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Introduction:
Silicon and germanium with symbol Si and Ge are the members
of group 14. Both are chemical elements have the atomic number 14 and 32
respectively. Si is a hard and brittle crystalline solid with a blue-grey metallic luster
and it is a tetravalent metalloid and semiconductor while Ge is a lustrous, hard,
grayish-white metalloid in the carbon group. Both react and form complexes with
oxygen in nature. 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. Elemental
germanium is used as a semiconductor in transistors and various other electronic
devices. Historically, the first decade of semiconductor electronics was based
entirely on germanium.
Today, the amount of germanium produced for semiconductor electronics is one
fiftieth the amount of ultra-high purity silicon produced for the same. Presently, the
major end uses are fiber optic systems, infrared optics, solar cell applications,
and light emitting diodes (LEDs). Germanium compounds are also used
for polarization catalysts and have most recently found use in the production
of nanowires. This element forms a large number of organometallic compounds,
such as tetraethyl germane, useful in organometallic chemistry
Most silicon is used commercially without being separated, and often with little
processing of the natural minerals. Such use includes industrial construction
with clays, silica sand, and stone. Silicates are used in Portland
cement for mortar and stucco, and mixed with silica sand and gravel to
make concrete for walkways, foundations, and roads. They are also used in white
ware ceramics such as porcelain, and in traditional quartz-based soda-lime glass and
many other specialty glasses. Silicon compounds such as silicon carbide are used as
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abrasives and components of high-strength ceramics. Silicon is the basis of the
widely used synthetic polymers called silicones.
Characteristics of silicon:
A silicon atom has fourteen electrons. In the
ground state, they are arranged in the electronic configuration [Ne]3s 23p2. From
these, four are valence electrons, occupying the 3s orbital and two of the 3p orbitals.
Like the other members of its group, the lighter carbon and the
heavier germanium, tin, and lead, it has the same number of valence electrons as
valence orbitals: hence, it can complete its octet and obtain the stable noble gas
configuration of argon by forming sp3 hybrid orbitals, forming tetrahedral
SiX4 derivatives where the central silicon atom shares an electron pair with each of
the four atoms it is bonded.
At standard conditions of temperature and pressure silicon is semiconductor and
resistivity decrease with increase in temperature. Silicon is an insulator at room
temperature. When silicon doped with the group 13 members like aluminum, boron
and gallium then p-type semiconductors are formed. Naturally occurring silicon is
composed of three stable isotopes, 28Si (92.23%), 29Si (4.67%), and 30Si
(3.10%). Out of these, only 29Si is of use in NMR and EPR spectroscopy.
Characteristics of Germanium:
Under standard conditions of
temperature and pressure, germanium is a brittle, silvery-white, semi-metallic
element. This form an allotrope known as α-germanium, which has a metallic luster
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and a diamond cubic crystal structure, the same as diamond. At pressures above
120 bar, it becomes the allotrope β-germanium with the same structure as β-tin. Like
silicon, gallium, bismuth, antimony, and water, germanium is one of the few
substances that expands as it solidifies (i.e. freezes) from the molten state.
Germanium is also a semiconductor. Zone refining techniques have led to the
production of crystalline germanium for semiconductors that has an impurity of only
one part in 1010, making it one of the purest materials ever obtained. The first
metallic material discovered (in 2005) to become a superconductor in the presence
of an extremely strong electromagnetic field was an alloy of germanium, uranium,
and rhodium.
Pure germanium suffers from the forming of whiskers by spontaneous screw
dislocations. If a whisker grows long enough to touch another part of the assembly
or a metallic packaging, it can effectively shut out a p-n junction. This is one of the
primary reasons for the failure of old germanium diodes and transistors.
Occurrence of Silicon and Germanium:
In the universe, silicon is the seventh most abundant element, coming
after hydrogen, helium, carbon, nitrogen, oxygen, and neon.Silicon makes up
27.7% of the Earth's crust by mass and it does not occur.
Germanium is created by stellar nucleosynthesis, Germanium has been detected in
some of the most distant stars and in the atmosphere of Jupiter.
Germanium's abundance in the Earth's crust is approximately 1.6 ppm. Only a few
minerals like argyrodite, briartite, germinates, and renierite contain appreciable
amounts of germanium, and none in mineable deposits. Some zinc-copper-lead ore
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bodies contain enough germanium to justify extraction from the final ore
concentrate.
Purification Method:
Both silicon and germanium are purified by a method known as “Zone Refining”
in which impurities are removed on the basis of melting points of impurity present
and extracted Si and Ge.
Zone Refining:
In this module highly purified metals are obtained. Metals
like Silicon, Germanium, Tellurium and Gallium are required in their high purified
form for their most applications, so to obtained these four metals a specialized
method called “zone refining” is used. Zone refining method was discovering by a
scientist W.G. Pfann in 1951.
Working Principle:
This technique works on the principle of “the impurities have
higher solubility in molten metal as compare to that solid metal. This difference
between the solubility of impurities makes it possible to segregate the impurities in
the metals to be refined”.
Construction:
It consists of a tabular zone refiner with an inert
environment.
In center of zone refiner, a rod of impure metal is hanged
out vertically.
Around the rod a circular heater is used.
To provide inert environment any inert gas is used.
At the bottom impurities were collected.
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DIAGRAME:
Following is the working diagram during the
purification when we need a highly purified metal for its most
applications. In diagram a tabular tube is shown in which an inert
atmosphere is created to prevent any unwanted or additional
reaction.
A Labeled Diagram of Zone Refining Apparatus
Working:
Take a tabular zone refiner and environment is set up by using any inert
gas like He, Ne etc. so that no any additional reaction is take place inside the zone.
An impure rod of Silicon or Germanium is hanged vertically in the zone. A circular
heater or radio frequency heater is coated around the impure rod of Si or Ge. There
are different molten zones in the zone. A high temperature is applied so that the the
rod is molted the impurities are moved with the movement of circular heater and the
pure metal solidified again on the upper side of the rod.
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As the rod move impurities move until reached at the bottom this process is repeated
again and again until 99.99% pure metal is obtained and at last the lower end of the
rod become concentrated with impurities and discarded from the rod. Same method
is used to purify both Si and Ge.
At the end of the process a highly purified rod of metal is obtained as shown in the
following fig.
Purified Metal Rod
Applications of Si and Ge as semiconductors:
Germanium as semiconductors:
Silicon-Germanium alloys are rapidly
becoming an important semiconductor material for high-speed integrated circuits.
Circuits utilizing the properties of Si-SiGe junctions can be much faster than those
using silicon alone. Silicon-germanium is beginning to replace gallium
arsenide (GaAs) in wireless communications devices. The SiGe chips, with high-
speed properties, can be made with low-cost, well-established production techniques
of the silicon chips industry.
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Solar panels are a major use of germanium. Germanium is the substrate of the wafers
for high-efficiency multifunction photovoltaic cells for space applications. High-
brightness LEDs, used for automobile headlights and to backlight LCD screens, are
an important application.
Because germanium and gallium arsenide have very similar lattice constants,
germanium substrates can be used to make gallium arsenide solar cells. The Mars
Exploration Rovers and several satellites use triple junction gallium arsenide on
germanium cells.
Germanium-on-insulator substrates are seen as a potential replacement for silicon
on miniaturized chips. Other uses in electronics include phosphors in fluorescent
lamps and solid-state light-emitting diodes (LEDs). Germanium transistors are still
used in some effects pedals by musicians who wish to reproduce the distinctive tonal
character of the "fuzz"-tone from the early rock and roll era, most notably the Dallas
Arbiter Fuzz Face.
Silicon as semiconductors:
Silicon wafer with mirror finish
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Most elemental silicon produced remains as a ferrosilicon alloy, and only about 20%
is refined to metallurgical grade purity (a total of 1.3–1.5 million metric tons/year).
An estimated 15% of the world production of metallurgical grade silicon is further
refined to semiconductor purity. This typically is the "nine-9" or 99.9999999%
purity nearly defect-free single crystalline material.
Monocrystalline silicon of such purity is usually produced by the Czochralski
process, is used to produce silicon wafers used in the semiconductor industry, in
electronics, and in some high-cost and high-efficiency photovoltaic applications.
Pure silicon is an intrinsic semiconductor, which means that unlike metals, it
conducts electron holes and electrons released from atoms by heat;
silicon's electrical conductivity increases with higher temperatures.
Pure silicon has too low a conductivity (i.e., too high a resistivity) to be used as a
circuit element in electronics. In practice, pure silicon is doped with small
concentrations of certain other elements, which greatly increase its conductivity and
adjust its electrical response by controlling the number and charge
(positive or negative) of activated carriers. Such control is necessary
for transistors, solar cells, semiconductor detectors, and other semiconductor
devices used in the computer industry and other technical applications. In silicon
photonics, silicon can be used as a continuous wave Raman laser medium to produce
coherent light.
In common integrated circuits, a wafer of monocrystalline silicon serves as a
mechanical support for the circuits, which are created by doping and insulated from
each other by thin layers of silicon oxide, an insulator that is easily produced on Si
surfaces by processes of Thermal Oxidation or Local Oxidation (LOCOS), which
involve exposing the element to oxygen under the proper conditions that can be
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predicted by the Deal–Grove model. Silicon has become the most popular material
for both high power semiconductors and integrated circuits because it can withstand
the highest temperatures and greatest electrical activity without suffering avalanche
breakdown (an electron avalanche is created when heat produces free electrons and
holes, which in turn pass more current, which produces more heat). In addition, the
insulating oxide of silicon is not soluble in water, which gives it an advantage
over germanium (an element with similar properties which can also be used in
semiconductor devices) in certain fabrication techniques.
Monocrystalline silicon is expensive to produce, and is usually justified only in
production of integrated circuits, where tiny crystal imperfections can interfere with
tiny circuit paths. For other uses, other types of pure silicon may be employed. These
include hydrogenated amorphous silicon and upgraded metallurgical-grade silicon
(UMG-Si) used in the production of low-cost, large-area electronics in applications
such as liquid crystal displays and of large-area, low-cost, thin-film solar cells. Such
semiconductor grades of silicon are either slightly less pure or polycrystalline rather
than monocrystalline, and are produced in comparable quantities as the
monocrystalline silicon: 75,000 to 150,000 metric tons per year.
The market for the lesser grade is growing more quickly than for monocrystalline
silicon. By 2013, polycrystalline silicon production, used mostly in solar cells, was
projected to reach 200,000 metric tons per year, while monocrystalline
semiconductor grade silicon was expected to remain less than 50,000 tons/year.
