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Band theory of solids

Conductivity in intrinsic smiconductors
Conductivity in extrinsic smiconductors
Effect of temperature on conductivity
Drude theory
Hall effect

Band theory of solids

Quantum physics describes the states of electrons in an
atom according to the four-fold scheme of quantum numbers. The
quantum numbers describe the allowable states electrons may
assume in an atom. Individual electrons may be described by the
combination of quantum numbers.
The electrons may change their statuses, given the presence
of available spaces for them to fit, and available energy. Since
shell level is closely related to the amount of energy that an
electron possesses, leaps between shell (and even subshell)
levels requires transfers of energy. If an electron is to move into a
higher-order shell, it requires that additional energy be given to
the electron from an external source. Conversely, an electron
leaping into a lower shell gives up some of its energy.
Not all leaps are equal. Leaps between different shells
require a substantial exchange of energy, but leaps between
subshells or between orbitals require lesser exchanges
When atoms combine to form substances, the outermost
shells, subshells, and orbitals merge, providing a greater number
of available energy levels for electrons to assume. When large
numbers of atoms are close to each other, these available energy
levels form a nearly continuous band wherein electrons may

Figure 1: Electron band overlap in metallic elements.

It is the width of these bands and their proximity to existing

electrons that determines how mobile those electrons will be
when exposed to an electric field. In metallic substances, empty
bands overlap with bands containing electrons, meaning that
electrons of a single atom may move to what would normally be a
higher-level state with little or no additional energy imparted.
Thus, the outer electrons are said to be free, and ready to move
at the beckoning of an electric field.
Band overlap will not occur in all substances, no matter how
many atoms are close to each other. In some substances, a
substantial gap remains between the highest band containing
electrons (the so-called valence band) and the next band, which is
empty (the so-called conduction band). See Figure 2.

Figure 2: Electron band separation in insulating substances

Materials that fall within the category of semiconductors

have a narrow gap between the valence and conduction bands.
Thus, the amount of energy required to motivate a valence
electron into the conduction band where it becomes mobile is
quite modest. (Figure 3)

Figure 3: Electron band separation in semiconducting substances, (a)

multitudes of semiconducting close atoms still results in a significant band
gap, (b) multitudes of close metal atoms for reference.

At low temperatures, little thermal energy is available to

push valence electrons across this gap, and the semiconducting
material acts more as an insulator. At higher temperatures,
though, the ambient thermal energy becomes enough to force
electrons across the gap, and the material will increase
conduction of electricity.

Pure semiconductors are relatively good insulators as
compared with metals, though not nearly as good as a true
insulator like glass. To be useful in semiconductor applications,
the intrinsic semiconductor (pure undoped semiconductor) must
have no more than one impurity atom in 10 billion semiconductor
Figure 4(a) shows four electrons in the valence shell of a
semiconductor forming covalent bonds to four other atoms. All
electrons of an atom are tied up in four covalent bonds, pairs of
shared electrons. Electrons are not free to move about the crystal
lattice. Thus, intrinsic, pure, semiconductors are relatively good
insulators as compared to metals.
Thermal energy may occasionally free an electron from the
crystal lattice as in Figure 4(b). This electron is free for conduction
about the crystal lattice. When the electron was freed, it left an

empty spot with a positive charge in the crystal lattice known as a

hole. This hole is not fixed to the lattice; but, is free to move

Figure 4: (a) Intrinsic semiconductor is an insulator having a complete

electron shell. (b)
However, thermal energy can create few electron hole pairs resulting in weak

The free electron and hole both contribute to conduction

about the crystal lattice. That is, the electron is free until it falls
into a hole. This is called recombination. If an external electric
field is applied to the semiconductor, the electrons and holes will
conduct in opposite directions. Increasing temperature will
increase the number of electrons and holes, decreasing the
resistance. This is opposite of metals, where resistance increases
with temperature by increasing the collisions of electrons with the
crystal lattice. The number of electrons and holes in an intrinsic
semiconductor are equal. However, both carriers do not
necessarily move with the same velocity with the application of
an external field. Another way of stating this is that the mobility is
not the same for electrons and holes.
Pure semiconductors, by themselves, are not particularly
useful. Though, semiconductors must be refined to a high level of
purity as a starting point prior the addition of specific impurities.
Semiconductor material pure to 1 part in 10 billion, may
have specific impurities added at approximately 1 part per 10
million to increase the number of carriers. The addition of a
desired impurity to a semiconductor is known as doping. Doping

increases the conductivity of a semiconductor so that it is more

comparable to a metal than an insulator.
Extrinsic semiconductors are made by introducing different
atoms, called dopant atoms, into the crystal.
We can get two types of extrinsic material:
1. n-type: The dopant atoms added to the semiconductor
crystal in this case are donor atoms. For silicon, we can
use phosphorus (P), arsenic (As) or antimony (Sb) as
donors. These are column V elements, with five
electrons in their outermost shell. When these atoms
are included in the silicon crystal, one of the electrons
in this shell can easily jump to the conduction band,
leaving a positively charged atom behind. This process
is sometimes called activation or ionization of the
donor atoms.
The positively charged donor atom that is left
behind after ionization is immobile and does not
contribute to conduction. The electron leaving the atom
by ionization does, and is counted in the electron
concentration n. Because the activation energy is low,
at room temperature almost all of the donor atoms
included in the crystal will give an electron to the
conduction band.
2. p-type: The dopant atoms in this case are acceptor
atoms. For silicon, we can use boron (B), Aluminum (Al)
and Gallium (Ga) as acceptors. These are column III
elements, with three electrons in their outermost shell.
When these atoms are included in the silicon crystal,
one of the electrons in the silicon valence band can
easily jump to the valence shell of one of the acceptor
atoms, leaving a hole behind and making the acceptor
atom negatively charged.

The negatively charged acceptor atom after an

electron joins its valence shell is immobile and does not
contribute to conduction. The hole left behind by that
electron does, and is counted in the hole concentration
p. Because the activation energy is low, at room
temperature almost all of the acceptor atoms included
in the crystal will accept an electron from the valence

Conductivity in Intrinsic Semiconductors

Conduction takes place in an intrinsic semiconductor due to
the movement of holes and electrons. Electrons and holes being
deflected by atoms and lattice defects, take an irregular path
through the conductor. The average rate at which they move is
called the drift velocity. The drift velocity per electric field
represents the mobility of the charge carrier.
The conductivity of the semiconductor due to holes (p) is
given by p=p.e.h, where p represents the number of holes per
unit volume of the semiconductor, h represents the mobility of
the hole and e is the charge on the electron (1.6 x 10-19 Coulomb).
The conductivity of the semiconductor due to electrons (e)
is given by e=n.e.e, where n represents the number of
electrons per unit volume of the semiconductor, e represents the
mobility of the electrons and e is the charge on the electron (1.6 x
10-19 Coulomb).
Therefore, the Total Conductivity of the semiconductor,
= p + e= p.e.h + n.e.e = e[p.h + n.e].
The temperature dependence of the intrinsic concentration
of electrons and holes in the semiconductor (ni) is given by ni =
n0.exp(-Eg/2kt) where n0 is constant at a given temperature, Eg
is the energy gap, k is the Boltzmann constant and T is the

temperature in Kelvin. The mobility of charge carriers (electrons

and holes) vary as T-m over a temperature range of 100 to 400 K
(For Si, m = 2.5 for electrons and 2.7 for holes and for Ge, m =
1.66 for electrons and 2.33 for holes).

Conductivity in Extrinsic Semiconductors:

In n-type semiconductors, hole concentration (p) is
negligible and electron concentration (n) is far greater than the
hole concentration. But the concentration of the electrons (n) will
be approximately equal to the concentration of donor atoms (ND).
But from the law of mass action (under thermal equilibrium), p x
n remains constant and also p x n remains independent of the
amount of doping by Donor (or Acceptor) impurities.
n x p = ni2 where ni represents the intrinsic concentration.
Thus in an n-type semiconductor, the concentration of holes is
given by p = ni2/n = ni2/ND.
Total Conductivity of the semiconductor, = p + e=
p.e.h + n.e.e = e[p.h + n.e]
But in n-type semiconductors, n>>p or p.h << n.e and
Therefore, = n.e.e = e.ND.e
In p-type semiconductors, p>>n or p.h >> n.e and
p=NA, the concentration of the Acceptor atoms. Therefore, the
conductivity of p-type semiconductor p is given by = NA.e.h.

Effect of Temperature on the Conductivity

n-type Semiconductor: As temperature increases, the
number of electrons jumping from the donor level to the
conduction band increases and thus the conductivity increases,
this rise in conductivity with temperature takes place only up to a
particular level till all the electrons from the donor level are
transferred to the conduction band. Thereafter, the conductivity

remains constant because all the electrons of the donor level are
now in the conduction band. This is called donor exhaustion
zone. Beyond this zone, increase in conductivity with rise in
temperature occurs entirely due to intrinsic conductivity.
p-type Semiconductor: As temperature increases, the
number of electrons jumping from the valence band to the
acceptor level increases and thus the conductivity increases, this
rise in conductivity with temperature takes place only up to a
particular level till all the acceptor atoms receive electrons from
the valence band and reach the acceptor saturation zone. In this
temperature zone, the conductivity remains constant since the
accepter level is now completely filled or maximum numbers of
holes have already been formed in the valence band. This is
called acceptor exhaustion zone. Thereafter, the intrinsic
conductivity becomes predominant on further rise in temperature.

The Drude theory

Before considering the effect of magnetic fields on
conductors, we need some model to describe the flow of currents
in response to electric fields. To do so we will use the Drude
theory of conductors. This is a simple classical model, and many
of its concepts extend to the quantum case.
The Drude model envisions a conductor as a gas of free
current-carrying charges.
The freely moving carriers suffer randomizing collision events on
average every seconds. The parameter is called the relaxation
time (One might think that collisions occur more often the faster
the particles are moving, so that could depend on the average
particle velocity V. However, well see that the thermal velocities
the carriers actually move with between collisions is very much
greater than V.), and is the only feature describing the (otherwise
unspecified) collision events.

Fig. 5: Example of a charge carriers random trajectory after four collision


Figure 5 indicates the basic idea. The solid black lines show a
specific trajectory of a charge carrier in the absence of any
external force. It proceeds with some constant velocity in some
direction until it experiences a thermal collision. The red dashed
lines indicate how each of these trajectories would be influenced
by a constant external force F: The particle now accelerates in the
direction of F consistent with its initial conditions dictated by the
last collision. When these paths are assembled, we see that F has
caused a net displacement x after the four collisions; the particle
has begun to drift in the direction of F.
For macroscopic quantities, only averages over all particles
are of interest. With the above assumptions, one can obtain an
equation of motion for the average momentum P, given by
dP P
+ =F

Here, P is interpreted as follows: a group of charge carriers

(say 1023 ) all have some specific average momentum P0 at t =
0, the groups average momentum P(t) at any future time is then

determined by this initial value and the first order equation

above. The average momentum P of the group evolves in time
like a single carrier subjected to the average external force F per
particle, but subjected additionally to a resistive damping. This
damping is a consequence of all the random collisions; when is
large collisions are uncommon.
For a constant force a terminal momentum is reached
independent of the initial conditions. This is in complete analogy
with the motion of an object falling through air: the object either
speeds up or slows down enough so that the air-resistance
counteracts its weight. In our case P becomes constant in time as
PF. Thus, if we apply a force F and wait long enough, a
steady state develops where, on average, each particle drifts with
a constant speed in the direction of F. In response to a constant
electric field (F = qE) a constant current of charge carriers is
established. The current density J is the average charge crossing
an (oriented) area per unit time. If there are n charge carriers per
unit volume with average (drift) velocity V=P/m, the associated
current density is J = nqV = nq x qE/m. Thus, we arrive at
Ohms law


q n

or E= J

where is the conductivity, and = 1/ the resistivity, of the


q2 n

Note that is inversely proportional to the relaxation time.

Since we expect that decreases with increasing temperature
(carrier collisions occur more often), we expect a metals
resistance to increase with temperature (which it does).
Now, consider what happens when we apply a magnetic field
B to a thin strip of material in which a current I is flowing, as
shown in Fig. 6.

Fig. 6: Hall Effect geometry again; the strip has a thickness , length l,
and height h.

Here, the applied field B is directed only in the z direction (into

the paper). The x-component of E drives the steady current I in
the x direction, and a y-component of E must appear to balance
the Lorentz force on the charge carriers: The equation of motion
(in SI units) is
dV 1
+ V= [ E+ VB]

Again, when a steady current flow is established the time

derivative of V at each point vanishes (Remember that V is not
the velocity of any given particle, but an average. Note that F is a
velocity-dependent force. When averaged, the single-particle
velocity v is replaced by the average V). Multiplying the above by
qn, the time-independent result can be written in terms of J as
J = E+


With the setup shown in Fig. 6 steady current can only flow
in the x direction J=J x^ , while B=B z^ . Performing the cross
product and resolving into components gives

Ex =J


Ey =


Along with Ohms law describing current flow along the strip,
we now have a component to the electric field in the transverse
direction proportional to J and B. The Hall Coefficient (or
Constant) RH is officially defined as this proportionality constant:
Ey = R H JB

The Drude model thus predicts

RH =


The Hall constant thus gives a direct indication of the sign of

the charge carriers; it is negative for electrons (q = -e) and
positive for holes (q = +e). Note its independence of our model
parameter : it turns out from a quantum mechanical analysis of
the problem that this formula generalizes to a wide class of
materials. Note also that the Hall field is large for low carrier
concentrations: we might expect that the effect will be harder to
detect in metals than in semi-conductors.
The Hall field Ey can be measured by the voltage difference
between points a and b (Fig. 6) since VH = Va Vb = Eyh, where h
is the sample height. The total current flowing through the strip is
I = J x (h). Thus, in terms of laboratory quantities we have the
equivalent definition of RH in terms of the Hall voltage and the
VH =


Where, again, is the thickness of the strip.

Hall Effect

The Hall Effect is due to the nature of the current in a

conductor. Current consists of the movement of many small
charge carriers, typically electrons, holes, ions or all three. When
a magnetic field is present that is not parallel to the direction of
motion of moving charges, these charges experience a force,
called the Lorentz force. When such a magnetic field is absent,
the charges follow approximately straight, 'line of sight' paths
between collisions with impurities, phonons, etc. However, when a
magnetic field with a perpendicular component is applied, their
paths between collisions are curved so that moving charges
accumulate on one face of the material. This leaves equal and
opposite charges exposed on the other face, where there is a
scarcity of mobile charges. The result is an asymmetric
distribution of charge density across the Hall element, arising
from a force that is perpendicular to both the 'line of sight' path
and the applied magnetic field. The separation of charge
establishes an electric field that opposes the migration of further
charge, so a steady electrical potential is established for as long
as the charge is flowing.
For a simple metal where there is only one type of charge
carrier (electrons) the Hall voltage VH can be computed by setting
net Lorentz force to zero as below

F=q(E + vxB), where E = VH/w, v = L/T, I = Q/T, Q =

Therefore, VH = - IB/nte where I is the current across the
plate length, B is the magnetic field, t is the thickness of the

plate, is the elementary charge, and n is the charge carrier

density of the carrier electrons.
The Hall coefficient is defined as
RH = Ey/jxB, where j is the current density of the carrier
electrons, and Ey is the induced electric field. In SI units, this
RH = Ey/jxB = VHt/IB = - 1/ne
(The units of RH are usually expressed as m3/C, or cm/G, or
other variants.) As a result, the Hall Effect is very useful as a
means to measure either the carrier density or the magnetic field.
Hall Effect in semiconductors when a currentcarrying semiconductor is kept in a magnetic field, the charge
carriers of the semiconductor experience a force in a direction
perpendicular to both the magnetic field and the current. At
equilibrium, a voltage appears at the semiconductor edges.
The simple formula for the Hall coefficient given above becomes
more complex in semiconductors where the carriers are generally
both electrons and holes which may be present in different
concentrations and have different mobilities. For moderate
magnetic fields the Hall coefficient is
RH= (p.h2 - n.e2)/[e(p.h + n.e)]


1. Switch 'ON' the Hall Effect set-up and adjustment current (say
few mA).

2. Switch over the display to voltage side. There may be some

voltage reading even outside the magnetic field. This is due to
imperfect alignment of the four contacts of the Hall Probe and is
generally known as the 'Zero field Potential'. In case its value is
comparable to the Hall Voltage it should be adjusted to a
minimum possible (for Hall Probe (Ge) only). In all cases, this
error should be subtracted from the Hall Voltage reading.
3. Now place the probe in the magnetic field and switch on the
electromagnet power supply and adjust the current to any
desired value. Rotate the Hall probe till it become perpendicular
to magnetic field. Hall voltage will be maximum in this
4. Measure Hall voltage and thermo emf for the corresponding
heater current.
5. Measure the Hall voltage as a function of magnetic field keeping
a suitable value of current as constant. Plot graph.
6. Measure the magnetic field by the Gaussmeter.

Sample : p-type Germanium
Residual magnetic field =90 gauss
Set magnetic field =3090 gauss
Probe current = 4 mA
Room Temp = 17C

Observation Table :


Temp. vs Hall Coefficient