Silicon Growth techniques

• Silicon was considered the material of choice for PV applications due

to
• Silicon is the second most abundant element in the earth’s crust
(oxygen is the first). It occurs naturally in silicate (Si-O containing)
rocks and sands
• It has excellent electronic properties
• Appropriate match of its energy gap to solar radiation,
• Environmental stability
 Metallurgical graded silicon from ore
MG-Si (98% pure poly C. Si(
The elemental silicon used in semiconductor device manufacture is produced from high purity quartz
and quartzite sands, which contain relatively few impurities. “metallurgical grade silicon” (MG-Si) growth
beginning with the conversion of quartz or quartzite sand in an electric arc furnace with graphite rods
submerged in crushed natural quartz as the silicon source and coke, coal, charcoal, and wood chips as
the reductants

It is a relatively low-energy-demanding process (12

kWh/kg), Silicon has a melting point of (1410° C),

𝑆𝑖 𝑂 2 +2 𝐶 2 000 𝐶 𝑆𝑖+ 2 𝐶𝑂
→

𝑆𝑖𝐶 + 𝑆𝑖 𝑂2 2 000 𝐶 𝑆𝑖 ( 𝑙 ) +𝐶𝑂 + 𝑆𝑖𝑂 (𝑔)

→
Quartz raw material
In the zone around the
electrode, the temperature is
high and SiO(g) and CO(g) will
form and travel to the top of
the furnace.

Silicon prepared in this manner is called

“metallurgical grade” since most of the
world’s production actually goes into steel-
making It is about 98% pure.
 Semiconductor grad SG-Si
MG-Si is not pure enough for direct use in electronics manufacturing. A small
fraction (5% – 10%) of the worldwide production of MG-Si gets further purified
for use in electronics manufacturing.
The purification of MG-Si to semiconductor (electronic) grade silicon is a multi-
step process, MG-Si is first ground in a ball-mill to produce very fine (75% < 40
µM) particles which are then fed to a Fluidized Bed Reactor (FBR). There the
MG-Si reacts with anhydrous hydrochloric acid gas (HCl), at approx. 300ºC
according to the reaction:
+50kcal/mole

The hydro-chlorination reaction 

Monosilane :(SiH4 ) gas, silicon tetrachloride (SiCl4 , trichlorosilane

( SiHCl3 ) , and dichlorosilane ( SiH2Cl2 ) (liquid)
 Distillation and Decomposition of Trichlorosilane
the SiHCl3 is distilled , resulting in extremely pure Trichlorosilane

Hydrogen reduction of trichlorosilane- Semins methode (1950-1960)

The high-purity trichlorosilane is then vaporized, diluted

with high-purity hydrogen, and introduced into the
deposition reactor. In the reactor, thin silicon rods called
slim rods supported by graphite electrodes are available for
the deposition of the chlorosilane to form silicon as a result
of the reaction
2 𝑆𝑖𝐻 𝐶𝑙 3 +2 𝐻 2 1 050 2 𝑆𝑖+ 6 𝐻𝐶𝑙
→
By deposition for 200-300 hr at around 1100°C, high-purity polysilicon rods of 150-200 mm in
diameter are formed. Thin method gave 370,000 tone of polysilicon in 2016
In principle, we have a vessel which can be
evacuated and that contains an "U" shaped
arrangements of slim Si rods which can be heated
from an outside heating source and, as soon as the
temperature is high enough (roughly 1000 oC) to
provide sufficient conductivity, by passing an
electrical current through it.

After the vessel has been evacuated and the Si rods

are at the reaction temperature, an optimized mix
of SiHCl3 (Trichlorosilane), H2 and doping gases
like AsH3 or PH3 are admitted into the reactor..
While the flux of H2 may be in the 100 liter/min range, the dopant gases
only require ml/min. All flow values must be precisely controlled and,
moreover, the mix must be homogeneous at the Si where the reaction
takes place.
 Single crystal Si
Growth from a Melt- Czochralski method (1916)
‫زوكرالسكى‬
The process used in growing these single
crystals is known as the Czochralski process after
its inventor, Jan Czochralski. The Czochralski
process is carried out in an evacuable chamber,
commonly referred to as a “crystal puller” that
holds a large crucible, usually quartz, and an
electric heating element . Semiconductor grade
polysilicon is loaded (charged) into the crucible
along with precise amounts of any dopants such
as phosphorus or boron that may be needed to
give the product wafers specified P or N
characteristics. Evacuation removes any air from
the chamber to avoid oxidation of the heated
silicon during the growth process The furnace is heated above 1500 ◦C,
since Si melting point is 1412 ◦C
Once the silicon charge is fully melted, a small seed crystal, mounted on a rod, is
lowered into the molten silicon. The seed crystal is typically about 5 mm in diameter
and up to 300 mm long. It acts as a “starter” for the growth of the larger silicon crystal
from the melt. The seed crystal is mounted on the rod with a known crystal facet
vertically oriented in the melt “Miller Indices”) of <100>, <110> or <111> are typically
chosen. The crystal growth from the melt will conform to this initial orientation, giving
the final large single crystal a known crystal orientation.

Following immersion in the melt, the seed crystal is slowly (a few mm/min) pulled from
the melt as the larger crystal grows. The pull speed determines the final diameter of
the large crystal. Both the crystal and the crucible are rotated during a crystal pull to
improve the homogeneity of the crystal and dopant distribution.

The method can form boules large enough to produce silicon wafers up to 450 mm in
diameter
 Float zone technique
A drawback to the CZ method is the inclusion of oxygen that comes from the crucible.

Higher purity silicon can be produced by a method known as Float Zone (FZ)
refining. In this method, a polycrystalline silicon ingot is mounted vertically in the
growth chamber, either under vacuum or inert atmosphere. The ingot is not in
contact with any of the chamber components except for the ambient gas and a
seed crystal of known orientation at its base.
Float zone technique
The ingot is heated using non-contact radio-frequency
(RF) coils that establish a zone of melted material in the
ingot, typically about 2 cm thick. In the FZ process, the
rod moves vertically downward, allowing the molten
zone to move up the length of the ingot, pushing
impurities ahead of the melt and leaving behind highly
purified single crystal silicon.
FZ silicon wafers have resistivities as high as 10,000
ohm-cm.
 Chemical Vapor Deposition
Both the Czochralski and Floated electrode techniques
are used to grow bulk single crystals. It is easy to grow a
thin layer of perfect crystal than a large perfect bulk
crystal. In most applications devices are fabricated out
of a thin layer grown on top of a bulk crystal. In such
cases the atoms forming the thin layer will tend to build
a single crystal with the same crystallographic
orientation as the substrate. The resultant film is said to
be deposited epitaxially on the substrate (homo-epitaxy
Si on Si, Hetero-epitaxial GaAs on Si)

The most common reaction for producing a Si film in

this way is given by
SiCl4 + 2H2 = (1200 oC) = Si + 4HCl;
(PH3) and arsine (AsH3) gas added as dopant
 Tungsten CVD

Ironically, W-CVD comes straight form nuclear power

technology. High purity Uranium (chemical symbol U) is
made by a CVD process using UF6 as the gas that
decomposes at high temperature.
 Metal organic Chemical Vapor Deposition
MOCVD

Base pressure 0.001

10-6 torr, working
pressure 1 torr

III–V compound
metal-organic compounds
trimethyl gallium [Ga(CH3)3]
 Oxide CVD
Whenever we need SiO2 layers, but can not oxidize Si, we turn to oxide CVD.
Again, we have to find a suitable chemical reaction between gases that only
occurs at high temperature and produces SiO2. There are several possibilities,
one is
SiH2Cl2 + 2NO2 =(900 C)= SiO2 + 2HCl + 2N2.
o

While this reaction was used until about 1985, a better reaction is
offered by the "TEOS (Tetraethýlorthosilicate) process:

S(C2H5O)4 =(720 oC)= SiO2 + 2H2O + C2H4.

 Silicon thin films Plasma Enhanced CVD
In a gas plasma, the atoms are ionized and both, free electrons and ions are
accelerated in the electrical field and thus gain energy which equilibrates by
collisions. However, while the heavy ions are hardly affected, the electrons are and
their temperature may attain 20.000 K
  Physical Processes for Layer Deposition
A "target" made of the material to be deposited is
bombarded by energetic ions which will dislodge atomes
of the target, i.e., "sputter  them off".
The ions necessary for the bombardment of the target are
simply extracted from an Ar plasma burning between the
target and the substrate.

Since the target electrode is always the cathode, i.e.

negatively charged, it will attract the Ar+ ions and thus is
bombarded by a (hopefully) constant flux of relatively
energetic Ar ions.
This ion bombardment will liberate atoms from the target
which issue forth from it in all directions.

Sputtered layers usually have a very bad crystallinity - very

small grains full of defects or even amorphous layers
result. Usually some kind of annealing of the layers is
necessary to restore acceptable crystal quality.