3.155J/6.152J Sept.

27, 2004

Oxidation of Si
Why spend a whole lecture on oxidation of Si?
Ge has high µe, µh , Ge stable… … but no oxide
GaAs has high µe and direct band… … no oxide

Why SiO2?
SiO2 is stable down to 10-9 Torr, T > 900°C
SiO2 can be etched with HF which leaves Si unaffected
SiO2 is a diffusion barrier for B, P, As
SiO2 is good insulator, ρ > 1016 Ωcm, Eg = 8 eV!
O2
SiO2 has high dielectric breakdown field, 500 V/µm
SiO2 dtOxide
SiO2 growth on Si ⇒ clean Si / SiO2 interface
Si
because DSi through SiO2 << DOxy through SiO2
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O2
Because DSi through SiO2 << DOxy through SiO2
SiO2 growth occurs at inside surface SiO2 dtOxide
Si + O2 → SiO2 Si
or
Si + 2H2O = SiO2 + 2H2
(faster growth,
more porous,
lower quality)

Unsaturated bond

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O2

SiO2 dtOxide
Si

Only when oxide is

patterned does it
cause problems
with planarity.

Extra free volume

in dangling bonds of
amorphous SiO2 =>

Implications different for field vs. patterned oxide.

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RCA cleaning station for removing organic

contaminants, Na+ and other ions as well as
native oxide (by HF-dip) from Si wafers.

Oxidation furnaces for controlled growth of

oxide layer on Si:
1050 C and steam for field oxide.

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Probably safe to say that

entire course of semiconductor industry would be

different without good SiO2 growth on Si wafer.

Device fabrication, especially MOS,

would be more difficult.

Depositing SiO2 or Al2O3 is not clean.

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It’s no accident that the world leader in

Si chip technology, Intel, has been led
by the flamboyant Hungarian, Andy
Grove.
As a young researcher at Fairchild
Semiconductor, he “wrote the book” on
SiO2 growth: the Deal-Grove model.

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SiOx growth Deal-Grove model of silicon oxidation

model is similar
to CVD
SiO2but
growth occurs O2
with extra step
added: at Si / SiO2 interface SiO2
oxygen because O2
D (SiO 2 ) >> D (SiO 2 )Si
Si
diffusion
through SiOx.

Growth Process limited by

O2 dead
layer SiO Si
1. P(O2) = Pg ∝ Cg Concentration C 2
g

2. Transport O2 to SiO2 surface across dead layer J1 J1 Cs

Co
3. Adhesion of Cs(O2) at SiO2 surface C0 J2 Ci
4. Diffusion O2 through SiO2 J2 J3
5. Chemical reaction rate J3 x

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Deal-Grove model of silicon oxidation

Oxide growth rate J1 = J2 = J3
O2 dead
Ideal gas law: PgV = NkT layer SiO
Concentration 2 Si
Cg
N P Cs
= Cg = g J1
V kT Co
J2 Ci
C0 = HPs = HkBTCs
(Cgg "- C
(C Css)) J3
JJ11 > D Henry’s law
tdead layer x
C "C
J2 = D 2 (SiO 2 ) C00 - Ci i
O
Turbulence => J3 = kiCi
x ox
J1 = hg(Cg - Cs) rate constant
Diffusion (D cm2/s)
ki (cm/s)

Equate ideal!gas & J1 Equate J2 & Henry to J3

to J2 & Henry " Ci = f n ( Pg ,hg ,H,DO 2 , x oxide ,k i )
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!
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Deal-Grove model of silicon oxidation

O2 dead
J1 = J2 = J3 layer SiO
Concentration 2 Si
Cg
" Ci = f n ( Pg ,hg ,H,DO 2 , x oxide ,k i ) J1
Cs
Co
J2 Ci
! HPg / ki J3
Ci = hg
1 x 1 h= x
+ ox + HkT
h DO2 k i
mass (ki = ks in text)
transport Diffusion Reaction
J J3
! J1 2

Slowest process controls concentration of oxygen at interface…

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HPg / ki
Ci = hg
1 x 1 h= very large
+ oxO2
+ HkT
h D ki
Growth
Limits: mass
limited by: transport diffusion reaction

Diffusion limited: ! Reaction-rate limited:

!
DO2/xox < ki, h, ki < h, DO2/xox

HPg DO2 Ci = HPg

Ci =
k i x ox

!
Slower process controls concentration of oxygen at interface,
which in turn controls growth rate…
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τ is the time
corresponding to growth
Oxide growth rate of pre-existing oxide

dx ox J Ck HPg / ki
Rate of growth= = 3 = i i, Ci =
dt n SiOx n SiOx 1 x 1
+ ox +
h DO2 k i

( nSiO = # O2 molecules in oxide / cm3 )

dx ox HPg /n SiOx
SiO = 2.2 x 10 / cm , dry
n! 22 3 =
! dt 1 x ox 1 rate depends on xoxide
4.4 x 1022 / cm3, H2O + +
h D ki

x ox
"1 x ox 1 % t
HPg SiO2
( $# h + + 'dx ox =
D ki &
(n dt
! Si
x0 0 SiO x xo t≈0
"1 1 %
A = 2D$ + ' (length)
2 # h ki &
x + Ax ox = B( t + " )
ox Si
! length 2
B = 2DH Pg n SiOx ( ) t>0
time

!
2
( )
" = x 0 + Ax 0 B (time)
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! !

x ox
"1 x 1% t
HPg SiO2
( $# h + Dox + k '&dx ox = (n dt
Si
x0 i 0 SiO x t≈0
"1 1%
2 A = 2D$$ + ''
x ox + Ax ox = B( t + " ) # h ki &
Si
! B = 2DH Pg n SiOx t>0
" = ( x + Ax 0 ) B
2
0
"A + A 2 + 4B(t + # )
x ox =
2 ! Rate constants A and B known experimentally;
! both ∝ D = D0e-Ea/kT
!
Parabolic and linear growth rates xox
! Thick oxide => parabolic rate constant, B
t
τ
2
x ox >> Ax ox "Quad
"" .Eq
# x ox = B( t + $ )

xox
Thin oxide => linear rate constant, B/A
B
! 2
x ox 2
<< Ax ox "Quad
"" .Eq
# x ox $ (t + % )
A
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How thick is thick, how thin is thin?? x 2ox + Ax ox = B( t + " )

x 2ox > Ax ox or x ox > A " thick

!
( wet oxidation is much faster than dry)
!

x ox > 0.165 µm,dry; > 0.226 µm,wet " thick

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( wet oxidation is much faster than dry)

DO 2 (SiO 2 ) < DH2 O (SiO 2 )

700-1200ºC, 1 atm, 0.1 µm / hr 750-1100°C, 25 atm , 1 µm / hr

=> dry oxide, denser, => wet oxide,
! use for gate oxide.
more porous, poorer diffusion barriers;
use for etch oxide, field oxide.

Dry O2 + 1-3% Cl; Cl is a metal getter ⇒ cleaner oxide.

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Exercise: calculate xOX grown for 1 hr. in dry oxidation at 1100 °C.

From table, A = 0.09 µm , B = 0.027 µm2 / hr, τ = 0.076 hr.

"A + A 2 + 4B( t + # )
x ox = = 0.14 µm (0.1 - 1.0 µm / hr is typical)
2

This is the oxide thickness grown over any thin native oxide present.

! Now you calculate xox for steam oxidation at same time and temp.
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Why is wet oxidation faster?

SiO2/Si interface, local charges
SiO2
O2 Si
Oxygen gradient exists in SiOx.
Oxide near the interface
is a sub oxide, SiOx, x < 2.
xox
cO2 SiO2 SiO, which is often
+ charged.
WHY?

Electronegativity Si Si Si
e- e-
Si2+
Si3+
O2- Si4+ O2- O2- O2-
O O O O
SiO2 SiO
SiO+ + e-

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SiO2/Si interface and dry vs. wet oxidation

Which species
SiO2
O2 Si diffuse quickly?

Large small
O -, O, H-, H, H+, h+
Slow fast
xox
cO2 SiO2 SiO+ SiO+
cO2 SiO2
e- . e- .
H+, h+
Gases unstable at 100oC, dissociate at surface.
Outside in oxide
O2 -> O + O- +
h+ cO2 SiO2 SiO+

2H2O -> O + O- + h+ + e- .
n(H+, H, H-) O-

What does dipole layer do to ions? O - + SiO+ -> SiO2

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Initial oxidation regime. x 2ox + Ax ox = B( t + " )

Deal - Grove: at small xox,

B
x ox = (t + " ) !
A
dx ox B
= = const.
dt A
!
cOx
! δx
SiO2 To explain this…
O2 Si
many models have been proposed.
It appears that SiO2 / Si interface is not sharp.
#x
small xox Oxide grows not just at xox but also at x ox "
2
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Structure of SiO2
Si Quartzite
Si O Si
Si Si Si
bridging
O O
Si Si Si oxygen
Si O Si
Si Si Si

disorder

Amorphous
tetrahedral fewer bridging O’s,
some non-bridging.
network

Network modifiers B, P
replace Si

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Effects of Dopants on Oxidation of Si → SiO2

max
c solid
We will see segregation coefficient for crystal growth: k= max
generally < 1
c liquid
Related parameter
c X (in Si)
for segregation of impurity X on oxidation: m=
! c X (in SiO2)
Impurity concentration profiles depend on m, Dx in Si, Dx in SiO2 and growth rate
(not shown below):
m > 1 ( oxide rejects impurity,
! X)
x x
D (SiO 2 ) < D (Si) Dx (SiO 2 ) > Dx (Si)
SiO2 Si SiO2 Si
J x (SiO 2 ) int = J x (Si) CX (0) CX (0)

m < 1( oxide consumes X )

Dx (SiO 2 ) < Dx (Si) Dx (SiO 2 ) > Dx (Si)
SiO2 Si SiO2 Si
CX (0) CX (0)

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Common dopants in Si enhance oxidation at higher concentration

boron phosphorus

CP

Oxide thickness vs. wet oxidation time Linear, B/A, and parabolic, B, rate constants
For three different boron concentrations vs. phosphorus concentration.

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Now, go grow
some glass!

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