Chemical Vapor Deposition

This presentation is partially animated. Only use the control panel at

the bottom of screen to review what you have seen. When using
your mouse, make sure you click only when it is within the light blue
frame that surrounds each slide.
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

APCVD LPCVD
Atmospheric Pressure CVD Low Pressure CVD
PECVD
Plasma Enhanced CVD
Chemical Vapor Deposition
CVD Applications

Customized Surfaces
Epitaxial Layers

Insulator Conductors
CVD
Silicon dioxide Polycrystalline
Silicon

Barriers
Silicon Nitride
Chemical Vapor Deposition
CVD Process

Input Flow Rate

Arrival Flow

Growth Rate
Rate

Film
Surface Reaction
Surface Reaction Rate
r
g

r g = 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 RAM’s 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( D µ )

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

5 1.67
R = 1.76 x 10 ( $
D /R) (1/ T ) ( T/ y ) (Z) P)
Growth
Boundary Layer
Thickness

$' " % 0.33

Reagent’s Gas Phase Coefficient
of Thermal Diffusion
Input Reactant Gas Flow

X X X X
1 2 3 4

Boundary layer develops along susceptor flow axis

Susceptor

flow pattern at this

X X X X
Distance Above Susceptor

Under developed
1 2 3 4

position along
susceptor
Velocity Gradient Profiles at Discrete Points along Flow Axis
Graphic Exaggerated for Visual Effect
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

flow pattern at this

X X X X

Under developed
1 2 3 4

position along
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

Boron codeposit only in High

Boron Mole Fractions in input
stream
0.01 Atm 1.0 Atm
o
1400 C

TiB2 & B Phase

Boron codeposition favored at
o higher pressures.
1200 C TiB 2 Phase

o
1000 C

0.6 H/HCl = 0.95

Reactant Gas Mole Fraction
B/(Ti + B)

K.E. Spear
7 th Conference on CVD 1979
Use Graphic for Educational Value Only Electrochemical Society Vol 79
Boron-Carbon CVD Phase Diagrams

10 -1 BCl 3 /CH 4 =4

B4 C + B
-2
10

B4 C + C 1600 0 C
B 1.0 Atm
-3
10

B4C
-4
10
Vapor Carbon

-4 -3 -2 -1 -0
10 10 10 10 10

Partial Pressure for Methane Bernard Ducarroir

J. Electrochem. Soc. 123 ,136, 1976
Use Graphic for Educational Value Only
Vanadium-Silicon-Hydrogen-Chloride CVD Phase Diagrams

1200 oC

1100 oC

1000 oC V5Si3

900 oC
VCl2 + V5Si3
VCl2 H/HCl = 0.95
0.6
P = 0.25 atm
Input Reactant Gas Mole Fraction
Si /(Si + V)

K.E. Spear
7th Conference on CVD 1979
Use Graphic for Educational Value Only Electrochemical Society Vol 79
 Vanadium-Silicon-Hydrogen-Chloride CVD Phase Diagram
Compos ition ratios for input gases of VCl 4 /SiC l4 /H2 are not equilibrium values

Trans port Processes vs Thermo dynamics

Task: Make a V5 Si3 film.

Procedure: From C VD Phase D iagram for a 900 o C deposition, an input gas mole
fraction of 0.20 can be used.

Problem: As V5 Si3 forms on surface, actual reagent gas Si mole fraction consumed
at surface is higher (0.375) than the input reactant gas ratio supplied
(0.20). Thus Si at surface is depleted, more Vanadium is ava ilable at the
surface and actual equilibrium shifts to production of V3 Si.

Procedure: Hold temperature constant but shift the input gas mole fraction to 0.5.

Problem: As V5 Si3 forms on surface, actual reagent vanadium gas mole fraction
consumed (0.625) is higher than the input gas mole fraction for vanadium.
Thus Vanadium at surface is depleted, more Silicon is available at the
surface and actual equilibrium shifts to production of VSi2 .
Reaction Kinetics

Titanium Diboron Deposition Arrhenius Plot

Reaction Temperatures (2000 K to 1000 K)

P = 0.263 Atm.
10.0
Input flow Rate = 462 cc /min

1.0
B/(B + Ti) = 0.66
Input Gases
Cl/(Cl + H) = 0.33
TiCl 4
BCl3
5.0 6.0 7.0 H2
8.0 9.0
-1
1/T (x 10 / K)

Besmann ,J. Electrochem. Soc.

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

10.0

(f)
1.0 (a)

1/T
Higher Surface Reaction Rates Lower Surface Temperatures

Use Graphic for Educational Value Only

 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 1/ T1
New Operating
Temperature Current
1/T
Operating Temperature

ln (r /r ) ' (q + / k ) (T &T / T T )
g2 g1 act 2 1 2 1
C) Operational Overviews
Polycrystalline Silicon (Polysilicon) H
Si
H H H
APCVD LPCVD
o o
575 to 650 C 575 to 650 C
25 PA to 130 PA 25 PA to 130 PA
Si 100% Silane 20% to 30% Silane
High Exposure Limit
Pyrophoric Si Si
Toxic ( 1 Atm but 90% N 2 )

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
H

Si Films Contain Hydrogen as

H H H Silanol (SiOH)
(Oxidation)
Hydride (SiH)
400 - 450 C Or Water
O2

SiO2 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 TEOS

H H H
H H
Si C
Si H C C
O O C H
O
H H H H H
CH2CH3
650 to 750 C (LPCVD) 650 to 750 C
NO 100 to 1000 std. cc / min
30 PA to 250 PA

SiO 2 SiO 2
High Temperature
Dichlorosilane
Cl

Si
Cl H H

Nitrous Oxide 850 to 900 C

(N 2O) LPCVD

SiO2
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
Cl
Cl H Si
H Si
H Si Cl H
Cl H
Cl H

N N
H H H
H H
H

Precursor
H N Si Cl

Cl
H 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)