Valence and Conduction Bands

Valence electrons : The outermost electrons of an atom i.e. those in the shell furthermost from the nucleus are
called valence electrons and have the highest energy or least binding energy.

Valence band: The band of energy occupied by the valence electrons is called the valence band and is, obviously,
the highest occupied band. It may be completely filled or partially filled with electrons but never empty.

Conduction band: The

next higher permitted
energy band is called
the conduction band
and may either be
empty or partially Eg Energy gap
filled with electrons. In
fact, it may be defined
as the lowest unfilled
energy band.
Fig-1: bands in a semiconductor

Forbidden energy gap: In conduction band, electrons can move freely and hence are known as conduction
electrons. The gap between these two bands is known as the forbidden energy gap (Eg). The electrons cannot exist
in the energy gap. Is is 0.72 eV for Ge and 1,1 eV for Si. All bands are shown in fig-1

Insulators, Conductors and Semiconductors

(i) Insulators. Stated simply, insulators are those materials in which valence electrons are bound very tightly to
their parents atoms, thus requiring very large electric field to remove them from the attraction of their nuclei. In
other words, insulators have no free charge carriers available with them under normal conditions.

In terms of energy bands, it means that insulators (Shown in fig-2a)

1. have a full valence band
2. have an empty conduction band
3. have a large energy gap (of several eV) between them

For conduction to take place, electrons must be given sufficient energy to jump from the valence band to the
conduction band.

(ii) Conductors. Put in a simple way, conducting materials are those in which plenty of free electrons are
available for electric conduction. In terms of energy bands, it means that electrical conductors are those which
have overlapping valence and conduction bands as shown in Fig. 2b.

(iii) Semiconductors. A semiconductor material is one whose electrical properties lie in between those of
insulators and good conductors. Examples are : germanium and silicon. It is shown in fig-2c.
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 Fig-2: Band diagram of (a) Insulator, (b) Metal and (c) Semiconductor

In terms of energy bands, semiconductors can be defined as those materials which

1. have almost an empty conduction band
2. almost filled valence band
3. a very narrow energy gap (of the order of 1 eV) separating the two.

At 0ºK, there are no electrons in the conduction band and the valence band is completely filled. However, with
increase in temperature, width of the forbidden energy bands is decreased so that some of the electrons are
liberated into the conduction band. In other words, conductivity of semiconductors increases with temperature.

Intrinsic Semiconductors

An intrinsic semiconductor is one which is made of the semiconductor material in its extremely pure form.
Common examples of such semiconductors are : pure germanium and silicon which have forbidden energy gaps
of 0.72 eV and 1.1 eV respectively.

Hole Formation in Semiconductors

The absence of electron in a bond
is called hole which is a positive
charge carrier. The formation is
explained below. Suppose the
covalent bond is broken at A and the
electron has moved through the
crystal lattice leaving behind a hole
in the covalent bond. An electron at
B may jump into the vacant hole at A
and later, an electron at C may jump Fig-3: Formation of electron and hole currents in a semiconductor

into the hole at B and so on. In this

way, by a succession of electron movements, a hole will appear at G and a negative charge would have moved from
G to A (fig-3).

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Charge carriers in an intrinsic semiconductor: An intrinsic semiconductor may be defined as one in which the
number of conduction electrons is equal to the number of holes. When a valence electron drifts from valence to
conduction band, a vacancy is created in the valence band and is known as hole. In an intrinsic semiconductor, the
number of holes in the valence band is equal to the number of electrons in the conduction band.

An electron is a negatively charge particle, Thus a hole created due the drift of electron is said to be positively
charge. Therefore, both electron and hole are charge carriers in intrinsic semiconductor.
There are two types of charge carriers in an intrinsic semiconductor.
 Negative charge carriers (electrons)
 Positive charge carriers (holes)
Current in intrinsic semiconductor = hole current + electron current

Fermi Level in an Intrinsic Semiconductor:

Fermi level : It is an energy level in crystal which lies between conduction

band and valence band. In intrinsic semiconductor, the Fermi level lies exactly
midway of conduction and valance bands as shown in fig-4.

The eV, unit of very small energy:

Fig-4: Fermi level in an intrinsic
semiconductor
The charge on a single electron is 1.6 × 10−19 𝐶. So one electron volt is
defined as the energy required by an electron to fall through a potential of one
volt

∴ 𝟏 𝒆𝑽 = 𝟏. 𝟔 × 𝟏𝟎−𝟏𝟗 𝑪 × 𝟏 𝒗𝒐𝒍𝒕 = 𝟏. 𝟔 × 𝟏𝟎−𝟏𝟗 𝑱

Extrinsic Semiconductors

Those intrinsic semiconductors to which some suitable impurity or doping

agent or dopant has been added in extremely small amounts (about 1 part in
108) are called extrinsic or impurity semiconductors.

The usual doping agents are :

1. Pentavalent atoms having five valence electrons (arsenic, antimony,
phosphorus) or
2. Trivalent atoms having three valence electrons (gallium, indium,
aluminium, boron).

Donor : Pentavalent doping atom is known as donor atom because it

donates or contributes one electron
to the conduction band of pure germanium.

Acceptor: The trivalent atom, on the other hand, is called acceptor atom
because it accepts one electron from the germanium atom.
Depending on the type of doping material used, extrinsic semiconductors Fig-5: N-type semiconductor and its
can be sub-divided into two classes: band diagram
(i) N-type semiconductors and (ii) P-type semiconductors.

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N-type Extrinsic Semiconductor. This type of semiconductor is obtained when
a pentavalent material like antimonty (Sb) is added to pure germanium crystal.
As shown in Fig-5a each antimony atom forms covalent bonds with the
surrounding four germanium atoms with the help of four of its five electrons.
The fifth electron is superfluous and is loosely bound to the antimony atom.

Hence, it can be easily excited from the valence band to the conduction band by
the application of electric field or increase in thermal energy. Thus, practically
every antimony atom introduced into the germanium lattice, contributes one
conduction electron into the germanium lattice without creating a positive hole.
Antimony is called donor (Nd ) impurity and makes the pure germanium an N-
type (N for negative) extrinsic semi-conductor.
The energy band of N-type semiconductor is shown in fig-5b

P-type Extrinsic Semiconductor. This type of semiconductor is obtained when

traces of a trivalent like boron (B) are added to a pure germanium crystal. In this
case, the three valence electrons of boron atom form covalent bonds with four Fig-6: P-type semiconductor and
surrounding germanium atoms but one bond is left incomplete and gives rise to its band diagram

a hole as shown in Fig. 4.

Thus, boron which is called an acceptor (Na ) impurity causes as many positive holes in a germanium crystal as
there are boron atoms thereby producing a P-type (P for positive) extrinsic semiconductor.

In this type of semiconductor, conduction is by the movement of holes in the valence band. Accordingly, holes
form the majority carriers whereas electrons constitute minority carriers. The process of conduction is called
‘deficit’ conduction. The energy band diagram is shown in fig-5

Number of electrons in conduction band is given by

𝑁𝑑 − 𝑁𝑎 𝑁𝑑 − 𝑁𝑎 2
𝑛= + √( ) + 𝑛𝑖2
2 2

Number of holes in valence band is given by

𝑁𝑎 − 𝑁𝑑 𝑁𝑎 − 𝑁𝑑 2
𝑝= + √( ) + 𝑛𝑖2
2 2

Majority and Minority Carriers Fig-7: Majority and minority carriers in extrinsic
semiconductor
In a piece of pure germanium or silicon, no free charge carriers
are available at 0ºK. However, as its temperature is raised to room temperature, some of the covalent bonds are
broken by heat energy and as a result, electron-hole pairs are produced. These are called thermally-generated charge
carriers.

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An intrinsic of pure germanium can be converted into a P- type semiconductor by the addition of an acceptor
impurity which adds a large number of holes to it. Hence, a P-type material contains following charge carriers:
(a) large number of positive holes—most of them being the added impurity holes with only a very small number of
thermally generated ones;
(b) a very small number of thermally-generated electrons. Obviously, in a P-type material, the number of holes
(both added and thermally-generated) is much more than that of electrons. Hence, in such a material, holes constitute
majority carriers and electrons form minority carriers as shown in Fig. 7a and 7b

Compensation and Space Charge Neutrality

When the concept of doping was introduced, it is assumed the

material contained either Nd donors or Na acceptors, so that the
extrinsic majority carrier concentrations were n0 = Nd or po = Na,
respectively, for the n-type or p-type material. Therefore, materials
are electrically neutral.

A semiconductor for which both donors and acceptors are present,

but Nd> Na. The predominance of donors makes the material n-type.

Assume an acceptor state is filled with a valence band electron with

a hole resulting in the valence band. This hole is then filled by Fig-8: Band diagram of compensated
semiconductor
recombination with one of the conduction band electrons. The resultant
concentration of electrons in the conduction band to be Nd  Na instead of the total Nd. This process is called
compensation.

By this process it is possible to begin with an n-type semiconductor and add acceptors until Na = Nd and no
donated electrons remain in the conduction band. In such compensated material, n0 = ni = p0 . With further acceptor
doping, the semiconductor becomes p-type with a hole concentration of Na – Nd. If the material is to remain
electrostatically neutral, the sum of the positive charges (holes and ionized donor atoms) must balance the sum of
the negative charges (electrons and ionized acceptor atoms):
𝑝 𝑜 + 𝑁𝑑+ = 𝑛𝑜 + 𝑁𝑎−
Carrier drift:

An electric field applied to a semiconductor will

produce a force equal to 𝐹𝑒 = ± 𝑒𝐸 on an electron /
hole. The charge will experience a net acceleration and
a net movement due to the force as shown in fig-9.
The net movement of charges due to the application of
electric field is called drift. This net drift of charges Fig-9 : Movement of charge due to applied electric field
produce drift current.

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Donor ionization energy: It is the energy necessary to elevate an electron
from donor level to conduction band. Example: ionization energy of As
donor in Si is 0.05 eV.
Acceptor ionization energy: It is the energy necessary to elevate an
electron from valence band to acceptor level. Example: ionization energy
of Boron acceptor in Si is 0.045 eV.

Mobility of charge carriers: The drift velocity is proportional to electric

field strength E, the constant of proportionality being called mobility μ.
The exact relation between the two is 𝑣𝑑 = 𝜇 𝐸.

Drift current in a semiconductor : Let us find the value of drift current

(i) Current density due to electron drift is 𝐽𝑒 = 𝑒𝜇𝑒 𝑛𝐸 where 𝜇𝑒 is
electron mobility, n is electron density and E is the electric field strength.
(ii) Current density due to hole drift is is 𝐽ℎ = 𝑒𝜇ℎ 𝑝𝐸 where p is hole
density.
Total current density due to electron and hole drift is
J = 𝐽𝑒 + 𝐽ℎ = 𝑒𝜇𝑒 𝑛𝐸 + 𝑒𝜇ℎ 𝑝𝐸 = e (𝜇𝑒 𝑛 + 𝜇ℎ 𝑝) E

Diffusion: It is gradual flow of charge from a region of high density to a

region of low density. It is a force free process based on non-uniform
distribution of charge carriers in a semiconductor crystal. It leads to an
electric current without the benefit of an applied field.

𝑑𝑝⁄
Current density due to hole diffusion is 𝐽 ℎ = − 𝑒𝐷ℎ 𝑑𝑥 .
Current density due to electron diffusion is 𝐽 𝑒 = 𝑒𝐷𝑒 𝑑𝑛⁄𝑑𝑥 .
Where carrier density gradient = 𝑑𝑛⁄𝑑𝑥, diffusion
constant = D

Combined Drift and Diffusion Currents:

In semiconductors, drift and diffusion processes may be
present simultaneously. The expressions for total electron
and hole densities become.

𝑑𝑝
𝐽 𝑒 = 𝑒𝜇𝑒 𝑛𝐸 + 𝑒𝐷𝑒 𝑑𝑛⁄𝑑𝑥 and 𝐽 ℎ = 𝑒𝜇ℎ 𝑝𝐸 − 𝑒𝐷ℎ ⁄𝑑𝑥

Electron hole generation and recombination: recombination results from the collision of an electron with a hole.
The process is essentially the return of a free conduction electron to the valence band and is accompanied by the
emission of energy.

In a semiconductor, thermal generation of electron-hole pairs also takes place continuously. Hence, there is net
recombination rate given by the difference between the recombination and generation rates.

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Relation Between D and μ : Both diffusion constant and mobility are statistical thermodynamic phenomena and
are related to each other by the following equation.
𝑒𝐷𝑒 𝑒𝐷ℎ 𝐷𝑒 𝐷ℎ 𝑘𝑇 𝑇
𝜇𝑒 = 𝑎𝑛𝑑 𝜇ℎ = 𝑜𝑟 = = =
𝑘𝑇 𝑘𝑇 𝜇𝑒 𝜇ℎ 𝑒 11,600
The relationship is known as Einstein’s equation.
At t = 23ºC, T = 300ºK, hence D/μ = 300/11,600 = 1/39 or μ = 39 D

Conductivity of Pure and P-type Germanium: the conductivity of pure semiconductor is given by
𝝈 = 𝒏𝒊 𝒆(𝜇𝑒 + 𝜇ℎ ) = 𝒑𝒊 𝒆 (𝜇𝑒 + 𝜇ℎ )
For P-type semiconductor
𝝈𝒑 = 𝒆(𝒏𝒑 𝜇𝑒 + 𝑝𝑝 𝜇ℎ )

*** See the solved problems in the power point lecture sheet

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