09/01/2023

INTRODUCTION
NANO-MATERIALS
Carbon allotrope structures in
nanoform: (A) fullerene C60;
(B) C70; (C) C540; (D) graphite;
(E) single-walled carbon
nanotube (SWCNT); (F)
amorphous carbon; (G)
multiwalled carbon nanotube
(MWCNT)
10/01/2023
Physics and Properties of Semiconductors materials: crystal structure
• Energies of electrons are quantized—that is, electrons are
permitted to have only specific values of energy. An electron may
change energy, but in doing so, it must make a quantum jump
either to an allowed higher energy (with absorption of energy) or
to a lower energy (with emission of energy).
• These states do not vary continuously with energy—that is,
adjacent states are separated by finite energies.
• Bohr model was eventually found to have some significant
limitations because of its inability to explain several phenomena
involving electrons.
• A resolution was reached with a wave-mechanical model, in
which the electron is considered to exhibit both wavelike and
particle-like characteristics.
• With this model, an electron is no longer treated as a particle
moving in a discrete orbital; rather, position is considered to be
the probability of an electron being at various locations around the
nucleus.
Orientations and shapes of p
electron orbitals.

Orientations and shapes of d

electron orbitals.
(a) The first three electron energy states for the Bohr hydrogen atom.
(b) Electron energy states for the first three shells of the wave-
mechanical hydrogen atom.
Quantum Numbers
• In wave mechanics, every electron in an atom is characterized by four parameters
called quantum numbers. The size, shape, and spatial orientation of an electron’s
probability density (or orbital) are specified by three of these quantum numbers.
• Shells are specified by a principal quantum number n, which may take on integral
values beginning with unity; sometimes these shells are designated by the letters K, L,
M, N, O, and so on, which correspond, respectively,
Comparison of the (a) Bohr and (b) Schematic representation of the relative
wavemechanical atom models in terms of energies of the electrons for the various
electron distribution. shells and subshells.
Electron Configurations
• Electron states—values of energy that are permitted for
electrons.
• Pauli exclusion principle, another quantum-mechanical
concept, which stipulates that each electron state can hold
no more than two electrons that must have opposite spins.
• For most atoms, the electrons fill up the lowest possible
energy states in the electron shells and subshells, two
electrons (having opposite spins) per state.
• When all the electrons occupy the lowest possible energies
in accord with the foregoing restrictions, an atom is said to
be in its ground state. Schematic representation of
• The electron configuration or structure of an atom the filled and lowest unfilled
represents the manner in which these states are occupied. energy states for a sodium
atom.
The valence electrons are those that occupy the outermost shell. These electrons are
extremely important; as will be seen, they participate in the bonding between atoms to form
atomic and molecular aggregates. Furthermore, many of the physical and chemical properties
of solids are based on these valence electrons.
(a) The dependence of repulsive,
attractive, and net forces on
interatomic separation for two isolated
atoms.

(b) The dependence of repulsive,

attractive, and net potential energies
on interatomic separation for two
isolated atoms.
Furthermore, the bonding energy for these two
atoms, E0, corresponds to the energy at this
minimum point (also shown in Figure, it represents
the energy required to separate these two atoms to
an infinite separation.
 Crystal structure
• The periodicity in a crystal is defined in terms of a symmetric array of points in space called
the lattice. We can add atoms at each lattice point in an arrangement called a basis, which can
be one atom or a group of atoms having the same spatial arrangement, to get a crystal.
• In every case, the lattice contains a volume or cell that represents the entire lattice and is
regularly repeated throughout the crystal.
primitive vectors r = pa + qb + sc

A two- dimensional lattice showing translation

of a unit cell by r = 3a + 2b.
 Energy bands

• In all conductors, semiconductors, and many insulating materials, only

electronic conduction exists, and the magnitude of the electrical conductivity
is strongly dependent on the number of electrons available to participate in
the conduction process.

• The number of electrons available for electrical conduction in a particular

material is related to the arrangement of electron states or levels with
respect to energy, and then the manner in which these states are occupied
by electrons.
• A solid consisting of a large number, say, N, of atoms initially separated from
one another.
• At relatively large separation distances, each atom is independent of all the
others and will have the atomic energy levels and electron configuration as if
isolated.
• Within close proximity of one another, electrons are acted upon.
• This influence is such that each distinct atomic state may split into a series of
closely spaced electron states in the solid, to form what is termed an electron
energy band.
• The extent of splitting depends on interatomic separation (Fig.) and begins with
the outermost electron shells, since they are the first to be perturbed as the
atoms coalesce.
• Within each band, the energy states are discrete, yet the difference between
adjacent states is exceedingly small. At the equilibrium spacing, band
formation may not occur for the electron subshells nearest the nucleus (Fig.)
• Gaps may exist between adjacent bands, as also indicated in the figure;
normally, energies lying within these band gaps are not available for electron
occupancy.
• The number of states within each band will equal the total of all states
contributed by the N atoms. For example, an s band will consist of N states, and
a p band of 3N states.
• With regard to occupancy, each energy state may accommodate two electrons,
which must have oppositely directed spins.
• Bands will contain the electrons that resided in the corresponding levels of the
isolated atoms. Of course, there will be empty bands and, possibly, bands that
are only partially filled.
• The electrical properties of a solid material are a consequence of its electron
band structure—that is, the arrangement of the outermost electron bands and
the way in which they are filled with electrons.
 The various possible electron band structures in solids at 0 K. (a) The electron
band structure found in metals such as copper, in which there are available
electron states above and adjacent to filled states, in the same band. (b) The
electron band structure of metals such as magnesium, wherein there is an overlap
of filled and empty outer bands. (c) The electron band structure characteristic of
insulators; the filled valence band is separated from the empty conduction band by
a relatively large band gap ( eV). (d) The electron band structure found in the
semiconductors, which is the same as for insulators except that the band gap is
relatively narrow.
For a metal, occupancy of electron states (a) before and
(b) after an electron excitation.
In a solid, many atoms are brought together, so that the split energy levels form essentially
continuous bands of energies. As an example, Fig. illustrates the imaginary formation of a
silicon crystal from isolated silicon atoms. Each isolated silicon atom has an electronic
structure 1s22s22p63s23p2 in the ground state. Each atom has available two 1s states, two 2s
states, six 2p states, two 3s states, six 3p states, and higher states. If we consider N atoms, there
will be 2N, 2N, 6N, 2N, and 6N states of type 1s, 2s, 2p, 3s, and 3p, respectively. As the
interatomic spacing decreases, these energy levels split into bands, beginning with the outer (n
= 3) shell. As the “3s” and “3p” bands grow, they merge into a single band composed of a
mixture of energy levels. This band of “3s–3p” levels contains 8N available states. As the
distance between atoms approaches the equilibrium interatomic spacing of silicon, this band
splits into two bands separated by an energy gap Eg. The upper band (called the conduction
band) contains 4N states, as does the lower (valence) band. Thus, apart from the low-lying and
tightly bound “core” levels, the silicon crystal has two bands of available energy levels
separated by an energy gap Eg wide, which contains no allowed energy levels for electrons to
occupy. This gap is sometimes called a “forbidden band,” since in a perfect crystal it contains
no electron energy states.
12/01/2023
Energy levels in Si as a function of interatomic spacing. The core levels (n = 1, 2) in Si are completely filled with
electrons. At the actual atomic spacing of the crystal, the 2N electrons in the 3s subshell and the 2N electrons in the
3p subshell undergo sp3 hybridization, and all end up in the lower 4N states (valence band), while the higher-lying
4N states (conduction band) are empty, separated by a band gap.
Semiconductor materials at 0 K have basically the same structure as insulators—a filled valence
band separated from an empty conduction band by a band gap containing no allowed energy
states (Fig.). The difference lies in the size of the band gap Eg , which is much smaller in
semiconductors than in insulators. For example, the semiconductor Si has a band gap of about
1.1 eV compared with 5 eV for diamond. The relatively small band gaps of semiconductors
allow for excitation of electrons from the lower (valence) band to the upper (conduction) band by
reasonable amounts of thermal or optical energy. For example, at room temperature a
semiconductor with a 1-eV band gap will have a significant number of electrons excited
thermally across the energy gap into the conduction band, whereas an insulator with Eg = 10 eV
will have a negligible number of such excitations. Thus an important difference between
semiconductors and insulators is that the number of electrons available for conduction can be
increased greatly in semiconductors by thermal or optical energy. In metals the bands either
overlap or are only partially filled. Thus electrons and empty energy states are intermixed within
the bands so that electrons can move freely under the influence of an electric field. As expected
from the metallic band structures of Fig., metals have a high electrical conductivity.
Typical band structures at 0 K
The direct and indirect semiconductors

In a typical calculation, a single electron is assumed to travel through a perfectly

periodic lattice. The wavefunction of the electron is assumed to be in the form of
a plane wave moving, for example, in the x-direction with propagation constant
k, also called a wavevector. The space-dependent wavefunction for the electron
is
߰݇ ‫ ݔ݇ ܷ = ݔ‬, ‫ݔݔ݆݇݁ ݔ‬
where the function U(kx, x) modulates the wavefunction according to the
periodicity of the lattice. Such wavefunctions are called Bloch functions after the
physicist Felix Bloch. In such a calculation, allowed values of energy can be
plotted vs. the propagation constant k. Since the periodicity of most lattices is
different in various directions, the (E, k) diagram must be plotted for the various
crystal directions, and the full relationship between E and k is a complex surface
which should be visualized in three dimensions.
Direct and indirect electron transitions in semiconductors: (a) direct transition with
accompanying photon emission; (b) indirect transition via a defect level.
• In a direct semiconductor such as GaAs, an electron in the conduction band
can fall to an empty state in the valence band, giving off the energy
difference Eg as a photon of light.
• An electron in the conduction band minimum of an indirect semiconductor
such as Si cannot fall directly to the valence band maximum but must
undergo a momentum change as well as changing its energy. For example, it
may go through some defect state (Et) within the band gap.
• In an indirect transition which involves a change in k, part of the energy is
generally given up as heat to the lattice rather than as an emitted photon.
• This difference between direct and indirect band structures is very important
for deciding which semiconductors can be used in devices requiring light
output. For example, semiconductor light emitters and lasers generally must
be made of materials capable of direct band-to-band transitions or of indirect
materials with vertical transitions between defect states.