Chapter 2. Homogeneous Semiconductors
Chapter 2. Homogeneous Semiconductors
Homogeneous Semiconductors
Homogeneous semiconductor : Semiconductor materials that consist of
one uniform material. For example, pure (intrinsic) Si or Si with impurities
uniformly distributed. We will discuss the concepts of “extrinsic” and
“nonuniformly doped semiconductors”.
The point of this chapter is to derive the electron and hole density near
the bottom of the conduction band and near the top of the valence band,
respectively.
top top
no = ∫ S ( E ) f ( E )dE = ∫ n( E )dE
EC EC
EV EV EV
po = ∫
bottom
S ( E )[1 − f ( E )]dE = ∫ S(E ) f
bottom
p ( E )dE = ∫ p( E )dE
bottom
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2.2 Pseudo-Classical Mechanics for Electrons in 1-D Crystals (p.49)
F = m*a (2.1)
h2 K 2
EK = (2.3)
2mo
Figure 1.13 The E-K diagram for the
free electron.
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h
For the free-electron case, de Broglie’s relation is valid : moν = P =
λ
Therefore, moν 2 P2
EK = =
2 2mo
dν
F = mo
dt
In addition, the velocity of the electron in the crystal is given by the group
velocity :
1 dE
v = νg = (2.4)
h dK
This is the expression for a parabola shown as broken line in Fig. 2.1(a).
The group velocity is given as [We already discussed this. See p.39 of
your handout]
dx 1 dE
νg = = (2.8) same as (1.43)
dt h dK
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Free Electron vs. Quasi-free Electron
h2 K 2
E = Eo + (2.2) : free electron
2mo
1 d 2E 2
E = EC + 2
K (2.7) : quasi-free electron
2 dK
Potential Kinetic
Energy Energy
1 d2E 2 h2 2
Since 2
K ⇔ K
2 dK 2mo
−1
d E
2
m* = h 2 2 (2.11)
dK
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Consider the cases shown in Fig. 2.1(b) and (c) : also parabola
[1] Near the minimum (E1, K1), we can expand the energy about K=K1.
1 d2E h 2 ( K − K1 ) 2
EK =
2 dK 2
( K − K1 ) 2
⇒ EK =
2m*
(2.13)
K = K1
[2] Near the minimum (E2, K2), the curvature of the E-K curve is negative.
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The force on an electron :
dE P dEC
F=− ⇔F=− (2.15)
dx dx
Electrons will collide with atoms, defects, or impurities (we call this phenomenon as
“scattering”, and we will discuss this later).
Figure 2.2 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.
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2.3 Conduction Band Structure (p.56)
For a semiconductor having a cubic unit cell structure and having an extremum at
K=0 (e.g., GaAs), the curvature is direction independent and
m* = mx* = my* = mz* (2.20)
or the effective mass is a scalar.
For Si and Ge, conduction band minima are not at K=0 (i.e., not a scalar).
Therefore, the effective mass depends on the direction in which the electron is
traveling. See Table 2.1 in p. 58.
The valence bands are qualitatively similar for most semiconductors: See Fig. 2.4.
If we consider the empty states to be the holes, then we can consider the holes to
have a positive charge along with a positive effective mass.
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2.5 Intrinsic Semiconductor (p.59)
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2.6 Extrinsic Semiconductor (p.62)
By adding dopant atoms (i.e., donors or acceptors), the number of electrons and
holes in the conduction and valence band, respectively, can be controlled: n ≠ p
In this case, we call the semiconductor as extrinsic semiconductor.
n-type : no > po p-type : no < po
3 valence electrons
5 valence
electrons
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Basic Diffusion Process : Add impurity using thermal
energy
Furnace
Carefully controlled quartz tube
Processing Temperature
800 – 1200oC for Si
Source 600 – 1000oC for GaAs
Gas : B2H6, AsH3, PH3
Liquid : BBr3, AsCl3, POCl3 Example
Solid : BN, As2O3, P2O5
4POCl3 + 3O2 → 2P2O5 + 6Cl2↑
2P2O5 +5Si → 4P + 5SiO2
Figure: Ion
Implanter
The 5th valence electron which did not participated in the covalent bonding is
loosely bounded, and can be easily separated and becomes the free electron.
Binding energy
Figure 2.6 Donors in a silicon crystal: (a) bond diagram of the crystal; (b) energy band
diagram of silicon doped with one phosphorus (donor) atom.
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2.6.2 Acceptors (p.66)
An empty state will be introduced if B is forced to make covalent bond with Si, so
that nearby electron can be easily jump into the empty state, causing a hole in the
valence band.
Figure 2.8 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.
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2.7 The Concept of Holes (p.67)
Hole has to be treated as a particle (like an electron) that carry current with a
positive charge.
Consider an n-type semiconductor with an electric field applied : the charge density
in the conduction band is –qn. Therefore, the electron current density
(amperes/unit area) J is
J = − qn υ (2.32)
where <υ> is the average velocity of the electrons. Equation (2.32) can be also
written as
q
J=− ∑
volume i
υi (2.32)
where the volume is the volume of the crystal and the summation is taken over the
velocities of the individual electrons.
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Does the Eq. (2.33) valid for electrons in the valence band? The answer is yes.
But…
Figure 2.9 States in the
valence band on the E-K
diagram. (a) All states are
full; (b) one state is empty
(hole), meaning there is an
electron with no opposing
electron at the same
energy but opposite K
vector and opposite
velocity.
1 dE
The velocity of an electron: υ = (2.34)
h dK
The velocity of an electron is proportional to the
curvature of the E-K diagram !
In Fig. 2.9(a), the E-K diagram is symmetrical (therefore, for each electron with
velocity υi there is an opposing electron with velocity - υi), and there is no empty
state. ⇒ J = 0
−q
J= ∑
volume i
υui (2.35) : The subscript u refers to the
unopposed electrons.
Equation (2.35) can be rewritten as
−q −q
J=
volume
∑ [ i hi ] volume
υ − υ = [∑ υ − ∑ υ ]
i hi (2.36)
It is reasonable to assign that the current is caused by the holes of charge +q.
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2.7.2 Effective Mass of Holes (p.69)
Previously we showed that when an electron is near the top of the valence band,
its effective mass is negative, since the curvature of the band is negative in that
region.
Now, if we consider the vacant states to be holes with positive charge, they must
also be considered to have a positive effective mass, equal in magnitude to the
(negative) effective mass of the unopposed electron.
Figure 2.10 Lorentz force on an electron in a p-type sample. (a) The unopposed
electrons (negative charge, negative effective mass) are accelerated downward; (b)
holes, which have positive charge and positive effective mass, are accelerated upward.
In either case the net result is the same: the sample becomes more negatively charged
at the bottom with respect to the top.
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2.8 Density-of-states Functions for Electrons in Bands (p.71)
Game Plan:
(1) Obtain the available energy states in the corresponding bands → S(E)
(2) Obtain the probability that a state at a given energy is occupied → f(E)
The density-of-state function S(E) is the number of states per unit volume per unit
energy, # of available states/cm3-eV
3/ 2
1 2mo
S(E) = 2 2
E − Eo (2.42) Refer to Appendix D
2π h
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For the density-of-state function S(E) in semiconductor, derive the equation for the
electron near the bottom of the conduction band, where the effective mass is
constant.
3/ 2 3/ 2
1 2mdse
*
1 2mdse
*
S(E) = E − EC = EK (2.43)
2π 2 h 2 2π 2 h 2
where m*dse is referred to as the density-of-states effective mass for electrons. For
the description of m*dse, see p. 57. m*dse is the weighted average of mII and m⊥).
Similarly, in the parabolic region near the top of the valence band,
3/ 2
1 2mdsh
*
S(E) = EV − E (2.44)
2π 2 h 2
where m*dsh is some combination of the light hole and heavy hole effective masses.
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Figure 2.11 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).
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2.9 Fermi-Dirac Statistics (p.73)
no = ∫ S ( E ) f ( E )dE
band
(2.48)
1
f (E ) = ( E − E f ) / kT (2.49)
1+ e
Where the energy Ef is a reference energy called the Fermi energy or Fermi level.
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1
f (E ) = ( E − E f ) / kT
1+ e
Ef
Figure 2.12 The Fermi-Dirac distribution function gives the probability of occupancy of
an energy state E if the state exists.
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The probability of a state being occupied by a hole is
1
f P (E ) = 1 − ( E − E f ) / kT
1+ e
or
1
f P (E ) = ( E f − E ) / kT
1+ e
Example 2.2 (p.76)
Estimate the probability of occupancy of a state at the bottom of the conduction
band in intrinsic Si at room temperature.
(sol.) From given information, we get E = Ec, @ room temperature, and EC-Ef ≈
Eg/2 = 0.56 eV. Now we have Eq. 2.49
1 1 1
f (E) = ( E − E f ) / kT
= ( E C − E f ) / kT
= = 4.4 × 10−19
1+ e 1+ e 1+ e ( 0.56 eV ) / ( 0.026 eV )
Therefore, under this condition, about one state in two billion available states is
occupied.
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2.10 Electron and Hole Distributions with Energy (p.76)
Figure 2.13 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.
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The total number of electrons and holes in the conduction and valence band,
respectively, at equilibrium are
top top top
EV EV EV
po = ∫ S(E) f
bottom
p ( E ) dE = ∫ p( E )dE = ∫ S ( E )[1 − f ( E )]dE
bottom bottom
(2.56)
Recall that most of the carriers are concentrated near the extrema of their
respective bands where effective mass is constant. Therefore, we use the Eqs.
(2.43) and (2.44) for calculating no and po.
3/ 2 3/ 2
1 2mdse
*
1 2mdse
*
S(E) = E − EC = EK (2.43)
2π 2 h 2 2π 2 h 2
3/ 2
1 2m *
S(E ) = dsh
EV − E (2.44)
2π 2 h 2
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Solve the Equations (2.55) and (2.56) :
Assumptions
1. Nondegenerate Semiconductor
2. top → ∞ and bottom → -∞
Ec
3kT
Ef exists here
3kT
Ev
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Equations (2.55) and (2.56) become
3/ 2 ∞
1 2mdse
*
E − EC e [
− ( E − E f ) / kT ]
no = 2 2
2π h ∫
EC
dE (2.57)
3 / 2 EV
1 2m *
EV − E e [ f
− ( E − E ) / kT ]
po =
2π 2 h
dsh
2 ∫
−∞
dE (2.58)
3/ 2
m kT
*
Let N C = 2 dse
(2.61) : Effective density of states in the
2πh 2 conduction band
3/ 2
mdsh
*
kT
NV = 2 2
(2.62) : Effective density of states in the
2πh valence band
no = N C e [ C f ]
− ( E − E ) / kT
Then (2.59)
po = NV e [ f V ]
− ( E − E ) / kT
(2.60)
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Useful relationship between no and po :
ni = N C e −[ ( E C − Ei ) / kT ] N C = ni e ( E C − E i ) / kT
−[ ( E i − EV ) / kT ]
⇒
ni = NV e NV = ni e ( Ei − EV ) / kT
Substitute into Equations (2.59) and (2.60), then:
( E f − E i ) / kT
no = ni e
(2.75)
( E i − E f ) / kT
po = ni e
Therefore
no po = N C NV e [ C f ]e [ f V ] = N C NV e −[ ( E C − EV ) / kT ] = N C NV e [ g ] = ni2
− ( E − E ) / kT − ( E − E ) / kT − E / kT
(2.65)
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Example 2.3 (p.80)
Find the intrinsic concentration ni for the case of Si at 300 K. The effective
masses are m*dse =1.09mo and m*dsh = 1.15mo.
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The Fermi energy level for an intrinsic semiconductor (see pp. 80-81), Ei :
EC + EV 3 mdsh
*
Ei = + kT ln * (2.72)
2 4 mdse
Find the energy by which Ei is offset from the midgap for Si at room temperature.
EC + EV 3 mdsh
*
Ei = + kT ln * EC
2 4 mdse
3 mdsh
*
Ei
⇔ Ei − Emidgap = kT ln * = 105
. meV
4 dse
m Emidgap
EV
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Fermi energy level as a function of the doping density : Using Equation (2.75)
n
E f − Ei = kT ln o (2.76)
ni
no ≈ N D + ni
po < ni
Figure 2.14 Electrons and holes in intrinsic and doped n-type material. In the doped case,
some of the electrons from the donors recombine with holes.
Typically,
no ≈ ND when ND >> ni
po ≈ NA when NA >> ni
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Example 2.5 (p.83)
Find the electron and hole concentration in GaAs doped with NA = 1016 cm-3, and
locate the Fermi level. The band gap of GaAs is 1.43 eV.
Ef – EV = 0.17 eV
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Property change due to semiconductor doping :
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Example 2.5 (p.83)
(sol.) Based on the given problem, we know that the starting material is p-type. In
addition, NA >> ni (1.08 x 1010/cm3).
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Figure 2.16 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.
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Electron concentration as a function of energy :
If we let Ek = E - Ec, then (refer to the derivation process shown in pp. 86-87)
n( E K ) = C E K e − E K / kT (2.84)
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2.11 Temperature Dependence of Carrier Concentrations in
Nondegenerate Semiconductors (p.89)
We already discussed
3/ 2 3/ 2
19 mdse
*
T
N C = 2.54 × 10 (2.63)
o
m 300
3/ 2 3/ 2
19 mdsh
*
T
NV = 2.54 × 10 (2.64)
mo 300
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In addition, the temperature dependence of Eg for Si is
4.73 × 10−4 T 2
E g ( T ) = 117
. − eV (2.86)
T + 636
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Now let us look at what happens in no in the conduction band at high temperature.
Assumptions :
(1) Uniformly doped and nondegenerated semiconductor
(2) Equilibrium
(3) 100% ionization
(4) Space charge neutrality is satisfied
Then po − no + N D+ − N A− = 0 ⇒ po − no + N D − N A = 0 (2.90)
no po = ni2 (2.66)
no = + + n 2
i (2.93)
2 2
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Figure 2.19 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.
At high temperature,
Si becomes intrinsic !
Similarly,
1/ 2
N A − N D N A − N D
2
ni2
po = + + ni
2
(2.95) no =
2 2 po
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Intrinsic T-region
Extrinsic T-region
Figure 2.20
Normalized plot
of n0/ND as a
function of
temperature.
This plot is for
ND = 1016 cm-3.
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2.12 Degenerate Semiconductors (p.94)
2.12.1 Impurity-Induced Band-Gap Narrowing
Figure 2.21 Under high doping concentrations, the formerly discrete donor levels
smear into a band, effectively narrowing the band gap by an amount ∆Eg.
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Figure 2.22 The states for the
higher donor levels can overlap if
the doping concentration is high
enough (dopant atoms close
enough together).
As the donor concentration increases, the shift in the conduction band also
increases : ∆EC = ECo – EC
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∆E g = E go − E g ( N D ) : impurity-induced band-gap reduction
[( ]
−1 / 4
∆E g = 4.372 × 10 − 11
N D )
0.5 − 4
(
+ 1272
. −6
× 10 N D )
0.25 − 4
... eV
Negligible
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We will skip 2.12.2 and 2.12.3.
Homework #2