PG Notes Semiconductors (Part - 1)

Physics Galaxy Notes

PG Notes on Semiconductors (Part - 1)

In all electronic devices in our surrounding the most important thing for proper operation of these devices is to control
the flow of charge particles. The material used in these devices must be capable to provide mobile charges and can govern the

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flow of these charges by some specific processes. In this chapter we’ll discuss the basic classification of materials as
conductors, insulators and semiconductors then we’ll discuss the physical properties of semiconductors and semiconductor
devices and how these devices are able to control the flow of mobile charges. First we’ll discuss the energy band theory for
solid structures.

Energy band Diagram

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We know that the potential energy between two charge particles q1 and q2 separated by a distance r is given as
Kq1q2
U= … (1)
r
Similarly in an atom potential energy of an electron in the electric field a nucleus of an atom (charge = + Ze) can be given
as
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KZe 2
U=– … (2)
r
At the distance very close to nucleus, the potential energy approaches to –  and on the surface of an atom at large
values of separation between electron and nucleus, U becomes zero. From equation-(2) we can see that the potential energy
of electron is inversely proportional to r, the distance of electron from nucleus. Thus the curve of variation of potential energy
with distance will be a rectangular hyperbola as shown in figure-1.
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Figure 1

If we carefully analyze the graph in figure-1. We can see that the closest electron in an atom is in 1s orbital. Say the
maximum distance of an electron from nucleus is r1s and the electron energy is E1s and according to classical theory electron
can move between a and b in the figure shown. Similarly the energies electrons in higher orbitals 2s, 2p, 3s etc. are also shown
in figure with respective energies E2s, E2p …… .

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PG Notes Semiconductors (Part - 1)
If we place two atoms very close to each other in such a way that some of their orbitals overlap. Like as shown in figure-2,
3s orbitals of the two atoms overlap each other. For this situation if we plot the energy of electrons in these atoms, the graph
of both the atoms simultaneously can be drawn as shown in figure-2(a)

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Figure 2

In this case the two atoms are brought so close that their 3s orbital gets overlapped and obviously all higher orbitals are
also overlapped as bigger then 3s orbitals. In figure-2(a). We can see that the electrons is 3s orbital of these two atoms can
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now move between g1 to h2 and hence are not attached to a particle atom. Figure-2(b) shows the single energy band diagram
for the two atoms. Between the two atoms at point X in figure-2(a) the two potential energy curve intersects above which all
orbitals get overlapped or we can say that above this point X, electrons in all the orbitals are not restricted to a particular atom.
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These electrons can move in the same orbital of other atom through overlapped region. In figure-2(b) we can see that above
point X all orbitals of both the atoms are represented by a common line like g1h2 for common 3s orbital. If interatomic
separation is decreased, the orbitals which were earlier below point X will come above it and their electrons will also become
free to move in the bigger common orbital.
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Now if we consider a piece of solid, composed of very large number of atoms regularly arranged in a lattice, the resultant
potential energy curve of electron in this solid can be shown by the curve in figure-3.

Here we can see that if we move through the lattice of atoms N1, N2, N3, ……, the potential energy varies periodically with
the interatomic separation. We can also see from the above figure that the electrons in the orbitals which are below the
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overlapping region (Here 1s, 2s, and 2p orbitals) like those positioned at points 1 and 2 are restricted to move only in the
orbitals of localized atoms and are called bound electrons of the lattice. The electrons which are in the orbitals overlapped (3s
and above in this case) like position at point 3 and 4 are not localized at any particular atom, these are free to move through
the overlapping orbitals in the whole lattice, are called free electrons of the lattice. These electrons are in the common
overlapped orbitals of all the atoms of lattice. These electrons have a large freedom to move in the whole lattice structure
which can conduct electricity through the lattice when a potential difference is applied across it, under some particular
conditions we’ll discuss later.

The Conduction Band

The region above the overlapping point of orbitals of atoms i.e. in graph region above point X. Where all existing
electrons can conduct electricity is called region of conduction bands.

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Figure 3

The energy band in a solid containing valance electrons we call valance band, it contains the outer most electrons of the
atoms. The lowest unfilled band of energy level which is just above valance band, we call conduction band in which electrons
can easily flow in the empty states of conduction band.

Energy Bands in Solid Lattice

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We know that in atoms, electrons can occupy only certain energy levels. In a lattice, however, the energy levels are
modified. In lattice it is found that electrons can move within certain energy bands. For example in hydrogen atom the
electrons in the orbitals 1s, 2s, 2p …… have fixed energies or all the electrons which exist in an orbital say 2s, will have same
energies but when several atoms are arranged in a solid lattice, due to their mutual interactions the energy levels for electrons
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are modified to energy band with a specific range of energies. Now in 2s energy band those electron can exist which have their
energies between E2s and E'2s and similarly for other higher energy bands. Figure-4(a) shows the energy levels in an atom and
figure-4(b) shows the similar corresponding energy bands in a solid lattice.
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Figure 4

Conductors Insulators and Semiconductors

An important property of solids is their electrical conductivity, that is the ability for electrons to move freely through the
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solid under the action of an external electric field produced by applying a potential difference across the solid. Some solids,
traditionally called insulators which are poor conductors of electricity like wood, diamond etc. Other solids are good conductors
of electricity. In this group of solids, metals are mainly included like copper, aluminium, silver etc. In between the above two
groups of solids, their is a third category of solids, called semiconductors. Although semiconductors are much poor in
electrical conductivity as compared to metals but it has been discovered that the conductivity of a semiconductors increases
with temperature, while that of metals decreases with temperature. This property of semiconductors made then very useful in
controlling the flow of electrons efficiently and a wide research branch of physics is open for physicist & electronics
engineers as semiconductor physics. Typical semiconductors used are silicon and germanium. Whether a solid is a conductor,
an insulator or a semiconductors, it depends on the energy band structure of solid.

Lets discuss the classification of conductors, insulators and semiconductors on the basis of energy band diagrams of
solid.

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Energy Band Diagrams of Conductors, Insulators and Semiconductors

We know that the electrons in outermost shells of an atom which participate in bond formation are called valence
electrons and this shell is called valance shell. In solids the energy band formed by a series of energy levels containing
valance electrons is called valence band.

Fermi Energy Level

The highest energy level in valance band, which an electron occupies is called Fermi energy level. For example let us
consider the case of a Na atom (Z = 11). In sodium the valence band is the band of 3s orbitals which are partially filled as
shown in figure-5 as its electron configuration is 1s2 2s2 2p6 3s1. Generally fermi energy level is defined at 0 K temperature.

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Figure 5
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At room temperatures and temperatures above 0 K, due to thermal agitations electrons are in energy levels above fermi
energy level in a lattice. At 0 K all energy levels upto fermilevel are filled and those above are empty.

Band Structures of Metals

We know that if a solid has free electrons in its conduction band (the overlapped region of common orbitals). These
electrons can conduct electricity and can be considered as a metal. Thus metals are those in which valence electrons exist in
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conduction band. There are two possibilities of band structure according to energy band theory under which solids are good
conductors of electricity.
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We again consider the case of sodium whose energy band diagram is shown in figure-6. Here the uppermost energy band
is partially filled. But when an electric field is applied on this substance, the electrons in this band gets some extra energy by
this electric field and excited to the empty levels in the same band and gains momentum and kinetic energy in the direction
opposite to electric field. The collective motion of all moving electrons in these levels (conduction band) constitutes an
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electric current. Thus good conductors of electricity are those solids whose uppermost occupied band (in the conduction
band) is partially field.

As we know for higher energy levels, the energy levels are very close and in solids energy band gets overlapped. In fact,
this overlapping of the uppermost bands is the common situation for most metals or good conductors.
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Now for another examplewediscuss thecaseof magnesium (Z = 12). The Mg atom has electronic configuration 1s2 2s2
2p 3s2. Here all energy levels are completely filled. The level just above 3s i.e. 3p is very close to 3s. Here corresponding 3s
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and 3p bands of solid magnesium gets overlapped as shown in figure-6.

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PG Notes Semiconductors (Part - 1)

Figure 6

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If in magnesium 3p band do not overlap with 3s, it would be an insulator because all electrons in 3s would be almost
frozen to their completely filled levels and would not be fully mobile to conduct electricity. But because of overlapping the
upper most electrons of 3s band have the lowest energy states of 3p available to then. In magnesium the total energy levels
available from 3s and 3p bands are 8 per atom (2 in 3s and 6 in 3p) and only 2 electrons per atom are there in the two bands
having 6 empty levels in which electrons can conduct electricity. Therefore magnesium is a good conductor. Thus we can say
that those substances whose atoms have completely filled energy levels but in solid state have their uppermost filled band

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overlap with an empty band (conduction band) are also good conductors of electricity.

Band Structure in Insulators

In a solid substance, a different situation might occur when the upper most or valance band is completely filled and does
not overlap with the next band, which is totally empty. Since all states of the valance band are occupied the electron motion
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is frozen or the electrons can not change their states within the band. The only possibility is to transfer the electron to the
empty next band (conduction band). The situation for such a solid is shown in figure.
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Figure 7

Fermi Energy Gap

It is the energy required to excite the uppermost electron in valance band (fermi energy level) to the conduction band. It
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is also called forbidden energy gap.

In solids when EF > 5 eV, electrons in valance band may be excited to conduction band and conduct electricity but this
possible only at very high temperature or when a high electric field is applied and these values of temperature or electric field
when current is conducted, this we call electric breakdown of insulator. Like in diamond, fermi energy gap is around 6 eV. This
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may be considered as a relatively large energy gap, that’s why diamond is a good insulator.

Thus insulators are those substances in which, the forbidden energy gap is large (more then 5 eV)

Band Structure in Semiconductors

The energy band structure of semiconductors is similar to that of insulators but in these solids the forbidden energy gap
is very small i.e. the conduction band is very close to the fermi level of valance band. This smaller gap makes it much easier
to excite the upper most electrons of the valance band into the conduction band. Generally the solids in which the energy gap
is less then 1.5 eV some of the upper most electrons gains this energy by thermal agitation at room temperature and shift to
conduction band. Due to this there becomes two possibilities of conduction. First, the uppermost electrons of valance band

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PG Notes Semiconductors (Part - 1)
which jumps to the next band, the conduction band behaves in a similar way as they would be in a metal and second, the
empty states in the valance band which are created due to shifting of some electrons to conduction band, the excited free
electron can conduct electricity and in valance band holes can conduct electricity. The band structure of semiconductors is
shown in figure-8.

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Energy bands and electron distribution in a semiconductor
Figure -8
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We can also conclude that in semiconductors conductivity rapidly increases with temperature because more electrons
are thermally excited from valance band to conduction band.

Types of Semiconductors

In previous section we’ve discussed that the conductivity of a semiconductor depends on temperature, the conductivity
increases with increases in temperature. This temperature dependent electrical conduction in semiconductors is called
intrinsic conductivity. The conductivity of a semiconductor can also be enhanced by the addition of some impurities in
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semiconductors, this technique is called doping. On the basis of conductivity semiconductors can be classified in two major
categories.
(1) Intrinsic Semiconductors
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(2) Extrinsic Semiconductors

Lets discuss these in details.

Intrinsic Semiconductors

These are pure semiconductor substances. Generally fourth group elements Germanium and silicon are used as pure
semiconductors. In solid state, each atom behaves as if there are 8 electrons in its valence shell due to formation of covalent
bonds. At very low temperature, the whole material behaves as an insulator.
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For a Si atom lattice the forbidden energy gap is 1.14 eV. This energy becomes available to the electron even at room
temperature and due to thermal agitation of the solid lattice structure electrons from a few covalent bonds come out and jump
to conduction band to conduct electricity. The bond from which electron is transferred to conduction band, a vacancy is
created. As discussed in previous section, this vacancy in valance band behaves as a positive electron and is called a hole.
When a potential difference is applied across the lattice, an electric field is established in the lattice structure due to which
electrons in conduction band and holes in valance band starts moving in opposite directions. Thus in a semiconductor
electron is a negative charge carrier and hole is a positive charge carrier. As the direction of flow of both carriers is opposite,
they constitute current in same direction. In this case when current flows in a pure semiconductor, these electrons and holes
are called intrinsic charge carriers.

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Figure 9

In an intrinsic semiconductor, the free electron density ne in conduction band is equal to the concentration of holes nh
in valance thus we have GA
ne = nh = ni … (1)

Here ni we call concentration of intrinsic charge carriers in conduction band and also in valance band. As we’ve
discussed value of ni increases with increases in temperature.

Theoretically the intrinsic concentration ni varies with temperature T according to relation

n i 2 = A0T 3 e–EF/kT … (2)

or n i = n0 e–EF/2kT
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Here EF is the energy gap or the energy required to break a covalent bond and generates a electron hole pair at 0 k
temperature, k is the Boltzmann constant and A0 is a constant independent of temperature T.
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Figure-9 shows the lattice of solid silicon in which all Si atoms are attached to their neighbouring Si-atoms by covalent
bonds. Actually in lattice atoms are arranged in a three dimensional array but here for simplicity we’ve drawn a two dimensional
arrangement of Si atoms and for clarity, the conduction band is shown separately. Due to thermal agitation some electrons
from valance band by breaking of covalent bonds shift to the conduction band and equal number of holes are created in the
valance band. Generally when one bond breaks and an electron is shifted to conduction band, the hold of Si nucleus on other
nearby electrons becomes tight and no near by bond will break. It is observed that one free electron hole pair is contributed
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by about 108 Si atoms.

Generation and Recombination of Electron Hole Pairs

In an intrinsic or pure semiconductors, the number of holes is equal to the number of free electrons. Due to thermal
agitation, continuously new electron hole pairs are generated per unit volume per second and other electron hole pairs
disappears due to recombination. Recombination means an electron from conduction band falls into a hole of empty covalent
band and reforms the bond again by release of energy and loss of one electron hole pair. The time h or e for which a hole or
electron exist before recombination is called mean life time of the hole or electron.

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Due to continuous generation and recombination of electron hole pairs, the average concentration of electrons and
holes in conduction and valance band remains constant but increase with temperature as if temperature increase rate of
generation of electron hole pairs by breaking covalent bond also increases. The average thermal energy absorbed in generating
electron hole pairs and the average energy released during recombination of electron and holes keeps the semiconductor
lattice in thermal equilibrium.

Mechanism of Conduction by Hole

We know that due to thermal agitation electron hole pairs are generated in conduction band and valance band by
breaking of bonds. In valance band when a bond is incomplete so that a hole exists, it is relatively easy for a valance electron
in a neghbouring atom to leave its covalent bond to fill this hole. An electron moving from a bond to fill a hole leaves a hole
in its initial position. Hence the hole effectively moves in the direction opposite to that of the electron. This hole in its new
position, may now be filled by an electron from another covalent bond, and the hole correspondingly move one step in the

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direction opposite to the motion of electron. This mechanism for conduction of electricity is due to flow of electrons but not
involving free electrons in conduction band.

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Figure 10
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Figure-10 illustrates how in valance band holes flow and participate in conduction of electricity as if it were a positive
charge carrier.

Extrinsic Semiconductors
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We’ve discussed that a pure semiconductors at room temperature have free electron hole pairs but the number of these
charge carriers is so small that conductivity of these intersic semiconductor is very small. If some specific impurity is added
in the pure semiconductor in a very small ratio of about 1 in 103 to 1 in 105 atoms, the conductivity can be significantly
increased, this procedure of adding impurity to a pure semiconductor crystal to improve its conductivity is called doping and
the impure semiconductor thus formed is called doped semiconductor.
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There are two types of doped semiconductors formed based on the two types of impurity atoms added to a pure
semiconductor. These are

(i) Pentavalent impurity atoms

Pentavalent impurity atoms have 5 valance electrons such as phosphorus (P) or arsenic (As). When these impurity
atoms are added to silicon structure, these have one excess electron then Si-atoms and this increases the electron concentration
after making all the covalent bonds (four bonds), as due to low impurity concentration each phosphorus atom is surrounded
by Si-atoms. These pentavalent impurity atoms are also called donor impurity atoms and the semiconductor produced is
called n-type semiconductor.
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Similarly trivalent impurity atoms have 3 valance electrons, such as aluminium (Al) or Indium (In). When these atoms are
added to pure silicon as being trivalent atoms and surrounded by tetravalent atoms, they accept one electron, that’s why
these are called acceptor impurity atoms and the semiconductor thus produced is called p-type semiconductor.

Now we will discuss these extrinsic semiconductors in detail.

n-Type Semiconductors

Figure shows the crystal structure obtained when silicon is doped with a pentavalent impurity like arsenic (As). When
arsenic impurity atoms are added to the silicon crystal in a very small ratio such as about 1 in 104 atoms. These atoms replace
some silicon atoms in the lattice. Four of five valance electrons of arsenic atoms occupy covalent bonds with the neighbouring
Si-atoms and fifth electron is normally unbound from the atom. The energy required to detech this fifth electron and shift to
conduction band is only about 0.05 eV and it is considerably less then that required to break a covalent bond (about 1.14 eV).

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Thus this extra electron can easily get transferred to the conduction band.

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Figure 11

Thus we can see that here each pentavalent impurity atom contributes one free electron to the conduction band.
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Figure-11 shows the energy-band diagram for n-types doped silicon structure. Here we can see that the fifth electrons of all
the donor impurity atoms occupy an energy level which is slightly below the conduction band with the small energy gap of
about Ed ~ 0.05 eV and it is easily excited to the conduction band.
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Figure 12

In n-type semiconductors, the number of electrons in conduction band can be increased by a large extent by adding more
donor impurity atoms. Not only does the number of electrons increase, but the number of holes decreases below that would
be available in the intrinsic semiconductors. In this case due to large number of electrons present, the rate of recombination
with the holes also increases hence number of holes also decreases.

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In this case the majority charge carriers are electrons and holes are called minority charge carriers. As the dominant
carriers are the negative electrons, this resultant semiconductor we call n-type semiconductor.

p-Type Semiconductor

As already discussed another type of semiconductor can be made by adding drivalent impurity atoms to silicon lattice
like aluminium (Al), gallium (Ga) or indium (In) which replace some silicon atoms from the lattice. As these atoms have 3
valance electrons. These atoms accept one electron from the valance bond in order to complete the four covalent bonds and
thus creates a hole in valance band. The band structure of silicon doped with indium (In) is shown in figure-13.

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Figure 13

Due to doping with trivalent atoms as these can accept an electron readily with the valance band of silicon, an emply
acceptor level is creeated just above the valance bond having a very small energy gap of about Ea = 0.05 eV and thus the
electrons of valance band of silicon are easily transferred to these levels and creating a hole corresponding to each acceptor
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impurity atom. This result in a semiconductor in which holes are in excess as compared to electrons in conduction band which
are due to electron hole pairs created by thermal agitation in the lattice thus in semiconconductor doped with trivalent
impurity atoms holes are majority charge carriers and electrons are minority charge carriers. As in this case dominant charge
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carriers are positive holes, this semiconductor we call p-type semiconductors.

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Carrier Concentration in Extrinsic Semiconductors and Mass-action Law

As we’ve discussed that n-type impurity increases number of electrons in the conduction band and due to increase in
recombination rate number of holes in valance band decreases below the concentration of intrinsic semiconductors. It is

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observed that in a semiconductor contineous recombination of electrons and holes takes place as well due to thermal
agitation contineous formation of electron hole pairs also takes place and the semiconductor remains in thermal equilibrium.
It has also been proved that in thermal equilibrium the product of electron and hole concentration in a semiconductor is a
constant independent of the amount of donor and acceptor impurity doping. This is given as

ne nh = ni2 … (1)

Here ni is the intrinsic concentration of charge carriers. This equation-(1) is called mas-action law. As already discussed
that the intrinsic concentration ni is a function of temperature.

Carrier Concentration in Semiconductors

As we’ve already discussed that only a small amount of energy is needed (about 0.05 eV) to ionize the impurity atoms.

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At temperature above 200 K, sufficient thermal energy is available to ionize all impurity atoms, thus in doped semiconductors
all impurity atoms remains in ionized state (donor impurities as positive ions and acceptor impurities as negative ions).

Now using mass-action law we can find the carrier concentration in a semiconductor. Let us assume, in a given
semiconductor ND is the concentration of donor impurity atoms & NA is that for acceptor impurity atoms and in conduction
and valance band and say the electron and hole concentration are ne and nh respectively. As the whole lattice is electrically

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neutral by conservation of charge we can say that the total concentration of nagative charges is equal to the concentration
of positive charges. Thus we can write

ND + ne = NA + nh … (1)
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Lets discuss about n-type semiconductor in which NA = 0. Since the number of electrons is much greater then the number
of holes in an n-type semiconductor we can say that electron concentration ne is approximately equal to the donor atom
concentration or donor atom density

ne ~
 ND … (2)

Now using mass-action law we can find the concentration of holes in an n-type semiconductors as
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ni2
nh = … (3)
ND
Similarly for a p-type semiconductor we can say that the hole concentration is approximately equal to the density of
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acceptor atoms, thus

nh ~
 NA … (4)
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and thus electron concentration in a p-type semiconductor can be given as

ni2
ne = … (5)
NA
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Electrical Conduction in Metals

We know that in a conductor when current flows, the current density J is related to drift speed of electrons in conductors
as

J = nevd … (1)

Where n is the free electron density in the conductor and e is the charge of electron. Drift speed of electrons is acquired
when an electric field E is established in the conductor. We know that the drift speed of electrons is directly proportional to
the electric field in the conductor, which is given as

vd  E

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or vd = µE … (2)

Here the proportionality constant µ is called the mobility of the electrons in the conductor. This term mobility (µ)
depends on temperature for a given material and its numerical value gives an idea that how much mobile the charge carrier is.
If temperature of a substance increases, the rate of collision between charge carriers increases and their flow becomes
difficult hence mobility decreases.

Now from equation-(1) & (2) we have

J = neµE … (3)

or J =E … (4)

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Here  = neµ is another constant, called conductivity of the conductor.

Electric Conduction in a Semiconductor

In a semiconductor both electrons and holes contribute to the conduction process. We’ve discussed that in lattice
structure, the mechanism by which holes and electrons move are different. Electrons move in conduction band where as

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holes drift in valance band due to shifting of electrons from one covalent band to another. Here we can see that in a
semiconductor electrons are more mobile as compared to holes hence their mobilities also differ. These charge carriers move
in opposite directions but as their charges are also opposite, the current due to each carrier is in same direction.

If ne and nh are electron and hole concentration and µe and µh are the mobilities of electrons and holes in the lattice then
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on establishing an electric field E in the lattice, the current density can be given as

J = ne e µe E + nh e µh E

or J = (e + h) E

or J =E … (1)
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Here  is the conductivity of the semiconductor which can be given as

 = e + h
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 = e (ne µe + nh µh) … (2)

For intrinsic semiconductors ne= nh = ni, thus

 = eni (µe + µh) … (3)

Thus if Ie and Ih are the current in lattice due to electrons and holes, total current can be given as

I = Ie + Ih … (4)
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