Chemical Vapor Deposition

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Introduction to Chemical Vapor Deposition

A) Chemical Vapor Deposition
CVD Types
CVD Uses
CVD Process
General CVD Reactor Concept
General CVD Process Advantages
General CVD Process Applications
B) Dealing with Engineering Science of CVD Reactions
Transport Processes
Laminar Flow Boundary Layer Concept
Other Susceptor to Flow Axis Options
Thermodynamics
Reaction Kinetics
C) Operational Overview
Polycrystaline Silicon
Silicon Dioxide
Nitride Films

Chemical Vapor Deposition

Current Options

LPCVD

APCVD
Atmospheric Pressure CVD

PECVD
Plasma Enhanced CVD

Low Pressure CVD

Chemical Vapor Deposition

CVD Applications

Customized Surfaces
Epitaxial Layers

Insulator
Silicon dioxide

CV
D

Barriers
Silicon Nitride

Conductors
Polycrystalline
Silicon

Chemical Vapor Deposition

CVD Process

Surface Reaction

r
g

rg

Film

Arrival Flow
Rate

Growth Rate

Input Flow Rate

Surface Reaction Rate

= Growth Rate of Film

Substrate

CVD Reactor Concept

Reaction Chamber
Susceptor
Controlled Thermal Environment

Film Surface

Controlled Pressure Environment

Hydrogen Carrier Gas

With additional film significant containing gas components

General CVD Process Advantages

Excellent Step Coverage
Large Throughput (100 A/min film growth)
Low Temperature Processing (450 to 1000 C)
Applicable to any Vaporization Source Technology
(Laser CVD for direct Writing)
General CVD Process Applications
Epitaxial Films
Enhance performance of Discreet and Integrated Bipolar Devices
Allow Fabrication of RAMs and CMOS in Bulk Substrate
Dielectrics
Insulation between Conducting Layers
Diffusion and Ion Implant Masks
Capping Dopant Films
Extracting Impurities
Passivation to Protect Structures from
Impurities
Moisture
Scratches
Polysilicon Conductors
Gate Electrodes
Conductors for Multilevel Metalizations
Contacts for Shallow Junction Devices

B) Dealing with Engineering Science of CVD Reactions

Transport Processes
Thermodynamics
Reaction Kinetics

Transport Processes
Turbulent Flow

No, to Many Particles.

Molecular Flow

No, to Low a Throughput

Laminar Flow ( Only One Left, Make Do)

Set Conditions For Laminar Flow ( Low Reynolds Number Value)

Tube Diameter

Gas Density
Gas Viscosity

R#= D V(

Reynolds Number
Linear Velocity

Laminar Flow Conditions

Diameter and velocity in tens of cm and cm/s will give
Reynolds numbers in laminar flow regime

Reagent Partial Pressure

Growth

1.67

= 1.76 x 10 ( D /R) (1/ T ) (

T/ y ) (Z) P)

Boundary Layer
Thickness

0.33
Reagents Gas Phase Coefficient
of Thermal Diffusion

Input Reactant Gas Flow

Boundary layer develops along susceptor flow axis

X
1

X
2

Under developed
flow pattern at this
position along
susceptor

Distance Above Susceptor

Susceptor

Velocity Gradient Profiles at Discrete Points along Flow Axis

Graphic Exaggerated for Visual Effect

X
1

X
2

Under developed
flow pattern at this
position along
susceptor

Trends in Gradients
Velocity Values
Increase Along Susceptor
Increase Above Susceptor
Temperature Values
Increase Along Susceptor
Decrease Above Susceptor
Reactant Concentration Value
Decrease Along Susceptor
Increase Above Susceptor

Velocity Gradient Profiles at Discrete Points along Flow Axis

Other Susceptor to Flow Axis Options

Design Factors Include Flow Direction and Wafer Angle

A) Input gas flow

B) Input gas flow

C) Input gas flow

D) Input gas flow

E) Input gas flow

Thermodynamics
CVD Phase Diagram
Give range of input conditions for CVD that could produce specific
condensed phases.
.
Presented as Function of Temperature or Pressure vs Mole Fraction

1200
1000

0.01 Atm

1.0 Atm

TiB 2 Phase

C
0.6

TiB2 & B Phase

1400

Reactant Gas Mole Fraction

B/(Ti + B)

Use Graphic for Educational Value Only

Boron codeposit only in High

Boron Mole Fractions in input
stream
Boron codeposition favored at
higher pressures.

H/HCl = 0.95

K.E. Spear
7 th Conference on CVD 1979
Electrochemical Society Vol 79

Boron-Carbon CVD Phase Diagrams

10

BCl 3 /CH

-1

=4

B4 C + B
10

-2

B4 C + C

B
10

1600 0 C
1.0 Atm

-3

B4C
10

-4

Vapor
10

-4

Carbon
10

-3

10

-2

10

-1

Partial Pressure for Methane

10

-0

Bernard Ducarroir
J. Electrochem. Soc. 123 ,136, 1976

Use Graphic for Educational Value Only

Vanadium-Silicon-Hydrogen-Chloride CVD Phase Diagrams

1200

1100

1000

900

V5Si3

C
VCl2 + V5Si3

VCl2

0 .6

In p u t R e a c ta n t G a s M o le F ra c tio n

H /H C l = 0 .9 5
P = 0.25 atm

S i /(S i + V )

U s e G r a p h ic fo r E d u c a tio n a l V a lu e O n ly

K .E . S p e a r
7 th C o n fe r e n c e o n C V D 1 9 7 9
E le c tr o c h e m ic a l S o c ie ty V o l 7 9

Vanadium-Silicon-Hydrogen-Chloride CVD Phase Diagram

C o m p os itio n rat io s for inp u t gase s o f V C l 4 /S iC l 4 / H 2 a re n o t equ i lib riu m valu e s

Trans port Processes vs Thermo dynamics

Task :

M ak e a V 5 S i 3 fi lm.

P roced ure:

F rom C VD Ph ase D iag ram fo r a 9 00 o C d epo sit io n, a n inp u t g as m o le

fractio n of 0 .20 can b e u sed.

P rob lem :

As V 5 S i 3 fo rm s on sur fac e, actu al reage n t g as S i m o le fract io n c o nsu m e d

at su rface is h ig her (0 .37 5 ) th a n th e in pu t rea cta nt ga s ra tio su pp l ied
(0 .20 ). Th us S i at su rfac e is d ep let ed , m or e Van ad iu m is a va ilab le at th e
su rface and actu al eq u il ibr ium sh ift s to p ro du ctio n of V 3 S i.

P roced ure:

Ho ld tem peratu re c on sta n t bu t sh ift th e in p u t gas m o le fract io n to 0 .5.

P rob lem :

As V 5 S i 3 fo rm s on sur fac e, actu al reage n t v an ad iu m g as m o le fr act ion

con su m ed (0 .62 5 ) is h ig he r th an th e inp u t gas m o le frac tio n fo r va n a d ium .
Th u s Van ad iu m a t su rfa ce is dep leted, m o re S ilic o n is av ailab le at t he
su rface and actu al eq u il ibr ium sh ift s to p ro du ctio n of VS i 2 .

Reaction Kinetics

Titanium Diboron Deposition Arrhenius Plot

Reaction Temperatures (2000 K to 1000 K)
P = 0.263 Atm.
Input flow Rate = 462 cc /min

10.0

1.0
B/(B + Ti) = 0.66
Cl/(Cl + H) = 0.33
5.0

Besmann ,J. Electrochem. Soc.

124 , 790 (1979)
Use Graphic for Educational Value Only

6.0

7.0
-1
1/T (x 10 / K)

8.0

9.0

Input Gases
TiCl 4
BCl 3
H2

Arrhenius Rate Profiles

10.0

(f)

(a)

1.0

1/T
Higher Surface Reaction Rates
Use Graphic for Educational Value Only

Lower Surface Temperatures

Arrhenius Isotherms

Surface Reaction Limiting Growth Rate

(f)

10.0

1.0

(a)
Partial Pressure Reactant Gas
Use Graphic for Educational Value Only

Operational Line for Deposition at Higher Pressure

Desired Growth
Rate

Best Fit Model Behavior based

On 5 Calibration Runs

rg2
rg1
Current
Growth Rate

1/ T 2

New Operating
Temperature

ln (r

g2

1/T

/r

g1

1/ T1
Current
Operating Temperature

T / T T )
) (q
/ k ) (T
act
2
1
2 1

C) Operational Overviews
Polycrystalline Silicon (Polysilicon)

Si
APCVD
o
575 to 650 C

Si
High Exposure Limit
Pyrophoric
Toxic ( 1 Atm but 90% N 2 )

H H H

LPCVD
o
575 to 650 C

25 PA to 130 PA
100% Silane

Si

25 PA to 130 PA
20% to 30% Silane

Si

Considerations
Temperature
At high temperatures get gas phase reactions that produce rough, loosely
adhering deposits and poor uniformity.
At low temperatures deposition rates are to slow for industrial situations.
Zone heating rear of furnace up to 15 oC hotter. (Better film uniformity)
Pressure (LPCVD)
Four popular ways to alter pressure.
Change gas flow rate but keep pumping speed constant.
Change pumping speed with constant flow rate
Change reacting gas or carrier gas with other held constant
Change both gases but keep there ratio constant.

Silicon dioxide

Si
(Oxidation)
400 - 450 C

SiO2

O2

Films Contain Hydrogen as

H

Silanol (SiOH)
Hydride (SiH)
Or Water

Amorphous Structure of SiO4 Tetrahedra

Low Temperature
Loose adhering deposits on side walls of reactor. ( Particles that can
contaminate the film.
At high silane pressures allows for gas phase reactions. ( Promotes
particle contamination and hazy films)
Fair step coverage
Low film density ( 2. 0 g/cm 3 )
Deposition rate complex function of Oxygen concentration
Easy chemical reaction. ( Low activation energy, 0.4 ev (10 kcal/mole) )
Film depends on gas phase transport of material to surface
Low temperature allows production of films that will serve as
insulation between aluminum levels in device.

Medium Temperature

Silane

Tetraethoxysilane
OCH 2CH3

Si
H

H
H

650 to 750 C
NO

SiO 2

Si
O

H
(LPCVD)

CH2CH3

TEOS
H

H
C

650 to 750 C
100 to 1000 std. cc / min
30 PA to 250 PA

SiO 2

High Temperature

D ic h lo r o s ila n e
C l

S i
C l

Nitrous Oxide

8 5 0 to 9 0 0 C

(N 2O )

LPCVD

S iO

Nonlinear pressure dependence that is function of wafer position.

Small amounts of Chlorine in films that tends to cause cracking in a poly layer)
Reagent depletion problems
Phosphorus doping is difficult. ( The phosphorus oxides are volatile at high
deposition temperatures.)
Excellent Uniformity

Cl
H

Si
Cl

Cl

Cl

Cl

H
H

N
H

H Si
Cl H

Si
H

N
H

Precursor
H

Si

Cl

Cl
Cl

Cl

Cl

First Monolayer
of Silicon Nitride
Pad Silicon Dioxide

Except for epi and parallel plate processes both sides of wafer are coated.
Equipment
Furnace with or without vacuum capability
Plasma Chamber
CVD is Crucial to Fabrication of IC's, Especially MOSFETS
(The Bottom Line)