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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.

density of electron and hole:

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

Semiconductor Engineering 53

2.2 Pseudo-Classical Mechanics for Electrons in 1-D Crystals (p.49)

the electron interaction with the periodic potential of the crystal. Therefore,

we can correctly predict the behavior of the electron in the crystal via the

classical equations. For example,

F = m*a (2.1)

h2 K 2

E = Eo + (2.2) : previously

2mo (1.44)

Kinetic Energy

h2 K 2

EK = (2.3)

2mo

Figure 1.13 The E-K diagram for the

free electron.

Semiconductor Engineering 54

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

−1

2 d E

2

mo = h 2 (2.5)

dK

Since the E-K curve is parabolic, d2E/dK2 is a constant and thus mo is

constant in energy.

Semiconductor Engineering 55

The Quasi-Free Electron : potential energy is periodic

your text.

Figure 2.1 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) K=0

an electron in a local

minimum, where it has a

different effective mass,

and (c) an electron near GaAs

the top of the band.

Semiconductor Engineering 56

Expansion of the E-K relation in a power series :

For an electron near the bottom of the band where E=Ec, the expansion at

K=0

0 Neglect these terms

dE 1 d 2E 2

E = EC + K + 2

K + HOTs (2.6)

dK 2 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

Semiconductor Engineering 57

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

Semiconductor Engineering 58

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

d E 2 at this minimum

m =h 2

* 2

dK

K = K1

[2] Near the minimum (E2, K2), the curvature of the E-K curve is negative.

results are valid only in the parabolic regions where m* is constant.”

Semiconductor Engineering 59

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.

Semiconductor Engineering 60

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.

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.

Semiconductor Engineering 61

2.4 Valence Band Structure (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.

the valence band in most

semiconductors, indicating (h)

the heavy hole band, (l) the light

hole band, and (s) the split-off

band.

Semiconductor Engineering 62

2.5 Intrinsic Semiconductor (p.59)

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.

Semiconductor Engineering 63

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

Semiconductor Engineering 64

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

Semiconductor Engineering 65

Basic Ion Implantation Process : Add impurity using

kinetic energy

Figure: Ion

Implanter

(b) Misorientation of the beam direction to all crystal axes. (c) Pre-damage on the crystal

surfaces.

Semiconductor Engineering 66

2.6.1 Donors (p.62)

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.

Semiconductor Engineering 67

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.

Semiconductor Engineering 68

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.

Semiconductor Engineering 69

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

Semiconductor Engineering 70

Therefore, J for the unopposed electrons is

−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)

0

−q −q

J=

volume

[ ]

∑ υi − ∑ υhi = volume

∑ υi +

q

volume

∑ υhi (2.38)

It is reasonable to assign that the current is caused by the holes of charge +q.

Semiconductor Engineering 71

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.

Semiconductor Engineering 72

2.8 Density-of-states Functions for Electrons in Bands (p.71)

to know the distribution of electrons and holes with energy.

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

Semiconductor Engineering 73

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.

Semiconductor Engineering 74

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).

Semiconductor Engineering 75

2.9 Fermi-Dirac Statistics (p.73)

per unit volume can be derived by

no = ∫ S ( E ) f ( E )dE

band

(2.48)

band is given by

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.

Semiconductor Engineering 76

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.

Semiconductor Engineering 77

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.

Semiconductor Engineering 78

2.10 Electron and Hole Distributions with Energy (p.76)

per unit volume can be derived by

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.

Semiconductor Engineering 79

The total number of electrons and holes in the conduction and valence band,

respectively, at equilibrium are

top top top

EC EC EC

(2.55)

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

Semiconductor Engineering 80

Solve the Equations (2.55) and (2.56) :

Assumptions

1. Nondegenerate Semiconductor

2. top → ∞ and bottom → -∞

Ec

3kT

Ef exists here

3kT

Ev

Degenerated !

Semiconductor Engineering 81

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)

Semiconductor Engineering 82

Useful relationship between no and po :

Therefore, Equations (2.59) and (2.60) become

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)

Semiconductor Engineering 83

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.

3/ 2 3/ 2

19 mdse

*

T

N C = 2.54 × 10 (2.63)

mo 300

3/ 2 3/ 2

19 mdsh

*

T

NV = 2.54 × 10 (2.64)

mo 300

At 300 K, Eg = 1.1242 eV and kT = 0.02586 eV.

Semiconductor Engineering 84

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

Semiconductor Engineering 85

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

Semiconductor Engineering 86

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.

NC = 4.4 x 1017 / cm3 and NV = 8.3 x 1018 / cm3

Therefore, from Equation (2.67), ni = 2.2 x 106 / cm3

Ef – EV = 0.17 eV

(2.66)

for the p-type GaAs of Example 2.5.

Semiconductor Engineering 87

Property change due to semiconductor doping :

Semiconductor Engineering 88

Example 2.5 (p.83)

= 4 x 1016 / cm3. Then 1 x 1017 / cm3 donors are doped. Find the room

temperature concentrations of electrons and holes in the original and final

materials.

(sol.) Based on the given problem, we know that the starting material is p-type. In

addition, NA >> ni (1.08 x 1010/cm3).

Ef – EV = 0.17 eV [from Eg. (2.60)]

no = ni2 / po = 2.9 x 103 / cm3

no = ND – NA = 1017 – 4 x 1016 = 6 x 1016 / cm3

EC – Ef = 0.16 eV [from Eg. (2.59)]

po = ni2 / no = 1.9 x 103 / cm3

Semiconductor Engineering 89

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.

Semiconductor Engineering 90

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)

concentration n(Ek) increases, reaches a

maximum, and then decreases

approximately exponentially.”

electrons are existed at very near the 2.5 kT = 0.065 eV

conduction band edge.

function n(E) as a function of energy

(energy on the vertical axis).

Semiconductor Engineering 91

2.11 Temperature Dependence of Carrier Concentrations in

Nondegenerate Semiconductors (p.89)

− E g / 2 kT

ni = N C NV e (2.85)

well).

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

Semiconductor Engineering 92

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

gap dependence of

silicon on temperature.

Semiconductor Engineering 93

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)

ni2

− no + N D − N A = 0 ⇒ no2 − no ( N D − N A ) − ni2 = 0 (2.92)

no

The solution is then

1/ 2

N D − N A N D − N A

2

no = + + n 2

i (2.93)

2 2

Semiconductor Engineering 94

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

Semiconductor Engineering 95

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.

Semiconductor Engineering 96

2.12 Degenerate Semiconductors (p.94)

2.12.1 Impurity-Induced Band-Gap Narrowing

Very remotely spaced ! Form miniband, causing 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.

Semiconductor Engineering 97

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

number of spatially overlapping equi-energy impurity states and also from the

broadening in energy of these impurity bands. At sufficiently high doping level,

even the ground states overlap.”

Semiconductor Engineering 98

∆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

room-temperature band gap

∆Eg as a function of donor

density in phosphorus-doped

silicon.

Semiconductor Engineering 99

We will skip 2.12.2 and 2.12.3.

Review Chap 2. By answering the question 2.16 (Review

Questions)

Homework #2

[2] Problem 2.26

[3] Problem 2.37

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