MSE 221

Lecture 3
Electrons and Holes
3D Density of States
Homework: Assigned Due
1. Cht. 1, 1-12 1/8/2019 1/22/2019
2. Cht. 2, 1-9 1/15/2019 1/29/2019
 Intrinsic semiconductors
All valence electrons reside in valence band
– Can electrons access enough energy to be
excited into the conduction band?

CB

VB
Simplified band structure
 Intrinsic carrier concentrations

• Thermal energy provides means to excite electron from

valence band into the conduction band
• No extrinsic sources provide the carriers
– Intrinsic carrier concentration
– ni = n (negative charged carriers)
• n = concentration of charge in material (cm-3)
– However, if charge is excited into the conduction band, there are
missing electrons – holes – are created at the top of the valence
band
– p (positive charged carriers) are also created when the electrons
are excited into the conduction band.

n = p = ni
Carriers from valence band excited
into the conduction band
 Determination of carrier concentration
• Density of states (see Mishra Appendix C)
– How many states are available in the
conduction band for electrons to occupy?

2 (m *) ( E − Ec )
3/ 2 1/ 2
N (E) = Mc
 2 3

– Why effective mass?

• Curvature determines available density of states
• Mc = # of pockets
– What about: direct gap, indirect gap, heavy
and light holes?
 Effective mass DOS

• m* for direct gap semiconductors

• For multiple carrier pocket conditions

m *DOS = (m *x m *y m *z )
1/ 3

• For heavy and light holes

(
m *DOS = m * 3/ 2
hh +m *
lh )
3/ 2 2 / 3
 Fermi Energy function

• EF = Fermi Energy
– Determined by the distribution of charge (+ and -)
• Fermi Function
1
f (E) =
 E − EF 
1 + exp  
 kT 
• Probability of occupancy of a conduction band
state energy at energy E
Electron density n (cm-3)
Density of states N(E) = allowed states per energy range per unit volume

𝐸𝑡𝑜𝑝 𝐸𝑡𝑜𝑝
For N(E) derivation
𝑛= න 𝑛 𝐸 𝑑𝐸 = න 𝑁 𝐸 𝐹 𝐸 𝑑𝐸
0 0
see Appendix H in Sze

Probability that electron occupies an electronic state

Fermi-Dirac distribution function vs E-Ef
9
Simplify Fermi distribution function

For >3kT above Ef 𝐹 𝐸 ≅ 𝑒 −(𝐸−𝐸𝑓)/𝑘𝑡

For >3kT below Ef 𝐹 𝐸 ≅ 1 − 𝑒 −(𝐸−𝐸𝑓)/𝑘𝑡

Electron and hole density vs energy distribution
𝐸𝑡𝑜𝑝 𝐸𝑡𝑜𝑝
𝑛= න 𝑛 𝐸 𝑑𝐸 = න 𝑁 𝐸 𝐹 𝐸 𝑑𝐸
0 0

Note n = p = ni only if Ef is exactly in the middle of the bandgap

 Fermi function

Linear Scale
1
x

f300( E)
0.5
f800( E)
Log Scale
1
0.1 x
0 0.01
0 0.5 1f ( E)  3
300 1 10 4
E 1 10
f800( E)1 10
5

1 10
6

1 10
7

1 10
8

1 10
9
0 0.5 1
E
 Carrier concentration

• For cases where n is not too large…


n =  N ( E ) f ( E )dE
Ec

1  2m * 
3/ 2 
(E − Ec )
1/ 2
n= 2  2 
2      E − EF 
dE
Ec exp   + 1
 kT 
 n and DOS

 EF − Ec 
n = N c exp  
 kT 
3/ 2
 m * kT 
N c = 2 2 
 2 

• Nc = Density of states available for electrons

in the conduction band
 p and DOS

• Similar derivation for p-type material

 Ev − EF 
p = N v exp  
 kT 
3/ 2
 m * kT 
N v = 2 2 
 2 
 Fermi level and intrinsic material

• ni = n = p = pi

 − Eg   − Eg 
3
 kT 
np = 4 2 
(m *e m *h ) exp 
3/ 2
 = N c N v exp   = ni
2

 2   kT   kT 
 − Eg 
3/ 2
 kT 
ni = pi = 2 2 
(m *e m *h )
3/ 4
exp  
 2   2kT 
Ec + Ev 3  m *h 
EFi = + kT ln  
2 4  m *e 
 ni vs. temperature

 − Eg 
ni = pi = N v N c exp  
 2 kT 

Constant value of
bandgap used

Is that reasonable?
Intrinsic carrier density vs T

Eg = 1.11 eV

300K values

Eg = 1.43 eV
 Eg dependence on temperature

T 2
Eg (T ) = Eg (0) −
T +

 is comparable to the Debye temperature

Debye temperature: Temperature above

which material behaves as a classical
material (thermal vibrations dominate
over quantum effects)
 GaAs bandgap temperature dependence

T
2
T 2
• Eg(0)=1.519 eV Eg ( T) = Eg0 −

Eg (T ) = Eg (0) −
+T
T = 2  3  400

•  = 5.405 x 10-4 (eV/K) T +

x

•  = 204 K 1.55

1.48

Eg( T )

1.42

1.35
0 100 200 300 400
T
 Extrinsic carrier concentration

• Donors
+1 valence electron (As in Si, Si in GaAs)
• Acceptor
-1 valence electron (B in Si, Be in GaAs)
• Hydrogenic impurity
Adjacent (periodic table) to replaced atom

 m *   o 
2

Ed = Ec − 13.6   eV Ed = Ec − Ed
 m   
Typical 3 – 40 meV for effective donor
Donor and acceptor levels

Ec Ed

Deep Levels (traps)

Ev Ea
Ionization Energies

Traps

Traps
 Charge conservation and EF

• The total of positive and negative charged

species must be the same

n+N = p+N −
A
+
D
i j
• Not all charged species are hydrogenic
– They can also be deep levels
 Hydrogenic Ionized impurities
e-

• N-type: Se on As site; P on a Si site

– Extra electron needs to be ionized (to free the extra electron)
• P-type: B on Si site; Zn on Ga site
– Missing electron (hole) also needs to be ‘ionized’
Periodic Table
 Silicon Orbitals
Z = 14
1s, 2s, 2p and 3s are filled, 3p has 2 electrons (out of possible 6)

3s and 3p merge
8 allowed states
4 are filled
4 are empty

28
Note similarity to carbon sp3 hybrid

Recall organic chemistry sp3 hybrid orbitals

Ground state

Hybridized state

http://catalog.flatworldknowledge.com/bookhub/4309?e=averill_1.0-ch09_s02
29
http://che.chonbuk.ac.kr/~nahmks/crystal.htm
Formation of silicon energy bands
Si and GaAs simplified energy-band diagrams

Note valence band simple compared to conduction band

Holes moving in established covalent bonds
Electron movement is more directionally dependent
31
Silicon – things to note

Constant energy ellipsoids near

the 6 conduction band minima
Indirect gap
need momentum change
with phonon interaction 32
GaAs – things to note

Direct bandgap implies

rotational symmetry
for conduction band

33
 Ionized Impurity Equations
+ ND
N =
 Ec − Ed − E F 
D
1 + g D exp − 
 kT 
− NA
NA =
 Ev + Ea − E F 
1 + g A exp − 
 kT 

• Ev value typically 0
• gD = spin degeneracy (= 2)
• gA = spin degeneracy (= 2) + two bands = 4
 What does this mean?

• Example
– Dope InP with 1016 cm-3 sulfur
– At room temperature, what is the ionized
dopant concentration?
• May need to know:
– Nc Conduction band DOS (4.5x1017 cm-3)
– Nv Valence band DOS (7.0x1018 cm-3)
– Dopant concentration ND=1016 cm-3
– Dopant energy level = 0.004 eV below C.B.
– Eg of InP: 1.35 eV
 Conservation of charge

• For S-doped InP

+
n= p+N D

 EF − Ec 
n = N c exp   + ND
 kT  N D =  Ec − Ed − EF 
1 + g D exp − 
 Ev − Ec   kT
p = N v exp  
 kT 
Set Ev = 0; Ec = Eg
Solve for EF
 Graph solution
• Shockley Diagram
– Plot each side of the equation as a function of EF
+
1 10
17 n= p+Nx

D
1 10
16

1 10
15

 E F − Ec 
1 10
14
n = N c exp  
( )
n EF
 kT 
1 10
13
EF
1 10
12

1 10
11

1 10
10
0 0.2 0.4 0.6 0.8 1 1.2 1.4
EF
 Analysis

• EF = 1.251 eV
• n = 9.8 x 1015 cm-3
• n  ND [98% at room temperature]

• How does carrier concentration change

with temperature
Temperature dependence and carrier
concentration

Linear scale
 Multiple carriers: compensation

• Hydrogenic (shallow) n-type and p-type dopants

• Compensation:
– At room temperature, extrinsic carrier concentrtion is
approximately the difference between the dopant
concetration from donors and dopant concetration from
acceptors
– However, this can be quantified using Shockley
diagrams

ND − N A
 Compensation
• Use same values as previous example
• Add 7x1015 cm-3 acceptor dopants (e.g. Zn)
– EA = 0.1 eV
1 10
19
x
Predict
1 10
18 1 x 1016 – 7 x 1015
1 10
17 3 x 1015
1 10
16

( ) ( )
p EF + ND EF 1 1015

n( EF) + NA2 ( EF)  14 Fermi level shifts slightly

1 10

1 10
13 toward lower values
EF = 1.21 eV
1 10
12

1 10
11
n(1.21) = 2.92x1015 cm-3
1 10
10
0 0.2 0.4 0.6 0.8 1 1.2 1.4
51 EF
Degenerate semiconductors
When Nd > Nc or Na > Nv, simplified equations are no longer valid
Classic definition: Ef within 3kT of Ec
Bandgap narrowing can be significant
In silicon, eg = 22 (N/1018)½ meV

Ec
Ed
Ef

Eg Eg

Ev

Normal Heavily Degenerate

Donor level becomes band
Donor band merges w Ec
Fermi level moves near Ec
 Energy levels for impurities

• Shallow impurities have slightly different

energy levels
• When electronegativity differences
between host and dopant are large,
change in energy level is also large
• If difference between hydrogenic level and
actual level is E, then E is proportional
to X, the electronegativity difference.
 Deep Level Impurities

• Some impurities are so different from the host species – or

they are stable on non-substituional (interstitial) sites – that
they do not exhibit hydrogenic behavior
• Examples:
– Transition metals (Fe in InP, Au in Si)
– Anti-site defects (AsGa)
• Theories concerning ‘activation’ energies
– Based on empirical results
– Difficulties identifying source of deep levels
– Acceptor or Donor (not necessarily related to position in bandgap
 Additional Reading Material

• C. Kittel, Introduction to Solid State Physics

• Seeger, Semiconductor Physics
• Burns, Solid State Physics
• McKelvey, Solid State and Semiconductor Physics
• Sze, Physics of Semiconductor Devices
• Blakemore, Semiconductor Statistics
• Bube, Electrons in Solids
• Many newer texts also available in the UCLA
Science and Engineering Library E-books
– Yu and Cardona, Fundamentals of Semiconductors