Module 2

➢ Introduction to Solids, Crystals and Electronic Materials

➢ Formation of Energy Bands
➢ Energy Band Model, Effective Mass
➢ Direct and indirect bandgap
➢ Elemental and compound semi-conductors
➢ Intrinsic and Extrinsic semi-conductors
➢ The density of states
➢ Carrier statistics
➢ Fermi Level
➢ Equilibrium carrier concentration, Quasi Equilibrium and Quasi-Fermi Level
 Solid-State Electronic Materials
• Electronic materials fall into three categories (w.r.t resistivity):

Insulators  > 105 -cm (diamond  = 1016 )

Semiconductors 10-3 <  < 105 -cm
Conductors  < 10-3 -cm (copper  = 10-6 )
 Insulators/Conductors
•Materials that have large bandgap energies (in the range of 3 to 6 electron-volts (eV))
are insulators, because at room temperature, essentially no free electron exists in the
material
•Materials that contain very large number of free electrons at room temperature are
conductors
Energy Band Model
 Semiconductors
•→ In a semiconductor, the bandgap energy is in the order of 1 eV. The
net flow of free electrons causes a current

•→ In a semiconductor, two types of charged particles contribute to the

current:
•negatively charged electrons
• positively charged holes
Semiconductors are a special class of elements having a conductivity
between that of a good conductor and that of an insulator
 Atomic Structure
An atom is composed of :
•Nucleus ( which contains positively charged protons and
neutral neutrons)
•Electrons (which are négative charged and that orbit the
nucleus)
 Valence Electrons
•Electrons are distributed in various shells at different distances from
nucleus
• Electron energy increases as shell radius increases.
•Electrons in the outer most Shell are called as valence electrons
•Elements in the period table are grouped according to the number of
valence electrons.
 Solid-State Electronic Materials
• Elemental semiconductors are formed from a single type of atom of
column IV, typically Silicon.

• Compound semiconductors are formed from combinations of elements of

column III and V or columns II and VI.

• Germanium was used in many early devices

• Silicon quickly replaced germanium due to its higher bandgap energy,

lower cost, and ability to be easily oxidized to form silicon-dioxide
insulating layers.
 Solid-State Electronic Materials (cont)
Bandgap is an energy range in a solid where no electron states can exist. It
refers to the energy difference between the top of the valence band and the
bottom of the conduction band in insulators and semiconductors
Semiconductor Materials (cont.)

Bandgap
Semiconductor
Energy EG (eV)
Carbon (diamond) 5.47
Silicon 1.12
Germanium 0.66
Tin 0.082
Gallium arsenide 1.42
Gallium nitride 3.49
Indium phosphide 1.35
Boron nitride 7.50
Silicon carbide 3.26
Cadmium selenide 1.70

Chap 2 - 10
 Covalent Bond Model
•Silicon has four electrons in the outer shell.
• Single crystal material is formed by the covalent bonding of each
silicon atom with its four nearest neighbors.

Silicon diamond lattice unit Corner of diamond lattice View of crystal

cell. showing four nearest lattice along a crystallographic
neighbor bonding. axis.
Silicon Covalent Bond Model (cont.)

Silicon atom

Chap 2 - 12
Silicon Covalent Bond Model (cont.)

Covalent bond

Silicon atom Silicon atom

Silicon Covalent Bond Model (cont.)

Silicon atom Covalent bonds in silicon

 Silicon Covalent Bond Model (cont.)

• What happens as the temperature

increases?

• Near absolute zero, all bonds are complete

• Each Si atom contributes one electron to each of the four bond pairs
• The outer shell is full, no free electrons, silicon crystal is an insulator

Chap 2 - 15
 Silicon Covalent Bond Model (cont.)

• Near absolute zero, all bonds are complete • Increasing temperature adds energy to the system and breaks bonds
• Each Si atom contributes one electron to each of in the lattice, generating electron-hole pairs.
the four bond pairs • The pairs move within the matter forming semiconductor
• The outer shell is full, no free electrons, silicon • Some of the electrons can fall into the holes – recombination.
crystal is an insulator
Silicon and Germanium

17
Bonding with the Valence Electrons
 Silicon Crystal
• → At 0°K, each electron is in its lowest possible energy state, and
each covalent bounding position is filled.

•→If a small electric field is applied, the electrons will not move →
silicon is an insulator
Silicon Atom Diagram at 0°K
 Intrinsic Silicon
• → If the temperature increases, the valence electrons will gain
some thermal energy, and breaks free from the covalent bond
→ It leaves a positively charged hole
• → In order to break from the covalent bond, a valence
electron must gain a minimun energy Eg: Bandgap energy
Silicon Atom Diagram at Ambient
Temperature
 Semiconductor Constants

•The concentration of electrons and holes directly influence the magnitde

of the current
• In an intrinsic semiconductor (a single crystal semiconductor) the densities
of holes and electrons are equal.
 Extrinsic Semiconductor / Doping
The characteristics of a semiconductor material can be altered significantly by the
addition of specific impurity atoms to the relatively pure semiconductor
material
These impurities, although only added at 1 part in 10 million, can alter the band
structure sufficiently to totally change the electrical properties of the material

A semiconductor material that has been subjected to the doping process is called an
extrinsic material

There are two extrinsic materials

• n -type
• p -type
n-type Semiconductor
• Both n -type and p -type materials are formed by adding a predetermined
number of impurity toms to a silicon base

• An n -type material is created by introducing impurity elements that have

five valence electrons ( pentavalent), such as antimony , arsenic , and
phosphorus

• Diffused impurities with five valence electrons are called donor atoms
• The four covalent bonds are still present

• There is, however, an additional fifth electron due to the impurity atom,
which is unassociated with any particular covalent bond

• This remaining electron, loosely bound to its parent (antimony) atom, is

relatively free to move within the newly formed n -type material

• The inserted impurity atom has donated a relatively “free” electron to the
structure
Effect of donor impurities on the energy band structure.
N-Type Semiconductor
p-type Semiconductor
• The p -type material is formed by doping a pure germanium or
silicon crystal with impurity atoms having three valence electrons.
• The elements most frequently used for this purpose are boron ,
gallium , and indium
• Diffused impurities with three valence electrons are called acceptor
atoms.
• There is now an insufficient number of electrons to complete the covalent bonds of
the newly formed lattice

• The resulting vacancy is called a hole and is represented by a small circle or a plus
sign, indicating the absence of a negative charge

• The resulting vacancy will readily accept a free electron

• The diffused impurities with three valence electrons are called acceptor atoms.
p-type Semiconductor
 Direct and Indirect Energy BandGap
In semiconductor physics, the band gap of a semiconductor can be of two basic types:
• Direct band gap
• Indirect band gap

Indirect Bandgap:
• The minimal-energy state in the conduction band and the maximal-energy state in
the valence band are each characterized by a certain crystal momentum (k-vector) in
the Brillouin zone.
• If the k-vectors are different, the material has an “indirect gap”
Direct Bandgap
• The band gap is called "direct" if the crystal momentum of electrons and holes is the same
in both the conduction band and the valence band; an electron can directly emit a
photon.

Examples of direct bandgap materials:

Amorphous silicon, InAs and GaAs
Examples of Indirect bandgap materials :
Crystalline Silicon and Ge.
 Elemental and Compound Semi Conductors
• The elemental semiconductors are those composed of single species of atoms, such
as silicon (Si), germanium (Ge), and tin (Sn) in column IV and selenium (Se) and tellurium (Te)
in column VI of the periodic table
• There are, however, numerous compound semiconductors, which are composed of two or more
elements
Example: Gallium arsenide (GaAs), for example, is a binary III-V compound, which is a combination
of gallium (Ga) from column III and arsenic (As) from column V

They also can be formed by elements from two columns, such as aluminum gallium arsenide (AlxGa1
− xAs)
INTRINSIC SEMICONDUCTORS

• The CB is separated from the

VB by an energy gap Eg,
called the bandgap.
• The energy level Ev marks the
top of the VB and Ec marks
the bottom of the CB.
• The energy distance from Ec
to the vacuum level, the width
of the CB, is called the
electron affinity χ.
ELECTRONS AND HOLES
• The only empty electronic states in the silicon crystal are in the CB
• An electron placed in the CB is free to move around the crystal and also respond to an applied
electric field because there are plenty of neighboring empty energy levels.
• An electron in the CB can easily gain energy from the field and move to higher energy levels
because these states are empty. Generally we can treat an electron in the CB as if it were free
within the crystal
• Since the only empty states are in the CB, the excitation of an electron from the VB requires a
minimum energy of Eg.
• Figure shows what happens when a photon of energy hf > Eg is incident on an electron in the
VB.
• This electron absorbs the incident photon and gains sufficient energy to surmount the
energy gap Eg and reach the CB. Consequently, a free electron and a “hole,”
corresponding to a missing electron in the VB, are created. In some semiconductors such
as Si and Ge, the photon absorption process also involves lattice vibrations
Thermal Generation
• In the absence of radiation, there is an electron–hole generation process going on in
the sample as a result of thermal generation.

• Due to thermal energy, the atoms in the crystal are constantly vibrating, which
corresponds to the bonds between the Si atoms being periodically deformed.
• When a wandering electron in the CB meets a hole in the VB, the electron has
found an empty state of lower energy and therefore occupies the hole

• The electron falls from the CB to the VB to fill the hole, as depicted in Figure e and
f. This is called recombination and results in the annihilation of an electron in the
CB and a hole in the VB. The excess energy of the electron falling from CB to VB in
certain semiconductors such as GaAs and InP is emitted as a photon

• In Si and Ge the excess energy is lost as lattice vibrations (heat).

 CONDUCTION IN SEMICONDUCTORS
• When an electric field is applied across a semiconductor as
shown in Figure , the energy bands bend
• The total electron energy E is KE + PE, but now there is an
additional electrostatic PE contribution that is not constant
in an applied electric field
• A uniform electric field Ex implies a linearly decreasing
potential V(x), by virtue of (dV∕dx) = −Ex
• All the energy levels and hence the energy bands must
therefore tilt up in the x direction, in the presence of an
applied field.
• Under the action of Ex, the electron in the CB moves to the left and immediately starts gaining
energy from the field

• When the electron collides with a thermal vibration of a Si atom, it loses some of this energy
and thus “falls” down in energy in the CB

• After the collision, the electron starts to accelerate again, until the next collision, and so on

• We recognize this process as the drift of the electron in an applied field, as illustrated in Figure
• The drift velocity vde of the electron is μeEx where μe is the drift mobility of the electron. In a
similar fashion, the holes in the VB also drift in an applied field, but here the drift is along the
field

• Notice that when a hole gains energy, it moves “down” in the VB because the potential energy of
the hole is of opposite sign to that of the electron.
Since both electrons and holes contribute to electrical conduction, we may write
the current density J, from its definition, as

where μe and μh are the electron and hole drift mobilities.

The drift mobility μe of the electrons in a conductor as

where τe is the mean free time between scattering events and me is the electronic
mass.
 Effective Mass of Electrons
The ideas on electron motion in metals can also be applied to the electron motion in the CB of a semiconductor

We must, however, use an effective mass m*e for the electron in the crystal rather than the mass me in
free space.
A “free” electron in a crystal is not entirely free because as it moves it interacts with the potential energy (PE) of the ions in
the solid and therefore experiences various internal forces
The effective mass m*e accounts for these internal forces in such a way that we can relate the acceleration a of the electron
in the CB to an external force Fext (e.g., −eEx) by
Fext = m*e a
just as we do for the electron in
vacuum by Fext = mea.
We can now speculate on whether the hole can also have a mass
As long as we view mass as resistance to acceleration, that is, inertia, there is no reason why the
hole should not have a mass
Accelerating the hole means accelerating electrons tunneling from bond to bond in the opposite
direction
Therefore, it is apparent that the hole will have a nonzero finite inertial mass because otherwise
the smallest external force will impart an infinite acceleration to it. If we represent the effective
mass of the hole in the VB by m*h , then the hole drift mobility will be

where τh is the mean free time between scattering events for holes.
For the current density further, we can write the conductivity of a semiconductor as

where n and p are the electron and hole concentrations in the CB and VB, respectively.
This is a general equation valid for all semiconductors.
ELECTRON AND HOLE CONCENTRATIONS
The general equation for the conductivity of a semiconductor, depends on n the
electron concentration, and p, the hole concentration.

The general equation that determines the free electron

and hole concentrations

where Eg= Ec − Ev is the bandgap energy

We define gcb(E) as the density of states in the CB, that is, the number of states
per unit energy per unit volume. The probability of finding an electron in a state
with energy E is given by the Fermi–Dirac function f (E)
Nc is a constant, that is, independent of the Fermi energy, and is called the effective density of states
at the CB edge.

Notice that Nc on the effective mass and has a small temperature dependence

If we take all the states in the conduction band and replace them with an effective concentration
Nc (number of states per unit volume) at Ec and then multiply this simply by the Boltzmann
probability function, f (Ec) = exp[−(Ec − EF)∕kT], we obtain the concentration of electrons at Ec, that
is, in the conduction band.

Nc is thus an effective density of states at the CB band edge.

We can carry out a similar analysis for the concentration of holes in the VB.

Multiplying the density of states gvb(E) in the VB with the probability of occupancy
by a hole [1 − f (E)], that is, the probability that an electron is absent, gives pE,
the hole concentration per unit energy. Integrating this over the VB gives the hole
concentration
 First, we note that this is a general expression in which the right-hand side, behaves as if it
were a constant for a given material at a given temperature; it depends on the bandgap
Eg but not on the position of the Fermi level.

In the special case of an intrinsic semiconductor, n = p, which we can denote as ni, the
intrinsic concentration, so that

we therefore have

This is a general equation that is valid as long as we have thermal equilibrium.

• If we somehow increase the electron concentration, then we inevitably reduce
the hole concentration

• The constant ni has a special significance because it represents the free

electron and hole concentrations in the intrinsic material.
• An intrinsic semiconductor is a pure semiconductor crystal in which the electron
and hole concentrations are equal
• By pure we mean virtually no impurities in the crystal. We should also exclude crystal
defects that may capture carriers of one sign and thus result in unequal electron and hole
concentrations
• Clearly in a pure semiconductor, electrons and holes are generated in pairs by thermal
excitation across the bandgap
• It must be emphasized that Equation

• is generally valid and therefore applies to both intrinsic and nonintrinsic (n ≠ p)

semiconductors.
• When an electron and hole meet in the crystal, they “recombine.” The electron falls
in energy and occupies the empty electronic state that the hole represents.

• Consequently, the broken bond is “repaired,” but we lose two free charge carriers.

• Recombination of an electron and hole results in their annihilation

• In a semiconductor we therefore have thermal generation of electron–hole pairs by
thermal excitation from the VB to the CB, and we also have recombination of
electron–hole pairs that removes them from their conduction and valence bands,
respectively

• The rate of recombination R will be proportional to the number of electrons and

also to the number of holes. Thus
• R ∝ np
 The rate of generation G will depend on how many electrons are available for excitation at Ev, that is,
Nv; how many empty states are available at Ec, that is, Nc; and the probability that the electron will
make the transition, that is,

so that

Since in thermal equilibrium we have no continuous increase in n or p, we must

have the rate of generation equal to the rate of recombination, that is, G = R.
Problem
 EXTRINSIC SEMICONDUCTORS
• By introducing small amounts of impurities into an otherwise pure Si crystal, it is possible to
obtain a semiconductor in which the concentration of carriers of one polarity is much in
excess of the other type. Such semiconductors are referred to as extrinsic semiconductors vis-
à-vis the intrinsic case of a pure and perfect crystal.
• For example, by adding pentavalent impurities, such as arsenic, which have a valency of
more than four, we can obtain a semiconductor in which the electron concentration is
much larger than the hole concentration. In this case we will have an n-type
semiconductor.
• If we add trivalent impurities, such as boron, which have a valency of less than four, then we find
that we have an excess of holes over electrons. We now have a p-type semiconductor.
n-TYPE DOPING
p-TYPE DOPING
Problem

Solution
Problem

Solution
Equilibrium Carrier Concentration

• Semiconductors contain majority and minority carriers. The more abundant charge
carriers are the majority carriers; the less abundant are the minority carriers.
• The equilibrium carrier concentration can be increased through doping.
• The total number of carriers in the conduction and valence band is called the
equilibrium carrier concentration.
• The product of minority and majority charge carriers is a constant.
• The number of carriers in the conduction and valence band with no externally applied
bias is called the equilibrium carrier concentration.

• For majority carriers, the equilibrium carrier concentration is equal to the intrinsic
carrier concentration plus the number of free carriers added by doping the
semiconductor.

• Under most conditions, the doping of the semiconductor is several orders of

magnitude greater than the intrinsic carrier concentration, such that the number of
majority carriers is approximately equal to the doping.

• At equilibrium, the product of the majority and minority carrier concentration is a

constant, and this is mathematically expressed by the Law of Mass Action.
The above equations show that the number of minority carriers decreases as the doping level
increases. For example, in n-type material, some of the extra electrons added by doping the material
will occupy the empty spots (i.e., holes) in the valence band, thus lowering the number of holes.
Charge carrier statistics
Quasi Equilibrium and Quasi Fermi Level
• When a semiconductor is in thermal equilibrium,
the distribution function of the electrons at the
energy level of E is presented by a Fermi–Dirac
distribution function.

• In this case the Fermi level is defined as the level

in which the probability of occupation of electron
at that energy is 1∕2. • When a disturbance from a thermal
equilibrium situation occurs, the
• In thermal equilibrium, there is no need to populations of the electrons in the
distinguish between conduction band, quasi- conduction band and valence band
Fermi level and valence band quasi-Fermi level as change.
they are simply equal to the Fermi level.
• If the disturbance is not too great or not changing too quickly, the bands each relax
to a state of quasi-thermal equilibrium.

• Because the relaxation time for electrons within the conduction band is much lower
than across the band gap, we can consider that the electrons are in thermal
equilibrium in the conduction band.

• This is also applicable for electrons in the valence band (often understood in terms
of holes)

• . We can define a quasi Fermi level and quasi temperature due to thermal
equilibrium of electrons in conduction band, and quasi Fermi level and quasi
temperature for the valence band similarly.