Semiconductor

Materials
 Band Theory
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The Silicon
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Atomic -
Structure - -
- Si -
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14 -
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Silicon: our primary example and
focus
Atomic no. 14 However, like all
14 electrons in three shells: 2 ) 8 ) 4 other elements it
i.e., 4 electrons in the outer "bonding" would prefer to have
shell
Silicon forms strong covalent bonds with
8 electrons in its
4 neighbors outer shell
Continue……….
Both atoms essentially share the pair of
electrons at the given energy level in
the outer sub-shell, with the two
electrons having opposite spins. This
forms a bonding attraction between the
two atoms which is not extremely
strong but is nonetheless powerful and
maintains a high degree of stability in
the material.
In the case of Silicon, each of
the 4 outer electrons enters into a
covalent bond with a neighbouring
atom.
 Band theory of a solid
• A solid is formed by bringing together isolated single atoms.
• Consider the combination of two atoms. If the atoms are far apart there is
no interaction between them and the energy levels are the same for each
atom. The numbers of levels at a particular energy is simply doubled

n=3 n=3

n=2 n=2

n=1 n=1

Atom 1 Atom 2

• If the atoms are close together the electron wave functions will
overlap and the energy levels are shifted with respect to each
other.
n=3 n=3 n=3

n=2 n=2 n=2

n=1 n=1 n=1

Atom 1 Atom 2 Atom 1 + 2

 In a silicon semiconductor
there are thousands of
atoms. For n number of
silicon atoms every energy
level splits into a band of
energy levels.

If the outermost shell of n

number of silicon atoms
interact with each other then
3s2 and 3p2 will split into
bands and form 3s2- 3p2
band. By splitting of 3s2 and
3p2 levels conduction and
valence bands formed.
However, there are some
electrons that can jump from
valence band to conduction Silicon has a similar band
band after formation. structure. The forbidden
gap is about 1 eV.
• A solid will have millions of atoms n=3
close together in a lattice so these
energy levels will creates bands each
separated by a gap. n=2

• Conductors:
n=1

– If we have used up all the

electrons available and a band is
still only half filled, the solid is Conduction band,
half filled with
said to be a good conductor. The electrons
half filled band is known as the
conduction band. Valence band,
filled with
bonds
• Insulators:
– If, when we have used up all the
electrons the highest band is full Empty
and the next one is empty with a conduction band
large gap between the two bands,
the material is said to be a good Large energy gap
insulator. The highest filled band
is known as the valence band Completely
filled Valence
while the empty next band is band,
known as the conduction band.
Semiconductors:
• Some materials have a filled valence band
just like insulators but a small gap to the Empty
conduction band
conduction band.
• At zero Kelvin the material behave just Small energy
gap
like an insulator but at room temperature, Valence bands,
filled with
it is possible for some electrons to acquire electrons
the energy to jump up to the conduction
band. The electrons move easily through
this conduction band under the application
of an electric field. This is an intrinsic At zero Kelvin – no conduction
semiconductor.

Conduction
band, with some
electrons

So where are all these materials

Top valence to be found in the periodic table ?
band now
missing some
electrons

At room temperature – some conduction

 Why semiconductors?
• SEMICONDUCTORS: They are here, there, and everywhere
• Computers, palm pilots, Silicon (Si) MOSFETs, ICs, CMOS
laptops, anything “intelligent”
• Cell phones, pagers Si ICs, GaAs FETs, BJTs
• CD players AlGaAs and InGaP laser diodes, Si photodiodes
• TV remotes, mobile terminals Light emitting diodes (LEDs)
• Satellite dishes InGaAs MMICs (Monolithic Microwave ICs)
• Fiber networks InGaAsP laser diodes, pin photodiodes
• Traffic signals, car GaN LEDs (green,
green blue)
blue
taillights InGaAsP LEDs (red,
red amber)
amber
• Air bags Si MEMs, Si ICs
• and, they are important, especially to Elec.Eng.& Computer
Sciences
 Introduction
Semiconductors are materials whose electrical
properties lie between Conductors and Insulators.

Ex : Silicon and Germanium

Give the examples of Conductors and Insulators!

Difference in conductivity
 Semiconductor Materials
• Elemental semiconductors – Si and Ge (column IV of periodic
table) –compose of single species of atoms
• Compound semiconductors – combinations of atoms of column
III and column V and some atoms from column II and VI.
(combination of two atoms results in binary compounds)
• There are also three-element (ternary) compounds (GaAsP) and
four-elements (quaternary) compounds such as InGaAsP.
Semiconductor
materials
 Semiconductor Materials
• The wide variety of electronic and optical properties of these
semiconductors provides the device engineer with great
flexibility in the design of electronic and opto-electronic
functions.
• Ge was widely used in the early days of semiconductor
development for transistors and diods.
• Si is now used for the majority of rectifiers, transistors and
integrated circuits.
• Compounds are widely used in high-speed devices and devices
requiring the emission or absorption of light.

• The electronic and optical properties of semiconductors are

strongly affected by impurities, which may be added in precisely
controlled amounts (e.g. an impurity concentration of one part
per million can change a sample of Si from a poor conductor to a
good conductor of electric current). This process called doping.
 Solid state structures
A crystalline solid is distinguished by the fact that atoms making the
crystal are arranged in a periodic fashion. That is, there is some basic
arrangement of atoms that is repeated throughout the entire solid.
Thus the crystal appears exactly the same at one point as it does at a
series of other equivalent points, once the basic periodicity is
discovered. However, not all solids are crystals (Fig. 2); some have no
periodic structure at all (amorphous solids), and other are composed
of many small regions of single-crystal material (polycrystalline
solids).

The periodic arrangement of atoms in crystal is called the lattice; the

lattice contains a volume, called a unit cell, which is representative of the
entire lattice and is regularly repeated throughout the crystal.
 Possible Semiconductor Materials
1. Very Expensive
Carbon C 6 2. Band Gap Large: 6eV
3. Difficult to produce without high contamination
1. Cheap
Silicon Si 14 2. Ultra High Purity
3. Oxide is amazingly perfect for IC applications
1. High Mobility
Germanium Ge 32 2. High Purity Material
3. Oxide is porous to water/hydrogen (problematic)

1. Only “White Tin” is semiconductor

Tin Sn 50
2. Converts to metallic form under moderate heat

1. Only “White Lead” is semiconductor

Lead Pb 82
2. Converts to metallic form under moderate heat
 The Silicon Atomic Structure
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- Si -
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14 -
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Silicon : It’s a Group 4 element which means it has 4 electrons
in outer shell

However, like all other elements it would prefer to have 8

electrons in its outer shell
 Bonding of Si atoms

This results in the covalent bonding of Si atoms in the crystal

matrix

A Covalent Bond Formed by the Sharing of

Electrons in an Outer Energy Level
 Electrons and Holes
Si and Ge are tetravalent elements – each atom of Si (Ge) has 4 valence
electrons in crystal matrix

T=0 all electrons are bound in For T> 0 thermal fluctuations can
covalent bonds break electrons free creating
electron-hole pairs
no carriers available for
conduction. Both can move throughout the lattice
and therefore conduct current.
 Electrons and Holes
For T>0
some electrons in the valence band receive
enough thermal energy to be excited
across the band gap to the conduction
band.
The result is a material with some electrons
in an otherwise empty conduction band and
some unoccupied states in an otherwise
filled valence band.
An empty state in the valence band is
referred to as a hole.
Electron-hole pairs in a semiconductor.
The bottom of the conduction band
If the conduction band electron and the
denotes as Ec and the top of the valence hole are created by the excitation of a
band denotes as Ev. valence band electron to the conduction
band, they are called an electron-hole pair
(EHP).
 Intrinsic Material
A perfect semiconductor crystal with no impurities or lattice defects is called an
intrinsic semiconductor.

At T=0 K – At T>0
No charge carriers Electron-hole pairs are generated
Valence band is filled with electrons
EHPs are the only charge carriers in
Conduction band is empty
intrinsic material

Since electron and holes are created in

pairs – the electron concentration in
conduction band, n (electron/cm3) is
equal to the concentration of holes in the
valence band, p (holes/cm3).
Each of these intrinsic carrier
concentrations is denoted ni.
Thus for intrinsic materials n=p=ni

Electron-hole pairs in the covalent bonding

model in the Si crystal.
 Increasing conductivity by temperature
As temperature increases, the number of free electrons and holes
created increases exponentially.

17
Carrier Concentration vs Temp (in Si)
1 10
16
1 10
15
1 10
14
1 10
13
Intrinsic C oncentration (cm ^-3)

1 10
12
1 10
11
1 10
ni 1 1010
T
9
1 10
8
1 10
7
1 10
6
1 10
5
1 10
4
1 10
3
1 10
100
150 200 250 300 350 400 450 500
T
Temperature (K)

Therefore the conductivity of a semiconductor is influenced by

temperature
 Increasing conductivity
• The conductivity of the semiconductor material
increases when the temperature increases.
• This is because the application of heat makes it
possible for some electrons in the valence band
to move to the conduction band.
• Obviously the more heat applied the higher the
number of electrons that can gain the required
energy to make the conduction band transition
and become available as charge carriers.
• This is how temperature affects the carrier
concentration.
• Another way to increase the number of
charge carriers is to add them in from an
external source.
• Doping or implant is the term given to a
process whereby one element is injected with
atoms of another element in order to change
its properties.
• Semiconductors (Si or Ge) are typically doped
with elements such as Boron, Arsenic and
Phosphorous to change and enhance their
electrical properties.
 Extrinsic Material

By doping, a crystal can be altered so that it has a

predominance of either electrons or holes. Thus there
are two types of doped semiconductors, n-type
(mostly electrons) and p-type (mostly holes). When a
crystal is doped such that the equilibrium carrier
concentrations n0 and po are different from the
intrinsic carrier concentration ni, the material is said
to be extrinsic.

Total number of electrons

III – Al – 13
IV – Si – 14
V- P - 15
Extrinsic Material – donation of electrons
An impurity from column V introduces an
n-type material energy level very near the conduction band
in Ge or Si. This level is filled with electrons
at 0 K, and very little thermal energy is
required to excite these electrons to the
conduction band. Thus, at about 50-100 K
nearly all of the electrons in the impurity
level are "donated" to the conduction band.
Such an impurity level is called a donor level,
and the column V impurities in Ge or Si are
called donor impurities. From figure we note
that the material doped with donor
impurities can have a considerable
concentration of electrons in the conduction
band, even when the temperature is too low
for the intrinsic EHP concentration to be
Donation of electrons from
appreciable. Thus semiconductors doped
a donor level to the
with a significant number of donor atoms
conduction band
will have n0>>(ni,p0) at room temperature.
This is n-type material.
 Extrinsic Material – Creation of holes
Atoms from column III (B, Al, Ga, and In) introduce impurity levels
in Ge or Si near the valence band. These levels are empty of
electrons at 0 K. At low temperatures, enough thermal energy is
available to excite electrons from the valence band into the
impurity level, leaving behind holes in the valence band. Since this
type of impurity level "accepts" electrons from the valence band, it
is called an acceptor level, and the column III mpurities are
acceptor impurities in Ge and Si. As figure indicates, doping with
acceptor impurities can create a semiconductor with a hole
concentration p0 much
greater than the conduction
band electron concentration n0
(this is p-type material).
 pn Junction
The interface separating the n and p regions is referred to as the
metallurgical junction.
For simplicity we will consider a step
junction in which the doping
concentration is uniform in each region
and there is an abrupt change in doping
at the junction.
Initially there is a very large density
gradient in both the electron and
hole concentrations. Majority carrier
electrons in the n region will begin
diffusing into the p region and
majority carrier holes in the p region
will begin diffusing into the n region.
If we assume there are no external
connections to the semiconductor,
then this diffusion process cannot
continue indefinitely.
 Diffusion
Let us assume that we have two boxes- one
contains red air molecules while another
one contains blue molecules. This could be
due to appropriate types of pollution.

Let us join these 2 boxes together

and remove the wall between them.

Each type of molecules starts to

move to the region of their low
concentration due to the
concentration gradient in the
middle.

Eventually there would be a homogeneous mixture

of two types of molecules.
 pn Junction
This cannot occur in the case of the charged particles in a p-n junction
because of the development of space charge and the electric field .
As electrons diffuse from the n
region, positively charged
donor atoms are left behind.
Similarly, as holes diffuse from
the p region, they uncover
negatively charged acceptor
atoms. These are minority
carriers.
The net positive and negative
charges in the n and p regions
induce an electric field in the
region near the metallurgical
junction, in the direction from
the positive to the negative
charge, or from the n to the p
region.
 pn Junction
The net positively and negatively charged regions are shown in Figure. These
two regions are referred to as the space charge region (SCR). The pn
junction is called metallurgical junction. Essentially all electrons and holes
are swept out of the space charge region by the electric field. Since the space
charge region is depleted of any mobile charge, this region is also referred to
as the depletion region
Density gradients still exist in the majority carrier concentrations at each edge
of the space charge region. This produce a "diffusion force" that acts the
electrons and holes at the edges of the space charge region. The electric field
in the SCR produces another force on the electrons and holes which is in the
opposite direction to the diffusion force for each type of particle. In thermal
equilib­rium, the diffusion force and the E-field () force exactly balance each

other.