21/05/2019

Solid State Devices

Energy Bands and Charge Carriers in
Semiconductors (part 1)
Reference Book: Solid State Electronic Devices (6th Edition) by Streetman and Banerjee
Supporting Book: Semiconductor Physics and Devices by Donald A. Neamen

 Outline of the Contents

 BONDING FORCES AND ENERGY BANDS IN
SOLIDS
 Bonding Forces in Solids
 Energy Bands

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BONDING FORCES AND ENERGY BANDS IN SOLIDS:

• we found that electrons are restricted to sets of discrete energy levels (En)
within atoms. Large gaps exist in the energy scale in which no energy
states are available.
• In a similar fashion, electrons in solids are restricted to certain energies
and are not allowed at other energies.
• The basic difference between the case of an electron in a solid and that of
an electron in an isolated atom is that in the solid the electron has a range,
or band, of available energies.
• The discrete energy levels of the isolated atom spread into bands of
energies in the solid because in the solid the wave functions of electrons
in neighboring atoms overlap, and an electron is not necessarily localized
at a particular atom.

BONDING FORCES AND ENERGY BANDS IN SOLIDS

Bonding Forces in Solids:
• The interaction of electrons in neighboring atoms of a solid serves the very
important function of holding the crystal together.
• Ionic bonding: Ionic bonding is the complete transfer of valence electron(s)
between atoms. It is a type of chemical bond that generates two oppositely
charged ions. In ionic bonds, the metal loses electrons to become a positively
charged cation, whereas the nonmetal accepts those electrons to become a
negatively charged anion. (example: NaCl stucture)
• An important observation in the NaCl
structure is that all electrons are tightly
bound to atoms.
• Once the electron exchanges have been
made between the Na and CI atoms to form
the Na+ and CI- ions, the outer orbits of all
atoms are completely filled. Since the ions
have the closed-shell configurations of the
inert atoms Ne and Ar, there are no loosely
bound electrons to participate in current
flow;
• as a result, NaCl is a good insulator.

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BONDING FORCES AND ENERGY BANDS IN SOLIDS

Bonding Forces in Solids:

• Metallic bonding: Metallic bonding is the force of attraction between valence

electrons and the metal ions. It is the sharing of many detached (outermost shell)
electrons between many positive ions, where the electrons act as a "glue" giving
the substance a definite structure. It is unlike covalent or ionic bonding.
• The electrons are loosely bound and is given up easily in ion formation. This
accounts for the great chemical activity in the alkali metals, as well as for their
high electrical conductivity.

BONDING FORCES AND ENERGY BANDS IN SOLIDS

Bonding Forces in Solids:
• Covalent bond : A covalent bond, also called a molecular bond, is a chemical
bond that involves the sharing of electron pairs between atoms. These electron
pairs are known as shared pairs or bonding pairs, and the stable balance of
attractive and repulsive forces between atoms, when they share electrons, is
known as covalent bonding.
• The bonding forces arise from a quantum mechanical interaction between the
shared electrons.
• each electron pair constitutes a
covalent bond.
• In the sharing process it is no
longer relevant to ask which
electron belongs to a particular
atom, both belong to the bond.
The two electrons are
indistinguishable, except that
they must have opposite spin
to satisfy the Pauli exclusion
principle.

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BONDING FORCES AND ENERGY BANDS IN SOLIDS

Bonding Forces in Solids:

• As in the case of the ionic crystals, no free electrons are available to the
lattice in the covalent diamond structure.
• By this reasoning Ge and Si should also be insulators. However, This is
the picture of an idealized lattice at 0K.
• An electron can be thermally or optically excited out of a covalent bond
and thereby become free to participate in conduction. This is an important
feature of semiconductors.
• Compound semiconductors such as GaAs have mixed bonding, in which
both ionic and covalent bonding forces participate.
• The ionic character of the bonding becomes more important as the atoms
of the compound become further separated in the periodic table, as in the
II-VI compounds.

BONDING FORCES AND ENERGY BANDS IN SOLIDS

EnergyBands:
• As isolated atoms are brought together to form a solid, various
interactions occur between neighboring atoms.
• The forces of attraction and repulsion between atoms will find a balance
at the proper inter-atomic spacing for the crystal.
• Let us focus on the outer most shell or valence shell, n=3; where two 3s
and two 3p electrons interact to form the four "hybridized“ sp3 electrons
when the atoms are brought close together.

Coulombic
Potential
well

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BONDING FORCES AND ENERGY BANDS IN SOLIDS

EnergyBands:
• Schematically the Coulombic potential wells of two atoms close to each
other along with the wave functions of two electrons centered on the two
nuclei are shown below.
• By solving the Schrbdinger equation for such an interacting system, we
find that the composite two electron wave functions are linear
combinations of the individual atomic orbitals (LCAO).
• The odd or anti-symmetric
combination is called the anti-
bonding orbital, while the even
or symmetric combination is the
bonding orbital.
• It can be seen that the bonding
orbital has a higher value of the
wave function than the anti
bonding state in the region
between the two nuclei.
• This corresponds to the covalent
bond between the atoms.

BONDING FORCES AND ENERGY BANDS IN SOLIDS

EnergyBands:
• To determine the energy levels of the bonding and the antibonding states,
it is important to recognize that in the region between the two nuclei the
coulombic potential energy V(r) is lowered compared to isolated
atoms(dashed lines).
• It is easy to see why the potential energy would be lowered in this region,
because an electron here would be attracted by two nuclei ,rather than just
one.
• From the rule of LCAO, the
number of new energy levels
for different orbitals need to be
equal to the number of atomic
orbitals before.
• Thus the original isolated
atomic energy level would be
split in to two, a lower bonding
energy level and a higher
antibonding level.

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BONDING FORCES AND ENERGY BANDS IN SOLIDS

EnergyBands:
• The important point to note in this discussion is that the number of
distinct LCAO, and the number of distinct energy levels, depends on the
number of atoms that are brought together.
• The lowest energy level corresponds to the totally symmetric LCAO and
the highest corresponds to the totally anti symmetric case, and the other
combinations lead to energy levels in between.