Carrier Densities in SC

ELEKTRONIKOS PAGRINDAI 2008 1
CHARGE CARRIERS IN SEMICONDUCTORS
Objectives:
• Discovery of the nature of charge carriers in intrinsic and extrinsic
semiconductors
• Finding on what, how and why densities of charge carriers in semiconductors
depend
• Calculation methods of of charge carrier densities in semiconductors
Content:
Charge carriers in intrinsic semiconductors
Nature of charge carriers
Fermi level in an intrinsic semiconductor
Densities of carriers
Charge carriers in extrinsic semiconductors
n-type semiconductors
p-type semiconductors
Compensation doping
Excess carriers and lifetime
VGTU EF ESK stanislovas.staras@el.vgtu.lt

Nature of charge carriers in intrinsic semiconductors
Carefully refined semiconductors are called intrinsic semiconductors. .

In a silicon crystal each atom is surrounded by four neighbour atoms. At 0 K
all valence electrons take part in covalent bonding and none are free to move
through the crystal.
At very low temperatures the

valence band is full (filled to
capacity) and the conduction band
is completely empty.
Thus, at a very low temperature
(close to 0 K) the crystal behaves
as an insulator.
As the temperature increases, the lattice vibrations arise. Some of the energy
of the lattice vibrations is transferred to the valence electrons. If sufficient
energy is given to an electron, it leaves a bond and becomes free.

The jump of an electron from the

valence band to the conduction
band corresponds to the release
of an electron from covalent
bonding. The minimum energy
required for that is equal to the
width of the forbidden band.
If the width of the forbidden band is less, electrons are released at lower
temperature.
When an electron is released, a positively charged vacancy appears. This

vacancy may be considered as a positive hole.
According to the energy band diagram an uncompleted allowed energy level in
the valence band corresponds to a hole.

Above occupied levels there are

unoccupied energy levels in the
conduction and valence bands.
The situation is similar to that in
conductors: electrons are able to accept
energy, change their velocity and
participate in conductivity.
… a hole behaves as a positive charge
carrier having a positive charge equal in
magnitude to the electronic charge.
... In the intrinsic semiconductor the number of electrons in the

conduction band equals to the number of holes in the valence band.
Charge carriers appear as a result of charge carrier generation.

Positive holes attract negative electrons. If an electron is drawn into the bond, it
recombines with a hole.
The jump of an electron from the conduction band to the valence band
corresponds to the recombination process.

Fermi level in an intrinsic semiconductor
Wv + Wc 3 mp
WF = + kT ln
2 4 mn
The Fermi level in an intrinsic

semiconductor lays at the middle
of the forbidden band.
If the Fermi level is below the bottom of the conduction

band, it is possible to use the simplified formula
f F (W ) ≅ e −(W −WF ) / kT
... The Maxwell-Boltzmann distribution function can be used for calculation of the
probability of occupation of energy levels in the conduction band.
The same conclusion can be made for holes in the valence band.

Densities of charge carriers in intrinsic semiconductors
We have derived the expression for density of electrons in a non-generate system.

Now it is necessary to take into account that conduction electrons exist in a crystal.
We must consider the effective mass:
2(2 πmn kT )3 / 2
n= e −(Wc −WF ) / kT = N c e −(Wc −WF ) / kT
h3
Acting in a similar way we can find density or holes in the valence band.
p=
(
2 2πmp kT )3 / 2 e −(W −W ) / kT = N
F v
e −(WF −Wv ) / kT
v
h3
np = N c N v e − (Wc −Wv ) / kT = N c N v e − ∆W / kT
np = ni pi = ni2 = pi2 ... The densities of electrons and

holes in an intrinsic semiconductor
ni = pi = np = N c N v e − ∆W / 2 kT are strongly dependent on
temperature and gap energy.

Densities of charge carriers in intrinsic semiconductors
ni = pi = np = N c N v e − ∆W / 2 kT
The number of conduction electrons and holes increases rapidly with the
increase of temperature and decreases with the increase of the gap
energy.
1 ∆W 1 1
ln ni = ln pi = ln(N c N v ) − ≅ a−b
2 2k T T
∆W
tan α ≅
2k
... Using the expressions for the densities of electrons and holes and taking into
account the condition n = p, it is possible to derive the formula for the Fermi
level in an intrinsic semiconductor.

Densities of charge carriers in intrinsic semiconductors. Problems
1. Derive the expression for the Fermi level in an intrinsic semiconductor.

2. Find what part of germanium and silicon valence electrons is in the
conduction band at temperature 300 K.
3. Find the ratio of carrier densities in germanium and silicon at room
temperature (T = 300 K).
4. Find how many times carrier density in the intrinsic germanium increases, if
the temperature increases from 20 to 1000C. Repeat the calculations for the
intrinsic silicon. Comment on the results.

Extrinsic (doped) semiconductors
The intrinsic carrier densities are very small and depend strongly on
temperature. In order to fabricate devices such as diodes or transistors, it is
necessary to increase the free electron or hole population. This is done
intentionally doping the semiconductor, i. e. adding specific impurities in
controlled amounts.
Doped semiconductor are called extrinsic semiconductors.
... The percentage of impurity in non-degenerate semiconductors must be
small (for example, about 10-5 % in the substrates for integrated circuits). Then
impurity atoms are isolated from each other by semiconductor atoms.
In order to have necessary conductivity type, donor and acceptor impurities are
used.

Charge carriers in the semiconductors doped with donor impurities
The elements from the column V of the periodic table, e. g. phosphorus (P),
arsenic (As) and antimony (Sb) are added to an intrinsic elemental
semiconductor to modify the semiconductor into an n-type semiconductor.
Let us consider silicon doped with phosphorus.

Each pentavalent atom occupies a site usually occupied by a silicon atom. Four
valence electrons are in covalent bonds, the fifth electron rotates round the
positively charged impurity atom.
The binding energy of this extra electron is small. In the case of phosphorus in
silicon it is only about 0.044 eV.
If the fifth electron gets such energy, it leaves the

impurity atom and becomes free.
The impurity atom becomes ionized.
... An electron and a positive ion appear as a result
of ionization of a donor impurity atom.

The free electron is in the conduction band. So

donor energy levels are in the forbidden band near
the bottom of the conduction band
At room temperature each donor impurity atom

donates an additional charge carrier – a negative
conduction electron. According to this
semiconductors that contain donor impurities are
called donor-type, electronic or n-type
semiconductors.
Because usually impurity density is small, donor

levels are isolated and are shown by the dashed line.

Charge carrier densities and Fermi level in extrinsic semiconductors strongly

depend on temperature and impurity density.
At 0 K all allowed energy levels in the valence band are filled by electrons. All
donor levels are filled by unbound electrons. The conduction band is free. So
charge carriers do not exist, and the semiconductor behaves as an insulator.
At 0 K the Fermi level is between the donor levels and the bottom of the
conduction band.
If the temperature increases, unbound

electrons obtain energy and jump to the
conduction band. So, in the low
temperature or impurity ionisation
range, density of conduction electrons
increases.

At some temperature, that is sufficiently lower than 300 K, all impurity atoms
become ionised and the density of conduction electrons becomes equal to the
donor density Nd.
If the temperature further increases, in the wide
range the density of conduction electrons
remains constant. This temperature range is
called the extrinsic range.
ni
nn ≅ N d pn = pi << pi
nn
... In the n-type semiconductor electrons are the majority carriers and
holes are the minority carriers.

In the extrinsic range
nn = N c exp[− (Wc − WF ) / kT ] = N d
Nc
WF = Wc − kT ln
Nd
... The Fermi level in the extrinsic range falls as the temperature
increases.
As the density of the intrinsic charge carriers increases with temperature, at

some temperature that is sufficiently higher than 300 K it becomes equal to Nd.
At higher temperatures thermally exited intrinsic carriers predominate. Then the
semiconductor obtains the properties of an intrinsic semiconductor.
In the high temperature or intrinsic range the Fermi level approaches the mid-
gap position.

... In the impurity ionisation (low temperature) range the density of electrons increases with
temperature.
In the extrinsic range (at middle temperatures) the density of electrons is almost constant.
At last in the intrinsic range (at high temperatures) the intrinsic carriers predominate and their
density increases with temperature.
Plotting the variable 1/T along the x-axis and lnn and lnp along the y-axis, we obtain curves
that may be approximated by the segments of a straight line.
Wc − Wd
f F (Wd ) = 1 / 2 n ≅ Nd / 2 Ts ≅
k ln (2 N c / N d )
∆W
ni = N d Ti =
k ln( N c N v / N d2 )
... In the vicinity of room temperature the conduction electron density in the n-
type semiconductor is approximately constant and equals to the density of donor
impurity atoms. The hole density is much lower than the intrinsic density and is
strongly dependent upon temperature.
At normal temperature carrier densities and Fermi level

depend on impurity density.
ni
nn ≅ N d pn = pi << pi
nn
If the donor density is higher, the Fermi level is higher, closer to the bottom of
the conduction band; the electron density is higher, the hole density is lower.
If the donor concentration is lower, the Fermi level is lower, closer to the middle
of the forbidden band.
... In the n-type semiconductor the Fermi level is always over the middle of the
forbidden band.

Charge carriers in the semiconductors doped with donor impurities.

Problems
1. How many charges and how many charge carriers appear as a result of
ionization of semiconductor atom?
donor atom ionization?
3. A germanium specimen is doped with phosphorus. Its density is 1016 cm–3.
Find densities of electrons and holes and position of the Fermi level at
temperature 300 K.
4. Silicon is doped with phosphorus. The Fermi level is in the forbidden band
at the distance of 0,044 eV from the bottom of the conduction band.
Impurity density is 1016 cm–3. Find the position of the Fermi level at
temperature 300 K.

Charge carriers in the semiconductors doped with acceptor impurities

Semiconductors with majority charge carrier density of holes are called p-type.
They can be produced adding impurities from column III of the periodic table, e. g.
boron (B), aluminium (Al), gallium (Ga) or indium (In) to intrinsic silicon or
germanium.
These p-type impurities are characterized by three valence electrons in their outer
shell.
Let us consider silicon doped with

boron.
The vacancy thus created by the
impurity is not a hole, since it is
bound to the atom.
At some temperature above 0 K the electron from a bond of a neighbouring parent

atom can fill the vacant site leaving a hole.
So dopants from column III accept electrons to create holes for conduction.
Therefore they are called acceptors.


The energy required by a valence electron to fill the vacancy created by an
impurity atom and thus to create a hole is of the similar magnitude to the
ionisation energy of a donor atom. So acceptors create discrete acceptor levels
just above the top of the valence band.
At 0 K acceptor levels are free. Electrons occupy the valence band of the
semiconductor. There are no charge carriers. Semiconductor has properties of
insulator.
If the temperature increases, electrons jump from the valence band to the
acceptor levels leaving holes in the valence band. So in the impurity ionisation
range the density of holes increases with temperature.

In the extrinsic range : pp ≅ N a

ni2 ni2
Density of electrons is small and increases with temperature: np = ≅
pp N a
... Positive holes are the majority carriers and electrons are the minority carriers
in the p-type semiconductor.
As the temperature in the extrinsic range is

raised, the Fermi level increases.
Nv
WF − Wv = kT ln
Na
At high temperatures the material becomes intrinsic and the Fermi level
approaches midway between the conduction and valence bands.

1 – low temperature, impurity ionization range;

2 – middle temperature, extrinsic conductivity range;
3 – high temperature, intrinsic conductivity range
In the extrinsic range:
ni2 ni2 Nv
pp ≅ N a np = ≅ WF − Wv = kT ln
pp N a Na

At normal temperature, Fermi level and carrier densities

depend on the impurity density.
pp ≅ N a np ≅ ni2 / N a
Nv
WF − Wv = kT ln
Na
If acceptor density is higher, the Fermi level is lower,

closer to the top of the valence band; the hole density
is higher, the electron density is lower.
If the acceptor density is lower, the Fermi level is
higher, closer to the middle of the forbidden band.
... The Fermi level below the middle of the forbidden band is the
characteristic feature of the band model of the p-type semiconductor.

Charge carriers in the semiconductors doped with acceptor impurities.

Problems
acceptor ionization?
2. Silicon plate is doped by boron. Its density is 1016 cm–3. Find carrier
densities and Fermi level at temperature 300 K.

Compensation doping
When both acceptor and donor impurities are added simultaneously to an
intrinsic semiconductor, the compensation takes place.
At higher donor density the crystal is n-type
semiconductor since n-type impurity predominates.
The free carriers supplied by the less concentrated
dopant recombine with an equal number of carriers
of the opposite type. So some of the donor states
are cancelled by acceptor states..
If
The process is called compensation.
At higher donor impurity density when N D ' >> N A ' ,
nn = N d ≅ N d '− N a ' pn = ni2 / N d
If N A ' >> N D ' ,
p p = N a ≅ N a '− N d ' np = ni2 / N a

Compensation doping
p-type material can be converted to the n-type and vice-versa, by the addition of
excess dopant atoms of the appropriate type.
If ni > N D − N A , the intrinsic charge carriers predominate. The semiconductor

has properties of the intrinsic compensated or near-fully compensated material.
The Fermi level lies near the middle of the forbidden gap.
Compensation doping is widely used in manufacturing of semiconductor devices

and integrated circuits.
The compensation is possible, if impurity density is not very high. Then the
distance between impurity atoms is relatively great and impurity atoms cannot
interact.
If impurity density increases, the distance between impurity atoms decreases.
When impurity density in silicon becomes approximately 1019 cm-3, degeneration
of the semiconductor arises. Then impurity levels split and allowed bands
appear.

Compensation doping
W
In the degenerate n-type semiconductor, conduction
and donor bands overlap and form the hybrid WF
conduction band. Energy levels at the bottom of the Wc
hybrid conduction band are occupied by electrons.
The Fermi level is above the bottom of the
conduction band.
Wv
In the degenerate p-type semiconductor, we have
overlapping of the valence and acceptor bands.
Then energy levels at the top of the hybrid valence W
band are not occupied by electrons. The Fermi level
is below the top of the valence band Wc
In both cases there are unoccupied allowed energy

levels over the levels that are filled by electrons. The Wv
situation is very similar to that in conductors. WF
Therefore conduction is possible even at 0 K in
degenerate semiconductors and they are sometimes
called semimetals.

Compensation doping. Problem
Germanium is doped with phosphorus and boron. Their densities are

1017 cm–3 and 1016 cm-3, respectively. Find carrier densities and position of
the Fermi level at 300 K.

Under thermal equilibrium the generation rate and the recombination rate are
equal and the carrier densities and remain constant.
The equilibrium may be disturbed by light or carrier injection.
Excess electrons and holes are always equal in number:
n = n0 + ∆n p = p0 + ∆p ∆n = ∆p. pn > ni 2 .
If the external excitation (activation) stops, the density of the excess carriers
reduces exponentially:
∆n(t ) = ∆p(t ) = ∆n0 exp(−t / τ) = ∆p0 exp(−t / τ)
The recombination of the excess carriers

may be radiative or nonradiative, direct
or indirect, band-to-band or through
recombination centres and traps.

n0 = nn + ∆n0 ,
p0 = pn + ∆p0 .
∆n(t ) = ∆p(t ) = ∆n0 exp(−t / τ) = ∆p0 exp(−t / τ)
The lifetime τ represents the average time a carrier remains free before it
recombines. During the lifetime the number of excess carriers reduces e times.
The recombination rate of the excess carriers is dependent on the lifetime:
d n d(∆n) ∆n d p d(∆p ) ∆p
= ... = − = ... = −
dt dt τ dt dt τ
In practical device design small lifetime may be desirable for high-speed
switching applications.
Nanosecond switching speed is realised using gold doping.

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ELEKTRONIKOS PAGRINDAI 2008 1

CHARGE CARRIERS IN SEMICONDUCTORS

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Nature of charge carriers in intrinsic semiconductors

Carefully refined semiconductors are called intrinsic semiconductors. .

At very low temperatures the

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Nature of charge carriers in intrinsic semiconductors

The jump of an electron from the

When an electron is released, a positively charged vacancy appears. This

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Nature of charge carriers in intrinsic semiconductors

Above occupied levels there are

... In the intrinsic semiconductor the number of electrons in the

Charge carriers appear as a result of charge carrier generation.

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Fermi level in an intrinsic semiconductor

The Fermi level in an intrinsic

If the Fermi level is below the bottom of the conduction

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Densities of charge carriers in intrinsic semiconductors

We have derived the expression for density of electrons in a non-generate system.

np = ni pi = ni2 = pi2 ... The densities of electrons and

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Densities of charge carriers in intrinsic semiconductors

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Densities of charge carriers in intrinsic semiconductors. Problems

1. Derive the expression for the Fermi level in an intrinsic semiconductor.

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Extrinsic (doped) semiconductors

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Charge carriers in the semiconductors doped with donor impurities

Let us consider silicon doped with phosphorus.

If the fifth electron gets such energy, it leaves the

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Charge carriers in the semiconductors doped with donor impurities

The free electron is in the conduction band. So

At room temperature each donor impurity atom

Because usually impurity density is small, donor

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Charge carriers in the semiconductors doped with donor impurities

Charge carrier densities and Fermi level in extrinsic semiconductors strongly

If the temperature increases, unbound

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Charge carriers in the semiconductors doped with donor impurities

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Charge carriers in the semiconductors doped with donor impurities

In the extrinsic range

As the density of the intrinsic charge carriers increases with temperature, at

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Charge carriers in the semiconductors doped with donor impurities

Charge carriers in the semiconductors doped with donor impurities

At normal temperature carrier densities and Fermi level

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Charge carriers in the semiconductors doped with donor impurities.

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Charge carriers in the semiconductors doped with acceptor impurities

Let us consider silicon doped with

At some temperature above 0 K the electron from a bond of a neighbouring parent

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Charge carriers in the semiconductors doped with acceptor impurities

VGTU EF ESK stanislovas.staras@el.vgtu.lt

Charge carriers in the semiconductors doped with acceptor impurities

In the extrinsic range : pp ≅ N a