Thin Film Silicon Dioxide

(primarily oxidation of silicon)

ECE 4752





Thanks to Prof. Brand and Bakir for some of the included slides.




Common Methodologies for Thin
Film Silicon Dioxide

Thermal Silicon Dioxide
Chemical Vapor Deposited SiO
2

Physical Vapor Deposited SiO
2
Sol Gel Deposited SiO
2

Electro-chemical (anodization) SiO
2
Ion Implantation of O
2
in Silicon (SIMOX Process)





Oxidation of Si? Thermal Oxidation
Silicon wafer is oxidized in an O
2

or water vapor atmosphere at
temperatures ranging from 900-
1200C
Ability to grow a high quality
thermal oxide has propelled Si
into the forefront of all
semiconductor technologies
Thermal oxidation consumes
silicon: for 1 m grown oxide,
approximately 440 nm of silicon
are consumed
Thermal oxidation generally
results in the best quality oxide


Sze, Fig. 11.3

t
Si
= 0.44 t
SiO2
Application of Thermal Oxidation
Thermal oxidation is used for
Growth of field oxide separating neighboring transistors
Growth of high quality gate oxide of MOS structure
Growth of diffusion mask (even though ion implantation is mostly
used for pre-deposition today)
When to use it and when not to use it
Use when highest quality silicon dioxide layers are required
Do not use when process temperature is restricted (e.g. after
aluminum metallization)

Structure of Thermal SiO
2
The form of thermally grown SiO
2
is
fused silica, which is an amorphous solid
SiO
2
is a glass (similar to window glass)
and can be reflown if heated above its
glass transition temperature
Fused silica consists of silicon atoms
sitting at the center of oxygen polyhedra;
the polyhedra are randomly connected at
bridging oxygen sites, i.e. O atoms that bond to two silicon atoms
Dry oxides have a larger ratio of bridging to non-bridging sites
compared to wet oxides, and are thus more stable
Doping SiO
2
with boron or phosphorus (so called network modifiers)
reduces the bridging-to-nonbridging ratio, which allows the glass to
reflow at lower temperatures, smoothing surface topographies (known
as phosphosilicate glass, PSG, and borophosphosilicate glass,
BPSG)
Campbell, Fig. 4.7
Structure of Thermal SiO
2
(a) Polyhedra (Tetrahedron) Basic Structure of SiO
2

(b) Quartz crystal (c) Amorphous SiO
2

Horizontal (Oxidation) Furnace
Horizontal furnace is most common furnace type; it comprises four
components: (1) the gas cabinet, (2) the furnace cabinet, (3) the
load station and (4) the computer controller
Resistive furnace heating elements are wound around fused silica
tube; wafers are placed vertically in fused quartz boat and inserted
into heated furnace tube using cantilevered load system
Sze, Fig. 11.2 http://www.thermcosystems.eu
Vertical (Oxidation) Furnace
Vertical furnace are similar to a horizontal furnace turned on
end; the wafers are pushed from below the furnace up into the
tube
Advantages of vertical furnaces:
Simplified wafer handling by pushing carrier up instead of
using long (transversally loaded) cantilevers; support system
can remain in tube during thermal process (long cantilevers
tend to warp)
Uniform spacing between wafers improves process
uniformity
Smaller cleanroom footprint compared to horizontal furnace
As a result, vertical furnaces have become the standard,
especially for large diameter wafer processing (200 and 300mm
wafers)

Figure 3.11 Furnaces used for oxidation and diffusion
(a) A three-tube horizontal furnace with multizone
temperature control
(b) Vertical furnace (Courtesy of Crystec, Inc.)
(a)
(b)
R. C. Jaeger 2002
3.1 Dry/Wet Thermal Oxidation
Reaction Chemistry

Dry Oxidation


Wet Oxidation




Si (solid) + O
2
(gas) SiO
2


Si (solid) + 2H
2
O(gas) SiO
2
+ 2H
2
Wet/Dry Oxidation Charts
Easiest way to determine
oxidation parameters (wet/dry,
temperature) for a desired
oxide thickness
If pre-oxidized wafer is further
oxidized at temperature T, the
final oxide thickness is found by
Finding first the time
required to grow the initial
oxide at the planned T
Add to the intended
oxidation time and find
resulting overall thickness

Sze, Fig. 11.8
Dry Thermal Oxidation
See also http://www.lelandstanfordjunior.com for an on-line calculator
Sze, Fig. 11.8
Wet Thermal Oxidation
Sze, Fig. 11.8
A <100> silicon wafer has a 2000- oxide on its surface

(a) How long did it take to grow this oxide at 1100
o
C
in dry oxygen?

(b)The wafer is put back in the furnace in wet oxygen
at 1000
o
C. How long will it take to grow an additional
3000 of oxide?
(a) According to Figure, it would take 2.8
hr to grow 0.2 m oxide in dry oxygen
at 1100
o
C.

(b) The total oxide thickness at the end
of the oxidation would be 0.5 m
which would require 1.5 hr to grow if
there was no oxide on the surface to
begin with. However, the wafer
thinks it has already been in the
furnace 0.4 hr. Thus the additional
time needed to grow the 0.3 m
oxide is 1.5-0.4 = 1.1 hr.
4.2 Deal-Grove Model for Oxidation
Diffusivity of Si in SiO
2
is several orders of magnitude smaller
than that of O
2
; thus, O
2
diffuses through the already existing
oxide and reacts with Si at the Si-SiO
2
interface, further growing
the oxide layer
As a result, the interface at which the SiO
2
grows is not exposed
to the environment and thus free of impurities
At room temperature, a native oxide layer with a thickness of
25 grows on top of silicon
Deal-Grove model is suitable for predicting thermal oxide
thicknesses > 30 nm
Assuming a dry oxidation, the Deal-Grove model considers
transport of O
2
through the stagnant gas layer to the SiO
2

surface, diffusion of O
2
through the SiO
2
layer and reaction of
the O
2
with Si at the SiO
2
-Si interface
Deal-Grove Oxidation Model
Oxygen flux by diffusion of O
2

through the stagnant gas layer



or more general


with thickness of stagnant gas
layer t
sl
and mass transport
coefficient h
g
C
g
is related to the partial
pressure of O
2
in the furnace
via the ideal gas law



C
g
oxygen conc. in gas far from wafer
C
s
oxygen conc. in gas at wafer surface
C
o
oxygen conc. in oxide at wafer surface
C
i
oxygen conc. at Si-SiO
2
interface
Campbell, Fig. 4.1


J
1
~ D
O2,gas
C
g
C
s
t
sl


J
1
= h
g
(C
g
C
s
)


C
g
=
n
V
=
p
g
kT
Deal-Grove Oxidation Model (cont.)
Oxygen flux by diffusion of O
2
through the oxide layer



Oxygen flux associated with oxygen reacting with Si at Si-SiO
2

interface

with chemical rate constant k
s
In equilibrium, the three fluxes must be equal, J
1
= J
2
= J
3
, resulting
in two equations with three unknowns C
s
, C
o
, and C
i
In addition, Henrys law states that the concentration of an
adsorbed species at a surface of a solid is proportional to the
partial pressure of that species in the gas above the solid


with Henrys gas constant H (not really a constant, but depending
on species, surface, T, etc.) as the proportionality constant





J
2
~ D
O2,SiO2
C
o
C
i
t
ox


J
3
= k
s
C
i


C
o
= Hp
g
= HkTC
s
Deal-Grove Oxidation Model (cont.)
The resulting three equations with three unknowns can be
solved, yielding



The oxide growth rate is given by the ratio of the oxygen flux J
[s
-1
cm
-2
] and the number N
1
of oxygen molecules per unit
volume of SiO
2
[cm
-3
]:



with D = D
O2,SiO2
; dry oxidation: N
1
= 2.2 10
22
cm
-3
(because O
2

diffuses); wet oxidation: N
1
= 4.4 10
22
cm
-3
(because O diffuses)

The above rate equation is a differential equation for t
ox
; it can
be solved assuming the boundary condition




C
i
=
Hp
g
1+
k
s
h
g
/ HkT
+
k
s
t
ox
D
C
i
0 for D 0
C
i

Hp
g
1+
k
s
h
g
/ HkT
for D









t
ox
(t = 0) = t
0


R =
dt
ox
dt
=
J
N
1
=
Hk
s
p
g
N
1
1+
k
s
h
g
/ HkT
+
k
s
t
ox
D



(

(
Diffusion limited
Reaction limited
Deal-Grove Oxidation Model (cont.)
The solution of the DE is







Typically, the coefficients A and B are known for a variety of
process conditions; for oxidation at atmospheric pressure, we have
k
s
<< h = h
g
/HkT and the growth rate becomes independent of gas
phase mass transport and thus reactor geometry; A and B are
proportional to D and thus will follow an Arrhenius function
The time is the time needed to grow the initial oxide thickness t
0
;
thus, the oxidation actually starts at time and at t=0, the oxide
thickness is t
0





t
ox
2
+ A t
ox
= B(t + t)
A = 2D
1
k
s
+
1
h
|
\

|
.
|
B =
2DHp
g
N
1
t =
t
0
2
+ A t
0
B


t
ox
=
A + A
2
+ 4B(t + t)
2
Deal-Grove Oxidation Model (cont.)
Thin Oxides: For sufficiently thin oxides, we can neglect the
quadratic term and the oxide thickness becomes


with the linear rate coefficient B/A [m/hr]
Thick Oxides: For sufficiently thick oxides, we can neglect the
linear term and the oxide thickness becomes

with the parabolic rate coefficient B [m
2
/hr]



t
ox
~
B
A
(t + t)


t
ox
2
~ B(t + t)
Campbell, Tab. 4.1
Linear/Parabolic Rate Coefficient
B B/A
Campbell, Figs. 4.2/4.3
Deal Grove Model Rate Constants
Impurity Segregation Coefficient

k =
EquilibriumImpurityConcentrationinSilicon
EquilibriumImpurityConcentrationinSiliconDioxide
Masking Diffusions using SiO
2

Determining the Thickness of SiO
2

1. Color Charts
2. Ellipsometry
3. Controlled Etching
4. Optical Interference
1. based on reflected light intensity spectra


n
ox
= real part of the oxide refractive index
= difference in the wavelength between the min
and max intensity in the fringe pattern spectra
Determining the Thickness of SiO
2

Practical Considerations
Metallic Impurity Gettering: Halogen species (Cl, F, etc.) are often
introduced to getter metallic impurities from the tube during an oxidation; this
also tends to increase the oxidation rate for thin oxides (linear term). HCl is
the safest to use (bubbled into the furnace as described in the diffusion
discussion) but is highly corrosive to the gas tubing; trichloroethylene (TCE)
and trichloroethane (TCA) are less corrosive but can be toxic. TCA can form
phosgene (COCl
2
) at high temperatures.
Thick Oxides: The growth of thick oxides is proportional to B and thus to the
oxygen partial pressure in the gas p
g
; thus, the growth rate can be increased
by growing the oxide at high pressure.
Thin Oxides: Most thin (t
ox
few hundred angstroms) dry oxides grow at a
rate faster than Deal-Grove predicts. Corrections can be made to work down
to ~ 300 , but modern MOS gate oxides are < 100 .
Orientation Dependence: Oxidation rate depends on orientation. MOS uses
<100> oriented wafers because it has the fewest atoms per cm
2
, results in
lower interface state density.
Isolation technology in
MOS processes

Provides isolation
between nearby devices

Fully recessed process
attempts to minimize
birds beak
Local Oxidation of Silicon
(LOCOS)
R. C. Jaeger 2002
Local Oxidation of Silicon
(LOCOS)