Chapter 3

Semiconductor Science
and Light-Emitting Diodes

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 3.1 Review of Semiconductor
Concepts and Energy Bands

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 A. Energy Band Diagrams, Density of States,
Fermi-Dirac Functions of Metals

(圖3.1)

 When brining together ~1023 Li atoms to form the metal crystal, the 2s energy level
slits into ~1023 closely spaced energy levels that effectively form 2s band.
 Fermi energy EF – Highest occupied energy level at 0 K.
 Work function Φ – Minimum energy required to move an electron from the metal.
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 E
州 只
T>0K EF

(圖3.2)
0

 At T > 0 K, some of the electrons are at energies above EF due to thermal

excitation.
 Density of states (DOS) g(E) represents the number of electronics states
(wavefunctions) in a band per unit energy per unit volume of the crystal.
According to the 3-D potential energy well assumption, 𝑔(𝐸) ∝ 𝐸 / .
D
gE) =< St . D gE) EƩ
z -
-

 The product of g(E) and Fermi-Dirac function f(E) is the electron

concentration per unit energy, nE.

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。
 Fermi-Dirac function
3-D potential energy well Density of states
1
g ( E )  4 (2me ) 3/ 2
h E 3 1/ 2
 AE 1/ 2 f (E) 
 E  EF 
1  exp  
(3.1.1)  k BT 
1
(3.1.2)
(

AVE . 1
EF 
texpm
n
Total number of electrons
per unit volume in the band g ( E ) f ( E ) dE (3.1.3)
0

2/3
 h  3n  2
At T = 0 K EFO     (3.1.4)
 8me   
At T > 0 K, EF decreases slightly with T, but this change is minor and can be ignored!
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 B. Energy Band Diagrams of Semiconductors

(圖3.3)

 At T = 0 K, all the bonds are occupied by valence electrons (no broken

bonds), and all the energy levels in the VB are normally
Λ
filled with electrons,
E vacuuw
whereas CB are normally empty.
cBP λ ptype
打 親和 ↑ hrypep
 χ – electron affinity, i.e., the width of the CB. )B
LB ↓ ntype
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子
力
 Electron - Hole Pair Generation

(圖3.4)

 A photon with an energy h greater than Eg can excite an electron from the VB to the
CB. When a photon breaks a Si-Si bond, a free electron and a hole in the Si-Si bond
is created, resulting in the photogeneration of an electron—hole pair (EHP). Note that
in some semiconductors, like Si and Ge, the photon absorption process also involves
lattice vibrations (not shown in Fig. 3.4). The electron in the CB moves with an
effective mass me*, which is not the same as the electron moving in vacuum.
 Thermal energy may also rupture bonds and create electron—hole pairs.
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 Hole Motion in a Semiconductor

(圖3.5)

Illustration of a hole in the valence band (VB) wandering around the crystal due to
the tunneling of electrons from neighboring bonds; and its eventual recombination
with a wandering electron in the conduction band.
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 3.2 Semiconductor Statistics

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 drpiny
oo

√
√

(圖3.6)

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 Electron Concentration in CB
Ec  
n gCB ( E ) f ( E ) dE (3.2.2)
Ec

DOS near EC When EC - EF >> kBT

gCB ( E )  4 (2me )3 / 2 h 3 ( E  Ec )1/ 2  E  EF 
f ( E )  exp   
 A( E  Ec )1 / 2  k BT 
~ Boltzmann function
 ( Ec  EF ) 
n  N c exp   (3.2.3)
 k BT  When EC - EF >> kBT, n << Nc

3/ 2
Effective DOS at CB Edge  2m k T  *
N c  2  e B
2
me* = Effective mass of
(depends on T and material)  h  an electron in the CB

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 Hole Concentration in VB

 ( EF  Ev ) 
p  N v exp   (3.2.4)
 k BT 

Effective DOS at VB Edge

3/ 2
 2m k T  *
N v  2  h B
2
 h 
mh* = Effective mass of a hole in the VB

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 Fermi Energy in Intrinsic Semiconductors EFi

 ( Ec  E F )   ( E F  Ev ) 
n p N c exp 
k T   N v exp 
k T 
 B   B 

1 1  Nc 
EFi  Ev  E g  k BT ln  
2 2  Nv 
1 3  me* 
 Ev  E g  k BT ln  * 
2 4 (3.2.5)
 mh 
1
 Ev  E g
2

me* = Electron effective mass (CB), mh* = Hole effective mass (VB)

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 Mass Action Law

 Eg 
np  n  N c N v exp   2
i  (3.2.6)

 k BT 
ni = intrinsic concentration

The np product is a “constant”, ni2, depending on the material

properties Nc, Nv, Eg, and the temperature. In an undoped
crystal, n = p = ni. If somehow n is increased (e.g. by doping),
p must decrease to keep np constant.

④Mass action law applies in thermal equilibrium

and in the dark (no illumination)
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 Average Electron Energy in CB

Ec  

ECB 
 Ec
EgCB ( E ) f ( E ) dE 3
 EC  k BT
Ec  
2
 Ec
gCB ( E ) f ( E ) dE

(3/2)kBT is also the average kinetic energy per atom in a

monatomic gas (kinetic molecular theory) in which the gas
atoms move around freely and randomly inside a container.

The electron in the CB behaves as if it were “free” with a

mean kinetic energy, < (1/2)*mev2> = (3/2)kBT, and an
effective mass me*.
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 Fermi Energy
Fermi energy is a convenient way to represent free carrier
concentrations (n in the CB and p in the VB) on the energy band
diagram. However, the most useful property of EF is in terms of a
change in EF. Any change EF across a material system represents
electrical work input or output per electron. In thermodynamics, its
rigorous definition is that EF is the chemical potential of the
electron, that is Gibbs free energy per electron.

EF = eV (3.2.7)

For a semiconductor system in equilibrium, in the dark, and with no

applied voltage or no emf generated, EF = 0 and EF must be uniform
across the system.

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 3.3 Extrinsic Semiconductor

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 A. n-Type and p-Type semiconductors
 n-type Si doped with As p Type
=

(圖3.7)

(donor impurity)
a

(a) The four valence electrons of As allow it to bond just like Si but the fifth electron is
left orbiting the As site. The energy required to release to free fifth-electron into the CB
is very small. (b) Energy band diagram for an n-type Si doped with 1 ppm As. There are
donor energy levels just below Ec around As+ sites.
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 Extrinsic Semiconductors: n-Type

 If Nd >> ni, then at room temperature, the

electron concentration in the CB will
nearly be equal to Nd, i.e. n ≈ Nd

 A small fraction of the large number of

electrons in the CB recombine with holes
(donor concentration Nd) in the VB so as to maintain np = ni2

Mass Action Law np = ni2

輕度摻雜 √
n = Nd >> ni and p = ni2/Nd << ni

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 Conductivity of a Semiconductor
or vp

 = ene + eph (3.3.1)

e = electron drift mobility, h = hole drift mobility

Ddriftvelouity
electron drift velocities vde = eEx
③ diffusisom
hole drift velocities vdh = hEx

Conductivity of n-type semiconductor

P
 ni2 
W

  eN d e  e  h  eN d e (3.3.2)
 Nd 
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二
一
 型
 p-type Si doped with Boron

(圖3.8)

(acceptor impurity)
ci 顆申 接收
e
& 卧

(a) Boron doped Si crystal. B has only three valence electrons. When it substitutes for a
Si atom one of its bonds has an electron missing and therefore a hole. (b) Energy band
diagram for a p-type Si doped with 1 ppm B. There are acceptor energy levels just
above Ev around B sites. These acceptor levels accept electrons from the VB and
therefore create holes in the VB.
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一
一
子
 Extrinsic Semiconductors: p-Type
(acceptor concentration Na)  If Na >> ni, then at room temperature, the
hole concentration in the VB will nearly
be equal to Na, i.e. p ≈ Nd

 A small fraction of the large number of

holes in the VB recombine with electrons
in the CB so as to maintain np = ni2
uga
Mass Action Law np = ni2
p = Na >> ni and n = ni2/Na << ni
Conductivity of p-type semiconductor

 ni2 
  eN a h  e  e  eN a h
 Na  州 \ a

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《
 Semiconductor Energy Band Diagrams

(圖3.9)

Intrinsic n-type Fermilevel p-type

n = p = ni n = Nd 接近 Londutm p = Na
p = ni2/Nd 2
hsnd n = ni /Na
np = ni2 np = ni2
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Fermi Level and Work Function of a Semiconductor

(圖3.9)

 ( E  EF )   The energy distance of θ

EF from2 Ec andθ
Ev
n  N c exp  c  determines the electron and hole concentrations.
 k BT 
 The work function  of a semiconductor (the
 ( EF  Ev )  energy distance from the Fermi level to the
p  N v exp  
 k B T  vacuum level) represents the average energy
required to remove an electron from a
√
(3.2.3&3.2.4) semiconductor.
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 Semiconductor Properties

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 B. Compensation Doping
A semiconductor doped with both donors and acceptors to control the properties.

 Donors more than acceptors

A p-type semiconductor doped with Na acceptors can be converted to an n-type
semiconductor by simply adding donors until the concentration Nd exceeds Na.

n = Nd  Na >> ni p = ni2/(Nd  Na)

 More acceptors than donors Na - Nas > n

An ①
n-type semiconductor doped with Nd donors can be converted to a p-type
semiconductor by simply adding acceptors until the concentration Na exceeds Nd.

√
p = Na  Nd >> ni n = ni2/(Na  Nd)
We cannot simultaneously increase the electron and hole concentrations
because that leads to an increase in the recombination rate which returns the
electron and hole concentrations to values that satisfy mass action law np = ni2.
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 C. Nondegenerate and Degenerate
Semiconductors

 Nondegenerate semiconductor – Number of states in the CB

(VB) far exceeds the number of electrons (holes), i.e., Nc >> n
and p << Nv. Pauli exclusion principle can be neglected and
electron statistics can be described by the Boltzmann
statistics, see Eq. (3.2.3).

 Degenerate semiconductor – Heavily doped semiconductors

with n ≳ Nc and p ≳ Nv (typically ~ 1020 cm-3). In this case ~

electron statistics needs to be described by Fermi-Dirac

statistics and the semiconductor is more metal-like behavior.

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 Degenerate Semiconductors (Heavily Doped)

(圖3.10)

 EF is within the band (CB for n-type and VB for p-type).

 Ec is pushed down so that the bandgap is narrower.
 A small DOS tail in the bandgap (band tailing) due to random
fluctuations in the potential energy of the electron.
 Mass action law is not valid (one cannot assume n = Nd or p = Na) .
on θ
y in lightly doped
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 D. Energy Band Diagrams in an Applied Field

 A change EF in EF within a

material system is equivalent
to electrical work per
electron or eV.

 The electron concentration is

uniform so that Ec-EF must
be constant, thus CB, VB,
and EF all bend by the same
amount.

(圖3.11)
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一十
 Example 3.3.1 Fermi levels in semiconductors
An n-type Si wafer has been doped uniformly with 1016 phosphorus (P) atoms
cm–3. Calculate the position of the Fermi energy with respect to the Fermi energy
EFi in intrinsic Si. The above n-type Si sample is further doped with 21017
boron atoms cm–3. Calculate position of the Fermi energy with respect to the
Fermi energy EFi in intrinsic Si at room temperature (300 K), and hence with
respect to the Fermi energy in the n-type case above.

Solution
hri =
np
expt)
P (Group V) gives n-type doping with Nd = 1016 cm–3, and since Nd >> ni in
intrinsic Si (1010 cm–3 from Table 3.1), we have n = Nd = 1016 cm–3.
For intrinsic Si, ni = Ncexp[(Ec  EFi)/kBT] √
√

For doped Si, n = Ncexp[(Ec  EFn)/kBT] = Nd √

EFi and EFn are the Fermi energies in the intrinsic and n-type Si.

Nd /ni = exp[(EFn  EFi)/kBT]

EFn  EFi = kBT ln(Nd/ni) = (0.0259 eV) ln(1016/1010) = 0.358 eV
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一一
 Solution continued
When the wafer is further doped with boron, the acceptor concentration, Na =
21017 cm–3 > Nd = 1016 cm–3. The semiconductor is compensation doped and
compensation converts the semiconductor to a p-type Si. Thus,

落籲
p = Na  Nd = 210171016 = 1.91017 cm–3.
For intrinsic Si,
p = ni = Nv exp[ (EFi  Ev)/kBT], √
For doped Si,
p = Nv exp[ (EFp  Ev)/kBT] = Na  Nd
EFp is the Fermi energy in the p–type Si.
p/ni = exp[ (EFp  EFi)/kBT]
EFp  EFi =  kBT ln(p/ni) =  (0.0259 eV)ln(1.91017/1.01010)
=  0.434 eV
V

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己
Example 3.3.2 Conductivity of n-Si σ= eMuuteMpp

Consider a pure intrinsic Si crystal. What would be its intrinsic conductivity at

300K? What is the electron and hole concentrations in an n-type Si crystal that has
been doped with 1016 cm–3 phosphorus (P) donors. What is the conductivity if the
drift mobility of electrons is about 1200 cm2 V-1 s-1 at this concentration of dopants.

Solution
The intrinsic concentration ni = 1×1010 cm-3, so that the intrinsic conductivity is
 = eni(e + h) = (1.6×10-19 C)( 1×1010 cm-3)(1450 + 490 cm2 V-1 s-1)
= 3.1×10-6 -1 cm-1 or 3.1×10-4 -1 m-1
Consider n-type Si. Nd = 1016 cm-3 > ni (= 1010 cm-3)
electron concentration n = Nd = 1016 cm-3
hole concentration p = ni2/Nd = (1010 cm-3)2/(1016 cm-3) = 104 cm-3 << n

The conductivity is
  eN d e  (1.6 1019 C)(11016 cm 3 )(1200 cm 2 V1s 1 )  1.92 Ω1cm 1
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 3.4 Direct and Indirect Bandgap
Semiconductors: E-k Diagrams √

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 Electrons in 1D Semiconductor Crystals
The electron potential energy (PE), V(x), inside the crystal is periodic with the
same periodicity as that of the Crystal, a. Far away outside the crystal, by choice,
V = 0 (the electron is free and PE = 0).

(圖3.12)
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 Electrons in 1D Semiconductor Crystals

d 2 2me
2
 2 [ E  V ( x )]  0 (3.4.1)
dx 

Periodic Potential Energy (PE)

V(x) = V(x + ma); m = 1, 2, 3 (3.4.2)

Bloch electron wavefunction

k(x) = Uk(x)exp(jkx) (3.4.3)

Periodic wavefunction depending on Traveling wave with wave vector k.

V(x) and has the same periodicity a k is quantized.
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 Electrons in Semiconductor Crystals

k(x,t) = Uk(x)exp(jkx)×exp(jEkt)

 Each k solution corresponds to a particular k and

represents a state with an energy Ek.

 Both exp(jkx) and exp(-jkx) are possible and represent

left and right traveling waves.

 Electron’s crystal momentum in x-direction = k

 External force Fext = d(k)/dt

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 E-k Diagram of a 1D Direct Bandgap
Semiconductor

(圖3.13)

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 E vs. k Diagrams and Direct and
Indirect Bandgap Semiconductors

(圖3.14)

0
E 導健

ㄟ
m
Recombination centers
may be crystal defects
or impurities.
E
=
薑尖
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水
 3.5 pn Junction Principles

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 A. Open Circuit
 Due to the hole(/electron) concentration
gradient, hole(/electron) diffuse toward the
n-region(/p-region) and recombine with the
electrons(/holes) near the junction, resulting
in the depletion region.

 Without applied bias or photoexcitation,

npoppo = nnopno = ni2 at all points.

 Positive ions in n-region and negative ions 0

in p-region form an internal electric field Ppo un 8
=

E0, which drives the holes and electrons in 0

the opposite direction to their diffusion.

①
←
 Total width of depletion region Wo = Wpo +
Wno. For overall charge neutrality,
0 NaWpo = NdWno (3.5.1)
(圖3.15)
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 Gauss’s law

dE d 2V  net ( x )
 2 
dx dx 
(Assume a step form of net (x),  = o r)

Built-in field and potential

eN dWno eN aW po
Eo    (3.5.2)
 
EoWo eN a N dWo2
Vo    (3.5.3)
2 2 ( N a  N d )

Eo in the –x direction is defined negative,

Vo is defined positive.
(圖3.15)
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Boltzmann Statistics (nondegenerate semiconductors)
Potential Energy

N2  ( E 2  E1 ) 
 exp    (3.5.4)
N1  k B T 
nEJaexp-
)(Na)
n po  eVo  N1 (Nd)
 exp   
nno  k BT 
(3.5.5) (ni2/Na) N2
pno  eVo  (ni2/Nd)
 exp   
p po  k BT 

k BT  p po  k BT  N a N d 
Vo  ln    ln  2 
e  pno  e  ni 
(3.5.6)
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B. Forward Bias and the Shockley Diode Equation
空全變窄 Bamdgp }

更多裁
Un .

擴散

(圖3.16)

 The applied voltage V drops mostly across the depletion region and reduces the built-in
field and potential barrier against diffusion to be Vo-V, resulting in the injection of
excess minority carriers.
 There is a large hole (electron) concentration gradient in the n-side (p-side) due to
minority carrier injection, resulting in two minority carrier diffusion fluxes constitute
the forward bias pn junction current.
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子
 Law of the Junction
ppo
Boltzmann Statistics
N2  ( E2  E1 ) 
 exp  
N1  k B T 
婚新久地
 e(Vo  V ) 
-

pn (0)
 exp   
p po  k B T 
 eVo   eV 
 exp   exp 
 k BT   k BT 

pno/ppo

 eV   eV 
pn 0  pno exp
 
 n p 0  n po exp 
 k BT   k BT 
(3.5.8&9)
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方
 Forward Bias: Diffusion Current

 Electric current (mainly due to the diffusion of minority carriers) is

constant through a pn junction under forward bias.
 Very little electric field in the neutral regions to give rise to drift.

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 Forward Bias: Diffusion Current (Long Diode)

For a nondegenerate semiconductor

Diffusion coefficient VEUE

kT drift
0
典 跟複合
D mzbility
 : drift mobility
e
Diffusion length

L  ( D )1/2  : recombination lifetime

In a long diode (ln >> Lh)

Excess hole concentration pn ( x' )  pn ( x' )  pno
濃度隨距離化
pn ( x' )   pn ( x' )(x' )(1 / Lh ) pn ( x' )   pn (0) exp(  x' / Lh )
(3.5.10)
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子
 lruydirde 擴散範圍
Hole diffusion
current in the n-side 0
θ
擴散載 複合程度

pn ( x' )  pn ( x' )  pno θ

刊始未擴散濃度
dpn ( x ' )  eDh   x' 
~

dpn ( x ' )
J D ,hole  eDh  eDh   pn (0) exp  
dx ' dx '  Lh   Lh 

  eV    ni2    eV  
pn (0)  pn (0)  pno  pno exp   1    exp   1
  k BT    N d    k BT  
√
At x’ = 0 J D ,hole
 eDh ni2    eV  
   exp   1
c =
eq
(3.5.12)
[exp ]
 Lh N d    k BT   √
陜州
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子
儿
 Forward Bias: Diffusion Current (Short Diode)
hor
lay scage

 Injected minority holes in the

n-side quickly diffuse without
recombination with electrons.

 Hole diffusion current remains

constant. That is, the excess
hole concentration decreases
(圖3.18) linearly in the n-side.

 eV 
pno exp   pno
dpn ( x ' ) p (0)  pno  k BT 
J D ,hole  eDh  eDh n  eDh
dx ' ln ln
 eDh ni2    eV  
   exp   1
 ln N d    k B T  
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 Forward Bias: Total Diffusion Current

√
 Shockley
√ long diode equation

 eDh eDe  2   eV  
J    ni exp   1 (3.5.13)
 Lh N d Le N a    k BT  
Jso
 Shockley short diode equation
√
 eDh eD  2   eV  
J   e ni exp
   1 (3.5.14)
l N 
 n d l p N a    k BT  

Jso depends on the doping and materials (e.g. bandgap) and temperature,
and is known as the reverse saturation current density. When a
reverse bias V = -Vr (>> kBT ) is applied, J = -Jso .
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 C. Minority Carrier Charge Stored in Forward Bias

戴 ↓+ 外部电路補

 For long diodes, the minority carrier with a recombination lifetime  is

replenished by external DC current at a rate I = Q/. = h e 
載 不会變合
 For short diodes, the minority carrier diffuse across the neutral region
(width l) in a transit time t = l2/2D. To maintain DC current operation,
I=Q/tt = th te 
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子
子
足
 tmmsit time

averuye time tar CamiertatmveOthrough a

certainnegim
= d

freae f
“
ax
re = =

σ z √ (4)

Dittusirm tausit time

Je = -

ebudpuaxs
ㄍㄨ

Ciet
Je = e e
是 = - enve

veditf _ Det
, =
上
不 定為等速運动
∂
抵 =
皆婆
shazt diode lineur h X -

nu4) =
hl
.
步
≈ 此
政 = 吃
c -涉
ㄨ

= } ih
e
③ L .
…
- tt
↓x
.

上 吃了
=

品 liz芒了 dx
=
Di { Ʃx)u4 -

= () ≥

D
擴散運动若爪涉及複合
也不 定是等速運 D
日
一
。
」。
。
一
一
一
 D. Recombination Current and the Total Current

(圖3.18)

擴久打 打量擴散 1 1 →
洞罩

 eABC eBCD  e 2 W p nM e 2 Wn pM
J recom      
 所合平均時膩
e h  e h (3.5.16)
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里
子
 Forward Bias: Recombination Current in SCL
 e(Vo  V ) 
pM  p po exp  
 2 k BT 
p po  N a
k BT  N a N d 
Vo  ln 2 
e  ni 
Assume Na = Nd

 eV 
pM  ni exp   nM (圖3.18)
 2 k BT 
General form
eni  W p Wn   eV    eV  
J recom     exp  J recom  J ro exp   1
2  e h   2 k BT    2 k BT  
Jro (3.5.17)
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likewise. For information regarding permission(s), write to: Rights and Permissions Department, Pearson Education, Inc., Upper Saddle River, NJ 07458.
Total Current = Diffusion + Recombination Current
 SCL recombination
  eV  
I recom  I ro exp   1
  2 k BT  
 Surface recombination

  eV  
I surf  I sro exp   1 (3.5.18)
  2 k BT  
 General diode equation
  eV  
I  I o exp   1 (3.5.19)
  k BT  
 : diode ideality factor (1 for diffusion-controlled, 2 for recombination-controlled)
S.O. Kasap, Optoelectronics and Photonics: Principles and Practices, Second Edition, © 2013 Pearson Education
© 2013 Pearson Education, Inc., Upper Saddle River, NJ. All rights reserved. This publication is protected by Copyright and w ritten permission should be obtained from the
publisher prior to any prohibited reproduction, storage in a retrieval system, or transmission in any form or by any means, electronic, mechanical, photocopying, recording, or
likewise. For information regarding permission(s), write to: Rights and Permissions Department, Pearson Education, Inc., Upper Saddle River, NJ 07458.
 Typical I-V characteristics of Ge, Si and GaAs
pn junctions

(圖3.20)

2  Eg 
Eg: Ge (0.66 eV), Si (1.12 eV), GaAs (1.42 eV) ni  exp  
 k BT 
S.O. Kasap, Optoelectronics and Photonics: Principles and Practices, Second Edition, © 2013 Pearson Education
© 2013 Pearson Education, Inc., Upper Saddle River, NJ. All rights reserved. This publication is protected by Copyright and w ritten permission should be obtained from the
publisher prior to any prohibited reproduction, storage in a retrieval system, or transmission in any form or by any means, electronic, mechanical, photocopying, recording, or
likewise. For information regarding permission(s), write to: Rights and Permissions Department, Pearson Education, Inc., Upper Saddle River, NJ 07458.