EE 143: Microfabrication Technology CTN 9/25/14

Lecture Module 2: Oxidation

EE 143
Microfabrication Technology
Fall 2014
Prof. Clark T.-C. Nguyen
Dept. of Electrical Engineering & Computer Sciences
University of California at Berkeley
Berkeley, CA 94720

Lecture Module 2: Oxidation

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Oxidation

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EE 143: Microfabrication Technology CTN 9/25/14
Lecture Module 2: Oxidation

Thermal Oxidation of Silicon

• Achieved by heating the silicon wafer to a high temperature
(~900oC to 1200oC) in an atmosphere containing pure oxygen
or water vapor
• Enabling reactions:
For dry oxygen: For water vapor:

Si + O2 → SiO2 Si + 2H2O → SiO2 + 2H2

Schematically:
56%

High T (~900oC – 1200oC) →

Si Wafer →
Si Wafer
In dry O2 44%
or
Water vapor

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Oxidation Modeling

(1) Initially: (no oxide @ surface)

gas stream

Growth rate determined by
Si
reaction rate @ the surface

(2) As oxide builds up:

gas stream

Reactant must diffuse to Si

oxide
surface where the oxidation
Si reaction takes place

Growth rate governed more
by rate of diffusion to the
silicon-oxide interface

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EE 143: Microfabrication Technology CTN 9/25/14
Lecture Module 2: Oxidation

Oxidation Modeling (cont.)

reactant concentration
N
Si NO = reactant conc. at oxide surface [in cm-2]
SiO2
NO
Ni = reactant conc. at Si-SiO2 interface

J ∂N ( x , t ) [Fick’s 1st
J = reactant flux = − D Law of
Ni ∂x
Diffusion]
Xox Diffusion coeff.
[in µm/hr or m/s]
distance
from
surface Si-SiO2 interface surface

( NO − Ni ) (1)
In the SiO2: J =D = constant
X OX Assumption that the
reactant does not
[in # particles/(cm2• s)] accumulate in the oxide.
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Oxidation Modeling (cont.)

At the Si-SiO2 interface:
Oxidation rate ∝ Ni ∴ J ∝ Ni J = ks Ni (2)

Reaction∴rate constant
Combining (1) and (2): @ Si-SiO2 interface
 NO − J 
 J  ks 
 N i =  ⇒ J = D 
 ks   X OX 
 
DJ  D
JX OX = DN O − → J  X OX +  = DN O
ks  ks 

∴ DN O
J= = Flux of reactants
D
X OX +
ks

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EE 143: Microfabrication Technology CTN 9/25/14
Lecture Module 2: Oxidation

Oxidation Modeling (cont.)

Find an expression for X OX (t ): oxidizing flux

Rate of change of oxide dX OX J DN O M

= = = (3)
layer thickness w/time dt M X OX + D k s

# of molecules of oxidizing = 2.2×1022 cm−3 for O2

species incorporated into a
unit volume of oxide = 4.4×1022cm−3 for H2O

Solve (3) for X OX (t ) : [Initial condition X OX (t = 0) = X i ]

X t
dXOX D NO M OX
DN O
=
∫ (X OX + k ) dX OX = ∫
D
dt
dt XOX + D ks X 0
i
M s

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Oxide Thickness Versus Time

Result:
additional time required time required to grow X i
to go from X i → X OX [Xi = initial oxide thickness]

A  4 B 
1
 2
X OX (t ) = 1 + 2 (t + τ ) − 1
2  A  

2D X i2 Xi
where A= τ= +
ks B (B A)
2 DN O  E 
B= D = DO exp  − A 
M  kT 
i.e., D governed by an Arrhenius
relationship → temperature dependent

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EE 143: Microfabrication Technology CTN 9/25/14
Lecture Module 2: Oxidation

Oxidation Modeling (cont.)

For shorter times:

oxide growth
 A2  B limited by reaction
(t + τ ) <<  ⇒ X OX (t ) =  (t + τ ) ⇒ at the Si-SiO2
 4B   A interface

Taylor expansion (first linear growth rate constant

term after 1’s cancel)

For long oxidation times: oxide growth diffusion-limited

 A2 
(t + τ ) >>  ⇒ X OX (t ) = B(t + τ ) ≈ Bt
 4 B 
t >> τ Parabolic
rate constant
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Oxidation Rate Constants

• Above theory is great … but usually, the equations are not

used in practice, since measured data is available

Rather, oxidation growth charts are used

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EE 143: Microfabrication Technology CTN 9/25/14
Lecture Module 2: Oxidation

Oxidation Growth Charts

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Using the Oxidation Growth Charts

Example: Growth Chart for <100> Silicon
• <100> silicon
• Starting oxide
thickness: Xi=100nm
• Want to do wet
oxidation @ 1000oC to
achieve Xox=230nm
• What is the time t
required for this?

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EE 143: Microfabrication Technology CTN 9/25/14
Lecture Module 2: Oxidation

Factors Affecting Oxidation

• In summary, oxide thickness is dependent upon:
1. Time of oxidation
2. Temperature of oxidation
3. Partial pressure of oxidizing species (∝ No)
• Also dependent on:
4. Reactant type:
Dry O2
Water vapor
faster oxidation, since water has a
higher solubility (i.e., D) in SiO2 than O2
5. Crystal orientation:
<111> ← faster, because there are more bonds
available at the Si-surface
<100> ← fewer interface traps; smaller # of
unsatisfied Si-bonds at the Si-SiO2 interface

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Factors Affecting Oxidation

6. Impurity doping:
P: increases linear rate const.
no affect on parabolic rate constant
faster initial growth → surface reaction rate limited
B: no effect on linear rate const.
increases parabolic rate const.
faster growth over an initial oxide → diffusion faster

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EE 143: Microfabrication Technology CTN 9/25/14
Lecture Module 2: Oxidation

Dopant Redistribution During Oxidation

• This must be considered and designed for when generating
any process flow, especially for transistor circuits, e.g.,
CMOS
• During oxidation, the impurity concentration at the Si-SiO2.
interface can increase (pile-up) or deplete, depending upon
the dopant type
• Whether a particular impurity depletes or piles up @ the
interface depends on:
1. Diffusion coefficient, D (of the impurity in SiO2)
2. Segregation coefficient, m:

impurity equil. conc. in Si

m=
impurity equil. conc. in SiO 2

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Dopant Behavior During Oxidation

• Segregation coefficient (m) and diffusion constant (D)
combine to determine dopant behavior during oxidation:

Dopant Behavior During

Impurity m D in SiO2
Oxidation
depl. f/Si surface, pile up
B <0.3 (small) Small
in oxide
depl. f/Si surface, depl.
B (oxidation w/H2) <0.3 (small) Large
from oxide
pile up in Si, very little
P, Sn, As ~10 (large) Small
diff. into SiO2
Ga 20 (large) Large depl. f/Si, depl. from oxide

So large that it depletes

e.g., wet oxidation
the dopant @ the Si
where H2 is present
surface despite
as a by-product.
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Copyright @ 2014 Regents of the University of California at Berkeley

EE 143: Microfabrication Technology CTN 9/25/14
Lecture Module 2: Oxidation

Dopant Redistribution During Oxidation

B B (oxidation w/ H2)

P, Sn, As Ga
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Copyright @ 2014 Regents of the University of California at Berkeley