Assignment on Microelectronics and

Semiconductor Technology

DEPARTMENT OF ELECTRICAL AND ELECTRONIC ENGINEERING

UNIVERSITY OF CHITTAGONG

August 2023
Contents

1 Bulk Technology 1
1.1 Important Terms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Silicon Purification Process For Semiconductor Applications . . . . . . . . . 2
1.3 Some More Important Terms . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.4 LEC (Liquid Encapsulated Czochralski) . . . . . . . . . . . . . . . . . . . . 3

2 The Czochralski Technique 5

2.1 The Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2 Segregation Coefficient . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.3 Method To Reduce Oxygen Impurities From Boule In CZ Process . . . . . 7
2.4 Method To Reduce Oxygen Impurities From Boule In CZ Process . . . . . . 9
2.5 Advantages of CZ Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

3 Bridgman Crystal Growth 11

3.1 Vertical Bridgman Crystal Growth . . . . . . . . . . . . . . . . . . . . . . . 12
3.2 Horizontal Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.3 Vertical versus Horizontal Method . . . . . . . . . . . . . . . . . . . . . . . 14
3.4 Advantages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.5 Drawbacks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.6 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

4 Float-Zone Crystal Growth 16

4.1 Doping in FZ Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

5 Traveling Heater Method 20

5.1 Crystal Growth of CdTe by THM Technique . . . . . . . . . . . . . . . . . 20
5.2 Why Traveling Heater Method is used in semiconductor technology? . . . 21

6 Alloy Technique 22
6.1 Formation of Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
6.2 Classification of Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

7 Gibbs Phase Rule 24

i
Contents ii

7.1 PT Diagram of A One-component System For The Different Number of

Phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

8 Epitaxial Growth Techniques 26

8.1 Epitaxial growth techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
8.1.1 Liquid phase epitaxy . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
8.1.2 Vapor phase epitaxy . . . . . . . . . . . . . . . . . . . . . . . . . . 29
8.1.3 Chemical vapor deposition . . . . . . . . . . . . . . . . . . . . . . . . 30
8.2 Physical vapor deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

Bibliography 51
Chapter 1

Bulk Technology

1.1 Important Terms

Ingot

A silicon column is created by melting silicon at a high temperature. Most wafers are
made of silicon extracted from sand. Silicon is the principal component of sand. To be
used as a raw material for semiconductors, the silicon in sand needs to be purified. Thus,
techniques to grow silicon crystals such as the Czochralski method are used. Silicon is
melted with high heat to create a highly pure silicon solution and then cooled into round
monocrystalline rods. This monocrystalline rod is called an ‘ingot’. A diamond saw is
used to cut an ingot into wafers of uniform thickness[1].

Wafer

In electronics, a wafer (also called a slice or substrate)is a thin slice of semiconductor, such
as crystalline silicon (c-Si), used for the fabrication of integrated circuits [2].

Chip

A chip is comprised of semiconductor material cut from a larger wafer of material that is
only a few millimeters on one side.

Boule

In the crystal growth technique, the newly created. material accurately replicates the
1
Chapter 1. Bulk Technology 2

crystal structure of the seed crystal. This newly created material, a single-crystal ingot is
known as Boule.

Alloy

An alloy is a compound that is constituted by the combination of multiple chemical ele-

ments of which at least one is a metal.

1.2 Silicon Purification Process For Semiconductor Appli-

cations

The starting material for silicon is a relatively pure form of sand (SiO2 ) called quartzite.
This is placed in a furnace with various forms of carbon (coal, coke, and wood chips).
Although several reactions take place in the furnace, the overall reaction is,

SiC (solid) + SiO2 (solid) → Si (solid) + SiO (gas) + CO (gas) (1.1)

This process produces metallurgical-grade silicon with a purity of about 98%. Next, the
silicon is pulverized and treated with hydrogen chloride (HCl) to form trichlorosilane
(SiHCl3 ): Si solid HCl gas.

300◦ C
Si (solid) + 3HCl (gas) −→ SiHCl3 (gas) + H2 (gas) . (1.2)

Trichlorosilane is a liquid at room temperature (boiling point 32°C). Fractional distilla-

tion 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) (1.3)

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.
Pure EGS! (EGS!) generally has impurity concentrations in the parts-per-billion range.
Chapter 1. Bulk Technology 3

1.3 Some More Important Terms

Furnace

A container that is heated to a very high temperature, so that substances that are put
inside it, such as metal, will melt or burn. This is how acronym is added EBSD! (EBSD!).

Fused Silica Crucibles

2” 5”: Melting dish round ceramic crucible can be used for Melting Gold, silver, brass,
copper, and, other metals. Crucible is a small size dish used for melting non-ferrous
precious metals.

Susceptor

A susceptor is a material used for its ability to absorb electromagnetic energy and convert
it to heat.

Monocrystalline Semiconductor Formation Method From A Polycrystalline

Semiconductor

Three methods have been developed to produce bulk single crystals for the epitaxial growth
of most semiconductors: the Czochralski, Bridgman, and float-zone methods. A fourth
technique, the Lely growth method, was also developed it to produce substrates when a
melt was not available.

1.4 LEC (Liquid Encapsulated Czochralski)

The starting materials (either pre-synthesized polycrystalline chunks or, in the case of
semi-insulating GaAs, elemental Ga, and As) are placed in the growth crucible along with
a pellet of boron trioxide. The crucible is placed inside a high-pressure crystal puller and
heated up. At 460°C the boron trioxide melts to form a thick, viscous liquid that coats the
entire melt, including the crucible (hence, liquid encapsulated). This layer, in combination
with the pressure in the crystal puller, prevents the sublimation of the volatile group V
element. The temperature is increased until the compound synthesizes (temperatures and
pressures are varied depending on which material is being produced). A seed crystal is then
dipped, through the boron trioxide layer, into the melt. The seed is rotated and slowly
Chapter 1. Bulk Technology 4

withdrawn and a single crystal propagates from the seed. Crystal growth is monitored by
the use of CCTV cameras and measurements of weights, temperatures, and pressures are
made at regular intervals.
Chapter 2

The Czochralski Technique

2.1 The Process

The Czochralski technique uses an apparatus called a crystal puller shown in Fig 2.1

Figure 2.1: (a) Schematic drawing of the Czochralski crystal puller. CW, clockwise;
CCW, counter clockwise.

The puller has three main components:

(a) A furnace, which includes a fused-silicon (SiO2 ) crucible, a graphite susceptor, a rota-
tion mechanism (clockwise as shown), a heating element, and a power supply. The crucible
rotates during the growth to prevent the formation of local hot or cold regions;

5
Chapter 2. The Czochralski Technique 6

Figure 2.2: (b) Photograph of polystalline silicon in a silica crucible. (c) Photograph of
a 200 mm diameter, (100)-oriented Si crystal being pulled from the melt. (Photographs
courtesy of Taisil Electronic Materials Corp., Taiwan.)

(b) A crystal-pulling mechanism that includes a seed holder and a rotation mechanism
(counter-clockwise);

(c) An ambient control that includes a gas source (such as argon to prevent contamination
of the molten silicon), a flow control, and an exhaust system.

In addition, the puller has an overall microprocessor-based control system to control pro-
cess parameters such as temperature, crystal diameter, pull rate, and rotation speeds, as
well as to permit programmed process steps. Also, various sensors and feedback loops
allow the control system to respond automatically, reducing operator intervention.

Expression for the maximum velocity at which the solid can be pulled:

2.2 Segregation Coefficient

As a crystal is pulled from the melt, the doping concentration incorporated into the crys-
tal (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

Cs
k0 = , (2.1)
Cl

where Cs and Cl are, respectively, the equilibrium concentrations of the dopant in the
solid and liquid near the interface.
Chapter 2. The Czochralski Technique 7

2.3 Method To Reduce Oxygen Impurities From Boule In

CZ Process

During the Czochralski growth process, several impurities will incorporate into the crys-
tal. Since the crucibles are made of fused silica (SiO2 ) and the growth process takes place
at temperatures around 1500°C, small amounts of oxygen will be incorporated into the
boule. To reduce the concentration of oxygen impurities, the boule is usually grown under
magnetic confinement. In this situation, a large magnetic field is directed perpendicularly
to the pull direction, generating a Lorentz force. This force changes the motion of the
ionized impurities in the melt to keep them away from the liquid-solid interface and there-
fore decrease the impurity concentration. Using this arrangement, the oxygen impurity
concentration can be reduced from about 20 parts per million (ppm) to as low as 2 ppm.

Considering a crystal being grown from a melt having an initial weight M0 with an initial
doping concentration C0 in the melt (i.e., the weight of the dopant per 1 g of melt). At a
given point of growth when a crystal of weight M has been grown, the amount of dopant
remaining in the melt (by weight) is S. For an incremental amount of the crystal with
weight dM, the corresponding reduction in the dopant (–dS) from the melt is Cs dM,
where Cs is the doping concentration in the crystal (by weight):,

−dS = Cs dM (2.2)

Now, the remaining weight of the melt is M0 –M, and the doping concentration in the
liquid (by weight), Cl , is given by,

S
Cl = (2.3)
M0 − M

Combining Eqn. 2.2 and 2.3 and substituting Cs /Cl = k0 yields,

 
dS dM
= −k0 . (2.4)
S M0 − M

Given the initial weight of the dopant, C0 M0 , we can integrate Eqn. 2.4 :

S M
−dM
Z Z
dS
= k0 . (2.5)
C0 M0 S 0 M0 − M
Chapter 2. The Czochralski Technique 8

Solving Eqn. 2.5 and combining it with Eqn. 2.3 gives,

M k0 −1
 
Cs = k0 C0 1 − . (2.6)
M0

Properties
1. Impurity removed.
2. Single crystal: diameter - 300mm.
3. Thickness 7.75 +25 m.
4. Si (100) ¿ Si (111).
5. Resistivity ¿ 1 ohm-m.
6. O2 concentration- 20-30 ppm.
7. Carbon concentration ¡ 0.2 ppm.

Why CZ process is widely used for crystal growing?

1. High growth rate.

2. Highly controllable.
3. High effectiveness.
4. Production of integrated circuits and electronic devices.
5. Lower production cost per wafer.

Why is Silicon Widely Used in Electronics?

1. Silicon is abundant. Silicon is widely used in electronics because of its abundance. It

makes up about 28% of the earth’s surface, so it’s widely available to use. Silicon can be
found in the form of silica sand or quartz.

2. Easy and Economical Manufacturing.

3. Superior Silicon Structure.

4. Moderate Band Gap: Allows silicon to be a stable element and helps reduce the chance
of leakage current.

5. High Doping Concentration: with 34% packing density, silicon wafers allow easy re-
placement of impurities’ atoms in the vacant areas of the lattice.

6. Strong Mechanical Strength: silicon wafers can withstand thermal, mechanical, and
gravitational stresses.

7. Easily forms Oxides.

Chapter 2. The Czochralski Technique 9

2.4 Method To Reduce Oxygen Impurities From Boule In

CZ Process

The starting materials (either pre-synthesized polycrystalline chunks or, in the case of
semi-insulating GaAs, elemental Ga, and As) are placed in the growth crucible along with
a pellet of boron trioxide. The crucible is placed inside a high-pressure crystal puller and
heated up. At 460°C the boron trioxide melts to form a thick, viscous liquid that coats the
entire melt, including the crucible (hence, liquid encapsulated). This layer, in combination
with the pressure in the crystal puller, prevents the sublimation of the volatile group V
element. The temperature is increased until the compound synthesizes (temperatures and
pressures are varied depending on which material is being produced). A seed crystal is then
dipped, through the boron trioxide layer, into the melt. The seed is rotated and slowly
withdrawn and a single crystal propagates from the seed. Crystal growth is monitored by
the use of CCTV cameras and measurements of weights, temperatures, and pressures are
made at regular intervals. For Czochralski growth of gallium arsenide, the basic puller is

Figure 2.3: Czochralski Crystal Growth System

identical to that for silicon. However, to prevent the decomposition of the melt during
crystal growth, a liquid encapsulation method is employed. The liquid encapsulant is a
molten boron trioxide (B2 O3 ) layer about 1 cm thick. Molten boron trioxide is inert to
the gallium arsenide surface and serves as a cap to cover the melt. This cap prevents
the decomposition of the gallium arsenide as long as the pressure on its surface is higher
than 1 atm (760 Torr). Because boron trioxide dissolves silicon dioxide, the fused-silica
crucible is replaced with a graphite crucible. To obtain the desired doping concentration
Chapter 2. The Czochralski Technique 10

in the grown crystal of GaAs, cadmium, and zinc are commonly used for p-type materials,
whereas selenium, silicon, and tellurium are used for n-type materials. For semi-insulating
GaAs, the material is undoped.

Limitations of CZ Method

The quartz crucible (SiO2 ) gradually dissolves and releases large quantities of oxygen into
the melt. More than 99% of this is lost as SiO gas from the molten surface, but the rest
stays in the melt and can dissolve into the single crystal silicon. Another impurity, however
with smaller concentrations, that is also introduced into the melt by the production process
itself is carbon. The silicon monoxide evaporating from the melt surface interacts with the
hot graphite susceptor and forms carbon monoxide that re-enters the melt.

As the crystal is pulled from the melt, the impurity concentration incorporated into the
crystal (solid) is usually different from the impurity concentration of the melt (liquid) at
the interface.

Typical oxygen and carbon concentrations are [O] 5-10 1017 cm−3 and [C] 5 - 10 1015
cm−3 , respectively, which lower the minority carrier diffusion length in the finished silicon
wafer.

Low homogeneity of the axial and radial dopant concentration in the crystal caused by
oscillations in the melt during crystal growth. This makes it difficult to attain high-
ohmic CZ-wafers with a resistivity exceeding 100 Ohm.cm. Furthermore, the high oxygen
concentration can lead to the formation of unwanted electrically active defects. These are
oxygen-related thermal double donors (TDD) and shallow thermal donors (STD) which
can seriously change the resistivity of the material.

2.5 Advantages of CZ Method

1. The Czochralski-technique allows big crystal diameters and lower production cost per
wafer– compared to the float-zone technique described in the following section.

2. Better compatibility with advanced CMOS processes.

3. Wafer made by CZ used in the electronics industry to make semiconductor devices such
as integrated circuits.
Chapter 3

Bridgman Crystal Growth

The Bridgman technique (also known as the Bridgman-Stockbarger method) is one of

the oldest techniques used for growing crystals. The Bridgman–Stockbarger technique is
named after Harvard physicist Percy Williams Bridgman(1882-1961) and MIT physicist
Donald C. Stockbarger (1895–1952). Similar to the Czochralski technique, the Bridgman
technique employs also crystal growth from melt. 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. In the
Bridgman technique, the crucible containing the molten material is translated along the
axis of a temperature gradient in a furnace, whereas in the Stockbarger technique, there is
a high-temperature zone, an adiabatic loss zone, and a low-temperature zone. These two
methods are very often not specifically differed in terminology. The difference between
the Bridgman technique and the Stockbarger 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. The
method involves heating polycrystalline material in a container above its melting point
and slowly cooling it from one end where a seed crystal is located. Single crystal material
is progressively formed along the length of the container. The process can be carried out
in a horizontal or vertical geometry.

11
Chapter 3. Bridgman Crystal Growth 12

3.1 Vertical Bridgman Crystal Growth

The principle of the Bridgman technique is directional solidification by translating a melt

from the hot zone to the cold zone of the furnace.

The Bridgman furnace works with three temperature zones. The upper zone with tem-
peratures above the melting point of silicon. The lower zone with a temperature below
melting point and an adiabatic zone as a baffle between the two.

At first, the polycrystalline material in the crucible needs to be melted completely in the
hot zone and brought into contact with a seed at the bottom of the crucible.

Part of the seed will be re-melted after contact with the melt. This provides a fresh
interface for crystal growth.

Figure 3.1: Vertical Method

The crucible is then translated slowly into the cooler section of the furnace.

The temperature at the bottom of the crucible falls below the solidification temperature
and the crystal growth is initiated by the seed at the melt-seed interface.

After the whole crucible is translated through the cold zone the entire melt converts to a
solid single-crystalline ingot.

Due to a directed and controlled cooling process of the cast, zones of aligned crystal lattices
are created.
Chapter 3. Bridgman Crystal Growth 13

Figure 3.2: Vertical Method

Merely 60% of the polycrystal silicon can be processed to wafers for photovoltaics. The
rest gets lost in the sawing and cutting process.

3.2 Horizontal Method

The Bridgman technique requires a two-zone furnace.

The materials which melt congruently do not decompose before melting and those do not
undergo phase transformation between the melting point and room temperature can be
grown as single crystals by the Bridgman technique.

The material to be grown is encapsulated in a glass or quartz tube and suspended in the
furnace having a suitable gradient for growth.

The tip of the ampoule is mainly conical-shaped to enhance the nucleation of a single
crystal.

The left-hand zone is maintained at a temperature of ca. 610 °C, allowing sufficient
overpressure of arsenic within the sealed system to prevent arsenic loss from the gallium
arsenide.

The right-hand side of the furnace contains the polycrystalline GaAs raw material held at
a temperature just above its melting point (ca. 1240 °C).

After melting the substance, the growth ampoule is moved from the hot zone to the cold
zone gradually. As the furnace moves from left to right, the melt cools and solidifies.
Chapter 3. Bridgman Crystal Growth 14

If a seed crystal is placed at the left-hand side of the melt (at a point where the temperature
gradient is such that only the end melts), a specific orientation of single crystal may be
propagated at the liquid-solid interface eventually to produce a single crystal.

The organic materials which have spherical molecules in cubic lattice can be quite rapidly
grown. The average growth rate to start with for most materials is 1 mm/h.

The temperature gradient of the solid-liquid interface in the Bridgman furnace is usually
lower than that in Czochralski growth; therefore the cracking can be easily avoided during
Bridgman growth.

Bridgman technique has been found to be an attractive technique for the growth of large
size good quality transparent single crystals in organic and inorganic materials.

A schematic diagram of a Bridgman two-zone furnace used for melt growths of single
crystal GaAs.

Figure 3.3: Schematics of the furnace and crucibl used for GaAs growth

3.3 Vertical versus Horizontal Method

The vertical Bridgman technique enables the growth of crystals in a circular shape, unlike
the D-shaped ingots grown by the horizontal Bridgman technique. However, the crystals
grown horizontally exhibit high crystalline quality (e.g. low dislocation density) since the
crystal experiences lower stress due to the free surface on the top of the melt and is free
to expand during the entire growth process. Instead of moving the crucible, the furnace
can be translated from the seed end while the crucible is kept stationary.

In this manner, directional solidification can be achieved, too.

A further modification is the so-called gradient freezing technique, with which neither the
crucible nor the furnace needs to be translated.
Chapter 3. Bridgman Crystal Growth 15

3.4 Advantages

1. The shape of the crystal is defined by the container no radial temperature gradients
are needed to control the crystal shape.
2. Low thermal stresses result in low level of stress-induced dislocations.
3. Crystals may be grown in sealed ampules (easy control of stoichiometry)
4. Relatively low level of natural convection easy control and maintenance.

3.5 Drawbacks

1. Confined growth (crucible may induce stresses during cooling).

2. Difficult to observe seeding and growing processes.
3. Changes in natural convection as the melt is depleted delicate crucible and seed prepa-
ration, sealing, etc.

3.6 Applications

1. Melts with volatile constituents: III-V compounds (GaAs, InP, GaSb) II-VI compounds
(CdTe).
2. Ternary compounds: Ga-xIn As, Ga-xnxSb, Hg-xCdxTe.
Chapter 4

Float-Zone Crystal Growth

A seed crystal is used at one end in order to start the growth. The whole process is carried
out in an evacuated chamber or in an inert gas purge.

The main advantage of the float-zone technique is the very low impurity concentration in
the silicon crystal as compared to CZ silicon(Carrier concentrations down to 1011 atom-
s/cm3 have been achieved).

The concentrations of light impurities, such as carbon and oxygen, are extremely low.
Another light impurity, nitrogen, helps to control micro-defects and also brings about an
improvement in the mechanical strength of the wafers, and is now being intentionally
added during the growth stages.

Additionally, the dopant concentration in the final crystal is rather homogeneous and
manageable which allows very high-ohmic (1-10 Kohm.cm) wafers as well as wafers with
a narrow specified electrical resistivity.

Float zone silicon is typically used for power devices and detector applications. It is good
for solar cells, power electronic devices (thyristors and rectifiers) that use the entire volume
of the wafer not just a thin surface layer, etc

Float-zone does not allow as large Si wafers as CZ does (200mm and 300mm) and radial
distribution of dopant in FZ wafer is not as uniform as in CZ wafer.

There is no need to use a quartz crucible as well as a hot graphite container.

16
Chapter 4. Float-Zone Crystal Growth 17

The main technological disadvantage of the FZ method is the requirement for a uniform,
crack-free cylindrical feed rod. A cost premium (100% or more) is associated with such
poly rods.

These crystals are more expensive and have very low oxygen and carbon and thus, are not
suitable for the majority of silicon IC technology.

At the present time, FZ Si is used for premium high-efficiency cell applications and CZ Si
is used for higher-volume, lower-cost applications.

Float-zone silicon is very pure silicon obtained by vertical zone melting.

The diameters of float-zone wafers are generally not greater than 150 mm due to the
surface tension limitations during growth.

A polycrystalline rod of ultra-pure electronic grade silicon is passed through an RF heating

coil, which creates a localized molten zone from which the crystal ingot grows.

The RF coil and the melted zone move along the entire ingot.

Figure 4.1: FZ Process

Since most impurities are less soluble in the crystal than in the melted silicon, the molten
zone carries the impurities away with it. The impurities concentrate near the end of the
crystal where finally they can simply be cut away (Dopants/impurities prefer to stay in
the liquid than in the solid).

This procedure can be repeated one or more times in order to further reduce the remaining
impurity concentration.

Doping is realized during crystal growth by adding dopant gases such as phosphine (PH3),
arsine (AsH3) or diborane (B2H6) to the inert gas atmosphere.
Chapter 4. Float-Zone Crystal Growth 18

Specialized doping techniques like core doping, pill doping, gas doping, and neutron trans-
mutation doping are used to incorporate a uniform concentration of impurity

A variety of heating systems can be used for the floating zone technique, including induc-
tion coil, resistance heater or more recently optical heating system.

Figure 4.2: Float Zone Pulling

4.1 Doping in FZ Growth

Gas doping

Dopants are introduced in gaseous form during FZ growth.

n-doping: PH3 (Phosphine), AsCl3 .

p-doping: B2H6 (Diborane), BCl3 .

Pill Doping

Drill a small hole in the top of the EGS rod, and insert the dopant. If the dopant has a
small segregation coefficient, most of it will be carried with the melt as it passes the length
Chapter 4. Float-Zone Crystal Growth 19

of the boule. Resulting in only a small non-uniformity. Ga and In doping work well this
way.

Figure 4.3: Schematics of the furnace and crucibl used for GaAs growth
Chapter 5

Traveling Heater Method

The Traveling Heater Method is a solution growth technique, which allows the prepara-
tion of bulk monocrystalline mixed-compound semiconductors. THM uses a moving axial
temperature gradient as the driving force to transfer polycrystalline feed at a controlled
rate to re-crystallize on a seed, thus growing monocrystalline material of the same average
composition.

5.1 Crystal Growth of CdTe by THM Technique

A single crystal seed of the desired composition and crystallographic orientation is placed.
This is surmounted by an appropriate amount of solvent material, preferably one of the
constituent elements of the material to be grown. This is followed by a fine-grained
polycrystalline source material with the same average composition as that of the seed.
After sealing under a vacuum or an inert gas (if necessary), the ampoule is then placed
in a furnace consisting of a concentric heat source positioned to surround the solvent
zone. The operating temperature and the amount of solvent material are determined by
the relevant phase diagram such that the solvent will be saturated at typically 20-mole
percent of the desired composition and the particular axial gradient. The ampoule is then
slowly lowered through the hot zone at a controlled rate, with or without rotation of the
ampoule. The precise location of the ampoule and charge, relative to the heater, ensures
that a portion of the seed and of the source material will dissolve until the solvent reaches
saturation and a dynamic equilibrium is established. As a consequence of the narrow
heater profile, the temperature at the seed solvent interface reduces and the melt becomes
locally supersaturated and crystallization occurs.
20
Chapter 5. Traveling Heater Method 21

5.2 Why Traveling Heater Method is used in semiconductor

technology?

It can be used to produce non-congruent melting materials, including families of ternary

and quaternary II-VI and III-V compounds, which can not be grown adequately by stan-
dard melt growth techniques. The process is conducted below the melting point of the
semiconductor, relatively low temperatures are involved, which reduces contamination and
vapor pressure-related problems. This leads to bulk crystals with improved dopant homo-
geneity, reduced dislocation densities, and excellent electrical properties. The dislocation
density is a measure of the number of dislocations in a unit volume of crystalline material.
Chapter 6

Alloy Technique

An alloy is a metallic solution or compound that is formed by the combination of multiple

chemical elements of which at least one is a metal. Because an alloy contains a mixture
of elements, one can categorize it as a solid solution or compound based on its final form.
Metals are, in general, insoluble in organic solvents, such as water, alcohol, ether, and
benzene. A metal can dissolve in another metal in molten state, forming a homogeneous
liquid mixture that cools to solidify to a solid mixture of alloys. Mixing multiple metals
or nonmetals can form homogeneous or heterogeneous alloys. Alloys are homogeneous in
liquid state but can be either homogeneous or heterogeneous in solid state.

6.1 Formation of Alloys

Combining several elements in different proportions forms an alloy. When an alloy consists
of two components, it is called a binary alloy. An alloy with three components is a ternary
alloy, and an alloy with four components is a quaternary alloy. The resulting metallic
substance has properties that are significantly different from those of its components.
Based on its formation, the alloy can be classified as: Homogeneous alloy and Mixture or
heterogeneous alloy. In a homogeneous alloy, the mixture consists of only one phase and
a mixture alloy is a combination of several phases. There are three possible phases in the
solid state: pure metal, intermediate alloy phase or compound, and solid solution. If the
metals get completely mixed a homogeneous phase is formed otherwise a heterogeneous
phase is formed.

22
Chapter 6. Title of Chapter Six 23

6.2 Classification of Alloys

There are several alloys of various metals, such as alloys of Aluminium, Potassium, Iron,
Cobalt, Nickel, Copper, Gallium, Silver, Tin, Gold, Mercury, Lead, Bismuth, Zirconium,
and rare earth. Based on the presence or absence of Iron, alloys can be classified into:
Ferrous alloys: Contain Iron as a major component. A few examples of ferrous alloys
are Stainless Steel, Cobalt, Gallium, Silver, Gold, Bismuth, and Zirconium. Non-ferrous
alloys: Do not contain Iron as a major component. For example, Aluminium, Brass,
Bronze, Copper, Tin, Nickel, Magnesium, and Titanium are some common non-ferrous
alloys.
Chapter 7

Gibbs Phase Rule

The Gibbs Phase Rule describes the possible number of degrees of freedom in a (closed)
system at equilibrium in terms of the number of separate phases and the number of chem-
ical constituents in the system, and can simply be written as, f=C-P+2. where C is the
number of components, P is the number of phases, and f is the number of degrees of free-
dom in the system. The number of degrees of freedom V) is the number of independent
intensive variables (i.e. those that are independent of the quantity of material present)
that need to be specified in value to fully determine the state of the system. Typical such
variables might be temperature, pressure, or concentration. This rule states that, for a
one-component one-phase system, there are two degrees of freedom.

7.1 PT Diagram of A One-component System For The Dif-

ferent Number of Phases

On a P-T diagram, pressure and temperature can be chosen independently. On the other
hand, for a two-phase system, there is only one degree of freedom and there is only one
pressure possible for each temperature. Finally, for a three-phase system, there exists only
one point with fixed pressure and temperature.

24
Chapter 7. Gibbs Phase Rule 25

Figure 7.1: Float Zone Pulling

Chapter 8

Epitaxial Growth Techniques

8.1 Epitaxial growth techniques

Majority of semiconductor devices, including transistors or diode lasers, require the depo-
sition of a series of thin layers on top of one of the polished wafer substrates.

This process of extending the crystal structure of the underlying substrate material into
the grown layer is called epitaxy.
The term epitaxy is a combination of two Greek words,epi (placed or resting on) and
”taxis” (arrangement or order), and refers to the formation of a single crystal film on top
of a crystalline substrate.

Homoepitaxy is employed when the film and the substrate are made of the same material
(Ex: growth of a thick GaAs layer (called a buffer layer) on a GaAs substrate), and het-
eroepitaxy is used when the film and the substrate are made of different materials ( Ex:
deposition of InGaAs on top of InP substrates (lattice matched growth); growth of GaN
on sapphire substrates (lattice mismatched growth).

The discovery of quantum wells and superlattices has revolutionized the area of semi-
conductor technology in terms of new devices. These devices require precise control and
uniformity of thickness, excellent homogeneity, high purity, very sharp interfaces between

26
Chapter 8. Epitaxial Growth Techniques 27

the substrate and epitaxial layers, and low misfit dislocations in the epilayers.

Epitaxial techniques have advanced to a level where such requirements can be met by a va-
riety of growth methods; These growth techniques include Liquid phase epitaxy (LPE), Va-
por phase epitaxy (VPE), Metalorganic chemical vapor deposition (MOCVD), and Molec-
ular beam epitaxy (MBE).

Epitaxy has a number of advantages over other techniques for growing thin films, including:

Highquality: The films grown by epitaxy are typically of very high quality, with few
defects. This is because the film and substrate have the same crystallographic orientation,
which minimizes the number of defects that can occur during growth.

Controlled composition: The composition of the film can be controlled very precisely
during epitaxy. This is because the atoms in the film are deposited from a source that is
known to have the desired composition.

Uniformity: The film thickness and composition are uniform across the entire surface
of the substrate. This is because the film is grown in a controlled environment, and the
growth conditions are the same throughout the substrate.

Interface properties: The interface between the film and substrate is very well-defined.
This is because the film and substrate have the same crystallographic orientation, which
minimizes the number of defects that can occur at the interface.
Chapter 8. Epitaxial Growth Techniques 28

8.1.1 Liquid phase epitaxy

The LPE growth technique involves the precipitation of material from a supercooled solu-
tion onto an underlying substrate. The LPE reactor includes a horizontal furnace system
and a sliding graphite boat.The composition of the layers that are grown on the substrate
depends mainly on the equilibrium phase diagram and to a lesser extent on the substrate.
The three parameters that can effect the growth are

• The melt composition .

• The growth temperature

• The growth time.

Liquid phase epitaxy is a thermodynamic equilibrium growth process. The composition

of the layers that are grown on the substrate depends mainly on the equilibrium phase
diagram and to a lesser extent on the orientation of the substrate. The three parameters
that can effect the growth are the melt composition, the growth temperature, and the
growth time.
Advantage:

• Simplicity of the equipment,

• High deposition rates

• High purity

Dis-advantage:

• Poor thickness uniformity

• High surface roughness

• Melt back effects,

• High growth rates which prevent the growth of multilayer structures with abrupt
interfaces.
Chapter 8. Epitaxial Growth Techniques 29

Figure 8.1: Cross-section of a liquid phase epitaxy system

8.1.2 Vapor phase epitaxy

Vapor phase epitaxy is also a thermodynamic equilibrium growth process.The VPE growth
technique involves reactive compounds in their gaseous form. A VPE reactor typically
consists of a quartz chamber composed of several zones set at different temperatures using
a multi-element furnace. The group III source materials consist of pure metal elements,
such as gallium (Ga) and indium (In), contained in a small vessel.. In the first zone, called
the group I11 species synthesis zone, which is maintained at a temperature Ts (-750-850
OC for GaAs or InP growth), the metal is in the liquid phase and reacts with the incoming
flow of hydrogen chloride gas (HCI) in the following manner to form group III-chloride
vapor compounds which can be transported to the growth region:

Gal + HClg − > GaClg + 1/2H2g (8.1)

Ing + HCl− > InClg + 1/2H2g (8.2)

The group V source materials are provided in the form of hydride gases, for example
arsine (AsH3) and phosphine (pH3). In the second zone, also called the group. V species
pyrolysis zone, which is maintained at a temperature T¿Ts, these hydrides are decomposed
Chapter 8. Epitaxial Growth Techniques 30

into their elemental group V constituents, yielding reactions like:

u 1−u
AsH3− > As4 + As2 + 3/2H2 (8.3)
4 2
v 1−v
P H3− > P 4 + P 2 + 3/2H2 (8.4)
4 2

where u and v represent the mole fraction ofAsH3 or P H3 which is decomposed into As4
or P4 , respectively. Finally, in the growth region, which is maintained at a temperature
TG (-680-750 ”C for GaAs or InP growth), the group 111-chloride and the elemental group
V compounds react to form the semiconductor crystal, such as GaAs or InP, onto a sub-
strate. There are two types of chemical reactions taking place in vapor phase epitaxy:
1.Heterogeneous reactions occur between a solid, liquid and/or vapor.
2.While homogeneous reactions only occur in the gas phase. During the growth of a semi-
conductor film in steady-state conditions, the overall growth process is limited by the
heterogeneous reactions.
During changes in the composition of the growing semiconductor, for example when switch-
ing the growth from InP to GaInAs, the process is limited by the mass transport in the
gas phase.

Figure 8.2: Location of heterogeneous and homogeneous chemical reactions taking place
during the vapor phase epitaxy growth process

8.1.3 Chemical vapor deposition

CVD, also known as vapor-phase epitaxy (VPE), is a process whereby an epitaxial layer
is formed by a chemical reaction between gaseous compounds. CVD can be performed at
atmospheric pressure (APCVD) or at low pressure (LPCVD). Chemical vapor deposition
(CVD) is the most useful method for the deposition of a wide variety of thin films in
semiconductor device fabrication. CVD is used to deposit, for example, polysilicon for
gate conductor, silica glass, doped silica glass such as borophosphosilicate glass (BPSG)
and phosphosilicate glass (PSG), silicon nitride for dielectric films, and tungsten, tungsten
Chapter 8. Epitaxial Growth Techniques 31

silicide, and titanium nitride for conducting films. There are three commonly used depo-
sition methods:

1.Atmospheric-pressure CVD.

2.Low-pressure CVD (LPCVD)

3.Plasma-enhanced chemical vapor deposition (PECVD, or plasma deposition).

LPCVD is a CVD process operated at subatmospheric pressures. Reduced pressures

can reduce unwanted gas-phase reactions and improve film uniformity across the wafer.It
suffers from low deposition rates.In a hot-wall LPCVD reactor as shown in Figure8.3 the
quartz tube is heated by a three-zone furnace, and gas is introduced at one end and
pumped out at the opposite end.

Figure 8.3: Hot-wall LPCVD reactor

Chapter 8. Epitaxial Growth Techniques 32

PECVD is an energy-enhanced CVD method in which plasma energy is added to the

thermal energy of a conventional CVD system.
The parallel-plate, radial-flow PECVD reactor shown in Figure8.4 consists of a cylindri-
cal glass or aluminum chamber sealed with aluminum endplates. Inside are two parallel
aluminum electrodes. An rf voltage is applied to the upper electrode, whereas the lower
electrode is grounded. The rf voltage causes a plasma discharge between the electrodes.
Wafers are placed on the lower electrode, which is heated to between 100° and 400o C by
resistance heaters. The reaction gases flow through the discharge from inlets located along
the circumference of the lower electrode. The main advantage of this reactor is its low de-
position temperature. However, its capacity is limited, especially for large-diameter wafers,
and the wafers may become contaminated if loosely adhering deposits fall on them. The
substrate surface not only receives active precursors but is subject to the bombardment of
charged species. The short-lived active species react and deposit on the surface, while the
thermal energy and ion bombardment continue to modify the deposited materials. The
plasma-enhanced deposited films tend to be of smaller grain size or even amorphous, and
contain amounts of impurities such as hydrogen, carbon or halide atoms. The combination
of low temperature, self-cleaning capability, and versatile film tunability has assured the
importance of PECVD in the semiconductor industry. To minimize deposits on the reactor
surfaces, limiting the plasma area is beneficial. The standard parallel-plate configuration
provides an efficient design to focus the deposition on the wafer. At the same time, the
reactor’s plasma capability also provides the potential for in-situ plasma cleaning by intro-
ducing etchant cleaning gases such as C2F6 or NF3 to remove silicon dioxide and silicon
nitride deposition from chamber surfaces. One limitation of plasma deposition involves
the potential charge imbedded in the film.
Chapter 8. Epitaxial Growth Techniques 33

Figure 8.4: Parallel-plate rf (radio frequency) plasma deposition reactor.

CVD processes

Chemical vapor deposition (CVD) is a method of forming a thin solid film on a substrate
by the reaction of vapor-phase chemicals that contain the required constituents. The CVD
process can be generalized in a sequence of steps:

1. Reactants are introduced into the reactor;

2. Gas species are activated and dissociated by mixing, heating, plasma, or other means;

3. Reactive species are adsorbed on the substrate surface;

4. Adsorbed species undergo chemical reaction or react with other incoming species to
form a solid film;

5. Reaction byproducts are desorbed from the substrate surface;

6. Reaction byproducts are removed from the reactor.

Chapter 8. Epitaxial Growth Techniques 34

CVD for Silicon: Four silicon sources have been used for VPE growth: silicon tetrachlo-
ride (SiCl4 ), dichlorosilane (SiH2 Cl2 ), trichlorosilane (SiHCl3 ), and silane (SiH4 ). Silicon
tetrachloride has been the most studied and has the widest industrial use. The typical
reaction temperature is 1200°C. Other silicon sources are used because of lower reaction
temperatures. The substitution of a hydrogen atom for each chlorine atom from silicon
tetrachloride permits about a 50°C reduction in the reaction temperature. The overall
reaction of silicon tetrachloride that results in the growth of silicon layers is:

SiCl4 (g) + 2H2 (g) → Si(s) + 4HCl(g) (8.5)

Figure 8.5: Three common susceptors for chemical vapor deposition: (a) horizontal, (b)
pancake, and (c) barrel susceptor.
Chapter 8. Epitaxial Growth Techniques 35

An additional competing reaction is taking place along with that given equation in 8.5

SiCl(g) <=> Si(s) + Cl2(g) (8.6)

As a result, if the silicon tetrachloride concentration is too high, etching rather than
growth of silicon will take place. Figure8.6 shows the effect of the concentration of silicon
tetrachloride in the gas on the reaction, where the mole fraction is defined as the ratio of the
number of molecules of a given species to the total number of molecules. Note that initially
the growth rate increases linearly with increasing concentration of silicon tetrachloride. As
the concentration of silicon tetrachloride is increased, a maximum growth rate is reached.
Beyond that, the growth rate starts to decrease and eventually etching of the silicon will
occur. Silicon is usually grown in the low-concentration region, as indicated in Figure8.6.

Figure 8.6: Effect of SiCl4 concentration on silicon epitaxial growth.

Chapter 8. Epitaxial Growth Techniques 36

The reaction of equation8.5 is reversible, that is, it can take placein either direction. If the
carrier gas entering the reactor contains hydrochloric acid, removal or etching will take
place. Actually, this etching operation is used for in-situ cleaning of the silicon wafer and
coating on the reactor chamber wall prior to epitaxial growth.

The dopant is introduced at the same time as the silicon tetrachloride during epitaxial
growth Figure8.5a. Gaseous diborane (B2 H6 ) is used as the p-type dopant, whereas phos-
phine (P H3 ) and arsine (AsH3 ) are used as n-type dopants.

Gas mixtures are ordinarily used with hydrogen as the diluent to allow reasonable control
of flow rates for the desired doping concentration. The dopant chemistry for arsine is illus-
trated in Figure8.7, which shows arsine being adsorbed on the surface, decomposing, and
being incorporated into the growing layer. Figure 8.7 also shows the growth mechanisms
at the surface, which are based on the surface adsorption of host atoms (silicon) as well as
the dopant atom (e.g., arsenic) and the movement of these atoms toward the ledge sites.15
To give these adsorbed atoms sufficient mobility for finding their proper positions within
the crystal lattice, epitaxial growth needs relatively high temperatures.

Figure 8.7: Schematic representation of arsenic doping and the growing processes.
Chapter 8. Epitaxial Growth Techniques 37

Metalorganic chemical vapor deposition:

Metalorganic chemical vapor deposition (MOCVD) is a deposition method for the growth
of semiconductor thin films. The MOCVD technology has established its ability to pro-
duce high quality epitaxial layers and sharp interfaces, and to grow multilayer structures
with thicknesses as thin as a few atomic layers.

MOCVD growth systems: The growth of epitaxial layers from III-V semiconductor
compounds is conducted by introducing controlled amounts of volatile compounds of alkyls
of group III elements, and either alkyls or hydrides of group V elements into a reaction
chamber in which a semiconductor substrate is placed on a heated graphite susceptor as
depicted in Figure8.8 .The heated susceptor has a catalytic effect on the decomposition of
the gaseous products, such that the semiconductor crystal growth takes place in this hot
region

Figure 8.8: Schematic diagram of a typical low-pressure MOCVD reactor

A typical MOCVD system consists of four major parts:

1.The gas handling system.
Chapter 8. Epitaxial Growth Techniques 38

2.The reactor chamber.

3.The heating system, and the exhaust and safety apparatus.

The gas handling system includes the alkyl and hydride sources, the valves, pumps and
other instruments necessary to control the gas flows and mixtures. Hydrogen (H), nitrogen
(N2 ), argon (Ar), and helium (He) are the most common inert carrier gases used in the
MOCVD growth process. In order to minimize contamination, the gas handling system
has to be cleanand leak tight.
Chapter 8. Epitaxial Growth Techniques 39

Alkyls sources are metalorganic or organometallic compounds, and they are liquids or
finely crushed solids usually contained in a stainless steel cylinder called bubbler. The
partial pressure of the source is regulated by precisely controlling the temperature and the
total pressure inside the bubbler.
Electronic mass flow controllers are used to accurately and reliably measure and/or control
the mass flow rate of hydride and carrier gases through the gas handling system. Thus,
by sending a controlled flow of carrier gas through the bubbler, a controlled mass flow in
the form of dilute vapors of the metalorganic compounds can be achieved.The mixing of
volatile compounds in the gas handling system is done in a manifold which first stabilizes
the flows, then mixes them and directs them either to the reaction chamber or into the
vent (waste). This manifold is designed to uniformly mix metalorganic and hydride source
materials prior to reaching the growth zone.

Inside the reaction chamber, the susceptor can be heated using any of the following three
methods: radio frequency (RF) induction heating, radiative (lamp) heating, and resistance
heating. The temperature of the substrate is measured using a thermocouple (chromel-
alumel) and/or a pyrometer. The exhaust system may include scrubbing systems, particu-
late filters and bumboxes, and is aimed at physically or chemically treating the unreacted
gases and byproducts from the reaction chamber which may still be toxic, pyrophoric or
flammable.

MOCVD growth process: There exist two types of fundamental processes occurring
during crystal growth: thermodynamic and kinetic. Thermodynamics determines the driv-
ing force for the overall growth process, and kinetics defines the rates at which the various
processes occur. Hydrodynamics and mass transport, which take into account the gas
velocities and temperature gradients in the vicinity of the hot susceptor, control the rate
of transport of material to the growing solid/vapor interface.

The rates of the chemical reactions occurring during growth, either homogeneously in the
gas phase, or heterogeneously at the growing interface, also play a role. Each of these fac-
tors will dominate some aspect of the overall growth process. A study of the dependence
of a macroscopic quantity, such as growth rate, on external parameters, such as substrate
temperature and input precursor (source) flow rates, gives insight into the overall growth
mechanism.
Chapter 8. Epitaxial Growth Techniques 40

To grow GaAs, we can use metalorganic compounds such as trimethylgallium Ga(CH3 )3

for the gallium component and arsine AsH3 for the arsenic component. Both chemicals
can be transported in vapor form into the reactor. The overall reaction is

AsH3 + Ga(CH3)3− > GaAs + 3CH3 (8.7)

A much-simplified description of the MOCVD growth process for III-V compounds, such
as the growth of GaAs by TMGa and AsH3, occurring near and at the substrate surface
is illustrated in Figure8.9.
The following step is followed:

1.In the first step, both AsH3 and Ga(CH3 )3 are carried by diffusion through the boundary
layer to reach the substrate.
2.The second step involves the surface reactions.
3.The third step is the formation of GaAs and the final step is the removal of the reaction
products.
Chapter 8. Epitaxial Growth Techniques 41

Figure 8.9: A simplified schentatic illustration of the GaAs growth process involving
different steps.

The growth rate s is illustrated in Figure8.10 which shows the typical growth rate profile
as a function of temperature.For a given flow of source materials, three regimes can be
observed for the growth rate.
At low temperatures (Figure8.10a), chemical reactions at the solid/vapor interface limit
the growth rate as they follow an Arrhenius relation of the form

Ea
k = A · e− RT (8.8)

where EA is an activation energy which characterizes the chemical reactions and is of the
order of a few eV.For intermediate temperatures (Figure8.10(b)), the growth rate is nearly
constant over a wide temperature range. This corresponds to a regime where the diffusion
or mass transfer across the boundary layer limits the growth rate.

The growth rate is then directly proportional to the flow or partial pressure of incoming
source materials and to their diffusion coefficients. In order to achieve a good growth rate
control and minimize the sensitivity to temperature, it is preferred to be in conditions
which yield a diffusion limited regime. When the partial pressure of the source materi-
als is increased, the temperature window over which the growth rate is constant is reduced.
Chapter 8. Epitaxial Growth Techniques 42

At high temperatures (Figure8.10(c)), the growth rate becomes independent of tempera-

ture and flow of source materials. In this regime, the rate is limited by the decomposition
of the growing crystal.
Chapter 8. Epitaxial Growth Techniques 43

Figure 8.10: Typical growth rate profile as a function of temperature

Molecular beam epitaxy

MBE is an epitaxial process involving the reaction of one or more thermal beams of
atoms or molecules with a crystalline surface under ultrahigh-vacuum conditions ( 10−8
Pa). MBE can achieve precise control in both chemical compositions and doping profiles.
Single-crystal multilayer structures with dimensions on the order of atomic layers can be
made using MBE.

Thus, the MBE method enables the precise fabrication of semiconductor heterostructures
having thin layers from a fraction of a micron down to a monolayer. In general, MBE
growth rates are quite low, and for GaAs, a value of 1 µm/hr is typical.
In this technique, the precursor sources are either solids which are sublimated or heated
above their melting points in effusion cells, or gases which are connected through an
injector and cracker.
The sources are evaporated in the form of beams of atoms or molecules at a controlled
rate onto a crystalline substrate surface held at a suitable temperature under ultra high
vacuum conditions, as illustrated in Figure8.11.
Chapter 8. Epitaxial Growth Techniques 44

The epitaxial layers crystallize through a reaction between the beams originating from the
sources and the heated substrate surface. The thickness, composition and doping level of
the epilayer can be very precisely controlled via an accurate control of the beam fluxes.
The substrate is mounted on a block and rotated continuously to promote uniform crystal
growth on its surface. The beam flux of the source materials is a function of their vapor
pressure which can be precisely controlled by their temperature.

Figure 8.11: Schematic diagram of an MBE growth system showing a few solid effusion
cells.

The thickness, composition and other properties of the epitaxial layers and heterostruc-
tures are directly controlled by the interruption of the unwanted atomic beams with spe-
cially designed shutters. An ultra high vacuum (UHV) level will ensure the beam nature
of the mass flow toward the substrate. This means that the atoms will not interact with
each other before reaching the substrate because they have a mean free path longer than
the distance between the cells and the substrate. The mean free path A of an atom or
molecule is expressed as:
1
A= √ (8.9)
2πnd2
P
n= (8.10)
kb T
Chapter 8. Epitaxial Growth Techniques 45

where kb is the Boltzmann constant, P and T are the pressure and absolute temperature
in the MBE growth chamber. The usual distance between the orifice of the cells and the
substrate in MBE reactors is about 0.2 m which is two orders of magnitude shorter than
the mean free path ofatoms or molecules (several tens of meters) at the usual operating
pressures in MBE
(10− 5 Pa).
The most important processes in MBE growth occur at the atomic level in the crystalliza-
tion zone and can be summarized into four fundamental steps illustrated in Figure8.12.

• Adsorption of the constituent atoms or molecules impinging on the substrate surface.

• Surface migration and dissociation of the absorbed species.

• Incorporation of the constituent atoms into the crystal lattice of the substrate or the
epilayer, at a site where sufficiently strong bonding exists. That site is usually at
the edge of a spreading atomic layer of the growing epitaxial crystal.

• And thermal desorption of the species that were not incorporated into the crystal
lattice.
Chapter 8. Epitaxial Growth Techniques 46

Figure 8.12: Schematic illustration ofthe surface processes during MBE epitaxial
growth, including: (I) the adsorption of the constituent atoms or molecules impinging on
the substrate surface, (2) the surface migration and dissociation of the absorbed species,
(3) the incorporation of the constituent atoms into the crystal lattice ofthe substrate or
the epilayer, and (4) the thermal desorption of the species not incorporated into the crys-
tal lattice.

MBE uses an evaporation method in a vacuum system. An important parameter for vac-
uum technology is the molecular impingement rate, that is, how many molecules impinge
on a unit area of the substrate per unit time. The impingement rate ϕ is a function of the
molecular weight, temperature, and pressure.
The equation can be expressed here

1
ϕ = P (2πmkT )− 2 (8.11)

2 P
ϕ = 264 × 1020 √ molecules cm−2 s−1 (8.12)
·M T
Chapter 8. Epitaxial Growth Techniques 47

8.2 Physical vapor deposition

Physical vapor deposition (PVD), sometimes called physical vapor transport (PVT), de-
scribes a variety of vacuum deposition methods which can be used to produce thin films
and coatings on substrates including metals, ceramics, glass, and polymers. PVD is char-
acterized by a process in which the material transitions from a condensed phase to a vapor
phase and then back to a thin film condensed phase. The most common PVD processes
are sputtering and evaporation.

Sputtering deposition is also called physical vapor deposition and is a physical process. A
typical sputtering deposition system is shown in Figure8.13. It contains a slab or target of
the desired metal which is electrically grounded and serves as the cathode. Under vacuum
conditions, argon gas is introduced into the chamber and is ionized into a positively charged
ion. These are accelerated toward the cathode target. By impacting the target, enough
metal atoms are dispersed such that they deposit onto the wafer surface. The main feature
of the sputtering method is that the target material is deposited on the wafer without
chemical or compositional change.
Chapter 8. Epitaxial Growth Techniques 48

Figure 8.13: . Cross-section schematic diagram of a typical sputtering system, which is

enclosed in a vacuum chamber and includes the wafers which are placed on a heater, and
a set of electrodes, one of which is made from the target material to be sputtered. Argon
gas is supplied and ionized so that ions can impact on the target to release atoms of the
material to be deposited

Sputtering involves the transport of material from a target to a substrate. It is accom-

plished by the bombardment of the target surface with gas ions, typically Ar but occasion-
ally other inert gas species (Ne, Kr) or reactive species such as oxygen or nitrogen. There
are basically two kinds of sputtering systems, dc and rf sputtering. The dc (direct cur-
rent) sputtering is usually used for metal film deposition. Figure8.14a shows the standard
sputtering system. There are two electrodes in the dc sputtering system. As a negative
dc bias is applied directly on the cathode electrode of the metal target, the stray elec-
trons accelerate and gain energy from the electric field to bombard Ar neutral atoms. If
the bombarding electrons have sufficiently higher energy than the argon ionization energy
(i.e., 15.7 eV), Ar is ionized and plasma is created. The positive argon ions in plasma are
accelerated toward the metal target and sputter metal atoms off. The glow region of the
plasma is a good conductor. At the start of Ar gas breakdown, the voltage between the
Chapter 8. Epitaxial Growth Techniques 49

two electrodes drops and hardly sustains a high field for the generation of plasma. The
secondary electrons emitted from the metal target during sputtering sustain the plasma.

Figure 8.14: (a) Standard sputtering, (b) long-throw sputtering, and (c) sputtering
with a collimator.

Long-Throw Sputtering: By moving the sample farther away from the cathode for
“long-throw” sputter deposition, as shown in Figure8.14 b, an increasing fraction of the
sputtered atoms is lost onto the sidewall of the chamber. This fraction is mainly deter-
mined by the target-to-substrate separation, dts, and scattering of the flux by the working
gas. The larger dts is, the wider the angular distribution. The atoms arriving at the
substrate are more likely to be closer to normal incidence than the conventional, short-
throw deposition. The throw distance of the “long-throw” sputter deposition needs to be
on the order of the cathode diameter. The process is limited in a practical sense by the
gas scattering, which is associated with the operating pressure of the system. To reduce
in-flight scattering, the mean free path for the sputtered atoms should exceed the throw
distance. For “long-throw” sputtering deposition, the working pressure is very low (less
than 0.1 Pa), again to reduce in-flight scattering. At such a low pressure, gas scattering
is less important and the dts can be greatly increased. This allows more deposits at the
bottom of high aspect features such as contact holes.

Collimated Sputtering In a long-mean-free-path deposition environment (mean free

path ¿ throw distance), geometric filtering of the deposition flux can be obtained by
placing a collimator between the target and the sample. The collimator serves as a simple
directional filter by collecting the atoms that impinge on its walls, as shown schematically
in Figure 20c. The degree of filtering is simply a function of the aspect ratio of the
collimator, where aspect ratio is defined as the thickness of the collimator divided by the
diameter of a tube.
Chapter 8. Epitaxial Growth Techniques 50

RF sputtering

Rf (radio-frequency, typically 13.56 MHz, a frequency chosen because of its non-interference

with radio transmitted signals) sputtering is usually used in cases of dielectric materials,
such as the high-k dielectrics. Figure 21 shows the standard rf sputtering system. Its has
several advantages: (a) its ability to sputter dielectrics as well as metals, (b) its ability
to operate in the bias-sputtering mode, and (c) its ability to permit sputter-etching of
substrates prior to deposition. When a time-varying potential is applied to a metal plate
behind the dielectric target in rf sputtering, another time-varying potential is developed
on the opposite target surface through the impedance of the target. Once the gas is broken
down by the acceleration of stray electrons from the electric field to start a discharge, the
current can flow from the plasma to the target surface. Since electrons are more mobile
than positive ions, more electrons are attracted to the front surface of the target during
the positive half cycle than are positive ions in the negative half cycle. Therefore, the
current is larger in the positive cycle than that in the negative cycle, as in a diode. The
resultant electron current causes the target surface to acquire an increasingly negative bias
voltage during successive cycles until the negative average dc voltage is sufficiently high to
retard the electrons’ arrival, so that the net charge arriving at the target surface is zero.
Since the target potential is negative with respect to the plasma, electrons are forced away
from the surface, yielding an ion sheath that is visible as a dark space (because there is
no optical emission from the recombination of electrons and ions) near the target surface.
Positive ions in the sheath are accelerated toward the target by the negative potential. To
prevent accumulation of excessive positive ions at the target surface, the frequency of the
applied voltage must be high. The frequency must be at least 106 Hz for any appreciable
sputtering to occur. Below this frequency, the average energy of the ions is reduced signif-
icantly as a result of positive ions accumulating on the target. RF-sputter etching is the
reverse of the sputtering process, and is also known as back sputtering, reverse sputtering,
ion etching, or sputter cleaning. The normal rf power flow is electrically reversed; the
substrate has a negative average dc voltage and an anode takes the place of the target.
RF-sputter etching is used to clean substrates prior to sputtering a film on them, or to
make patterns on substrates. Bias-sputtering is the bombardment by energetic positive
ions of a growing film that has a negative bias. This technology can remove impurities on
the growing film. Usually, it is used for substrate surface cleaning before dielectric film
deposition.
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