ELL211: Physical Electronics

Madhusudan Singh

IIT Delhi

Winter 2022

ELL211 Instructors (IIT Delhi) ELL211 Winter 2022 1 / 12

 Lecture 6: Silicon crystal growth, doping methods

ELL211 Instructors (IIT Delhi) ELL211 Winter 2022 1 / 12

Recap
Class problem with solved example.
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Nature of band filling in metals, semiconductors and insulators, and e↵ect on
conductivity.
Temperature dependence of bandgaps. Situations in which bandgap temperature
dependences should be accounted for.
Why chemical modification of semiconductors is necessary: current levels.
Example: a commercial device. Types of chemical modifications.
Generation and recombination in intrinsic semiconductors. Temperature
dependence of rates.
Point defects in crystals. Intrinsic and extrinsic point defects. Interstitial and
substitutional point defects. Strain in lattice. n- and p-type dopants in Si.
Di↵ering contribution to carrier scattering, and to carrier population, from
interstitial and substitutional defects. Need of dopant activation anneals.
Ease of ionization, screening and the e↵ect of the dielectric constant. Ionization
energies in Si. Location of defect energy levels corresponding to doping.
Temperature dependence of ionization of donors and acceptors. Charge balance
and law of mass action. Estimating carrier concentrations from material and
temperature data.
Temperature dependence of net carrier population: definition of extrinsic
semiconductors. Three temperature-dependent regimes. Impact on material choice
and
ELL211 device(IIT
Instructors design.
Delhi) ELL211 Winter 2022 2 / 12
Class problem
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Question: Calculate the number of holes (at 300K) in Si doped with 1 ⇥ 1016 cm 3 P atoms

and subsequently annealed.

The temperature at which the sample is held is 300K. So, each carrier has around
⇠ kB T ⇡ 25.9 meV of energy.
Since the material is doped with P atoms, the donor defect level is about 44 meV
below the conduction band. Hence, we can estimate the fraction of ionized donors:
0 44 meV 1
z }| {
ND+ B EC E D C
= exp B
@
C ⇡ 18.29%
ND kB T A
|{z}
25.9 meV

Strictly speaking, the equation defined last time (and used above) is not valid (CB is
less than 3kB T away from the donor level). Hence, this 18.29% estimate is incorrect.
In practice, this turns out to be an underestimate, and we usually assume full
ionization at 300K.
Hence, the number of electrons can be calculated as:
⇣ ⌘ ⇣ ⌘2 1.45 ⇥ 1010
2

1.45 ⇥ 1010 + 1 ⇥ 1016 · p = 1.45 ⇥ 1010 ) p ⇡ = 22 500 cm 3

1 ⇥ 1016

ELL211 Instructors (IIT Delhi) ELL211 Winter 2022 3 / 12

Bonus problem
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Question: In the previous problem, for Si doped with 1 ⇥ 1016 cm 3 P atoms, at what
temperature does the equation used become valid, and what is the value of the ionized fraction
in that case?
The energy that 3kB T needs to be compared against is EC ED . We need to find T
such that, EC ED 3kB T .
44 meV⇥1.602⇥10 19 J eV 1
This will happen at T  3⇥1.38⇥10 23 J K 1
= 170.26 K = 102.89 C.
3
At this temperature, the value of the ionized fraction would be e ⇡ 5%.

ELL211 Instructors (IIT Delhi) ELL211 Winter 2022 4 / 12

Czochralski growth
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Modern method: Jan Czochralski during WW1.
Major improvements: Henry Walther (Bell Labs) for
growth of NaCl. Gordon Teal and John Little (Bell
Labs) (1948): CZ-Ge crystals.
First application to semiconductor-grade Si:
Pietenpol and Ohl (Bell Labs) (1949). Followed up
by Gordon Teal.
TMelting (Si) = 1415 C. Starter material: 9 9 pure
(99.999999999%) quartzite (SiO2 ) ore. Not pure
enough.
Process:
Melt. Introduce seed crystal.
Pull. Rate set by freezing and diameter. Lifting
speed ⇠ 0.02 mm min 1 to 200 mm min 1 . Source: Uni. Kiel
Rotation rate ⇠ 35 min 1 .
Segregation of impurities: a) Macro (length), b)
Micro (dopant striations), c) Precipitates.

ELL211 Instructors (IIT Delhi) ELL211 Winter 2022 5 / 12

Czochralski growth
Materials used here are bound by Fair Use for educational purpose.
Modern method: Jan Czochralski during WW1.
Major improvements: Henry Walther (Bell Labs) for
growth of NaCl. Gordon Teal and John Little (Bell
Labs) (1948): CZ-Ge crystals.
First application to semiconductor-grade Si:
Pietenpol and Ohl (Bell Labs) (1949). Followed up
by Gordon Teal.
TMelting (Si) = 1415 C. Starter material: 9 9 pure
(99.999999999%) quartzite (SiO2 ) ore. Not pure
enough.
Process:
Melt. Introduce seed crystal.
Pull. Rate set by freezing and diameter. Lifting
speed ⇠ 0.02 mm min 1 to 200 mm min 1 .
Rotation rate ⇠ 35 min 1 .
Segregation of impurities: a) Macro (length), b)
Source: Wikipedia
Micro (dopant striations), c) Precipitates.
Finished boule can be quite heavy.

ELL211 Instructors (IIT Delhi) ELL211 Winter 2022 5 / 12

Czochralski growth
Materials used here are bound by Fair Use for educational purpose.
Modern method: Jan Czochralski during WW1.
Major improvements: Henry Walther (Bell Labs) for
growth of NaCl. Gordon Teal and John Little (Bell
Labs) (1948): CZ-Ge crystals.
First application to semiconductor-grade Si:
Pietenpol and Ohl (Bell Labs) (1949). Followed up
by Gordon Teal.
TMelting (Si) = 1415 C. Starter material: 9 9 pure
(99.999999999%) quartzite (SiO2 ) ore. Not pure
enough.
Process:
Melt. Introduce seed crystal.
Pull. Rate set by freezing and diameter. Lifting
speed ⇠ 0.02 mm min 1 to 200 mm min 1 .
Rotation rate ⇠ 35 min 1 .
Segregation of impurities: a) Macro (length), b)
Micro (dopant striations), c) Precipitates.
Finished boule can be quite heavy. Source: PVA TePla

Logistical issues.
ELL211 Instructors (IIT Delhi) ELL211 Winter 2022 5 / 12
Phase Diagrams
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What happens when we

introduce dopants?
Ge-Si

Source: PhaseDiagram-Web

ELL211 Instructors (IIT Delhi) ELL211 Winter 2022 6 / 12

Phase Diagrams
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What happens when we

introduce dopants?

Si-B

Source: PhaseDiagram-Web

ELL211 Instructors (IIT Delhi) ELL211 Winter 2022 6 / 12

Phase Diagrams
Materials used here are bound by Fair Use for educational purpose.

What happens when we

introduce dopants?

Si-As

Source: PhaseDiagram-Web

ELL211 Instructors (IIT Delhi) ELL211 Winter 2022 6 / 12

Phase Diagrams
Materials used here are bound by Fair Use for educational purpose.

What happens when we

introduce dopants?

Can we predict how much

doping we can do? Solid
solubilities.

Source: F. A. Trumbore

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Solid solubilities in Si
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ELL211 Instructors (IIT Delhi) Source: ELL211

F. A. Trumbore Winter 2022 7 / 12
Identifying Si wafer crystal directions
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Source: cnx.org
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Purer than CZ-Si
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Intrinsic Si resistivity ⇠ 230 k⌦ cm.

CZ-Si: 20 ⌦ cm. Quite impure.

Source: Altermatt, et al.

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Purer than CZ-Si
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Intrinsic Si resistivity ⇠ 230 k⌦ cm.

CZ-Si: 20 ⌦ cm. Quite impure.
Source of impurities: crucible. Get rid
of it? Float zone process.

ELL211 Instructors (IIT Delhi) ELL211 Winter 2022 9 / 12

Purer than CZ-Si
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Intrinsic Si resistivity ⇠ 230 k⌦ cm.

CZ-Si: 20 ⌦ cm. Quite impure.
Source of impurities: crucible. Get rid
of it? Float zone process.
Local melting of the rod. Diameters
limited to below 6 inch.

Source: Stefano Meroli

ELL211 Instructors (IIT Delhi) ELL211 Winter 2022 9 / 12

MOSFETs
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Di↵usion
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For doping, we need to introduce
P/As or B. Two mechanisms for
substitutional doping:
Direct exchange; and
Vacancy exchange. 6 bonds broken

Impurities tend to be:

Interstitial (P, B, As, Al, Ga, Sb,
Ge), or;
Substitutional (O, Au, Fe, Cu, Ni,
3 bonds broken
Zn, Mg)
Analysis of di↵usion: Fick’s law. Two
kinds of di↵usion limits: @C @2C
=D 2
Predeposition. Constant source at @t @z
the surface: dose control.
Complementary error function.
Drive-in. Fixed initial impurity dose
at the surface: profile control.
Gaussian.

ELL211 Instructors (IIT Delhi) ELL211 Source: Prof. N. Cheung.

Winter 2022 11 / 12
Di↵usion
Materials used here are bound by Fair Use for educational purpose.
For doping, we need to introduce
P/As or B. Two mechanisms for
substitutional doping:
Direct exchange; and
Vacancy exchange.
Impurities tend to be:
Interstitial (P, B, As, Al, Ga, Sb,
Ge), or;
Substitutional (O, Au, Fe, Cu, Ni,
Zn, Mg)
Analysis of di↵usion: Fick’s law. Two
kinds of di↵usion limits:
Predeposition. Constant source at
the surface: dose control.
Complementary error function.
Drive-in. Fixed initial impurity dose
at the surface: profile control.
Gaussian.
Di↵usion is an activated/Arrhenius
Eact
process: D = D0 e kB T
. Source: Uni. Kiel.
ELL211 Instructors (IIT Delhi) ELL211 Winter 2022 11 / 12
Ion Implantation
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Predep and drive-in: can’t do lightly

doped regions. Needed for scaled
VLSI and power devices.
Poor junction depth control.
Channel doping in MOSFETs: to
adjust VT .
1973: first commercial implanters.
Dose range: 1 ⇥ 1011 cm 3
to
1 ⇥ 1016 cm 3 . Energy
⇠ 10 keV to 200 keV.
Feed gas is cracked at negative
filament. For Si process: BF3 , AsH3 ,
PH3 . Ions generated are a mix of
species: B, B+ ,BF2 + , etc. Accelerated
using a negative potential.
Magnetic field helps channel and
separate ions. Wafers are exposed at
di↵erent
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