Semiconductor Crystals - November 8, 2005

After studying this section, you should be able to explain:

What are semiconductor crystals? How do I calculate the band gap in these crystals?
What causes Excitations to form electron-hole pairs? What is Intrinsic Conduction:
Electron-hole pair formation? What is Extrinsic Conduction: Doping? What is
Recombination and Carrier Lifetime? What are Compound Semiconductors?

__________________________________________________________________________
What are Semiconductor Crystals?
Semiconductor crystals are characterized lower concentration of charge
carriers (either electrons or holes) than metals.

At room temperature,

their electrical conductivity is ~10

They have band gaps much

-5

to 10 S/m.
5

narrower than insulators (0.2-6.5eV).

Sources of Excitations of electron-hole pairs
1. Thermal Excitations Thermal energy (heat) causes electrons to cross
the band-gap.
2. Optical Excitations Photons having energy, h, large enough to excite
electrons across the band-gap.
3. Impurities Doping pure semiconductors with atoms having more or fewer
electrons causes energy states associated with dopant to donate to the
conduction band or accept from the valence band.

Heat Input
(T)

Electrons excited
from Valence to
Conduction Band
{D(), f(), n}

Conduction

Hole Left behind

in the Valence
Band (D(h), f(h),
p)

Under applied
field, , e and h
move creating
current (e, h)

Intrinsic Semiconductors (No impurities states)

Intrinsic conduction arises when there is a low impurity concentration in
the semiconductor and so increase in temperature determines the electrical
properties.

Semiconductors showing intrinsic conductivity have small band

gaps so that thermal excitations are enough to cause electrons to move from
the valence band to the conduction band.

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Semiconductor Crystals

When the band gap is large

relative to temperature, there will be few intrinsic carriers and

conductivity will drop.
The band gap energy (Eg) is the energy difference between the lowest
unoccupied band and the highest valence band.
Band Gap = Conduction Band Edge Valence Band Edge
Conductivity arises from electron mobility in the conduction band and hole
(vacant sites left behind by electrons) mobility in the valence band.

Band Gap in Semiconductor Crystals

Semiconductor materials are characterized by a strong temperature
dependence of conductivity.

Typically, these materials have a lower

concentration of charge carriers (either electrons or holes) than metals.

At room temperature, their electrical resistivity is ~10-2 to 109 ohm-cm.
Semiconductor Type
III-V (trivalent-

Al, Ga, In

N, As, P

pentavalent)
II-VI (divalent-

Zn, Cd, Hg

S, Se, Te, O

hexavalent)
IV-IV (Diamond Type)

C, Si, Ge, Sn

C, Si, Ge, Sn

Measurement of Intrinsic Conductivity

Band gap is determined by Optical Absorption measurements of two types:
1. Direct Optical Absorption Measurements: Photons are absorbed at
frequenciesg reveal the crystal to have a band gap of E g g .

Such

measurements are made by scanning the range of photon frequencies until

absorption occurs.
2. Indirect Optical Absorption Measurements: Indirect absorption are
made when the band gap is too large for a single photon to be absorbed,
then indirect absorption occurs.

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Semiconductor Crystals

In this case, a phonon is emitted in

the excitation process, so that, g E g where is the phonon

frequency.

Typically, E g is greater than

3. Temperature dependence of Electrical Conductivity: The intrinsic

conductivity and carrier concentration is controlled by the ratio of
energy gap to temperature since the carrier concentration (n or p) is
proportional to kbT / Eg.

The exact equation is obtained by integrating

the product of conduction band Density of States (called D()) with the
Fermi-Dirac distribution (called f()).
n or p

D( ) f ( )d

The range on the integration is Ec to

for n-type (electron carriers)

and - to Ev for p-type (hole carriers)

The bulk carrier concentration determined using Hall measurement
(http://www.eeel.nist.gov/812/meas.htm).

Temperature dependence of the

carrier concentration can be used to calculate the band gap.

Calculation of Intrinsic Electron Charge Carrier Concentration
We must use the density of states and the Fermi-Dirac function to calculate
the intrinsic charge carriers for Electrons.
Fermi Dirac Function, f():
The Fermi-Dirac Distribution gives the probability that an energy level, ,
will be occupied by an electron:
f ( )

1
.
exp[( ) / k B T ] 1

In the case of semiconductors, we wish to calculate the number of electrons

excited to the conduction band at temperature, T.

In this case, we call

the Fermi Level (the highest occupied level of the valence band).

In most

cases, >>kBT, resulting in the Fermi-Dirac distribution taking the form

of the Boltzman Distrubution,

f ( ) exp / k B T
Density of States Function, D():
The Density of States is defined as the number of orbitals per unit energy
(or dN/d).
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Semiconductor Crystals

dN
V
D( )

d
2 2

3/ 2

2m e *

( k E c )1 / 2

Intrinsic electron charge carrier concentration:

The concentration of electrons in the conduction band then becomes, n,
where

D( ) f ( )d

Ec

*
1 2me
n
2 2 2

1
n
2 2

2me *

3/ 2

( E

c)

1/ 2

Ec

3/ 2

k BT

exp

d
k BT

exp

( E

c)

1/ 2

Ec

d
exp
k BT

Integrating yields
m *k T
n 2 e B2
2

3/2

Ec

k BT

exp

Here, the density of states function uses the effective hole mass (which is
different than the effective electron mass).

In fact, the effective hole

mass is larger due to the following:

1. Band curvature in E(k) near top and bottom of band
2. Band curvature in E(k) leads to higher correction to electron/hole
mass (always fractional)
3. Higher correction leads to lower effective mass.

Density of occupied electron states vs. Density of electron states

Conduction Band
Eg
0

Energy Gap
Valence Band

Density of states D() for semiconductors in the

vicinity of the energy gap is parabolic at the bottom of
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Semiconductor Crystals
the conduction band and the top of the valence band.

Density of electron and hole states, D() assumes a parabolic shape near
the energy gap given by the parabolic function (i.e. there are more energy
bands as we move away from the energy gap.

(However, fermi distribution

actually causes a reduction of density of occupied electron states near top

of conduction band.)
We have examined the density of electron D() states.
be occupied by electrons.

Not all states will

In order to determine the density of occupied

electron states {D()f()}, we have employed the Fermi-Dirac Function!!!

Now, lets Calculate the density of occupied electron states, Ne

Conduction Band
Eg
Valence Band
Energy Gap
0
Density of occupied states is D()f() decreases exponentially to
approach zero assymptotically in the conduction band away from the
energy gap.

Calculation of Intrinsic Hole Charge Carrier Concentration

We will again use the density of states and the Boltzmann function to
calculate the intrinsic charge carriers for Holes.
Fermi Dirac Function, f():
For holes, the distribution becomes 1-f()electrons.
f ( ) 1 exp / k B T
exp / k B T

Density of States Function, D():

The equation for the density of states is

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Semiconductor Crystals

3/ 2

dN
V 2 me
D( )

d 2 2 2

( E v k )1 / 2

Intrinsic electron charge carrier concentration:

The concentration of holes in the conduction band then becomes, p, where
p

D( ) f ( )d

Ec

Resulting in
m *k T
p 2 h B2
2

3/ 2

Ev

k
T
B

exp

Calculating the Energy Gap from Electron and Hole carrier concentration
Measurements
Multiplying n and p, we can have an equation which does not depend on the
fermi energy (it cancels).

The product only depends on the magnitude of

Eg.
m *k T
if p 2 h B2
2

3/ 2

Ev

exp
k BT

m *k T
n 2 e B2
2

3/ 2

Ec

exp
k BT

Ev


Ec
exp
exp
exp

k BT
k BT
k BT
k BT

then np N c N v exp

Eg

np N c N v exp

k
T
B

with
mh * k B T

2 2

Nv = 2

3/ 2

and

me * k B T

2 2

Furthermore, for an intrinsic semiconductor, n=p.

n p

3/ 2

Nc = 2

Thus,

N c N v exp[( E g ) / 2k bT ]

Given the value of the Energy Gap, we can now calculate the Fermi Energy
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Semiconductor Crystals

The fermi energy is located within the energy gap, however, we are not
certain where.
We can determine the location of the fermi level for intrinsic
semiconductors by the following:
In intrinsic conduction, one electron excitation to the conduction level
produces one hole in the valence level, therefore, n = p and

Ec

n N c exp
k BT
And

p N v exp v
k BT
Ec
E
N v exp v

k
T
k
T
B
B

N c exp

Ec

exp
k B T
Nv

Nc
E

exp V
k
T
B

E c EV
Nv

exp
Nc
k BT

2 E c EV
Nv

exp
Nc
k
T
B

2 E g
Nv
exp
Nc
k BT

or

3/ 2

N v mh*

Since

N c me*

2 E g
Nv
exp
Nc
k BT

mh*

3/ 2

m*
e

Taking the ln of both sides, we have,

2 E g

3 mh*

2 ln m *

k BT

Simplification yields the Fermi energy,

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Semiconductor Crystals

Eg
2

m*
3
k B T ln h*
4
me
7

However, Since the energy gap (e.g. Si = 1.1 eV) is much larger than
kbT=0.025eV (near room temperature).

We see that for Intrinsic

Eg

Semiconductors, the Fermi level lies at the center of the Band Gap:

Intrinsic Carrier Mobility, eor h

The intrinsic carrier mobility is defined as the drift velocity per unit
electric field.

The units of carrier mobility is [m/s/J] or [s/kg].

=|v|/E

in units of [s/kg]

The electrical conductivity, , is defined as =ne2/m.

In terms of carrier mobility, this conductivity can be written as:
=(e + h)
=(nee + peh)
where n and p are the electron and hole concentrations, respectively.
Hence, the conductivity can be thought of as the sum of the contribution
due to electrons and the contribution due to holes.
By comparison of the electrical conductivity based upon the drift velocity
of electrons within the Fermi sphere, we see that the intrinsic carrier
mobility becomes:
e=ee/me and h=e h/mh
where e and h are the time between collisions with ion cores.
Temperature Dependence of mobility during Intrinsic conduction
There is a temperature dependence of carrier mobility.

This temperature

dependence is thought to be small compared with the temperature dependence

of carrier concentration dependence of exp(-Eg/2kbT).

In other words, the

temperature dependence of intrinsic conduction is thought to be controlled

by the formation of electron-hole pairs rather than the mobility of
electrons and holes.

Impurity atoms enter the structure by either substitution of the lattice

atoms or by fitting into interstitial sites (e.g. tetrahedral, octahedral,
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Semiconductor Crystals

or cubic interstices).

In general, atoms which have similar size to the

host structure atoms will occupy substitutional sites rather than

interstitial sites.

We will confine our discussion of dopants in

semiconductors to those which occupy substitutional sites.

Types of Impurities
Since Si and Ge (Group 4 elements) are tetrahedrally coordinated and there
are 4 valence electrons on each atom (Figure 1).

If an impurity atom from

Group 5 (e.g. As, P, Sb) is added as a dopant element, there will be an

extra valence electron left unbonded and free to participate in conduction
(Figure 2).

Alternatively, if an impurity element from Group 3 (e.g. B,

Al, Ga, In) is added as a dopant element, there will be an extra hole left
over to participate in conduction (Figure 3).

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Semiconductor Crystals

Si

Si

Si

Si

Si

Si
Figure 1. Tetrahedrally Coordinated Silicon
Si

excess
electron

Si

Si

+
As

Si

Si
Figure 2. Tetrahedrally Coordinated Silicon doped with As (Group 5 element). A
conduction electron is left over. The result is an n-type semiconductor.
Conduction eSi

Si

+
Conduction
hole

Si

Si

Si
Figure 3. Tetrahedrally Coordinated Silicon doped with B (Group 3 element). A
conduction hole is left over. The result is a p-type semiconductor.

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Semiconductor Crystals

10

Donors are substitutional atoms which give up an electron to the crystal

(e.g. Group 5 elements).

Acceptors are substitutional atoms which consume

an electron (leaving behind a hole).

Donor State Electron Mobility
The donor electron is attracted by coulomb potential to the impurity ion.
This potential is defined by
E=e/r
where is the static dielectric constant of the crystal after doping, r is
the distance traversed by the electron in the presence of the electric
field, and e is the electronic charge.
The donor ionization energy is given by, Ed=(me4)/(82h2)

Materials having high dielectric constants will inhibit electron mobility

in a given electric field.

Therefore, insulating materials are known for

having a high dielectric constant.

Materials such as SiO2, ZrO2, and Al2O3

have high dielectric constants and are sometimes called dielectric

materials.

(An interesting sidenote: as the semiconductor industry moves

toward smaller and smaller devicesMoores Law, the SiO2 gate dielectrics
used to insulate silicon are becoming too thin to inhibit electron
tunneling (e.g. current across the dielectric occurs)thereby leading to
the study of materials having higher dielectric constants than SiO2 to
substitute as gate dielectrics.)

A donor level (dashed line) is near the conduction band.

Since electrons

conduct, these are known as n-type conductors.

As we increase our donor dopant concentration, we have an increase in the

fermi energy.

From equations which show the exponential dependence of

concentration on fermi level, we know that this is a logarithmic increase:

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Semiconductor Crystals

11

Ef

Log Nd or Na

An acceptor level is near to the valence band.

Ionization Energy and Bohr Radius of Donor States (pp 222)
Before the electron can participate in conduction, it must first be
liberated from the donor (e.g. As in Figure 2).

The energy required to

ionize the donor impurity can be estimated as

Ed

e 4 me
2
2

13.6 me
in eV.
2 m

Notice that this is equivalent to the ionization energy of atomic hydrogen

upon 2.
(Side note on effective mass, me pp 209-214.

We note that effective mass

is mass after we accounting for effects due to the energy band curvature.
We may assume that me=0.2m in Si and me=0.1m in Ge).
The Bohr radius of the donor atom is :

ad

0.53 *
in Angstroms
2
me e
me / m

Significance of the Bohr radius arises when we attempt to understand

conduction in doped semiconductors.

The Bohr radius must be large enough

to result in overlapping of impurity bands (~80Ang for very small effective

electron massas in Si me*=0.2m and Ge me*=0.1m).

Electron conduction,

thus, occurs by movement of electrons from one donor impurity to the next.
One final note is that electrons transport from one unoccupied donor site
(e.g. As+) to another unoccupied donor site.

If an electron already exists

at the donor site (e.g. As ), then transport of the next electron will not
0

occur.
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Semiconductor Crystals

12

Acceptor State Electron Mobility (pp 224)

Acceptors will receive electrons from the neighboring atoms, leaving behind
holes in the host lattice structure.

Ionization energies of acceptors

requires the input of energy (because the host lattice must form a hole).
Relative to Intrinsic Conduction
Intrinsic conduction occurs in pure, undoped semiconductors.

In this case,

the number of electrons and holes are equal.

Thermal Ionization of Donors and Acceptors

Donor and acceptors may be ionized by increasing temperature.

The equation

governing this temperature effect is the same as the equation for thermal
ionization of hydrogen,

Ed
n n o N d exp
2k B T

where

no 2

me k B T

2
2

where Nd is the donor

concentration.

We may write ,
Nd + (Si/Ge) Nd+ + e- + (Si/Ge) for the donor reaction with the host
lattice
Na + (Si/Ge) N

+ h + (Si/Ge)
+

for the acceptor reaction with the host

lattice

As such, the law of chemical equilibrium suggests that the reaction

equilibrium constant, k is
k=[ Nd+] [e-]/[ Nd ] for the donor reaction
k=[ Na-][h+] /[Nd ] for the acceptor reaction.
We may call the electron carrier concentration, n=[e-].

Therefore, n=[ Nd+]

satisfies charge neutrality.

Likewise, we may call the hole carrier concentration, p= [h+] = [ Na-]
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Semiconductor Crystals

13

Recombination Lifetime
By law of mass action, product of n and p yields an expression which, at a
given temperature T, is proportional to the rate at which an electronhole pair will recombine in the reaction e+h=photon (called the
recombination reaction).

The emitted photon will have an energy equal to

that of the band gap,

Eg = h
This quantity is useful if we consider that an incoming photon will
generate excess electron-hole pairs above the concentration formed via
thermal excitations and doping.
Excess Charge carrier produced by optical excitations:
Extrinsic: Without radiation, we have a balance between thermal excitation
and recombination.
electron-hole pairs.

In the presence of radiation, we increase the number of

With optical production, a much greater change is

produced in the minority carrier concentration (10^4 holes increase to

10^14 holes increase by a factor of million while 10^16 electrons increase
by 10^10

factor of 1 part in 1 million.

Intrinsic: Without radiation, equal number of electron-hole pairs.

Increase in the number of electron hole pairs after optical excitation.
In extrinsic cases, after the light is removed, the decrease in carrier
concentration depends on excess minority charge carrier (since it was most
effected) in an equation of the form: exp(-t/ where is the excess
minority carrier lifetime.

The minority carrier lifetime depends on dopant

concentration and other defects which may effect the recombination

reaction.

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Semiconductor Crystals

14