QUANTUM WELLS, WIRES AND DOTS

 Quantum well: One dimension of a large size material is

reduced to nano range while the other two dimensions remain
large.
 Quantum wire: Two dimensions are reduced and one remains
large.
 Quantum dot: The extreme case of this process of size
reduction in which all three dimensions reach the nanometer
range.

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 The word quantum is associated with the fact that the changes
in properties are quantum mechanical in nature.
 Figure 9.1 illustrates these processes of diminishing the size
for the case of rectilinear geometry.
 Figure 9.2 presents the corresponding reductions in curvilinear
geometry.
 We are interested in all the three ways, i.e the dimensionality
effects that occur when one, two or all three dimensions
become small.
 We are interested in the electronic properties altered by these
changes.

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PREPARATION OF QUANTUM NANOSTRUCTURES

 Bottom-up method: One approach to the preparation of a

nanostructure is to collect, consolidate and arrange individual
atoms and molecules into the structure.
 This is carries out by a sequence of chemical reactions
controlled by catalysts.
 It is a process that is widespread in biology. For example,
catalysts called “enzymes” assemble amino acids to construct
living tissue that forms and supports the organs of the body.

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 Top-down method: Opposite approach starts with a large
scale object or pattern and gradually reduce its dimensions.
 Lithography is the technique used for accomplishing this.
 Fig.9.3a shows a GaAs square quantum well located on a
substrate.
 Fig.9.3b shows the final products, i.e. a quantum wire or a
quantum dot produced by lithography.

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 The steps to be followed in this process are outlined in
Fig.9.4.
 The first step of the lithographic procedure is to place a
radiation-sensitive resist on the surface of the sample
substrate, as shown in Fig.9.4a.
 The sample is then irradiated by an electron beam in the
region where the nanostructure will be located, as shown in
Fig.9.4b.
 This can be done by using either a radiation mask that
contains the nanostructure pattern, as shown, or a scanning
electron beam that strikes the surface only in the desired
region.
 The radiation chemically modifies the exposed area of the
resists.
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 Third step (Fig.9.4c) is the application of the developer to
remove the irradiated portions of the resist.
 Fourth step (Fig.9.4e) is the insertion of an etching mask into
the hole in the resist.
 In fifth step (Fig.9.4f), the areas of the quantum well not
covered by the etching mask are chemically etched away to
produce the quantum structure.
 Finally, the etching mask is removed to provide the desired
quantum structure (Fig.9.4g).
 Electron beam lithography uses an electron beam for the
radiation.
 Other types of lithography employ electromagnetic radiation
such as visible light, ultraviolet light or X-rays. Neutral atom
beams (e.g., Li, Na, K, Rb, Cs) or charged ion beams (e.g.,
Ga+) are also utilized.
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 A multiple quantum well structure fabricated by lithography is
illustrated in Fig.9.5.

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 This produces a 24-quantum-dot array. There are 6 columns,
each containing 4 stacked quantum dots as shown in Fig. 9.6.

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 Fig.9.7 shows the main peak of the photoluminescence
spectra. These peaks are due to localized excitons.
 The photoluminescence spectrum from the quantum dot
array is more than 100 times stronger than the spectrum
obtained from the initial multiple quantum wells.
 This magnitude of enhancement has been obtained from initial
samples containing, typically, a 15-period superlattice of
alternating 3nm thick layers of Si and Si0.7Ge0.3 patterned into
quantum dot arrays consisting of 300nm-high columns with
60nm diameters and 200nm separations.

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SIZE AND DIMENSIONALITY EFFECTS

Size Effects
 Let us look at the nanostructure sizes relative to various
parameters of the system.
 We select the type III-V semiconductor GaAs as a typical
material.
 It has fcc structure and the unit cell contains four Ga and four
As atoms.

 Its lattice constant is a = 0.565 nm and the volume of the unit

cell is (0.565)3 = 0.180 nm3.

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 This puts each Ga atom in the center of a tetrahedron of As
atoms corresponding to the grouping GaAs4 and each As atom
has a corresponding configuration AsGa4.

 In a cubic nanometer, there are about 22 Ga and 22 As atoms.

 A cube-shaped quantum dot of 10nm side, contains 5.56 x 103

unit cells.

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 The question arises as to how many of the atoms are on the
surface.
 If the initial cube is taken in the form of Fig.2.6 and
nanostructures containing n3 of these unit cells are built up,
then it can be shown that the number of atoms NS on the
surface, the total number of atoms NT and the size d of the
cube are given by

 Here a is the lattice constant of GaAs.

 Table 9.1 tabulates NS, NT, d and the fraction of atoms on the
surface NS/NT, for various values of n.

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 For small n, large percentage of atoms are on the surface.
 An analogous table can be constructed for cylindrical quantum
structures as well.

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 Now, let us look at the number of charge carriers in
quantum nanostructures.
 We know, a charge carrier in a conductor or semiconductor in
an applied electric field is scattered by phonons and defects.
 An electron or hole moving with a drift velocity v will, on the
average, experience a scattering event every  seconds, and
travel a distance l called the mean free path between
collisions, where
l = ν (9.4)
 Mean free paths in metals depend strongly on the impurity
content and in ordinary metals typical values might be in the
low nanometer range, about 2 to 50 nm.
 In very pure samples they will, of course, be much longer.

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 Various types of defects in a lattice can interrupt the forward
motion of conduction electrons and limit the mean free path.
 All of these can bring about the scattering of electrons, and
thereby limit the electrical conductivity.
 In bulk materials, the mean free path is much smaller than
the size of the materials.
 But when the dimensions approach or become less than l,
the resistivity depends mainly on scattering at the
boundaries of crystal.

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 Another size effect arises from the level of doping of a
semiconductor.
 For typical doping levels of 1014 to 1018 donors/cm3, a quantum
dot cube 100 nm on a side would have, on the average, from
10-1 to 103 conduction electrons.
 A similar analysis can be made for quantum wires and quantum
wells.
 Table 9.2 demonstrates that these quantum structures are
typically characterized by very small numbers or concentrations
of electrons that can carry current.

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Conduction Electrons and Dimensionality

 We are accustomed to studying electronic systems that

exist in three dimensions and are large or macroscopic in
size.
 In bulk materials, the conduction electrons are delocalized and
move freely throughout the entire material, such as a Cu wire.
 The situation changes when one or more dimensions of the
material becomes so small that it approaches several times
the spacings between the atoms in the lattice.
 When this occurs, the delocalization is impeded and the
electrons experience confinement.

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 For example, consider a flat plate of Cu that is 10 cm long,
10cm wide and only 3.6nm thick.
 This thickness corresponds to the length of only 10 unit cells.
This means that 20% of the atoms are at the surface of the Cu.

 Quantum well: The conduction electrons would be delocalized

in the plane of the film, but confined in the narrow dimension.
 Quantum wire: The conduction electrons are delocalized in
the length of the wire, but confined in the transverse directions.
 Quantum dot: A tiny cube, a short cylinder or a sphere with
low nanometer dimensions, exhibits confinement in all three
spatial dimensions.
 Fig.9.1, Fig.9.2 and Table 9.3, summarize these cases.

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Fermi Gas and Density of States
 The electrical properties of good conductors in bulk form are
explained by the delocalized conduction electrons that move
freely in the material.
 These electrons act like a gas called a Fermi gas.
 This model gives a good explanation of Ohm’s law, i.e. V = IR.
 At T = 0 K, the electrons of the Fermi gas occupy all the lattice
points in reciprocal space upto Fermi radius kF. This gives the
Fermi energy EF ,

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 The number of conduction electrons with a particular energy
depends on the value of the energy and also on the
dimensionality of the space.
 Table 9.4 and Fig.9.9 give the N(E) for various dimensions.
 Table 9.4 and Fig.9.10 give the D(E) for various dimensions.
 The DOS decreases with increasing energy for one
dimension, is constant for two dimensions and increases
with increasing energy for three dimensions.
 These equations and plots of the DOS are very important in
determining the electrical, thermal and other properties of
metals and semiconductors.

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Potential Wells

 Due to the confinement, the motion of the electrons become

limited by the physical size of the region in which they move.
 The influence of electrostatic forces becomes more
pronounced and the electrons become restricted by a
potential barrier that must be overcome before they can
move more freely.
 More explicitly, the electrons become isolated in a potential
well.
 A simple model that exhibits the principal characteristics of such
a potential well is a square well in which the boundary is very
sharp or abrupt.

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 Square wells can exist in one, two or three dimensions. For
simplicity, we describe a 1D case.
 From the standard quantum mechanics for an infinitely deep
square potential well of width “a” in one dimension, the
coordinate x has the range of values –a  x  +a inside the well,
and the energies there are given by the expressions

 Here, is the ground state energy and the

quantum number n assumes the values n = 1, 2, 3, …..
 In Fig.9.11, these energy levels and wavefunctions are plotted.

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 An infinite square well has an infinite number of energy
levels, with ever-widening spacings as the quantum number n
increases.
 If the well is finite, then its quantized energies, En all lie below
the corresponding infinite well energies and there are only a
limited number of them.
 Figure 9.12 illustrates the case for a finite well of potential
depth V0 = 7E0 . This has only 3 allowed energies.
 No matter how shallow the well, there is always at least one
bound state E1.
 We know that the degeneracy of the energy levels is 2 for all
1D potential wells.

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 Another important variety of potential well, is one with a
curved cross section.
 For a circular cross section of radius “a” in 2-dimensions, the
potential is given by V = 0 in the range 0 <  < a, and has the
value Vo at the top and outside, where  = (x2 + y2)1/2 and tan 
= y/x in polar coordinates.
 The particular finite well sketched in Fig.9.13 has only 3
allowed energy levels with the values E1, E2 and E3.
 There is also a 3D analog of the circular well in which the
potential is zero for the radial coordinate r in the range 0  r  a
and has the value Vo outside, where r = (x2 + y2 + z2)1/2.
 Another type of commonly used potential well is the parabolic
well, which is characterized by the potentials V(x)= ½kx2, V()
= ½k2 and V(r) = ½kr2 in 1, 2, and 3 dimensions, respectively.
 Fig.9.14 provides a sketch of the potential in the 1D case.
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 The energy of a 2D infinite rectangular square well

 This depends on two quantum numbers, nx = 0,1,2,3,… and ny

= 0,1,2,3,…. Here n2 = nx2 + ny2.
 This means that the lowest energy state E1 = E0 has two
possibilities, namely, nx = 0, ny = 1 and nx =1, ny = 0. So the
total degeneracy is 4.
 The energy state E5 = 25E0 has more possibilities since it can
have, for example, nx = 0, ny = 5 or nx = 3 and ny = 4, and so on.
Hence, its degeneracy is 8.

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Partial Confinement

 Confinement and delocalization coexist.

 In a 3D Fermi sphere, the energy varies from E = 0 at the origin
to E = EF at the Fermi surface. Similarly, for the 1 and 2D
analogs.
 When there is confinement in one or two directions, the
conduction electrons will distribute themselves among the
corresponding potential well levels that lie below the Fermi
level along confinement coordinate directions.
 The electrons will delocalize in the remaining dimensions by
populating Fermi gas levels in the delocalization directions of
the reciprocal lattice.

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 Table 9.5 lists the formulas for the energy dependence of N(E)
and D(E) for quantum dots, quantum wires and quantum wells.

 Figure 9.15 shows plots of N(E) and D(E) as a function of

energy for the nanostructures listed in Table 9.5.
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 We see that the N(E) increases with E and hence the four
nanostructure types vary only qualitatively from each other.
 However, it is the density of states D(E) that determines the
various electronic and other properties and these differ
dramatically for each of the three nanostructure types.
 This means that the nature of the dimensionality and of the
confinement associated with a particular nanostructure have a
pronounced effect on its properties.
 These considerations can be used to predict properties of
nanostructures and one can also identify types of
nanostructures from their properties.

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Properties Dependent on Density of States

 We have discussed the density of states D(E) of conduction electrons

and have shown that it is strongly affected by the dimensionality of a
material.
 Phonons also have a density of states DPH(E) that depends on
the dimensionality and it also influences some properties of solids.
 But our principal interest is in the density of states D(E) of the
electrons.
 In this section, we discuss some of the properties of solids that
depend on the DOS.

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 Specific heat of a solid depends on the phonon density of
states DPH(E).
 At low temperatures, another contribution comes from the
electronic specific heat Cel of a conductor arising from the
conduction electrons. This depends on the electronic DOS at
the Fermi level: Cel = π2D(EF)kB2T/3.
 Magnetic susceptibility arising from the conduction electrons,
called the Pauli susceptibility, is given by the expression
el = µB2D(EF). This is temperature independent.

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 X-ray Emission Spectroscopy: When a good conductor such
as Aluminium is bombarded by fast electrons with just enough
energy to remove an electron from a particular inner core
energy level, the vacant level left behind constitutes a hole.
 An electron from the conduction band can fall into the
hole, with the simultaneous emission of an X-ray in the
process.
 The intensity of the emitted X-radiation is proportional to
the DOS of the conduction electrons because the number of
electrons with each particular energy that jumps down to fill the
hole is proportional to D(E).
 Therefore, a plot of the emitted X-ray intensity versus the X-ray
energy E has a shape very similar to a plot of D(E) vs E.
 These emitted X-rays for Aluminum are in the energy range
from 56 to 77 eV.
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 Some other properties and experiments that depend on the
density of states are:
 Photoemission spectroscopy.
 Seebeck effect (thermopower).
 Optical absorption determinations of dielectric constant.
 Fermi contact term in NMR.
 de Hass-van Alphen effect.
 Superconducting energy gap and Josephson junction tunneling
in superconductors depends on D(E).

EXCITONS
 We have already seen Weak and Strong Confinements of
Excitons.
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SINGLE-ELECTRON TUNNELING

 To use quantum nanostructures in devices, we have to

couple them to their surroundings, to each other or to
electrodes that can add or subtract electrons from them.
 Figure 9.16 shows an isolated quantum dot coupled to two
leads through tunneling. There is a source lead that
supplies electrons and a drain lead that removes electrons for
use in the external circuit.

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 The applied voltage Vsd causes a current flow I, with electrons
tunneling into and out of the quantum dot.
 According to Ohm’s law V=IR. The main contribution to the value of
R arises from the process of electron tunneling from source to
quantum dot and from quantum dot to drain.
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 Figure 9.17 shows the addition to the circuit of a
capacitor-coupled gate terminal.

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 This device functions as a FET.
 The applied gate voltage Vg provides a controlling electrode or
gate that regulates the resistance R of the active region of the
quantum dot. Consequently, it regulates the current flow I
between the source and drain terminals.
 Our present interest is in the passage of electrons, one by
one, through nanostructures based on circuitry of the type
sketched in Fig.9.17.
 In devices, the quantum dots are in the low nanometer
range and the attached electrodes can have cross sections
comparable in size.

 For large or macroscopic objects, the current flow is

continuous and the discreteness of the individual electrons
passing through the device manifests itself by the presence of
current fluctuations or shot noise.
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 For disk and spherical shaped dots of radius r, the capacitance
is given by

 Here, ε/ε0 is the dielectric constant of the semiconducting

material that forms the dot.
 For the typical quantum dot material GaAs, we have
ε/ε0=13.2, which gives the very small value C = 1.47 x 10-18 r
farad for a spherical shape of radius r in nanometres.

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 The electrostatic energy E of a spherical capacitor of charge Q
(for Q >> e) is changed by amount E  eQ/C when a single
electron is added or subtracted, corresponding to the change in
potential V = E/Q

 For a nanostructure of radius r = 10nm, this gives a change in

potential of 11 mV, which is easily measurable.
 This potential is large enough to impede the tunneling of the
next electron.

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 Two quantum conditions must be satisfied for the
observation of the discrete nature of the single electron
transfer to a quantum dot.
 First one is that the capacitor single electron charging
energy e2/2C must exceed the thermal energy kT.
 Second is that the Heisenberg uncertainty principle be
satisfied by the product of the capacitor energy e2/2C and the
time  = RTC required for charging the capacitor

 Here RT is the tunneling resistance of the potential barrier.

These two tunneling conditions correspond to

where h/e2 = 25.813 kΩ is the quantum of resistance.

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 Fig.9.18 shows the I-V characteristics of the circuit.
 When the voltage across the quantum dot is scanned, then the
current jumps in increments every time the voltage
changes by the value of Eq.(9.13).
 This is called a Coulomb blockade because the electrons are
blocked from tunneling except at the discrete change in the
voltage values.
 The step structure observed in the I-V characteristic is called a
Coulomb staircase because it involves the Coulomb charging
energy e2/2C of Eq.(9.15a).

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 Another example of single-electron tunneling is provided by
a line of ligand-stabilized Au55 nanoparticles.
 These gold particles have FCC structure close-packed cluster
that approximates the shape a sphere of diameter 1.4nm.
 The cluster of 55 gold atoms is encased in an insulating coating
called a ligand shell that is adjustable in thickness and has a
typical value of 0.7 nm.
 Single-electron tunneling can take place between two of these
Au55 ligand-stabilized clusters when they are in contact, with the
shell acting as the barrier for the tunneling.

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 Fig.9.19 shows the experiments carried out with linear arrays of
these Au55 clusters.
 An electron entering the chain at one end was found to tunnel
its way through.
 Estimates of the interparticle capacitance gave Cmicro  10-18 F
and the estimated interparticle resistance was RT  100MΩ.

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