cbapter 9

Classification of Solids

9.1 INTRODUCTION

We have already discussed some of the important properties of conducting

materials. In this chapter, let us discuss about semiconductors of different types
and their applications in detail.

.2 CLASSIFICATION OF SOLIDS ON THE BASIS

OF BAND THEORY
---------------------- - - ----

Based on the energy band structure, the arrangement of electrons and forbidden
bands, solid materials are classified into the following three categories:
(i) Conductors
(ii) Insulators, and
(ill) Semiconductors
Let us briefly discuss these materials briefly and more on semiconducting
materials.

9.2.1 Conductors
Material which conduct electric current when a potential difference is applied
across them, are known as conductors. In case of a conductor, the valence band
is completely filled, while the c~uction band i~alftill.ed, as shown in Fig. 9.1.
Therefore, when a small potential differ~nce is applied to a solid material, it
provide sufficient energy to the electron in the valence band to shift to the
conduction band. Thus, the shifting of electrons from the valence band to the
unfilled conduction band results in the flow of current in the material. Examples
for some good conductors are copper, lithium, etc.

9.2.2 Insulators
r- Solid materials which do not conduct electric current under normal conditions
are known as insulators. In insulators, the valence band is completely filled and
. it has no electron in the conduction band. Further, the forbidden energy gap will
 Classification Theory of Solids 9.3
9.2 Materials Science

I Degeneracy I I
• • I Empty Conduction band
(contains few electrons
6 6N------·
at room temperature)

") 2
2N
I •• Conduction
(half filled)
band
~ 1 eV
Forbidden
energy gap
2N Valence band Energy Valence band (with
(fully filled) (eV) few hole at room
) 2
temperature)
(a) Energy level diagram (b) Energy band

Fig. 9.1 Conductors-Lithium atom

Fig. 9.3 Energy bands in semiconductors
be very high when compared with a conductor. The energy band diagram of an
insulator (for example, ebonite) is shown in Fig. 9.2. Therefore, the energy sulphide (CdS), etc., are known as compound semiconductors. Some of the
required to shift an electron from the valence band to the conduction band to oxide semiconductors are Bi203, T~03' Zn03, CU20, etc.
make electrical conduction possible, is very high. Hence, it is not possible to Let us discuss the different types of semiconductors and their applications in
provide enough energy by an ordinary electric field. However, one can achieve detail.
electrical conduction in an insulator with very high voltage, known as breakdown
9.3 CLASSIFICATION OF SEMICONDUCTORS
voltage.
Semiconductors are of two types and are classified on the basis of the
Empty conduction
concentration of electrons and holes in the materials:
band (i) Pure or intrinsic semiconductors, and
(ii) Doped or extrinsic semiconductors
Forbidden band Let us discuss the above two types of semiconductors in detail.

9.3.1 Pure or Intrinsic Semiconductors

Energy Highly pure semiconductors are called •
Valence band
(eV)
intrinsic semiconductors, which means • Electron .0.
that the concentration of electrons must ';ii<
Fig. 9.2 Energy bands in insulators be equal to the concentration of holes. : \
I I

In order to understand the electrical • '.• " _ •

9.2.3 Semiconductors conducting property in a semiconducting .®!~~~~@~_~~!@.
Semiconductors (for example, silicon or germanium) are materials whose material, let us first consider the arrange- • " • '. •
electrical conductivity lies between that of conductors and insulators. The ment of atoms in a material, say, silicon l i
conductivity of semiconductors is in the order of 104 to 10-4 mho m-1. The (or germanium). Both germanium and sili- ~
magnitude of the forbidden energy gap of a semiconductor lies in between the con have four valence electrons as shown • 0·
in Fig. 9.4. •
forbidden energy gap of insulators and conductors, as shown in Fig. 9.3.
Semiconducting materials, whether elemental, compound or oxide, are crys- Let us consider the crystal arrangement Fig. 9.4 Two dimension~l ~r:ange-
of silicon (or germanium). Silicon atom is ment of atoms In silicon at
talline solids in nature. Well known semiconductors, such as silicon and germa- .. while the valence T=OK
nium, are elemental semiconductors, while gallium arsenide (GaAs), cadmium represented by a CIrcle,
electron is marked by black dots. The central silicon atom is surrounded by four
 Classification Theory of Solids 9.5
9.4 Materials Science
------ ----------------------
• Electron Conduction band
valence electrons constituting a covalent bond between two atoms, due to the
sharing of valence electrons.
o Hole
•
If we consider the crystal structure at 0 K, all the valence electrons are
engaged in forming covalent bonds with the neighbours. Therefore, no free
electron is available. At this stage, the material does not conduct current due to
the lack of mobile charges, i.e. at 0 K, the material behaves as an insulator.
Electrical conduction can be more lucidly explained by considering the energy Energy Valence band
level diagram of silicon at 0 K, as shown in Fig. 9.5. At 0 K, the valence band
(eV) o
is completely filled and there is no empty space in the valence band. Therefore, Fig. 9.7 Energy band diagram of silicon at T > 0 K
electrons can shift from the valence band to the conduction band through the
forbidden gap. The shifting of electrons is not possible even for a large applied charges, the movement of electrons and holes give rise to an electric current in
field strength at 0 K. the same direction. The conductivity of germanium is higher than silicon due to
its lower energy gap.
Conduction band
9.3.2 Extrinsic Semiconductors
The application of intrinsic semiconductors is restricted due to its low
Eg conductivity. In electronic devices, high conducting semiconductors are more
essential. The concentration of either electrons or holes in a semiconductor is
I increased depending upon the requirements in the electronic devices.
This can be carried out simply by adding impurities (one atom in 107 host
Energy
(eV) atoms) to the intrinsic semiconductors. The process of adding impurity to the
intrinsic semiconductors is known as doping. The doped semiconductor is
Fig. 9.5 Energy band diagram of silicon at T = 0K called as extrinsic semiconductor. The concentration of electrons and holes are
not equal in an extrinsic semiconductor.
However, the thermal energy is sufficient to liberate an electron from the Extrinsic semiconductors are classified into two categories based on the
valence band at room temperature. When the temperature of the intrinsic concentration of the charge carriers namely:
semiconductor is raised, the atoms in silicon vibrate about their mean position.
(i) n-type semiconductors, and
This provides sufficient energy to the electrons due to which the breaking of the
covalent bonds takes place as shown in Fig. 9.6. The broken electron is now said (ii) p-type semiconductors
to be a free electron. (i) n-type Semiconductors When a pentavalent atom such as arsenic (antimony,
When an electrical field is applied, the free bismuth, phosphorus) is added as a dopant to the tetravalent silicon atom, the
electron acquires sufficient energy and shifts
from the valence band to the conduction band. '.'
®
I ,
arsenic atom will occupy one site of the silicon atom. Thus, out of five free
I I electrons in arsenic, four electrons make covalent bonds with the four neigh-
I I
This results in the creation of a hole in the bouring silicon atoms and the fifth one is loosely bound to the silicon atom, as
"
.
\.
valence band, as shown in Fig. 9.6. The free shown in Fig. 9.8.
electrons move in the conduction band, while 0!~~~~0~~~~!@
: \ The energy required to ionise the fifth electron is very less and hence, the
the holes move in the valence band. Thus, I
I
I
I thermal energy of the material shifts the free electron to the conduction band.
, I

electrons and holes are moving opposite to

each other, as shown in Fig. 9.7.
When a potential difference is applied
G Each arsenic atom contributes one free electron to the crystal and hence, it is
called a donor impurity. In this type of semiconductor, the concentration of
charge carriers (i.e., electrons) is more than that of holes. Therefore, these
across a silicon/germanium crystal, the elec- Fig. 9.6 Two dimensional ar- erniconductors are called n-type semiconductors. In an n-type semiconductor,
rangement of atoms in
tric force experienced by the electrons and silicon at T > 0 K electrons are the majority carriers while holes are the minority carriers.
holes are opposite. Ihus. due to the opposite
9.6 Materials Science

• 9.4 ELEMENTAL AND COMPOUND

•,@,. SEMICONDUCTORS
I ,

•
( • \
I
\ •
I
I
t Conduction band Semiconductors are the materials that are having a resistivity in between that of
a metal and an insulator. In semiconductors, the conduction band and the valence
...._--- \, 1," _-_....... :;;-
•
.®. .
,," <:
,@, • • @. ~
,/" ......• ~
If----------------.J

- .--.- -.- -- .---

... .>
..... - - ..... - -
band is separated by an energy gap in the order of 1 eY. Some semiconductors
such as Si and Ge are made up of only one type of atoms. These semiconductors
• -,
....•..... _-_ ,'
",....
', .•..... _-_......
••• ,,".
~
Q)

Donor level are said to be elemental semiconductors. Some semiconductors like GaAs, InP,
I \ Ol
I
I
• \
I
-
Q) InSe, CdS, CdSe, etc., are made up of two different materials. They are binary
'-: iTI 1-1 --------------,

semiconductors. A semiconductor made up of two or more than two different

\ • I
,
, , I

types of atoms is said to be a compound semiconductor.

Valence band
.@. In a semiconductor, the electrical conductivity is due to the movement of the
• electrons and holes. The equation for the conductivity of a semiconductor is
(a) With free electrons (b) Energy at donor level

Fig. 9.8 Doping in n-type semiconductors

(J = neu, + pe f.lh (9.1)
where n is the concentration of electron, p the concentration of hole and, u, and
(ii) p-type Semiconductors Instead of a pentavalent atom, the addition of a are respectively the mobilities of electron and hole.
f.lh

trivalent atom indium (In) to the tetravalent silicon atom, occupies the crystal site The energy gap of Si at room temperature is 1.1 eV and that of Ge is
of the silicon atom as shown in Fig. 9.9 . 0.72 eY. The properties of Si and Ge are listed in Table 9.1.

• Table 9.1 Physical Properties of Si and Ge

.@.
, ,
, , Property Ge Si
I • \

t
I \
I
I
I
I
Conduction band Eg (eV) 0.72 1.1
Nc(cm-3) 1.04 x 1019 1019
\ 0 I
...._--- "\ ,,' $" ~I .J 2.8 X
• .: ....
,' 'I" ........• ~ Nv (cm") 6 x Wig 1.04 X Wig
.® .. • -, ,,',
@ ",
•• ,/.
@. ~ Q)
nj (cm'") 2.4 x 1013 1.45 X 1010
<; _-_ ..••.•
,' ', <; _--_... ~
Acceptor level u, (cm2 V-I S-I) 3900 1350
,
I
•
\
I
e> (cm2 V-I S-I)
I I
Q) Ilb 1900 450
c
Density (gm cm-3)
I ,
\
\ • I
I w I~----------------. 5.32 2.33
\ I
Atomic weight 72.6 28.1
.@. Valence band
Atomic number 32 14

(a) With vacancy

• (b) Energy at acceptor level
€r 16 11.9

Fig. 9.9 Doping in p-type semiconductors GaAs is a semiconductor of group III and group V in the periodic table. It
is one of the mostly studied semiconducting material. It has a direct band gap
The three valence electrons in indium make covalent bonds with the three of 1.42 eV at room temperature. The gallium arsenide devices are nearly 2.5
neighbouring silicon atoms, whereas the fourth bond has an empty space known times faster than Si devices and the noise of the GaAs devices is low. Since the
as hole due to the deficiency of one electron. Therefore, when a trivalent atom cost of a GaAs device is nearly 10 times greater than that of a Si devices and
is added to silicon, it creates a hole in the valence band. The dopant (indium) the density of GaAs is high, it is not possible to materialise GaAs for device
accept an electron from the neighbouring silicon atom to form a covalent bond applications.
and hence, it is called an acceptor. The hole in the valence band moves freely Table 9.2 lists the energy gap of some groups IV, group II-VI and groups Ill-
and hence, the current flows through the material. This type of electrical V semiconductors. Consider the semiconductors with one element common
conduction will take place only when the dopant valency is less than that of the such as ZnS, ZnSe and ZnTe. From Table 9.2, it is found that the energy gap
parent atom. Such semiconductors are called p-type semiconductors. In a p-type decreases with the increase in atomic weight. Some compound semiconductors,
semiconductor, holes are the majority current carriers and electrons are the
minority current carriers.