OXIDATION- Overview

Process Types

Details of Thermal Oxidation

Models

Relevant Issues

Uses

As a part of a structure

e.g. Gate Oxide

or hard mas!s

e.g. In "itride #tch$ implant mas! ...

Protecting the silicon surface %Passivation &

Insulator %I'D(IMD&

As part of )mild etch* %oxidation ( removal cycles&

+hether useful or not$ automatically forms in am,ient

"ative Oxide % - ./ A thic!&

except 01terminated 2i %333&

Processes

Thermal Oxidation %0eating&

Dry vs +et

#lectrochemical Oxidation %Anodi4ation&

Oxide %and nitride&

adhere 5ell to the silicon

good insulator

6rea!do5n voltage 3/ M7(cm

889 :an ma!e a very thin gate

Structure

Tetrahedral 2tructure

each 2i to four O

each O to t5o 2i

2ingle crystal ;uart4 %density ..< g(cm

=
&

used silica %density ... g(cm

=
&

Reaction 5ith 5ater

>Time Domain :7D
.
/ Si O Si H Si OH Si OH + +

2i1O0 termination is sta,le

structure is more porous than 2i1O12i

Thermal Oxidation
Dry oxidation
. .
Si O SiO +
. . .
. . Si H O SiO H + +

Dense oxide formed

%good ;uality$ lo5 diffusion&

slo5 gro5th rate

"##D TO ?##P
+AT#R O@T O T0#
2A2T#M
+et oxidation

Overall reaction

Relatively porous oxide formed

%lo5er ;uality$ species diffuse faster&

2till good ;uality compared to

electrochem oxidation$ for
example

faster gro5th rate

+et oxide for mas!ing Dry oxide for gate ox

Wet Oxidation

Proposed Mechanism
.
Si O Si H O SiOH SiOH + +
.
. . Si OH Si Si Si O Si H + +

0ydration near 2ilicon( 2ilicon oxide interface

Oxidation of silicon

0ydrogen rapidly diffuses out

2ome hydrogen may form hydroxyl group

.
3
.
Si O H SiOH +

Diusivities in Oxide

Oxygen diffuses faster %compared to 5ater&

2odium and 0ydrogen diffuse very fast

+ater
Oxygen
0ydrogen
2odium
3(T
D
i
f
f
u
s
i
v
i
t
y

%
l
o
g

s
c
a
l
e
&

Oxide !rowth "Thermal#
2i Oxide
Original 2i surface

To o,tain 3 unit of oxide$

almost half unit of silicon is
consumed %/.BB&

Oxidation occurs at the

2i(2iO
.
interface

i.e. Oxidi4ing species has

to diffuse through )already
existing* silicon oxide

Oxide !rowth "Thermal#
2ilicon Oxide Air %6'&

At any point
of time$ amount
of oxide is
varia,le )x*

@sually$
concentration of
oxidi4ing species
%0
.
O or O
.
& is
sufficiently high
in gas phase

889 2aturated
in the oxide
interface
x
Distance
:
o
n
c
e
n
t
r
a
t
i
o
n
o
i

Oxidation $inetics

At steady state
diffusion through oxide 8 reaction rate at the 2i(2iO
.

interface

Oxygen diffuses faster than +ater

0o5ever$ 5ater solu,ility is very high %3/// times&

889 #ffectively 5ater concentration at the interface is

higher

889 5et oxidation faster

dN
% D
dx

% &
o i
N N
D
x

i
&ate ' N
o
i
N
N D
'x D

+
At steady state
Diffusion
Reaction

Oxidation $inetics

Oxide Gro5th Rate

o
DN
%
D
x
'

+
lux at
steady state
dx
dt
8 lux( C oxidi4ing species per unit volume %of 2iO
.
&
n 8 ... D 3/
..
cm
1=
for O
.
8 B.B D 3/
..
cm
1=
for 0
.
O
%
n
o
DN dx
D
dt
x
'

+
/
i
x x at t
#;n
Initial :ondition

<./.=x3/
.=
molecules

83 mol of oxide 8 x g of
oxide

8 y cm= of oxide %from

density&

... x 3/
..
molecules(cm
=

One O
.
per 2iO
.
T5o 0
.
/ per 2iO
.

Deal-!rove (odel
.
/
. .
% &
DN D
x x t
' n
+ +
2olution
( )
.
i i
x x
)
)
A
+
.D
A
'

.
o
DN
)
n

5here
( )
.
x x
t
)
)
A
+
OR
is the time needed to gro5 the )initial* oxide

A and 6 depend on diffusivity EDF$ solu,ility and C

oxidi4ing species per unit volume EnF

A and 6 5ill ,e different for Dry and +et oxidation

6ruce Deal G Andy Grove

*inear + Para,olic &e-imes

'inear vs Para,olic Regimes

?inetic :ontrolled vs Mass Transfer :ontrolled

Initially faster gro5th rate$ then slo5er gro5th rate

% &
)
x t
A
+

7ery short Time

.
% & x ) t +

'onger Time
If one starts 5ith thin oxide %or ,are silicon&
3
.
.
B
/.H 3 % & 3
)
x A t
A

_


+ +
' )


,
.
% &
B
A
t
)
+ =
( )
.
B
A
t
)
+ ?
( )
.
B
A
t
)
+ ?

.x/onential &e-ime

0ypothesis 3

:harged species forms

holes diffuse faster ( set up electrical field

diffusion I drift 889 effective diffusivity high

space charge regime controls

length 8 3H nm for oxygen$ /.H nm for 5ater

889 5et oxidation not affected

or dry oxidation$ one finds that is not 4ero in the model

fit

A corresponding to an initial thic!ness of .H nm provides

good fit

Initial gro5th at very high rate

Approximated ,y exponential curve

If one starts 5ith ,are oxide

.x/onential &e-ime

0ypothesis .

In dry oxidation$ many )open* areas exist

oxygen diffuses fast in silicon

hence more initial gro5th rate

once covered ,y silicon di oxide$ slo5 diffusion

0ypothesis =

#ven ,efore reaction %at high temp&$ oxygen dissolved in

silicon %reasona,le diffusion&

once temp is increased$ H nm ;uic! oxide formation

Tem/ 0ariation o
*inear1Para,olic 2oe
'inear J6(AK
Para,olic J6K
2olu,ility and Diffusion function of temp
> May G 24e

.ect o Do/in-

Doping increases oxidation rate

2egregation

ratio of dopant in silicon ( dopant in oxide

e.g. 6oron
incorporated in oxideL
more porous oxide

more diffusion

para,olic rate
constant is higher

P not incorporated in
oxide

no significant
change in para,olic
rate constant
> May G 24e

Issues

"a diffuses fast in oxide

@se :l during oxidation

helps trap "a

helps create volatile compounds of heavy metals

%contaminant from furnace etc&

use =M 0:l or Tri chloro ethylene %T:#&

RefN 7'2I a,rication Principles ,y 2.?. Ghandhi

.lectrochemical

@se neutral solution and apply potential

Pt as counter electrode %0ydrogen evolution&

@se Ammonium hydrogen Phosphate or Phosphoric acid or

ammonia solution

2ilicon diffuses out and forms oxide

Increase in oxide thic!ness 889 increase in potential needed

self limiting

Oxide ;uality poor

@sed to oxidi4e controlled amount and strip

for diagnosis