HISTORY OF SILICON DIODE

Silicon was discovered by Jns Jacob Berzelius, a Swedish chemist, in 1824 by heating chips
of potassium in a silica container and then carefully washing away the residual by-products.
Silicon is the seventh most abundant element in the universe and the second most abundant
element in the earth's crust. Today, silicon is produced by heating sand (SiO2) with carbon to
temperatures approaching 2200C.
Two allotropes of silicon exist at room temperature: amorphous and crystalline. Amorphous
appears as a brown powder while crystalline silicon has a metallic luster and a greyish colour.
Single crystals of crystalline silicon can be grown with a process known as the Czochralski
process. These crystals, when doped with elements such as boron,
gallium, germanium, phosphorus or arsenic, are used in the manufacture of solid-state electronic
devices, such as transistors, solar cells, rectifiers and microchips.
Silicon dioxide (SiO2), silicon's most common compound, is the most abundant compound in the
earth's crust. It commonly takes the form of ordinary sand, but also exists as quartz, rock crystal,
amethyst, agate, flint, jasper and opal. Silicon dioxide is extensively used in the manufacture of
glass and bricks. Silica gel, a colloidal form of silicon dioxide, easily absorbs moisture and is
used as a desiccant.
Silicon forms other useful compounds. Silicon carbide (SiC) is nearly as hard as diamond and is
used as an abrasive. Sodium silicate (Na2SiO3), also known as water glass, is used in the
production of soaps, adhesives and as an egg preservative. Silicon tetrachloride (SiCl4) is used to
create smoke screens. Silicon is also an important ingredient in silicone, a class of material that is
used for such things as lubricants, polishing agents, electrical insulators and medical implants.

HOW SILICON DIODE IS MADE

Silicon metal is made from the reaction of silica (silicon dioxide, SiO2) and carbon materials like
coke, coal and wood chips. Silica is typically received in the form of metallurgical grade gravel.
This gravel is 99.5% silica, and is 3 x 1 or 6 x 1 in (8 x 3 cm or 15 x 3 cm) in size. The coal is
usually of low ash content (1-3% to minimize calcium, aluminium, and iron impurities), contains
around 60% carbon, and is sized to match that of the gravel. Wood chips are usually hardwood of
1/2 x 1/8 inch size (1 x. 3 cm size). All materials are received as specified by the manufacturer.
The basic process heats silica and coke in a submerged electric arc furnace to high temperatures.
High temperatures are required to produce a reaction where the oxygen is removed, leaving
behind silicon. This is known as a reduction process. In this process, metal carbides usually form
first at the lower temperatures. As silicon is formed, it displaces the carbon. Refining processes
are used to improve purity.

HISTORY OF GERMANUIM

First proposed to exist by Dmitri Mendeleyev in 1871 based on gaps in his newly created
Periodic Table of Elements, germanium was discovered by the German chemist Clemens
Winkler in the mineral argyrodite (Ag8GeS6) in 1886. Today, germanium is primarily obtained
from the smelting of zinc ores and from the by-products of burning certain types of coal.
The largest use of germanium is in the semiconductor industry. When doped with small amounts
of arsenic, gallium, indium, antimony or phosphorus, germanium is used to make transistors for
use in electronic devices. Germanium is also used to create alloys and as a phosphor in
fluorescent lamps. Both germanium and germanium oxide (GeO) are transparent to infrared
radiation and are used in infrared optical instruments and infrared detectors. Some germanium
compounds seem to be effective in killing some types of bacteria and are currently being studied
for use in chemotherapy.

HOW

Year

Cost
($/kg)[59]

1999

1,400

2000

1,250

2001

890

2002

620

2003

380

2004

600

2005

660

2006

880

2007

1,240

2008

1,490

2009

950

GERMANUIM IS MADE

About 118 tonnes of germanium was produced in 2011 worldwide, mostly in China (80
t), Russia (5 t) and United States (3 t). Germanium is recovered as a by-product

from sphalerite zinc ores where it is concentrated in amounts of up to 0.3%, especially from
sediment-hosted, massive ZnPbCu(Ba) deposits and carbonate-hosted ZnPb deposits. A
recent study found that at least 10,000 t of extractable germanium is contained in known zinc
reserves, particularly those hosted by Mississippi-Valley type deposits, while at least 112,000 t is
contained in coal reserves. In 2007 35% of the demand was met by recycled germanium.
While it is produced mainly from sphalerite, it is also found in silver, lead,
and copper ores. Another source of germanium is fly ash of coal power plants which use coal
from some coal deposits with a large concentration of germanium. Russia and China used this as
a source for germanium. Russia's deposits are located in the far east of the country
on Sakhalin Island. The coal mines northeast of Vladivostokhave also been used as a germanium
source. The deposits in China are mainly located in the lignite mines near Lincang, Yunnan; coal
mines near Xilinhaote, Inner Mongolia are also used.
The ore concentrates are mostly sulfidic; they are converted to the oxides by heating under air, in
a process known as roasting:
GeS2 + 3 O2 GeO2 + 2 SO2
Part of the germanium ends up in the dust produced during this process, while the rest is
converted to germanates which are leached together with the zinc from the cinder by sulfuric
acid. After neutralization only the zinc stays in solution and the precipitate contains the
germanium and other metals. After reducing the amount of zinc in the precipitate by the Waelz
process, the residing Waelz oxide is leached a second time. The dioxide is obtained as precipitate
and converted with chlorine gas or hydrochloric acid to germanium tetrachloride, which has a
low boiling point and can be distilled off:
GeO2 + 4 HCl GeCl4 + 2 H2O
GeO2 + 2 Cl2 GeCl4 + O2
Germanium tetrachloride is either hydrolyzed to the oxide (GeO2) or purified by
fractional distillation and then hydrolyzed. The highly pure GeO2 is now suitable for the
production of germanium glass. The pure germanium oxide is reduced by the reaction with
hydrogen to obtain germanium suitable for the infrared optics or semiconductor industry:
GeO2 + 2 H2 Ge + 2 H2O
The germanium for steel production and other industrial processes is normally reduced using
carbon:
GeO2 + C Ge + CO2

HISTORY OF GALLIUM ARSENIDE

Gallium was discovered by Lecoq de Boisbaudran when he was studying Zinc in

1875AD
Lecoq did not discover it by accident. He had been searching for it for years and since he
knew about Dmitri Mendeleev's periodic trends, he had a hunch that it would be the next element
by zinc and might be found in zinc ore. He was correct and found in Gallium
Albert the Great was an Alchemist in 1250 AD and was the first to form almost pure
Arsenic. Many different people tried to experiment with it and come up with new ideas on what
technologies gallium arsenide could best be used for. However, the technologies of its time did
not work well with the compound. Many ideas were circulating on how best to used Gallium
arsenide technology. The many new ideas and scientists that were involved in developing
Gallium Arsenide technology has been muddled and lost through history. Because of the
complicated nature with the technologies that were developed with gallium arsenide, it is
difficult to pinpoint specific dates or scientists that discovered its uses. Now, it had has been
developed to serve many purposes. In 1907, the British discovered infrared emission from
Gallium Arsenide this was called electroluminescence

HOW GALLIUM ARSENIDE IS MADE

In the compound, gallium has a +3 oxidation state. Gallium arsenide single crystals can
be prepared by three industrial processes

The vertical gradient freeze (VGF) process (most GaAs wafers are produced using this
process).
Crystal growth using a horizontal zone furnace in the Bridgman-Stockbarger technique,
in which gallium and arsenic vapors react, and free molecules deposit on a seed crystal at the
cooler end of the furnace.
Liquid encapsulated Czochralski (LEC) growth is used for producing high-purity single
crystals that can exhibit semi-insulating characteristics.
Alternative methods for producing films of GaAs include:
VPE reaction of gaseous gallium metal and arsenic trichloride:
2 Ga + 2 AsCl3 2 GaAs + 3 Cl2
MOCVD reaction of trimethylgallium and arsine:
Ga (CH3)3 + AsH3 GaAs + 3 CH4
Molecular beam epitaxy (MBE) of gallium and arsenic:
4 Ga + As4 4 GaAs or 2 Ga + As2 2 GaAs
Oxidation of GaAs occurs in air and degrades performance of the semiconductor. The surface
can be passivated by depositing a cubic gallium (II) sulfide layer using a tert-butyl gallium
sulfide compound such as (BuGaS)7

COMPARISON BETWEEN SI, GE AND GAAS DIODES

So far in our discussion on diodes, Si was the semiconductor material chosen as the base
material. But what difference does it make if we use diodes whose base material is Germanium
or Gallium Arsenide? In this section we shall try to find the answer to this question by comparing
their characteristics and their response time.
The graph shown below compares the characteristics of Silicon, Germanium and Gallium
Arsenide diodes.

Si, Ge and GaAs diodes are compared based on the following points.

Forward characteristics

Reverse characteristics

Forward characteristics: (Refer to the graph shown above). It is quite clear from the graph that
the general shape of the curve for all three type of semiconductor diodes is same. However the
threshold voltage of all the three diodes is different. The threshold voltage for Ge, Si, and GaAs
diodes is 0.3, 0.7 and 1.2 V respectively. Thus if a Si diode is connected in a circuit in forward
bias configuration, the voltage drop across the diode would be 0.7 V (assuming correct operation
of diode). If Ge diode is used, then the voltage drop would be about 0.3 V and for GaAs diodes
the voltage drop would be about 1.2 V.
Reverse characteristics: (Refer to the graph shown above). The characteristics curve of Ge, Si
and GaAs diodes looks quite similar. However they are not same. The reverse saturation current
of GaAs is least as compared to Si and Ge. The reverse saturation current of Si is more than that
of Ge. Typical values of reverse saturation current are 1 pA, 10 pA and 1A for GaAs, Si and Ge
diodes respectively.
It is also clear from the above graph that the reverse breakdown voltage of all the three types of
diodes are also different. The reverse breakdown voltage of GaAs is highest while that of Ge is

lowest. Typical value of reverse breakdown voltage for Ge is less than 100 V, with maximum
around 400 V. The reverse breakdown voltage of Si and GaAs diodes lies between 50 V and 1
kV.

Reference:
http://galliumarsenide101.weebly.com/historical-background-of-gaas.html
http://education.jlab.org/itselemental/ele014.html
http://education.jlab.org/itselemental/ele032.html
https://en.wikipedia.org/wiki/Gallium_arsenide#Preparation_and_chemistry
http://www.madehow.com/Volume-6/Silicon.html
https://en.wikipedia.org/wiki/Germanium#Production
http://conceptselectronics.com/diodes/comparison-si-ge-gaas-diodes