Ch2 Nanotech

Nanotechnology
101751
Prof. Ehab AlShamaileh
2024
In this course we will be studying various types
of nanostructures.
The materials used to form these structures
generally have bulk properties that become
modified when their sizes are reduced to the
nanorange.
The present chapter presents background
material on bulk properties of this type.
Size Dependence of Properties
• Microscopic properties become averaged when investigating bulk materials.

• At the macro- or large-scale range ordinarily studied in traditional fields of
physics such as mechanics, electricity and magnetism, and optics, the sizes of
the objects under study range from millimeters to kilometers.
• The properties that we associate with these materials are averaged properties,
such as the density.
• When measurements are made in the micrometer or nanometer range, many
properties of materials change, such as mechanical, ferroelectric, and
ferromagnetic properties.
• Nanoscale level is roughly from 1 to l00 nm.
• Many important nanostmctures are composed of the group
IV elements Si or Ge, type III-V semiconducting compounds
such as GaAs, or type II-VI semiconducting materials such as
CdS.
• These semiconductor materials will be used to illustrate
some of the bulk properties that become modified with
incorporation into nanostructures.
2.1.2. Crystal Structures
Most solids are crystalline with their atoms arranged in a long-
range order. Amorphous materials such as glass and wax have
short-range order.
Liquids also have short-range order, but lack long-range order.
Gases lack both long-range and short-range order.
The general or oblique Bravais lattice has two unequal lattice
constants a # b and an arbitrary angle q between them.
For the perpendicular case when q = 90°, the lattice becomes
the rectangular type.
For the special case a = b and q = 60°, the lattice is the
hexagonal type formed from equilateral triangles.
Each lattice has a unit cell, indicated in the figures, which can
replicate throughout the plane and generate the lattice.
A crystal structure is formed by associating with a lattice a
regular arrangement of atoms or molecules.
Figure 2.2 presents a two-dimensional crystal structure based

on a primitive rectangular lattice containing two diatomic
molecules A-B in each unit cell.
A single unit cell can generate the overall lattice.

In three dimensions there are three lattice constants, a, b,
and c, and three angles: a( between b and c; b between a
and c, and g between lattice constants a and b).
There are 14 Bravais lattices, ranging from the lowest-

symmetry triclinic type in which all three lattice constants
and all three angles differ from each other (a # b # c and
a # b # g), to the highest-symmetry cubic case in which all
the lattice constants are equal and all the angles are 90o
(a = b = c and a = b = g = 90o).
There are three Bravais lattices in the cubic system:
1) a primitive or simple cubic (SC) lattice in which the atoms

occupy the eight apices of the cubic unit cell (Fig. 2.3a)
2) a body-centered cubic (BCC) lattice with lattice points (atoms)

at the apices and in the center of the unit cell (Fig. 2.3b)
3) a face-centered cubic (FCC) Bravais lattice with atoms at the

apices and in the centers of the faces (Fig. 2.3c).
In two dimensions the most efficient way to pack identical circles (or spheres) is
the equilateral triangle arrangement shown in Fig. 2.4a, corresponding to the
hexagonal Bravais lattice of Fig. 2.ld. A second hexagonal layer of spheres can
be placed on top of the first to form the most efficient packing of two layers, as
shown in Fig. 2.4b. For efficient packing, the third layer can be placed either above
the first layer with an atom at the location indicated by T or in the third possible
arrangement with an atom above the position marked by X on the figure. In the first
case a hexagonal lattice with a hexagonal close-packed (HCP) structure is generated,
and in the second case a face-centered cubic (FCC) lattice results. The former is easy to
visualize, but the latter is not so easy to picture.
2.1.3. Face-Centered Cubic Nanoparticles
Most metals in the solid state form close-packed lattices.

• Ag, Al, Au, Co, Cu, Pb, Pt, and Rh, rare gases Ne, Ar, Kr, and Xe,
are face-centered cubic (FCC).
• Mg, Nd, Os, Re, Ru, Y, and Zn, are hexagonal close-packed (HCP).
An atom in each of the two close-
packed lattices has 12 nearest
neighbors.
Figure 2.5 shows the 12 neighbors that

surround an atom (darkened circle)
located in the center of a cube for a
FCC lattice.
These 13 atoms constitute the
smallest theoretical nanoparticle for
an FCC lattice.
Figure 2.5. Face-centered cubic unit cell.
Purely metallic FCC nanoparticles such as Au55 tend to be very reactive and have
short lifetimes.
They can be ligand-stabilized by adding atomic groups between their atoms and on
their surfaces.
The Au55 nanoparticle has been studied in the ligand- stabilized form
Au55(PPh3)12C16 which has the diameter of - 1.4 nm, where PPh, is an organic
group.
Further examples are the magic number nanoparticles Pt309( 1, 10-
phenantroline)36O30 and Pd561 (1,1O-phenantr0line) 360200.
When mass spectra were recorded for sodium nanoparticles NaN it was found
that mass peaks corresponding to the first 15 electronic magic numbers N =
3,9,20,36,61,. . . were observed for cluster sizes up to N = 1220 atoms (n = 15),
and FCC structural magic numbers starting with N = 1415 for n = 8 were observed
for larger sizes.
2.1.4. Tetrahedrally Bonded Semiconductor Structures
The zinc blende or ZnS structure

2.1.5. Lattice Vibrations
Atoms in a crystal (residing at particular lattice sites) in reality they

undergo continuous fluctuations in the neighborhood of their regular
positions in the lattice.
These fluctuations arise from the heat or thermal energy in the lattice,
and become more pronounced at higher temperatures.
Every type of lattice has its own characteristic modes or frequencies of

vibration called normal modes, and the overall collective vibrational
motion of the lattice is a combination or superposition of many, many
normal modes.
For a diatomic lattice such as GaAs, there are low-frequency modes
called acoustic modes, in which the heavy and light atoms tend to vibrate
in phase or in unison with each other, and high-frequency modes called
optical modes, in which they tend to vibrate out of phase.
2.2. ENERGY BANDS
2.2.1. Insulators, Semiconductors, and Conductors
When a solid is formed the energy levels of the atoms broaden and form bands with
forbidden gaps between them.
The electrons can have energy values that exist within one of the bands, but cannot
have energies corresponding to values in the gaps between the bands.
The lower energy bands due to the inner atomic levels are narrower and are all full of
electrons, so they do not contribute to the electronic properties of a material.
The outer or valence electrons that bond the crystal together occupy what is called a
valence band.
For an insulating material the valence band is full of electrons that cannot move since
they are fixed in position in chemical bonds. There are no delocalized electrons to carry
current, so the material is an insulator.
The conduction band is far above the valence band in energy, as shown in
Fig. 2.11a, so it is not thermally accessible, and remains essentially
empty. In other words, the heat content of the insulating material at
room temperature T = 300 K is not sufficient to raise an appreciable
number of electrons from the valence band to the conduction band, so
the number in the conduction band is negligible. Another way to express
this is to say that the value of the gap energy Eg far exceeds the value kBT
of the thermal energy, where kB is Boltzmann’s constant.
In the case of a semiconductor the gap between the valence and
conduction bands is much less, as shown in Fig. 2.1 1 b, so Eg is closer
to the thermal energy kB T, and the heat content of the material at
room temperature can bring about the thermal excitation of some
electrons from the valence band to the conduction band where they
carry current.
The density of electrons reaching the conduction band by this thermal

excitation process is relatively low, but by no means negligible, so the
electrical conductivity is small; hence the term semiconducting.
A material of this type is called an intrinsic semiconductor.

A semiconductor can be doped with donor atoms that give electrons to the
conduction band where they can carry current. The material can also be doped
with acceptor atoms that obtain electrons from the valence band and leave
behind positive charges called holes that can also carry current. The energy levels
of these donors and acceptors lie in the energy gap, as shown in Fig. 2.12. The
former produces n-type, that is, negative-charge or electron, conductivity, and
the latter produces p-type, that is, positive-charge or hole, conductivity. The
conductivity in semiconductors are temperature-dependent, as is the intrinsic
semiconductivity.
A conductor is a material with a filled valence band, and a
conduction band partly filled with delocalized conduction
electrons that are efficient in carrying electric current.
The positively charged metal ions at the lattice sites have

given up their electrons to the conduction band, and
constitute a background of positive charge for the delocalized
electrons.
Figure 2.11 c shows the energy bands for this case.
In actual crystals the energy bands are much more

complicated than is suggested by the sketches of Fig. 2.11,
with the bands depending on the direction in the lattice.
2.2.2. Reciprocal Space
2.2.3. Energy Bands and Gaps of Semiconductors

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Nanotechnology

Size Dependence of Properties

• Microscopic properties become averaged when investigating bulk materials.

Figure 2.2 presents a two-dimensional crystal structure based

A single unit cell can generate the overall lattice.

There are 14 Bravais lattices, ranging from the lowest-

1) a primitive or simple cubic (SC) lattice in which the atoms

2) a body-centered cubic (BCC) lattice with lattice points (atoms)

3) a face-centered cubic (FCC) Bravais lattice with atoms at the

Most metals in the solid state form close-packed lattices.

Figure 2.5 shows the 12 neighbors that

The zinc blende or ZnS structure

Atoms in a crystal (residing at particular lattice sites) in reality they

Every type of lattice has its own characteristic modes or frequencies of

The density of electrons reaching the conduction band by this thermal

A material of this type is called an intrinsic semiconductor.

The positively charged metal ions at the lattice sites have

In actual crystals the energy bands are much more

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