Semiconductors in equilibrium

Equilibrium concentration of electrons and holes

Mass action law
Intrinsic semiconductors
Extrinsic semiconductors
Semiconductors recap

• Band structure of a semiconductor:

• Charge carriers:
negative electrons in C.B.
positive holes in V.B.

 1 
ik ⋅r 
• Bloch theorem: Ψnk ( r ) = 3 / 2 e unk ( r )
L
• Periodic boundary conditions impose the wave vector and momentum values to be
 2π  2π   h
k = (k x , k y , k z ) = n= ( n x , n y , nz ) p = k = n
L L L
• Fermi-Dirac distribution:
1
f (E) =
1 + e( E − EF ) / kT
• Task: To find the equilibrium electron and hole concentrations, n0 and p0
Effective mass approximation

• Most generally:

 
f ( E ( p )) , p0 = 3 ∑ (1 − f ( E ( p )) )
2 2
n0 = 3
L 
∑
p ∈C . B . L p ∈V . B.

• Difficult, because E ( p ) is a complicated function

• But at room temperatures, most of the conduction electrons live near the bottom of
the conduction band, and most of the holes live near the top of the valence band.

• Can use the effective mass approximation:

 1   2
Near the bottom of C.B. EC ( p ) ≅ EC 0 + ∗
( p − pC 0 )
2me
 1   2
Near the top of V.B.: EV ( p ) ≅ EV 0 − ∗
( p − pV 0 )
2mh
Replacing a sum with an integral

• Focus on electrons (the results for holes will be analogous):

2 
n0 = 3
L 
∑ f ( E ( p )) 
E ( p ) ≅ Ec +
1   2
∗
( p − p0C )
p ∈C . B . 2me
• The same energy E can be realized by many different momentum values,
 
provided that | p − p0C | is the same

• Density of states in the conduction band ~ degeneracy of the energy level E =

# of momentum states in a shell ( E , E + dE )
gC ( E ) =
L3 dE
 h
• Momentum values (periodic boundary conditions) p = n
L
separated by h/L, a tiny number. Can replace
2 
L3 
∑
p ∈C . B .
f ( E ( p )) → ∫ dE gC ( E ) f ( E )
Electron density of states

• Density of states in C.B.

# of momentum states in a shell ( E , E + dE )

gC ( E ) =
L3 dE
4π p 2dp
# of momentum states in ( E , E + dE ) =
( h / L)3
 1 2
• Assume for simplicity that E ( p ) ≅ EC + ∗
p
2me

me∗
• Then p 2 = 2me∗ ( E − EC ) ; dp = dE
2( E − EC )

4π (2m )
∗ 3/ 2

• Result: gC ( E ) = e
E − EC
h3
Electron and hole density of states

• But the conduction band may have several equivalent minima. Then:

4πν C (2m )
∗ 3/ 2
gC ( E ) = e
E − EC
h3

• The only new parameter: νC = the number of equivalent minima in the conduction
band

• Hole density of states in the valence band:

νV = the number of equivalent maxima in the valence band

4πν V (2m )
∗ 3/ 2
gV ( E ) = h
EV − E
h3
Boltzmann approximation

• If e( E − EF ) / kT >> 1 , we can approximate 1.0

Fermi-Dirac
T = 0.1 EF

Boltzmann
0.8
1
f (E) = ( E − E F ) / kT
≅ e −( E − EF ) / kT 0.6
1+ e

f (E)
0.4

0.2
• For conduction electrons, this is a good
approximation provided that E − E > 3kT 0.0
0 E1F
C F E
If this condition does not hold, need to work with the full Fermi-Dirac distribution

• For holes, if E F − EV > 3kT , we can approximate

1
1 − f (E) = ≅ e( E − EF ) / kT
1 + e( EF − E ) / kT
• Note that at room temperature (300 K), kT = 0.0259 eV, so EF should not be within
0.1 eV of the band edges for Boltzmann approximation to be valid.
Conduction electron concentration

• With Boltzmann’s approximation

4π (2m )
∞ ∗ 3/ 2 ∞
n0 = ∫ dE gC ( E ) e −( E − E F ) / kT
= e
∫ dE E − EC e −( E − EF ) / kT
EC
h3 EC

• After integration: n0 = N C e − ( EC − EF ) / kT

with the effective density of states in the conduction band.

2(2πm kT ) ∗ 3/ 2

NC = e
3
h
• Interpretation:

NC = the number of states near the bottom of the C.B. that are available for
electrons

e − ( EC − EF ) / kT = probability for a particular state in the C.B. to be occupied

Electron and hole concentrations

• Concentration of conduction electrons: n0 = N C e − ( EC − EF ) / kT

2(2πm kT ) ∗ 3/ 2
• Conduction band effective density of states: NC = e
3
h

• For holes, a similar analysis gives: p0 = NV e( EV − EF ) / kT

2(2πm kT ) ∗ 3/ 2

• The effective density of hole states in the valence band NV = h

3
h

• Note: at 300 K, the combination

(mekT )3 / 2 has the value of approx. 1018 cm-3.
h3
• Note: NC, V ~ T3/2. Can determine NC, V at any temperature if it is known at some

particular temperature.
Electron effective density of states: Exercise

At T = 300 K, the effective density of electron states in a semiconductor is 1020 cm-3.

What is the effective density of states at 200 K?
Mass action law

• To figure out the equilibrium concentrations

n0 = N C e − ( EC − EF ) / kT , p0 = NV e( EV − EF ) / kT
we need to know the Fermi energy. Will do later.

− ( EC − EV ) / kT − E g / kT
• But note that the product n0 p0 = N C NV e = N C NV e
is independent of EF. This statement is known as the mass action law.

• Knowledge of one concentration allows you to determine the other.

• Mass action law is valid only under the Boltzmann approximation, i.e. EF not too
close to the band edges.
Intrinsic semiconductors: charge carrier concentrations

• Concentrations: n0 = N C e − ( EC − EF ) / kT , p0 = NV e( EV − EF ) / kT

− E g / kT
• Mass action law: n0 p0 = N C NV e

• Intrinsic semiconductors are pure materials without any impurities

• Each electron that gets promoted into the conduction band leaves behind exactly one
hole in the valence band  the concentrations of the conduction electrons and holes
are exactly equal. It is usually denoted with as ni:
n0 = p0 = ni
− E g / kT
• From mass action law ni2 = N C NV e
• Another expression of the mass action law:

n0 p0 = ni2
Mass action law: exercise

Estimate electron concentration (= hole concentration) in an intrinsic semiconductor with

Eg = 1 eV and in a dielectric with Eg = 6 eV at 300 K. Take a reasonable value for NC
and NV, e.g. 1019 cm-3. Estimate the free electron concentration in the dielectric at its
melting temperature, assumed to be 1000 K.
Intrinsic charge carrier concentration: exercise

The temperature dependence of the bandgap in Si is given by

4.77 ⋅ 10−4 eV/K 2

E g = 1.166 eV − T
T + 636 K
At T = 300 K, the intrinsic carrier concentration in Si is 1010 cm-3. Find ni at 400 K.
Intrinsic semiconductors: Fermi energy

• We have:
− ( EC − E F ) / kT ( EV − E F ) / kT − E g / kT
ni = n0 = N C e = p0 = N V e = N C NV e

• Can find Fermi energy EFi in intrinsic semiconductors. Since the two boxed
expressions are equal, then
EC + EV kT  NV 
E Fi = + ln 
2 2  NC 
2(2πme kT ) 2(2πmh kT )
∗ 3/ 2 ∗ 3/ 2

• But NC = 3
, NV =
h h3
EC + EV 3kT  mh∗ 
Then
EFi = + ln ∗ 
2 4  me 
At zero temperature, Fermi energy is located exactly in the middle of the band gap.

As the temperature increases it shifts linearly towards one of the band edges.
Fermi energy vs. temperature: exercise

The holes in a hypothetical intrinsic semiconductor are ten times heavier than the
electrons. The bandgap is 1 eV. Find the difference EF – EV at 300K. At what
temperature is Fermi energy 0.6*Eg above the valence band edge?
Extrinsic semiconductors: Doping

• Doping in semiconductors: use of chemical substances (impurities) to alter the

semiconductor’s performance in devices and is a welcome practice

• Donors: give electrons away to the lattice.

E.g.: an element from column V (As or P) added to Si.

The impurity atom then will turn into a positively charged ion.

• Acceptors: catch the host lattice electrons, in other words, give holes to the lattice.
E.g.: an element from column III (B or Ga) added to Si.

The impurity atom then will turn into a negatively charged ion.

• Amphoteric doping: Si in GaAs may substitute either Ga (group III) or As (group V)

and therefore Si can act as a donor or as an acceptor.

• Compensated semiconductor: doped with both donor and acceptor impurities.

Extrinsic semiconductors: Mass action law

• Practically relevant case: Concentration of impurities is at least several orders of

magnitude smaller than the host atom concentration.

• Then, band structure of the semiconductor is practically unaffected by impurities.

− E g / kT
• Mass action law n0 p0 = ni2 = N C NV e remains valid

• Example: If ni = 1011 cm-3 and n0 = 1016 cm-3, then p0 = 1022/1016 = 106 cm-3

• Donor impurities: electrons are majority charge carriers

holes are minority carriers
n-type semiconductor

• Acceptor impurities: holes are majority charge carriers

electrons are minority carriers
p-type semiconductor
Extrinsic semiconductors: Donor energy levels

• A donor that has given its electron to the lattice turns into a positively charged ion. It
can capture a conduction electron, thus turning into a neutral hydrogen-like atom.

• When captured by an ionized donor, an electron has energy levels similar to

hydrogen. We know what they are:
ke2me e 4 Ry
• In hydrogen En = − 2 2
=− 2
2 n n
Ionization energy = E∞ - E1 = Ry = 13.6 eV

ke e 2
• In semiconductor: U (r) = − ⇒ must replace ke → ke / ε r
εr r
must replace me → me∗ (conductivity)
me∗ / me 1
Energy levels: En = EC − Ry
ε r2 n 2
me∗ / me me∗ / me
Donor ionization energy Edi = EC − E1 = Ry = (13.6 eV ) ⋅
ε 2
r ε r2
Extrinsic semiconductors: Donor energy levels
me∗ / me
• Donor ionization energy Edi = Ry
ε r2
1
• Typically, me∗ / me ~ 1, ε r ~ 10 ⇒ Edi ~ 13.6 = 0.14 eV
100
• Thermal energy at 300 K : kT = 0.0259 eV. Hence, Edi/kT ~ 5, not a large number. It
is much easier to ionize a donor than to promote an electron from the valence band
to the conduction band.

• Orbit radius of a captured electron:

in hydrogen:
2
rH = 2
≈ 0.53 Å
ke me
in a semiconductor:
 2ε r εr
rd = ∗ 2
= rH ∗ ~ 10 Å
ke me e me / me
(several lattice constants)
Extrinsic semiconductors: Acceptor energy levels

• An acceptor atom takes an electron from the valence band of the host semiconductor
lattice, thereby turning into a negatively charge ion.

• An ionized acceptor atom can capture a positively charged hole, thus turning into a
neutral antihydrogen-like atom.

• Its ionization energy relative to the valence band edge

ke2mh∗e 4 mh∗ / me
Eai = Ea − EV = = Ry
2 ε r
2 2
ε r2

• Orbit radius of a hole captured by an acceptor:

εr
ra = rH
mh∗ / me
Complete ionization: charge carrier concentration

• Complete ionization: all donor and acceptor atoms are ionized

+
Donor impurities  positively charged ions of concentration N d ≅ N d
−
Acceptor impurities  negatively charged ions of concentration N a ≅ N a

• Need to determine equilibrium electron and hole concentrations n0 and p0

• First guess:

Without donors and acceptors, we have n0 = p0 = ni

Each donor atom contributes one electron and each acceptor atom contributes
one hole to the lattice.

Then we should have: n0 = ni + Nd , p0 = ni + Na ???

• THIS GUESS IS WRONG

Reason 1: Electrons contributed by the donors recombine with the holes
already present in the semiconductor. Holes contributed by the acceptors
recombine with the electrons already present in the semiconductor.
Reason 2: The mass action law n0 p0 = ni2 is violated.
Complete ionization: charge carrier concentration

• Charge neutrality equation: n0 + N a− = p0 + N d+

• Complete ionization: N a− ≅ N a , N d+ ≅ N d

• Then: n0 + N a = p0 + N d 2 equations with 2 unknowns,

n0 and p0
• Mass action law: n0 p0 = ni2

Nd − Na  Nd − Na 
2
• Solution:
n0 = +   + ni
2

2  2 
Na − Nd  Na − Nd 
2

p0 = +   + ni
2

2  2 
• In practice:
n-type Nd > Na: use the “long expression” for n0 and mass action law for p0
p-type Na > Nd: use the “long expression” for p0 and mass action law for n0
Complete ionization: exercise

A compensated semiconductor with the intrinsic carrier concentration ni = 1010 cm-3 is

doped with Nd = 1016 cm-3 donors and Na = 1011 cm-3 acceptors. Determine n0 and
p0.
Complete ionization: exercise

In an n-type semiconductor with intrinsic concentration of 1010 cm-3, concentration of

electrons is 25 times as high as concentration of holes. Find the concentration of
electrons, holes, and donor impurities, assuming complete ionization.
Complete ionization: Fermi energy

• General result:

n0 = N C e − ( EC − EF ) / kT = N C e − ( EC − EFi + EFi − EF ) / kT = ni e − ( EFi − EF ) / kT ,

p0 = NV e( EV − EF ) / kT = NV e( EV − EFi + E Fi − E F ) / kT
= ni e( EFi − EF ) / kT

• Concentrations n0 and p0 are now known.

EC + EV 3kT  mh∗ 
• Intrinsic Fermi energy is also known: EFi = + ln ∗ 
2 4  me 
• Fermi energy in a doped semiconductor:
n0 p0 n-type p-type
E F = E Fi + kT ln = EFi − kT ln EC EC
ni ni
EF
• n-type: n0 > ni, p0 < ni  EF > EFi EFi EFi
EF
• p-type: p0 > ni, n0 < ni  EF < EFi EV EV
Complete ionization: exercise

A p-type semiconductor has the bandgap Eg = 0.8 eV and ni = 2·109 cm-3. At what
concentration of acceptors will Fermi energy be above the valence band edge by ΔE =
0.2 eV ? Assume T = 300 K, me* = mh*, and Nd = 0.
Complete ionization: exercise

A compensated semiconductor with the intrinsic carrier density ni(300 K) = 1010 cm-3 and
Eg = 0.9 eV is doped with Nd = 1016 cm-3 donors and Na = 1012 cm-3 acceptors.
Determine Fermi energy relative to the intrinsic Fermi energy at T = 234 K in the
complete ionization limit.
Degenerate semiconductors

• Doping level can be so high that EF may happen to be inside the conduction band (n-
type doping) or inside the valence band (p-type doping).

• For this to happen, dopant concentration must be comparable to the effective

densities of states NC, NV.

• Degenerate semiconductor have properties closer to metals than to semiconductors.

• Our simplified theory cannot be applied to degenerate semiconductors, because

Boltzmann’s approximation does not hold true for these materials.
Statistics of donors and acceptors

• Total concentration of donors: N d = N d0 + N d+

neutral ionized

• Total concentration of acceptors: N a = N a0 + N a−

We neglect the possibility of multiple ionization and the possibility of electron capture
by donors and hole capture by acceptors

• Charge neutrality equation: n0 + N a− = p0 + N d+ 



• Mass action law: n0 p0 = ni2


2
+
N −N N −N
− + −

• Solution:
n0 = d
+  a d a
 + ni2
2  2 
2
N −N−
N −N+ − +

p0 = a
+  d a d
 + ni2
2  2 
Statistics of donors

• An electron bound to a neutral donor has hydrogen-like quantum states α. A donor

can be either ionized or have an electron in the ground state.

• A donor is a system in contact with the heat bath of conduction electrons.

• Grand canonical probability to have n electrons bound to a donor (with n = 0, 1)
1  E F n − Eα( n )   EF n − Eα( n ) 
pnα = exp  , Z = ∑ ∑ exp 
Z  kT  n =0, 1 α  kT 
• If n = 0 (ionized donor) only one state with zero energy: Eα( n =0 ) = 0
( n =1)
• If n = 1 (neutral donor): E ground = Ed = EC − Edi
This state is doubly degenerate (spin). Then α =s=±½
Z = 1 + 2e( EF − Ed ) / kT
from n = 0 from n = 1 and s = ± ½
Statistics of donors

• Probability to have no electrons in the ground state (= probability for the donor atom
to be ionized):
1 1
p0 = pionized = =
Z 1 + 2e( EF − Ed ) / kT
• Probability to have a neutral donor:

2e( EF − Ed ) / kT 1
pneutral = 1 − pionized = ( E F − Ed ) / kT
=
1 + 2e 1
1 + e( Ed − EF ) / kT
2
+ Nd
• Concentration of ionized donors: N = N d pionized =
1 + 2e( EF − Ed ) / kT
d

Nd
• Concentration of neutral donors: N = N d pneutral =
0
d
1
1 + e( Ed − EF ) / kT
2
Statistics of acceptors

• A neutral acceptor atom = a negatively charged acceptor ion + a hole in the

hydrogen-like ground state.

• Holes have spin +½ and –½

• Also, in some semiconductors (such as Silicon!) there are two types

of holes: heavy and light. Then, electron degeneracy factor 2 must
be replaced with 4 if both heavy and light holes are present. But if
holes of just one type are present in a semiconductor, hole
degeneracy factor must remain 2.

• We will assume hole degeneracy factor of 4.

Na
• Concentration of neutral acceptors: N = N a pneutral =
0
a
1 ( EF − Ea ) / kT
1+ e
4
− Na
• Concentration of ionized acceptors: N a = N a pionized =
1 + 4e( Ea − EF ) / kT
Numerical determination of EF, n0, and p0

• Neutrality equation: n0 + N a− = p0 + N d+

• Mass action law: n0 p0 = ni2

• Electron concentration (assume n-type):
2
−( E F − E Fi ) / kT N −N +
N −N − + −

n0 = ni e = + 
d a d a
 + ni2
2  2 
• Ionized donor concentrations:

+ Nd Nd Nd
N = ( E F − Ed ) / kT
= ( E F − EC + EC − Ed ) / kT
=
1 + 2e 1 + 2e 1 + 2e( EF − EC + Edi ) / kT
d

− Na Na Na
N = ( Ea − E F ) / kT
= =
1 + 4e 1 + 4e( Ea − EV + EV − EF ) / kT 1 + 4e( Eai + EV − EF ) / kT
a

• Both sides of the boxed equation depend on EF. Can solve numerically for EF. Once
this is done, n0 and p0 follow immediately.
Fermi energy and charge carrier densities: numerics

• Parameter values (hypothetical semiconductor):

E g = 1 eV , N C (300 K ) = NV (300 K ) = 1019 cm −3

N d = 1015 cm −3 , N a = 0, Edi = 0.05 eV
1.0

Notes: 0.9

0.8

EF [eV]
As T→ 0, EF → (Ed+EC)/2
0.7
•
0.6 intrinsic

freeze-out
0.5

• At T < 100 K, n0 goes to zero on cooling. complete

This is electron freeze-out effect. 1016
ionization

n0, p0 [cm-3]
Donors capture all free electrons. 1015
n0

1014
• There is a broad temperature range p0
13
10
where n0 = Nd. This is complete ionization. 0 200 400 600 800 1000
In this temperature range ni(T) << Nd. T [K]

• At still higher temperatures ni(T) >> Nd, and n0 ≈ p0 ≈ ni (intrinsic regime).

Statistics of donors: exercise

Eg = 1 eV and effective densities of states at 300 K

A semiconductor with
NC = NV= 1018 cm-3 is doped with Nd = 1014 cm-3 donors. Donor ionization energy
is Edi = 0.05 eV.
(a) Find the fraction of ionized donors at room temperature.
(b) Find the temperature at which half of the donors are ionized.
(c) Find concentration of electrons at 10 K.