Physics of Semiconductor

Materials
5. Semiconductors in Equilibrium

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 Topics
 Thermal-equilibrium concentration of electron and holes

 Intrinsic carrier concentration

 Intrinsic Fermi-level position

 Dopant atoms and energy levels

 Extrinsic carrier concentration and temperature dependence

 Ionization energy of dopant atoms in silicon

 Fermi level in extrinsic semiconductor

 Degenerate semiconductors

 Fermi level in two systems in contact with each other and at thermal
equilibrium.
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In this chapter, we will:
 Derive the thermal-equilibrium concentrations of electrons and
holes in a semiconductor as a function of the Fermi energy level.

 Discuss the process by which the properties of a semiconductor

material can be favorably altered by adding specific impurity
atoms to the semiconductor.

 Determine the thermal-equilibrium concentrations of electrons

and holes in a semiconductor as a function of the concentration of
dopant atoms added to the semiconductor.

 Determine the position of the Fermi energy level as a function of

the concentrations of dopant atoms added to the semiconductor.
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• Equilibrium, or thermal equilibrium, implies that
no external forces such as voltages, electrical
fields, magnetic fields, or temperature gradients
are acting on the semiconductor

• All properties of the semiconductor will be

independent of time in this case.

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 MODELING AND SIMULATION OF MICROELECTRONIC DEVICES
 Current is the rate at which charge flows.
 Current is determined by flow rate and density of charge carriers.
 The density of electron and holes is related to the density of states function and
the Fermi distribution (or probability) function.

Particles that can freely move and contribute to the current flow (conduction)
 In a semiconductor, two types of charge carrier
1. Electron in conduction band
2. Hole in valence band 5
How to count number of carriers, n?

Assumption; Pauli exclusion principle

If we know
1. No. of energy states Density of states (DOS)

The probability that energy states is

2. Occupied energy states occupied
“Fermi-Dirac distribution function”

n = DOS x “Fermi-Dirac distribution function”

No. of e- at E (in CB) n(E) = gc(E)fF (E)

DOS at E Fermi-Dirac
probability function

No. of holes at E (in VB) p(E) = gv(E)[1-fF (E)]

 No of states (seats) above EC for electron

No of states (seats) below Ev for hole

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 Fermi-Dirac distribution (or probability) function

• The probability that a quantum state at an energy E will be occupied by

an electron
• The ratio between filled and total quantum states at any energy E

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 conduction band

valence band

EF; the energy below which all states are filled with electron and above which all states are
empty at 0 K
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MODELING AND SIMULATION OF MICROELECTRONIC DEVICES

No of carrier
E

free electron
e e
No of free electron Ec
Ec

Ev Ev free hole
No of free hole e
e

1
g(E) x f (E)
Thermal equilibrium concentration of electrons, no

∞
This equation is valid for
both intrinsic and extrinsic
EC
semiconductors

Condition:
E - EF >> kT

Boltzman approximation
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Comparison of Fermi-Dirac probability function and
Maxwell-Boltzmann approximation

3KT

Maxwell-Boltzmann approximation and Fermi-Dirac function

are within 5% of each other when E-EF ≥3KT
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Gamma function: 1
𝜋
2

Nc= effective density of states function in the CB

This equation is valid for both intrinsic and

extrinsic semiconductors
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Problem 1:
Calculate the thermal equilibrium electron concentration in Si at T= 300 K.
Assume that Fermi energy is 0.25 eV below the conduction band. The value of Nc for Si
at T=300 K is 2.8 x 1019 cm-3. Boltzmann’s constant ( k) = 8.62 10-5ּ eV/K= 1.38 10-23 J/K.

Ec
0.25 eV
EF

Ev
Thermal equilibrium concentration of hole, po

Nv= effective density of states

function in the VB

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MODELING AND SIULATION OF MICROELECTRONIC DEVICES
Problem 2:

Calculate the thermal equilibrium hole concentration in Si at T= 300 K.

Assume that Fermi energy is 0.27 eV above the valence band. The value of Nv for Si at
T=300 K is 1.04 x 1019 cm-3.

Ec

EF
0.27 eV
Ev

 NC and Nv are constant for a given material (effective mass) and temperature
 Position of Fermi energy is important

 If EF is closer to EC than to Ev, n>p

 If EF is closer to Ev than to EC, n<p
 The Intrinsic Carrier Concentration
Effective density of states function and effective mass values

For an intrinsic semiconductor

Intrinsic electron concentration = Intrinsic hole concentration
ni = pi
Intrinsic carrier concentration

Why?

 charge carriers due to thermal excitation

 thermally generated electrons and holes always created in pairs.
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 Intrinsic Semiconductor
Intrinsic Fermi level

Intrinsic carrier concentration

Commonly accepted values of ni at T=300 K

Semiconductor Ni The intrinsic carrier
Si 1.5 x 1010 cm-3 concentration is a very
GaAs 1.8 x 106 cm-3 strong function of T.
Ge 2.4 x 1013 cm-3
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Problem 3:
• Calculate the intrinsic carrier concentration in silicon at T = 300 K. The
values of Nc and Nv for silicon at T= 300 K are 2.8 x 1019 cm-3 and 1.04 x
1019 cm-3, respectively. Assume the bandgap energy of silicon is 1.12 eV
and does not vary over this temperature range.

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 Application of the intrinsic semiconductors

 High Electron Mobility

Transistor
 High resistivity substrate for RF
circuits
 amorphous-Si Solar Cells

Where is the intrinsic Fermi level?

Structure of solar cell

EFi (Intrinsic Fermi level): EF at which electron and hole

concentration becomes equal

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Electron concentration Hole concentration

Even in intrinsic semiconductor, Fermi level is not exactly at

centre between conduction and valence bands.
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Problem 4:
Calculate the position of the intrinsic Fermi level with respect
to the center of the bandgap in silicon at T=300 K. The density
of states effective carrier masses in silicon are m*n= 1.08m0
and m*p = 0.56m0.

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 The extrinsic Semiconductor
Acceptor and Donor Impurities:
In Si four e-s in the valence shell participate in bonding.
• atom with more than 4 valence electrons (donor impurity)
• less than 4 (acceptor impurity).

Intrinsic Si lattice

Si lattice doped with donor impurity

 At very low temperature, the donor (excess) electron is still

bound to the impurity atom.
 However, the donor electron is loosely bound to the impurity
atom and can become free with small amount of thermal energy.
Impurity atom is then ionized and positively charged.
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Donor electron energy level:

The energy level, Ed, is the energy state of the donor e-.

 little energy required to move donor electrons from donor states to CB

 positively charged donor ions (P+) are fixed but donor e-s in the CB can move
through the crystal generating a current.

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Acceptor Impurity:

 One covalent bond is incomplete for Si.

 With little thermal energy, a valence e- can break from another covalent bond and
can occupy this position, thus creating a hole at the location of the broken covalent
bond.
 The acceptor impurity is then ionized and negatively charged.

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Acceptor Energy Level:

 little energy required to move valence e-s to acceptor levels.

 negatively charged acceptor ions(B-) are fixed but holes in the VB can move through the
crystal generating a current.
 The group III atom accepts an e- from the VB and so is referred to as an acceptor
impurity atom.
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Electron concentration vs. temperature in n-type semiconductor

e- concentration vs. T showing partial

ionization, extrinsic and intrinsic regions.

e- concentration vs. T in extrinsic semiconductor

 At low T, donor impurities are partially ionized. As T increases the % of ionized donor
impurities also increases
 Once all donor impurities are ionized, there is no increase in carrier concentration.
Even though intrinsic carrier concentration continues to increase, it is still small
compared to extrinsic concentration.
 At high T, intrinsic carrier concentration dominates and electron concentration
continues to increase again. 29
 Ionization energy (IE)

The IE is the energy necessary to

remove an e- from the neutral atom.

In case of donor atoms, the IE is defined as

the energy required to elevate an e- from the
donor level to CB.

 In the next few pages, we will calculate the approximate IE for donor atoms.
 We use Bohr atomic model for these calculations. For H atom, Bohr model and quantum
mechanics give similar results.
 Donor impurity atom can be visualized as one donor e- orbiting the positively charged
donor ion. This condition is similar to that in a H atom.
 However we have to consider permittivity of Si instead of permittivity of free space.
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 Angular Momentum Quantization
• Bohr proposed that circumference of e- orbit = integer number of λ
𝟐𝝅𝒓 = 𝒏𝝀n
P = mv and 𝝀= h/p
𝒉𝒓 𝒉𝒓 𝒏𝒉
𝐿 = 𝑚𝑣𝑟 = = =
𝝀 𝟐𝝅𝒓/𝒏 𝟐𝝅

angular momentum of e- is quantized.

Ionization energy calculation

Coulomb attraction force= Centripetal force

Angular momentum quantization

rn is the radius of the orbit

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 Bohr radius =

 r1/a0=45 or r1=23.9 Å
 This radius ~ 4 lattice constants of Si.
 Each unit cell contains 8 Si atoms.
 Donor e- thus loosely bound to the donor atom.
 We will next find the approximate IE.
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Another form (relation between EF and EFi)-If we add and subtract an intrinsic Fermi
energy in the exponent of previous Equation
Intrinsic carrier concentration

n0p0=ni2
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Problem 5:
Calculate the thermal equilibrium concentrations of
electrons and holes for a given Fermi energy. Consider
silicon at T = 300 K so that Nc = 2.8 x 1019 cm-3 and Nv =
1.04 x 1019 cm-3. Assume that the Fermi energy is 0.25
eV below the conduction band. If we assume that the
bandgap energy of silicon is 1.12 eV, then the Fermi
energy will be 0.87 eV above the valence band.

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Condition for the
Boltzmann approximation

EC-EF > 3KT

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 The Fermi–Dirac Integral
If the impurity concentration is very high, Fermi level will be very close to CB
or VB.
No Boltzmann approximation Use The Fermi-Dirac Integral

Boltzman approximation

Only if EC-EF > 3KT

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 thus, the Fermi energy is actually in the CB.
This function, called the Fermi–Dirac integral
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 Degenerate Semiconductors
If the impurity atoms are very close each other...

 Donor electrons interact with each other

 The single discrete donor energy will split into a band

 The band may overlap the CB

 If the concentration exceed Nc , EF lies within the CB

Degenerated Semiconductor

Nd > Nc (n-type) Na > Nv (p-type)

Fermi level in the CB: Metallic conduction 41

 Statistics of donors and acceptors

How many electrons still in the donor levels compared to the

total number of electrons?

 depends on the T and the Fermi level....

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 Probability function for donor & acceptor levels

similar for holes:

g=degeneracy factor; 4 for GaAs and Si acceptor levels

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Moderate temperature
Ed-EF>>kT

If Ed-EF >> kT, then even Ec-EF >> KT

Then,

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Fraction of electrons still in the donor states

With P doping of Nd=1016 cm-3, at T=300 K, nd/(nd+n0)= 0.41%

Almost complete ionization of the donor states at Room T.

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Problem 6:

Determine the fraction of total electrons still in the donor states at T = 300
K. Consider phosphorus doping in silicon, for T = 300 K, at a concentration of
Nd=1016 cm-3, Nc = 2.8 x 1019 cm-3 , and EC-Ed = 0.045 eV.

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Extremely low temperature (T= 0 K)
No electrons from the donor state are thermally elevated into the CB or
nd = N d when no electrons from the VB are elevated into the
acceptor states; this effect is called Freeze-out.

EF > Ed

Energy-band diagram at T = 0 K for n-type

 The opposite of complete ionization occurs at T= 0 K. At absolute zero degrees, all

e-s are in their lowest possible energy state; that is, for an n-type semiconductor,
each donor state must contain an e-, therefore nd =Nd or Nd+ = 0. We must have,
exp[(Ed- EF)/kT] = 0. Since T = 0 K, this will occur for exp (-∞) = 0, which means that EF > Ed.
 The Fermi energy level must be above the donor energy level at absolute zero.
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High temperature

(because of thermally generated electrons)

(because of thermally generated holes)

At very high T behavior is just like the intrinsic semiconductor

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Between T = 0 K, freeze-out, and T = 300 K, complete ionization, we have
partial ionization of donor or acceptor atoms.
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 Compensated semiconductor

 Both donor and acceptor impurities in the same region

 If Nd > Na n-type compensated semiconductor
 If Nd < Na p-type compensated semiconductor
 If Nd = Na completely compensated (will behave like
intrinsic material)
 Practical semiconductor is always compensated
semiconductor. Eg. Substrate is predoped usually p-type.
All other dopings are done on top of this.

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 Charge neutrality

Ionized acceptors

Ionized donors

The energy-band diagram of a compensated semiconductor

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Using the relation n0p0=ni2

n0 is not simply Nd

Similarly in p-type semiconductor,

Minority carrier concentration

p0=ni2/n0 (n-type material)
n0= ni2/p0 (p-type material)
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 Position of Fermi Energy Level
Where is the Fermi level of a n-type extrinsic semiconductor?

Position of Fermi level for n-

N-type: Nd>>ni then n0≈Nd type semiconductor.

Another expression for the n-type

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Where is the Fermi level of a p-type extrinsic semiconductor?

P-type: Na>>ni then p0≈Na Position of Fermi level for

p-type semiconductor.

Another expression for the p-type

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Variation of EF with doping concentration

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 Variation of EF with T

 At higher temperatures, the semiconductor

becomes more intrinsic. ni increases and Variation of EF with T for d/t
Fermi level moves towards mid-gap doping concentrations

 At T=0, Fermi level is above Ed in n type and

below Ea in p-type semiconductor 56
EF must be equal when different systems are in contact and in thermodynamic
equilibrium

Consider a material A, with Fermi level EFA. material B with Fermi level EFB.
Bands below EFA are full and above are empty.

When A and B are brought in contact, electrons will flow from A into lower energy states of B, until thermal
equilibrium is reached.
Thermal equilibrium EF same in A & B

The Fermi energy of (a) material A in thermal equilibrium, (b) material B in thermal equilibrium, (c) materials A
and B at the instant they are placed in contact, and (d) materials A and B in contact at thermal equilibrium.
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Summary

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