Czochralski process

The Czochralski process is a method of crystal growth used to

obtain singlecrystals of semiconductors (e.g. silicon, germanium
and galliumarsenide),metals(e.g. palladium, platinum, silver, go
ld), salts and synthetic gemstones. The process is named after
Polish scientist Jan Czochralski,[1] who invented the method in
1915 while investigating the crystallization rates of metals.[2] He
made this discovery by accident, while studying the
crystallization rate of metals: instead of dipping his pen into his
inkwell, he dipped it in molten tin, and drew a tinfilament,
which later proved to be a single crystal.[3]
The most important application may be the growth of large
cylindrical ingots, or boules, of single crystal silicon used in the
electronics industry to make semiconductor
devices like integrated circuits. Other semiconductors, such as
gallium arsenide, can also be grown by this method, although
lower defect densities in this case can be obtained using variants
of the Bridgman-Stockbarger technique.
Application[edit]
Monocrystalline silicon (mono-Si) grown by the Czochralski
process is often referred to as monocrystalline Czochralski
silicon (Cz-Si). It is the basic material in the production
of integrated circuits used in computers, TVs, mobile phones
and all types of electronic equipment and semiconductor
devices.[4] Monocrystalline silicon is also used in large quantities
by the photovoltaic industry for the production
of conventional mono-Si solar cells. The almost perfect crystal
structure yields the highest light-to-electricity conversion
efficiency for silicon.
Production of Czochralski silicon[edit]

Crystal of Czochralski grown silicon.

High-purity, semiconductor-grade silicon (only a few parts per
million of impurities) is melted in a crucible at 1,425 °C
(2,597 °F; 1,698 K), usually made of quartz. Dopant impurity
atoms such as boron or phosphorus can be added to the molten
silicon in precise amounts to dope the silicon, thus changing it
into p-type or n-type silicon, with different electronic properties.
A precisely oriented rod-mounted seed crystal is dipped into the
molten silicon. The seed crystal's rod is slowly pulled upwards
and rotated simultaneously. By precisely controlling the
temperature gradients, rate of pulling and speed of rotation, it is
possible to extract a large, single-crystal, cylindrical ingot from
the melt. Occurrence of unwanted instabilities in the melt can be
avoided by investigating and visualizing the temperature and
velocity fields during the crystal growth process.[5] This process
is normally performed in an inert atmosphere, such as argon, in
an inert chamber, such as quartz.
Crystal sizes

Due to the efficiencies of common wafer specifications, the

semiconductor industry has used wafers with standardized
dimensions. In the early days, the boules were smaller, only a
few inches wide. With advanced technology, high-end device
manufacturers use 200 mm and 300 mm diameter wafers. The
width is controlled by precise control of the temperature, the
speeds of rotation and the speed the seed holder is withdrawn.
The crystal ingots from which these wafers are sliced can be up
to 2 metres in length, weighing several hundred kilograms.
Larger wafers allow improvements in manufacturing efficiency,
as more chips can be fabricated on each wafer, so there has been
a steady drive to increase silicon wafer sizes. The next step up,
450 mm, is currently scheduled for introduction in
2018.[6] Silicon wafers are typically about 0.2–0.75 mm thick,
and can be polished to great flatness for making integrated
circuits or textured for making solar cells.
The process begins when the chamber is heated to
approximately 1500 degrees Celsius, melting the silicon. When
the silicon is fully melted, a small seed crystal mounted on the
end of a rotating shaft is slowly lowered until it just dips below
the surface of the molten silicon. The shaft rotates
counterclockwise and the crucible rotates clockwise. The
rotating rod is then drawn upwards very slowly—about 25 mm
per hour when making a crystal of ruby[7]—allowing a roughly
cylindrical boule to be formed. The boule can be from one to
two metres, depending on the amount of silicon in the crucible.
The electrical characteristics of the silicon are controlled by
adding material like phosphorus or boron to the silicon before it
is melted. The added material is called dopant and the process is
called doping. This method is also used with semiconductor
materials other than silicon, such as gallium arsenide.
Incorporating impurities

When silicon is grown by the Czochralski method, the melt is

contained in a silica (quartz) crucible. During growth, the walls
of the crucible dissolve into the melt and Czochralski silicon
therefore contains oxygen at a typical concentration of 1018
cm−3
. Oxygen impurities can have beneficial or detrimental effects.
Carefully chosen annealing conditions can give rise to the
formation of oxygen precipitates. These have the effect of
trapping unwanted transition metal impurities in a process
known as gettering, improving the purity of surrounding silicon.
However, formation of oxygen precipitates at unintended
locations can also destroy electrical structures. Additionally,
oxygen impurities can improve the mechanical strength of
silicon wafers by immobilising any dislocations which may be
introduced during device processing. It was experimentally
shown in the 1990s that the high oxygen concentration is also
beneficial for the radiation hardness of silicon particle
detectorsused in harsh radiation environment (such
as CERN's LHC/HL-LHC projects).[8][9] Therefore, radiation
detectors made of Czochralski- and Magnetic Czochralski-
silicon are considered to be promising candidates for many
future high-energy physics experiments.[10][11] It has also been
shown that the presence of oxygen in silicon increases impurity
trapping during post-implantation annealing processes.[12]
However, oxygen impurities can react with boron in an
illuminated environment, such as that experienced by solar cells.
This results in the formation of an electrically active boron–
oxygen complex that detracts from cell performance. Module
output drops by approximately 3% during the first few hours of
light exposure.[13]

The Bridgman–Stockbarger technique is named after Harvard

physicist Percy Williams Bridgman (1882-1961) and MIT
physicist Donald C. Stockbarger (1895–1952). The technique
includes two similar but distinct methods primarily used for
growing boules (single crystal ingots), but which can be used for
solidifying polycrystalline ingots as well.
The methods involve heating polycrystalline material above its
melting point and slowly cooling it from one end of its
container, where a seed crystal is located. A single crystal of the
same crystallographic orientation as the seed material is grown
on the seed and is progressively formed along the length of the
container. The process can be carried out in a horizontal or
vertical orientation, and usually involves a rotating
crucible/ampoule to stir the melt.[1]
The Bridgman method is a popular way of producing
certain semiconductor crystals such as gallium arsenide, for
which the Czochralski process is more difficult. The process can
reliably produce single crystal ingots, but does not necessarily
result in uniform properties through the crystal.[1]
The difference between the Bridgman[2] technique and
Stockbarger[3] technique is subtle: While both methods utilize a
temperature gradient and a moving crucible, the Bridgman
technique utilizes the relatively uncontrolled gradient produced
at the exit of the furnace; the Stockbarger technique introduces a
baffle, or shelf, separating two coupled furnaces with
temperatures above and below the freezing point. Stockbarger's
modification of the Bridgman technique allows for better control
over the temperature gradient at the melt/crystal interface.
When seed crystals are not employed as described above,
polycrystalline ingots can be produced from a feedstock
consisting of rods, chunks, or any irregularly shaped pieces once
they are melted and allowed to re-solidify. The
resultant microstructure of the ingots so obtained are
characteristic of directionally solidified metals and alloys with
their aligned grains.
A variant of the technique known as the horizontal directional
solidification method or HDSM developed by Khachik
Bagdasarov starting in the 1960s in the Soviet Union uses a flat-
bottomed crucible with short sidewalls rather than an enclosed
ampoule, and has been used to grow various large oxide crystals
including Yb:YAG (a laser host crystal),[4] and sapphire crystals
45 cm wide and over 1 meter long.[5]
Epitaxy refers to the deposition of a crystalline overlayer on a
crystalline substrate.
The overlayer is called an epitaxial film or epitaxial layer. The
term epitaxy comes from the Greek roots epi (ἐπί), meaning
"above", and taxis(τάξις), meaning "an ordered manner". It can
be translated as "arranging upon". For most technological
applications, it is desired that the deposited material form a
crystalline overlayer that has one well-defined orientation with
respect to the substrate crystal structure (single-domain epitaxy).
Epitaxial films may be grown from gaseous or liquid precursors.
Because the substrate acts as a seed crystal, the deposited film
may lock into one or more crystallographic orientations with
respect to the substrate crystal. If the overlayer either forms a
random orientation with respect to the substrate or does not form
an ordered overlayer, it is termed non-epitaxial growth. If an
epitaxial film is deposited on a substrate of the same
composition, the process is called homoepitaxy; otherwise it is
called heteroepitaxy.
ypes[edit]
Homoepitaxy is a kind of epitaxy performed with only one
material, in which a crystalline film is grown on a substrate or
film of the same material. This technology is used to grow a film
which is more pure than the substrate and to fabricate layers
having different doping levels. In academic literature,
homoepitaxy is often abbreviated to "homoepi".
Heteroepitaxy is a kind of epitaxy performed with materials that
are different from each other. In heteroepitaxy, a crystalline film
grows on a crystalline substrate or film of a different material.
This technology is often used to grow crystalline films of
materials for which crystals cannot otherwise be obtained and to
fabricate integrated crystalline layers of different materials.
Examples include silicon on sapphire, gallium nitride (GaN)
on sapphire, aluminium gallium indium phosphide (AlGaInP)
on gallium arsenide (GaAs) or diamond
or iridium,[1] and graphene on hexagonal boron nitride.[2]
Heterotopotaxy is a process similar to heteroepitaxy except that
thin-film growth is not limited to two-dimensional growth; the
substrate is similar only in structure to the thin-film material.
Pendeo-epitaxy is a process in which the heteroepitaxial film is
growing vertically and laterally at the same time. In 2D crystal
heterostructure, graphenen nanoribbons embedded in hexagonal
boron nitride[3][4] are an example for pendeo-epitaxy. Epitaxy is
used in silicon-based manufacturing processes for bipolar
junction transistors (BJTs) and modern complementary metal–
oxide–semiconductors (CMOS), but it is particularly important
for compound semiconductors such as gallium arsenide.
Manufacturing issues include control of the amount and
uniformity of the deposition's resistivity and thickness, the
cleanliness and purity of the surface and the chamber
atmosphere, the prevention of the typically much more highly
doped substrate wafer's diffusion of dopant to the new layers,
imperfections of the growth process, and protecting the surfaces
during the manufacture and handling.
Applications[edit]
Epitaxy is used in nanotechnology and in semiconductor
fabrication. Indeed, epitaxy is the only affordable method of
high quality crystal growth for many semiconductor materials.
In surface science, epitaxy is used to create and
study monolayer and multilayer films of adsorbed organic
molecules on single crystalline surfaces. Adsorbed molecules
form ordered structures on atomically flat terraces of single
crystalline surfaces and can directly be observed via scanning
tunnelling microscopy.[5] In contrast, surface defects and their
geometry have significant influence on the adsorption of organic
molecules[6]
Methods[edit]
Epitaxial silicon is usually grown using vapor-phase epitaxy
(VPE), a modification of chemical vapor deposition. Molecular-
beam and liquid-phase epitaxy (MBE and LPE) are also used,
mainly for compound semiconductors. Solid-phase epitaxy is
used primarily for crystal-damage healing.
Vapor-phase[edit]
Silicon is most commonly deposited by doping with silicon
tetrachloride and hydrogen at approximately 1200 to 1250 °C:[7]
SiCl4(g) + 2H2(g) ↔ Si(s) + 4HCl(g)
 This reaction is reversible, and the growth rate depends
strongly upon the proportion of the two source gases. Growth
rates above 2 micrometres per minute produce polycrystalline
silicon, and negative growth rates (etching) may occur if too
much hydrogen chloride byproduct is present. (In fact,
hydrogen chloride may be added intentionally to etch the
wafer.) An additional etching reaction competes with the
deposition reaction:
SiCl4(g) + Si(s) ↔ 2SiCl2(g)
Silicon VPE may also use silane, dichlorosilane,
and trichlorosilane source gases. For instance, the silane
reaction occurs at 650 °C in this way:
SiH4 → Si + 2H2
This reaction does not inadvertently etch the wafer, and
takes place at lower temperatures than deposition from
silicon tetrachloride. However, it will form a
polycrystalline film unless tightly controlled, and it
allows oxidizing species that leak into the reactor to
contaminate the epitaxial layer with unwanted
compounds such as silicon dioxide.
VPE is sometimes classified by the chemistry of the
source gases, such as hydride VPE and metalorganic
VPE.
Liquid-phase[edit]
Liquid-phase epitaxy (LPE) is a method to grow semiconductor
crystal layers from the melt on solid substrates. This happens at
temperatures well below the melting point of the deposited
semiconductor. The semiconductor is dissolved in the melt of
another material. At conditions that are close to the equilibrium
between dissolution and deposition, the deposition of the
semiconductor crystal on the substrate is relatively fast and
uniform. The most used substrate is indium phosphide (InP).
Other substrates like glass or ceramic can be applied for special
applications. To facilitate nucleation, and to avoid tension in the
grown layer the thermal expansion coefficient of substrate and
grown layer should be similar.
Centrifugal liquid-phase epitaxy is used commercially to make
thin layers of silicon, germanium, and gallium
arsenide.[8][9] Centrifugally formed film growth is a process used
to form thin layers of materials by using a centrifuge. The
process has been used to create silicon for thin-film solar
cells[10][11] and far-infrared photodetectors.[12] Temperature and
centrifuge spin rate are used to control layer
growth.[9] Centrifugal LPE has the capability to create dopant
concentration gradients while the solution is held at constant
temperature.[13]
Solid-phase[edit]
Solid-phase epitaxy (SPE) is a transition between the amorphous
and crystalline phases of a material. It is usually done by first
depositing a film of amorphous material on a crystalline
substrate. The substrate is then heated to crystallize the film. The
single crystal substrate serves as a template for crystal growth.
The annealing step used to recrystallize or heal silicon layers
amorphized during ion implantation is also considered one type
of Solid Phase Epitaxy. The Impurity segregation and
redistribution at the growing crystal-amorphous layer interface
during this process is used to incorporate low-solubility dopants
in metals and Silicon.[14]
Molecular-beam epitaxy[edit]
Main article: Molecular-beam epitaxy
In molecular beam epitaxy (MBE), a source material is heated to
produce an evaporated beam of particles. These particles travel
through a very high vacuum (10−8 Pa; practically free space) to
the substrate, where they condense. MBE has lower throughput
than other forms of epitaxy. This technique is widely used for
growing periodic groups III, IV, and V semiconductor
crystals.[15][16]
Doping[edit]
An epitaxial layer can be doped during deposition by adding
impurities to the source gas, such as arsine, phosphine,
or diborane. The concentration of impurity in the gas phase
determines its concentration in the deposited film. As in
chemical vapor deposition (CVD), impurities change the
deposition rate. Additionally, the high temperatures at which
CVD is performed may allow dopants to diffuse into the
growing layer from other layers in the wafer ("out-diffusion").
Also, dopants in the source gas, liberated by evaporation or wet
etching of the surface, may diffuse into the epitaxial layer
("autodoping"). The dopant profiles of underlying layers change
as well, however not as significantly.
Minerals:
n mineralogy, epitaxy is the overgrowth of one mineral on
another in an orderly way, such that certain crystal directions of
the two minerals are aligned. This occurs when some planes in
the lattices of the overgrowth and the substrate have similar
spacings between atoms.[17]
If the crystals of both minerals are well formed so that the
directions of the crystallographic axes are clear then the epitaxic
relationship can be deduced just by a visual inspection.[17]
Sometimes many separate crystals form the overgrowth on a
single substrate, and then if there is epitaxy all the overgrowth
crystals will have a similar orientation. The reverse, however, is
not necessarily true. If the overgrowth crystals have a similar
orientation there is probably an epitaxic relationship, but it is not
certain.[17]
Some authors[18] consider that overgrowths of a second
generation of the same mineral species should also be
considered as epitaxy, and this is common terminology
for semiconductor scientists who induce epitaxic growth of a
film with a different doping level on a semiconductor substrate
of the same material. For naturally produced minerals, however,
the International Mineralogical Association (IMA) definition
requires that the two minerals be of different species.[19]
Another man-made application of epitaxy is the making of
artificial snow using silver iodide, which is possible
because hexagonal silver iodide and ice have similar cell
dimensions.[18]
Isomorphic minerals[edit]
Minerals that have the same structure (isomorphic minerals)
may have epitaxic relations. An example is albite NaAlSi
3O
8 on microclineKAlSi
3O
8. Both these minerals are triclinic, with space group 1, and with
similar unit cell parameters, a = 8.16 Å, b = 12.87 Å, c = 7.11 Å,
α = 93.45°, β = 116.4°, γ = 90.28° for albite and a = 8.5784 Å, b
= 12.96 Å, c = 7.2112 Å, α = 90.3°, β = 116.05°, γ = 89° for
microcline.
Polymorphic minerals
Minerals that have the same composition but different structures
(polymorphic minerals) may also have epitaxic relations.
Examples are pyrite and marcasite, both FeS2,
and sphalerite and wurtzite, both ZnS.[17]
Rutile on hematite
Some pairs of minerals that are not related structurally or
compositionally may also exhibit epitaxy. A common example
is rutile TiO2 on hematite Template:Fe.[17][20] Rutile
is tetragonal and hematite is trigonal, but there are directions of
similar spacing between the atoms in the (100) plane of rutile
(perpendicular to the a axis) and the (001) plane of hematite
(perpendicular to the c axis). In epitaxy these directions tend to
line up with each other, resulting in the axis of the rutile
overgrowth being parallel to the c axis of hematite, and the c
axis of rutile being parallel to one of the axes of hematite.[17]
Hematite on magnetite
Another example is hematite Fe3+
2O
2+
3 on magnetite Fe
Fe3+
2O
4. The magnetite structure is based on close-
packed oxygen anions stacked in an ABC-ABC sequence. In this
packing the close-packed layers are parallel to (111) (a plane
that symmetrically "cuts off" a corner of a cube). The hematite
structure is based on close-packed oxygen anions stacked in an
AB-AB sequence, which results in a crystal with hexagonal
symmetry.[21]
If the cations were small enough to fit into a truly close-packed
structure of oxygen anions then the spacing between the nearest
neighbour oxygen sites would be the same for both species. The
radius of the oxygen ion, however, is only 1.36 Å[22] and the Fe
cations are big enough to cause some variations. The Fe radii
vary from 0.49 Å to 0.92 Å,[23] depending on the charge (2+ or
3+) and the coordination number (4 or 8). Nevertheless, the O
spacings are similar for the two minerals hence hematite can
readily grow on the (111) faces of magnetite, with
hematite (001) parallel to magnetite (111).[21]