CHEMICAL VAPOR

DEPOSITION (CVD) AND

PHYSICAL VAPOR
DEPOSITON (PVD)
TECHNIQUES
Haris Mehmood
Dilawaiz Fazal
MS-59 Electrical
 CHEMICAL VAPOR DEPOSITION

 In CVD, gases are introduced into the

deposition reactor that react and form the
desired film on the substrate.

 Thin Film deposition are done through

these different CVD schemes.
(APCVD, LPCVD, PECVD, MOCVD)

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PHYSICAL VAPOR DEPOSITION (PVD)

 PVD is used to deposit thin films by the

condensation of a vaporized form of the
material onto the surface.

 Example include evaporation (MBE) and

sputter deposition.

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 ATMOSPHERIC CHEMICAL
VAPOR DEPOSITION (APCVD)

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 ATMOSPHERIC PRESSURE CVD
 Simplest CVD process at an atmospheric
pressure of 760 torr.

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 ATMOSPHERIC PRESSURE CVD

 Wafers are heated by graphite susceptor which

in turn is heated by RF coils
 Wafers are usually placed at some tilt angle from
horizontal to ensure equal gas flows
 The films deposited by CVD can be doped by
arsine (AsH3), phosphine (PH3) and B2H6
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 ATMOSPHERIC PRESSURE CVD

 CHEMICAL REACTION

APCVD is mostly used for epitaxial silicon deposition.

SiCl4 + 2H2 → Si + 4HCl

This reaction occurs at the growing surface on the

substrate at the temperature of 1150-1300oC for 3 -5
minutes and at atmospheric pressure (760 torr)

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 ATMOSPHERIC PRESSURE CVD

 DEPOSITION RATE
Measure of how fast the film can be grown on the
substrate. Figure shows the concent.
and fluxes in the gas-phase boundary
layer and at the wafer surface.
F1 = hG (CG-CS) ------- (i)
F2 = kSCS ----------------(ii)

hG is the mass transfer coefficient.

kS is the chemical surface reaction rate

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 ATMOSPHERIC PRESSURE CVD
The mass transfer coefficient is a diffusion rate constant that relates the
mass transfer rate (n), mass transfer area (A), and concentration
gradient (Δc) as driving force:

hG = n / (A*Δc)

According to the steady state conditions, the two fluxes must be equal
to each other:

CS = CG ( 1 + kS / hG ) -1

The deposition rate is given by

v = F/N

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 ATMOSPHERIC PRESSURE CVD
 ADVANTAGES
- Low equipment cost
- SiCl4 is non-toxic, inexpensive and easy to purify
- High deposition rates

 DISADVANTAGES
- SiCl4 requires higher temperature than silane process
- Periodic manual cleaning of injectors are required

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 ATMOSPHERIC PRESSURE CVD
 VLSI APPLICATIONS
- Used for making thick oxides
- Epitaxial is used to improve the performance of
dynamic random access memory devices and CMOS ICs
as APCVD manufactures good quality epitaxial silicon
layer

 HAZARDS AND SAFETY PRECAUTIONS

The by-product of epitaxial silicon reaction, HCl gas, is
very dangerous and toxic. Brief exposure of the gas to
the operator can occur during manual cleaning.
Respirators, acid gloves, safety glasses are to be worn to
minimize the risk involved.
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 LOW PRESSURE CHEMICAL
VAPOR DEPOSITON (LPCVD)

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 LOW PRESSURE CVD

 LPCVD reactors opearte at medium vacuum pressure

(30-250 Pa).
 Wafers stand vertically, perpendicular to the gas flow.

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 LOW PRESSURE CVD
 CHEMICAL REACTIONS

LPCVD deposition of Silicon Oxide (LTO)

SiH4 + O2 → SiO2 + 2H2 (at 430oC)
LPCVD deposition of Silicon Oxide (HTO)
SiH2Cl2 + 2N2O→ SiO2 + 2HCl + 2N2 (at 900oC)
LPCVD deposition of Silicon Nitride
3SiH2Cl2 + 4NH3→ Si3N4 + 6HCl + 6H2 (at 750oC)
LPCVD deposition of Polysilicon and Metals
SiH4 → Si + 2H2 (at 600oC)
WF6 + 3H2 → W + 6HF
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 LOW PRESSURE CVD
 DEPOSITION RATE

We have DG proportional to
1/Ptot

Lowering the pressure of the

gas stream increases the
diffusion and extends the
higher temperature (1/T).
Use PV = nRT Law.

Since hG is larger at lower

pressure, surface reaction
will be carried out at low pace.
See Figure for clarification. 15
 LOW PRESSURE CVD
 ADVANTAGES
- Lower chemical reaction temperature as compared to
APCVD
- Good step coverage and uniformity
- Less dependance on gas flow dynamics
- Highly pure sample obtained

 DISADVANTAGES
- Lower deposition rate than APCVD
- Frequent use of toxic and flammable gases such as
ammonia, silane, fluorine, hydrogen fluoride, HCl, etc.
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 LOW PRESSURE CVD
 VLSI APPLICATIONS
- Gate contacts in MOS and interconnected lines made by LPCVD-
assisted Polysilicon
- Thick oxides are used for isolation between metal interconnects.
- Silicon Nitride is used for encapsulation
- Oxide/Nitrides are used in FLASH memories
- Metals for interconnected lines in CMOS

 HAZARDS AND SAFETY PRECAUTIONS

Ammonia, silane are very dangerous, flammable and toxic. Brief
exposure of the gas to the operator can occur during manual
cleaning. Personal proctective equipment is worn to minimize the
risk such as Respirators, acid gloves, safety glasses, armguards,
aprons.

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PLASMA ENHANCED CHEMICAL
VAPOR DEPOSITION (PECVD)

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 PLASMA ENHANCED CVD

 PECVD is mostly used to deposit dielectrics

 The plasma is created by RF power ionizing some of the
reacting gases between the two electrodes. The energetic
species are used to help form the films on top of the wafers.
 Presence of plasma lowers the temperature at which reaction
is possible.
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 PLASMA ENHANCED CVD
 CHEMICAL REACTIONS

3SiH4 + 4NH3→ Si3N4 + 24H2 (below 350oC)

PECVD is carried out at the frequency ranging from 100

kHz to 40 MHz. The process does not require deep
vacuum so the reduced pressure between 50 mTorr to
5 Torr is used.

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 PLASMA ENHANCED CVD
 DEPOSITION RATE
PECVD has lower deposition rate than that of APCVD and LPCVD.

 ADNAVTAGES
- Lower process temperature
- Films of good dielectric properties
- Good conformal step coverage

 DISADVANTAGES
- The highly energetic plasma gases can pose damage to the
substrate
- High cost of equipment and toxic byproduct

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 PLASMA ENHANCED CVD
 VLSI APPLICATIONS
- PECVD nitride is suitable for passivation layers
- PECVD processed products are used in VLSI-DRAM
memory cells
- PECVD a-Silicon is used in solar cells
- Used for depositing materials like Silicon Oxide, Silicon
Nitride, Carbon, Amorphous Silicon and polysilicon

 HAZARDS AND SAFETY PRECAUTIONS

Silane and Si3N4 are very dangerous and toxic. Brief
exposure of the gas to the operator can occur during
manual cleaning. Personal proctective equipment is worn
to minimize the risk such as Respirators, acid gloves,
safety glasses, armguards, aprons.
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MOLECULAR BEAM EPITAXY
(MBE)

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 MBE
 MBE is used to deposit single
crystals.
 MBE creates a molecular
beam of material by
evaporating it under ultra-
high vacuum (5 e-11 mbar
pressure) and is focused on
the substrate by effusion cells
 RHEED (reflection high
energy electron diffraction) is
used to monitor film growth
 Mass spectrometer collects
stoichiometric data
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 MBE
 CHEMICAL REACTION
To deposit silicon layer, Si2H6 is evaporated in the effusion cells
to give silicon

Si2H6 → 2Si + 3H2 (at 600oC)

 DEPOSITION RATE
Slow deposition rates require proportionally better vacuum. In
MBE, evaporation is carried out at very low deposition rates. For
good epitaxy, we want rate to be

R < (constant) e –Ed/(k*Tc)

where Ed = desorption energy

Tc = epitaxy critical temperature

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 MBE
 ADVANTAGES
- Well-controlled process
- Grow film with good crystal stucture
- often use multiple sources to grow alloy films
 DISADVANTAGES
- Low growth rate
- Sophisticated and expensive equipment
 VLSI APPLICATIONS
- Used in high frequency receivers (portable phones)
- Optoelectronics (DVD, Digital Computers)
- For producing superconductors (YBa2Cu3O7-8)
- Used in silicon process technology
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 METAL ORGANIC CHEMICAL
VAPOR DEPOSITION (MOCVD)

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Compare of epitaxial methods
Growth method time features limit
MBE 1958 Deposit epilayer at Hard to grow materials
(Molecular Beam 1967 ultrahigh vacuum with high vapor pressure
Epitaxy)
MOCVD 1968 Use metalorganic Some of the sources like
(Metal-Organic compounds as the AsH3 are very toxic.
Chemical Vapor sources
Deposition)

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2. The MOVCD growth system

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Reactor-1

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MOCVD Growth System

Reactor
Gas handle
system

Vacuum and
Exhaust system
Computer
Control

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 Gas handling system
The function of gas handling system is mixing of the gas that will
enter the reactor. Timing and composition of the gas entering the
reactor will determine the epilayer structure.
 
Leak-tight of the gas panel is essential, because the oxygen
contamination will degrade the growing films’ properties.

 
Accurate control of flow rate, pressure and temperature can ensure
the stable and repeat.

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 Exhaust system
Pump and pressure controller
For low pressure growth, we use mechanic pump and pressure
controller to control the growth pressure. The pump should be designed
to handle large gas load.

 Waste gas treatment system and safety concerns

The treatment of exhaust gas is a matter of safety concern.
The MOCVD system for GaAs and InP use toxic materials like AsH 3 and
PH3. The exhaust gases still contain some not reacted AsH3 and PH3,
Normally, the toxic gas need to be removed by using chemical scrubber
and extra safety precautions need to be carried out to minimize the
risks involved.

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 3. Metalorganic compound
MOCVD is used for preparing compound semiconductors.
The vapor pressure of the MO source is an important consideration
in MOCVD, since it determines the concentration of source material
in the reactor and the deposition rate. Too low of a vapor pressure
makes it difficult to transport the source into the deposition zone
and to achieve reasonable growth rates. Too high of a vapor
pressure may raise safety concerns if the compound is toxic.

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 Vapor pressure of most
common MO compounds
Compound P at 298 K A B Melt point
(torr) (oC)

(Al(CH3)3)2 TMAl 14.2 2780 10.48 15

Al(C2H5)3 TEAl 0.041 3625 10.78 -52.5
Ga(CH3)3 TMGa 238 1825 8.50 -15.8
Ga(C2H5)3 TEGa 4.79 2530 9.19 -82.5
In(CH3)3 TMIn 1.75 2830 9.74 88
In(C2H5)3 TEIn 0.31 2815 8.94 -32
Zn(C2H5)2 DEZn 8.53 2190 8.28 -28
Mg(C5H5)2 Cp2Mg 0.05 3556 10.56 175
Log[p(torr)]=B-A/T

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Reaction

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 6. MOCVD grow GaN and
related materials
TMGa

NH3

1150oC
1050oC
Temperature 550oC

High Buffer Epilayer

temperature layer Growth
treatment

Ga(CH3)3+NH3 GaN+CH4

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Two Step MOCVD Growth procedure
Advantages:
• Highly flexible—> can deposit semiconductors, metals,
dielectrics.
•Used for preparing compound semicondutors

Disadvantages:
•HIGHLY TOXIC! Very expensive source material.
•Environmental disposal costs are high

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