2.

Semiconductor fabrication techniques

q
Fabrication of pure materials
Czochralsky growth

Universidad Politcnica de Madrid

Purity
E
Expressed
d iin N
Ns ((nines)
i
)
purity of 99.9999 % = 6N
Generally, a minimum of 7N purity it is needed for IC applications

Calculate the purity of a 500 gr Si crystal containing 61014 cm-3 impurities of As

D
Density
it off Si = 2.53
2 53 gr/cm
/ 3, Atomic
At i weight
i ht = 28 gr/mol
/ l

mol
500 gr of Si
28gr

6.0231023 atoms
= 17.86 mol; X
= 1.071025 atoms
mol

cm 3
500 gr of Si
= 197.6 cm3;
2 .53 gr

1.071025 atoms
atoms density =
= 5.411022 atoms/cm3
3
197.6 cm

5.411022 6 1014
P it =
Purity
x 100 = 99.9999988
99 9999988
5.411022

7
7.5N
5N

Universidad Politcnica de Madrid

Obtention of high-purity
high purity Silicon as raw material
Earth crust (aprox. outer 100 kms) is formed by different types of silicates.
Silicate = Si + O + some other element
In fact: Silicon constitutes 26% of earths crust and Oxygen 49%
First obtention of pure crystalline Silicon (1854, Deville)
Pure Silicon presents high chemical reactivity.
PROBLEM it iis diffi
PROBLEM:
difficult
lt to
t keep
k
it pure.

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Raw Material
R
M t i l
SiO2 (98-99,5%)
Reduction in
furnace with
carbon electrodes

SiO2 + 2C
Si + 2CO
@ 3000C

Metalurgical grade
(MG) Si (98-99,5%)
Hydro-chlorination
H
d
hl i ti
(Siemens method)
Cl3HSi
10-4 % = 1 ppm
Cl3HSi reduction on a
polycrystalline Si rod
Zone Refining
g
Electronic or
Semiconductor grade

Si + ClH

Cl3HSi + Cl4Si + (B, Fe, Ni chlorides)

Fractional distillation

Cl3HSi + H2

Si(pol ) + 3ClH
Si(poly)

Cl3B
Cl3Fe
Cl3Au
@1200C 1ppm

Polycrystalline Si
10-6 % = 10 ppb (8N)
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3000C

Universidad Politcnica de Madrid

Obtention of metallurgical-grade
metallurgical grade Silicon (MG-Si)
(MG Si)
SiO2 + 2C Si + 2CO
Raw material: SiO2 (quartz)
Reduction of SiO2 in an electrical oven with graphite electrodes
Metallurgical Si (MG-Si)
98-99 % purity
(diff
(different
applications)
li i
)

SiO2

(T 3000C)

Carbon

Graphite electrodes

Main impurities found in MG-Si:

C B
C,
B, P
P, Al
Al, Fe
Fe, Ti
Ti, Cr
Cr,
V, Mn, Ni, Cu, O2

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Applications of MG-Si
MG Si
Alloys with Al, Mg and Cu to increase their resistance
Deoxidizing steel
Ferric alloys: makes them chemically inert
Raw material for: silicones, polymers, etc.
Raw
a material
ate a for
o the
t eO
OBTENTION
O of
o SEMICONDUCTOR
S
CO UC O - g
grade
ade Silicon
S co (SG-Si)
(SG S )

.
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Purification of MG-Si to SG-Si (ultra purity 8N) SIEMENS

1.- Chlorination (MG-Si) + 3 HCl SiHCl3 + H2 (@ 300C)
Impurities (Fe, Al, B) form chlorides (FeCl3, AlCl3, BCl3)

2 Fractional
2.F ti
l Di
Distillation
till ti
Impurities of Al, P, B, Fe, Cu y Au
SiHCl3 has low boiling
gp
point ((31.8C))
SiHCl3 of purity 10-4 % = 1ppm (6N)

3.- Deposition on Silicon rods

SiHCl3 + H2 Si (poly) + 3 HCl (1200C)
4.- Purification by Zone Refining
4.
Polycristalline Si of semiconductor grade
Purity of 10-6 % = 10 ppb (8N)
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Deposition
p
on Silicon rods
SiHCl3 + H2 Si (poly) + 3 HCl (1200C)

Universidad Politcnica de Madrid

Purification by Zone Refining

SOLID
SLIDO

LIQUID
LQUIDO

Equilibrium Segregation Coefficient

Cs
k0 = C
l
Cl

Cs
Impurities distribution at the solid-liquid interface

GaAs

Si
Dopant

ko

0.5

7.0x10-4

Se

0.1

0 07
0.07

Sn

0 08
0.08

Li

1.0x10-2

Te

0.064

0.5

1.0

n/p

0.35

Ge

0.018

n/p

Sb

0.023

Si

2.0

n/p

Te

2.0x10-4

Be

3.0

Al

2.8x10-3

Mg

0.1

Ga

8.0x10
8
0 10-33

Zn

0 42
0.42

0.8

Cr

5.7x10-4

s.i.

Au

2.5x10-5

deep

Fe

3.0x10-3

s.i.

Dopant

ko

As

0.3

Bi

Type

Type

k0 << 1
difficult doping
k0 >1
easyy contamination
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Purification by Zone Refining

Process in a furnace under inert g

gas ((N2)

Heater melts a small region at a time

(Float Zone system).
After the molten zone passes along the
rod, impurities concentrate at one end.
In practice, the process is repeated
several times

Impurity profiles after 1 cycle (left) and many cycles (right)

Universidad Politcnica de Madrid

Fabrication of Monocrystalline Wafers

Once ultra pure Silicon has been obtained (semiconductor grade)

Thi iis POLYCRYSTALLINE material

This
t i l
Need to obtain bulk monocrystalline material for
further technological processes (i.e. epitaxial growth)

M th d
Methods:
Czochralski (particularly for Silicon)
LEC (liquid encapsulated Czochralski ) for GaAs
Floating Zone
Bridgman (particularly for GaAs)
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Czochralski Method (1916)

Prof. Jan Czochralski (1885-1953)

Universidad Politcnica de Madrid

Czochralski Method (1916)

1450 C
C
Vg = 2 cm/hour

Doping issues:
Segregation coefficient
Vertical inhomogeneous distribution
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Czochralski Method (1916)

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LEC (Liquid Encapsulated Czochralski ) for GaAs

Why
y special
p
for GaAs?
Incoherent decomposition
Pieces of B2O3 (boron trioxide) are also
added to the crucible together with
elemental Ga and As
At 460C the boron trioxide melts to
form a thick, viscous liquid which coats
p
),
the entire melt ((hence encapsulated),
preventing the sublimation of As.

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Floating Zone
Lower contamination
Doping
p g with PH3,
3 AsH3,
3 B2H6
Radial inhomogeneity (difussion)

Conceptually similar to the zone refining,

but using a monocrystalline seed
Vg = 2 cm/hour

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Bridgman Technique

Schematics of growth furnace and heating distribution

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Doping distribution

SOLID
SLIDO

Cs
k0 =
Cl
Segregation
Coefficient
(k0 < 1)

LIQUID
LQUIDO

Cl
Cs
Impurities distribution
aten
thelasolid-liquid
interface
Distribucin
de impurezas
frontera slido-lquido

Initial melt with weight M0 (gr) and impurities concentration C0 (per unit weight)
As the crystal grows the impurity concentration in the solid (Cs) and the liquid
(Cl) will NOT be constant: Cs and Cl are time-dependent:

Before crystal growth: M0,C0 and

After some growth time, t:

M0 C0 = total amount of impurities (melt)

Weight of the crystal: M (solid)

Weight of the melt: M0- M (melt)
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 After some time, t:

Weight of the crystal: M

Weight of the melt: M0- M

Now if the total amount of impurities in the melt at this time is: S
S
= Cl(t)
p y concentration in the melt (p
(per u. weight):
g ) Cl=
Impurity
M0-M

[[1]]

If the crystal weight increases by dM (at t + dt), the amount of impurities

)) [[2]]
in the melt should decrease byy dS = Cs dM ((with Cs((t))
Substituting [1] and [2] in
and integrating

Cs
k0 =
Cl

M dM
dS
where:
k0

0
S
M0 M
C0 M 0

dM
dS

k 0
S
M

M
0

C s k 0C0 1
M0

k 0 1

C0 Cl ((t=0))
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Cl(t)

C s k 0 C0 1
M0

Different values of k0
k 0 1

This leads to an inhomogeneous

impurity concentration as the
crystal growth proceeds
Non-uniform doping along the
length of the ingot.
Only for ko values close to 1,
distribution is homogeneous
M/M0
Universidad Politcnica de Madrid

Real case:
accummulation
at the interface
Effective
Eff
ti
segregation
coefficient
(far from interface)
k0 =
k =
e

Cs
C l(0)

Cs
C

Doping needs V
Zone refining needs V
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Problem
A Silicon ingot, which should contain 1016 boron atoms / cm3, is to be grown by the Czochralsky technique.
Determine:
a)
b)

What concentration of boron atoms should be in the melt to give the required concentration in the ingot ?
If the initial load of silicon in the crucible is 60 Kg
Kg, how many grams of boron should be added ?

Data:
k0 of B in Silicon = 0
0.8
8
23
Nav= 6.023x10 at/mol
Molecular weight of B = 10.8 gr/mol
Molecular weight of Si = 28.08 gr/mol
Si= 2.53
2 53 gr/cm3

Universidad Politcnica de Madrid

Problem:
A Silicon ingot doped with phosphorous (P) is to be grown by the Czochralsky technique.
Determine:
a)

The grams of P that should be added to 1 Kg of Silicon in the crucible to obtain a concentration of
1x1016 cm-3 in the crystal at the beginning of the growth.

b) The P concentration that will have the most external layers of the grown Silicon crystal when 50% of the
weight of the crystal has been grown.
Data:
k0 of P in Silicon = 0.35
Nav= 6.023x1023 at/mol
Molecular weight of P = 30.97 gr/mol
Molecular weight of Si = 28.08 gr/mol
Si= 2.53 gr/cm3

Universidad Politcnica de Madrid

Once the monocrystalline ingot of Silicon (or GaAs) has been

obtained,
bt i d
Need to obtain wafers that will be used as main substrates
for additional technological processes.
Electrical and chemical properties of the wafers need to be
controlled very carefully
Critical Steps

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Typical Processes to obtain wafers from the ingot

(a) cropping
(b) grinding

(c) orientation flatting

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Wafer identification

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SG-Silicon (poly)

edge
g contouring
g

cleaning

CZ growth

Cropping
grinding
final ingot orientation flattening

lapping
pp g

etching
g

inspection

heat treatment

wafering

polishing
p
g

packaging

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Universidad Politcnica de Madrid

Once monocrystalline wafers are obtained :

Epitaxial growth
Different technological processes depending on the device to be
fabricated
All processes are made
d using
i epitaxial
it i l layers
l
The device quality will depend on the quality of the epitaxial process.

Next classes will cover the 3 most common methods of

epitaxial
p
g
growth of semiconductors

Liquid Phase Epitaxy (LPE)

Molecular Beam Epitaxy (MBE)
Vapor Phase Epitaxy (VPE and MOVPE)

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