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SILICON

Advantages of Si over Ge
Si has a larger bandgap(1.1 eV for Siversus 0.66
eV for Ge)
Si devices can operate at a higher temperature
(150 C vs100 C)
o

Intrinsic resistivityis higher (2.3 x 105-cm vs 47


-cm)
SiO2 is more stable than GeO2 which is also water
soluble
Si is less costly

Point
Deffects

Any non-silicon atoms incorporated into the lattice at either a


substitutional or interstitial site are considered point defects.
Point defects are important in the kinetics of diffusion and oxidation.
Moreover, to be electrically active, dopants must occupy substitutional
sites in order to introduce an energy level in the bandgap.

Dislocations
defects.

are

line

Dislocations in a lattice
are dynamic defects.
That is, they can diffuse
under applied stress,
dissociate into two or
more dislocations, or
combine
with
other
dislocations.
Dislocations in devices
are
generally
undesirable,
because
they act as sinks for
metallic impurities and
alter diffusion profiles.

Planar Deffects
Two typical area or planar defects are twins and
grain boundaries
l
Twinning represents a change in the crystal
orientation across a twin plane, such that a mirror
image exists across that plane
l
Grain boundaries are more disordered than twins
and separate grains of single crystals in
polycrystalline silicon
l
Planar defects appear during crystal growth, and
crystals having such defects are not considered
usable for IC manufacture and are discarded
l

Metallurgical Grade Silicon (MGS)


SiO2 + 2 C Si + 2 CO
Using this method, silicon carbide (SiC) may also form from an excess
of carbon in one or both of the following ways:
SiO2 + 2 C SiO + 2 CO or SiO2 + 3 C SiC + 2CO.
However, provided the concentration of SiO2 is kept high, the silicon
carbide can be eliminated by the chemical reaction
2 SiC + SiO2 3 Si + 2 CO.
Refining : Oxidizing with Mg, Al or Ca
4 Al + SiO2 Si + Al2O3
2 Ca + SiO2 Si + 2CaO
2 Mg + SiO2 Si + MgO

Electronic Grade Silicon (EGS) - Siemens Process


Electronic-grade silicon (EGS), a polycrystalline material of high purity, is
the starting material for the preparation of single crystal silicon. EGS is
made from metallurgical-grade silicon (MGS) which in turn is made from
quartzite, which is a relatively pure form of sand. MGS is purified by the
following reaction:
Si(solid) + 3HCl (gas) SiHCl3 (gas) + H2 (gas) + heat
The boiling point of trichlorosilane(SiHCl3) is 32oC and can be readily
purified using fractional distillation. EGS is formed by reacting
trichlorosilanewith hydrogen:
2SiHCl3
SiH2Cl2 + SiCl4
SiH2Cl2
Si
+ HCl
2SiHCl3 (gas) + 2H2 (gas) 2Si (solid) + 6HCl (gas)
SiHCl3 + HCl
H2 + SiCl4

Electronic Grade Silicon Union Carbide Process


SiCl4 + 2 H2 + Si

4 SiHCl3

The purified trichlorosilane is then treated in two separate steps


through fixed bed columns filled with quarternary ammonium ion
exchange resins acting as catalyst to.
2 HSiCl3 H2SiCl2 + SiCl4
3H2SiCl2 SiH4 + 2HSiCl3
Above products are separated by distillation. Silane is further purified by distillation and
then pyrolysed to produce polysilicon onto heated silicon seed rods mounted in a metal
bell-jar reactor:
SiH4 --------> 2H2 + Si

Czochralski Growth
Ar

Rotation of crucible and crystal in opposite


Directions improves growth and doping
uniformity

Oxygen incorporation - important for


intrinsic gettering 1017-1018 cm-3

Carbon contributes to native


defects 1015-1016 cm-3

The Czochralski(CZ) process, which accounts for 80% to 90%


of worldwide silicon consumption, consists of dipping a small
single-crystal seed into molten silicon and slowly withdrawing
the seed while rotating it simultaneously.
The crucible is usually made of quartz or graphite with a fused
silica lining. After the seed is dipped into the EGS melt, the
crystal is pulled at a rate that minimizes defects and yields a
constant ingot diameter.

Float Zone Method for Crystal Growth


An alternative process is the float
zone process which can be used for
refining or single crystal growth.
No crucible - no impurities
High resistivity Si

EGS

Add Dopants (gas)


PH3 B2H6
ESG

Float-Zone Process, The float-zone process has some advantages over the Czochralski
process for the growth of certain types of silicon crystals.The molten silicon in the float-zone
apparatus is not contained in a crucible, and is thus not subject to the oxygen contamination
present in CZ-Sicrystals.The float-zone process is also necessary to obtain crystals with a high
resistivity(>> 25 W-cm).

Epitaxial Growth
Epitaxy means the growth of a single
crystal film on top of a crystalline substrate.
For most thin film applications (hard and
soft coatings, optical coatings, protective
coatings) it is of little importance.
However, for semiconductor thin film
technology it is crucial.

Types of Epitaxy
Homoepitaxy
The film and the substrate are the same material.
Often used in Si on Si growth.
Epitaxially grown layers are purer than the substrate and
can be doped independently of it.

Heteroepitaxy
Film and substrate are different materials.
Eg: AlAs on GaAs growth
Allows for optoelectronic structures and band gap
engineered devices.

Heterotopotaxy
It is a process similar to heteroepitaxy except that thin film growth is not
limited to two-dimensional growth; the substrate is similar only in structure
to the thin-film material.
Pendeo-epitaxy
Is a process in which the heteroepitaxial film is growing vertically and
laterally at the same time.
Epitaxy is used in silicon-based manufacturing processes for bipolar
junction transistors (BJTs) and modern complementary metaloxide
semiconductors (CMOS), but it is particularly important for compound
semiconductors such as gallium arsenide.
Manufacturing issues include control of the amount and uniformity of the
deposition's resistivity and thickness, the cleanliness and purity of the
surface and the chamber atmosphere, the prevention of the typically much
more highly doped substrate wafer's diffusion of dopant to the new layers,
imperfections of the growth process, and protecting the surfaces during the
manufacture and handling.

Heteroepitaxy
Trying to grow a layer of a different material on
top of a substrate leads to unmatched lattice
parameters.
This will cause strained or relaxed growth and
can lead to interfacial defects.
Such deviations from normal would lead to
changes in the electronic, optic, thermal and
mechanical properties of the films.