Semiconductor Purification

Silicon and Germanium are two of the most widely used Semiconductor materials. Among these two Silicon has
wide spread use as it has various favorable factors associated with the material given below as:

• In earth, it is most abundant element after oxygen. About 27.6% of the

earth's crest is made up of Silicon.
• Silicon is very cheap as its raw materials from which it is extracted is
found everywhere in nature.
• There are economical and effective methods of crystallization for Silicon.
• Building layer in the MOS devices, Silicon oxide is used as an excellent
insulator.
• It has efficient response to solar radiation and light
• Silicon is easy for doping by impurities
Silicon is generally prepared by chemical decomposition of compounds like SiO, SICI, and SCI, Through different
chemical reaction, Silicon, is chemically prepared with impurity concentration of about one part per million. Then
purified Silicon is melted and cast into ingots. This ingot is polycrystalline in nature as it consists of a large number
of small single crystals having random orientation with respect to another. The required purity level in Silicon is
obtained by a method known as zone refining. Zone refining works on the principle that the impurities have higher
solubility in the melt as compared to that in one the solid" which was discovered by the scientist William Gardner
Pfann. In this process, an impure Siingot is taken. The rod is placed in a tubular zone refiner. Inside the refiner, an
inert gas environment is maintained. A series of circular mobile heating coils are placed along the rod. The heater
moves along the rod from one end to another. At a time, heater melts the particular zone of rod where impurity is
present. As the heater moves, the molten part of previous zone gets solidified again. During solidification, the
impurity of previous zone move to newly heated zone. In other words, as the heater shift from one zone to another,
the impurity also shifts to succeeding molten zone of the ingot. During the process, when the heater reaches to
other end of impure rod, the impurity gets collected there. As the impurity prefers to remain in the melt thus could
be swept to the other end of the rod. The process is repeated continuously till high purity is obtained. The other end
with concentrated impurity is then cut and removed.
 Single Crystal Growth
• To produce the device grade Silicon single crystals, the impurity concentration must
be reduced. So, the polycrystalline ingots must be transformed into the large single
crystals. The methods for growing large single crystals of Silicon has been developed
in last few decades. So, now a days highly sophisticated IC's can be produced at
reasonable price. Some of the methods used for single crystal growth are as:
• Czochralski Method
• Bridgman-Stockbarger Method 
• Floating Zone Method
• Epitaxy
 1. Czochralski Method

• It is a method of crystal growth used to obtain single crystal of

Semiconductors. Silicon wafer (Semiconductor) is a thin piece of
Semiconductor material used in integrated circuits for fabrication
process. Czochralski process of manufacturing Silicon wafer involves
the following steps:
• Preparation of high purity of molten Silicon
• Dipping the seed crystal
• Pulling seed upward
I. Preparation of highly pure molten Silicon
• In this method, highly pure Silicon is used as molten form to produce
the single crystal Silicon. SiO2, can be used to prepare highly pure
Silicon. Then, the substance is heated to its melting point into a
crucible (pot) made of quartz. The supersaturated molten Silicon will
become source of Silicon wafer.
 II.  Dipping the seed crystal
• Seed crystal is a small piece of single crystal material which is used to
grow a large crystal of some material. When it is dipped into the
saturated molten solution of Silicon and then cooled, large crystal will
grow.
 III.  Pulling seed upward
• The seed will be extracted from the molten Silicon pool and rod will be
pulled upward and rotated at the same time. During this process, the
rod and crucible rotate in opposite direction to minimize the effect of
contraction in the melt. The temperature gradient, pulling rate and
rotation speed are the factors that influences the size of crystal during
the manufacturing of single crystal Silicon. As the seed crystal is
slowly raised upward, the molten Silicon will solidify as same as seed.
Therefore, this process is called 'growing' as it produces a new crystal
of Silicon from molten Silicon is called ingot which can be grown 300
mm to 400 mm in diameter. The diagram of single crystal growth by
Czochralski method is shown in figure .
 3. Bridgman-Stockbarger Method
• This method is named after physicists Percy Williams Bridgman and Donald C.
Stockbarger. It involves following three steps:
• Sealing the starting material in a crucible
•  Melting
• Crystal growth by passing the crucible through the temperature gradient zone.
The material is placed in a crucible having a conical tip. The sample which is initially
polycrystalline is first melted in an upper furnace that is maintained a few degrees above
the melting point. The melt with crucible now moves down where it gets slowly cooled
into lower furnace with a temperature a few degrees below the melting point. Crucible is
rotated simultaneously to stir the melt while lowering it (crucible). A small crystal is
formed at the tip of the crucible. This crystal acts as the seed for the rest of melt and as
the crucible continues to the lowered a single crystal is grown. The diagram of single
crystal growth by Bridgmann-Stockbarger method is shown in figure .
 3. Floating Zone Method
• The two methods just described have the disadvantages that the melt tends to dissolve some of the oxygen
from the walls of the crucible (usually made of silica SiO2). The floating zone method solve the problem that
provide with crucible altogether as shown in the figure 34. This method is based on zone of melting process.
The production takes place under vacuum or in an inert gas medium. It consists a high purity polycrystalline
rod of raw material and monocrystalline (single crystal) seed crystal. They are held face to face in a vertical
position and are rotated with radio frequency (R.F.) heating coil. Both are partially melted.
• When the molten zone is moved along the polycrystalline rod the molten Silicon solidifies into a single
crystal and with this, the material gets purified. Most of the impurities are more soluble in melt than in the
crystal. A seed crystal is used at one end in order to start growth. With this impurities can be removed as they
prefer to go to the liquid phase. Due to the surface tension limitation during the growth the diameter of float
zone wafer (wafer: a round thin piece) are generally not greater than 150 mm.
• The important part of this growth technique is that the molten part of the sample is supported by the solid
part. After the heating coils move over the whole polySilicon rod, it converts to a single crystal Silicon ignot.
 4. Epitaxy
• The deposition of a crystalline over layer on a crystalline substrate is
known as epitaxy. The over layer is called an epitaxial film or epitaxial
layer. If the over layer either forms a random orientation with respect
to the substrate or does not form an ordered over layer, it is termed as
non-epitaxial growth. The term epitaxy comes from Greek roots 'epi'
means above and 'taxis' means to an ordered manner.
 VPE
• In vapour phase, epitaxy (VPE) atoms of Silicon from a vapour are deposited on the substrate in a layer which has the
same crystal structure and orientation as the substrate. Therefore, the substrate serves as the seed crystal into which the
epitaxial layer grows. This first layer in turn serves as the substrate for the second layer and so on.
• Single crystal wafer of Silicon are placed in a heated chamber called reactor. Gaseous compound of Silicon (SiC) together
with the appropriate reactant gas are introduced into the reactor. The temperature of the reactor is adjusted in such a way, it
can liberate Silicon by the decomposition of the compound. For example, at 1250°C the following reaction occurs:
• SiCl4 + H2 Si + HCl
• Few Si atoms released in the reaction are deposited on the substrates, forming epitaxial layers. These layer will be of high
purity if the chemicals used for the reaction are highly pure. The Silicon VPE may also use pyrolytic decomposition of
silane. (Pyrolytic: chemical change because of heat)
• SiH4 650C Si + 2 H2
This reaction is not reversible and takes place at lower temperature.
 LPE SPE
• In liquid phase epitaxy, the • Solid phase epitaxy is usually
substrate is dissolved into the done by depositing a film of
melt of the material to be amorphous material on a
deposited. It takes place at a crystalline substrate. The
temperature well below the
substrate is heated to crystallize
melting point of the substrate
material. The substrate acts as the film.
seed for material crystallizing
directly from the melt.
 MBE
• In molecular beam epitaxy, an evaporated beam of
particles is produced by heating a source material.
These particles travel through a very high vacuum to
the substrate where they get condensed. During this
process, substrate temperature varies from 400°C to
900°C.