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Extrinsic Semiconductors
Recombination
Carrier Transport
Minority Carrier Injection

n-type Doping
A pure Si lattice is entirely made up of Si atoms. Imagine if
some Group V elements like As or P are introduced in small
quantities as impurities. This will ensure that the diamond
structure of the host lattice is retained.
As has 5 valence electrons. When As takes up its position in
the lattice, 4 of these valence electrons bond with 4
neighbouring Si atoms, & the fifth electron is left unbonded.
It is left orbiting around the As+ ion core. This being the
outermost electron of As, the ionization energy required to
free this electron is very low, typically ~ 0.05 eV.
The average thermal energy of lattice vibration at a
temperature T is 3kT = 0.07 eV at room temperature.

As+
e-

Arsenic doped Si crystal. The four valence electrons of As allow it to

bond just like Si but the fifth electron is left orbiting the As site. The
energy required to release to free fifth-electron into the CB is very
small.

 Thus at room temperature, this electron will be free in the

semiconductor.
In terms of the energy band diagram, this electron will be
occupying a state in the CB.
The addition of As introduces localized electronic states at
the As site.
The energy Ed of these states is ~0.05 eV below EC, meaning
thereby that by gaining an energy 0.05 eV, an electron can
free itself from the As atom and get released to occupy an
empty state in the CB.
The CB now has an electron, but the localized energy state Ed
is now ionized (As+).

Electron Energy

CB

~0.03 eV

Ec
Ed

As+

As+

As+

As+

Ev
As atom sites every 106 Si atoms

x Distance
into
crystal

 As+ ions are immobile.

As atoms are called donor atoms or donor impurity.
At elevated temperatures (> 100K) all donor atoms are
ionized.
The process introduces free electrons in the CB. (Note: unlike
in an intrinsic semiconductor, this process is NOT
accompanied by creation of equal number of holes in VB)
The Ed level created by the impurity is called donor level.
If Nd is the donor atom concentration, there is a major
contribution of electron concentration in CB due to Nd.
Electrons (in CB) and equal number of holes (in VB) can also
be produced by the intrinsic property of Si (ni).
If Nd is >> ni, then it can be assumed that the total n Nd, &
by law of mass action, p = ni2/Nd.

p-type Doping
By adding an element of Group III as impurity, like B. Al, Ga,
etc, we can introduce holes in valence band.

h+

B-

B-

Free

(a)

(b)

Boron doped Si crystal. B has only three valence electrons. When it

substitutes for a Si atom one of its bonds has an electron missing and
therefore a hole as shown in (a). The hole orbits around the B- site by
the tunneling of electrons from neighboring bonds as shown in (b).
Eventually, thermally vibrating Si atoms provides enough energy to
free the hole from the B- site into the VB as shown.

 The energy needed to free the hole from the influence of

the B- ion is typically 0.05 eV.
In terms of the energy band diagram, this hole will be
occupying a state in the VB.
The addition of B atoms introduces localized electronic
states Ea (called acceptor states) at the B site.
The energy Ea of these states is about 0.05 eV above Ev,
meaning that by gaining an energy 0.05 eV, an electron
can move from the top of VB to occupy an acceptor state
Ea.
The VB now has a hole, but the localized energy state Ea is
now ionized (B-).

Electron energy
B atom sites every 106 Si atoms

x Distance

Ec

Ea

into crystal

B-

h+

B-

B-

B~ 0.05eV

Ev
VB

Energy band diagram for a p-type Si doped with 1 ppm B. There are
acceptor energy levels just above Ev around B- sites. These acceptor
levels accept electrons from the VB and therefore create holes in the VB.

 B- ions are immobile.

B atoms are called acceptor atoms or acceptor impurity
At elevated temperatures (> 100K) all the acceptor atoms are
ionized.
The process introduces holes in the VB. (Note: unlike in an
intrinsic semiconductor, this process is NOT accompanied by
creation of equal number of electrons in CB)
The Ea level created by the impurity is called acceptor level.
If Na is the acceptor concentration, then at room temperature,
there is a major contribution to hole concentration in VB due
to Na. Electrons (in CB) and equal number of holes (in VB)
can also be produced by the intrinsic property of Si (ni).
If Na is >> ni, then it can be assumed that the total p Na, and
by law of mass action, n = ni2/Na.

Compensation Doping
It is possible to compensate for excessive doping of donor
impurities by adding some acceptor impurities and vice
versa and thus help achieve the required semiconductor
properties.

If Nd > Na, and (Nd Na) >> ni, the effective electron
concentration in the compensated material is n (Nd Na)
and the corresponding p = ni2/n

 If Na > Nd, and (Na Nd) >> ni, the effective hole concentration
in the compensated material is p (Na Nd) and the
corresponding n = ni2/p
The above arguments assume that the temperature is high
and that all donors and acceptors are ionized. This is always
the case at room temperatures (300K) and above.
It is wrong to assume that if both dopings are high, both n
and p will be high. This is because, the probability of both
electrons and holes recombining will be very high and a
sizeable number of electron hole pairs will be lost through
recombination.

Conductivity in a Semiconductor
In the presence of an E-field, electrons in conduction band
gain energy from the field and move in a direction opposite
to that of the field.
They also collide due to thermal vibrations of lattice and lose
energy. This results in electrons drifting, with a drift velocity
vde.
Similar process results for holes in valence band, in an
opposite direction, with a drift velocity vdh.
Total current density
where
n = electron conc. in CB and p = hole conc. in VB,
e = electronic charge

 The drift mobilities are defined as

is the mean free time between scattering events, m* is the

effective mass of electrons and holes.
Considering the fact that J = . x , where is the
conductivity, and x is the electric field,

n-type Semiconductor:
The total conductivity of this extrinsic semiconductor is

At low temperatures, not all donors are ionized, and the

equation is not valid.
p-type Semiconductor:
The total conductivity of this extrinsic semiconductor is

At low temperatures, not all acceptors are ionized.

Temperature Dependence of Conductivity

T < Ts

Ts < T < Ti

T > Ti

CB
EF
Eg

As+ As

As

As

+
+
+
+
EF As As As As

EF

As+ As+ As+ As+

VB

(a)T=T1

(b)T=T2

(c)T=T3

(a) Below Ts, the electron concentration is controlled by the ionization of

the donors. (b) Between Ts and Ti, the electron concentration is equal to
the concentration of donors since they would all have ionized. (c) At high
temperatures, thermally generated electrons from the VB exceed the
number of electrons from ionized donors and the semiconductor behaves
as if intrinsic.

 For an intrinsic semiconductor, we know that

n or p is produced by thermal excitation across a bandgap

energy Eg.
In the same manner for an n-type semiconductor at low
temperature (when thermal excitation is not possible and the
only way n can be generated is through donor states)

The factor arises because the donor occupation statistics is

different from the usual F-D distribution function.

 There are three temperature regions of interest:

1. Low temperature region (T<Ts). n reaches a maximum of Nd
in this range, called ionization range
2. Medium temperature region (Ts<T<Ti). All donors are
ionized and the temperature is still low enough, so no
significant thermal generation of carriers, and n continues to
remain at Nd in this extrinsic range.
3. High temperature region (T>Ti). In this range, the thermally
generated carriers exceed Nd and the semiconductor behaves
as if it is intrinsic. This range is called intrinsic range.

ln(n)
INTRINSIC
slope = -Eg/2k

ln(Nd)

EXTRINSIC

Ts

IONIZATION
slope = E/2k

Ti
ni(T)

1/T

The temperature dependence of the electron concentration in an n-type

semiconductor.

 ni at room temperature (300K)

for Si is reported as 1.5 x 1010
cm-3 though of late, authors of
many text books use a value of
1x1010 cm-3 or even 9.69x109
cm-3.

600oC 400oC
L

200oC

27oC 0oC

1018

Intrinsic Concentration (cm-3)

Based on the expressions for

Nc and Nv , the temperature
dependence of n or p for an
intrinsic semiconductor, or for
a semiconductor in the
intrinsic range, is given by

2.4 1013 cm-3

1015

Ge
1012

1.45 1010 cm-3

109

Si
106

103

2.1 106 cm-3

GaAs
1

1.5

2.5
3.5
3
4
1000/T (1/K)
The temperature dependence of the intrinsic concentration.
2

Drift Mobility: Temperature & Impurity Dependence

At low temperatures, scattering
by ionized impurities is
predominant and mobility is e
scattering dependent.
It can be shown that the
ionized impurity limited
scattering is given by

KE = 1/2mev2

KE > |PE|
KE |PE|

rc
As+
KE < |PE|

Scattering of electrons by an ionized impurity

where NI is the concentration of all ionized impurities.

Mobility decreases with increasing scattering centres (NI).
Increased T reduces scattering radius and increases mobility.

 At high temperature, mobility is limited by lattice scattering.

The lattice scattering limited mobility can be shown to be
given by
Mobility decreases with increasing temperature and
increasing lattice vibration.
Combined effect of two scattering processes:

The scattering process having the lowest mobility

determines the overall drift mobility

Electron Drift Mobility(cm2 V-1s-1)

50000

L T -1.5

10000

Nd

=1014

Ge
Nd =1013

Nd =1016
Nd =1017

1000

Nd =1018
100

Nd

=1019

Si

T1.5

10
70

100

Temperature (K)

800

Log-log plot of drift mobility vs temperature for n-type Ge and n-type

Si samples. Various donor concentrations for Si are shown. Nd are in
cm-3. The upper right inset is the simple theory for lattice limited
mobility whereas the lower left inset is the simple theory for impurity
scattering limited mobility.

Drift Mobility(cm2 V-1s-1)

2000
1000

Holes

Electrons

100
50

1015

1016

1017

1018

1019

Dopant Concentration, cm-3

1020

The variation of the drift mobility with dopant concentration in Si for

electrons and holes

Drift Mobility: Temperature Dependence

INTRINSIC

log(n)

Resistivity

LOGARITHMIC SCALE

log( )

Semiconductor

Metal
T

EXTRINSIC
Lattice
scattering

log( )

IONIZATION
T

High Temperature

-3/2

3/2

T
Impurity
scattering

1/T

Low Temperature

Temperature dependence of electrical conductivity for a doped (ntype) semiconductor.

Metal
Fermi filling
function

Energy band
to be filled
EC,V

EF

Overlapping Ev, Ec

At T = 0, energy levels below EF are

filled with electrons, while all levels
above EF are empty.

Electrons are free to move into empty

states of conduction band with only a
small electric field E, leading to high
electrical conductivity!

Moderate T

Semiconductor
T>0
Conduction band
(Partially Filled)

At T > 0, electrons have a probability to

be thermally excited from below the
Fermi energy to above it.

EF

EC
EV

Valence band
(Partially Empty)

Insulator
Conduction band
(Empty)

T>0

EC

Eg

EF
Valence band
(Filled)

At T = 0, lower valence band is filled with

electrons and upper conduction band is
empty, leading to zero conductivity.

E
V

Fermi energy EF is at midpoint of

large energy gap (2-10eV)
between conduction and valence
bands.

At T > 0, electrons are NOT thermally

excited from valence to conduction band,
leading to zero conductivity.

At T = 0, valence band is filled with

electrons and conduction band is empty,
leading to zero conductivity.

At T > 0, electrons thermally excited

from valence to conduction band, leading
to partially empty valence and partially
filled conduction bands.

Degenerate & Non-degenerate semiconductors

The general expression for electron concentration in CB is

Nc is a measure of the density of states in CB.

If n << Nc, then there are fewer electrons than the available
states and Paulis Exclusion Principle can be neglected. The
statistics is then described by Boltzmanns statistics.
All equations formulated so far here are with this condition,
and such semiconductors for which n << Nc or p << Nv are
called non-degenerate semiconductors.

 In a degenerate semiconductor, n>> Nc or p >> Nv brought

about by heavy doping.
Such large concentration of impurity states, result in their
energy states forming band of energy that overlap with the
conduction band (for n-type) or the valence band (for the ptype).
E
Impurities
forming
a band
g(E)

CB

CB

EFn
Ec

Ec
Ev
EFp

Ev

VB
(a)

(b)

Recombination & Minority Carrier Injection

Direct & Indirect Recombination
Recombination is a process wherein an electron in the CB meets a hole in
the VB and fills it. The electrons and holes that take part in the process
are consequently annihilated.
On the energy band diagram, recombination is represented by returning
an electron in CB (higher energy state) into a hole in the VB (lower
energy state).
In order for the conservation of energy to be valid for this recombination
process, the excess energy is lost in the form of photon of energy E = h.
Conservation of linear momentum must also be met in this
recombination. The wavefunction of the electron in the CB will have a
certain momentum hkcb . Similarly, the electron wavefunction in the VB
will have a certain momentum hkvb.
Momentum conservation requires kcb = kvb.

Energy
CB
Ec

cb(kcb)

h = Eg

vb(kvb)

Ev

VB

Distance

Direct recombination in GaAs. kcb = kvb so that momentum conservation

is satisfied

 In elemental semiconductors like Si and Ge, the electronic

states with kcb = kvb occur deep in the middle of VB, which are
fully occupied, so direct recombination is impossible.
In compound semiconductors like GaAs and InSb, the
electronic states with kcb = kvb occur right at the top of VB,
which are essentially empty (contain holes), so direct
recombination is possible.
Consequently, a free electron in the CB edge Ec of GaAs can
drop down to an empty electronic state at the top of valence
band and maintain kcb = kvb.
The photon energy released in the process makes it a clear
choice as material for light emission.

 Elemental semiconductors like Si and Ge undergo indirect

recombination. The Ec to Ev transition process usually
involves a third body, usually an impurity atom or a crystal
defect (like dislocations, vacancies) that create a localized
energy state somewhere in the middle of the bandgap.
These are called recombination centres, that capture an
electron in the CB. The bound electron, waits for a hole in the
VB with which it can recombine.
In this type of two stage transitions, energy is lost in the form
of lattice vibrations, called phonons.
Sometimes, the impurity states of defect states act as mere
trapping centres rather than recombination centres.

CB
Ec
Er
Ev

Er

Er

Phonons

Recombination
center

VB

(a) Recombination
CB
Ec

Ev

Et

Et

Et

Trapping
center

VB

(b) Trapping

Recombination and trapping. (a) Recombination in Si via a recombination center which has a
localized energy level at Er in the bandgap, usually near the middle. (b) Trapping and
detrapping of electrons by trapping centers. A trapping center has a localized energy level in the
band gap.

Minority Carrier Lifetime

What happens when an n-type Si doped with 5x1016 cm-3
donors is uniformly illuminated with appropriate
wavelength light to generate electron-hole pairs (EHPs) ?
CB
Ec
Ed

Ev
VB
Low level photoinjection into an n-type semiconductor in which
nn < nno

 For this n-type semiconductor, electrons are majority carriers

& holes are minority carriers. We use a subscript n to define
n or p type semiconductor.
nno = electron conc. in n-type at thermal equilibrium in the
dark (majority carrier conc.)
pno = hole conc. in n-type at thermal equilibrium in the dark
(minority carrier conc.)
nno.pno = ni2
When the semiconductor is illuminated, excess EHPs are
generated. Electron & hole conc. dynamically changes.
Suppose at any instant:
nn = electron concentration in n-type = nno + nn
pn = hole concentration in n-type = pno + pn
where n and p are the excess majority & minority conc.

 Since the excess carriers are created as EHPs,

nn = pn
Obviously the law of mass action is not obeyed:
nn.pn ni
Also
A low level injection causing a 10% change in nno will have
the following effects:
There is no significant change in nn but pn the minority
carrier concentration is altered significantly.

Low level injection in an n-type semiconductor does not affect

nn but drastically affects the minority carrier concentration pn.

 What happens when the illumination is removed?

Illumination

- + - -- - - - + - -

+
-

- + - + + +- + - - + -+ - + - + - - + - - + +
- +
- + - - - + -+ +
-

n-type semiconductor in Illumination with h >E

g
the dark.
creates excess holes:
pn = pno<< nno
pn = pno+ pn = nn

C
- - + - - - + - - - - + +
+ - - +
- + - - - + -+

+
-

In dark after
illumination. Excess
holes are disappearing
by recombination.

Illumination of an n-type semiconductor results in excess electron

and hole concentrations. After the illumination, the recombination
process restores equilibrium; the excess electrons and holes simply
recombine.

 Once the illumination is removed, the excess holes

recombine with the available electrons & disappear, in a
short period of time.
The rate of recombination can be described by a minority
carrier lifetime h, which is the average time the hole exists
in the VB from the time it is generated till it recombines
with an electron in the CB.
When both generation and recombination takes place
simultaneously,
Rate of increase in excess hole conc.
= Photogeneration rate - Recombination rate of excess holes

 If the illumination is removed at time t = 0, Gph = 0 and the

solution is:

G and pn(t)
Gph
Illumination

0
pno+ pn( )

pn(t') = pn(0)exp(-t'/ h)

hGph
pno
0

toff

Time, t
t'

Diffusion & Conduction Equations

Electrons in CB & holes in VB can be considered as particles.
When such particles have some distribution in space, with a
certain concentration gradient, then diffusion occurs.
Particle flux is defined as the number of particles crossing
unit area per unit time
If the particle has a charge Q, current density J = Q.
The flux of electrons is governed by Ficks First Law:

-ve sign indicates that the direction of flux is opposite to the

direction of increasing conc. Const. of proportionality is De.

n(x,t)

Net electron diffusion flux

Electric current

n1

n(x,t)

n2

xo
xo-

xo +
(a)

x o -

xo

(b)

x o +

 In the figure, there are

Semitransparent electrode
n-Type Semiconductor

Diffusion current due to

electrons along -ve x

Electron Diffusion

Light

Electron Drift
Hole Diffusion
Hole Drift

Ex

Drift current due to

electrons along +ve x
Diffusion current due to
holes along +ve x
Drift current due to holes
along +ve x

When there is an electric field and also a concentration gradient, charge

carriers move both by diffusion and drift. (Ex is the electric field.)

 Einsteins Relation:

Continuity Equations
Excess carrier concentration decays exponentially as a
function of time when optical illumination is removed. What
happens when the optical illumination is constantly present?
p(x,t)

Semiconductor
z

Jh + Jh

Jh
x

x+ x

y
x

Consider an n-type semiconductor with an element of

volume A.dx across which hole concentration is p(x,t).

 Without illumination, at thermal equilibrium, the value of

hole concentration is pno .

-ve sign indicates that some excess holes are lost along x due
to recombination, as they move along x.
Due to continuous illumination, there also exist continuous
photogeneration at a constant rate, Gph and a recombination
rate due to minority carrier lifetime
Net rate of increase in hole concentration

This is the Continuity equation for holes.

 Jh is the hole component of current density. It is made up of

drift and diffusion components.
There is a similar equation for net rate of excess electron
concentration.
If we consider uniform illumination everywhere, then Jh is
uniform along x. This gives

Steady State Continuity Equations:

Consider a continuous illumination at one end of a long ntype slab. There is no bulk photogeneration, Gph = 0.
In such a case, under steady state condition,

Jh contains drift & diffusion components, Assuming that the

drift component is negligible (say, electric field is negligible),
then simplifying the expression for Jh & noting that
pn(x) = pno + pn(x)

Lh is called diffusion length of holes = (Dhh)1/2

Excess concentration

xo

n-type semiconductor

Light

pn(0)
nn(0)

pn(x)

Diffusion

nn(x)
x
(a)

We assume a weak injection, one end is illuminated. The

layer that absorbs the light is very thin. The excess holes
created will have a steady state continuity equation. Suppose
the illumination causes excess hole conc. at x = 0 to be pn(0).
Solution is given by

 Obviously at the other end of the long bar, there are no

excess holes. The only hole conc present is the equilibrium
value pno.
The concentration gradient causes a diffusion hole current,
which are prominent only near the illuminated end.
There will be a steady state distribution of excess electrons
for this example

where Le is the diffusion length of electrons = (Dee)1/2

Currents (mA)

Diffusion
Drift

ID,h

Idrift,e

0
4

ID,e
0

20

40

(b)

60

80

x ( m)