electronics Engineers.
2003IEEE)

Figure 9.25. Schematic cross sections: (a) conventional bulk MOSFET

and (b) dual gate FET.

Figure 9.28. Representation of emerging technologies in a 3-D space of

speed, size and cost2,37. (From Ref. 37 by permission of the Institute of
Electrical and Electronics Engineers. 2003IEEE )

Figure 9.29. Schematic cross-section of a carbon nanotube field effect

transistor (CNFET). (Adapted from Ph.Avouris,Acc.Chem.Res.35,
1026(2002) with kind permission of Ph. Avouris.)

Quantum confinement in semiconductors

In an unconfined (bulk) semiconductor, an electron-hole pair is typically
bound within a characteristic length called the Bohr exciton radius. If the
electron and hole are constrained further, then the semiconductor's
properties change. This effect is a form of quantum confinement, and it is a
key feature in many emerging electronic structures.
Quantum confined semiconductors include:

quantum wells, which confine electrons or holes in one dimension

and allow free propagation in two dimensions.

quantum wires, which confine electrons or holes in two spatial

dimensions and allow free propagation in the third.

quantum dots, which confine electrons in all three spatial

dimensions

The particle in a box (or the infinite potential well or infinite square well) is a
simple idealized system that can be completely solved within quantum
mechanics. The infinite potential well is a finite sized region in space (the box)
with an infinite potential at its boundaries (the walls). A particle experiences no
forces while inside the box, but as the walls are 'infinitely high', it is constrained
to remain in the box. This is similar to the situation of a gas confined in a nonporous container.
Figure considers the 1-dimensional case, where the motion of the particle is
considered only in a single dimension - the direction of the quantum
confinement.

Quantum wells
A quantum well is a potential well that confines particles, which were
originally free to move in three dimensions, to two dimensions, forcing
them to occupy a planar region. The effects of quantum confinement take
place when the quantum well thickness becomes comparable at the de
Broglie wavelength of the carriers (generally electrons and holes), leading
to energy levels called "energy subbands", i.e., the carriers can only have
discrete energy values.

Ec

Egap for
AlxGa1xAs

Ev

Egap for
GaAs

thickness of
GaAs layer

Figure 8.2. Schematic energy band diagram of GaAs/GaAlxAs1-x quantum

well. An electron (represented by its wavefunction ) can be considered
as partially confined in the quantum well of width equal to the GaAs
thickness. The barrier height E is equal to the difference in the energies
of the bottom of the conduction band Ec for the two layer materials. Ev is
the energy of the top of the valence band and Egap is the band gap energy.

hard precipitate particles

dislocation

Figure 8.3. Precipitate particles of spacing acting as obstacles to

dislocation motion.

Quantum wells
Quantum wells are formed in semiconductors by having a material, like
gallium arsenide sandwiched between two layers of a material with a
wider bandgap, like aluminium arsenide. These structures can be
grown by molecular beam epitaxy or chemical vapor deposition with
control of the layer thickness down to monolayers.
Because of their quasi-two dimensional nature, electrons in quantum
wells have a sharper density of states than bulk materials. As a result
quantum wells are in wide use in diode lasers, specifically blue lasers.
They are also used to make HEMTs (High Electron Mobility
Transistors), which are used in low-noise electronics. Quantum well
infrared photodetectors are also based on quantum wells, and are used
for infrared imaging.
By doping either the well itself, or preferably, the barrier of a quantum
well with donor impurities, a two-dimensional electron gas (2DEG) may
be formed.

(a)

(b)

(c)

Figure 8.1. Schematic representations of nanocomposite materials with

characteristic length scale: (a) nanolayered composites with
nanoscalebilayer repeat length ; (b) nanofilamentary (nanowire)
composites composed of a matrix with embedded filaments of nanoscale
diameter d; (c) nanoparticulate composites composed of a matrix with
embedded particles of nanoscale diameter d.

Figure 8.7. Transmission electron micrographs of binary nanoparticle

assemblies. (a) Fe3O4(4nm)-Fe58Pt42 (4nm) assembly; (b) Fe3O4 (8nm)Fe58Pt42 (4nm) assembly; Fe3O4 (12 nm)- Fe58Pt42 (4 nm) assembly. (From
Ref. 46 bypermissionofMacmillanMagazinesLtd.)

Quantum wires
In condensed matter physics, a quantum wire is an electrically conducting wire,
in which quantum effects are affecting transport properties. Due to the
confinement of conduction electrons in the transverse direction of the wire,
their transverse energy is quantized into a series of discrete values E0
("ground state" energy, with lower value), E1,...
One consequence of this quantization is that the classical formula for
calculating the electrical resistivity of a wire is not valid for quantum wires
(where is the resistivity, l is the length, and A is the cross-sectional area of
the wire).
Instead, an exact calculation of the transverse energies of the confined
electrons has to be performed to calculate a wire's resistance. Following from
the quantization of electron energy, the resistance is also found to be
quantized.

Figure 8.5. Scanning electron micrograph of electrodeposited FeCo

nanowires (the polycarbonate matrix in which the wires were embedded
has been completely dissolved).

Quantum wires
The importance of the quantization is inversely proportional to the diameter of
the nanowire for a given material.
From material to material, it is dependent on the electronic properties,
especially on the effective mass of the electrons. In simple words, it means that
it will depend on how conduction electrons interact with the atoms within a given
material.
Semiconductors show clear conductance quantization for large wire transverse
dimensions (100 nm) because the electronic modes due to confinement are
spatially extended and thus they have low energy separations. This means that
they can only be resolved at cryogenic temperature (few kelvins) where the
thermal excitation energy is lower than the inter-mode energy separation.
For metals, quantization corresponding to the lowest energy states is only
observed for atomic wires. Their corresponding wavelength being thus
extremely small they have a very large energy separation which makes
resistance quantization perfectly observable at room temperature.

Carbon nanotubes as quantum wires

It is possible to make quantum wires out of metallic carbon nanotubes,
at least in limited quantities. The advantages of making wires from
carbon nanotubes include their high electrical conductivity (due to a high
mobility), light weight, small diameter, low chemical reactivity, and high
tensile strength.
It has been claimed that it is possible to create macroscopic quantum
wires. With a rope of carbon nanotubes, it is not necessary for any
single fiber to travel the entire length, since quantum tunneling will allow
electrons to jump from strand to strand. This makes quantum wires
interesting for commercial uses.

Quantum dots
A quantum dot is a semiconductor whose excitons are confined in all three
spatial dimensions. As a result, they have properties that are between
those of bulk semiconductors and those of discrete molecules.
Different sized quantum dots emit different color light due to quantum
confinement.
QD were discovered by Louis E. Brus, who was then at Bell Labs and is now a chemistry
professor at Columbia University. The term "Quantum Dot" was coined by Mark Reed, who was
then at Texas Instruments and is now a professor of applied physics at Yale University.

Colloidal synthesis of quantum dots

Colloidal semiconductor nanocrystals are synthesized from precursor compounds dissolved
in solutions, much like traditional chemical processes. The synthesis of colloidal quantum
dots is based on a three component system composed of: precursors, organic surfactants,
and solvents. When heating a reaction medium to a sufficiently high temperature, the
precursors chemically transform into monomers. Once the monomers reach a high enough
supersaturation level, the nanocrystal growth starts with a nucleation process. The
temperature during the growth process is one of the critical factors in determining optimal
conditions for the nanocrystal growth. It must be high enough to allow for rearrangement
and annealing of atoms during the synthesis process while being low enough to promote
crystal growth. Another critical factor that has to be stringently controlled during nanocrystal
growth is the monomer concentration. The growth process of nanocrystals can occur in two
different regimes, focusing and defocusing. At high monomer concentrations, the critical
size (the size where nanocrystals neither grow nor shrink) is relatively small, resulting in
growth of nearly all particles. In this regime, smaller particles grow faster than large ones
(since larger crystals need more atoms to grow than small crystals) resulting in focusing of
the size distribution to yield nearly monodisperse particles. The size focusing is optimal
when the monomer concentration is kept such that the average nanocrystal size present is
always slightly larger than the critical size. When the monomer concentration is depleted
during growth, the critical size becomes larger than the average size present, and the
distribution defocuses as a result of Ostwald ripening.

Figure 7.3. La Mer model for the growth stages of nanocrystals.

Figure 7.4. Synthetic apparatus for the preparation of nanocrystals.

Figure 7.6. Atomic Force Microscope images of Ge clusters on two types

of surfaces. Graphite in the left two panels, and SiO 2 in the right. The line
plots on the figure give vertical profiles of line cuts through the AFM
images directly above and give the quantitative size information.

Figure 7.7. Illustration of high-energy ion implantation process to

fabricate quantum dots.

Figure 7.8. Illustration of a cross sectional view of Si quantum dots

formed in a glass matrix via ion implantation. Note that the random
arrangement and spherical shape of the quantum dot particles is
expected for quantum dots implanted in an amorphous media.

Figure 7.9. Photoluminescence spectra from Si (400 keV, 1.53 x 1017

cm-2) implanted SiO2 as implanted and after annealing at 950 and
1100 C. (From Ref. 4 by permission of the American Institute of
Physics.)

Quantum dots
There are colloidal methods to produce many different semiconductors,
including cadmium selenide, cadmium sulfide, indium arsenide, and indium
phosphide. These quantum dots can contain as few as 100 to 100,000
atoms within the quantum dot volume, with a diameter of 10 to 50 atoms.
Other methods for synthesis are also used. Individual quantum dots can be
created from two-dimensional electron or hole gases present in remotely
doped quantum wells or semiconductor heterostructures called lateral
quantum dots. The sample surface is coated with a thin layer of resist. A
lateral pattern is then defined in the resist by electron beam lithography. This
pattern can then be transferred to the electron or hole gas by etching, or by
depositing metal electrodes (lift-off process) that allow the application of
external voltages between the electron gas and the electrodes.
The energy spectrum of a quantum dot can be engineered by controlling the
geometrical size, shape, and the strength of the confinement potential. Also
in contrast to atoms it is relatively easy to connect quantum dots by tunnel
barriers to conducting leads, which allows the application of the techniques
of tunneling spectroscopy for their investigation.
Confinement in quantum dots can also arise from electrostatic potentials
(generated by external electrodes, doping, strain, or impurities).

Figure 7.10. Scanning electron micrograph of quantum dot patterns on a

GaSb surface induced by Ar-ion sputtering with an ion energy of 500 eV.
The dots show a hexagonal ordering with a characteristic wavelength that
depends on ion energy. The insets show the corresponding distribution of
the nearest-neighbor distance. (From Ref. 5 by permission of the
American Physical Society.)

Quantum dots
An immediate optical feature of colloidal quantum dots is their coloration.
While the material which makes up a quantum dot defines its intrinsic energy
signature, the quantum confined size of the nanocrystal is more significant at
energies near the band gap. Thus quantum dots of the same material, but with
different sizes, can emit light of different colors. The physical reason is
quantum confinement effect.
The larger the dot, the redder (lower energy) its fluorescence spectrum.
Conversely, smaller dots emit bluer (higher energy) light. The coloration is
directly related to the energy levels of the quantum dot.

Electromagnetic
radiation is
characterized by its
wavelength (or
frequency) and its
intensity. When the
wavelength is within
the visible spectrum
(the range of
wavelengths humans
can perceive,
approximately from
380 nm to 740 nm), it
is known as "visible
light".

Quantum dots
Quantitatively speaking, the bandgap energy that determines the energy (and
hence color) of the fluoresced light is inversely proportional to the square of
the size of the quantum dot.
Larger quantum dots have more energy levels which are more closely spaced.
This allows the quantum dot to absorb photons containing less energy, i.e.
those closer to the red end of the spectrum. Recent articles in nanotechnology
and other journals have begun to suggest that the shape of the quantum dot
may well also be a factor in the coloration, but as yet not enough information
has become available.
The lifetime of fluorescence is determined by the size. Larger dots have more
closely spaced energy levels in which the electron-hole pair can be trapped.
Therefore, electron-hole pairs in larger dots live longer and thus these large
dots show a larger lifetime.

Fluorescence emission spectra of CdTe quantum dots of

different sizes.

Quantum dots in biology

In modern biological analysis, various kinds of organic dyes are used.
However, with each passing year, more flexibility is being required of these
dyes, and the traditional dyes are often unable to meet the expectations. To
this end, quantum dots have quickly filled in the role, being found to be
superior to traditional organic dyes on several counts,
brightness (owing to the high quantum yield)
stability (much less photodestruction).
The improved photostability of quantum dots for example, allows the
acquisition of many consecutive focal-plane images that can be
reconstructed into a high-resolution three-dimensional image. Another
application that takes advantage of the extraordinary photostability of
quantum dot probes is the real-time tracking of molecules and cells over
extended periods of time. For single-particle tracking, the irregular blinking
of quantum dots is a minor drawback.

INVITROGEN: Qdot Nanocrystal

Multicolor immunofluorescence imaging with Qdot secondary antibody

conjugates.
Laminin in a mouse kidney section was labeled with an anti-laminin primary
antibody and visualized using green-fluorescent Qdot 565 IgG. PECAM
(platelet/endothelial cell adhesion molecule; CD31) was labeled with an anti
PECAM-1 primary antibody and visualized using red-fluorescent Qdot 655
IgG. Nuclei were stained with blue-fluorescent Hoechst 33342.

INVITROGEN: Qdot Nanocrystal

INVITROGEN: Qdot Nanocrystal

INVITROGEN: Qdot Nanocrystal

Qdot bioconjugate is a generic term to describe Qdot nanocrystals coupled to
proteins, oligonucleotides, small molecules, etc., which are used to direct binding of the
quantum dots to targets of interest. Examples of Qdot bioconjugates include
streptavidin, protein A, and biotin families of conjugates. Qdot bioconjugates are often
used as simple replacements for analogous conventional dye conjugates when their
unique performance characteristics are required to achieve optimal results.
Most dye conjugates are synthesized by attaching one or more fluorophores to a single
biomolecule; however, the large surface area afforded by the nanocrystal fluorophore
allows simultaneous conjugation of many biomolecules to a single Qdot nanocrystal.
Advantages conferred by this approach include increased avidity for targets, the
potential for cooperative binding in some cases, and the use of efficient signal
amplification methodologies. For example, combining biotin-functionalized products
with the streptavidin labels allows for successive enhancements in signal via
"sandwiching" (streptavidin/biotin/streptavidin/etc.) following an initial labeling step.
Standard fluorescence microscopes are an excellent and widely available tool for the
detection of Qdot bioconjugates. These microscopes are often fitted with bright white
light lamps and filter arrangements; Qdot nanocrystals efficiently absorb white light
using broad excitation filters, and the outstanding photostability of Qdot bioconjugates
allows the microscopist more time for image optimization.

Conclusions
Semiconductor materials can be miniaturized in order to
achieve discrete (quantum) electronic properties.
Quantum dots are electronically confined in all three spatial
directions, that makes them accept and emit light of narrowly
defined energies.
Of all quantized semiconductors, QDs are most often used
in biology.