1.

0 SILICON CRYSTAL GROWTH-EPITAXY

The basic technique for silicon crystal growth from the melt, which is material in
liquid form, is the Czochralski technique. The Czochralski process is the most
common and most advanced method for semiconductor single crystal growth. The
process is named after Polish scientist Jan Czochralski, who discovered the method
in 1916 while investigating the crystallization rates of metals. A substantial
percentage (> 90%) of the silicon crystals for the semiconductor industry are
prepared by the Czochralski technique and virtually all the silicon used for
fabricating integrated circuits is prepared by this technique.
The starting material for silicon is a relatively pure form of sand (SiO 2) called
quartzite. This is placed in a furnace with various forms of carbon (coal, coke, and
wood chips). Although a number of reactions take place in the furnace, the overall
reaction is
SiO2 (solid) + SiC (soild) → Si (solid) + SiO (gas) + CO (gas) (1)
This process produces metallurgical-grade silicon, MGS with a purity of about 98%.
Next, the silicon is pulverized and treated with hydrogen chloride (HCl) to form
trichlorosilane (SiHCl3):
Si (solid) + 3HCl (gas) → SiHCl3 (gas) + H2 (gas) + heat (2)
The trichlorosilane is a liquid at room temperature (boiling point 32°C). Fractional
distillation of the liquid removes the unwanted impurities. The purified SiHCl3 is then
used in a hydrogen reduction reaction to prepare the electronic-grade silicon (EGS):
SiHCl3 (gas) + H2 (gas) → Si (solid) + 3HCl (gas) (3)
This reaction takes place in a reactor containing a resistance-heated silicon rod, that
serves as the nucleation point for the deposition of silicon. The EGS, a polycrystalline
material of high purity, is the raw material used to prepare device-quality, single-
crystal silicon [is the starting material for the preparation of single crystal silicon]. Pure EGS
generally has impurity concentrations in the parts-per-billion range.
1.2 THE CZOCHRALSKI TECHNIQUE
Czochralski growth (CZ process): The set up for crystal growth by this method is
shown in Fig. 1. The crystal is grown from EGS in molten state kept in a quartz lined
graphite crucible. The melt is heated to a temperature of 1690K which is slightly
greater than the melting point of silicon (1685K). The centre of the melt is at lowest
temperature. The crystal growth is started by dipping a seed of single crystal silicon
into the melt.
The seed is suspended over the crucible by a holder attached to a rotating arm. The
seed is Inserted into the melt by lowering the arm. As the bottom of the seed melts,
the direction of motion of the arm is reversed. During this operation, the crucible is
rotated to provide stirring and uniform heating of the melt. When the arm moves
upward the melt in contact with the seed solidifies to form crystalline silicon with
the structure of the seed, resulting in a larger crystal. The crystal growth stops when
the crucible is depleted of melt.

Fig. 1 Czochralski crystallization process

After the ingot has been grown, it must be sliced, polished, and etched prior to
device fabrication as shown in Fig. 2. The slicing operation is usually performed with
a diamond-coated stainless steel saw blade. During this process approximately 30%
of the ingot is lost as “saw dust.”

Figure 2 Silicon Ingot

Fig.3 A puller rod with seed crystal for growing single-crystal silicon by the Czochralski
method

The polishing and etching operations ensure that the faces of the wafer are parallel
and free from surface contamination.
1.2.1 DESCRIPTION

1. The pure material which is to be grown in the form of single crystal is taken in the
crucible.

2. The material is heated above the melting point using induction heater.

3. Thus melt is obtained in the non-reacting crucible. A small defect free single crystal,
called seed crystal is introduced into the melt.

4. The seed crystal is attached to a rod, which is rotated slowly.

Figure 4 Czochralski method process (License: Public domain)

5. The seed crystal is rotated and gradually pulled out of the melt.

6. A single crystal grows on the seed crystal.

7. The seed crystal acts as i) a nucleation centre ii) heat sink through which the latent
heat of solidification escapes.
 8. The temperature difference between the melt and the seed crystal establishes the
desired growth condition.

9. The seed is slowly withdrawn from the melt by pulling and rotating such that the
crystal diameter is gradually increased to the desired value.

10. The seed crystal is dipped into a melt held at a temperature slightly above the
melting point.

11. The shape of the crystal is initially in the form of thin neck and then the diameter
of the crystal is increased to the required size. This is known as necking procedure.

12. By using necking procedure and pulling mechanism, bulk single crystals can be
obtained by Czochralski method.

ADVANTAGES

1. It produces large single crystal [thus, higher production rate]

2. It allows convenient chemical composition of crystal.
3. The dopant distribution in the crystal will be uniform.
4. It is fast and high controllable.
5. There is no direct contact between crucible walls and crystal which helps to
produce unstressed single crystal.
6. Saves cost and time.

LIMITATIONS

1. High vapour pressure of the materials can be used.

2. Possibility of liquid phase encapsulation occurs during solidification.
3. It may produce contamination of melt by the crucible.
4. Presence of impurities oxygen, carbon etc.
5. Possible segregation of constituents.
NOTE: As a crystal is pulled from the melt, the doping concentration
incorporated into the crystal (solid) is usually different from the doping
concentration of the melt (liquid) at the interface. The ratio of these two
concentrations is defined as the equilibrium segregation coefficient k0:
more
To make p-type or n-type silicon, a precisely controlled quantity of Boron or
Phosphorus is added to the melt. The concentration of impurity in the melt (liquid
state) is usually less than that in the grown crystal (solid state). The ratio of
concentration of impurities in the solid state (Cs) to the impurity in liquid state (Cl)
at equilibrium is known as segregation constant (ko)-
𝐶𝑠
𝑘0 =
𝐶𝑙
The maximum concentration of impurities that can be introduced into a semi-
conductor at a given temperature T is known as solid solubility. Solid solubility
increases with increase in temperature.

Table 2.1 summarizes the segregation coefficients of common impurities in silicon

*The segregation coefficient of oxygen is somewhat controversial. Values closer to

1.0 are sometimes quoted. Note that most values are below 1, which means that
during growth the dopants are rejected into the melt. Consequently, the melt
becomes progressively enriched with the dopant as the crystal grows.

The values in the table show why B would be better than Al for intentionally doping
bulk Si grown by the Czochralski method.
First, one would need 400 times more Al in the melt than B to achieve the same bulk
doping level in the boule.
Second, as the melt is used up in forming the solid the number of Al atoms in liquid
is relatively unchanged while the Si is consumed.
Thus, the Al concentration in both the liquid and solid rises increasingly rapidly as
the crystal grows. By contrast, because B is removed from the liquid at nearly the
same rate as Si, the concentration in the melt and hence in the solid remains nearly
constant.

The distribution of an impurity in the grown crystal can be described mathematically

by the normal freezing relation:
Cs = kC0 (1 − X)k−1 (2).

where X is the fraction of the melt that has solidified, Co is the initial melt concentration,
Cs is the solid concentration, and ko is the segregation coefficient.
The oxygen content in crystal grown by CZ process is high (5 x 1017 to 2 x 1018 cm-3).
This is due to the reaction of silicon in the melt with the quartz lining of crucible. This
oxygen may become electrically active during subsequent process. Czochralski
process is not used when material with resistivity more than 10 cm is required.
A boule (crystal) is a single-crystal ingot produced by synthetic means
(crystallization).

EXAMPLE 1
A silicon ingot that should contain 1016 boron atoms/cm3 is to be grown by the
Czochralski technique. What concentration of boron atoms should be in the melt to
give the required concentration in the ingot? If the initial load of silicon in the
crucible is 60kg, how many grams of boron (atomic weight 10.8) should be added?
The density of molten silicon is 2.53 g /cm3.
SOLUTION
Table 2.1 shows the segregation coefficient 𝑘0 for boron is 0.8. We assume that
𝐶𝑠 = 𝑘𝑜 𝐶𝑙 throughout the growth. Thus, the initial concentration of boron in the melt
will be

EXAMPLE 2
A silicon crystal is to be grown by Czochralski method, and it is desired that the ingot
contains 1016 phosphorous atoms/cm3 and density of Silicon is 2.33g/cm3.
a. What concentration of phosphorus atoms should the melt contain to give this
nimpurity concentration in the crystal during the initial growth? For phosphorus in
Silicon, 𝑘0 = 0.35.
b. If the initial load of Si in the crucible is 5kg, how many grams of phosphorus should
be added? [Atomic weight of phosphorus is 31, Avogadro number = 6.023 x 1023
atoms/mole]
solution
𝐶𝑠
𝑘0 =
𝐶𝑙
But 𝐶𝑠 = 1016 𝑎𝑡𝑜𝑚𝑠/𝑐𝑚3 , 𝑘0 = 0.35
𝐶𝑠 1016
𝐶𝑙 = = = 2.86 × 1016 𝑎𝑡𝑜𝑚𝑠/𝑐𝑚3
𝑘0 0.35
OR Cl = 2.86 × 1016 cm−3
Weight of silicon = 5kg = 5 × 103 g
𝑤𝑒𝑖𝑔ℎ𝑡 5000
Volume of Silicon = 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 = = 2.146 × 103 cm3
2.33
Neglecting the change in volume on adding phosphorus atoms;

Number of phosphorus atoms = Number of phosphorus atoms/cm3 × Volume of

Silicon
= 2.86 × 1016 × 2.146 × 103
Number of phosphorus atoms = 6.138 × 1019
weight/mole
Weight of phosphorus = × total number of atoms
atoms/mole

31
= × 6.138 × 1019
6.02 × 1023
= 0.00316
Weight of phosphorus = 3.16 × 10−3 g
Since the P concentration in the growing crystal is only about one-third of that in
the melt, Si is used up more rapidly than P in the growth. Thus, the melt becomes
richer in P as the growth proceeds, and the crystal is doped more heavily in the
latter stages of growth. This assumes that 𝑘0 is not varied; a more uniformly doped
ingot can be growth by varying the pull rate (and therefore 𝑘0 ) appropriately. Modern
Czochralski growth system use computer controls to vary the temperature, pull rate,
and other parameters to achieve fairly uniformly doped ingots.
EXAMPLE 3
A silicon crystal is to be grown by Czochralski process and is to contain 5 x 10 15 boron
atoms/cm3. Given k0 = 0.8 for boron in Si, atomic weight of boron = 10.81 g/mole,
density of silicon = 2.33 g/cm3. Avogadro number = 6.023 x 1023 atoms/mole.
a. Determine the initial concentration of boron atoms in the melt to produce the
required density.
b. If initial amount of silicon in the crucible is 50 kg, how many grams of boron
should be added.
 1
1 ppm = 1 part per million = 106

NOTE: It is often desirable to express the impurity content in ppb, which really
means atoms of impurity /billion silicon atoms and not parts by weight or parts by
volume.
Thus, 1 ppb = 5 X 1022 atoms/cm3.

EXERCISE 1
1. A Czochralski crystal is grown with an initial antimony concentration in the melt
of 1 × 1016 cm3 . After 70% of the melt has been used up in pulling the crystal, pure
silicon is added to return the melt to its original volume. Growth is then resumed.
What will the antimony concentration be in the crystal after 30% of the new melt
has been consumed by growth? Assume 𝑘0 = 0.02 for antimony.
2. A single crystal boule of silicon is grown by Czochralski process to an average
diameter of 320 mm with length = 1500 mm. The seed and tang ends are removed,
which reduces the length to 1150 mm. The diameter is ground to 300 mm. A 90-mm
wide flat is ground on the surface which extends from one end to the other. The
ingot is then sliced into wafers of thickness = 0.40 mm, using an abrasive saw blade
whose thickness = 0.33 mm. assume that the seed and tang portions cut off the ends
of the starting boule were conical in shape;
Determine:
a. The original volume of the boule in mm3.
b. How many wafers are cut from it, assuming the entire 1150 mm length can be
sliced; and
c. The volumetric proportion of silicon in the starting boule that is wasted during
processing.
3. Describe the main difference between the Czochralski method of crystal growth
and epitaxial growth. Which of these approaches can be applied to grow
multilayered crystalline structures?
(b) Explain the role of the lattice mismatch for the regimes of self-organizing growth
of nanostructures. For which of the following heterostructures is the formation of
nano-islands possible: GaAs/AIAs (the lattice constants of GaAs and AIAs are a, 55.64
and 5.66 Å, respectively), GaAs/InAs (a, = 5.64 and 6.06 Å) and Si/Ge (a. = 5.43 and
5.65 Å).
(c). Why do semiconductor devices need epitaxial layer?
(d). What is the purpose of epitaxial growth?
EXERCISE 2

EXERCISE 3
a) A Czochralski grown crystal is doped with boron. Why is the boron
concentration larger at the tail end of the crystal than at the seed end?
b) Why are single crystals of silicon generally grown at a temperature just
below the melting temperature?
c) Why is the impurity concentration larger in the centre of the wafer than at its
perimeter?
EXERCISE 4
A silicon wafer 1-mm thick having a diameter of 200 mm contains 5.41 mg of boron
uniformly distributed in substitutional sites. Find the
(a) boron concentration in atoms/cm3 and,
(b) average distance between boron atoms.
EXERCISE 6
a. How do you grow silicon ingots?
b. Which method is most suitable for silicon crystal growth in silicon wafer
preparation?
c. What is melt growth?

EXERCISES 7
Why are single crystals of silicon generally grown at a temperature just below the
melting temperature?
What are the seasons for requiring single crystals in the semi-conductor industry?
2.0 EPITAXIAL FILM GROWTH
Epitaxy or epitaxial growth refers to the growth of a single crystal film on top of a
crystalline substrate. It is a phenomenon in which a secondary phase nucleates and
grows on a crystalline substrate that has a similar atomic structure and influences
the orientation of the overgrowth.
Epitaxy is a Greek word composed of two parts, namely epi meaning “above” and
taxis which means “an ordered manner” respectively. Thus, epitaxy refers to
ordered arrangement on some materials; oriented growth of epilayers on a single
crystalline substrate, so that the two atomic planes in contact have planar unit cells
that match each other. Epitaxy is a term applied to the process of growing a
monocrystalline film on a substrate.
Epitaxial growth techniques have largely superseded the bulk growth for electronic
circuit fabrication because the devices to be fabricated needs only few micron
dimensions. The lattice structure of the initial crystal directs the growth of the
deposited crystal. Hence, is the process of depositing a thin layer/coating (0.5 to 20
microns) of single-crystal material over a single-crystal substrate, usually
through chemical vapor deposition (CVD). The CVD process usually involves the
hydrogen reduction of high purity silicon tetrachloride (SiCl4), trichlorosilane
(SiHCl3), or dichlorosilane (SiHCl2) to form solid silicon.
Epitaxy is commonly done through chemical vapor deposition, which is basically a
process that forms a non-volatile solid film on a substrate from reactions of the
appropriate chemical vapours.
There are four major chemical sources of silicon for commercial epitaxial deposition:
1) silicon tetrachloride (SiCl4);
2) trichlorosilane (SiHCl3);
3) dichlorosilane (SiH2Cl2); and
4) silane (SiH4).
The growth rate of an epitaxial layer depends on several factors, which include:
1) the chemical sources;
2) the deposition temperature; and
3) the mole fraction of reactants.
The goal of epitaxial growth is to create a layer of material with uniform and
controlled thickness, composition, and electrical, chemical, and optical properties
for fabrication of a device or an integrated circuit.
Modern devices require very sophisticated structure, which are composed of thin
layers with various compositions. Quality, performance and lifetime of these devices
are determined by the purity, structural perfection and homogeneity of the epitaxial
layers. Epitaxial crystal growth resulting in epitaxial layer perfection, surface
flatness and interface abruptness depend on number of factors like: the epitaxial
layer growth method, the interfacial energy between substrate and epitaxial film,
as well as the growth parameters – thermodynamic driving force, substrate and layer
misfit, substrate misorientation, growth temperature, etc.
The use of epitaxial growth, therefore reduces the growth time, wafering cost and
eliminates the wastages caused during growth, cutting, polishing etc. The major
advantage of the epitaxy is the uniformity in the composition, controlled growth
parameters and better understanding of the growth itself.
Advantages of epitaxial growth include careful compositional control and reduced
concentrations of unwanted defects and impurities.
The growth of an epitaxial layer over the substrate offers some advantages,
including improvements in the performance of bipolar devices, prevention of latch-
up in CMOS circuits, and improved doping control.
ADVANTAGES OF EPITAXY GROWTH
• Better structural & Electrical properties
• Growth is carried out at low temperature- decrease in concentration of both
chemical and crystalline defects. Also, the Melt is subjected to less chemical
contamination from surrounding
• The ability to control material thickness and carrier concentration
• Possibility to grow p-n junction & other multilayer structures
• Superior electrical properties due to the lower defect density
The disadvantages of epitaxy include higher cost of wafer fabrication, additional
process complexities, and problems associated with defects in the epi layer.
One of the main commercial applications of epitaxial growth is in the semiconductor
industry, where semiconductor films are grown epitaxially on semiconductor
substrate wafers.
APPLICATIONS OF EPITAXIAL LAYERS
The applications of epitaxial layers are in various segments:
• Discrete and Power Devices
• Epitaxial for MOS Devices
• Integrated Circuits
• Epitaxy is also being used in CMOS VLSI circuitry.
• Epitaxial shapes are also used in unipolar devices such as junction field-effect
transistors (JFETs), VMOS, and DRAM technology.
2.1 TYPES OF EPITAXIAL GROWTH
2.1.1 HOMOEPITAXY
Homoepitaxy is a type 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 often used to grow a film which is more pure than the substrate and to fabricate
layers having different doping levels (e.g., doped Si on Si wafer substrate).
Homoepitaxy is generally carried out in a quartz chamber. A susceptor is placed
inside the reaction chamber. It performs two functions. It provides physical support
to the Si wafers. Secondly it provides uniform thermal environment. The process of
epitaxial growth is carried out at a very high temperature.

Figure 1. (a) Schematic of bulk lattice parameters, or atomic spacings, of the film and
substrate materials if they were not constrained in any way. (b) Typical strain in a
film, where the entire film is constrained by the substrate, which is much thicker than
the film. (c) An unusual case where all of the strain is at the interface, for example
when mechanically soft layers are used for compliance at the interface. d) A relaxed
film where dislocations form between the film and substrate (below the arrows
shown) to minimize the strain in the film.
2.1.2 HETEROEPITAXY
Heteroepitaxy is a type 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(SOS) [In SOS, Si Layer is deposited on Sapphire substrate under controlled
conditions] , gallium nitride (GaN) on sapphire, aluminium gallium indium
phosphide (AlGaInP) on gallium arsenide (GaAs) or diamond or iridium,
and graphene on hexagonal boron nitride (hBN).
Epitaxial growth requires some degree of mobility of the atoms and nuclei on the
surface. An “epitaxial temperature” necessary for epitaxial growth in specific
systems and under specific deposition conditions is sometimes specified.
Heteroepitaxy occurs when a film of different composition and/or crystalline films
grown on a substrate. In this case, the amount of strain in the film is determined by
the lattice mismatch Ԑ:
𝑎𝑓 − 𝑎𝑠
𝜀=
𝑎𝑓

𝜀 = (+) means the film is in baxial tension.

𝜀 = (−) means the film is in baxial compression.
Where 𝑎𝑓 and 𝑎𝑠 are the lattice constants of the film and the substrate. The film and
substrate could have similar lattice spacings but also have very different thermal
expansion coefficients. If a film is then grown at a high temperature, then it can
experience large strains upon cooling to room temperature. In reality, 𝜀 < 9% is
necessary for obtaining epitaxy. If 𝜀 is larger than that, the film experiences a
volumetric strain that builds with each layer until a critical thickness. With increased
thickness the elastic strain in the film is relieved by the formation of dislocations
which can become scattering centres that damage the quality of the structure.
Heteroepitaxy is commonly used to create so-called bandgap systems thanks to the
additional energy caused by de deformation. A very popular system with a great
potential for microelectronic applications is that of Si–Ge.

2.2 TECHNIQUES OF SILICON EPITAXY

Some of the silicon epitaxy techniques are-
2.2.1 Liquid Phase Epitaxy:
Liquid phase epitaxy means the growth of thin films from metallic solution on an
oriented crystalline substrate
The solvent element can either be a constituent of the growing solid e.g. In or Ga, or
it can be some other low melting metals like Sn, Bi or Pb, which is incorporated into
the solid only as a dopant. The solvent contains a small quantity of solute e.g. As in
Ga for epitaxial growth of GaAs layers which is transported towards the liquid-solid
interface. The process is best controlled if this transport occurs only by diffusion,
i.e., the driving force in the solution is a concentration gradient of the solute. The
growth boats are commonly designed such that essentially, only diffusion
perpendicular to the interface occurs; convection and surface tension related
transport are suppressed. The temperature gradient is minimized by utilizing larger
dimension of the substrate compared to the height and radius of curvature.
Applying these constraints, the LPE process can be treated as a one-dimensional
diffusion process in which the growth rate is found to be diffusion limited.
The solution technique is used in liquid-phase epitaxy (LPE) to grow crystals on a
substrate. The substrate is immersed in a saturated quantity of solute solution.
Many crystals used in modern electronics and optoelectronic devices, such as
gallium arsenide, are grown using this method.
The liquid phase epitaxial (LPE) growth apparatus simply allows a growth solution of
the desired composition to be placed in contact with the substrate for a certain time
under controlled temperature conditions. In this technique, supersaturation necessary
for deposition is achieved by reducing the temperature. The relationship between the
temperature and solubility as predicted by the phase diagram has to be utilized in
understanding the growth process. Besides thermodynamic consideration, there are
other factors such as diffusion of constituents in the solution, nucleation and the
mechanism of growth at the surface and convection as the result of temperature and
compositional gradients that affect the LPE process.

Figure 2.1: Schematic diagram of LPE tipping growth apparatus

There are three principal LPE growth techniques: tipping, dipping and sliding. In the
tipping technique, the substrate is held tightly at the upper end of a graphite boat and
the growth solution is placed at the other end. Initially the substrate wafer is well clear
of the solution and the furnace is heated to form solution. The solution is brought into
contact with the substrate by tipping the substrate. The furnace is then slowly cooled
and an epitaxial layer is grown on the substrate. The solution remains in contact with
the substrate for the defined temperature interval and growth is terminated by tipping
the furnace back to its original position. The solution remaining on the film surface is
removed by wiping and dissolving in a suitable solvent. The original tipping furnace is
shown in Figure 2.1.
Figure 2.2: LPE growth apparatus employing the dipping technique
The dipping technique uses a vertical furnace as shown in Figure 2.2. The solution is
contained in a graphite or alumina crucible at the lower end of the furnace. The
substrate fixed in a movable holder is initially positioned above the solution. At the
desired temperature, growth is initiated by immersing the substrate in the solution and
it is terminated by withdrawal of the substrate from the solution.

Figure 2.3: Horizontal slider LPE system

The apparatus used for the tipping and dipping techniques is very simple and easy to
operate. However, growth of multiple layers by these techniques would require
considerably more complex apparatus. The third LPE technique, the sliding technique,
uses a multibin graphite boat to grow multiple epitaxial layers. Figure 2.3 shows a LPE
system with sliding technique. The principal components of this apparatus are a massive
split graphite barrel with a graphite slider, a fused silica growth tube to provide a
protective atmosphere and a horizontal resistance furnace. The graphite barrel has the
desired number of solution chambers depending on the number of layers to be grown,
and the slider has two slots for the precursor seed substrate and the growth substrate.
The substrate is brought into contact with the solutions by motion of the barrel over
the slider. This operation can easily be automated. The fused silica tube is usually within
a heat pipe thermal liner in the furnace to ensure uniform temperature. Alternatively, a
multizone furnace without a heat pipe can also be used. Growth is usually carried out
in an atmosphere of hydrogen.
[The major advantage of the LPE is that the growth temperature can be well below
the melting point of the compound semiconductor which is being decomposed.
Furthermore, equipment is simple and inexpensive, also non-hazardous.
Key problem in the production of the epilayer is that the composition of relatively
small volumes of each melt will rapidly change as crystal growth proceeds. LPE is
too simple to grow more complicated nanostructures, because of the difficult
thickness and composition control, etc.]
2.2.2 Molecular Beam Epitaxy (MBE):
Molecular beam epitaxy is a process of depositing epitaxial thin films from molecular
or atomic beams on a heated substrate under ultra-high vacuum (UHV) conditions.
Figure 2.4 shows a schematic diagram of a typical MBE system. The beams are
thermally generated in Knudsen-type effusion cells which contain the constituent
elements or compounds of the desired epitaxial films. The temperature of the cells
is accurately controlled to give the thermal beams of appropriate intensity. The
beam fluxes emerging from these non-equilibrium effusion cells are generally
determined experimentally in most cases using movable nude ionization gauge
placed in the substrate position. The cells are made from non-reactive, refractory
materials which can withstand high temperatures and they do not contribute to the
molecular beams. Pyrolytic Boron Nitride (PBN) or high purity graphite are used as
the cell materials. The cell consists of an inner crucible and an outside tube which is
wound with Ta or Mo wires for resistive heating. A chemically stable W-Re
thermocouple facilitates precise control of the cell temperature which is very
essential for achieving constant growth rates since small temperature fluctuations
of the order of ±1℃ can result in ±2 to 4% fluctuations in molecular beam intensity.
The various cells are all placed and angled in such a way that their beams converge
on the substrate for epitaxial growth. Individual shutters provided for each cell and
the cell temperature can be computer controlled to achieve high reproducibility and
little human interventions. The cells are individually surrounded by a liquid nitrogen
shroud to prevent cross heating and cross contamination.

Figure 2.4: Schematic of MBE system

The MBE technique has a number of advantages over other techniques. The most
important aspect of MBE is the deposition rate (typically less than 3,000 nm per
hour) that allows the films to grow epitaxial. These deposition rates require
proportionally better vacuum to achieve the same impurity levels as other
deposition techniques. A particular advantage is that it permits growth of crystalline
layers at temperatures where solid- state diffusion is negligible. Since chemical
decomposition is not required for growth, deposition species need require only
enough energy to migrate along the substrate surface to crystalline bonding site.
The impurity dopant incorporation during molecular beam epitaxial growth is
possible by having an additional source of the dopant. As a result, MBE has rapidly
established itself as a versatile technique for growing elemental and compound
semiconductor films. Thus, using MBE, it is possible to produce multilayered
structures including superlattices with layer thickness as low as 10A0 for DH lasers
and wave-guide applications.
However, there are few limitations in the epitaxial growth of compound
semiconductors by MBE technique. The ultra high vacuum apparatus is very
expensive. Frequent shutdowns are required to replenish the source materials and
opening the UHV apparatus. A major problem is the difficulty in growing phosphorus
containing materials. Phosphorous is found to be bounce around the system
ultimately collected in vacuum pumps.
During the MBE process, growth can be monitored in situ by a number of methods:
RHEED, low energy electron diffraction (LEED); auger electron spectroscopy (AES),
modulated beam mass spectrometry (MBMS).

[It is a non-CVD technique of epitaxial growth. It includes evaporation instead of

deposition. It is suitable for Silicon devices. In molecular beam epitaxy, the Silicon
along with the dopants is evaporated and is transported at a very high velocity to
the substrate. The process is carried out in ultra-high vacuum. The substrates are
kept at a low temperature. As a result, condensation takes place and the Si and
dopants condense on substrates. MBE is generally carried out under a vacuum of
10-8 or 10-10 Torr. And in a temperature range of 500 0C to 9000C.]

Advantages of MBE
I. MBE involves only physical evaporation but no chemical reactions.
II. It is carried out at low temperature, so it does not suffer from out diffusion
and auto doping.
III. Doping can be precisely controlled and different complicated doping profiles
can be obtained.
IV. The growth rate can be precisely controlled.
V. It is suitable for VLSI as thin epitaxial layers can be grown.
VI. There are no boundary layer problems. Growth rate is equal at all the places
in the chamber.
VII. Linear doping profiles, as needed in varactor diodes, can be obtained.
Disadvantages of MBE
I. MBE has low throughput.
II. It is an expensive technique
2.2.3 VAPOUR PHASE EPITAXY
The principles of VPE can be described in the following steps:
i. Transport of reactants to the substrate region
ii. Transfer of reactants to substrate surface
iii. Adsorption of reactants on substrate
iv. Surface processes such as reaction and kinetics
v. Desorption of products
vi. Transfer of products to main gas stream
vii. Exhausting of gases away from reaction chamber
The steps ii and vi involve transfer of reactants to and fro from the crystal surface
and are called mass transport process. The steps iii, iv and v represent chemical
reactions on the crystal surface.
Vapour Phase Epitaxy (VPE) is one of the commonly used techniques for the growth
of III-V compound semiconductors. In this technique, growth is carried out by
vapourizing the source material for III-V compounds; inorganic or organic materials
which react with the other materials to form the compound semiconductors on the
substrate. Growth is controlled by the partial pressures of the each of the
components of the source materials. Two different forms of the vapour phase
epitaxial growth are:
• chloride vapour phase epitaxy
• hydride vapour phase epitaxy
The main practical difference between the two system is just the input gas supply.
The two processes can be outlined in the table below:
The chloride VPE involves group V transport using trichloride (e.g., AsCl3) and group
III transport by the formation of chloride (e.g., GaCl). Crystal growth is carried out in
a hot walled reactor and the chemical reactions are reversible making it possible to
etch as well as grow. Inherent advantages of trichloride VPE over other vapour phase
growth methods arise from the fact that AsCl3 and PCl3 can be distilled into very
pure liquids.
AS4 + 4GaCl + 2H2 4GaAs + 4HCl (3.1)
Hydride VPE is an epitaxial growth technique often employed to produce
semiconductors such as GaN, GaAs, InP and their related compounds, in which
hydrogen chloride is reacted at elevated temperature with the group-III metals to
produce gaseous metal chlorides, which then react with ammonia to produce the
group-III nitrides. Both the source reactions and the deposition reactions are done
inside a hot walled quartz reactor. The reactions occur under near equilibrium
conditions, and since they are reversible, controlled in- situ etching is possible.
The perfection of the thin film depends crucially on the mode of growth of the deposit.
Three such modes are usually identified:
• Frank-van der Merwe (one perfect monolayer at a time);
• Volmer-Weber (island growth), and a combination of the two called
• Stranski-Krastanov (one or more perfect layers followed by island growth).
The three common growth modes have the following characteristics:
• Frank-van der Merwe: each layer of deposited atoms is completed before the
next layer starts to form. The surface at any instant will be flat or will contain a
few monolayer steps. [Layer-by-layer growth, wetting]
𝛾𝑠𝑢𝑏𝑠𝑡𝑟𝑎𝑡𝑒 ≥ 𝛾𝑓𝑖𝑙𝑚 + 𝛾𝑖𝑛𝑡𝑒𝑟𝑓𝑎𝑐𝑒

𝛾𝑠𝑢𝑏𝑠𝑡𝑟𝑎𝑡𝑒 = surface energy of substrate

𝛾𝑓𝑖𝑙𝑚 = surface energy of film

𝛾𝑖𝑛𝑡𝑒𝑟𝑓𝑎𝑐𝑒 = interface energy between film and substrate

Growing layer reduces surface energy, leading to complete wetting of the surface, and
thus smooth, layer-by-layer growth.
• Volmer-Weber (island growth): each deposited atom attaches to an island (or
incipient particle); islands grow appreciably before joining up to cover the
substrate completely. The surface at any instant will not be flat, and the
substrate may not be entirely covered. [island growth, non-wetting]
Growing layer increases the interface energy and its own surface energy, leading to
layer “balls up” on the substrate.

• Stranski-Krastanov: initially the deposited atoms form one or more perfect

layers but this is followed by island growth. The surface is therefore initially flat
but develops to become less flat. [Layer-by-layer followed by island growth]
Initially, 𝛾𝑠𝑢𝑏𝑠𝑡𝑟𝑎𝑡𝑒 ≥ 𝛾𝑓𝑖𝑙𝑚 + 𝛾𝑖𝑛𝑡𝑒𝑟𝑓𝑎𝑐𝑒

Finally, 𝛾𝑠𝑢𝑏𝑠𝑡𝑟𝑎𝑡𝑒 < 𝛾𝑓𝑖𝑙𝑚 + 𝛾𝑖𝑛𝑡𝑒𝑟𝑓𝑎𝑐𝑒 (due to strain effect)

Typically, first layer wets surface but subsequent layers do not. Change in balance of
forces is often due to strain in the growing layer, typically due to a mismatch in lattice
constants between the substrate and the deposited layer.

EXERCISES
1. Find the average molecular velocity of air at 300 K (the molecular weight of air is
29).
2. The distance between source and wafer in a deposition chamber is 15 cm.
Estimate the pressure at which this distance becomes 10% of the mean free path of
source molecules.
3. Explain the role of the lattice mismatch for the regimes of self-organising growth
of nanostructures. For which of the following heterostructures is the formation of
nano-islands possible:
GaAs/AlAs (the lattice constants of GaAs and AlAs are (𝑎0 =
̇ ̇
5.64 and 5.66𝐴,respectively), GaAs/InAs (𝑎0 = 5.64 and 6.06𝐴) and Si/Ge (𝑎0 =
5.43 and 5.65𝐴̇)
4. Describe the main difference between the Czochralski method of crystal growth
and epitaxial growth. Which of these approaches can be applied to grow
multilayered crystalline structures?
5. What Is the Purpose of the Epitaxial Layer?
b. What Are the Key Parameters to Be Controlled in Epitaxial Growth?
c. Why Is Epitaxy Required in semi-conductor industry?