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Chapter 2

Homogeneous
Semiconductors

One uniform material like pure


Silicon
The reduced, or first Brillouin, zone.
From quasi - free electron model,
2 2 2 2 2
Figure 1.16
h K h K p
E = Eo + , EK = =
2mo 2mo 2mo
−1
2⎛ d E ⎞
2
mo = h ⎜⎜ ⎟
2 ⎟
⎝ dK ⎠

Electrons at near the bottom of the band


⎛ dE ⎞ ⎛ 1 d 2E ⎞ 2
E = EC + ⎜ ⎟ K + ⎜⎜ ⎟ K + HOTs
2 ⎟
⎝ dK ⎠ ⎝ 2 dK ⎠
⎛ 1 d 2E ⎞ 2
≈ EC + ⎜⎜ ⎟K
2 ⎟
⎝ 2 dK ⎠
The E-K diagram for (a) an electron at the bottom of the conduction band at K = 0, where the velocity and
kinetic energy are both zero and thus the total energy is equal to the potential energy; (b) an electron in a local
minimum, where it has a different effective mass, and (c) an electron near the top of the band.
Figure 2.1

1 d 2E
EK = ( K − K 1 )2

2 dK 2
h 2 ( K − K1 )
2
=
2m*
An external electric field is applied across a bar of semiconductor. (a) The physical picture; (b) the energy
band diagram. Electrons in the conduction band are accelerated to the right; they travel at constant energy
between collisions.
Figure 2.2

dEC
F =− = − qξ
dx
brings idea of band bending or
the slope in the conduction band edge
The E-K diagrams for three common semiconductors. The crystallographic direction is shown on the K axis.
The slope of the E-K curve must be zero at the Brillouin zone edge, unless multiple bands coincide there.
Figure 2.3

conduction band

minimum at K ≈ 0.85
a
the curvature is different in
different directions.
m||* = 0.92mo , m⊥* = 0.197 mo

m* = 0.067 mo conduction band conduction band


at near K ≈ 0 2π minimum at the zone dege.
minimum at K ≈ 0.85
symmetric cubic structure
a m||* = 1.64mo , m⊥* = 0.082mo
the curvature is different in
m =m =m
* *

*
|| different directions.
m||* = 0.92mo , m⊥* = 0.197 mo

2-3
m* = weighted sum of m||* and m⊥*
In conductivity calculations, use
conductivity effective mass mce*
In electron concentration calculations,
*
use density of states effective mass mdse

Table 2.1 Effective masses for electrons near the bottom of the conduction
band in units of the rest mass of the free electron

Material m* ( K = 0) m||* m⊥* mce* *


mdse

Si 0.92 0.197 0.26 1.09


GaAs 0.067 0.067 0.067
Ge 1.64 0.082 0.12 0.56
InP 0.077 0.077 0.077
The E-K diagram for the valence band in most semiconductors, indicating (h) the heavy hole band, (l) the
light hole band, and (s) the split-off band.
Figure 2.4

The valence band structures are similar for most semiconductors.


The effective mass for the electron negative at the top pf the valence band.
A few empty state near the top of the band. – holes. Positive charges with positive effective mass.
H – heavy hole (smaller curvature)
L – light hole (higher curvature)
Split off by and energy Δ, due to spin-orbit coupling
Table 2.2 Effective masses for holes in the valence bands of several
semiconductors

Material mlh* *
mhh *
msh Δ, eV
*
mch *
mdsh
Si 0.16 0.48 0.24 0.044 0.36 1.15

GaAs 0.082 0.45 0.15 0.34 0.34 0.48

Ge 0.044 0.28 0.08 0.29 0.21 0.292

InP 0.08 0.4 0.15 0.11 0.3 0.42


In thermal generation, a valence electron acquires some extra energy and moves into the conduction band.
(a) Physical picture or bond diagram; (b) energy band diagram. In recombination (c) an electron from the
conduction band falls into a hole in the valence band, and both the electron and the hole disappear. It is also
possible for an electron to lose energy by colliding with something (c, right) in which case it may remain in the
conduction band. In the collision case, the electron continues to exist.
Figure 2.5

Intrinsic semiconductors
no = po = ni
o indicates concentration at equalibrium.
i indicates equalibrium concentration at equalibrium.
Donors in a silicon crystal: (a) bond diagram of the crystal; (b) energy band diagram of silicon doped with one
phosphorus (donor) atom.
Figure 2.6

2-6
(a) The discrete energy states in a single phosphorus ion. (b) The energy band diagram for a semiconductor
crystal containing a donor atom. For the discrete atom, an electron must have an energy equal to Evac or
higher to escape the influence of the nucleus. In the semiconductor, the electron must have an energy of EC
or greater to escape the influence of the donor ion. (c) Energy diagram for a donor in GaAs.
Figure 2.7

mce* q 4
En = EC −
2(4πε ) n 2 h 2
2

(
13.6 mce* / mo q 4
= EC − 2
)
eV
n (ε / ε o )2

4πεn 2 h 2 ε / εo 2
rn = * 2
= 0 .053 *
n nm
mce q mce / mo

GaAs doped with tellurium. The lattice constant is 0.565 nm.


The measured donor level is 0.0059 eV.
mce* / mo = 0.067, ε / ε o = 13.2
0.0052
En = EC − 2
eV
n
rn = 10.4n 2 nm
mce* q 4
En = EC −
2(4πε ) n 2 h 2
2

(
13.6 mce* / mo q 4
= EC − 2
)
eV
2(ε / ε o )
2
n
4πεn 2 h 2 ε / εo 2
rn = * 2
= 0.053 * n nm
mce q mce / mo

Si doped with phosphor. The lattice constant is 0.543 nm. The measured donor level is 0.045 eV.

mce* / mo = 0.26, ε / ε o = 11.8


0.025
En = EC − 2
eV
n
rn = 2.4n 2 nm
Acceptors in a semiconductor. (a) bond diagram; (b) energy band diagram. An electron is excited from the
valence band to the acceptor state, leaving behind a quasi-free hole.
Figure 2.8

*
13.6 mch
En = EC − 2
/ mo q 4(eV
)
n (ε / ε o )2

ε / εo
rn = 0.053 *
2
n nm
m / mo
ch
States in the valence band on the E-K diagram. (a) All states are full; (b) one state is empty (hole), meaning
there 2-9
is an electron with no opposing electron at the same energy but opposite K vector and opposite velocity.
Figure 2.9

Hole current

J = + qp < vh >
To determine the current-voltage relation, we have to know the
distribution of electrons (and holes) with energy.

1. How the available states are distributed in energy. – density


of states
2. The probability that a state at given energy is occupied. –
Fermi Dirac statistics
The density of states functions for electrons in the conduction band and the valence band. The density of
states versus energy plot is superimposed on the energy band diagram (energy versus position x).
Figure 2.11

The density of states function


3/ 2
1 ⎛ 2mo ⎞
S (E ) = ⎜ ⎟ E − Eo
2π 2 ⎝ h 2 ⎠

In the parabolic region of the E − K diagram,


3/ 2
1 ⎛ 2mdse
*

S (E ) = ⎜
2 ⎜ 2 ⎟
⎟ E − EC
2π ⎝ h ⎠
3/ 2
1 ⎛ 2mdse*

= ⎜ ⎟ EK
2π 2 ⎜⎝ h 2 ⎟⎠

In the parabolic region near the top of the valence band


3/ 2
1 ⎛ 2mdsh*

S (E ) = ⎜ ⎟ EV − E
2π 2 ⎜⎝ h 2 ⎟⎠
n(E ) : the number of electrons per unit volume per unit energy
S (E ) : the density of states function
f (E ) : the Fermi - Dirac probability function

n(E ) = S (E ) f (E )

In a given band at equalibrium, the total number of electrons


per unit volume in the entire energy band.
no = ∫ S (E ) f (E )dE
band

1
f (E ) = (E − E f )/ kT
1+ e
The Fermi-Dirac distribution function gives the probability of occupancy of an energy state E if the state
exists.2-12
Figure 2.12

Fermi - Dirac distribution for electron


1
f (E ) = (E − E )/ kT
1+ e f
Fermi - Dirac distribution for hole
1
f p (E ) = 1 − f (E ) = 1 − (E − E )/ kT
1+ e f
1
= (E − E )/ kT
1+ e f
Example 1.1 When can the Boltzmann approximation safely be used?

( )
f (E ) = e
− E − E f / kT
Boltzmann statistics
1
Fermi Dirac statistics f (E ) = (E − E f )/ kT
1+ e

(E − E f )/ kT (
− E −E )/ kT
If e ≥ 10, then e f
≤ 0.1,
1 1
(E − E f )/ kT ≥ 1 + 10 = 0.09009
1+ e
− (E − E f )/ kT 1
e ≈ (E − E f )/ kT within 10% error
1+ e
E − E f > kT ln (10 ) = 2.3kT

If we are calculating the probability of the occupancy of a state that is


greater than the 2.3kT away from the Fermi level, we can use simple
approximation form.
Example 2.4 Estimate the probability of occupancy of a state at the bottom of
the conduction band in intrinsic Si at room temperature.

The band gap of Si 1.12 eV


E f is approzimately at the midgap.
EC − E f = 0.56 eV
1 1
f (E ) = =
(E − E )/ kT 1 + e 0.56 / 0.026
1+ e C f
1 −10
= = 4 . 4 × 10
1 + 2.26 ×109
The distribution of the electrons near the bottom of the conduction band, n(E), is the product of the density of
states distribution S(E) times the probability of occupancy of states f(E) at a particular energy. The
distribution of holes near the top of the valence band p(E) is the product of the density of states distribution
times the probability of vacancy of states at a particular energy. (a) n type, (b) p type.
Figure 2.13
n( E ) = S ( E ) f ( E )
The total number of electrons in the conduction band
3/ 2
1 ⎛ 2m *
⎞ ∞ [( ) ]
no = ∫ n(E )dE =
top

− E − E f / kT

2 ⎜
dse
⎟⎟ E − EC e dE
EC 2π ⎝ h 2
⎠ EC

p(E ) = S (E )[1 − f (E )] = S (E ) f p (E )
The total number of holes in the valence band
3/ 2
1 ⎛ 2m *
⎞ [( ) ]
p(E )dE =
EV EV
po = ∫ ∫
− E f − E / kT
⎜⎜ dsh
⎟⎟ EV − E e dE
bottom 2π ⎝ h
2 2
⎠ −∞
[( ) ]
− EC − E f / kT
no = N C e
where the effective density of states in the conduction band
3/ 2 3/ 2 3/ 2
⎛ m kT ⎞
* ⎛ 9.11× 10 kg 1.38 × 10 ⋅ 300 J ⎞
−31 − 23
⎛ mdse
*
⎞ ⎛ T ⎞
3/ 2

N C = 2⎜⎜ ⎟
dse
= 2⎜ ⎟ ⎜⎜ ⎟⎟ ⎜ ⎟
2 ⎟
⎝ 2πh ⎠ ⎜
⎝ (
2(3.14 ) 1.06 × 10 J ⋅ s
−34 2 ⎟
⎠ ) ⎝ mo ⎠ ⎝ 300 ⎠
3/ 2 3/ 2
19 ⎛ mdse ⎞
*
⎛ T ⎞
= 2.47 × 10 ⎜⎜ ⎟⎟ ⎜ ⎟ cm -3
⎝ mo ⎠ ⎝ 300 ⎠

[( ) ]
− E f − EV / kT
po = NV e
where the effective density of states in the valence band
3/ 2 3/ 2 3/ 2
⎛ mdsh kT ⎞ 19 ⎛ mdsh ⎞
* *
⎛ T ⎞

NV = 2⎜ ⎟
2 ⎟
= 2.47 ×10 ⎜⎜ ⎟⎟ ⎜ ⎟ cm -3
⎝ 2πh ⎠ ⎝ mo ⎠ ⎝ 300 ⎠
no po = N C NV e ( EC − EV )/ kT = N C NV e
− E g / kT
= ni2
Law of mass action

Example 2.3 Find intrinsic concentration of Si at room temperature.


The effective masses are mdse
*
= 1.09mo and mdsh
*
= 1.15mo

= 2.81 ⋅ 3.05 × 10 −19 e − (1.1242 )/ (2×0.02586 )


− E g / 2 kT
ni = N C NV e
= 2.93 ×10 −19 ⋅ e − 21.7 = 1.06 ×1010 electrons/cm 3
Let Ei be Fermi energy level of intrinsic semiconductor. Is the Ei
level located in the middle of the band gap?
no = po = ni = N C e −[( EC − Ei )/ kT ] = NV e −[( Ei − EV )/ kT ]
N C e −[( Ei − EV )/ kT ]
= −[( EC − Ei )/ kT ] = e ( EC + EV − 2 Ei )/ kT
NV e
3/ 2
EC + EV kT NV EC + EV kT ⎛ m *

Ei = + ln = + ln⎜⎜ dsh
*
⎟⎟
2 2 NC 2 2 ⎝m dse ⎠
EC + EV 3kT ⎛ mdsh
*

= + ln⎜ * ⎟⎟

2 4 ⎝ mdse ⎠

Example 2.4 Find the energy by which Ei is offset from midgap for
Si at room temperature.
3 ⎛ 1.15 ⎞
Ei − Emidgap = kT ln⎜ ⎟ = 0.75 ⋅ 0.026 ⋅ 0.0536 = 0.00104
4 ⎝ 1.09 ⎠
The electron concentration for semiconductor
[( ) ] [( ) ] (E f − Ei )/ kT
= ni e ( EC − Ei )/ kT ⋅ e
− EC − E f / kT − EC − E f / kT
no = N C e = ni e
The effect of rasing the Fermi level from the midgap
⎛n ⎞
E f − Ei = kT ln⎜⎜ o ⎟⎟
⎝ ni ⎠

The hole concentration for semiconductor


[( ) ] [( ) ] (Ei − E f )/ kT
= ni e ( Ei − EV )/ kT ⋅ e
− E f − EV / kT − E f − EV / kT
po = N V e = ni e
The effect of lowering the Fermi level from the midgap
⎛p ⎞
Ei − E f = kT ln⎜⎜ o ⎟⎟
⎝ ni ⎠
Electrons and holes in intrinsic and doped n-type material. In the doped case, some of the electrons from the
donors recombine with holes.
Figure 2.14

For n - type semiconductors,


no ≈ N D when N D >> ni

For p - type semiconductors,


po ≈ N A when N A >> ni

2-14
Eample 2.5 Find the electron and hole concentrations in GaAs doped
with NA=1016cm-3, and locate the Fermi level. Eg = 1.43 eV.

3/ 2 3/ 2
⎛m *
⎞ ⎛ T ⎞
N C = 2.47 ×1019 ⎜⎜ dse
⎟⎟ ⎜ ⎟ cm −3 = 2.47 ×1019 ⋅ (0.017 )(1) = 4.3 ×1017 cm −3
⎝ mo ⎠ ⎝ 300 ⎠
3/ 2 3/ 2
19 ⎛ mdsh ⎞
*
⎛ T ⎞
NV = 2.47 × 10 ⎜⎜ ⎟⎟ ⎜ ⎟ cm −3 = 2.47 × 1019 ⋅ (0.33)(1) = 8.2 × 1018 cm −3
⎝ mo ⎠ ⎝ 300 ⎠
(
− E g / 2 kT )
ni = N C NV e = 1.87 × 1018 ⋅1.14 × 10 −12 = 2.14 × 10 6 cm −3
( )
− E f − EV / kT
po ≈ N A = 1× 1016 cm −3 = NV e
⎛ p ⎞ ⎛ 1016 ⎞
The Fermi level is E f − EV = − kT ln⎜⎜ o ⎟⎟ = −0.026 ln⎜⎜ ⎟ = 0.17eV
18 ⎟
⎝ NV ⎠ ⎝ 8.2 × 10 ⎠

no =
ni2
=
(
2.14 × 106 )
2

= 4.6 ×10 − 4 cm −3
po 1016
Energy band diagram for the p-type GaAs of Example 2.5.
Figure 2.15

⎛ po ⎞ ⎛ 1016 ⎞
The Fermi level is E f − EV = − kT ln⎜⎜ ⎟⎟ = −0.026 ln⎜⎜ ⎟ = 0.17eV
18 ⎟
⎝ NV ⎠ ⎝ 8.2 × 10 ⎠

2-15
Example 2.6 A simple silicon is doped with a background concentration of NA
= 4 x 1016cm-3. then 1017 cm-3 donors are added. Find the room temperature
concentrations of electrons and holes in the orginal and final materials and draw
the energy diagram for each.

N A = 4 × 1016 cm −3 ≈ po , ni = 1.06 × 1010 cm −3 ,


NV = 2.47 × 1019 (1.15)
3/ 2
= 3.05 × 1019 cm −3
⎛ po ⎞ ⎛ 4 × 1016 ⎞
E f − EV = − kT ln⎜⎜ ⎟⎟ = −0.026 ln⎜⎜ ⎟ = 0.17eV
19 ⎟
⎝ NV ⎠ ⎝ 3.05 × 10 ⎠

no =
ni
2
=
(
1.06 × 1010 )
2

= 2.81× 103 cm −3
po 4 × 1016
For n - type material
no = N D − N A = 1017 − 4 × 1016 = 6 × 1016 cm −3
⎛ ND ⎞ ⎛ 6 × 1016 ⎞
EC − E f = − kT ln⎜⎜ ⎟⎟ = −0.026 ln⎜⎜ ⎟ = 0.16eV
3/ 2 ⎟
⎝ 2.47 × 10 (1.09) ⎠
19
⎝ NC ⎠

po =
(
ni2 1.06 ×1010
=
)
2

= 1.9 ×103 cm −3
no 6 ×1016
The energy band diagrams for Example 2.6: (a) uncompensated p-type material; (b) compensating donors are
added to make the material net n type.
Figure 2.16

Only acceptor levels Both the donor and acceptor levels

2-16
The electron distribution function n(E) as a function of energy (energy on the vertical axis).
Figure2-17
2.17 n(E ) = S (E ) f (E )
3/ 2 3/ 2
1 ⎛ 2mdse*
⎞ 1 ⎛ 2mdse*

S (E ) = ⎜ ⎟ E − EC = ⎜ ⎟ EK
2π 2 ⎜⎝ h 2 ⎟⎠ 2π 2 ⎜⎝ h 2 ⎟⎠
( ) ( ) ( )
f (E ) = e
− E − E f / kT − E − EC + EC − E f / kT − E K + EC − E f / kT
=e =e
3/ 2
1 ⎛ 2mdse*
⎞ − (EC − E f )/ kT
n(E ) = ⎜
2 ⎜

2 ⎟
e E K e − EK / kT
2π ⎝ h ⎠
dn( EK ) ⎡ ⎛ 1 ⎞ ⎛⎜ 1 ⎞⎟⎤ − EK / kT
= 0 = C ⎢ EK ⎜ − ⎟+⎜ ⎥e
dEK ⎢⎣ ⎝ kT ⎠ ⎝ 2 EK ⎠⎥⎦ ⎟

⎛1 ⎞
n(EK ) peak = n⎜ kT ⎟
⎝2 ⎠
Average kinetic energy of the conduction electrons

∫ EK n(EK )dEK 3
< EK >= 0

= kT
∫ n(E )dE
0
K K
2

The wavelength of the conduction electron,


2m* EK 2π 2πh 2πh
wave vector K = = , λ = =
h2 λ 2m* E K 3
2m* kT
2

For free electrons in GaAs, λ =


2π 1.06 × 10 −34 (
= 24nm
)
(
3(0.067 ) 9.1×10 −31 (0.026 ) 1.6 × 10 −19 ) ( )
Energy band-gap dependence of silicon on temperature.
Figure 2.18

2-18
Plot of electron concentration n0 as a function of temperature in n-type silicon for four values of net doping.
Also indicated is the temperature dependence of ni.
Figure 2.19

2-19
Normalized plot of n0/ND as a function of temperature. This plot is for ND = 1016 cm−3.
Figure 2.20

2-20
Under high doping concentrations, the formerly discrete donor levels smear into a band, effectively narrowing
gap by an amount ΔEg.
2-21
the band
Figure 2.21

Non-degenerate semiconductors – lightly doped so that the impurity


energy states are not overlapping.

Degenerate semiconductors – heavily doped so that impurity energy


states are overlapping. This lowers the bottom of the conduction band.
This is called impurity induced bandgap narrowing.

ΔE g = ECo − EC
= E go − E g ( N D )
The states for the higher donor levels can overlap if the doping concentration is high enough (dopant atoms
close enough together).
Figure 2.22

2-22
Reduction of room-temperature band gap ΔEg as a function of donor density in phosphorus-doped silicon.
Figure 2.23

[(
ΔE g = 4.372 ×10 −11
ND ) + (1.272 ×10
0.5 −4 −6
ND )
− 0.25 −4
] eV
band gap narrowing small for N D << 1018
( )
− ECo − E f / kT
no = N C e
Otherwise,
( )
− ECo − ΔE g − E f / kT
no = N C e
2-23
Plot of energy band diagram of a degenerate semiconductor. The intrinsic energy gap Eg0, the actual energy
gap Eg, and the apparent band gap E*g are indicated.
band 2-24
Figure 2.24

In the case of Fermi energy level crossing into the conduction band
due to heavy doping, the energy need for electrons to be conducting
is apparent band gap E*g because below the Fermi energy level the
states are filled with other electrons already.

ΔE = E go − E
*
g
*
g
Carrier concentrations in degenerate semiconductors
no po = ni2 = N C NV e − Ego / kT nondegerate

ECo : intrinsic conduction band edge


EC : actual conduction band edge
EC* : apparent conduction band edge(Fermi energy level)
ΔE g* ≈ ΔEC* = ECo − EC*
no = N D
( )
− E f − EV / kT − E g* / kT ( )
− E go − ΔE g* / kT
po = NV e = NV e = NV e
− E go / kT (ΔE )/ kT
* ⎡ N D (ΔE g* )/ kT ⎤ − E go / kT
no po = N D NV e e g
=⎢ e ⎥ C V
N N e
⎣ C
N ⎦
⎡ N D (ΔE g* )/ kT ⎤
=n ⎢ 2
i e ⎥ degenerate n - type
⎣ NC ⎦
⎡ N A (ΔE g* )/ kT ⎤
no po = n ⎢2
i e ⎥ degenerate p - type
⎣ NV ⎦
Apparent band-gap narrowing as a function of impurity concentration for uncompensated n-type and
p-type Si.
Figure 2.25

Curve fitting
⎛ ND ⎞
ΔE g* ( N D ) = 18.6 ln⎜ ⎟ meV n - type for N > 1017
cm −3

⎝ 7 ×10 ⎠
17 D

⎡ ⎡ ⎤
2 ⎤
⎛ ⎞ ⎛ ⎞
ΔE g ( N D ) = 9 ⎢ln⎜ 17 ⎟ + ⎢ln⎜ 17 ⎟⎥ + 0.5 ⎥ meV
N N
* A A
p - type for N A > 1017 cm −3
⎢ ⎝ 10 ⎠ ⎣ ⎝ 10 ⎠⎦ ⎥
⎣ ⎦

2-25
Figure 2P.1

2-26
Figure 2P.2

2-27
Figure 2P.3

2-28
Figure 2P.4

2-29
Figure 2P.5

2-30