Silicon and its properties
Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid
with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group
14 in the periodic table: carbon is above it; and germanium, tin, and lead are below it. It is relatively
unreactive. Because of its high chemical affinity for oxygen, it was first purified and characterize in 1823
by Jons Jakob Berzelius. Its oxides form a family of anions known as silicates. It’s melting and boiling points of
1414 °C and 3265 °C respectively are the second-highest among all the metalloids and nonmetals, being only
surpassed by boron. Silicon is the eighth most common element in the universe by mass, but very rarely
occurs as the pure element in the Earth's crust. Metalloids are elements with properties intermediate
between metals and non-metals.
Flerovium
Flerovium is a super heavy artificial chemical element with the symbol Fl and atomic number 114. It is an
extremely radioactive synthetic element. The element is named after the Flerov Laboratory of Nuclear
Reactions of the Joint Institute for Nuclear Research in Dubna, Russia, where the element was discovered in
1998.
Doping
The process of adding substances to a pure semiconductor for the purpose of modulating its electrical
properties is known as doping. The doping means the introduction of impurities into a semiconductor crystal
to the defined modification of conductivity. For example silicon can be doped with
Boron (trivalent-3 valence electron) forming p-type of semiconductor
Phosphorus (pentavalent-5 valence electron) forming n-type semiconductor
These impurities atoms are known as dopants.
Why doping needed
Semiconductors are intrinsic in nature that is the
number of electron and holes are equal. It is only when
we doped a semiconductor; the electrons or holes
become majority charge carrier. The one that become
majority is responsible for the flow of current.
Doping means the introduction of impurities into a
semiconductor crystal to the defined modification of
conductivity. Two of the most important materials
silicon can be doped with, are boron (3 valence
electrons = trivalent) and phosphorus (5 valence
electrons = pentavalent). Other materials are
aluminum, indium (3-valent) and arsenic, antimony (5-
valent).
The dopant is integrated into the lattice structure of the semiconductor crystal, the number of outer electrons
define the type of doping. Elements with 3 valence electrons are used for p-type doping, 5-valued elements
for n-doping. The conductivity of a deliberately contaminated silicon crystal can be increased by a factor of
106
The n-type doping
The 5-valent dopant has an outer electron more than the silicon atoms. The four outer electrons combine
with ever one silicon atom, while the fifth electron is free to move and serves as charge carrier. This free
electron requires much less energy to be lifted from the valence band into the conduction band, than the
electrons which cause the intrinsic conductivity of silicon. The dopant, which emits an electron, is known as an
electron donor (donare, lat. = to give).
The dopants are positively charged by the loss of negative charge carriers and are built into the lattice, only
the negative electrons can move. Doped semimetals whose conductivity is based on free (negative) electrons
are n-type or n-doped. Due to the higher number of free electrons those are also named as majority charge
carriers, while free mobile holes are named as the minority charge carriers.
Arsenic is used as an alternative to phosphorus, because its diffusion
coefficient is lower. This means that the dopant diffusion during subsequent
processes is less than that of phosphorus and thus the arsenic remains at the
position where it was introduced into the lattice originally. Diffusion
coefficient is the quantity of substance that in diffusing from one region to
another passes through each unit of cross section per unit of time when the
volume concentration gradient is unity.
The p-doping
In contrast to the free electron due to doping with phosphorus, the 3-valent dopant effect is exactly the
opposite. The 3-valent dopants can catch an additional outer electron, thus leaving a hole in the valence band
of silicon atoms. Therefore the electrons in the valence band become mobile. The holes move in the opposite
direction to the movement of the electrons. The necessary energy to lift an electron into the energy level of
indium as a dopant, is only 1 % of the energy which is needed to raise a valence electron of silicon into the
conduction band.
With the inclusion of an electron, the dopant is negatively
charged, such dopants are called acceptors (acceptare, lat. = to
add). Again, the dopant is fixed in the crystal lattice, only the
positive charges can move. Due to positive holes these
semiconductors are called p-conductive or p-doped. Analog to n-
doped semiconductors, the holes are the majority charge carriers,
free electrons are the minority charge carriers.
Doped semiconductors are electrically neutral. The terms n- and p-type doped do only refer to the majority
charge carriers. Each positive or negative charge carrier belongs to a fixed negative or positive charged
dopant.
N- and p-doped semiconductors behave approximately equal in relation to the current flow. With increasing
amount of dopants, the number of charge carriers increases in the semiconductor crystal. Here it requires
only a very small amount of dopants. Weakly doped silicon crystals contain only 1 impurity per 1,000,000,000
silicon atoms, high doped semiconductors for example contain 1 foreign atom per 1,000 silicon atoms.
Electronic band structure in doped semiconductors
By the introduction of a dopant with five outer electrons, in n-doped semiconductors there is an electron in
the crystal which is not bound and therefore can be moved with relatively little energy into the conduction
band. Thus in n-doped semiconductors the donator energy level is close to the conduction band edge, the
band gap to overcome is very small.
Analog, through introduction of a 3-valent dopant in
a semiconductor, a hole is available, which may be
already occupied at low-energy by an electron from
the valence band of the silicon. For p-doped
semiconductors the acceptor energy level is close the
valence band. Band model of doped semiconductors
The p-n junction
When we place p-type and n-type semiconductors in contact
with one another, a p-n junction is formed. The p-n junctions are
basic components of most common electrical devices. While
semiconductors doped with either n-type dopants or p-type
dopants are better conductors than intrinsic semiconductors,
interesting properties emerge when p- and n-type
semiconductors are combined to form a p-n junction
Manufacturing of the hyperpure silicon
The manufacture of the hyperpure silicon for photovoltaics occurs in two stages. The oxygen is removed to
produce metallurgical grade silicon. It is further refined to produce semiconductor grade silicon. An
intermediate grade with impurity levels between metallurgical silicon and semiconductor grade silicon is
often termed solar grade silicon.
Metallurgical Grade Silicon
Silica is the dioxide form of silicon (SiO2) and occurs naturally in the form of quartz. While beach sand is also
largely quartz, the most common raw material for electronic grade is high purity quartz rock. Ideally the silica
has low concentrations of iron, aluminum and other metals. The silica is reduced (oxygen removed) through a
reaction with carbon in the form of coal, charcoal and heating to 1500-2000 °C in an electrode arc furnace.
SiO2 + C → Si + CO2
The resulting silicon is metallurgical grade silicon (MG-Si). It is 98% pure and is used extensively in the
metallurgical industry.
The transition metals in the silicon result in deep levels in the band gap and the high recombination activity
make metallurgical grade silicon unsuitable for use in electronics. In addition, boron and phosphorous dopant
impurities are much too high in concentration (>50–100 ppmw) to allow suitable compensation procedures.
Ferrosilicon
An even greater production of silicon is in the form of ferrosilicon that is manufactured using a similar process
to that described above but is done in the presence of iron. Ferrosilicon is used extensively in metals
manufacturing. It is 98–99% pure, with a major contamination of carbon, alkali-earth and transition metals,
and hundreds of ppmw of B and P
Electronic Grade Silicon (Siemens process)
A small amount of the metallurgical grade silicon is further refined for the semiconductor industry. Powdered
MG-Si is reacted with anhydrous HCl at 300 °C in a fluidized bed reactor to form SiHCl 3
Si + 3HCl → SiHCl3 + H2
During this reaction impurities such as Fe, Al, and B react to form their halides (e.g. FeCl3, AlCl3, and
BCl3). The SiHCl3 has a low boiling point of 31.8 °C and distillation is used to purify the SiHCl 3 from the
impurity halides. The resulting SiHCl3 now has electrically active impurities (such as Al, P, B, Fe, Cu or Au) of
less than 1 ppba.
Finally, the pure SiHCl3 is reacted with hydrogen at 1100°C for ~200 – 300 hours to produce a very pure form
of silicon.
SiHCl3 + H2 → Si + 3HCl
The reaction takes place inside large vacuum chambers and the silicon is deposited onto thin polysilicon rods
(small grain size silicon) to produce high-purity polysilicon rods of diameter 150-200mm. The process was first
developed by Siemens in the 60's and is often referred to as the Siemens process.
Purifications of silicones
Silicone is always found in contaminated or in impure form. For different purposes such as use of silicone in
industry and doping of silicone, purification is required. The Purifications of silicones is done by following
processes.
Zone refining
It is also known as zone melting, floating zone process and travelling melting zone. It is define as
A technique for the purification of a crystalline material and especially a metal in which a molten region
travels through the material to be refined, picks up impurities at its advancing edge, and then allows the
purified part to recrystallize at its opposite edge
It is a purification technique for crystalline substances in which a heating system passes slowly over a bar of
the material to be refined, creating a molten region that carries impurities with it across the bar.
Zone refining is particularly used when metals are required in high degree of purity. It is based on the principle that
when an impure metal in a molten state is allowed to cool, only the metal crystallizes while the impurities remain
present in the molten state (mass) or melt. So the zone refining process of metals is based on the principle of greater
solubility of the impurities in the molten state than in the solid.
Zone refining is a process in which organic and inorganic compounds are purified. Like distillation and gas and
liquid chromatography, zone refining is dependent on the distribution of material between two phases.
However, the distribution in zone refining is between the solid and liquid phases, while the distribution in
distillation and gas chromatography is between the liquid and vapor phases.
When a homogeneous liquid mixture is cooled, the composition of the solid that crystallizes out is usually
different from that of the liquid: the purification of a substance by zone refining relies on this difference.
Zone refining was developed in 1952 by William G. Pfann at the Metallurgical Research Department of Bell
Telephone Laboratories to purify materials used in the semiconductor industry. Pfann found that by passing a
molten zone down a rod of silicon or germanium, he could cause the impurities to move in the direction of
the molten zone. Repeating this process multiple times reduced the impurities in the main part of the rod to a
few parts per billion, and then concentrated them at the end of the rod.
High-speed zone refining
While used successfully to purify organic chemicals, zone refining is time consuming—purification takes days.
The MiniZone high-speed zone refiner from Design Scientific (Holland, Mich) reduces that time to hours. It
concentrates impurities in a sample or purifies chemicals, with purity of 99.999% (5N) or higher.
The compact instrument can purify 1–20 g of sample at a time. Controls include melt temperature, freeze
temperature and zone migration rate. Any thermally stable sample that is a solid between –10 °C and + 300 °C
can be purified.
Purification process
In zone refining, a short molten zone travels slowly through an elongated sample of a crystalline material. A
molten zone traversing a solid sample has two liquid–solid interfaces—a melting interface and a freezing
interface. At the melting interface, the composition does not change; at the freezing interface, the impurities
favor the liquid phase because the crystal structure tends to exclude molecules that do not fit into the crystal
lattice. Passing the molten zone(s) through the sample many times concentrates the impurities at one end,
leaving the opposite end highly purified.
This method is particularly used when metals are required in high degree of purity. It is based on the principle
that when an impure metal in a molten state is allowed to cool, only the metal crystallizes while the
impurities remain present in the molten state (mass) or melt.
The impure metal converted into a rod which is heated at one end with a circular heater. A narrow zone of
metal is melted. The heater is slowly moved along the rod. The pure metal recrystallizes out of melt while the
impurities remain in the melt which moves along with the melted zone of the rod with the movement of
heater. The process is repeated several times. The end of rod where impurities have collected is cut off. This
method is employed for the purification of germanium, silicon, gallium etc, which are used in semi –
conductors.
