EE5508 Semiconductor Fundamentals

Department of Electrical and Computer Engineering

National University of Singapore

Prof. Wu Yihong

Room: E4-8-3
E-mail: [email protected]

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

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 1 𝑑𝑑𝑑𝑑 E k disperion near 𝐸𝐸𝐶𝐶 and 𝐸𝐸𝑉𝑉
Group velocity:
ℏ 𝑑𝑑𝑘𝑘 (lumped into effective mass)

𝑚𝑚𝑒𝑒∗

Si 𝐸𝐸𝐶𝐶
𝐸𝐸𝐺𝐺
𝐸𝐸𝑉𝑉
Band diagram
∗
𝑚𝑚ℎℎ
∗
𝑚𝑚𝑙𝑙𝑙

Bandgap LO phonon
(eV) (meV)
K Diamond 5.47 163

Silicon 1.12 60
1st BZ
Germanium 0.74 31

1 THz → 4.1 meV Bandgap is 20-30 times larger

Group velocity: 𝑑𝑑𝜔𝜔/𝑑𝑑𝑑𝑑 than LO phonon energy

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

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Coverage of Part I (cont’d)
Statistics & electrical properties of semiconductors
Lecture 6
Lecture 5

5 2 1
Ec 4
Ed 6 3 n

Donor level
ED
 ∑i
v
vd = i =1

E n
Acceptor level
EA - - -
Ea electrons
Ev

Intrinsic semiconductors
Extrinsic semiconductors Basic electrical transport
properties of semiconductors

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

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 Outline of Lecture 5

Thermal-equilibrium carrier concentration and Fermi

level of intrinsic semiconductor

Impurity doping of semiconductor and ionization energy

of dopants

Thermal-equilibrium carrier concentration and Fermi

level of extrinsic semiconductor

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

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Intrinsic semiconductors

 As far as electrical properties are concerned,

semiconductors can be divided into two major Each Si
types: intrinsic and extrinsic. atom has
4 valence
 The former refers to semiconductors without electrons
the presence of any impurities and defects,
and all the valence electrons form atomic
bonds with neighboring atoms.
 The latter refers to semiconductors doped
either intentionally or unintentionally with
Conduction Conduction
impurities. Band Band
(unfilled) (partially filled)
 In an intrinsic semiconductor, there are no
Electrons
movable charges at zero temperature, and
therefore, there is no electrical conduction.
Energy
Electrons Thermal
Eg excited excitation
 At finite temperature, however, electrical
conduction occurs through thermal excitation Holes
holes
of electrons from the valence band to the Valence Band
(filled with Valence Band
conduction band and at the same time electrons) (partially filled)
creating holes at the valence band; both of
which contribute to electrical conduction. T=0K T>0K

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

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Carrier density in intrinsic semiconductors

 At finite temperature, electrons in conduction bands and holes in the

valence bands can be calculated by using the concepts of density of states
and Fermi distribution:
number of electrons per
∞ unit energy per unit
 At T = 0, Number of
electrons per unit
𝑛𝑛 = � 𝐷𝐷𝐶𝐶 𝐸𝐸 𝑓𝑓𝑒𝑒 𝐸𝐸, 𝑇𝑇 𝑑𝑑𝑑𝑑 volume in unit of
𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠/[𝑒𝑒𝑒𝑒 � 𝑐𝑐𝑐𝑐3 ]
volume per unit 𝐸𝐸𝐶𝐶
energy interval: 𝐷𝐷𝐶𝐶 𝐸𝐸

 At T = 0, number of
electrons per unit E E
𝐷𝐷𝐶𝐶 𝐸𝐸 𝑓𝑓𝑒𝑒 𝐸𝐸, 𝑇𝑇
volume within dE:
𝐷𝐷𝐶𝐶 𝐸𝐸 𝑑𝑑𝑑𝑑

 At 𝑇𝑇 ≠ 0, number of dE
electrons per unit
volume within dE: Small
𝐷𝐷𝐶𝐶 𝐸𝐸 𝑓𝑓𝑒𝑒 𝐸𝐸, 𝑇𝑇 𝑑𝑑𝑑𝑑 energy
interval
 Total number of
electron per unit
volume above 𝐸𝐸𝐶𝐶 : fe n(E)
∞ Density of states Fermi distribution
∫𝐸𝐸 𝐷𝐷𝐶𝐶 𝐸𝐸 𝑓𝑓𝑒𝑒 𝐸𝐸, 𝑇𝑇 𝑑𝑑𝑑𝑑
𝐶𝐶

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

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Carrier density in intrinsic semiconductors

 Recap of formulae and definition of parameters (single band and

single valley):

∞ n : electron density; p: hole density

𝑛𝑛 = � 𝐷𝐷𝑐𝑐 (𝐸𝐸)𝑓𝑓𝑒𝑒 (𝐸𝐸, 𝑇𝑇)𝑑𝑑𝑑𝑑 DC : density of states for electrons
𝐸𝐸𝑐𝑐
𝐸𝐸𝑣𝑣 D V : density of states for holes
𝑝𝑝 = � 𝐷𝐷𝑣𝑣 (𝐸𝐸)𝑓𝑓ℎ (𝐸𝐸, 𝑇𝑇)𝑑𝑑𝑑𝑑
−∞
f e : Fermi distribution for electrons
3/2
1 2𝑚𝑚𝑒𝑒∗ f h : Fermi distribution for holes
𝐷𝐷𝐶𝐶 (𝐸𝐸) = 2 𝐸𝐸 − 𝐸𝐸𝑐𝑐
2𝜋𝜋 ℏ2 m*e : electron effective mass
3/2
1 2𝑚𝑚ℎ∗ m*h : hole effective mass
𝐷𝐷𝑉𝑉 (𝐸𝐸) = 2 𝐸𝐸𝑣𝑣 − 𝐸𝐸
2𝜋𝜋 ℏ2
1
EF : Fermi level (near the middle of bandgap
𝑓𝑓𝑒𝑒 (𝐸𝐸) = (𝐸𝐸−𝐸𝐸 )/𝑘𝑘 𝑇𝑇 for intrinsic semiconductors)
𝑒𝑒 𝐹𝐹 𝐵𝐵 + 1
1
𝑓𝑓ℎ (𝐸𝐸) = (𝐸𝐸 −𝐸𝐸)/𝑘𝑘 𝑇𝑇
𝑒𝑒 𝐹𝐹 𝐵𝐵 + 1

Density of states of 3/ 2
1  2m 
free electron derived D( E ) =   E
in Lecture 3 2π 2   2 

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

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Carrier density in intrinsic semiconductors (cont’d)

 Since kBT (= 25.9 meV at RT) << Eg (bandgap) is always satisfied for most
common semiconductors, Fermi distribution can be approximated by
Boltzmann distribution, therefore ∞
Note: ∫ 𝑥𝑥 1/2 𝑒𝑒 −𝑥𝑥 𝑑𝑑𝑑𝑑 =
𝜋𝜋
0 2
EV
∞
n = ∫ Dc ( E ) f e ( E , T )dE p=∫ DV ( E ) f h ( E , T )dE
Ec −∞
3/2
1  2m  * 3/2
1 EV 1  2mh*  1
∫ EV − E dE
∞
∫Ec 2π 2  2  E − Ec ( E= dE
2π 2   2 
e
e − EF )/ k BT
+1 −∞ e( EF − E )/ kBT + 1
3/2 3/2
∞ 1  2me*  EV 1  2mh* 
∫Ec 2π 2  2  E − Ec e( E=
F − E )/ k BT
dE ∫−∞ 2π 2   2 
EV − Ee( E − EF )/ kBT dE

3/2 3/2
 me*k BT   EC − EF   mh*k BT   EF − EV 
2 2 
exp  −  = 2  2π  2  exp − 
 2π    k B T     k BT 
 E − EF   EF − EV 
= N C exp  − C  = N exp − 
 k B T 
V
 k B T 

NC: effective density of states in NV: effective density of states in

the conduction band the valence band

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

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Carrier density in intrinsic semiconductors (cont’d)

Consider the case that 𝑚𝑚𝑒𝑒∗ = 𝑚𝑚𝑒𝑒 free electron mass and 𝑇𝑇 = 300 𝐾𝐾

3/2
𝑚𝑚𝑒𝑒∗ 𝑘𝑘𝐵𝐵 𝑇𝑇
𝑁𝑁𝐶𝐶 = 2
2𝜋𝜋ℏ2
3/2 3/2
0.512 × 106 × 25.9 × 10−3 𝑒𝑒𝑒𝑒/𝑐𝑐 2 � 𝑒𝑒𝑒𝑒
=2
6.28 × (6.582 × 10−16 )2 (𝑒𝑒𝑒𝑒 � 𝑠𝑠)2
3/2 3/2
1.326 × 102 1
=2
2.72 × 10−32 (𝑐𝑐 � 𝑠𝑠)2
𝐾𝐾𝐵𝐵 𝑇𝑇 = 25.9 𝑚𝑚𝑚𝑚𝑚𝑚 (at RT)
3/2 3/2
1.326 × 102 1 𝑚𝑚𝑒𝑒 = 0.512 × 106 𝑒𝑒𝑒𝑒/𝑐𝑐 2
=2 𝑚𝑚−3
2.72 × 10−32 9 × 1016 𝑐𝑐 = 3 × 108 𝑚𝑚/𝑠𝑠

= 2.52 × 1025 𝑚𝑚−3 ℏ = 1.054 × 10−34 𝐽𝐽 � 𝑆𝑆

= 6.582 × 10−16 𝑒𝑒𝑒𝑒 � 𝑠𝑠

Electron density in Cu: 𝑛𝑛 = 8.49 × 1028 𝑚𝑚−3

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

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Carrier density in intrinsic semiconductors (cont’d)

 Effective density of states (single band and valley):

3/ 2 3/ 2
 me*k BT  m k T 
*
N C = 2 
2  NV = 2 
h B

 2π 
2
 2π 
 For semiconductors with multiple valleys (Mc) and anisotropic effective
mass, effective density of states are given by
3/2 3/2
m k T   mdh k BT 
N C = 2  de B2  M C NV = 2  
Mc = 6 for Si
 2π    2π  
2

 Here, mde and mdh are density of states effective mass for electrons and
holes:

mde ( m1*m2*m3* )1/3

= mdh ( mlh*3/2 + mhh
= *3/2 2/3
)
Derivation
is given in
appendix A Here, mi* (i=1, 2, 3) is effective mass of electrons along the principal
axes of the constant energy surface.

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

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Fermi-level in intrinsic semiconductors

 For intrinsic semiconductors, n = p, therefore

3/2 3/2
*
m k T   EC − EF  *
 mdh k BT   EF − EV 
2 de B
 M c exp  − =  2 2 
exp  − 
 2π  
2
 k B T   2π    k B T 

EC + EV 3k BT  mdh *
 EC + EV k BT  NV 
EF
⇒= + ln  * 2/3
=  + ln  
2 4 m M
 de c  2 2 N
 C

This term is very small

Ec as Nv/Nc ~ 1

EF For intrinsic
semiconductors, Fermi
level lies near the
Ev middle of the bandgap

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 Carrier density in intrinsic semiconductors (cont’d)

 For a given semiconductor, the product of np is

3/2 3/2
m k T   EC − EF
*
 m k T 
*
 EF − EV 
=np 2 M c   exp −
de B
×
 2 dh B
 exp − 
 2π   π
2 2
 k BT   2    k B T 
3
 k T   E 
*
4 M c  B 2  ( mde ) exp  − g 
* 3/2
mdh
 2π    k BT 
This is the so-called law of mass action.
 As n = p for intrinsic semiconductors, 𝑛𝑛𝑛𝑛 = 𝑛𝑛𝑖𝑖2 , and
3/2 At RT, 𝑘𝑘𝐵𝐵 𝑇𝑇 = 25.9 𝑚𝑚𝑚𝑚𝑚𝑚
 k T   E 
ni ( m m ) M exp  − g 
2 B 2  * * 3/4 1/2

 2π  
de dh c
 2 k BT  𝑬𝑬𝒈𝒈 (𝒆𝒆𝒆𝒆) 𝒏𝒏𝒊𝒊 (𝒎𝒎−𝟑𝟑 )
*
let m=
e
*
m=
h m (rest mass of free electron) 0.1 3.6 × 1024

21 3/2 1/2  Eg  −3
0.5 1.6 × 1021
ni = 4.83 × 10 T M c exp  −  (m )
 2 k BT  1 1.0 × 1017
(T is in unit of K) 1.5 6.3 × 1012

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

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Carrier density in intrinsic semiconductors (cont’d)

Remarks on law of mass action

𝑎𝑎𝑎𝑎 + 𝑏𝑏𝑏𝑏 ⇌ 𝑐𝑐𝑐𝑐 + 𝑑𝑑𝑑𝑑 𝑑𝑑(𝑙𝑙𝑙𝑙 𝐾𝐾) ∆𝐻𝐻

=
𝑑𝑑𝑑𝑑 𝑘𝑘𝐵𝐵 𝑇𝑇
∆𝐻𝐻: standard enthalpy
change of the reaction
(per molecule)

𝑛𝑛𝑛𝑛 𝐸𝐸𝑔𝑔
= exp − 𝐸𝐸𝑔𝑔 : equivalent to heat absorbed
𝑁𝑁𝐶𝐶 𝑁𝑁𝑣𝑣 𝑘𝑘𝐵𝐵 𝑇𝑇

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

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Temperature dependence of the bandgap
 The band-gap energy of semiconductors
tends to decrease with increasing 1.6

temperature. When temperature increases, 1.4

the amplitude of atomic vibrations increase, 1.2

Bandgap (eV)
1
leading to larger interatomic spacing.
0.8
 The relationship between band gap energy 0.6

and temperature can be described by 0.4

GaAs Si Ge
Varshni's empirical expression (named after Y. 0.2
0
P. Varshni): 0 200 400 600 800

𝛼𝛼𝑇𝑇 2 Temperature (K)

𝐸𝐸𝑔𝑔 𝑇𝑇 = 𝐸𝐸𝑔𝑔 0 −
𝑇𝑇 + 𝛽𝛽

Material 𝑬𝑬𝒈𝒈 (𝟎𝟎) 𝜶𝜶 (× 𝟏𝟏𝟏𝟏−𝟒𝟒 ) 𝜷𝜷

GaAs 1.519 5.405 204
Si 1.170 4.73 636
Ge 0.744 4.774 235

Varshni, Y.P., "Temperature dependence of the energy gap in semiconductors". Physica 34 (1): 149–154 (1967).

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Carrier density in intrinsic semiconductors (cont’d)

 The Fermi level is a measure of the total chemical potential (or

electrochemical potential) of electrons in a body.
 The Fermi level of a body is a thermodynamic quantity, which
corresponds to the thermodynamic work required to add one
electron to it.
 In the band structure picture, the Fermi level can be considered to
be a hypothetical energy level of an electron, such that at
thermodynamic equilibrium this energy level would have a 50%
probability of being occupied at any given time at finite
temperature. All the energy levels below Fermi level are fully
occupied provided that there are no electron states available at 0K.
1 Ec
f (E , T ) =
 E − EF (T )  EF
1 + exp  EF
 k B T 
Fully occupied at 0K DOS = 0 in this region
Ev
𝑓𝑓 𝐸𝐸, 𝑇𝑇 = 0.5
Fully occupied at 0K
when 𝐸𝐸 = 𝐸𝐸𝐹𝐹 (𝑇𝑇) Metal
Semiconductor

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Carrier density in Ge, Si, and GaAs

 The right figure shows the intrinsic

carrier density as a function of
temperature for Ge, Si, and GaAs:
3/2
𝑘𝑘𝐵𝐵 𝑇𝑇 ∗ ∗ 3/4 1/2 𝐸𝐸𝑔𝑔
𝑛𝑛𝑖𝑖 = 2 (𝑚𝑚𝑑𝑑𝑑𝑑 𝑚𝑚𝑑𝑑𝑑 ) 𝑀𝑀𝑐𝑐 exp −
2𝜋𝜋ℏ2 2𝑘𝑘𝐵𝐵 𝑇𝑇

 As l𝑛𝑛(𝑛𝑛𝑖𝑖 ) ∝ 1/𝑇𝑇, it is convenient to plot

𝑛𝑛𝑖𝑖 in a semi-log plot (1000/T is used
instead of 1/T because we are mainly
interested in carrier concentrations near
300K).

Commonly accepted carrier concentrations

for Si, GaAs, and Ge at 300 K:

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

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 Outline of Lecture 5

Thermal-equilibrium carrier concentration and Fermi

level of intrinsic semiconductor

Impurity doping of semiconductor and ionization energy

of dopants

Thermal-equilibrium carrier concentration and Fermi

level of extrinsic semiconductor

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Conductivity control of semiconductors
 The ability to grow large and pure
single crystals contributed significantly
to the advance of semiconductor Sand

technologies.
 On the other hand, intrinsic (or pure) Purified
semiconductors are of less practical polycrystalline
silicon
interest (at least from electrical
conduction point of view) because at
normal temperature the carrier
densities are very low.
 Although intrinsic carrier
concentrations can be increased by
using semiconductors with smaller
bandgaps, such kind of
semiconductors are not so useful Silicon wafer /
because they are too sensitive to substrate
temperature variation. Ingot silicon

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Conductivity control of semiconductors
 From device application point
of view, the materials of choice
are such that they exhibit low
intrinsic carrier density at room
temperature, but their
conductivity can be altered by
adding a controlled amount of
impurity atoms – a process
called doping. MOSFET

 Controlled doping of donor

(providing additional electrons) Si substrate
and acceptor (providing
additional holes) impurities to Thin film Litho etch
pure semiconductors is of
paramount importance in the Dicing/packaging
operation of semiconductor
devices. Chips

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Extrinsic semiconductors
 Additional electrons (holes) can
be introduced into intrinsic
semiconductors through doping
of impurity atoms with more
(less) valence electrons as
compared to the host atom.

 When properly chosen, the

additional electrons/holes 4 valence 3 valence 5 valence
loosely bound to the impurity electrons electrons electrons
atoms will be able to escape the
impurity atoms at room
temperature.
- +
 This will lead to n-type (with P B

movable electrons) and p-type

(with movable holes) extrinsic
semiconductors. excess electron hole
EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010
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Ionization energy of dopant
 The ionization energy of  Same formula can be used to calculate
hydrogen atom is 13.6 eV. the ionization energy of impurity atoms
in semiconductors by replacing the m0
1 𝑒𝑒 2 1 with effective mass m* and ε0 with
𝐸𝐸𝑛𝑛 = − = −13.6𝑒𝑒𝑒𝑒
8𝜋𝜋𝜀𝜀0 𝑛𝑛2 𝑎𝑎0 𝑛𝑛2 dielectric constant of the Note: here 𝑚𝑚∗ is
dimensionless, e.g.,
semiconductor ε = εrε0 : normalized to 𝑚𝑚0
Here, a0 = 0.053 nm is the 1 𝑒𝑒 2 𝑚𝑚∗ 13.6
radius of the lowest orbit of 𝐸𝐸𝑛𝑛 = −
8𝜋𝜋𝜀𝜀𝑟𝑟 𝜀𝜀0 𝑛𝑛2 𝑎𝑎 𝜀𝜀𝑟𝑟
= − 2 2 𝑒𝑒𝑒𝑒
𝜀𝜀𝑟𝑟 𝑛𝑛
0 𝑚𝑚∗
the electron around the
hydrogen nucleus (m0: mass 𝜀𝜀𝑟𝑟 =11.7 for Si
of free electron, ε0: dielectric
𝑚𝑚𝑒𝑒∗
constant of vacuum) - - Hydrogenic
P atom
𝜀𝜀𝑟𝑟 𝜀𝜀0
ℎ2 𝜀𝜀0
𝑚𝑚0 𝑎𝑎0 =
𝜀𝜀0 𝜋𝜋𝑚𝑚0 𝑒𝑒 2 𝑚𝑚𝑒𝑒∗
𝐸𝐸𝑑𝑑 = 2 × 13.6 𝑒𝑒𝑒𝑒 (for donar)
𝜀𝜀𝑟𝑟
Note: here 𝑚𝑚𝑒𝑒∗ and 𝑚𝑚ℎ∗
Hydrogen atom are normalized to 𝑚𝑚0 𝑚𝑚ℎ∗
𝐸𝐸𝑎𝑎 = 2 × 13.6 𝑒𝑒𝑒𝑒 (for acceptor)
𝜀𝜀𝑟𝑟

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

21
Ionization energy of dopant in Si

 Shallow impurity levels are very

useful for controlling the
conductivity of semiconductors:
e.g., B, Al, Ga, In (acceptors) and
P, As, Sb (donors) in Si.

 Deep impurity levels are

undesirable for semiconductors,
e.g., La, Y, Zr, Hf, Ta in Si.

 Very deep impurity levels are

damaging and may make
semiconductors very resistive,
e.g., Fe, Cu, Ni, Cr, Mn, Au in Si.

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

22
Impurity levels in Si and GaAs

Shallow Si
dopants

GaAs

GaAs:Cr is a
semi-insulator

Very useful as
substrate

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

23
Cr-doped GaAs: a useful substrate material
Typical specs of commercial semi-insulating GaAs wafer

https://global-sei.com/sc/products_e/gaas/semi.html
GaAs

Resistivity of GaAs doped by

transition metal impurities

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

24
Degenerate semiconductors (n-type)
 When donor concentration is low,
dopants form discrete energy levels.
 When dopant concentration is sufficiently
high (e.g., comparable to the effective
density of states), they may interact with
each other to form donor energy band;
when the band widens, it may overlap
with the bottom of the conduction band.
 In the meantime, electron density in the
conduction band will increase and Non-degenerate semiconductor
eventually exceeds the effective density
of states Nc; when this happens, the
Fermi level will move into the conduction
band. This type of semiconductor is called
a degenerate n-type semiconductor.
 A degenerate semiconductor behaves like
a metal.
𝑛𝑛 = 𝑁𝑁𝐶𝐶 𝑒𝑒𝑒𝑒𝑒𝑒 −
𝐸𝐸𝐶𝐶 − 𝐸𝐸𝐹𝐹
→ 𝐸𝐸𝐶𝐶 − 𝐸𝐸𝐹𝐹 = −𝑘𝑘𝐵𝐵 𝑇𝑇ln
𝑛𝑛 Degenerate semiconductor
𝑘𝑘𝐵𝐵 𝑇𝑇 𝑁𝑁𝐶𝐶
EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010
25
Critical doping concentration
 The critical doping concentration (𝑁𝑁𝑐𝑐 ) can be estimated from
the Mott criterion when the distance of the impurities
becomes comparable to their Bohr radius:
3 1/3
𝑎𝑎𝐵𝐵 = 𝑁𝑁
4𝜋𝜋 𝑐𝑐

Critical doping concentration

for various semiconductors (at
room temperature)

Marius Grundmann
(Springer, 2021)

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

26
 Outline of Lecture 5

Thermal-equilibrium carrier concentration and Fermi

level of intrinsic semiconductor

Impurity doping of semiconductor and ionization energy

of dopants

Thermal-equilibrium carrier concentration and Fermi

level of extrinsic semiconductor

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

27
Ionization of dopants
 At T = 0 K, the additional
Ed
electrons (holes) stay loosely
+
bounded to the impurity EC

atoms.
T=0K Eg Donor levels
 For shallow donors occupied by Releasing loosely
electrons bounded extra
(acceptors), the loosely EV electron into
bounded extra electrons conduction band
(holes) will be thermally
excited into conduction Ionization of
(valence) band at finite EC donor atoms
temperature to form movable + + + + + + + +

carriers. T = 300 K Eg
Ionized donors
 Nearly all donors and EV
remain fixed in
the lattice, and
acceptors are ionized at room are positively
temperature for impurities charged
with a small ionization energy.
EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010
28
Impurity ionization energy v.s. impurity energy level

By convention, the same symbol Ed is used to denote both impurity

ionization energy and impurity energy level, it should not be confused
with each other, e.g., the following applies to the donor case:

Ed (donor ionization energy)

EC = Eg = 1.12 eV
45 meV
Ed (donor energy level)
=1.12 eV – 0.045 eV = 1.075 eV
Eg = 1.12 eV

EV = 0 (reference)

Based on this convention, 𝐸𝐸𝑑𝑑 is 0.045 eV when it denotes donor

ionization energy, but it is 1.075 eV when it refers to donor energy level.

The same convention also applies to acceptors

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

29
Ionization of impurity atoms (cont’d)
⇒ In general case, ionization rate (un-occupied rate of impurity energy level)
can be calculated using Fermi-Dirac statistics.
⇒ For a donor density of N d ,the density of un-ionized donor is thus given by
Nd
nd = Ed : donor energy level
1  Ed − E F 
1 + exp   EF : Fermi level
gd  k B T 
(Here, g d is to account for ground-state degeneracy of donor level;
g d = 2 for spin degeneracy only) Donors release
electrons to CB

⇒ Density of ionized donor (or un-occupied) EC

is given by + + + +
+
N=
d N d − nd nd
N d+ = N d − nd
Nd
= EV
 E F − Ed 
1 + g d exp  
 k BT 
EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010
30
Ionization of impurity atoms (cont’d)
⇒ Similarly, for an acceptor density of N a ,the density of un-ionized acceptor is
Na
na =
1  E − Ea  Ea : acceptor energy level
1 + exp  F  EF : Fermi level
ga  k B T 
(g a accounts for both spin and band degeneracy of the acceptor energy level;
g a = 4 for Ge, Si and GaAs because each acceptor level can accept 2 electrons of
different spins and the impurity level is double-degenerate due to heavy hole
and light hole bands at k = 0)

⇒ Density of ionized acceptor (or un-occupied acceptor level) is given by

− EC
N=
a N a − na
Na −
N= N a − na
= a na
 Ea − E F 
1 + g a exp   Acceptor grabs electron
 k BT 
- - - -
to create hole in VB Ea
EV

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

31
Carrier statistics in extrinsic semiconductors
Total electron density: n
 In semiconductors with
both donors and Electrons due to Thermally excited
acceptors, movable ionized donors electrons across the gap

carriers can be generated

from both ionization of EC
impurity atoms and + + + + Un-ionized
thermal excitation of donor
N d+ = N d − nd
intrinsic carriers.

 At equilibrium, electron −
N=
a N a − na
and hole densities are - - - - Un-ionized
determined by the charge EV
acceptor

neutrality equation:
n + ( N a − na ) =p + ( N d − nd ) Holes due to Thermally excited
ionized acceptors holes across the gap

Net negative Net positive

charge charge Total hole density: p

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

32
Carrier statistics in extrinsic semiconductors

 Regardless of the origin, electrons in conduction band and holes in

valence band satisfy the following statistics:
 EC − EF   E F − EV 
n = N C exp −  and p = NV exp − 
 k BT   k BT 

 Law of mass action also applies to extrinsic semiconductors:

 E − EF   E − EFi   E − EFi   E − EFi 

n = N C exp − C  = N C exp − C  exp F  = ni exp F 
 k BT   k BT   k BT   k BT 
 E − EV   E − EV   E − EF   E − EF 
p = NV exp − F  = NV exp − Fi  exp Fi  = ni exp Fi 
 k BT   k BT   k BT   k BT 

⇒ np = ni2

This relation always holds when the semiconductor is in thermal equilibrium.

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

33
Carrier statistics in extrinsic semiconductors

𝑚𝑚𝑑𝑑𝑑𝑑 𝑘𝑘𝐵𝐵 𝑇𝑇
3/2
 E − EF   E − EV  m k T 
3/2
𝑁𝑁𝐶𝐶 = 2𝑀𝑀𝑐𝑐
2𝜋𝜋ℏ2 n = N C exp − C  p = NV exp − F  NV = 2  dh B2 
 k BT  k BT  2π  
 

n + ( N a − na ) =p + ( N d − nd )

Na
N a − na = Nd
 E − EF  N d − nd =
1 + g a exp a   E − Ed 
 k BT  1 + g d exp F 
 k BT 

 E − EF  Na  E − EV  Nd
N C exp − C  + = NV exp − F  +
 k BT  1 + g exp − EF − Ea   k BT  1 + g exp − Ed − E F 
a  k BT 
d  k BT 
  

This equation, in principle, can be solved to find EF, which in turn can be used to find
electron and hole concentrations, though the process is quite tedious.
EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010
34
Intrinsic v.s. extrinsic semiconductors

Adding more
electrons from
ionization of donors
leads to decrease
of holes; why?

From

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

35
Intrinsic v.s. extrinsic semiconductors

Adding more holes from

ionization of acceptors
leads to decrease of
electrons; why?

From

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

36
Carrier statistics in extrinsic semiconductors
 General case: 𝑛𝑛𝑑𝑑 =
𝑁𝑁𝑑𝑑
≈0
- Material contains both donors and 1 𝐸𝐸 − 𝐸𝐸
1 + 𝑔𝑔 𝑒𝑒𝑒𝑒𝑒𝑒 𝑑𝑑𝐾𝐾 𝑇𝑇 𝐹𝐹
𝑑𝑑 𝐵𝐵
acceptors
- Both donors and acceptors are completely
𝑁𝑁d − 𝑛𝑛𝑑𝑑 ≈ 𝑁𝑁𝑑𝑑 , 𝑁𝑁𝑎𝑎 − 𝑛𝑛𝑎𝑎 = 𝑁𝑁𝑎𝑎
ionized [(Ed-EF ) >> kBT and (EF-Ea ) >> kBT ]
- Thermally excited intrinsic carriers co-exist
with carriers from dopants 𝑛𝑛 + 𝑁𝑁𝑎𝑎 = 𝑝𝑝 + 𝑁𝑁𝑑𝑑 𝑁𝑁𝑎𝑎
𝑛𝑛𝑎𝑎 = ≈0
1 𝐸𝐸 − 𝐸𝐸
Thermally excited 1 + 𝑔𝑔 𝑒𝑒𝑒𝑒𝑒𝑒 𝐹𝐹𝐾𝐾 𝑇𝑇 𝑎𝑎
𝑎𝑎 𝐵𝐵
electrons
𝑛𝑛𝑖𝑖2
𝑛𝑛 + 𝑁𝑁𝑎𝑎 = + 𝑁𝑁𝑑𝑑
𝑛𝑛
𝑛𝑛𝑖𝑖2
EC + 𝑁𝑁𝑎𝑎 = 𝑝𝑝 + 𝑁𝑁𝑑𝑑
𝑝𝑝
+ + + + + + + +
EF
2
- - - - - - - - 𝑁𝑁𝑑𝑑 − 𝑁𝑁𝑎𝑎 𝑁𝑁𝑑𝑑 − 𝑁𝑁𝑎𝑎
𝑛𝑛 = + + 𝑛𝑛𝑖𝑖2
EV 2 2

2
𝑁𝑁𝑎𝑎 − 𝑁𝑁𝑑𝑑 𝑁𝑁𝑎𝑎 − 𝑁𝑁𝑑𝑑
Thermally 𝑝𝑝 = + + 𝑛𝑛𝑖𝑖2
2 2
excited holes

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

37
Low-temperature region
- n-type semiconductor (Na = 0 )
- low temperature: kBT < Ed, ND >> ni2/n
ignored T
0
𝐸𝐸𝐶𝐶 − 𝐸𝐸𝐹𝐹 𝑁𝑁𝑎𝑎 𝐸𝐸𝐹𝐹 − 𝐸𝐸𝑉𝑉 𝑁𝑁𝑑𝑑 800 K
𝑁𝑁𝐶𝐶 exp − + = 𝑁𝑁𝑉𝑉 exp − +
𝑘𝑘𝐵𝐵 𝑇𝑇 𝐸𝐸 − 𝐸𝐸𝑎𝑎 𝑘𝑘𝐵𝐵 𝑇𝑇 𝐸𝐸 − 𝐸𝐸𝐹𝐹
1 + 𝑔𝑔𝑎𝑎 exp − 𝐹𝐹 1 + 𝑔𝑔𝑑𝑑 exp − 𝑑𝑑
𝑘𝑘𝐵𝐵 𝑇𝑇 𝑘𝑘𝐵𝐵 𝑇𝑇 700 K

600 K
𝐸𝐸𝐶𝐶 − 𝐸𝐸𝐹𝐹 𝑁𝑁𝑑𝑑 𝐸𝐸𝑑𝑑 − 𝐸𝐸𝐹𝐹
𝑁𝑁𝐶𝐶 exp − = exp
𝑘𝑘𝐵𝐵 𝑇𝑇 𝑔𝑔𝑑𝑑 𝑘𝑘𝐵𝐵 𝑇𝑇 500 K
EC
400 K
+ + + +
𝐸𝐸𝐶𝐶 + 𝐸𝐸𝑑𝑑 𝑘𝑘𝐵𝐵 𝑇𝑇 𝑁𝑁𝑑𝑑 EF 300 K
𝐸𝐸𝐹𝐹 = + ln
2 2 𝑔𝑔𝑑𝑑 𝑁𝑁𝐶𝐶
200 K

EV 100 K
𝐸𝐸𝐶𝐶 − 𝐸𝐸𝐹𝐹 𝑁𝑁𝑑𝑑 𝐸𝐸𝑑𝑑 − 𝐸𝐸𝐹𝐹
𝑛𝑛2 = 𝑁𝑁𝐶𝐶 exp − exp 0K
𝑘𝑘𝐵𝐵 𝑇𝑇 𝑔𝑔𝑑𝑑 𝑘𝑘𝐵𝐵 𝑇𝑇
Compare with intrinsic case :
1 𝐸𝐸𝑔𝑔
𝑛𝑛𝑖𝑖 = 𝑁𝑁𝐶𝐶 𝑁𝑁𝑉𝑉 2 exp − ; (𝐸𝐸𝑔𝑔 = 𝐸𝐸𝐶𝐶 − 𝐸𝐸𝑉𝑉 )
𝐸𝐸𝐶𝐶 − 𝐸𝐸𝑑𝑑 2𝑘𝑘𝐵𝐵 𝑇𝑇
𝑛𝑛 = (𝑁𝑁𝐶𝐶 𝑁𝑁𝑑𝑑 /𝑔𝑔𝑑𝑑 )1/2 exp −
2𝑘𝑘𝐵𝐵 𝑇𝑇 Donor levels play the role of valence band

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

38
Low-temperature region
- p-type semiconductor (Nd = 0 )
- low temperature: kBT < Ea, NA >> ni2/p 0 T

 E − EF  Na  E − EV  Nd 800 K
N C exp  − C + =NV exp  − F +
 k BT  1 + g exp  − EF − Ea   k BT  1 + g exp  − Ed − E F 
ignored a  k BT 
d  k BT  700 K
 
⇓ 600 K

 E − EF  Na EC
NV exp  V 500 K
=
 k BT  1 + g exp  Ea − EF 
a  k T  400 K
 B 
 E − EF  Na  E − Ea  300 K
EF
NV exp  V = exp  F  - - - -
 k BT  ga  k BT  200 K
EV
EV + Ea k BT  g a NV 
=EF + ln   100 K
2 2  Na 
0K
⇓
Compare with intrinsic case :
1/2  E − EV  1 𝐸𝐸𝑔𝑔
p ( NV N a / g a ) exp  − a  𝑛𝑛𝑖𝑖 = 𝑁𝑁𝐶𝐶 𝑁𝑁𝑉𝑉 2 exp − ; (𝐸𝐸𝑔𝑔 = 𝐸𝐸𝐶𝐶 − 𝐸𝐸𝑉𝑉 )
 2 k BT  2𝑘𝑘𝐵𝐵 𝑇𝑇
Acceptor levels play the role of conduction band

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

39
Intermediate temperature region
- n-type semiconductor (Na = 0 )
- Intermediate temperature (all donors ionized): NC >> Nd >> ni
T

800 K
2
Nd − Na  N − Na  2
n= +  d  + ni ≈ N d 700 K
2  2 
600 K
⇓
500 K
 E − EF  EC
N C exp − C  = N d + + + + + + +
k BT EF + 400 K
 
300 K
⇓
200 K
N  EV
EF = EC − k BT ln C  100 K
 Nd 
0K

This is the saturation region in which carrier

density is independent of temperature.

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

40
Intermediate temperature region
- p-type semiconductor (Nd = 0 )
- Intermediate temperature (all acceptors ionized): NV >> Na >> ni
T

2
N − Nd  N − Nd  2 800 K
p= a +  a  + ni ≈ N a
2  2  700 K

⇓ 600 K
EC
 E − EF  500 K
NV exp V  = N a
 k BT  400 K
⇓ EF - - - - - - - -
300 K
N  EV
E F = EV + k BT ln V  200 K
 Na 
100 K

0K
This is the saturation region in which carrier
density is independent of temperature.

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

41
High-temperature region
- High temperature: ni > Nd or Na

EC T
+ + + + + + + +
(n-type) EF
800 K

700 K
EV
600 K

500 K
(p-type)
400 K

EC 300 K

200 K
This is the intrinsic region in which EF
carrier concentration is - - - - - - - - 100 K
determined by the thermally
EV 0K
excited intrinsic carriers.

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

42
 EC
An intuitive picture + + + +
about extrinsic EF

semiconductor

EV
Extrinsic semiconductor

1.12 eV
1 2
1 𝐸𝐸𝑔𝑔 In intermediate
𝑛𝑛𝑖𝑖 = 𝑁𝑁𝐶𝐶 𝑁𝑁𝑉𝑉 2 exp − temperature range 45 meV
2𝑘𝑘𝐵𝐵 𝑇𝑇
Ec  E − Ed 
n = ( N C N d / g d )1/ 2 exp − C 
 2 k BT 
EF EF

Equivalent to a narrow
Ev bandgap semiconductor
with a single energy level
Intrinsic valence band

 Electrons and holes are created simultaneously;  Electrons and holes can be generated separately
 Increase carrier concentration, but unable to control depending on dopant type;
type of conduction (i.e., n or p).  Able to control type of conduction (i.e., n or p)

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

43
Temperature-dependence of carrier density and Fermi-level
for n-type semiconductor

Low-T
 E   E − Ed  T
N d + N C exp  − g 
n= =n ( N C N d / g d )1/2 exp  − C 
 2 k BT   2 k BT 
800 K

700 K
n ≈ Nd
#3 600 K

500 K
#3 #2 Region #1
400 K
1/T
300 K
 NC  #2
E=
F EC − k B T ln   200 K
 Nd 
100 K
#1
0K

EC + EV k BT  NV 
EF + ln  
2 2 NC  EC + Ed k BT  N d 
=EF + ln  
2 2  gd N C 

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

44
Variation of Fermi Energy with Doping
Concentration and Temperature
Fermi level gradually moves up
(down) from the middle of bandgap
with increasing donor (acceptor)
concentration.

 Fermi level gradually approaches

middle of bandgap or intrinsic Fermi
level with increasing temperature.
 The lower the dopant concentration
the faster it approaches the intrinsic
Fermi level.

Semiconductor Devices, 3rd Ed., S. M. Sze and M. K. Lee

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010
45
Question:
Assume we have a silicon sample doped with arsenic at a concentration of 1016 cm-3. The
ionization energy of arsenic is approximately 54 meV. At 300 K, the intrinsic carrier
concentration of Si is ni = 6.73 × 109 cm-3, and the bandgap is 1.12 eV. Make reasonable
assumptions and answer the following questions.

(i) Compute the electron concentration in the conduction band.

(ii) Compute the Fermi level and indicate it in the energy band diagram.

(iii) Compute the fraction of dopants that are ionized and compare it with the assumption
made in part (i) of this question.

(iv) Compute the hole concentration in the valence band and compare it with the
assumption made in part (i) of this question.

Solution:

(i) Since arsenic is a shallow donor in Si, we can assume complete ionization at room
temperature, therefore,

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

46
 (ii)

𝐸𝐸𝐹𝐹 − 𝐸𝐸𝐹𝐹𝐹𝐹 𝑛𝑛 1016

𝑛𝑛 = 𝑛𝑛𝑖𝑖 exp → 𝐸𝐸𝐹𝐹 − 𝐸𝐸𝐹𝐹𝐹𝐹 = 𝑘𝑘𝐵𝐵 𝑇𝑇𝑙𝑙𝑙𝑙 = 0.0259 × 𝑙𝑙𝑙𝑙 ≈ 0.368 𝑒𝑒𝑒𝑒
𝑘𝑘𝐵𝐵 𝑇𝑇 𝑛𝑛𝑖𝑖 6.73 × 109

(iii)
𝐸𝐸𝐹𝐹
𝑁𝑁𝑑𝑑+ 1
= 0.368 𝑒𝑒𝑒𝑒
𝑁𝑁𝑑𝑑 1 + 𝑔𝑔 exp 𝐸𝐸𝐹𝐹 − 𝐸𝐸𝑑𝑑
𝑑𝑑 𝑘𝑘𝐵𝐵 𝑇𝑇 𝐸𝐸𝐹𝐹𝒊𝒊

1.12
𝐸𝐸𝐹𝐹 − 𝐸𝐸𝑑𝑑 = 0.368 − − 0.054 = −0.138
2

𝑁𝑁𝑑𝑑+ 1
= ≈ 99% 99% of donors are ionized
𝑁𝑁𝑑𝑑 1 + 2 exp −0.138
0.0259

(iv) 𝑛𝑛𝑛𝑛 = 𝑛𝑛𝑖𝑖2

𝑛𝑛𝑖𝑖2 (6.73 × 109 )2
𝑝𝑝 = = = 4529
𝑛𝑛 1016

This is much smaller than the electron concentration, confirming that the assumption of a
primarily n-type semiconductor (with negligible hole concentration) is valid.

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Appendix A: density of states effective mass

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

48
Appendix A: density of states effective mass

EE5508 Semiconductor Fundamentals Lecture 5 Wu Yihong 09/09/2010

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Appendix A: density of states effective mass

For multiple valleys (Z)

1/2
 m 3

 *
de
* 
*
=Z ⇒ mde =Z 2/3 ( m1*m2*m3* )1/3
m
 1 m m3 
2

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Appendix B: density of states effective mass

3/2 3/2 3/2

 mdh k BT   mlh k BT   mhh k BT 
NV 2=  2 
2 2 
+ 2 2 
 2π    2 π    2π  
3/2
⇒ mdh = mlh3/2 + mhh
3/2

⇒ mdh = ( mlh3/2 + mhh

3/2 2/3
)

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