Epitaxial

Presentation by
P. KARUPPANAN
Assistant Professor,
Department of Electronics and Communication Engineering
Motilal Nehru National Institute of Technology Allahabad
Email: karuppanan1982@gmail.com
 Outline of the Presentation
1. Epitaxy -overview
2. Types of Epitaxy
3. Why Epitaxial Growth?
4. Scheme of Epitaxial-growth / Steps & Parameters
5. Epitaxial Deposition Techniques
1. Vapour Phase Epitaxial (VPE) or Chemical
Vapor Deposition (CVD) -
MOCVD/OMVPE/OMCVD/MOVPE
2. Molecular Beam Epitaxial (MBE)
3. Liquid Phase Epitaxial (LPE)
6. Overview of Epitaxy Techniques 2
 Epitaxy
 The term Epitaxy comes from the
Greek word meaning ‘ordered upon’
introduced by L. Royer at 1936.

 Epitaxy means the growth of a single

crystal film on top of a crystalline
substrate with controlled thickness
and doping

 For most thin film applications (hard

and soft coatings, optical coatings,
protective coatings) it is of little
importance. Its different from thin
film deposition that deposit
polycrystalline or amorphous film

 However, for semiconductor thin film

technology it is crucial.
 Epitaxial Growth
 High Quality Film (1μm or less thickness) deposited on a high
quality substrate.

 Epitaxial layer thickness 1 to 100 μm with Low DOPING

concentration. (substrate/wafer thickness= 500-800 μm)

 Lightly doped epitaxial P-type layer (10 Ohm-cm) can be grown on a

heavily P-doped substrate wafer (0.2 Ohm-cm)

 To ensure high crystalline quality, the

lattice parameters of the thin layer
should match with that of the substrate
(to minimize strain).

 Ordered, crystalline growth

Epitaxial growth
 Why Epitaxial Growth
 While Si is not the ideal material from an electronic and optical point of
view, its abundance, ease of processing and availability of a good native
oxide have made it the backbone of semiconductor industry.

 Combining Si substrates with compound semiconductor films would

enable higher optoelectronic functionality and higher speeds. However,
there are severe lattice mismatch and chemical compatibility issues between
Si and most III-V alloys that preclude direct growth.

 Metal-Semiconductor Hetero-epitaxy: Metal-semiconductor structures are

used for contact applications.
 Epitaxial growth allows increased electron mobility through a junction.
 Epitaxial growth is useful for applications that place stringent demands on a
deposited layer:
 High purity, Low defect density, Abrupt interfaces, Controlled doping
profiles
 High repeatability and uniformity, Safe, efficient operation
 Can create clean, fresh surface for device fabrication
 Why Epitaxial Growth (Cont…)
 Engineered wafers
 Clean, flat layer on top of less ideal Si substrate
 On top of SOI structures
 Ex.: Silicon on sapphire
 Higher purity layer on lower quality substrate (SiC)
 In CMOS structures
 Layers of different doping
 Ex. p- layer on top of p+ substrate to avoid
latch-up
 To make layer which is not available in
nature
 Very important in III-V semiconductor
production
 Bipolar Transistor (Needed to produce
buried layer)
 III-V Devices (Interface quality key,
Hetero-junction Bipolar Transistor,
LED, Laser).
 Types of Epitaxy
Homoepitaxy:
 The film and the substrate are the same material.
 Often used in Si on Si growth
 Epitaxially grown layers are purer than the substrate and can be
doped independently of it.

Heteroepitaxy:
 Film and substrate are different materials.(Growth of AlAs on Si or
GaAs on Si).
 Trying to grow a layer of a different material on top of a substrate
leads to unmatched lattice parameters.
 This will cause strained or relaxed growth and can lead to interfacial
defects.
 Such deviations from normal would lead to changes in the electronic,
optic, thermal and mechanical properties of the films.
 Allows for optoelectronic structures and band gap engineered
devices.
Principle of Epitaxial-growth

8
 Scheme of Epitaxial-growth Steps & Parameters

Steps: Parameters:
1. Absorption of ad atoms 1. Growth temperature
2. Surface diffusion 2. Growth pressure
3. Epitaxial growth 3. Flow amount of reactants
4. Evaporation of atoms 4. Substrate and treatment
Principle of Epitaxial-growth

10
 Epitaxial Growth Rate – S M Sze

Undoped Epi − Layer on Uniformly Doped Substrate

Ns –Concentration co-
 NS  x − xepi  efficient of the substrate
N1 ( x , t ) =
1 + erf   Ne- Concentration co-
2  2 D t 
 S  efficient of the epitaxial
D- Diffusion co-efficient
Doped Epi − Layer on Undoped Substrate
NE   x − xepi  v x  x + xepi 
N 2 ( x, t ) = 1 + erfc  + exp x
erfc 
2 2 D t  D  
  E  E  2 DE t 
 Epitaxial Growth Rate S M SZe (Cont…)
J S = kS N S

 Dg 
Jg =  (N g − N S ) = hg (N g − N S )
 δ 
 

Gas diffuses from JS = Jg

gas stream and
reacts at the surface Ng
Mass Transfer Limited : v ≅ hg for k S >> hg
N

Ng
Surface Reaction Limited : v ≅ k S for hg >> k S
N

JS k S hg N g
Growth Rate v= =
N k S + hg N
 Epitaxial Growth Rate S M SZe (Cont…)
Reversible Deposition Process at 1200o C
SiCl4 ( gas ) + 2 H 2 ( gas ) ↔ Si (solid ) + 4 HCl ( gas )

HCl in Input Stream can be Used to Clean Surface

Competing Etching Reaction

SiCl4 ( gas ) + Si (solid ) ↔ 2 SiCl2 ( gas )

Alternative - Pyrolytic Decomposition of Silane

o
SiH 4 600
 C
→ Si + 2 H 2
Temperature dependence of the
silicon epitaxial growth process
for four different sources.
The growth is surface-reaction-
limited in region A and is mass-
transfer-limited in region B.
Epitaxial Growth Rate by Balwinder

1-
Epitaxial Growth Rate by Balwinder (Cont.)

1-
Epitaxial Deposition Techniques

16
 Epitaxial Deposition Techniques
Epitaxial growth can be performed at temperatures
considerably below the melting point of the substrate
crystal. A variety of methods are used to provide the
appropriate atoms to the surface of the growing layer.
1. Vapor Phase Epitaxy/Chemical vapor deposition /
PECVD (Plasma-Enhanced Chemical Vapor
Deposition)
2. Liquid phase epitaxy (grown from a Melt)
3. Molecular beam epitaxy (an evaporation of the
elements in a Vacuum)
With this wide range of epitaxial growth techniques, it is
possible to grow a variety of crystals for device applications,
having properties specifically designed for the electronic and
optoelectronic device being made.
 Epitaxial Deposition Techniques (Cont…)
Liquid Phase Epitaxy
 Reactants are dissolved in a molten solvent at high temperature
 Substrate dipped into solution while the temperature is held
constant
 Example: SiGe on Si
 Bismuth used as solvent
 Temperature held at 800°C
 High quality layer
Molecular Beam Epitaxy
 Very promising technique
 Beams created by evaporating solid source in UHV
 Not ideal for large area layers or abrupt interfaces
 Thermodynamic driving force relatively very low
Epitaxial Deposition Techniques (Cont…)
 MOMBE---means when Metel Organic Source used for MBE

 Sputtering--- the layer quality is very poor. Thus it is used for

making contact with the help of metal related source.

 HVPE---Hydride Vapor Phase Epitaxy

 Pulse laser Deposition (PLD)

 Reactive Evaporation

 Electron Beam Plasma Technique

 Solvo thermal Method

*Advantages, Disadvantages, and Applications of all these
techniques are very much important. Please collect all the
information……………….
 Vapor Phase Epitaxy

Metal Organic Chemical Vapour

Deposition
Vapor Phase Epitaxy

21
 Vapor Phase Epitaxy (Cont…)
• Reactants introduced as gases
• Material to be deposited bound to ligands (A substance as an atom,
molecule, radical or ion). The Ligands dissociate, allowing desired
chemistry to reach surface
• Some desorption, but most adsorbed atoms find proper crystallographic
position. Example: Deposition of silicon
– SiCl4(g) + 2H2(g) ↔ Si(s) + 4HCl(g),
– SiCl4 introduced with hydrogen, Forms silicon and HCl gas
– SiH4 breaks via thermal decomposition
– Reversible and possible to do negative (etching)
Precursors for VPE
• Must be sufficiently volatile to allow acceptable growth rates
• Heating to desired Temperature must result in pyrolysis
• Less hazardous chemicals preferable
– Arsine highly toxic; use t-butyl arsine instead
• VPE techniques distinguished by precursors used
 MOCVD/OMVPE/OMCVD/MOVPE
 MOCVD stands for Metal-Organic Chemical Vapour Deposition.
 MOCVD is a technique that used to grow/deposit thin solid films,
usually semiconductors, on solid substrates (wafers) using organo
metallic compounds as sources.

 The films grown by MOCVD are mainly used for the fabrication of
electronic and optoelectronic devices.

 The electronic and optoelectronic devices produced by MOCVD are

used in cell phones , optical communication, optical storage (CD,
DVD), traffic lights, bill boards (LEDs), lighting and solar cells.

 Using MOCVD we can build up many layers, each of a precisely

controlled thickness, to create a material which has specific optical
and electrical properties.
 Why MOCVD?
 Epitaxial films can be grown from solid, liquid, or gas phases. It is
easier to control the growth rate in gas phase Epitaxy by
controlling the flow of gases.
 High grown layers quality, Highest flexibility
 Faster growth rate than MBE, can be a few microns per hour;

 Multi-wafer capability easily achievable. Different materials can be

grown in the same system.

 Doping uniformity/reproducibility, Economically advantageous.

 High throughput and no ultra high vacuum needed (compared to
MBE),
 Precision in deposition thickness and possible sharp interfaces growth
–thus, it is very suitable for hetero-structures, e.g., multi quantum
wells (MQW)

 Higher temperature growth; growth process is thermodynamically

favorable
 MOCVD Limitations
 Many materials that we wish to deposit have very low vapour
pressures and thus are difficult to transport via gases

 Not abruptable process as MBE due to gas flow issues

 Human Hazard, that is, Toxic and corrosive gases are to be handled

 High temperatures

 Complex processes

 Carbon contamination and unintentional Hydrogen incorporation

are sometimes a problem
 Schematic of MOCVD

Main parts:
1. Source Supply System
2. Reactor
3. Exhaust System
 MOCVD System
Source Supply System: The different sources which are used are shown in Fig.
 TMI (Trimethylindium) and TEG (Triethylgalium) are used as source
material for In and Ga respectively.
 NH3 is used as a source material for nitrogen.
 N2 is used as a carrier gas to bring TMI and TEG into the reactor.
 H2 gas is used for the thermal treatment of the substrate.
 Reactive gases are fed in to the reactor through the mass flow controllers
(MFC)

Reaction Chamber/ Reactor:

 Epitaxial vapor growth is made inside the reactor at different conditions
(temperature, pressure, gas flow).
 The substrates are placed on the susceptor.
 Reactive gases are then fed into the reactor and these gases react on the
substrate and form a grown film.
 The heating method of this reactor is RF induction heating.
 MOCVD System (Cont…)
Exhaust System:
The exhaust system consists of rotary and diffusion pump.
When reactions are take place, the exhaust gases are then
released to air through rotary pump and exhaust fan.

The deposition reaction, which takes place inside the reactor, for the
grown of the nitride film is known as pyrolysis.

The formation of solid InN and GaN film on the substrate are
happened by the following chemical reactions in vapor phase with the
organometallic reactant species. For this reason it is called organo-
metal vapor phase epitaxy.
 MOCVD System (Cont…)
(CH3)3 In + NH3 →→ 3CH4(v) + InN(s)
Trimethal indium gas) (Amonnia gas) (Methane gas) (on the substrate)
(C2H5)3 Ga + NH3 →→ 3C2H6(v) + GaN(s)
Triethylgalium gas) (Amonnia gas) (Ethane gas) (on the substrate)
(CH3)3 Ga + AsH3 →→ 3CH4 + GaAs
Trimethylgallium gas) (Arsene gas) (Methane gas) (on the substrate)
(CH3)3 In + PH3 →→ 3CH4 + InP
Trimethylgallium gas) (Phosphene gas) (Methane gas) (on the substrate)

Transport
and Growth
Mechanisms
 MOCVD System (Cont…)

Deposition process takes place on the substrates (wafers)

 Epitaxial silicon deposition
Advantages of epitaxial wafers over bulk wafers
• Offers means of controlling the doping profile (e.g. lightly doped on
heavily doped possible)
• Epitaxial layers are generally oxygen and carbon free
• Gases used in silicon epiittaxy

Concentration of species at different positions along a horizontal reactor

(carrier gas should be H2)
SiCl4 + 2H2 → Si + 4HCl
 Chemical reactions

2AsH3 (gas) → 2As (solid) + 3H2 (gas)

 Polycrystalline silicon deposition
SiH 4 600
 °C
→ Si + 2H 2 H2 carrier gas for solid curves
1. Application: gate of MOSFET.
2. Usually deposited in a LPCVD chamber at 25-150Pa, 600-650oC,
10-20nm/min.
3. SiH4 is preferred because of its lower deposition temperature.
4. Usually amorphous when deposition at <575oC; but may be
polycrystalline if deposition rate is low enough.
5. Columnar grain structure/texture, and the grain will grow when
annealed. When annealed, amorphous Si will become polycrystalline
Si with even large grain size than poly-Si under same annealing.
 Silicon nitride deposition
• Application:
oMasks to prevent oxidation for LOCOS process
oFinal passivation barrier for moisture and sodium contamination
oEtch stop for Cu damascene process
oPopular membrane material by Si backside through-wafer wet etch.

• PECVD SiH 4 + NH 3 200

− 400° C
→ SiN x H y + H 2

• LPCVD 3SiH 4 + 4 NH 3 650

− 800° C
→ Si3 N 4 + 12 H 2

3SiCl2 H 2 + 4 NH 3 650
− 800° C
→ Si3 N 4 + 6 HCl + 6 H 2
• Can also deposit nitride using silane at 700-900oC by APCVD
(Atmospheric Pressure CVD); or use N2 gas instead of NH3.
• Low-stress nitride deposition using DCS (dichloro-silane SiCl2H2)
34
 Silicon dioxide deposition
Sputtered oxide has poorer step coverage than CVD.
APCVD has been used for many years, but today LPCVD (Low Pressure
CVD) and PECVD (Plasma - Enhanced CVD) are more popular.
• Silane based LPCVD

• TEOS (tetra-ethoxy-silane). LPCVD 650-800°C, PECVD

350°C. Lower sticking coefficient, thus more conformal film.

• Silane based PECVD

• Others

SiCl2H2 + 2N2O → SiO2 + 2N2 + 2HCl (etches Si), ∼900oC,

film contain Cl.
TEOS + Ozone (O3). Ozone is more reactive and lowers
deposition temperature to ∼400oC.
 Material Source should be
 Sufficiently volatile

 High enough partial pressure to get good growth rates

 Stable at room temperature

 Produce desired element on substrate with easily removable by-

products

 Growth of III-V semiconductors:

 Group III: generally metalorganic molecules (trimethyl- or triethyl-
species)
 Group V: generally toxic hydrides (AsH3; PH3 flammable as well);
alternative: alkyls (TBAs, TBP).
 Applications

Laser diode Transistors LED

Solar Cells
Molecular Beam Epitaxy
 Molecular Beam Epitaxy (MBE)
1. MBE process developed -> 1960s at Bell Lab by J. R. Arthur & Alfred Y. Cho.

2. Growth of epitaxial films on a hot substrate from molecular beams under ultra-
high vaccum conditions(10−8–10−12 Torr).

3. For III-V semiconductors (also used for IV, II-Vis, metals, oxides etc.)

4. The absence of carrier gases, as well as the ultra-high vacuum environment, result
in the highest achievable purity of the grown films.

5. MBE is widely used in the manufacture of semiconductor devices, including

transistors, and it is considered one of the fundamental tools for the development of
nanotechnologies

6. It is also used for the deposition of some types of organic semiconductors. In this
case, molecules, rather than atoms, are evaporated and deposited onto the wafer.

7. MBE systems can also be modified accordingly to the needs. Oxygen sources,
for examples, can be incorporated for depositing oxide materials for advanced
electronic, magnetic and optical applications, as well as for fundamental research.
Molecular Beam Epitaxy (MBE) system
Molecular Beam Epitaxy System (Cont)
 Working Principles of MBE System (Cont.)
1. Here in MBE reactants are introduced by molecular beams.
2. Create beams by heating source of material to melting point in an
effusion (or Knudsen) cell.
3. Both solid and gas source can be used.

4. Pyro-lytic boron nitride (PBN) is chosen for crucibles which is

chemically stable up to 1400’C).
5. Molybdenum and Tantalum are widely used for shutters.
6. Ultrapure materials are used as source.

7. The solid source (sublimation) provides an angular distribution of

atoms or molecules in a beam.
8. The gaseous elements can crack/condense on the wafer where they
may react with each other
9. Several sources (several beams of different materials) aimed at
substrate
 Working Principles of MBE System (Cont.)
10. UHV gives source molecules a large mean free path, forming a
straight beam.

11. Beam impinges on a heated substrate (600’C).

12. The beams can be shuttered in a fraction of second. A computer

controls shutters in front of each furnace, allowing precise control of
the thickness of each layer, down to a single layer of atoms. Intricate
structures of layers of different materials may be fabricated this
way. Such control has allowed the development of structures where
the electrons can be confined in space, giving quantum wells or even
quantum dots.

13. Incident molecules diffuse around the surface to the proper crystal
sites and form crystalline layers.
 Working Principles of MBE System (Cont.)
14. Atoms on a clean surface are free to move until finding correct
position in the crystal lattice to bond
15. Characterization tools allow growth to be monitored in-situ.
16. During operation, Reflection High-Energy Electron Diffraction
(RHEED) is often used for monitoring the growth of the crystal
layers.
17. Mass spectrometer for monitoring the residual gases and checking
source beams for leaking.
18. A cryogenic screening around the substrate as a pump for residual
gases.
19. Such layers are now a critical part of many modern semiconductor
devices, including semiconductor lasers and light-emitting diodes.

20. The term "beam" means that evaporated atoms do not interact with
each other or vacuum-chamber gases until they reach the wafer, due
to the long mean free paths of the atoms.
MBE Abilities
Effusion Cell Construction
 RHEED
 Reflection High Energy Electron
Diffraction for monitoring the
growth of the layer
 Probe only few monolayers.
 Information about the state of the
layers (2D, 3D etc.)
 Information about the crystallinity.
 Measures the lattice parameter
 Growth rate can be obtained from
RHEED oscillation A typical MBE system*

Molecular Beam Epitaxy

In-situ Characterization
MBE Applications
 MBE Applications (Cont…)
Novel structures as quantum devices
Silicon/Insulator/Metal Sandwiches
Superlattices
Microelectronic Devices

TEM image of MBE Growth of Ultra-Thin InGaAs/AlAsSb

Quantum Wells
MBE in Industry
 Benefits and Drawbacks of MBE
Advantages Limitations
 Clean surfaces, free of an oxide  Expensive (106 $ per MBE
layer chamber)
 In-situ deposition of metal  ATG instability
seeds, semiconductor materials,
and dopants
 Low growth rate (1μm/h)  Very complicated system

 Precisely controllable thermal  Epitaxial growth under ultra-

evaporation high vacuum conditions
 Seperate evaporation of each
component
 Substrate temperature is not
high
 Ultrasharp profiles
 MBE vs MOCVD
Both of these techniques allow crystals to be deposited on a substrate
one monolayer at a time with great precision.
Both techniques can produce highly epitaxial films with excellent
abruptness, allowing thin layers to be formed.
These techniques are very useful for artificial crystal structures such
as “superlattices” and “quantum wells”.

MOCVD: Gases are let into the reactor at high pressure ~ 1 torr
MOCVD has a higher growth rate and less downtime.
It also has no issues regarding phosphor deposition.
MBE: Always done under UHV conditions,
with pressures below 10-8 torr
The UHV of MBE allows for better in situ diagnostic techniques to be
employed.
Substrate temperatures are lower in MBE.
MBE is relatively safer
 MBE vs MOCVD (Cont…)
MBE
Mainly useful for research lab experiments.
Not efficient for mass production!

MOCVD
Useful for lab experiments & For mass
production!

MANY MILLIONS OF
$$$$ FOR BOTH!!!!!
 MBE vs MOCVD (Cont…)

 MBE: reactions occur only at the substrate

 MOCVD: parasitic reactions can occur before the

reactant species reach the substrate.

 MBE growth, unlike MOCVD growth, is not

thermodynamically favorable and is governed by
Kinetics
Liquid Phase Epitaxial
(LPE)

56
 Liquid Phase Epitaxy (LPE)
 LPE involves the precipitation of a crystalline film from a
supersaturated melt on to a substrate.

 The temperature is increased until a phase transition occurs and

then reduced for precipitation.

 By controlling cooling rates the kinetics of layer growth can be

controlled.
 Once can have either continuous reduction with the substrate
(equilibrium cooling) or separate reduction in increments followed by
contact with the substrate (step cooling).

 It is a low cost method yielding films of controlled composition,

thickness and lower dislocation densities.

 Disadvantages are rough surfaces and poor thickness uniformity.

Liquid Phase Epitaxy (LPE)
Overview of Epitaxy Techniques

59
 Overview of Epitaxy Techniques (Cont...)

Techniques Strengths Weaknesses

LPE (liguid phase Simple, High purity Scale economies Inflexible,
epitaxy) Non-uniformity

HVPE( hydride Well developed Large scale No Al alloys Complex process/

vapor phase reactor control difficult,
epitaxy) Hazardous sources

MBE Simple process, Uniform, As/P alloy difficult,

Abrupt interface In-situ
monitoring
MOCVD Most flexible, Large scale
OMVPE production Abrupt interface
OMCVD Simple reactor, High purity,
selective in situ monitoring
MOVPE
Expensive ,
Low throughput
Expensive sources Most
parameters to control
Accurately Hazardous
precursors
We have divided these epitaxial defects in four categories: 3D
defects (epi-stacking faults and inclusions), 2D defects (stacking
faults), 1D defects (dislocations), and 0D defects (point defects).
Stacking fault tetrahedra, misfit and threading dislocations in
heteroepitaxial (111) CdTe / (001) GaAs. Plane view transmission
electron microscopy 61
 Summary of Epitaxy Techniques
1. Epitaxy means the growth of a single crystal film on top of a
crystalline substrate with controlled thickness and doping
2. Epitaxial layer thickness 1 to 100 μm with Low DOPING
Homoepitaxy- The film and the substrate are the same material.
3. Heteroepitaxy:-Film and substrate are different materials.(Growth of
AlAs on Si or GaAs on Si).
4. Epitaxial Growth Rate- Gas/liquid/molecules reactant species
diffuses from gas/liquid/molecules stream and reacts at the surface to
grow the epitaxial layer on the Substrate/Wafer.
5. A variety of methods are used to provide the appropriate atoms to the
surface of the growing layer.
1. CVD/VPD - Growth rate: ~2 µm/min.
2. LPE (grown from a Melt) - Growth rate: 0.1-1 µm/min
3. MBE - Growth rate: 1µm/hr.
6. Epitaxial defects in 4 categories: 3D defects (epi-stacking faults and
inclusions), 2D defects (stacking faults), 1D defect (dislocations),
and 0D defects (point defects). 62
Thank You

Any ???

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