Chapter – 4

SEMICONDUCTING MATERIALS

4.1 Introduction

What are semiconductor materials?

Semiconductors are that class of materials which are neither a good conductor nor a good insulator. A
semiconductor is solid crystalline material whose electrical conductivity is intermediate between that of a
conductor and an insulator. They have four valence electrons. Eg. Carbon, Silicon, germanium.

Semiconductor materials such as silicon (Si), germanium (Ge) and gallium arsenide (GaAs), have
electrical properties somewhere in the middle, between those of a "conductor" and an "insulator". They are not
good conductors nor good insulators (hence their name "semi"-conductors). They have very few "free electrons"
because their atoms are closely grouped together in a crystalline pattern called a "crystal lattice". However,
their ability to conduct electricity can be greatly improved by adding certain "impurities" to this crystalline
structure thereby, producing more free electrons than holes or vice versa. These impurities are called donors or
acceptors depending on whether they produce electrons or holes. This process of adding impurity atoms to
semiconductor atoms (the order of 1 impurity atom per 10 million (or more) atoms of the semiconductor) is
called Doping.

The most commonly used semiconductor material by far is silicon. It has four valence electrons in its outer most
shell which it shares with its adjacent atoms in forming covalent bonds. The structure of the bond between two
silicon atoms is such that each atom shares one electron with its neighbor making the bond very stable. Silicon
atoms are arranged in a definite symmetrical pattern making them a crystalline solid structure. A crystal of pure
silicon (silicon dioxide or glass) is generally said to be an intrinsic crystal (it has no impurities).

Fig.2. The diagram above shows the structure and lattice of a 'normal' pure crystal of Silicon.

Semiconductors are of two types. They are (i) Intrinsic(pure) and (ii) Extrinsic(impure)

4.2 Intrinsic Semiconductors: Semiconductors in their absolute pure state are known as Intrinsic
semiconductors. These have negative temperature coefficient. The higher the temperature of a semiconductor
lower is its resistance and better is its conduction. In general semiconductors have small energy gap between
valence band and conduction band, even at ordinary room temperature there are many electrons which possess
sufficient energy to jump across the small energy gap into conduction band. When an electron jumps into
conduction band it creates a hole in the valence band. The hole infact is the loss of electron. The free electron
and the hole form an electron-hole pair, higher the temperature the greater is the number of free electrons and

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therefore the holes. It the temperature is brought down to 00K(-2730C) the intrinsic material will act as a good
insulator.

The electrons in the conduction band and hoes in the valence band moves in a random fashion within the crystal
due to their thermal energy. When an external field is applied to the semiconductor, a drift velocity is
superimposed on the random thermal motion of the charge carriers, i.e., electrons and holes. The drift of the
electrons in the conduction band and that of holes in the valence band produce an electric current. The electrons
move towards the positive electrode, whereas the holes towards the negative electrode (Fig. 3). The currents
produced by the movement of electrons and holes in opposite directions and since the electron carries a negative
charge and the hole a positive charge. Thus, the conventional current flows within the semiconductor from the
positive electrode to the negative electrode. The energy of a hole is measured downward from the top of the
valence band.

Figure.3 Conduction in Intrinsic Semiconductor

Figure.4 Fermi Energy level for Intrinsic material

The motion of the electrons in the valence band may be considered to be equivalent to the motion of holes in the
opposite direction. Obviously, the holes also contribute to the conductivity. When an electronhole pair is
thermally created, a valence electron in a neighbouring atom can have sufficient thermal energy to jump into the
position of the hole and reconstruct the covalent bond. In doing so, the electron leaves a hole in its initial
position. Effectively, the hole moves from one position to the other position. Thus the holes move in the
direction opposite to that of the valence electrons. That is why a hole behaves like a free positive charge equal in
magnitude to the electronic charge. The electrons in the conduction band move more easily than the electrons
which cause the motion of holes in the valence band. Hence the contribution to the electric current by the
electrons in the conduction band is more than that by the holes in the valence band. The salient features of an
intrinsic semiconductor can be summarised as follows:
(i) The number of electrons in the condution band is equal to the number of holes in the valence band. In
equilibrium, the electron concentration n and hole concentration p are equal, i.e. n = p = ni, where ni is termed as
intrinsic concentration.
(ii) The Fermi level lies exactly between the valence and conduction bands (EF = Eg/2). (Fig.4).
(iii) The contribution of the electrons to the electric current is more than that due to the holes.
(iv) About 1 atom out of 103 atoms of an intrinsic semicondutor contributes to the conduction.
(v) An electron and hole can behave as a pair bound to each other. Such a bound pair is usually referred as
exciton. An exciton is electrically neutral and so does not take part in electrical conduction.

4.3 Extrinsic Semiconductors: Extrinsic semiconductors or impure semiconductors are those which have been
doped i.e impurities are added purposely into their crystal structure. The impurities are added in very small and
carefully controlled quantities. The process of adding impurities is called doping, and the impurities themselves
are called dopents. The extent to which the impurity has been added is called the doping level. ( 1 atom in 108).
Pure semiconductor is of no practical use as the no.of charge carriers in them is very small, can treat them as
close to insulators. By doping we increase the no.of charge carriers and therefore the conductivity of the
semiconductor material. Hence we can treat extrinsic materials as close to conductors. Depending upon the
impurity added extrinsic semiconductors can be further classified into (i) N-type & (ii) P-type semiconductors.

4.2.1 N-type Semiconductors

In order for silicon crystal to conduct electricity, we need to introduce an impurity atom such as Arsenic,
Antimony or Phosphorus into the crystalline structure making it extrinsic (impurities are added). These atoms
have five outer electrons in their outermost co-valent bond to share with other atoms and are commonly called

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"Pentavalent" impurities. This allows four of the five electrons to bond with its neighbouring silicon atoms
leaving one "free electron" to move about when an electrical voltage is applied (electron flow). As each
impurity atom "donates" one electron, pentavalent atoms are generally known as "donors".

Antimony (symbol Sb) is frequently used as a pentavalent additive as it has 51 electrons arranged in 5 shells
around the nucleus. The resulting semiconductor material has an excess of current-carrying electrons, each with
a negative charge, and is therefore referred to as "N-type" material with the electrons called "Majority Carriers"
and the resultant holes "Minority Carriers". Then a semiconductor material is N-type when its donor density is
greater than its acceptor density. Therefore, a N-type semiconductor has more electrons than holes.

Fig.5 The diagram above shows the structure and lattice of the donor impurity atom Antimony.

The impurity atom has five valence electrons. After donating one electron, it is left with +1 excess charge. It
then becomes a positively charged immobile ion. It is immobile because it is held tightly in the crystal by the
four covalent bonds as shown in Fig.5.
It is important to understand that in N-type semiconductors, although electrons (negative charges) are the
majority carriers, but the semiconductor doped with impurity remains electrically neutral. Free electrons and
holes are generated in pairs due to thermal energy and negative charge of electrons donated by impurity atoms is
exactly balanced by positive charge of the immobile ions. Representation of an N-type semiconductor is shown
in Fig.6
Since N-type semiconductors have extra free electrons, and pure semiconductors do not, the energy band
diagram for a doped semiconductor is slightly different from that of a pure semiconductor. In effect, another
energy level exists; a level for the donor electron, which is closer to the conduction band.(figure.6) The
forbidden band for the donor electron is much narrower than the forbidden band for the valence electron; so one
can see that it is much easier to cause electron flow in an N-type semiconductor.

4.2.2 P-Type Semiconductors

If we introduce a "Trivalent" (3-electron) impurity into the crystal structure, such as Aluminium, Boron,
Gallium or Indium, only three valence electrons are available in the outermost covalent bond meaning that the
fourth bond cannot be formed. Therefore, a complete connection is not possible, giving the semiconductor
material an abundance of positively charged carriers known as "holes" in the structure of the crystal. As there is
a hole an adjoining free electron is attracted to it and will try to move into the hole to fill it. However, the
electron filling the hole leaves another hole behind it as it moves. This in turn attracts another electron which in
turn creates another hole behind, and so forth giving the appearance that the holes are moving as a positive
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charge through the crystal structure (conventional current flow). As each impurity atom generates a hole,
trivalent impurities are generally known as "Acceptors" as they are continually "accepting" extra electrons.

Fig.7 The diagram above shows the structure and lattice of the acceptor impurity atom boron.

Boron (symbol B) is frequently used as a trivalent additive as it has only 5 electrons arranged in 3 shells around
the nucleus. Addition of Boron causes conduction to consist mainly of positive charge carriers results in a "P-
type" material and the positive holes are called "Majority Carriers" while the free electrons are called "Minority
Carriers". Then a semiconductors is P-type when its acceptor density is greater than its donor density. Therefore,
a P-type semiconductor has more holes than electrons.

The energy band diagram of P-type semiconductor also differs from that of the pure superconductor. Since there
is an extra number of holes, which tend to attract electrons, they aid in starting current flow. As a result, the
acceptor energy level is also somewhat higher than that of the valence band. However, it is not as high as the
donor level (Fig. 8). P-type semiconductors will conduct easily than pure semiconductors, but not quite as easy
as N-type semiconductors.

4.3 Merits of Semiconductor materials

1. The devices are much smaller in size and lighter in weight
2. When used as rectifiers and transistors they do not require a heater or filament as is required in electron
tube rectifiers and valves.
3. They consume low power resulting in high efficiency
4. They are almost shock proof.
5. They operate on low voltages
6. They have long life and hardly show ageing effects.
7. The resistance of semiconductors decreases nonlinearly with rise in temperature.

4.4 Factors affecting semiconductors

The resistance of semiconductor materials can be controlled by the following factors
1. Temperature: The resistance of the semiconductors decreases with the increase in temperature. This
property is used in thermistors.

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 2. Illumination: The resistance of semiconductor is low in light and increases in darkness. This property
is used in photo conductive cells.
3. Voltage: The resistance of semiconductor varies with applied voltage. This property is used in
varistors.
4. Electric Field: The resistance of semiconductor greatly depends on the magnitude of elcctric field. The
current in a semiconductor does not follow ohm’s law and increases far more rapidly than the voltage.
This property is used in transistors, amplifiers.
5. Impurities: The resistance of semiconductor varies greatly when a small amount of impurity is
introduced in it. This property is used in rectifiers.

4.6 Drift and Diffusion currents

The flow of charge current through a semiconductor material is of two types namely drift & diffusion.
The net current that flows through a (PN junction diode) semiconductor material has two components
(i). Drift current and (ii). Diffusion current

Drift current :
When an electric field is applied across the semiconductor material, the charge carriers attain a certain drift
velocity Vd , which is equal to the product of the mobility of the charge carriers and the applied Electric Field
intensity E . Vd = μ * E

Drift velocity Vd = (mobility of the charge carriers)x( Applied Electric field intensity).

Holes move towards the negative terminal of the battery and electrons move towards the positive terminal of the
battery. This combined effect of movement of the charge carriers constitutes a current known as “ drift current”.
Thus the drift current is defined as the flow of electric current due to the motion of the charge carriers under the
influence of an external electric field. Drift current due to the charge carriers such as free electrons and holes are
the current passing through a square centimeter perpendicular to the direction of flow.

(i) Drift current density Jn , due to free electrons is given by

Jn = q n μn E A / cm2
(ii) Drift current density JP, due to holes is given by
JP = q p μp E A / cm2
Where, n - Number of free electrons per cubic centimeter.
p - Number of holes per cubic centimeter
μ n – Mobility of electrons in cm2 / Vs
μ p – Mobility of holes in cm2 / Vs
E – Applied Electric filed Intensity in V /cm; q – Charge of an electron (1.6 x 10-19 coulomb).
Diffusion current:

It is possible for an electric current to flow in a semiconductor even in the absence of the applied voltage
provided a concentration gradient exists in the material.

A concentration gradient exists if the number of either electrons or holes is greater in one region of a
semiconductor as compared to the rest of the region.

In a semiconductor material the charge carriers have the tendency to move from the region of higher
concentration to that of lower concentration of the same type of charge carriers. Thus the movement of charge
carriers takes place resulting in a current called diffusion current.

4.6 PN Junction

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The semiconductor diode is formed by simply bringing P and N type materials together
(constructed from the same base—Ge or Si). At the instant the two materials are “joined” the
electrons and holes in the region of the junction will combine, resulting in a lack of carriers in the
region near the junction. This region of uncovered positive and negative ions is called the
depletion region due to the depletion of carriers in this region.
Since the diode is a two-terminal device, the application of a voltage across its terminals leaves
three possibilities: no bias (VD = 0 V), forward
bias (VD > 0 V), and reverse bias (VD < 0 V),
Each is a condition that will result in a response
that the user must clearly understand if the
device is to be applied effectively.

No Applied Bias (VD = 0 V)

Under no-bias (no applied voltage) conditions,
any minority carriers (holes) in the n-type
material that find themselves within the
depletion region will pass directly into the p-type material. Figure 1. Diode without Bias
The closer the minority carrier is to the junction, the greater the attraction for the layer of
negative ions and the less the opposition of the positive ions in the depletion region of the n-type
material. For the purposes of future discussions we shall assume that all the minority carriers of
the n-type material that find themselves in the depletion region due to their random motion will
pass directly into the p-type material. Similar discussion can be applied to the minority carriers
(electrons) of the p-type material. This carrier flow has been indicated in Figure1. for the minority
carriers of each material. The majority carriers (electrons) of the n-type material must overcome
the attractive forces of the layer of positive ions in the n-type material and the shield of negative
ions in the p-type material to migrate into the area beyond the depletion region of the p-type
material. However, the number of majority carriers is so large in the n-type material that there
will invariably be a small number of majority carriers with sufficient kinetic energy to pass
through the depletion region into the p-type material.

Again, the same type of discussion can be applied to the majority carriers (holes) of the p-type
material. The resulting flow due to the majority carriers is also shown in Fig. A close examination
of Fig. 1.14 will reveal that the relative magnitudes of the flow vectors are such that the net flow
in either direction is zero. This cancellation of vectors has been indicated by crossed lines. The
length of the vector representing hole flow has been drawn longer than that for electron flow to
demonstrate that the magnitude of each need not be the same for cancellation and that the doping
levels for each material may result in an unequal carrier flow of holes and electrons. In summary,
therefore:
In the absence of an applied bias voltage, the net flow of charge in any one
direction for a semiconductor diode is zero.

Reverse-Bias Condition (VD < 0 V)

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If an external potential of V volts is applied across the p-n junction such that the positive terminal
is connected to the n-type material and the negative terminal is connected to the p-type material
as shown in Fig, the number of uncovered positive ions in the depletion region of the n-type
material will increase due to the large number of “free” electrons drawn to the Figure 2:
Diode with Reverse Bias
positive potential of the applied voltage. For similar reasons, the number of uncovered negative ions will
increase in the p-type material. The net effect, therefore, is a widening of the depletion region. This
widening of the depletion region will establish too great a barrier for the majority carriers to
vercome, effectively reducing the majority carrier flow to zero as shown in Figure 2. The number
of minority carriers, however, that find themselves entering the depletion region will not change,
resulting in minority-carrier flow vectors of the same magnitude indicated in Fig. 1 with no
applied voltage.
The current that exists under reverse-bias conditions is called the reverse saturation
current and is represented by Is.
The reverse saturation current is seldom more than a few microamperes except for high-power devices.

Forward-Bias Condition (VD > 0 V)

A forward-bias or “on” condition is established by applying the positive potential to the p-type
material and the negative potential to the n-type material as shown in Figure3. For future
reference,
A semiconductor diode is forward-biased when the association p-type and positive
and n-type and negative has been established.
The application of a forward-bias potential VD will
“pressure” electrons in the n-type material and holes
in the p-type material to recombine with the ions near
the boundary and reduce the width of the depletion
region as shown in Fig.3. The resulting minority-
carrier flow of electrons from the p-type material to
the n-type material (and of holes from the n-type
material to the p-type material) has not changed in
magnitude (since the conduction level is controlled
primarily by the limited number of impurities in the
material), but the reduction in the width of the depletion Figure.3 Diode with Forward Bias
region has resulted in a heavy majority flow across the junction. An electron of the n-type
material now “sees” a reduced barrier at the junction due to the reduced depletion region and a
strong attraction for the positive potential applied to the p-type material.
As the applied bias increases in magnitude the depletion region will continue to decrease
in width until a flood of electrons can pass through the junction, resulting in an exponential rise in
current as shown in the forward-bias region of the characteristics of Figure.4 Note that the
vertical scale of Fig.4 is measured in milliamperes (although some semiconductor diodes will
have a vertical scale measured in amperes) and the horizontal scale in the forward-bias region has
a maximum of 1V(0.3 for Ge, 0.7 for Si diode). Typically, therefore, the voltage across a
forward-biased diode will be less than 1 V. Note also, how quickly the current rises beyond the
knee of the curve.

The current equation of the diode is given by

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 Where
Is = Reverse saturation current or current due to minority charges
VD = Forward Bias voltage applied
η = ideality factor or Quality factor or emission coefficient (usually ranges from 1 to 2)
VT = Thermal voltage
K – Boltzman constant : 1.38 X 10-23 J/oK
q - Charge of Electron : 1.602 X 10-19 Coulombs

Figure .4 Diode Characteristics

4.7 Applications of semiconducting materials

1. Rectifiers: used for converting AC power into DC power, in power supply unit.
2. Transistors: used in many electronic systems for amplification, signal processing, etc.
3. Photoconductive cells: These are basically light dependent resistors. Cadmium sulphide is used in
these cells. These are used for measuring quality of light(light meter), light operated relays, switches,
breakers and alarms.
4. Temperature sensitive resistors or thermistors: These are thermally sensitive resistors. These are made
from oxides of certain metals such as copper, iron,zinc. These are used for temperature measurement
and control, voltage regulation and in timing circuits.
5. Varistors: The resistance of semiconductor materials changes with applied voltage. The varistors are
used in voltage stabilizers and motor speed control.
6. Strain gauges: Strain gauges are extensively used in measuring the tensile strength of materials and
change in dimensions of structures.
7. Photo diode and photovoltaic cell: Photo diodes are used as switches to detect light as in the case of
photographic exposure meter, automatic aperture control of cameras.

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 8. Integrated circuits: These are very popular in electronics and electrical engineering, they are built by
using some monolithic techniques comprising hundreds of different semiconductor devices on a single
compact chip. These are much reliable circuits

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4.8 Manufacturing Processes of Semiconductors(Diode)

Manufacturing is the process by which raw materials are converted into finished products. The input to the
manufacturing are semiconductor materials, dopants, metals and insulators. After manufacturing the final
finished product can be semiconductor devices(diodes, transistors etc.), Integrated circuits(IC’s), Printed circuit
boards(PCB’s), and ultimately various commercial electronic systems and products( computers, cellular phones,
digital cameras). Here we look the various processes of manufacturing diodes.

Diffused junction: A semiconductor substrate ( eg P-type), (substrate is a device whose reactivity is increased
by a specific enzyme) is put in a furnace at high temperature of about 1000 0C. Nitogen gas with phosphorous is
passed in the vapour form. At this temperature the compound breaks down and phosphorous atoms deposited on
the substrate surface, slowly diffuse into the semiconductor. Maximum concentration of the diffusing impurity
occurs at the surface and gradually falls towards inside. The junction depth can be controlled by controlling time
and temperature. To prevent diffusion in the unwanted regions silicon dioxide of few microns is grown over
selected areas by photolithographic technique.

Epitaxy: Epitaxy is the growth of one crystalline substance on another so that both have the same crystal
structure. Epitaxial layers are used in the manufacture of semiconductor devices. Here a single layer of silicon
doped with N or P type semiconductor of required resistivity is taken, later it is doped with other impurity.
While doping the crystallographic structure of the substrate is maintained.

Ion Implementation: In this process ions of desired impurity are first accelerated in vacuum to high energies
and then shot at the semiconductor surface. The ions penetrate to a depth of few microns through the crystal
lattice. The substance is then heated to restore the crystal structure and for diffusion of impurities into the
semiconductor.

Alloy Junction: The desired semiconductor say of N type is deposited with an opposite type of impurity say
aluminium, silicon, indium or germanium. It is then put into furnace in an inert atmosphere and temperature is
increased. A thin film of melt is then formed at the interface. The melt is cooled to get solidified into a single
crystal form.

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